description stringlengths 2.98k 3.35M | abstract stringlengths 94 10.6k | cpc int64 0 8 |
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BACKGROUND OF THE INVENTION
The present invention relates to a laundry waste water treatment and wash process and in particular to such a process using only ozone as the cleaning and disinfecting product.
Typically ozone is generated when oxygen, O 2 , is exposed to ultraviolet light or an electrical charge which breaks it down to individual oxygen molecules. Some of these recombine into ozone, O 3 . Ozone is the triatomic, allotropic form of oxygen O 2 . It is an unstable gas with a pungent odor and it is normally produced in low concentrations. The chemically active O 3 then acts as an oxidant to break down compounds it comes in contact with.
When ozone is created by an ozonator, air is subjected to an electric discharge commonly known as a corona which is produced by an electric charge between parallel or concentric electrodes separated by a dielectric to prevent a spark discharge. Normally a blower forces air between the electrodes and when an alternating potential from 6,000-30,000 volts, depending upon the thickness of the air space and the dielectric material, is applied to the electrodes, the part of the oxygen in the air is transformed into charged oxygen atoms, ions, which conduct the electric current. Some of these ions recombine to form pre-atom molecules O 3 or ozone. Because the ozone is unstable, it is important to remove the ozone as quickly as possible after it is produced and normal ozonators provide a minimum air velocity for sufficient operation to remove the ozone from the electrodes. Increasing the frequency of the power supply to the ozonator increases both the current and the yield of ozone; however, very high frequencies often require water cooling of the electrodes. Because of its instability, the ozone must be generated at the point of application and prior art systems often do not produce enough ozone for a particular application.
Since ozone is a powerful oxidant, it is well-known as a sterilizing and preserving agent as well as a chemical oxidizing agent. Among the uses for ozone are the sterilization and preservation of foods such as cheese, eggs, meat, poultry, fruit and so forth. Using ozone as a food preservation agent was known in the Republic of Germany in the early 20th century. It is also well-known in Australia to preserve meat using ozone in the mid-1930's. Ozone is well-known in the purifying and cleaning of water for a variety of purposes including drinking, bathing, cleaning and so forth.
Ozone also is used to control airborne organics, bacteria and viruses by chemically reacting with them. This makes ozone useful in health care applications as a disinfectant such as patient and operating rooms, physical therapy rooms, laundry and disposal rooms, food service industries, hotels, restaurants, livestock industries among others.
The prior art has recognized the usefulness of ozone with laundry washing processes. For example, Japanese Patent No. 2,149,293 relates to a wet clothes washing unit comprising a washing tank, a foaming device with a nozzle for dispersion of bubble generation and an ozone generator for feeding ozone containing air into the nozzle. The ozone is ejected in the form of bubbles through a porous plate which is transmitted to the wash water and laundry which helps clean the laundry without mechanical stirring to remove stains by a bleaching action. Spanish Patent No. 2,006,978 relates to an ozone generator for washing machines having an internal electrode encapsulated in the glass tube and a coaxial metal tube as an external electrode. Air is drawn by a pump over the generator electrode and passed into the wash bath. Japanese Patent No. 86-218,645 describes an electric washing machine with a built in bleaching function which incorporates an ozone generator and air diffuser pipe for blowing ozone into the washing machine to bleach clothes without using a bleaching agent. Belgian Patent No. 899,577 discloses a washing machine which agitates clothes with compressed air and ozone blown into the washing chamber. German Patent No. 3,232,057 discloses a washing machine with an ozone generator to kill bacteria using an ozone atomizer spray and feed channel which lead into the cleaning fluid vessel and acts during the rinsing phase. Another German Patent No. DE 3,007,670 describes a detergent free laundering process of textiles using an aqueous solution of bromide or bromic acid and ozone.
The present invention relates to a laundry waste water and wash treatment process wherein water is continually recycled and filtered in a washing machine system using ozone as the primary disinfecting, cleaning and bleaching agent. With this system, it is not necessary to use conventional detergents and soaps which make the water unusable except for an initial cleaning process. The process contemplates recycling the water, both during the cleaning cycle and the rinse cycle, without adverse effects to the washing process. Rather, ozone washed laundry exhibits a high quality of cleanliness and freedom from bacteria as well as providing an aesthetically clean looking and smelling laundry product.
In a preferred embodiment, water is recycled from a collection sump and is pumped to a storage tank where it is stored until it is needed for a wash cycle. When a wash cycle begins, the water is pumped from the storage tank, through a filtered line into a holding tank. The water is the holding tank is treated with ozone which is entrained into the holding tank water as it is being stored. The water in the holding tank is kept in a continual state of flow by being pumped from the tank bottom through a filter and returned to the top of the tank. When a wash cycle is activated, water is pumped directly to a washing machine or machines for use in a conventional wash cycle. After the wash cycle is complete, the water is drained into the sump and a rinse cycle is initiated by pumping additional water from the holding tank into the machines. With the present system there is no need for the water to be heated thereby enabling the fluid to be kept in a closed cycle system. Additional water is periodically added to either the storage tank or holding tank to compensate for the loss of water in the system due to evaporation, spillage and to replace the water removed by the wet laundry.
With the present system, using recycled water, water savings is considerable. When used in commercial and institutional locations, millions of gallons of water per year can be saved. The problem of eliminating waste water and the treatment of this water which in previous systems would eventually find its way back into the ecological water supply is eliminated. The ozonated wash water eliminates the use of soap and other sour and toxic chemicals and the resulting environmental degradation caused thereby. Not least of all, the present system increases the capacity of the washing machines in use, eliminates the use for hot water and generally greatly reduces the cost of laundry operations.
Among the objects of the present invention are the provision of an ozone laundry waste water treatment and wash system which saves water, eliminates the need for hot water, soap and chemicals and greatly reduces the costs of operation of the various systems.
These and other objects will become apparent with reference to the following drawings and specification.
DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a closed loop laundry waste water treatment and wash system in accordance with the present invention.
FIG. 2 illustrates a corona discharge unit used in the system of FIG. 1.
FIG. 3 illustrates a detail of the unit of FIG. 2.
FIG. 4 is a top plan view of an ozonator used with the system of FIG. 1.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to the drawings, the laundry waste water treatment and wash process includes a series of washing machines 10 such as are found in a commercial laundry institution, laundromat or similar establishment. Each machine is capable of being operated independently of the other and is supplied with water through a water supply line 12 connected to a water holding tank 14 which pumps the wash water into the machines 10 using a supply pump 13. The washing machines 10 are drained into a sump 16 which collects the waste water for recycling. After a wash cycle is completed, the water from the sump 16 is pumped by a sump pump 15 or gravity fed through a resupply line 17 to a storage tank 18 where it is collected. Prior to the initiation of a wash cycle, the water from the storage tank 18 is fed by a pump 19 through a filter 20 into the holding tank 14. A supply of fresh water may also be added through line 22 from a source (not shown) through a suitable valve 23 to replace the water which is lost during the wash cycle due to spillage, evaporation and the wetting of the laundry being washed. The holding tank 14 is provided with at least one and preferably a series of ozonators 24 which inject ozone into the water in the holding tank 14 at a controlled rate.
The ozone is entrained from the ozonators 24 through an ozone supply line 32 by an ozone pump 34 into the holding tank 14 using a nozzle 36 which directs the ozone against a rotating impeller 38 attached to and driven by a motor 40. The impeller 38 aids in thoroughly mixing the ozone within the water held in the holding tank 14. It will be appreciated that the motor 40 may be a submersible type or may be located outside the holding tank 14 with a suitable mechanical connection to the impeller 38.
The water in the holding tank 14 is continuously circulated using a recirculation pump 26 which pumps water from the bottom of the holding tank 14, through filters 28 and 30, and back into the top of the tank 14. This recirculation of the water, continuously cleans the water using the filters 28 and 30 and also creates a continuous agitation of the water in the holding tank which further aids in mixing the ozone in the water being stored in the holding tank 14.
Referring to FIGS. 2 and 3, the ozonators 24 are formed of a plurality of corona discharge units 50. Each unit includes an evacuated glass envelope 51 which is generally cylindrical in shape having closed ends 52 and 54. The interior of the glass envelope 51 includes a permanently fixed electrode 56 having conductive leads 58 which are connected to a high voltage transformer (not shown) having a high voltage output, for example 10,000 volts. The interior of the envelope 51 is filled with an inert gas such as argon or the like or a combination of such gases. The outside surface of the glass envelope 51 is formed with a helical rib 55 extending the length of the envelope. The rib 55 ma be glass integrally formed with the outside of the envelope or may be a teflon wrap or other similar material adhered to the outside of the envelope after it is made. The outer portion of the corona discharge unit 50 is formed with a metallic sleeve 57 closely fit to the helical rib 55 on the outside of the glass envelope 51 forming an air tight seal between the glass envelope 51 along the rib 55 and the metallic sleeve 56. This creates a helical air flow path from the top of the corona discharge unit 50 to the bottom. When the high voltage is impressed across the electrode 56, an electric field is produced which interacts with the inert gas creating a corona charge on the outside of the glass envelope 51. The corona charge interacts with the oxygen in the air, breaking it down into individual oxygen molecules O. Some of these molecules recombine into the unstable O 3 form which is ozone. Air flows across the outside of the envelope 51 in the helical path formed between the envelope 51 and the outer metallic sleeve 56. This aids in breaking down the oxygen to ozone due to the increased time the air remains across the surface of the charged envelope 51. Preferably the air is either drawn by suction or pumped from one end of the tube to the other to facilitate continuous air flow and collection of the ozone.
FIG. 4 illustrates a typical ozonator 24 as seen in plan. The ozonator 24 is formed with a series of corona discharge units 51 placed lengthwise in an outer housing 60 to create multiple sources of ozone. Typically 6 to 10 corona discharge units 51 are used with each ozonator, however, it will be appreciated that any number may be provided depending upon the requirements of the system. The housing 60 is provided with water cooled tubes 62 which circulate water or other cooling fluid within the ozonator to cool the corona discharge units.
Whereas FIG. 4 illustrates only a partially filled outer housing, it will be appreciated that the housing is sized to accommodate the number of corona discharge units and water cooled tubes.
As can be seen from the schematic of the wash system, a continuous, closed fluid flow loop is provided. In a typical closed loop washing system, such as might be found in an institution, commercial laundry or the like, a series of washing machines 10, each capable of washing a 125 pound load, are connected to a source of ozonated water washing fluid held in the water holding tank 14, capable of holding from 500 to 1,000 gallons of ozonated water. The machines 10 typically are designed to hold between 30 and 90 gallons of water for a given wash cycle. The washing fluid in the holding tank 14 is continuously circulated from the bottom of the tank to the top of the tank using the recirculating pump 26 which pumps the washing fluid from the bottom of the holding tank 14 through a series of filters 28 and 30 back into the top of the tank 14. This recirculation of the water aids in cleaning the water with the filters and also in mixing the ozone in the ozonated water washing fluid. The pump may be continuously or intermittently operated in order to keep the ozone evenly circulated within the water.
In a typical system using the present invention, the water is kept at room temperature and requires no soap or detergent during the washing process. Water from the storage tank 18 is pumped through the filter 20 to the holding tank 14. When a wash cycle is initiated, the ozonated water is pumped to the machines for the wash cycle. When the wash cycle is terminated, the used wash water is drained into the sump 16 and is eventually pumped back to the storage tank 18. Additional ozonated water is pumped to the machines for the rinse cycle and discharged to the sump when the rinse cycle is complete. Automatic level controls (not shown) such as float switches or level sensors control the transfer of water between the various storage and collecting areas. The recycled water is properly filtered using state of the art filter units so the water used in subsequent wash cycles is clean.
As indicated above, the system loses water by evaporation, spillage and splashing and through being carried away by the laundry at the completion of a cycle. This loss is replaced from a standard supply source of cold water. The replacement water represent only a small fraction of the amount of water used in similar systems where the use of soap, detergent and bleaches requires the wash water be disposed of and replaced after each use. It will be appreciated that modifications may be made in the system and apparatus described hereinabove in keeping within the scope of the present invention as defined in the following claims. | A method and apparatus for washing laundry without hot water and detergent using a closed loop ozonated wash water system wherein wash water maintained in a storage tank is ozonated by an ozone generator prior to use in a washing machine. The spent wash water is collected, filtered and reused thereby eliminating waste water disposal problems and resulting in considerable water and energy savings. The ozone generator includes a unique air flow configuration to maximize ozone generation resulting in a high efficiency washing system. | 3 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the preparation of crimped tow using a stuffer box in combination with a pair of crimping rollers to feed molded tow to the stuffer box and in addition to these elements, a pair of molding rollers for molding the tow before the tow enters the crimping rollers. The addition of the molding rollers not only improves the uniformity of the crimped tow, but also improves the edge quality of the tow and reduces processing runability malfunctions resulting from the sliding resistance of the crimped tow through the stuffer box. More specifically, in one embodiment, a tow of parallel filaments is molded into a rectangular cross section by a pair of parallel, rotatable molding rollers cooperating with a pair of side plates arranged to define a rectangular mold nip through which the tow is fed. In addition to molding the tow, the molding rollers pull the tow to the molding rollers and squeeze the tow to remove any residual liquid finish from the surface thereof. Subsequent to the molding rollers, the molded tow is fed through a similar rectangular nip defined by the crimping rollers. From the crimping rollers, the molded tow material is fed into a stuffer box wherein it is crimped.
2. Prior Art
In prior art apparatuses, continuous filament tow is typically pulled, dewatered, rectangularly molded and fed by a single pair of smooth, cylindrical parallel, rotatable crimping rollers in conjunction with side plates into a rectangular stuffer box, referred to in some references as a crimping chamber. The stuffer box generally forms a substantially rectangular closed pressure zone having a weighted discharge door or flapper at the exit thereof. As the tow is fed by the crimping rollers into the stuffer box, the filaments loop back and forth upon itself and against the resistance of the inner walls of the stuffer box, forming a crimped wad. This wad is compressed in its passage through the stuffer box by the friction of the side walls and the weighted discharge flapper. The action of the crimping rollers in continuously feeding tow into the chamber produces crimps in the tow which can be later effectively set by heat or fluid treatment. The crimped tow is discharged from the stuffer box at a rate proportionate to the infeed of the crimping rollers.
Each of the crimping rollers is rotatable in opposite directions and positioned along with a side plate at each end thereof to form a rectangular nip to allow the tow to be rectangularly molded between the two rollers and two side plates. By this action, the tow is pulled through the nip, and molded, conforming to the rectangular configuration of the space between the crimping rollers and side plates, as well as squeezing any hydraulic finish from the tow.
The crimping rollers are generally arranged such that one of the rollers is adjustable, for example, by a hydraulic cylinder while the other roller is fixed. For the rollers to perform all the functions of pulling, molding, dewatering and feeding the tow requires a significant force applied by the adjustable roller against the tow material. In particular, for a 250 mm tow, between 12 and 15 tons of force are applied to the adjustable roller to accomplish all the desired functions. This high force in the nip results in decreased life of the equipment parts such as the bearings and has been found to damage the tow material including damage to the filaments. One type of damage is filament distortion, for example changing the configuration of the filaments from round to oblong which is undesirable. Furthermore, it has been found that the high nip forces press the tow material against the side plates resulting in burning or fusion of the material at the side plates. This fusion results from elevated temperatures of the tow material being excessively pressured against the side plates.
Optimally crimped tow material is produced when resistance to the rectangularly molded tow by walls of the stuffer box is evenly distributed. One factor in achieving even resistance is by feeding uniformly molded tow material into the stuffer box. This requires the preceding crimping rollers to mold the tow material to have a uniform rectangular cross section. When the molded tow is nonuniform, uneven resistance occurs between the tow and the walls of the stuffer box resulting in uneven resistance to the feeding of the tow into the stuffer box. The condition induces slack in the tow entering the stuffer box further compounding the problem. Conditions resulting from the increased resistance to the incoming tow material is erratic operation of the crimping apparatus and nonuniform crimping of the tow. Hence, it is desirous for the crimping rollers to feed uniformly rectangular molded tow to the stuffer box.
In another apparatus for crimping tow, feed rollers have been installed prior to the crimping rolls for the purpose of pulling and dewatering the tow. Such feed rollers are not pressurized as the crimping rollers and provide limited molding of the tow. Although such feed rollers are known to satisfactorily perform these two functions, their use have proved unsatisfactory in improving the uniformity of the molded tow. It has been found the problem of nonuniformly molded tow is still fed from the crimping rollers to the stuffer box resulting in the resistance against such feeding as described above. Adding the additional feeding rollers has been found to result in the tow being thinned out at the lateral edges thereof which is known as doglegging. It is believed by the inventor that the thinning of the tow of the lateral edges results in loss of crimp because of the reduced contact of the lateral edges with the crimping rollers.
The following references are directed to various apparatuses used for crimping filament or fiber tow that include at least a stuffed box and crimping rollers.
U.S. Pat. No. 3,353,239 to Heijnis discloses a method and apparatus for crimping tow. Prior to entering a conventional stuffer box crimping apparatus which includes a crimping roller and stuffer box, the tow is passed through a pair of guide rollers designated 2. The improvement disclosed in this patent is with respect to the crimping rollers having ridged surfaces to better grip the tow and crimp the tow in a direction perpendicular to the crimp produced in the stuffer box. It is further disclosed that the guide rollers may also have a similar surface configuration as the crimping rollers. The use of the ridged or curved surface configuration is stated to improve the bite of the roller surfaces and favorably influence the multi-directional crimp produced in the tow. A nonuniform clearance or nip results from such surface configurations.
U.S. Pat. No. 4,004,330 to Stanley discloses a crimping apparatus for stuffer crimping a textile tow material by use of a conventional stuffer box crimper. Included in the crimper is one additional roller (17" in FIG. 7) mounted parallel and contiguous with the peripheral surface of the crimping rollers. The additional roller serves to improve the feed of the tow to the nip of the crimping rollers.
U.S. Pat. No. 4,095,318 to Abbott et al generally discloses a crimping apparatus shown in FIGS. 1 and 2 including a stuffer box, crimping rollers and feed rollers designated 16. The feed rollers and crimping rollers ar driven by the gear system 28 connected back to a motor 21.
U.S. Pat. No. 3,813,740 to Heijnis discloses a crimping apparatus for stuffer box crimping a filament or fiber tow of at least 5,000 total denier. Tow, prior to entering a conventional stuffer box crimper which includes a pair of crimping rollers and stuffer box, is passed through a series of gear wheels. These geared wheels mold the tow into a tow band having a more parallel alignment to insure uniformity and excess of crimp of the tow in a crimper housing.
European Patent Application 0 159 285 A2 to Okada discloses a crimping apparatus for stuffer box crimping a filament or fiber tow including a pair of side plates coacting with the crimping rollers to define a rectangular nip through which the tow is passed. The molded tow is then passed to an adjacent stuffer box.
Improvements disclosed in the prior art are directed to improving the feeding of the tow material to the crimping rollers, but not the rectangular molding of the tow material prior to entering the crimping rollers. These improvements are not particularly advantageous to overcome the problems of achieving uniformly crimped tow material. When additional rollers are added to pull the tow material and to dewater it, for example, improved mold uniformity of the tow material is not achieved because the crimping rollers are still totally performing the molding step. Therefore, improved feeding of the tow material to the crimper rollers does not improve the overall mold uniformity of the tow material. In fact, it has been seen that improved feeding may result in additional problems of processing the tow material.
In addition to improving the uniformity of the crimped tow material, it is desirable to improve the apparatus by reducing the applied forces to the crimper rollers. Forces of 10 to 15 tons are currently applied to crimper roller to allow the rollers to pull, dewater, mold and feed the tow. Lower forces not only reduce equipment wear, but also improves the quality of the tow material by decreasing the deformation of the filaments within the tow. Furthermore, fusion of the lateral sides of the tow is reduced.
There remains a need to develop an apparatus for stuffer box crimping which will not only improve the moldability of the tow material, but also improve the processing of the tow material, so that the overall quality of the crimped tow material is improved.
It is a further aim or aspect of the present invention to not only improve the quality of the stuffer box crimped tow material, but also produce the crimped to material being uniform nondeformed filaments by significantly reducing the forces applied to the crimper rollers.
SUMMARY OF THE INVENTION
The present invention combines a set of molding rollers which are effective in pulling, dewatering and molding tow material with a set of crimping rollers which ar effective in maintaining the molded configuration of the tow and feeding molded tow to a stuffer box. The invention uses the combination of the molding rollers and crimping rollers in a unique manner to mold and feed tow to a crimping stuffer box so as to yield not only an improvement in the quality of the crimped tow, but also in the processing of the tow. In particular, the present invention comprises a pair of molding rollers coacting with a pair of side plates to pull, dewater and mold the tow and a pair of crimping rollers coacting with another pair of side plates for maintaining the molded configuration of the tow and feeding the molded tow to a stuffer box.
In the broadest sense, the present invention comprises an apparatus for crimping a continuous tow comprising: a pair of parallel, rotatable molding rollers and a pair of side plates coacting to define a nip therebetween, and exerting pressure on said tow passing therethrough to mold said tow into a cross sectional configuration of the nip; and a pair of parallel, rotatable crimping rollers and a pair of side plates coacting to define a nip therebetween and exerting pressure on said molded tow passing therethrough to maintain the configuration of molded tow and to feed the molded tow to a stuffer box chamber for producing a crimp in said tow, said stuffer box chamber having an inlet positioned adjacent said crimping rollers and an outlet for conducting the crimped tow therethrough.
In the broadest sense, the present invention also comprises a crimped textile fibrous tow made by the above apparatus.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic side view of the stuffer box crimping apparatus of the invention illustrating the arrangement of the tow with respect to the molding rollers, crimping rollers and stuffer box.
FIGS. 2A and B are schematic front views of A) the molding rollers and B) the crimping rollers illustrating the relationship of the rollers, side plates and tow nipped through the rollers.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The principles of the present invention are particularly useful when embodied in a stuffer box crimping apparatus for crimping continuous tow as shown schematically in FIG. 1 and generally indicated by the numeral 10.
The crimping apparatus 10 is generally used to crimp a continuous tow of man-made fiber filaments, referred to herein as tow and designated as 12. Such man-made filaments include nylon and similar textile materials, such as will come readily to the mind of a person skilled in the textile arts. Prominent among suitable textile materials are polyesters (e.g. polyethylene terephthalate), the nylons (polycarbonamides), e.g., 66 nylon (i.e. polyhexamethylene adipamide), also 6-nylon, 11 nylon, 610 nylon, and fiber-forming copolymers thereof, including terpolymers. Other suitable polymeric materials for yarns or strands to be treated according to this invention include most of the thermoplastic fiber-forming materials, such as polyhydrocarbons (e.g. polyethylene, polypropylene), polyacrylonitrile and copolymers of acrylonitrile with other vinyl compounds, also copolymers of vinyl chloride and vinylidene chloride, and polyurethanes. Tow suitable for stuffer box crimping generally has a denier from about 20,000 to about 5,000,000. This list is simply exemplary and is not intended to be exhaustive of suitable compositions, most or all of which are thermoplastic.
According to this invention, thus far considered, the tow is withdrawn from a suitable source of supply, which may be heated by or between successive sets of rolls without sliding contact with a heated oiled surface and is stuffed while hot into a stuffer box crimping apparatus within which it is subjected to longitudinal compression to buckle it into crimped configuration. The entering tow usually is pulled into the roll nip and the juxtaposed apparatus entrance from along the common internal tangent thereto extended therefrom. The crimped tow is pushed and then, if the tow is not previously heated, the crimped tow goes through an oven followed by cutting into staple fibers.
The tow filaments enter the stuffing chamber at desired crimping temperature, which is dependent upon the composition, denier, processing rate, time in the chamber, etc., and often is within the range of ambient and 400° F. So long as it is under substantial crimping compression it preferably is kept under adiabatic conditions, or with addition (or subtraction) of heat such as may be required to compensate for heat loss (or frictional heating) and thereby to maintain essentially constant temperature conditions until completion of crimping.
The diagrams illustrate tow stuffer box apparatus used for treatment of multifilaments. Although many, if not all, of the suitable compositions are drawable to increased length, usually resulting in orientation of their component macromolecules longitudinally, detailed consideration of drawability of the yarns or strands being treated has been deferred in this application in the interest of orderliness and simplicity of description and illustration.
It has been customary to accomplish such orientation of drawable textile yarns or strands by a drawing process removed or unrelated in location and time (being prior, usually long prior) with respect to whatever crimping process is applied thereto to enhance their bulk, cover, hand, texture, etc. Most crimping processes tend to extend the subject yarn or strand axially while deforming it transversely of the longitudinal axis as in edge crimping, gear-crimping, jet-crimping, and twist-crimping. While there might be reason to believe that it would be feasible to perform such an extensional crimping process soon after drawing, as together with performance of one or more additional steps, the same is not true of a compressive or compressional crimping process, such as stuffer crimping. Reference is made to U.S. Pat. No. 4,004,330 which schematically illustrates and discloses a complete process used to process tow including stuffer-box crimping. It is not intended to limit the use of the present invention to such a process, but to include the description to place the present invention in a frame of reference on how it would be used in the textile industry.
Now referring to the present invention as schematically shown in FIG. 1, the crimping apparatus 10 comprises a pair of molding rollers 20 for pulling and molding the incoming tow 12 into molded tow 14, a pair of crimping rollers 40 disposed downstream of the molding rollers 20 for feeding the molded tow material to an adjacent stuffer box 60. The molding rollers 20 and crimping rollers 40 are rotated by a drive means 70 that coordinates the speeds of the two sets of rollers.
The pair of molding rollers 20 include a stationary upper roller 22 and a movable lower roller 24. It is understood these rollers could be reversed, i.e. movable upper roller and stationary lower roller. Each of the molding rollers 22, 24 are solid cylindrical members having smooth cylindrical surfaces (in some case the surfaces could be rough) and end shoulders 22a, 24a at each end of cylindrical surfaces to form the intersection of two surfaces perpendicular to each other. Integral with each of the end shoulders 22a, 24a and projecting outwardly perpendicular to the surface of the end shoulders 22a, 24a are the shafts 23, 25 that may be regarded as stub shafts. Generally, each of the molding rollers 22, 24 have a diameter from about 30 mm to about 250 mm and a length from about 10 mm to about 360 mm. Preferably, the molding rollers 22, 24 have a length equal to that of the length of the crimping rollers 40. These rollers are generally made of stainless steel or steel and could have a rubber coating over the cylinder surface wherein the surface hardness of the rubber is from about 40 to about 60 shore hardness. These rollers require construction that can withstand forces up to 20 tons resulting from the pressure exerted on the rollers to mold the tow material.
The upper roller 22 is mounted on the crimping apparatus 10 to allow for driven rotation, but stationary as to lateral or vertical movement. To this end, the shafts 23 are mounted in bearings (not shown) fixedly mounted on the crimping apparatus 10. The lower roller 24 is mounted to allow for driven rotation and vertical movement to and from the upper roller 22. To this end, the shafts 25 are mounted on a carriage 27 to allow for the rotation of the roller 24. The lower roller 24 and upper roller 22 are interconnected by a drive belt 29 to drive the upper roller 22. In preferred embodiments, the lower roller 24 and upper roller 22 are driven by a universal gear box including flexible universal joints to allow for changing the spacing between the rollers 22, 24. A hydraulic cylinder 28 is affixed to the carriage 27 to enable the carriage 27 and lower roller 24 to move to and from the upper roller 22 when the hydraulic cylinder 28 is activated.
The lower roller 24 is positioned with respect to the upper roller 22 such that the cylindrical surface of the two rollers are radially separated from each other and the cylindrical surfaces are parallel. The distance between the cylindrical surfaces of the two rollers 22, 24 forms part of a rectangular molding nip 26. Forming the ends of the rectangular molding nip 26 are two stationary disk-like side plates 30, 31, one side plate being located at each end of the rollers 22, 24 as shown in FIG. 2A. In particular, each of the side plates have flat surfaces that are held in contact with the end shoulders 22a, 24a of the rollers 22, 24 to define the rectangular molding nip 26. To this end, the side plates 30, 31 have an aligned central axis designated 32 extending parallel to the rational axis 22', 24' of the respective rollers 22, 24. Each of the side plates 30, 31 are held in position by a suitable holder 33, 34 that maintains the side plates 30, 31 in contact with the rollers 22, 24. To avoid excessive wear of the rollers 22, 24 and the holders 33, 34, each of the side plates 30, 31 is made of a material having a hardness less than that of the rollers. In particular, it is preferred that the side plates be made of brass.
Rotary motion is transferred through the shaft 25 to the lower roller 24 by the drive means 70. As shown schematically, in FIG. 1 the drive mean 70 includes an electric motor 72 suitably connected by a drive chain 76 to a variable gear box 78 which in turn is connected by a drive chain 80 to a sprocket (not shown) mounted on the shaft 25. The lower roller 24 is rotated at a controlled speed to cause the tow to be pulled through the molding nip 26. This occurs when the tow is sandwiched between the stationary driven upper roller 22 and the driven lower roller 24. The tow 12 is drawn through a rectangular molding nip 26 defined by the rollers 22, 24 an a pair of rotatable disk-like side plates 30, 31.
With this arrangement, the tow 12 is pulled into the stuffer box crimping apparatus 10, dewatered and molded to the configuration of the rectangular molding nip 26. Pressure is exerted o the tow 12 by the action of the lower roller 24 being pressed towards the upper roller 22 wherein the rollers are rotating as indicated by arrow a in FIG. 1. The amount of pressure exerted may be from 1/10 tons to 20 tons. As the tow passes through the molding nip 26, it is pressed out against the side plates 30, 31 rubbing thereagainst. The resulting molded tow 14 has the desired rectangular configuration corresponding to that of the molding nip 26.
The pair of crimping rollers 40 of the present invention essentially contain the same elements of the pair of molding rollers 20, mounted in a similar fashion and operated in the same manner. However, the pair of crimping rollers serve a different purpose than the pair of molding rollers 20 in the present invention. The crimping rollers 40 maintain the molded configuration of the molded tow and feed the tow to the stuffer box 60.
To avoid excess redundancy herein, the elements of the crimping rollers 40 will only be described in sufficient detail to allow one skilled in the art to understand the similarity of operation of the molding rollers 20 and crimping rollers 40. Reference is made to FIGS. 1 and 2B wherein the crimping rollers 40 are schematically shown in the crimping apparatus 10. To this end, the pair of crimping rollers 40 include a driven upper roller 42 and a movable lower crimping roller 44. Each of the crimping rollers 42, 44 have smooth cylindrical surfaces and end plates 42a, 44a mounted at each end of the cylindrical surfaces. Mounted on each of the end plates 42a, 44a, and projecting outwardly perpendicular therefrom are stub shafts 43, 45. The size and configuration of the crimping rollers 42, 44 are the same as the molding rollers 22, 24 described herein.
At each longitudinal end of the rollers 42, 44 is found a disk-like side plate 50, 51 that cooperate with the rollers 42, 44 to define a rectangular crimping nip 46 shown in FIG. 2B.
The stationary upper crimping roller 42 is mounted on the crimping apparatus 10 to allow for driven rotation, but stationary as to lateral or vertical movement in a fashion similar to that of the stationary upper molding roller 22. The movable lower crimping roller 44 is mounted similarly to the lower molding roller 24 to allow for driven rotation in vertical movement to and from the stationary upper roller 42. To this end, the shafts 45 of the lower roller 44 are mounted on a movable carriage 47. The lower roller 44 and upper roller 42 are interconnected by a drive belt 49 to drive the upper roller 42. A hydraulic cylinder 48 is affixed to the carriage 47 to enable the carriage 47 and lower roller 44 to move to and from the upper stationary roller 42.
The lower roller 44 is directly rotated by the drive means 70 through a drive belt 74 directly connecting the two units together. As well known in the mechanical arts, pulleys or other devices would be used on the shaft in the drive means to connect the roller and drive means together. The pair of crimping rollers are rotated at a controlled speed which may be slower than, equal to, or faster than the controlled speed of the pair of molding rollers 20. A determination as to the relationship of these speeds is based on experimental practice to obtain the optimum tension of the tow to the pair of crimping rollers 20.
As shown in FIG. 1, the molding rollers 20 and the crimping rollers 40 are horizontally separated by a distance designated d and measured from the center points of the stub shafts 23, 45. It has been found the preferred distance between the rollers is from about 5.5 inches to about 15 inches. This distance has been found to be dependent on the amount of in-process shrinkage of the tow and the stability of the tow.
The crimping rollers 40 serve to pull the incoming tow from the molding rollers 20, maintain the molded configuration of the tow material, and feed the molded tow into the stuffer box 60. As one skilled in the art would appreciate, such maintenance of the molded configuration allows for the desired uniform configuration of the tow.
The molded tow material 16 is then fed into the stuffer box 60 which includes an inlet 62 adjacent to and downstream of the crimping rollers 40, a pair of parallel spaced upper and lower plates 63, 64, a pair of parallel spaced side plates not shown in FIG. 1 but disposed on opposite sides of the upper and lower plates to define therein an elongated rectangular crimping chamber 65 for the passage of the tow 16. At the exit end of the chamber 65 is the flapper 66 hinged on one end and movable by hydraulic cylinder 68.
The molded tow 16 is fed into the stuffer box 60 by the crimping rollers 40 and pressed strongly during its advance against the inner walls of the inner surfaces of the upper and lower plates 63, 64, as well as the side plates defining the stuffer box chamber and the motion is opposed by the flapper 66. The velocity of the tow material is reduced in accordance with further advance so that the area of contact between the filaments and inner walls comes to increase. This action results in the crimp of the tow.
Trials have been conducted that compare the present invention with conventional prior art processes for crimping polyester tow material.
EXAMPLE 1
A high tensity, semi-dull, polyester 1.5 dpf, 315,000 total denier tow was processed in accordance with this invention. In particular, the tow was drawn from storage cans, heated to about 200° C. and spray coated with a suitable lubricant finish. The distance between the nip points of the molding rollers and the crimping rollers was set at 11". The size of the stuffer box was 1.5 inches wide by 1 inch high by 12 inches long. The ending crimp was 13 crimps per inch.
Once the tow of polyester filaments was crimped and heat set, the crimped tow was tested for crimped tow uniformity and edge quality. The crimped tow uniformity in a visual test wherein an inspector visually inspects the tow across its width excluding its edges to determine the variability in the crimp frequency. The resulting variability is measured on a scale of 1-5 wherein 5 represents uniform crimp frequency, that is, no variability in the number of crimps per inch. The following is a correlation between the scale and the variability in the crimp frequency:
______________________________________Scale Crimp Variability______________________________________5 None - Uniform4 About 2 CPI range of variability3 About 4 CPI range of variability2 About 6 CPI range of variability1 More than 10 CPI range of variability______________________________________
In particular, the inspector looks across the width of the tow excluding the 0.25 inches of each edge. In the inspection, a determination is made as to the variance of the number of crimps per inch (CPI) from the specified CPI. For instance if the specified crimp frequency is 10 CPI, and the actual crimp frequency varies from 9 to 11 CPI, then the crimped tow uniformity would be 4.
The Edge Quality measurement is the average of measurements for 3 variables including edge snags, edge fusion and primary crimp frequency at the edges. Edge snags are broken filaments protruding out from the edge of the tow and are subjectively measured as follows:
______________________________________Scale Edge Snags______________________________________5 No snags4 Light intermittent3 Light continuous2 Heavy intermittent1 Heavy continuous______________________________________
The second variable is edge fusion which is indicative of the amount of melting or lack thereof that has occurred on the tow edge due to heat buildup. Edge fusion is measured as follows:
______________________________________Scale Edge Fusion______________________________________5 Primary crimp is visible4 Light fusion, some primary crimp visible3 Moderate fusion2 Heavy fusion1 Fused and Tight______________________________________
The third variable is the primary crimps at the edges. This variable is measured like the crimped tow uniformity except at the edges and based on the following scale:
______________________________________Scale Edge Crimp Variability______________________________________5 None - Uniform4 About 2 CPI range3 About 4 CPI range2 About 6 CPI range1 Microcrimping______________________________________
Edge quality is determined by summing the three measurements and dividing by 3 to arrive at a value.
Experiments A and B are controls, wherein the tow material was not processed through the pair of molding rollers. The pneumatic pressure applied to the pair of crimping rollers was 55 lb/in 2 .
In Experiment C, the tow material was processed through both the molding and crimping rollers wherein 55 lb/in 2 pneumatic pressure was applied to each pair of rollers.
In Experiments D-H, the pneumatic pressure to the molding rollers and crimping rollers was varied. In particular, Experiments G and H, only 10 lb/in 2 was applied to the molding rollers and only 35 lb/in 2 was applied to the crimping rollers.
TABLE 1______________________________________ Pneumatic Pressure Crimped Tow Edge Molding/Crimping Uniformity Quality______________________________________Experiment A 0/55 2 3.0Experiment B 0/55 1.5 3.0Experiment C 55/55 3.0 4.16Experiment D 55/45 4.0 4.5Experiment E 55/35 2.5 3.83Experiment F 55/30 3.5 3.5Experiment G 10/35 4.0 4.5Experiment H 10/35 4.33 4.33______________________________________
Control Experiments A and B illustrate the lower crimped tow uniformity and edge quality when compared to the improved values of Experiments C-H. In particular, the variability in the crimp frequency in control experiments A and B is more than 6 CPI and has an edge quality of 3.0. Immediate improvements in both the crimped tow uniformity and edge quality are evidenced by the data when the molding rollers are added as in Experiment C. In particular, the crimped tow uniformity improves from a variability of 6 CPI to 4 CPI and the edge quality improves to in excess of 4.0. In Experiments G and H where the pneumatic pressures have been reduced, the crimped tow variability is less than 2 CPI and the edge quality has improved to in excess of 4.3.
Thus, it is apparent that there has been provided in accordance with the invention, a crimping apparatus including a pair of molding rollers and a pair of crimping rollers in addition to the stuffer box that fully satisfies the objects, aims and advantages as set forth above. While the invention has been described in conjunction with the specific embodiments thereof and in the examples, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art, in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications and variations that fall within the sphere an scope of the invention. It is not intended for the invention to be limited by the theory offered by the applicants, but only for the matter of clarification or explanation of the invention. | An apparatus for crimping a continuous tow of textile material including a pair of molding rollers for initial molding and pulling of the tow, a pair of crimping rollers for molding and feeding the two to a stuffer box crimper wherein the tow is crimped. The novel pair of molding rollers includes the two spaced rotatable rollers cooperating with a side plate at each end of the nip between the rollers to define a rectangular space. Tow material is passed through the space wherein the tow is pressed and molded to the rectangular configuration. After the initial molding, the tow is passed through the pair of crimping rollers and fed into the stuffer box wherein the tow is crimped. Using the novel apparatus to crimp the tow drastically improves the uniformity of the crimped tow and the processibility or the tow. Furthermore, the novel apparatus allows for a significant reduction in the forces applied to the molding rollers and crimping rollers resulting in the reduction of filament distortion in the tow material. | 3 |
This is a divisional of application Ser. No. 09/384,649, filed on Aug. 27, 1999 now U.S. Pat. No. 6,444,743.
FIELD OF INVENTION
The present invention relates to the recycling of spent tire curing bladders, which essentially contain cured butyl rubber, by grinding the bladders into fine size, particles for use as a filler in rubber compositions.
BACKGROUND OF THE INVENTION
Heretofore, spent or old tire bladders used in shaping the internal portion of a tire in a curing mold have generally been scrapped and discarded as a solid waste material in a landfill. Some of the tire curing bladders have been recycled by cutting the same in the form of a shoe sole, a beach tong, and the like.
SUMMARY OF INVENTION
A rubber blend composition suitable for use in a tire as for the innerliners thereof is made by mixing rubber compounds such as halobutyl rubber containing additives therein with fine size particles derived from grinding old, spent tire curing bladders. The blend when used as an innerliner for a tire has good physical properties such as air retention.
DETAILED DESCRIPTION
Curing bladders are utilized for making tires for off-the-road vehicles such as tractors, earth-moving equipment, and the like, as well as for on the road vehicles such as passenger cars, trucks, buses, and the like. Curing bladders are typically made from butyl rubber and contain conventional amounts of various rubber additives such as carbon black, oil, zinc oxide, generally phenolic curing aids and optionally small amounts of sulfur and sulfur accelerators. The amount of the various additives will vary from manufacturer to manufacturer, but generally include from about 20 to about 100 and desirably from about 40 to about 65 parts by weight of carbon black for every 100 parts by weight of butyl rubber (PHR), from about 2 to about 20 and desirably from about 5 to about 15 parts by weight of oil PHR, from about 3 to about 15 parts by weight of phenolic curing resins PHR, and very small amounts of zinc oxide such as from about 1.0 to about 8 parts by weight PHR.
It is an important aspect of the present invention that the generally spent, old, or used cured curing bladders are ground into fine size particles. The particle size according to U.S. Standard Mesh is generally from about 30 mesh to about 200 mesh and desirably smaller than 60 mesh such as from about 60 mesh to about 100 mesh. Generally any rubber grinding method or process can be utilized so long as the rubber is not scorched or degraded during grinding thereof. One particular method of grinding involves grind the rubber in the presence of water, which keeps the rubber temperature low to prevent reversion. A more detailed description of such a preferred grinding method is set forth in U.S. Pat. Nos. 4,374,573; 4,714,201; 5,238,194; and 5,411,215, which arc hereby fully incorporated by reference. Cryogenically ground rubber can also be utilized.
While the innerliner rubber can contain butyl rubber, preferably it contains halobutyl rubbers such as chlorobutyl or bromobutyl rubber. More preferably, the innerliner rubber is predominately bromobutyl rubber with optionally small amounts of natural rubber therein as from about 0 or 0.1 to about 50 percent by weight and desirably about 5 to about 15% by weight based upon the total weight of the butyl rubber and the natural rubber (PHR). The innerliner rubber cart contain various conventional or typical innerliner additives such as carbon black; oil; curing aids such as sulfur, sulfur-containing compounds, and the like; vulcanizing accelerators such as amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithio-carbamates, and the like; various anti-oxidants such as phenylene diamines; various antiozonates; various aliphatic acids such as stearic acid; zinc oxide; various waxes such as micro-crystalline wax; various peptizers; various retarders, various resins, various fillers such as clays; silica; silica coupling agents; and the like. While the amount of the various additives will vary from one tire manufacturer to another, they generally include from about 20 to about 100 and desirably from about 50 to about 90 parts by weight of carbon black PHR, from about 5 to about 20 parts by weight of oil PHR, from about 0.5 to about 4.0 parts by weight of stearic acid PHR, from about 0.5 to about 8 parts by weight of zinc oxide PHR, from about 0.1 to about 3.0 parts by weight of sulfur PHR, from about 0.5 to about 5.0 parts by weight of sulfur accelerators, and the like.
According to the present invention, from about 1 to about 60 parts by weight and desirably from about 2 to about 20 parts by weight of ground cured curing bladder rubber particles are added to 100 parts by weight of an uncured innerliner rubber and blended in any conventional or typical manner. Suitable mixing methods include blending in a Banbury, mixing on a two-roll mill, or the like. More specifically, the fine ground cured curing bladder or rubber particles containing additives therein are added to butyl and/or halobutyl polymers, carbon black, stearic acid, oils and resins in a Banbury mixer and mixed to form an innerliner master batch. Zinc oxide, sulfur, and accelerators are then added to the master batch and blended as in a Banbury mixer to form the blended rubber composition of the present invention. The blended innerliner rubber compound-cured curing bladder particles are processed in a calender to form sheets of any desired width and thickness. In the assembly of a tire, the sheeted rubber innerliner-curing bladder rubber particle blend is applied to a tire assembly machine and the various other tire components applied thereto. The tire is then formed into its final shape and cured in a curing press.
The present invention is environmentally friendly inasmuch as spent or old curing bladders do not end up in landfills but rather are recycled into useful products such as a tire innerliner. When utilized as a tire innerliner, good retention, or substantially no loss of properties such as high air impermeability, is obtained. The utilization of the ground curing bladder rubber particles can also result in a cost saving in the preparation of a tire innerliner.
The present invention will be better understood by reference to the following examples, which serve to illustrate but not to limit the invention.
EXAMPLE 1
The following innerliner formulations were prepared:
Control
Example 1
Example 2
COMPOUND A
Halobutyl
90.00
90.00
90.00
Natural Rubber
10.00
10.00
10.00
Carbon Black
65.00
65.00
65.00
Retarder
0.15
0.15
0.15
Oil
11.00
11.00
11.00
Resin
11.50
11.50
11.50
60 Mesh Ground curing Bladder
—
4.00
11.50
Stearic Acid
2.00
2.00
2.00
Zinc Oxide
3.00
3.00
3.00
Accelerator
1.30
1.30
1.30
Sulfur
.50
.50
.50
COMPOUND B
Halobutyl
65.00
65.00
65.00
Natural Rubber
35.00
35.00
35.00
Carbon Black
65.00
65.00
65.00
Oil
7.00
7.00
7.00
Resin
4.00
4.00
4.00
Processing Aid
0.30
0.30
0.30
60 Mesh Ground curing Bladder
—
4.00
15.00
Stearic Acid
2.00
2.00
2.00
Zinc Oxide
3.00
3.00
3.00
Accelerator
1.30
1.30
1.30
Sulfur
.50
.50
.50
A masterbatch was prepared by adding the halobutyl rubber, the natural rubber, carbon black, retarder, oil, resin, processing aid, stearic acid, and ground curing bladder to a Banbury and mixing for 45 seconds to two minutes and discharging at a temperature of from about 240° F. to about 280° F. Then, zinc oxide, accelerator, and sulfur were added to the masterbatch and mixed in the Banbury for 45 seconds to 2 minutes and discharged at a temperature of about 160° F. to about 250° F.
The above formulation was tested with regard to air retention and the results thereof are set forth in Table I.
TABLE I
Tire Air Retention Test on Ground Curing Bladders in Innerliner
(180 Day Test)
TEST
(CONTROL)
EX. 1
EX. 2
% Avg. Air Loss/month
A
A w/4 phr
A w/15 phr
1.56
1.51
1.56
% Avg. Air Loss/month
B
B w/4 phr
B w/15 phr
2.35
2.35
2.06
The air retention test was conducted by inflating a tire to a specific pressure depending upon the type and load range of the tire. The tire was tested in an environmentally controlled room. It was allowed to grow for a minimum of 48 hours. The pressure was then re-set to the test inflation (depending upon the type and load range of the tire). The date, time, ambient temperature, barometric pressure and tire pressure were recorded for 180 days.
As apparent from the table, air retention of the tire was generally maintained or even improved with the addition of the recycled ground fine sized curing bladder rubber.
While in accordance with the patent statutes, the best mode and preferred embodiment have been set forth, the scope of the invention is not limited thereto, but rather by the scope of the attached claims. | Rubber compositions such as tire innerliners contain significant amounts of ground, fine size tire curing bladder rubber as a filler. Critical properties such as air retention are not affected and spent or old curing bladder rubber which would otherwise go to a landfill is effectively recycled. | 2 |
FIELD OF THE INVENTION
This invention relates to a solvent extraction process for removing gossypol (a toxic pigment) from cottonseed. The extraction is conducted with a solvent solution comprised of: a water miscible organic solvent, water and an acid which is strong enough to prevent gossypol from binding to cottonseed protein, but not so strong that it hydrolyses a substantial amount of the cottonseed protein.
BACKGROUND OF THE INVENTION
Unlike other commercial oilseeds, cottonseed contains a toxic pigment, gossypol, which prevents it from being a feed for animals, other than those that have a rumen. That is, while some whole cottonseed is fed to mature ruminants, most of it is separated into oil and meal, typically by solvent extraction using hexane. As used herein, cottonseed meal, or flour, refers to the whole residue remaining after most of the oil has been removed. Before the oil and meal can be used as a food source, the gossypol must be removed or deactivated. In addition, unfavorable growing, harvesting, or storage conditions can cause cottonseed to mold and become contaminated with a mold metabolite aflatoxin, which, because it is carcinogenic, must be removed, or destroyed. The presence of such toxic components prevents cottonseed from reaching its full potential as a food source, especially in countries that grow cotton but not soybeans. In the intact cottonseed, the gossypol is concentrated in glands that are covered with a hydrophilic coating, which keeps the gossypol from coming into contact with other components of the seed. Originally, gossypol was deactivated by pressing, or expelling, the oil out of moist seeds at relatively high temperatures, such as at temperatures from about 110° to 130° C. Under these conditions, the glands are ruptured by hot moisture, releasing gossypol. Most of the gossypol reacts with protein, thereby forming bound gossypol, which is insoluble. The rest reacts with phospholipids and other low molecular weight components of the seed to give products that are soluble in oil and other organic solvents, as is any unreacted gossypol. The gossypol in these soluble products is referred to as free gossypol. Total gossypol is the sum of bound gossypol and free gossypol. Total gossypol content of meals made by such a process are typically from about 0.7 to 1.0 wt. %. While binding to protein is advantageous in that it acts to detoxify the gossypol, it is disadvantageous because it reduces the nutritive value of the meal by reducing the available lysine content.
Currently, separation is done by expression, or by extraction of the oil from flaked kernels at elevated temperatures with a solvent such as hexane, or a combination of expression and extraction. The most common method used today is solvent extraction, but unless a separate moist heating preconditioning step is included, meals produced by this method will contain unruptured glands and excessive amounts of free gossypol. Furthermore, it is well known that adverse physiological effects can occur with some meals containing high total gossypol, even though free gossypol is within acceptable limits.
Hence, it has long been recognized that a process is needed that could reduce the total gossypol of cottonseed meal by removing gossypol instead of binding it to protein. Various processes have been developed in an attempt to accomplish this. For example, multistep processes in which both the oil and gossypol are extracted with different solvents, in different steps, are known. For example, U.S. Pat. No. 4,359,417, teaches a two step process comprising first extracting cottonseed flakes with an 85% aqueous ethanol solution at about 110° F., which removes some of the gossypol with the remainder becoming bound to the meal. This is followed by a second extraction but with a 95% ethanol solution at 175° F., which removes the oil. Although such a process has merit, it can do no better than produce a meal which still contains from 0.29 to 0.45 wt. % total gossypol and 0.019 to 0.045 wt. % free gossypol.
Another reference, Canella and Sodini (Journal of Food Science, 42:1218-1219 (1977)), discloses a method wherein hexane extraction of raw cottonseed at 25° C. is used to produce a cottonseed meal, followed by room temperature extraction with n-butanol containing HCl at carefully controlled pH of about 4.5, in order to obtain a product which contains 0.34 wt. % total and 0.07 wt. % free gossypol. One disadvantage of such a process is that the high boiling point of n-butanol makes its removal from the meal difficult. Further, the one-solvent processes that have been described in the art generally use mixed solvent systems which are not suitable for food use. For example, U.S. Pat. No. 3,557,168 teaches the use of a hexane-acetone mixture and U.S. Pat. No. 2,950,198 (King et al, 8/1960) teaches the use of a hexane-acetone-water mixture. Both of these processes leave residues which produce a strong objectionable catty odor in the meal, thus making them unsuitable for food use. Further, U.S. Pat. No. 4,747,979 teaches the use of a chlorinated hydrocarbon as one component of their mixed solvent, which of course is also unsuitable for food use.
Although other separation processes, such as the liquid cyclone process taught in U.S. Pat. No. 3,615,657 can yield solid products containing less than about 0.3 wt. % total gossypol from glanded seed, such low gossypol fractions account for only about 50% of the total meal. The remaining fraction contains relatively high total gossypol concentrations.
Also, U.S. Pat. No. 4,219,469, teaches the use of a solvent solution comprised of: a non-polar solvent, such as hexane; a polar solvent, such as ethanol; and a food grade acid, such as citric acid; to obtain protein isolates from cottonseed. The isolates are improved because of their improved coloration. Gossypol is not significantly removed by the process of this reference.
Furthermore, in conventional processes for producing cottonseed meal, a small amount of the gossypol which is present in the seed, is bound to phospholipids and extracted with the oil. This is in contrast to the major portion which is bound to protein and remains in the meal. Another patent, U.S. Pat. No. 3,062,876 discloses that the soluble bound gossypol can be dissolved in methyethylketone (MEK) and hydrolyzed in the presence of phosphoric acid. It is stressed that MEK be used because the bound gossypol must be soluble in the acidic solution used for hydrolysis.
The potential use of gossypol as a male contraceptive is an added incentive for the need for a process that can separate unmodified gossypol from both cottonseed oil and meal, instead of binding it to the meal. Consequently, there still exists a need in the art for more effective processes for removing gossypol, as well as other non food grade components from cottonseed.
SUMMARY OF THE INVENTION
In accordance with the present invention, there is provided a process for the extraction of gossypol from cottonseed, which process comprises:
(a) contacting cottonseed with a solvent solution comprised of: (i) a water miscible organic solvent; (ii) water; and (iii) an acid which is characterized as being strong enough to prevent binding of the gossypol to the cottonseed protein, but not so strong that it will hydrolyze a substantial portion of the cottonseed protein; under conditions providing extraction of gossypol from said cottonseed by said solvent solution, thereby producing cottonseed meal of reduced gossypol content and solvent solution having gossypol therein; and
(b) separating said cottonseed meal of reduced gossypol content from said solvent solution having gossypol therein.
In a preferred embodiment of the present invention, the water miscible solvent is selected from the water miscible alcohols, esters, ethers, nitriles and mixtures thereof, and is present in a weight ratio of solvent solution to cottonseed of from about 12 to 1 to about 1 to 1, and the cottonseed is in the form of kernels, flakes or a meal.
In other preferred embodiments of the present invention, the acid present is such that it is able to provide the solvent solution with a pH of from about 2 to about 5.
In yet other preferred embodiments of the present invention, the solvent solution is comprised of about 2 to 12 wt. % water and from about 75 to 95 wt. % solvent and the extraction is conducted at a temperature from about 50° C. up to, but not including, the boiling point of the solvent.
In still further preferred embodiments of the present invention, the water miscible solvent is selected from the group consisting of the C 1 to C 3 monohydric alcohols and the acid is selected from the tribasic acids: citric acid, ascorbic acid, phosphoric acid, and mixtures thereof.
The present invention also includes cottonseed meals of reduced gossypol content (and optionally reduced aflatoxin and/or fat content) produced by the processes of the instant invention. Other aspects, objects and advantages of the present invention will become readily apparent from the ensuing description.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In general, the solvent solution of the present invention contains: a water miscible organic solvent, the aforementioned acid, and water. The water content of the combination of both the cottonseed and the solvent solution should range from about 2 to 32 wt. %, preferably from about 2 to 14 wt. %, and more preferably from about 4 to 12 wt. %. The amount of water required in the solvent solution will be affected by the water already present in the cottonseed. After preparation for extraction, the cottonseed kernels, flakes, or full fat meal, usually contains from about 2 to 14 wt. % water. Preferably, the weight percent of water in the solvent should be at least 12 wt. % minus the wt. % of water in the cottonseed product. The upper limit of water concentration is set by the minimum functional concentration of the other two components, the solvent and the acid, which will be discussed in detail below.
In order to inhibit binding of gossypol without significant hydrolysis of protein, the pH of the solvent solution should be from about 2 to about 5, preferably from about 2 to about 4, and more preferably from about 2 to about 3. Depending on the equivalent weight and pK (negative logarithm of the first dissociation constant of the acid) the effective amount of acid will usually range from about 1 to 20 wt. % acid, preferably from about 2 to 10 wt. % acid. Preferred acids are those having equivalent weights of less than about 80 and a pK of from about 2 to about 4.2. Acetic acid, which has a pK of 4.75, is unsuitable for use herein. Nonlimiting examples of preferred acids, are both organic and inorganic (e.g. tribasic inorganic or organic acids) and include phosphoric, citric, and ascorbic acids, and mixtures thereof. More preferred are phosphoric (eq.wt.=33, pK=2.1) and citric (eq.wt. =64, pK =3.1) acids, which at concentrations of 0.1 to 0.4 molar give pHs from about 3.2 to 2.3. Most preferred are food grades of these acids, so that residual acid in the cottonseed meal or flakes would not preclude approval for food use.
Non-limiting examples of water miscible organic solvents usable in the present invention include: alcohols, esters, ethers, nitriles, and mixtures thereof. Preferred are the water miscible organic solvents. More preferred are the C 1 to C 3 monohydric alcohols, most preferably are those that are suitable for use in food processing, such as ethanol, which is non-toxic, has favorable oil- and acid-solubility, is easy to recover for recycling, and is a standard article of commerce. Maximum concentration of organic solvent in the solvent solution is determined by subtracting the required water and acid concentrations from 100 wt. %, i.e. about 99 wt. % for extraction of cottonseed containing more than 12 wt. % water using the minimum amount of acid. The minimum concentration will depend on the specific organic solvent and is determined by the requirement that both oil and gossypol be soluble in the solvent solution. The minimum will be highest for low extraction temperatures and lowest for extractions carried out under pressure at temperatures above the normal boiling point of the solvent. In general, the solvent solution will contain about 70 to about 98 wt. % organic solvent, preferably about 75 to about 95 wt. %, more preferably about 80 to about 90 wt. %. Most preferred is about 83 to about 92 wt. % ethanol, which corresponds to use of commercial 95 vol. % ethanol to prepare 0.1 to 0.4 molar solutions of citric and phosphoric acid.
The present invention can be practiced in a variety of ways. For example, the extraction can be performed in a batch mode. As in any extraction process, a single equilibration of the cottonseed flakes with the solvent, followed by separation of the two phases, yields a miscella containing extracted oil and gossypol, and a marc consisting of residual flakes saturated with absorbed miscella. In order to remove all of the oil and gossypol, the equilibrium process must be repeated several times with fresh solvent. The number of cycles required will be dependent on such things as the strength of the solvent, the solvent to flakes ratios, the temperature and pressure conditions, and the desired degree of oil and gossypol removal. In general, for maximum removal, from about 5 to 10 cycles may be required using the most preferred solvents at about 78° C. and atmospheric pressure, with about a 3 to 1 wt. ratio of solvent to flakes in the first cycle, and a 2 to 1 wt. ratio in subsequent cycles.
In general, the process of the present invention may be carried out over a wide range of temperatures. This range will generally be from about 50° C. up to about 90° C. It is also understood that the extraction can also be run at elevated temperatures and pressures, preferably up to those pressures which can be safely practiced with the type of equipment used in commercial cottonseed extraction. This pressure can be up to about 60 psig at temperatures up to about 130° C, more preferably from about 3 to about 10 psig, at temperatures of from about 70° C to about 90° C, preferably from about 80° C to about 90° C
The present invention can also be practiced in a continuous process wherein the solvent solution is preferably run countercurrent to the cottonseed and the residence time of the cottonseed, in contact with fresh solvent, will determine the extent of oil and gossypol removal. Such determinations of residence times etc. are within the ordinary skill of those in the art, given the teachings herein, and need not be discussed further. It is preferred to rinse the cottonseed meal of reduced gossypol content (after the step of contacting) With fresh solvent, which may be similar to that used in the extraction but without added acid in order to recover acid absorbed by the cottonseed. Thus, the fresh solvent may include a water miscible organic solvent selected from the group consisting of alcohols, esters, ethers, nitriles and mixtures thereof.
The term cottonseed, as used herein, is meant to include cottonseed in any form. That is, the present invention can be practiced on cottonseed in any form (e.g. kernels, flakes, meal, full fat, wholly defatted prior to the step of contacting, partially defatted prior to the step of contacting, etc.), although it is preferred not to us whole seed because of the difficulty of achieving an effective extraction. Also, ground kernels present a problem of fines which makes separation of the meal from miscella difficult.
The foregoing detailed description is given merely for purposes of illustration. Modifications and variations may be made therein without departing from the spirit and scope of the invention.
The following examples are presented for illustrative purposes only and are not to be taken as limiting the scope of the claims hereof.
EXAMPLE 1
Full-fat cottonseed meals, containing 8% moisture, were flaked using conventional flaking rolls set at 0.008 inches. A 300 gram (g) portion of the flakes and a 95 vol. % ethanol solution (800g) were placed in a jacketed, stainless steel, cylindrical extractor (6" diam.×6" deep) fitted with a 12 mesh stainless steel retaining screen at the bottom. Hot (79° C) water was circulated through the jacket. Solvent was recirculated through the flakes at a rate of 1 liter (L)/min for 10 min. Miscella (ca 300 g) was drained from the extractor and the flakes were reextracted under the same conditions using 600 g portions of solvent solution. After the seventh extraction, each extraction being about 10 min in duration, the spent flakes were washed with 650 g of 95 vol. % ethanol to remove acid absorbed by the meal. Spent flakes were allowed to air dry at room temperature (ca 25° C) over night and then oven dried at 1010 C for one hour. They were then ground with a Wiley mill to pass a 20 mesh screen, analyzed for residual lipids, total gossypol, and free gossypol. The solvent solutions were comprised of 0.1 and 0.4M citric acid, prepared using anhydrous citric acid, and 0.1 and 0.34M phosphoric acid, prepared using 85 wt. % orthophosphoric acid, all in 95 vol. % ethanol. For comparison, an extraction of the same lot of flakes was made using 95 vol. % ethanol without tribasic acid. The results are shown in Table I below for full fat flakes which initially contained 26.3 wt. % lipids, 8 wt. % moisture, 1.08 wt. % total gossypol and 1.06 wt. % free gossypol.
TABLE I______________________________________ wt. % wt. % wt. % RESIDUAL TOTAL FREESOLVENT LIPIDS GOSSYPOL* GOSSYPOL*______________________________________No acid 0.75 1.08 0.080.1M citric 1.1 0.40 0.020.4M citric 1.1 0.09 0.0070.1M 0.5 0.27 0.02phosphoric0.34M 1.4 0.03 0.005phosphoric______________________________________ *Moisture- and oilfree basis. Conventional hexane extraction left 1.46 wt. % total gossypol, of which 0.56 wt. % was free gossypol, in the meal.
This example shows that the present invention provides a u very substantial reduction in the concentration of total gossypol and free gossypol, as compared to extraction with ethanol alone or extraction with hexane.
EXAMPLE 2
As shown in the following Table II below, when cottonseed containing aflatoxin, chiefly aflatoxin B1, is processed as described in Example 1 hereinabove, aflatoxin, as well as gossypol, are removed from the meal.
TABLE II__________________________________________________________________________ wt. % ppb wt. % wt. % RESIDUAL B1 TOTAL FREESOLVENT LIPIDS AFLATOXIN* GOSSYPOL* GOSSYPOL*__________________________________________________________________________None** 26.2 69 1.00 0.91No Acid 0.94 3.6 0.80 0.010.1M citric 0.87 3.8 0.22 0.010.4M citric 2.3 3.4 0.09 0.060.1M phosphoric 1.1 3.7 0.08 0.010.34M phosphoric 5.1 2.9 0.05 0.004__________________________________________________________________________ *Moisture- and oilfree basis. **Unprocessed fullfat flakes; as is basis.
Conventional hexane extraction left 37.5 ppb aflatoxin, 1.24% total-, and 0.84% free- gossypol, all moisture- and oil-free basis by weight, in the meal.
EXAMPLE 3
The process of the instant invention is intended primarily for use on full-fat flakes that contain very little bound gossypol (total minus free); however, as illustrated in this example a significant reduction in total gossypol content of partially defatted or fully defatted meals and other products containing large amounts of bound gossypol can be achieved by extraction with solvents described herein.
A 300 g sample of cottonseed flakes, similar to those used in Example 1, were extracted with 95 vol. % ethanol in a Soxhlet apparatus for 4 hours, which removed most of the oil and converted most of the gossypol from free to bound form. The resulting defatted meal, which contained 6.5 wt. % residual lipids, 1.40 wt. % total gossypol and 0.02 wt. % free gossypol, was extracted three times using 800, 600, and 600 g of acidified 95 vol. % ethanol as indicated in Table III below. Each extraction was at 78° C. for 20 min.
TABLE III______________________________________ wt. % RE- wt. % wt. % SIDUAL TOTAL FREE LIPIDS* GOSSYPOL* GOSSYPOL*______________________________________Starting Material 6.5 1.40 0.02(i.e. defattedmeal)0.4M citric acid 0.29 0.88 0.12in 95 vol. %ethanol0.34M phosphoric 0.13 0.52 0.09acid in 95 vol. %ethanol______________________________________ *Moisture- and oilfree basis. | The present invention is drawn to a process for extraction of gossypol for cottonseed using a solvent solution which includes: (a) a water miscible organic solvent; (b) water; and (c) an acid which is strong enough to prevent binding of gossypol to cottonseed protein but which is not so strong as to hydrolyze a substantial portion of the cottonseed protein. The present invention also includes cotton seed meals of reduced gossypol content (and optionally reduced aflatoxin and/or fat content) produced by the aforementioned extraction. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is directed toward a compact light condensing illuminator and particularly to a light condensing illuminator including a collimated light source which transmits light to a ruled mirror reflector system for concentration of the light after passage through a lens.
2. Description of the Prior Art
Illuminators for use in such devices as overhead projectors have of necessity been rather large and of substantial vertical height in order to accommodate a large reflector or a lens having disposed at its focal center a high powered light source in order to provide sufficient illumination power. In such projectors not only is the resultant equipment quite large but also its construction adds to its increased weight and diminishes the prospects of it being a suitable portable instrument.
From an operator's standpoint, it is frequently necessary to place subject material for projection upon the projector stage and either refer to it by pointer or annotate the subject material by marking its surface during the course of any discussion or presentation which the operator may be making. Such projectors, for the most part, have significant side glare which is controllable but generally only through the use of costly specially designed lens systems or louvered screens to prevent glare in the direction of the operator. These added devices or elements also increase the size and weight of the unit.
Projectors of this kind are expensive to manufacture and thus to procure because of their mass and of the cost of parts necessary to provide power to meet acceptable projector standards.
In overhead projectors and other instruments which use large condensing illuminators, a pair of high powered Fresnel lenses are generally disposed in a face-to-face relationship. One inherent undesirable feature of double high powered Fresnel lenses is side glare as hereinbefore mentioned. Such units first receive illumination from a high powered standard light source at one of the Fresnel lenses to collect the widely dispersed light and pass it to the second of the Fresnel lenses to condense the light at some point or distance from the lens. In such high power lenses, there is a great loss of light at the extremities of the lens, which accounts for the low efficiency of high power Fresnel lenses at the edges. Further, vignetting is a serious problem encountered in the use of high power Fresnel lenses. The distances of the light paths from the source filament to the lens vary greatly. When comparing, for example, the path of light traversing the axis of the lamp with the path of light directed toward the extremity of the lens the distance difference is at its maximum. The greater light path distance between the source and the lens edge causes the edge of the lens or projection screen to look substantially darker than its center area.
The use of ruled or grooved mirror optical elements to reflect or otherwise act upon light rays is well known in the art. Planar grooved reflectors have been used, for example, as disclosed in U.S. Pat. No. 3,877,802 entitled "Method of Enlarging Images Without Lenses and Display Devices Utilizing the Same" issued Apr. 15, 1975 for inventor M. Greenspan. In the Greenspan disclosure, an object of the invention, to which the disclosure is so directed, provides for a lenseless system of enlarging images along at least one of the orthogonal axes without depending upon the radiation properties of a point source of light.
SUMMARY OF THE INVENTION
This invention provides a highly efficient illuminator system of relatively inexpensive simplified construction and design and of unusual compactness to provide highly concentrated light which is especially amplified from the level of light originating from a selected collimated light source. A collimated light source of suitable construction and one which, for example, is commercially available is acceptable for serving as the illumination light source in the present invention. Collimated light is directed at a reference surface which is configured to reflect the light uniformly in parallel paths onto a reflective surface of substantially greater size. The second reflective surface uniformly transmits the light in paths of substantially equal length to a lens for condensing the light rays ideally at a point or small area which is at a preselected distance from the lens.
The first reflective surface, which is the smaller of the two surfaces, is generally planar and is disposed in the path of the collimated light to intercept substantially all of the collimated light. The planar reflector is disposable at variable angles to the path of the collimated light. Preferably, the planar reflector is skewed to cut across the light path such that the light which emanates from the collimated light source travels different distances to reach the boundaries of the planar reflector. Whatever the angle that the mirror is inclined to the collimated light path, it is preferred that the center axis of the light path pass through the center of the first reflective surface.
Both planar reflectors are configured to most efficiently receive and reflect the light transmitted to the surfaces of each. Preferably, the surfaces are grooved in a saw-tooth or stepped configuration when viewed in cross-section. Continuous reflective surfaces which have discontinuous slope such as grooved mirrors, gratings, ruled or echelon marked optical elements enable preselected disposition and orientation of the reflective surfaces while controlling the direction of the reflected light. Other configurations are acceptable but may not be as desirable because of their inefficiency. The reflective grooves, for example, may be utilized at an undersurface or second surface of the planar reflector. The first reflective surface is disposed to have its grooves inclined to the path of the collimated light from the light source with its orientation selected to provide for uniform illumination within the boundaries of the designed instrument. The second reflective surface is disposed to receive the light and transmit it in parallel light paths.
A low powered Fresnel lens is disposed for receiving the parallel light rays reflected from the second planar reflector and condenses the light at a preselected distance from the lens. This inventive system provides for a greater amplitude of illumination at the preselected area.
Alternative configurations of the inventive illumination system include, for example, systems having a plurality of collimated light sources. When considering an embodiment according to the principles of this invention, which is generally in the shape of a very thin square box, collimated light sources are preferably disposed on a given side of the box unit proximate the corner where the given side intersects the side mounting the planar reflective surface to which the light source transmits its collimated light. Particularly, good results can be obtained by mounting two collimated light sources on one given side of the box unit at opposite ends of the given side. In this configuration two diametrically opposed planar reflective mirrors are used. A third configuration might include two collimated light sources mounted on opposite sides of the box unit both of which are proximate to one wall which supports a single planar reflective surface. Alternative embodiments which could include two collimated light sources at diagonally opposite corners of the box unit or alternatively light sources at all four corners of a box unit are possible.
This invention has applications which can relate to illumination for optical imaging systems and processes and apparatus which encompass the principles of diascopic imaging. Diascopic imaging is defined as imaging operative upon light generally transmitted through an object or transparency which is intended to be viewed.
Other applications include illuminators such as medical lamps which concentrate the light energy at an examination area for use, for example, during surgery to illuminate the work area of the practitioner. Another practical application includes a transparency illuminator for graphical data transfer instruments. In such an application the concentrated illumination is 15 to 80 times the illumination provided by conventional thin illuminators. Such a graphical data transfer instrument is disclosed in U.S. Pat. No. 3,770,347, issued Nov. 6, 1973 to W. R. Ambrose et al.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a partially exploded schematic diagram of a uniform wide aperture illuminator illustrating light ray paths according to the principles of the present invention.
FIG. 2 is a longitudinal view of a portion of the embodiment as illustrated in FIG. 1.
FIG. 3 is a plan view of a portion of the embodiment as illustrated in FIG. 1.
FIG. 4 is a partial illustration of an alternate embodiment of a reflective element illustrated in FIG. 1.
FIG. 5 is a partial perspective of the reflective element illustrated in FIG. 4.
FIG. 6 is a section of the reflective element of FIG. 5 as viewed in the direction of arrows 6--6 of FIG. 5.
FIG. 7 is a partial illustration of alternate reflective embodiments of elements illustrated in FIG. 1.
FIG. 8 is an illustration of the coordinate system used to calculate angular values illustrated throughout FIGS. 4-7.
FIG. 9 is a partial sectional view of a Fresnel lens included in the illustration of the embodiment of FIG. 1.
FIG. 10 is a partial illustration of an alternate embodiment of an element illustrated in FIG. 1.
FIG. 11 is a partial schematic illustration of an overhead projector including an embodiment according to the principles of this invention.
FIG. 12 is a partial exploded view of a lamp incorporating the principles of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In FIG. 1 a uniform wide aperture illuminator is schematically illustrated and includes as its principal components a collimated light source 10, a first reflector planar surface 12 for receiving collimated light, a second reflector planar surface 14 for receiving light transmitted from the first reflector 12 and a Fresnel lens 16 for receiving parallel light rays reflected from the reflector 14. As illustrated, illumination originates at the filament 18 of the light source 10 and radiates the light energy to a paraboloid shaped lamp reflector 20 of the light source 10 to transmit the light along exemplary light ray path 22 which originates from the center of the filament 18 and light ray paths 24, 26, 28 and 30, respectively representing light rays which radiate approximately from the extreme outward dimensions of the aperture of the lamp reflector 20.
The light rays 22, 24, 26, 28 and 30 are respectively directed toward the respective four corners of the outward boundaries of the planar reflective surface 12. The reflector 12 is grooved and orientated, as explained hereinafter in greater detail, to reflect the respective light rays 22', 24', 26', 28' and 30' in a downward direction to be received by the second reflector surface 14. The second reflector surface 14 also includes grooves for reflecting the received light rays in a parallel path. Respective rays 22", 24", 26", 28" and 30" are parallel to each other and can be uniform in intensity and are directed from the planar surface to the Fresnel lens 16. The grooves of reflector 14 are not necessarily of the same configuration as those of reflector 12, as hereinafter explained in more detail.
The Fresnel lens 16 is of sufficient size to receive the reflected light rays from the second reflector 14 and to refract the respective rays less than the ray passing directly through the center of the lens. The refracted rays are then condensed as rays 22"', 24"', 26"', 28"', and 30"' toward a point F and concentrated at the point F which is located a distance D from the Fresnel lens 16.
In illuminators for optical imaging systems the distance D is generally equal to the distance from an object plane, which would be disposed on or near the surface of the Fresnel lens, to the entrance pupil of the imaging system. In devices for illuminating such as for lamps which are used to illuminate work task areas, distance D can be the focal length of the Fresnel lens. It may be desirable that the design distance be more or less than the focal length of the lens depending upon the specific application.
In designing illuminators which incorporate the principles of this invention, the elements are selected and arranged to provide for a specially compact unit and one which has a height h, as illustrated in FIG. 2, which is substantially less in dimension than either of the other coordinate dimensions l x and l y as illustrated in FIGS. 2 and 3, which define the length of each of the sides of the designed unit.
As best seen in FIG. 3 the paraboloid shaped reflector 20 is disposed at one side of the embodiment to project its collimated light beam, having a width W, to impinge upon the first reflector surface 12 at an inclined angle. It is desirable that light ray 22 which originates from the filament 18 be received approximate the center of the reflector 12 which can be defined by the intersection of the imaginary diagonals extending between the opposite corners of reflector 12. Additionally, the reflector 12 is of such size to substantially receive all of the illumination which radiates from the collimates light source 10.
Collimated light sources of any suitable type will perform satisfactorily including laser types of continuous emission or a pulsed laser for photography applications. Also condensing lenses can be implemented with a suitable source.
A collimated light source provides the significant advantage of eliminating the necessity of critically positioning the light source with respect to the first reflective surface. Further, the first or side wall reflector 12 is disposed to reflect the exemplary light rays 32 downward as best seen in FIG. 2 and at right angles to the grooves of reflector 14 as best seen in FIG. 3. The orientation and relationship of the flat planar reflector surfaces 12 and 14 causes the examplary light rays 32, illustrated in FIGS. 2 and 3, to be reflected upward and parallel to each other as illustrated by exemplary light rays 34. These parallel light rays 34 are directed toward the Fresnel lens 16.
The number of light sources useful in an embodiment according to the principles of this invention is dependent upon the specific application under consideration. Size limitations and space restrictions will frequently dictate the location of such light sources. It will be appreciated that light sources such as light source 10 can be disposed at any one or any number of corners about the compact pancake shaped unit as illustrated in FIGS. 1-3. In addition locations at other than the corners is possible with the box unit being a convenient reference system.
The illustrations of FIGS. 4, 5, 6, 7, 8 and 10 and the equations which are hereinafter set forth in the disclosure are complementary to each other and are specified for a collimated light source disposed at the left-hand-side forefront of the illustration of the embodiment of FIG. 1. As hereinbefore mentioned, the reflector 12 has grooves which are preferably of saw-tooth cross-sectional configuration as illustrated in FIGS. 5 and 6. The orientation of the wall reflective surface with respect to the base reflector is of significant concern to the design of embodiments according to the principles of this invention. The grooves of both the base mirror and the side mirror are ideally parallel and linear and are disposed upon the substantially flat planar surface of each. The number of grooves per unit measurement is of variable value and is sufficient to prevent grooves from being super imposed on the image of the object under study. Whether grooves are visible at the image is a function of the distance between grooves, the distance between the grooves planar surface and the object under study, and the device in use. The tilt of the grooves of wall mirror 12 to the base reflector which has its grooves substantially parallel to the plane of the wall mirror is particularly important as is the inclination of the plane of the wall mirror 12 to the plane of the base mirror 14. The equations and relationships hereinafter set forth identify a method of computation of these relationships identified as the pitch angle, tilt of the grooves and inclination of the plane and are exemplary of equations useful in constructing apparatus according to the principles of the present invention. It should be noted, for example, that the groove surface 36, as shown in FIG. 6, is not of special concern where a single light source is in use. However, it will be appreciated that it is of concern if, for example, two illumination sources are used at opposite corners of the illumination with a single reflective side mirror. The side reflective mirror pitch angle is specified as β 1 as illustrated in FIG. 6. It should be noted that angle β 1 is measured in a plane perpendicular to the grooves, as shown in FIGS. 5 and 6, and is measured from the reflective side of the groove. The side or wall mirror positioning or orientation is specified by the groove tilt angle ρ x which is measured in the plane of the mirror as illustrated in FIG. 4 and by the mirror tilt angle ρ y as illustrated in FIG. 7. In FIG. 7, angle ρ y1 illustrates reflective wall 12 as tilted toward the base mirror 14 to become wall 12' and is a positive ρ y angle, whereas angle ρ y2 is a negative measurement when wall 12 is tilted back to become wall 12".
The three parameters β 1 , ρ x and ρ y are related to the original input variables l x , l y , h and W as illustrated in FIGS. 2 and 3 by the following set of equations:
A = [sin β.sub.1, -cos β.sub.1, o] (a)
N.sub.x = A.sub.x cos ρ.sub.y + (A.sub.z cos ρ.sub.x + A.sub.y sin ρ.sub.x) sin ρ.sub.y (b)
N.sub.y = A.sub.y cos ρ.sub.x - A.sub.z sin ρ.sub.x (c)
N.sub.z = (A.sub.z cos ρ.sub.x + A.sub.y sin ρ.sub.x) cos ρ.sub.y - A.sub.x sin ρ.sub.y (d) ##EQU1##
N.sub.x.sup.2 + N.sub.y.sup.2 + N.sub.z.sup.2 = 1
Vectors A and N may be considered dummy variables for calculation purposes only which need not be defined. However, it is convenient to interpret them as follows:
A is the unit surface normal vector (outward) from the groove face before rotation of the side mirror through angles ρ x , ρ y ; and
N is the unit surface normal vector from the groove face after rotation of the side mirror through angle ρ x (about the x axis) then through angle ρ y (about the y axis).
The coordinate system selected which pertains to the above set of equations is a right-hand rectangular system and is as shown in FIG. 8.
In the preferred embodiment, the pitch angle β 2 , of the base mirror groove, as illustrated in FIG. 7, is defined by: ##EQU2## where
β 2 is defined as that part of the included angle between the perpendicular to the base and the side of the groove from which the light is reflected;
h is defined as the height of the side mirror; and
l x is defined as the length of the base mirror as measured in the direction across the grooves of the mirror.
The relationship expressed by the above set of equations allows angle β 1 to be specified. For instance, if it is desired that the bottom and side mirrors be made from the same mold, angle β 1 is equal to angle β 2 . Having specified angle β 1 the equations can be solved for angles ρ x and ρ y to determine the appropriate orientation of the side mirror.
If angle ρ y is specified, as for instance with a vertical side wall where angle ρ y is equal to zero, then the equations can be solved for the appropriate groove angle β 1 and groove tilt angle ρ x .
The equations, as set forth within the disclosure, correspond to the right-hand rectangular coordinate vector system, as illustrated in FIG. 8. Parallel light rays which are reflected from the second reflective surface 14 are received by the Fresnel lens 16, as illustrated by exemplary light ray 34 in FIG. 9. The exemplary light ray 34 is refracted at the front surface 38 of the Fresnel lens 16 to pass within the lens 16 as refracted light ray 34'. It is further refracted at the back surface 40 of the Fresnel lens to pass upwardly toward the condensing point F of FIG. 1 as light ray 34".
The Fresnel lens 16 useful in numerous applications for an illuminator, according to the principles of this invention, has an f number, defined as the ratio of the focal length of the lens to the diameter of the lens, which has a value which is relatively high, for example with respect to applications for overhead projectors, and is roughly in a range which is 1 or greater. A single surface Fresnel lens is preferred and it is preferable to have the lens grooves faced toward the reflective mirror to correct for abberations and improve efficiency. A Fresnel lens which is corrected for spherical abberation when used at the focal point is preferred.
Mirrors 12 and 14 do not introduce power into the system. The light enters the mirrors collimated and leaves them collimated. It is possible to further generalize this system by introducing some Fresnel mirror power into the mirrors. For instance, cylindrical power could be introduced into a mirror by making the pitch angle an appropriate function of position measured perpendicular to the grooves as illustrated by FIG. 10. As illustrated, it is necessary that β b be less than β a since the light rays received at the respective grooved surfaces are to be deviated through different angles. Power is most easily added by modifying the base mirror 14, but can be incorporated into the wall mirror or both if it is preferred to have two dimensional power, which can also be provided by one mirror.
The reflective mirrors and Fresnel lens may be of any suitable material including acrylic or polycarbonate plastic. The mirrors may be fabricated by casting or molding by injection, extrusion or pressing or diamond cut and coated with suitable reflective materials, such as aluminum or silver. Replication techniques such as metal electroforming are suitable processes. It will be appreciated that dust shields or heat absorbers may be incorporated or that diffusers may be added for particular applications and included, for example, at the undersurface of the Fresnel lens.
Satisfactory embodiments for specific applications, for example, have included outside unit dimensions of approximately 11 by 11 by 2 inches, acrylic plastic aluminized mirrors, 0.5 millimeter groove spacing and approximately 104° included groove angles.
Two applications of devices embodying the present invention are illustrated in FIGS. 11 and 12. FIG. 11 illustrates an overhead projector 42 including a condensing illuminator according to the illustrations of FIGS. 1-3, with a tiltable and focusable projection lens assembly 44. The projection lens assembly 44 has an aperture sufficient to accept the condensed light directed toward the spot F, as illustrated in FIG. 1, and is located at the spot F. A transparency would generally be placed upon lens surface 40 for projection onto a screen not illustrated. In FIG. 12, a lamp 46 for use, for example, in the dental or medical profession, is illustrated as having two collimated light sources 48 and 50 separately providing illumination to wall reflective mirrors 52 and 54, respectively, with a single base mirror 56. The Fresnel lens 58 concentrates the light at an area 60 disposed upon a task work area 62.
A myriad of other application exist such as drafting table lamps or other light tables. | A compact light condensing illumination system for the concentration of light at an area provides a light source capable of having a relatively shallow reflector with a relatively small aperture directing collimated light toward a planar reflector of rectangular configuration having a mirrored surface configured with relatively short grooves extending at an angle to the direction of the collimated light to uniformly reflect the light toward a planar grooved mirror disposed substantially at a right angle to the first mirrored surface and of relatively large surface to reflect the light in substantially parallel rays to a Fresnel lens of relatively low power for condensing of the light rays to concentrate the light at a preselected distance from the Fresnel lens. | 5 |
BACKGROUND OF THE INVENTION
The present invention relates to a method of producing a pocket opening having a flap, a piping strip, and a pocket bag on an automatic sewing machine, and a device for carrying out this method.
The assignee Durkoppwerke GmbH manufactures a sewing machine under the name Durkopp 745 by means of which pocket openings having flaps can be produced automatically.
For this purpose, the workpiece which is to be provided with the pocket opening, for instance the front part of a jacket or trousers, or a part of a coat, is aligned on the work plate which is located in front (that is, in advance) of the sewing region. Above this there is arranged, on the one side, a flap-application and transfer device such as is known, for instance, from Federal Republic of Germany OS 26 56 720, equivalent to U.S. Pat. No. 4,281,606 and, on the other side, an application device for the piping strip and the pocket bag. The disclosures of this document and all other prior art materials cited herein are expressly incorporated by reference. The piping strip and the pocket bag are inserted into the appropriate application device and aligned, and the flap is inserted into the application device. The piping strip, pocket bag and flap are lowered onto the workpiece, and fixed there by means of the sewing-material clamp, whereupon all parts are transported into the sewing region.
The length of the applied flap is detected by an optical sensor which is functionally connected with the control of the sewing machine and the formation of the seam is so controlled that the seam extends precisely over the entire length of the flap. After the piping strip and the pocket bag are sewed together to the workpiece, on the one hand, and after the flap, piping strip and workpiece are sewed together on the other hand, the pocket opening is cut in known manner (Federal Republic of Germany OS 34 04 758, equivalent to U.S. Pat. No. 4,589,358).
In the case of a pocket opening produced by this method, the free end of the pocket bag which is connected to the piping strip must then be sewn to the flap in order to close the pocket bag, which requires a relatively complicated operation.
According to another method, it is also known to place half of a pocket bag on the flap and half on the piping strip, sew them together to the workpiece and then close the two pocket bag halves in simple manner to each other, for instance by an overcast stitch. Since the flap is covered in this way by the half of the pocket bag which rests on it, the length of the flap cannot be detected by an optical sensor after it is transported into the sewing region, so that it is necessary to work with a constant seam length. There is the disadvantage here that, as a result of manufacturing tolerances, the prefabricated flaps differ in length from one another, so the proper formation of the seam does not always take place.
SUMMARY OF THE INVENTION
In view of these disadvantages in the prior art, the main object of the present invention to provide a method for the production of a pocket opening having a flap and a pocket bag which makes it possible to control the seam to be formed as a function of the specific length of the flap, and without the known disadvantages.
A further important object is to provide a device for carrying out the method which is of simple construction and assures dependable work.
This object with respect to the method can be achieved by a method of providing a workpiece with a pocket opening having a flap and a pocket bag on an automatic sewing machine, comprising the steps of:
aligning the workpiece at a point in advance of a sewing region with respect to a direction of transport, placing the flap on the workpiece and a pocket bag blank on the flap and securing the flap and pocket bag blank relative to the workpiece;
then transporting the workpiece, flap, and pocket bag blank into the sewing region while maintaining their relative position;
locating a sensor at a predetermined point in advance of the needles of the sewing machine;
during said transport, lifting part of the pocket-bag blank off the flap and thereby exposing the flap to the sensor; and thereby detecting the leading and trailing ends of the flap during the transport;
replacing the lifted part of the pocket-bag blank on the flap after the flap passes by the sensor in the direction of transport, and sewing the flap, pocket-bag blank and workpiece together; and
controlling the automatic sewing machine such that the sewing of the seam is controlled by the detected presence of the flap.
One advantageous feature of the method invention is that it is possible in making a pocket opening to produce both a seam length which is precisely adapted to the length of the flap, and also to form the pocket bag by simply sewing together the two pocket-bag halves. In this way, a pocket opening of high quality can be produced at low cost within a short period of time.
Advantageous further developments of the method are disclosed and claimed herein.
A device for carrying out the method can be a device for providing a workpiece with a pocket opening which includes a flap and a pocket bag, on an automatic sewing machine which has a sewing point, comprising:
means for receiving a workpiece, a flap, and a pocket bag blank and securing them relative to one another;
transport means for transporting the workpiece, flap, and pocket bag blank in a transport direction to the sewing point of the automatic sewing machine while maintaining them in their relative position;
sensor means at a predetermined point upstream from said sewing point for detecting the presence of said flap; and
control means responsive to said sensor means for controlling the sewing machine and the transport means so as to begin sewing a seam to attach said workpiece, flap, and blank a predetermined time after a leading end of the flap is detected by the sensor, and to stop sewing said seam a predetermined time after a trailing end of the flap is detected by the sensor.
One particularly advantageous feature of the invention is the folder, which allows traditional sewing machines to be rapidly and inexpensively converted for making pocket openings by the method of as disclosed and claimed herein. Other advantageous embodiments of the device are disclosed and claimed herein.
Other objects, features and advantages of the invention will be appreciated from the following detailed description of an embodiment thereof, with reference to the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagrammatic view of a sewing machine according to a preferred embodiment of the invention;
FIG. 2 is a perspective detail view showing the folder, which forms part of the sewing machine;
FIG. 3 is a perspective view showing the folder, the gripper arranged in front of it (toward the right in FIG. 1), and one of the halves of the sewing-material clamp;
FIG. 4 shows the arrangement of FIG. 3 during the phase of transport of the sewing material;
FIG. 5 is a simplified diagrammatic side view showing the starting position of the application and transfer devices of the sewing machine;
FIG. 6 is a view similar to FIG. 5 showing the application and transfer devices after the folding of the piping strip and the transfer of the flap, but before the start of the transport of the sewing material; and
FIG. 7 is a block diagram of the control system.
DETAILED DESCRIPTION
Structure of the Sewing Machine
FIG. 1 is a diagrammatic view of a sewing machine for the production of pocket openings which includes a double-needle sewing machine 20 having a knife 22 which carries out vertical cutting movements arranged between the needle bars or needles 21, 21a. It also includes a gripper 11, a sewing-material clamp which is horizontally displaceable and consists of two halves 25, 25a, and a cutting device formed of two wedge-shaped knives 36, 37 arranged behind the place of sewing (downstream in the transport direction) and below the top surface of the frame 30.
In front of the place of sewing (upstream with respect to the transport direction) an optoelectronic sensor 7 is arranged above the folder 6 and, together with a reflective foil 40 glued onto the sewing-material clamp half 25, forms a light barrier. The sewing-material clamp 24 is connected to a clamp drive 28 and can be transferred horizontally below the sewing place, as defined by the needle bars 21, 21a, from the transfer region I into the cutting region II (x-direction).
The sewing machine is provided with a microcomputer control which, in addition to the formation of the stitch, also controls the auxiliary equipment. For this purpose, the sewing-material clamp 24 is operatively connected with a pulse generator in order to detect the transport path over which it moves. The sensor 7 is also connected to the microcomputer control and, in combination with the data representing the path over which the sewing-material clamp moves, provides the necessary data for the formation of the seam and the control of the wedge-shaped knives 36, 37 (Federal Republic of Germany OS 34 04 758). A block diagram of the control system is shown in FIG. 7.
The gripper 11 is swingably arranged in advance of (upstream from) the sewing place, with respect to the direction of transport, and above the work plate 27 (as seen in the plane of FIG. 1) and is adapted to be lowered vertically onto the work plate 27. In the starting position, as indicated in FIG. 5, the gripper 11 is raised and swung backwards, so that it is vertically above the piping strip applicator 34, the latter being arranged inclined relative to the work plate 27.
On its lower side 12, the gripper 11 is provided with lowerable needles (not shown in detail) which are moved outward in order to grip the piping strip 10 and are then drawn in again after the piping strip has been placed on the workpiece 3.
The gripper 11 is provided with a nose 13 (FIG. 3) on the side thereof which supports the flap 1, together with the applied half of the pocket-bag blank 2. This nose 13 protrudes from the gripper 11 in the direction of the flap 1, and is located at the end of the gripper 11 adjoining the folder 6. It is so shaped that it lifts the pocket-bag blank 2, lying on the flap 1, off from the gripper 11.
The gripper 11 is well known per se from the publicly distributed Durkopp 745 sewing machine; as well as from the publications DURKOPP Instructions 745-5, -7, -15, pp. 71-78; Spare Parts List, FIG. 24 published Oct. 1986, and FIG. 26, published Oct. 1987; and from the published brochure DURKOPP UND ADLER 745. All of the foregoing are expressly incorporated by reference herein.
FIG. 2 shows the folder 6, which includes a bridge 5, a bridge carrier 5a, and a guide plate 4. A yoke 8 with a guide plate 18 fastened thereon is mounted swingably on the bridge carrier 5a. The folder mounte 6 is arranged fixed in space at a location in advance of the sewing place. For this purpose there is fastened on the bridge carrier 5a another carrier 29 which, in turn, is connected, in a manner not shown in detail, to the sewing machine 20. The folder 6 also has a foot 14 formed on the bridge 5. The folder 6 does not lie directly on the work plate 27 but is raised therefrom to such an extent that the workpiece 3 and the piping strip 10 resting on it can be moved below the folder 6.
The rectangular guide plate 4 is arranged via two screws 26 on the bridge carrier 5a, spaced from it, and has a projection 17 which protrudes from the lower edge and extends in the direction of transport. The spacing must be selected large enough that, on the one hand, the flap 1 can be moved between the bridge 5 and the guide plate 4. As a general rule this can be easily arranged, since the bridge carrier 5a is wider (thicker) than the bridge 5. On the other hand, the spacing must be small enough for the sensor 7 arranged above the folder to be able to cover the region Z between bridge 5 and guide plate 4. A bend 9 is formed in the front quarter of the rectangular part of the guide plate 4 in such a manner that the front part of the guide plate 4 is at a smaller distance from the bridge 5 than its rear part. The projection 17 extends horizontally in the direction of transport and toward the bridge 5 at an angle of approximately 10° to the XZ-plane. It terminates about 5 mm away from the bridge 5, as measured in the Y-direction.
The yoke 8 is fastened swingably over the bridge 5 on the bridge carrier 5a. This yoke is bent in the direction of the foot 14 and is provided at its lower end with an approximately triangular guide plate 18. The lower edge of the guide plate 18 extends, slightly arched, at an angle of about 65° to the vertical, in the direction toward the bridge carrier 5a. In its lowest position, the yoke 8 strikes against a stop 43 formed on the bridge 5, so that the lowest corner of the guide plate 18 extends approximately to the lower edge of the guide plate 4. As shown in FIG. 2, the yoke 8 is bent in the XZ-plane so that the projection 17 formed on the guide plate 4 is enclosed between the bridge 5 and the guide plate 18.
Furthermore, the guide plate 18, which is perpendicular to the XY-plane, is inclined to the XZ-plane at an angle of about 10°, just like the projection 17 of the guide plate 4. Projection 17 and guide plate 18 are accordingly arranged in part parallel to each other. At a point on the guide plate 18 corresponding to the front edge of the projection 17 (i.e., at the point designated 41), the guide plate 18 is so bent that it passes from its course parallel to the projection 17 into a course parallel to the bridge 5. That is, the projection 17 of the guide plate 4 terminates in the transport direction at about the location of the bend 41 formed in the guide plate 18.
The purpose of the guide plate 18 is to bring the flap 1 together with the part of the pocket-bag blank 2 which was raised by the nose 13 away from the gripper 11 and then passed along the outer surface of the guide plate 4. Thus, the flap 1 and the blank 2 are brought together before they reach the sewing place.
In the basic position, the yoke 8 which bears guide plate 18 is held normally at all times in the lowermost position by the spring plate 19 which is fastened by the screws 16 also to the bridge carrier 5a. That is, the yoke 8 is pressed against the stop 43 on the bridge carrier 5a by the spring plate 19. By this swingable arrangement of the yoke 8 and the guide plate 18, it is assured that the pocket-bag blank 2 will always be dependably held against the flap 1 even if the blank consists of thicker material.
In front of the bridge 5, as seen in the direction of transport of the material (X-direction), the knife guard 15 is developed in known manner, within which guard the knife 22 travels upon the cutting of the pocket insert (Z-direction), the guard keeping both the flap 1 and the pocket-bag blank 2 which rests on it away from the knife 22, thus preventing damage to said parts.
Operation of the Sewing Machine
The course of production of a pocket opening with pocket bag will now be explained with reference to FIGS. 5 and 6. In this connection it should be pointed out that the sewing machine is substantially known and that some of the additional equipment such as the transfer devices, sewing-material clamp and gripper have been sold for a long time by the assignee of the present invention (see the publication "DURKOPP & ADLER, KATALOG IMB '88").
Referring to FIGS. 1 and 5, the workpiece 3 which is to be provided with the pocket opening is aligned by means of marking lights in region I, in front (in advance) of the sewing machine 20. The flap 1 is placed on the application plate 32 which is arranged above the work plate 27 and aligned with the stop 42. One half of the pocket-bag blank 2 is placed on the flap 1. It should be noticed that at this point in time, the clamp 33 of the transfer device (not shown in detail) cannot contact both the flap 1 and the pocket-bag blank 2. The piping strip 10 is placed and aligned on the piping strip applicator 34 and the other half of the pocket bag 2a is placed and aligned on the application plate 31.
The sewing-material clamp 24 moves into the transfer region I and descends onto the workpiece 3. In this connection, the end position which it is to assume is so determined that the gripper 11 can subsequently be swung precisely between the two clamp halves 25, 25a (as will be seen hereinbelow in connection with FIG. 6). At the same time, the gripper 11 descends in the direction of the application plate 34, grips the piping strip 10 via the needles (not shown in detail here) arranged on its lower side 12, moves back into the starting position, carries out a swinging motion (arrow A) until it is directly above the sewing-material clamp 24 in a position between the clamp halves 25, 25a and in line with the sewing needles 21, 21a, and then descends onto the workpiece 3.
Now referring to FIG. 6, the fold plates 38 and 38a are displaced in the direction of the gripper 11, as a result of which the piping strip 10 is folded around the gripper 11. The clamps 33 and 33a of the transfer devices close and are swung so that the flap 1 with the pocket-bag blank 2 resting on it comes to rest on the fold plate 38 of the sewing-material clamp 24 and the pocket-bag blank 2a comes to rest on the fold plate 38a. The flap clamps 39, 39a are then closed, as a result of which the flap 1 and the pocket-bag half 2 on the one hand, and the pocket-bag half 2a on the other hand, are fixed in the sewing-material clamp 24.
FIG. 6 shows the position now assumed by all parts of the sewing material. The clamps 33, 33a are loosened and the sewing-material clamp 24 is transported in the direction toward the sewing needles 21, 21a. The piping strip 10 is held so forcefully by the folding plates 38, 38a that upon the displacement of the sewing material clamp 24 it is pulled along with the latter, below the gripper 11 and the folder 6.
The further course of the process is best seen from FIGS. 3 and 4, which provide a partial perspective view of the gripper 11, with the folder 6 arranged fixed in place downstream from it in the travel direction, and with the flap 1 and the pocket-bag blank 2 clamped in the clamp half 25.
From FIG. 3 it can be seen that part of the flap 1 is turned up against the gripper 11. The pocket-bag blank 2, which is shown in dashed lines, has its corner which is toward the sewing needle 21 turned away from the gripper 11 by the nose 13 formed on the latter. Note that the blank 2 overlies the flap 1 as seen in FIG. 3, but the flap 1 is visible because the blank 2 is shown in phantom. During the transport of the sewing-material clamp 24, the clamp half 25 pulls the flap 1 between the nose 13 and the gripper 11 so that, as it travels further, it passes into the intermediate space Z which is formed by the guide plate 4 and the bridge 5 within the fold stamp 6, while the pocket-bag blank 2 moves along the side 4a (FIG. 3) of fold plate 4 facing away from the bridge 5.
The optical sensor 7, which is arranged above the fold stamp 6 and covers the region Z between the bridge 5 and the guide plate 4, forms a light barrier with the reflective foil 40 which is arranged on the sewing-material clamp half 25. At the moment when the edge of the flap 1 interrupts this light barrier, the pulse generator, which is operatively connected with the sewing-material clamp 24, is switched on by the microcomputer control and the transport path now moved over is detected. Since the distance from the sensor 7 to the sewing needles 21, 21a is fixed, a known number of pulses, which must then be counted from the time of the detection of the edge by the sensor 7 until the start of the formation of the seam in order to let the first stitch be formed at the beginning of the flap 1, is also fixed.
During the further course of the transport of the workpiece, the pocket-bag blank 2 enters into the region between the yoke 8 and the guide plate 4 (FIG. 4) and, since the downstream region of the guide plate 4 and the yoke 8 extend at an angle of about 10° to the bridge, the blank 2 again comes into contact with the flap 1. At the place where the two parts 1 and 2 again lie against each other, the stitch is formed and the flap 1, together with the pocket-bag blank 2 and the piping strip 10, is sewn onto the workpiece 3.
At the same time, the pocket-bag blank 2a (not shown in detail here), which is guided on the other side of the gripper 11, is also sewn to the piping strip 10 and the workpiece 3.
The knife 22, which is arranged between the needles and downstream from the needles in the direction of transport, cuts the pocket opening during the transport of the sewing material. When the rear edge of the flap 1 reaches the sensor 7, the light barrier is again released and the sensor 7 gives off a signal to the electronic control. From the defined distance of the sensor 7 from the needles 21, 21a, the distance is determined over which the sewing-material clamp must still move until the stitching is stopped so that the end of the seam will coincide with the end of the flap, and at the same point, the formation of the cut by the knife 22 is interrupted.
The number of pulses of the pulse generator which have taken place, from the time the light barrier is interrupted until the time it is released, is stored in the electronic control in known manner and constitutes a measure of the length of the flap. These stored data serve in known manner (Federal Republic of Germany OS 34 04 758) to control the wedge-shaped knives 36, 37.
Although the present invention has been described in relation to a particular embodiment thereof, many other variations and modifications and other uses will become apparent to those skilled in the art. It is preferred, therefore, that the present invention be limited not by the specific disclosure herein, but only by the appended claims. | A method and apparatus for automatically making a pocket opening having a flap and a pocket bag, one half of the pocket-bag blank being sewn to the workpiece together with the flap and the piping strip. The formation of the seam takes place as a function of the detected presence of the flap. During the transport of the workpiece, flap, and blank to the sewing place, the part of the pocket-bag blank which rests on the flap is lifted off of the flap, the presence of the flap is detected by an opto-electronic sensor, and the pocket bag is again placed on the flap before the parts are sewn together. The sewing machine is controlled in response to the sensor so that the seam corresponds precisely to the length of the flap. The pocket-bag blank is lifted off and replaced on the flap by a folder which has an arrangement of guide plates for carrying out the invention. | 3 |
FIELD OF INVENTION
[0001] The present nvention describes an improved process for the preparation of Dabigatran Etexilate (1), a pharmaceutically acceptable salt for the treatment of thromboses, cardiovascular diseases etc., and its intermediates involved in the synthesis.
BACKGROUND OF THE INVENTION
[0002] Dabigatran Etexilate, chemically known as β-Alanine, N[[2-[[[4-[[[(hexyloxy)carbonyl]amino]iminomethyl]phenyl]amino]methyl]-1-methyl-1H-benzimidazol-5-yl]carbonyl]-N-2-pyridinyl-, ethyl ester, methanesulfonate, is a thrombin inhibitor. Dabigatran etexilate was first described in International patent application WO 98/37075 and the process for manufacture was reported in WO 2006/000353 and also in J. Med. Chem, 2002, 45, 1757 by N. Hauel et al.
[0003] Two general routes have been reported for the synthesis of Dabigatran etexilate. The first processwas disclosed in WO98/37075 and a modification of the first route has been described in WO 2006/000353. Both the synthetic routes start from the 3-nitro-4-methylamono-benzoic acid and are presented in Scheme 1.
[0000]
[0004] Both the routes involved three common intermediates II, III and VI, of which VI can be obtained from either IV or V depending on the substituted glycine used for the synthesis. According to the previous reports, all the intermediates required column purification to prepare substantially pure Dabigatran and the processes are not suitable for industrial scale production of the same. The synthesis of intermediate II has been reported in several patents and require either a chromatographic purification or a tedious purification procedure such as converting into the HCl salt followed by recrystallization to obtain 97% pure intermediate II. In both cases, the yield is less than 50%. Similarly, Intermediate III is one of the key intermediates in the Dabigatran synthesis and the process involves the reduction of nitro group either by hydrogenation in presence of Pd/C or in presence of sodium dithionate.Both the methods resulted in the formation of product with higher level of impurities. WO 2002/004397 reports the product as a solid and in US 20110082299 the intermediate is reported as a dark red coloured viscous liquid and used without further purification. However, it is essential that the key intermediate III must be very pure to obtain the intermediate VI as very purecompound thereby isolating the Dabigatran API with required purity in the final stage.
[0005] Similarly, the intermediates IV and V prepared by either CDI or PPA mediated coupling with glycine derivatives tbllowed by acetic acid mediated cyclizationresulted in the formation of highly impure products, and purified by either column chromatography or by converting the crude reaction mixture to suitable salts. Both the methods afforded low yield and purity thereby the process is not suitable for the commercial scale production of Dabigatran.
OBJECT OF THE INVENTION
[0006] The primary object of the invention is to develop an improved process Rif the industrial scale production of Dabigatran.
[0007] Another object of the invention is to provide a is to provide a suitable purification method for preparation of intermediate II.
[0008] Another aspect of the invention is to provide an improved process for preparation of compound of formula III.
[0009] Further object of the invention is to provide an efficient process for preparation of compound of formula IV.
DETAILED DESCRIPTION OF THE INVENTION
[0010] Most of the prior art processes for the synthesis of Dabigatran requires tedious purification methods for the intermediates II, III, IV, V and VI. In earlier reports, the intermediate II was purified either by preparing the HCl or HBr salt or by column chromatography, which resulted low yield and purity of II.
[0011] One aspect of the invention was to obtain a suitable method fur purifying the intermediate II in the free base form. The known art for the purification of intermediate II is by converting it in to the corresponding acid salts and recrystallization of the salt, which in turn would result in the yield loss.
[0012] Inventors have found a novel method of purifying the free base of intermediate II by recrystallizing the compound in an aprotic solvent such as hexane, toluene, xylene etc. Preferably the solvent used was hexane or a mixture of toluene and hexane.
[0013] The temperature used for the recrystallization was from 50-100° C. followed by cooling to 30-0° C.
[0000]
[0014] The reduction of intermediate II to the corresponding amino compound (III) was reported using hydrogenation in presence of Pd/C or with sodium dithionate. Both the methods yielded the product with higher level of impurities, which needs lengthy purification methods. The main drawback with the reported sodium dithionate reduction in WO 2009111997 was the formation of impurities. The intermediate III was isolated as brown viscous oil and proceeded to the next stage without further purification. The inventors have fbund that such process without purification results in low yields and low purity of the Formula IV, the key intermediate in the dabigatran synthesis.
[0015] Another aspect of the invention was to develop an economical and scalable process for the preparation of III without affecting the yield and purity. Inventors have found that the combination of sodium dithionate with an organic or inorganic base as reducing agent dramatically simplified the reduction process and yielded intermediate III with excellent yield and purity as a solid.
[0016] The inorganic base used was Na 2 CO 3 , K 2 CO 3 , NaHCO 3 and the like or an organic base such as triethyl amine, pyridine, DIPEA and preferably potassium carbonate.
[0017] The reduction was carried out in presence of a base in a water miscible solvent such as tetrahydrofuran, alcohols, acetone, or ether solvents in combination with water preferably in a mixture of dioxane and water. The product was purified by recrystallization using ethyl acetate as solvent.
[0000]
[0018] Since intermediate IV is a key intermediate in the synthesis of Dabigatran, substantially pure IV is necessary to achieve good conversion and purity in the next stages of the process. In the prior art the synthesis has been achieved by the CDI mediated amide formation in THF at 66-70° C. fur 5 h, followed by the acetic acid mediated cyclization. The reaction produces a highly impure intermediate IV and it required tedious procedure for the purification such as column chromatography or converting it into the corresponding acid salts, In US 20110224441, the intermediate IV was purified by making the oxalate salt, in WO 2008095928 as the HBr salt and in WO 98/37075 the same was purified by column chromatography.
[0019] Another object of the invention provides an improved process fur the conversion of intermediate III to IV using DCC or EDC optionally in the presence of HOBt at 25-35° C. followed by acetic acid mediated cyclization to the corresponding benzimadazole intermediate IV. The advantage of the new methodology compared with the reported CDI mediated coupling reaction is the milder reaction conditions and low level of impurity formation during the process.
[0020] The reaction may also be carried using DCC or EDC in presence of an activating agent such as HOBT, N-hydroxy succinimide, DMAP etc. in aprotic solvent at temperatures ranging from 20-40° C.
[0021] The present invention also provides a method for purifying the intermediate IV in the free base form by recrystallization using a suitable solvent. The solvent used for the recrystallization was selected from ethyl acetate, isobutyl acetate, isopropyl acetate, IPA at temperatures ranging from 0-25° C. and preferably ethyl acetate or IPA.
[0000]
[0022] Intermediate VI was prepared by the reaction of IV with HCl and ethanol followed by reaction with ammonium carbonate using a known art for converting cyano to the corresponding amidines.
[0023] Dabigatran synthesis was completed by the reaction of intermediate VI with n-hexyl ehloroformate in presence of a suitable base in a protic solvent or water or mixture of water and an organic solvent.
[0024] Finally the dabigatran free base was converted in to the mesylate salt by reacting with methanesulphonic acid in acetone.
[0025] The present invention is schematically represented as follows.
[0000]
[0026] In conclusion, the authors have disclosed an improved industrial scale process for the synthesis of Dabigatran and its intermediates.
EXAMPLE 1
[0027] Preparation of Ethyl 3-[[4-(methylamino)-3-nitrobenzoyl](pyridin-2-yl)amino]-propanoate (II)
[0000]
[0028] 100 g of compound I was dissolved in 1 L of dichloromethane under nitrogen atmosphere and cooled to 0-5° C. Thionyl chloride was added to the reaction mixture for 1 h and the reaction mixture was boiled to reflux. Maintained the reaction mass under the same temperature for 5-6 h. After completion of the reaction, excess thionyl chloride was removed by co-distillation with dichloromethane and finally the solvent was completely removed under vacuum. The acid chloride was then dissolved in dichloromethane under an inert atmosphere and triethyl amine was added to the reaction mixture. To the reaction mixture was added slowly a solution of ethyl-3-(pyridine-2-ylamino) propanoate in dichloromethane. The reaction mixture was maintained at the same temperature for another 6-12 h. After completion of the reaction, the reaction mass was diluted water and extracted the product with dichloromethane. The combined organic layers were separated and dried over anhydrous sodium sulphate. The solvent was distilled off under vacuum and the product was purified by hexane.
[0029] Yield: 80%, HPLC: >98%
EXAMPLE 2
[0030] Preparation of Ethyl 3-[[3-amino-4-(triethylamino)benzoyl](pyridin-2-yl)amino]-propanoate (III)
[0000]
[0031] 100 g of compound II was dissolved in 1 L of a mixture of dioxane and water and heated the reaction mixture to 50° C. Sodium dithionate (4.5 equiv.) and potassium carbonate (0.3 equiv.) was added to the reaction mixture and maintained at the same temperature for 2-6 h. After completion of the reaction, filtered the reaction mixture and evaporated the solvent. Water was added to the crude mixture and extracted the product with ethyl acetate. The organic layer was dried over anhydrous sodium sulphate and filtered. The solvent was removed under vacuum yielded the compound III as a brown viscous liquid. The product was purified by recrystallization from ethylacetate.
[0032] Yield 80%; HPLC: >98%
EXAMPLE-3
[0033] Preparation of 3-([2-[(4-cyanophenyl amino)-methyl]-1-methyl-1H-benzimidazole-5-carbonyl]-pyridin-2-yl-amino)ethyl Propionate (IV).
[0000]
[0034] 100 g of compound III was dissolved in dichloromethane under nitrogen atmosphere. Added 41 mL of triethyl amine and 39 g of HOBT to the reaction mass and stirred tzar 15 minutes. Cooled to 20° C. and added 77 g of N-(4-Cyanophenyl) glycine and a solution of DCC in dichloromethane to the reaction mass and stirred for 30 minutes. Filtered the precipitated solids, dried the filtrate with anhydrous sodium sulphate and removed solvent under vacuum. Acetic acid was added to the crude mass and refluxed for 2-6 h. After completion of the reaction, cooled the reaction mixture to room temperature and water was added. The pH of the solution was adjusted to 6-8 and extracted the product with dichloromethane. The organic layer was collected, dried over sodium sulphate and removed under vacuum. The crude material obtained was purified by recrystallization in ethyl acetate.
[0035] Yield: 84%, HPLC: >97%
EXAMPLE-4
[0036] Preparation of N-[([(amidinophenyl)-amino]methyl)-1-methyl-1H-benzimidazole-5-carbonyl]-N-(2-pyridyl)-3-aminopropionic Acid (VI)
[0000]
[0037] 100 g of compound IV was dissolved in a mixture of 500 mL of dichloromethane and 50 mL of ethanol and cooled the reaction mixture to 0° C. Dry HCl gas was passed through the solution for 5-7 h and stirred the reaction mixture at room temperature for another 36 h. After completion of the reaction, ethanol was removed from the reaction mixture and 200 g of ammonium carbonate and 500 mL of ethanol was added. Stirred the reaction mass for another 24 h. Filtered the solids and the solvent was removed under vacuum. The product was purified by recrystallization using a mixture ethyl acetate and ethanol.
[0038] Yield: 90%, HPLC: >98%
EXAMPLE-5:
[0039] Preparation of Ethyl N-[(N′-hexyloxycarbonyl)amidino]phenyl)amino[methyl)-1-methyl-1H-benzimidazole-5-carbonyl]-N-(2-pyridyl)-3-aminopropionate Mesylate (VI)
[0000]
[0040] Method: A
[0041] 50 g of compound VI was dissolved in 400 ml of acetone and 250 ml of Water,Cool reaction mixture to 10-15° C. 30 g of Potassium carbonate added lot wise and 3.25 ml of n-hexyl chloroformate was added slowly to the reaction mixture and stirred for another 1 h. After completion of the reaction the precipitated product is filtered of washed with acetone/Water and material was recrystallized by using acetone and Water. Product is dissolved in 250 ml of acetone and cooled to 10-15° C. 7 g of methane sulphonic acid in acetone was slowly added to the reaction mixture with stirring and the precipitated material was isolated by filtration. The product was purified by recrystallizating from acetone. Yield: 60 g (80-85%) HPLC purity 99.5%.
[0042] Method B:
[0043] 100 g of compound VI was dissolved in 500 mL of dry dichloromethane and cooled the reaction mixture to 0-5° C. 100 mL of triethyl amine was slowly added to the reaction mixture and stirred for 15 minutes. Added 65 mL of n-hexyl chloroformate to the reaction mixture for a period of 15 minutes and the stirring was continued for another ih. After completion of the reaction, water was added to the reaction mixture and extracted the product with dichloromethane. The organic layer was dried over anhydrous sodium sulphate and removed the solvent under vacuum. The crude reaction mixture was purified by recrystallization using ethyl acetae. The product thus obtained was dissolved in 500 mL of acetone and cooled the solution to 0-5° C. 10 mL of Methane sulphonic acid was slowly added to the reaction mixture. The precipitated solid was isolated and purified by recrystallization using acetone.
[0044] Yield 75%, HPLC: ≧99.5% | The present invention describes an improved process for the preparation of Dabigatran Etexilate (Formula-I), a pharmaceutically acceptable salt for the treatment of thromboses, cardiovascular diseases etc. and intermediates involved in the synthesis. | 2 |
TECHNICAL FIELD
[0001] This invention generally relates to flip chip assembly. More specifically to a flip chip assembly and a method of forming the flip chip assembly.
BACKGROUND
[0002] Flip chip mounting is an increasingly popular technique for directly electrically connecting an integrated circuit chip to a substrate such as a circuit board. In this configuration, the active face of the chip is mounted face down, or “flipped” on the substrate. The electrical bond pads on the flip chip are aligned with corresponding electrical bond pads on the substrate, with the chip and substrate bond pads electrically connected by way of an electrically conductive material. The flip chip mounting technique eliminates the use of bond wires between a chip or chip package and the substrate, substantially increases the reliability of the chip-to-substrate bond.
[0003] As a means for mounting integrated circuit chips to a substrate, there has been known a number of methods which form solder portions, such as solder bumps and solder precoats, on the integrated circuit chip and joins the integrated circuit chip to a substrate by means of the solder portions. Typically, the soldering process involves applying a flux to substrate and mounting the integrated circuit chip to a substrate, and heating and melting the solder to join the solder portions. After the solder joints have been formed, the assembly is subjected to cleaning to remove flux residues to enhance the reliability after the mounting.
[0004] Additionally the resulting assembly typically undergoes further thermal cycling during additional assembly operations. The final assembly also is exposed to wide temperature changes in the service environment. The integrated circuit chip is typically silicon and the substrate may be epoxy, or ceramic. Both the material of the integrated circuit chip and the substrate frequently have thermal expansion coefficients that are different from one another, and are also different from the thermal expansion coefficient of solder. The differential expansion that the assembly invariably undergoes results in stresses on the solder bonds which can cause stress cracking and ultimately failure of the electrical path through the solder bond. To avoid solder bond failures due to mechanical stress, the gap between the surfaces joined by the bond is typically filled with an underfill material.
[0005] Conventionally, the underfill material is dispensed between the chip and the substrate. The underfill material is typically provided as a liquid adhesive resin that can be dried or polymerized. The underfill material provides enhanced mechanical adhesion and mechanical and thermal stability between the flip chip and the substrate, and inhibits environmental attack of chip and substrate surfaces. The underfill material also fills the gaps between the bumped electronic parts and the board to reinforce the joints. The underfill resin is then hardened by heat treatment, thus completing the mounting process.
[0006] The mounting process described above, however, poses the following problems as the use of such solvents as fluorocarbon are not considered environmentally safe. Further, the cleaning process after soldering has become complicated and risen in cost, which, combined with on-going reductions in the size of integrated circuit chip, has contributed to making the cleaning process technically difficult. As to the underfill resin, since the gaps between the integrated circuit chip and the substrate is minimized to a need for smaller components filling of the underfill after the mounting of electronic components difficult, resulting in unstable quality of the assembly. In addition to this quality problem, the above conventional mounting method has another problem that it requires two heating processes for the mounting of each component, one for soldering and one for hardening the resin, thus complicating the process. Additionally, in some cases entrapped air, or incomplete wetting of the surfaces of the space being filled, inhibits flow or prevents wicking, causing voids in the underfill. The above method also has another problem that it requires two heating processes. One for mounting the integrated circuit chip to the substrate and the other for hardening the resin, thereby complicating the process and the time for manufacturing the assembly.
[0007] Therefore, there is a need in the flip-chip bonding industry to have a process that substantially reduces cure time for the underfill and at the same time having a more reliable bond.
SUMMARY
[0008] In accordance with one aspect of the present invention a semiconductor assembly comprises an electronic component such as an integrated circuit chip attached to a substrate such as a circuit board. The electronic component is provided with a solder pad that forms a metallurgical bond with the top surface of a bond pad provided in the substrate.
[0009] In yet another aspect, a first method of bonding the electronic component to a substrate is disclosed. The method comprises the step of forming a solder pads on a surface of the electronic component. The solder pads are preferably Au/Sn eutectic solder pads. Forming a bond pad on a surface of the substrate. The bond pad comprises a top layer formed of gold. Placing an underfill material on top of the surface of the substrate. The method also comprises the step of heating the electronic component and the substrate. Moving the electronic component towards the substrate such that the solder pads are aligned above the bond pads and forming a diffusion bond between the solder pads and the top layer of the bond pads.
[0010] In yet another aspect of the present invention, a second method of bonding the electronic component to a substrate is disclosed. The method comprises the step of forming a solder pads on a surface of the electronic component. The solder pads are preferably Au/Sn eutectic solder pads. Forming a bond pad on a surface of the substrate. The bond pad comprises a top layer formed of gold. Placing an underfill material on top of the surface of the substrate. The method also comprises the step of heating the electronic component and the substrate. Moving the electronic component towards the substrate such that the solder pads are aligned above the bond pads and heating the assembly such that the solder material reflows and forms a metallurgical bond with the top layer of the bond pads on the substrate.
[0011] Further aspects, features and advantages of the invention will become apparent from consideration of the following description and the appended claims when taken in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] [0012]FIG. 1 is a cross sectional view of the electronic component mounted on top of a substrate to form the electronic assembly in accordance with the teachings of the present invention;
[0013] [0013]FIGS. 2A to 2 H is a cross sectional representation of forming a solder pad on the electronic component in accordance with the teachings of the present invention;
[0014] [0014]FIG. 3A is a cross sectional representation of the electronic component being mounted to a substrate by a first method in accordance with the teachings of the present invention;
[0015] [0015]FIG. 3B is a cross sectional representation of forming a bond between the electronic component and the substrate by the first method, in which the solder pad of the electronic component pierce an underfill film on the substrate to form the bond with the top layer, in accordance with the teachings of the present invention;
[0016] [0016]FIG. 4A is a cross sectional representation of the electronic component being mounted to a substrate by a second method in accordance with the teachings of the present invention;
[0017] [0017]FIG. 4B is a cross sectional representation of forming an intermediate bond between the electronic component and the substrate by the second method, in which the solder pad of the electronic component pierce an underfill film on the substrate to form the bond with the top layer, in accordance with the teachings of the present invention; and
[0018] [0018]FIG. 4C is a cross sectional representation of forming a bond between the electronic component and the substrate by the second method, in which bond is formed by the reflow of the solder pad on top of the top layer, in accordance with the teachings of the present invention.
DETAILED DESCRIPTION
[0019] The following description of the preferred embodiment is merely exemplary in nature and is in no way intended to limit the invention or its application or uses.
[0020] Referring in particular to FIG. 1 an electronic assembly, such as a semiconductor assembly is generally shown and represented by reference numeral 10 . The assembly 10 comprises an electronic component 12 positioned above a substrate 14 . Electronic component 12 is an integrated circuit or a flip chip adapted for mounting on a substrate 14 by a flip-chip process.
[0021] The electronic component 12 is comprises a base 16 . Preferably the base 16 is formed of silicon and has an active surface 18 . A plurality of electrically conductive electrodes 20 are mounted on the active surface 18 of the electronic component 12 . The electrodes 20 include an integrally attached eutectic solder pad 22 . As will be explained in details later the electronic component 12 is directly attached to the substrate 14 through the solder pad 22 formed on the active surface 18 of the electronic component 12 .
[0022] Referring in particular to FIGS. 2A to 2 H, a method of forming the eutectic solder pad 22 on the active surface 18 of the electronic component 12 is shown. The method comprises the step of first forming the electrodes 20 . A first layer 24 of an electrode base is deposited on the active surface 18 (shown in FIG. 2A). Preferably, the first layer 24 is formed of aluminum. A second layer 26 preferably of Ti/W alloy and Au is deposited on top of the first layer 24 by the sputtering deposition process (shown in FIG. 2B). Alternatively, the first layer 24 may be pretreated with zincate and subject to electroless nickel deposition. A photoresist material 28 is then etched on the active surface 18 and partially over the second layer 24 (shown in FIG. 2C). A third layer 30 preferably of gold is then electroplated on top of the second layer 26 (shown in FIG. 2D). This step is then followed by electroplating a fourth layer 32 preferably tin on top of the third layer 30 (shown in FIG. 2E). The photoresist material 28 is then removed and the second layer 26 is etched away from the active surface 18 of the substrate 16 (shown in FIGS. 2F and 2G).
[0023] Referring in particular to FIG. 2H, in order to form the eutectic solder pad 22 , the third layer 30 and the fourth layer 32 are reflowed to form eutectic solder pad 22 . Preferably, the eutectic solder pad 22 is formed of gold/tin alloy. Alternatively, other metals such as tin/lead alloys may be used to form the eutectic solder pad 22 . As shown in FIG. 2H, the eutectic solder pad 22 is dome shaped having a bottom periphery 23 . As will be explained later, the dome shape of the eutectic solder pad 22 will facilitate the bonding of the electronic component 12 to the substrate 14 . Although the dome shaped is preferred, it must be understood that the solder pad 22 may have other shapes.
[0024] Referring in particular to FIG. 1, the substrate 14 also defines a base 15 . The substrate 12 is preferably a printed circuit board and the base 15 is formed a composite material or a ceramic material. The base 15 has a surface 34 on which plurality of substrate bond pads 36 are mounted. The substrate bond pads 36 facilitate the bonding of the electronic component 12 to the substrate 14 . The substrate bond pads 36 are preferably composed of a first layer 40 preferably a solder wettable copper. The first layer 40 is coated with a second layer 42 of a second metal. Preferably, the second metal forming the second layer 42 is nickel. Finally, a top layer 44 of a third metal is coated or deposited on top of the second layer 42 . In the preferred embodiment, the third metal forming the top layer 44 is gold. Alternatively, the substrate bond pads 36 have a composition of Ti/Ni/Au or other metals may be used that adheres well to the materials used to form the solder pad 22 .
[0025] In order to substantially increase the reliability of the bonding between the electronic component 12 and the substrate 14 , an underfill material 46 is disposed on the surface 34 of the substrate 14 . The underfill material 46 is disposed such that the underfill material 46 forms a thin layer over the top layer 44 of the substrate bond pads 36 . Preferably, the underfill material 46 is in form of a film and contains 30% to 40% of a solid filler material. The underfill material 46 reduces the thermal expansion stresses caused due to the difference in the coefficient of thermal expansion of the electronic component 12 and the substrate 14 . The solid filler material in the underfill material 46 is preferably an inorganic material such as silica. Alternatively, the filler may comprise an organic materials such as resin.
[0026] The first method of bonding the electronic component 12 to the substrate 14 is now described by referring to FIGS. 3A to 3 D. As shown in FIG. 3A, the active surface 18 of the electronic component 12 having the solder pad 22 is placed above the surface 34 of the substrate 14 . The electronic component 12 is held above the substrate 14 by a holding means (not shown). The electronic component 12 is flipped such that solder pad 22 directly face the surface 34 of the substrate 14 . The electronic component 12 is then heated to a temperature in the range of 220° C. to 260° C. through a heating element (not shown). The substrate 14 is also simultaneously heated to a temperature of about 75° C. to 100° C. The heating of the substrate 14 will result in softening of the underfill material 46 . The electronic component 12 is then moved towards the substrate 14 as shown by arrows 45 such that the solder pad 22 is aligned on top of the substrate bond pads 36 . The method further comprises the step of applying pressure on the electronic component 12 such that the solder pad 22 penetrate the underfill material 46 to directly contact the top layer 44 of the substrate bond pads 36 (shown in FIG. 3B). In this method the electronic component 12 and the substrate 14 are heated below the melting point of the solder pad 22 such that diffusion or a thermo-compression bond is formed between the solder pad 22 and the top layer 44 of the substrate bond pad 36 . As seen in FIG. 3B, the dome shape of the solder pad 22 is retained and only the bottom periphery 23 of the solder pad 22 forms a bond with the top layer 44 of the substrate bond pad 36 . Preferably, the bond is formed at around 250° C.
[0027] [0027]FIGS. 4A to 4 C represent the alternative process of attaching the electronic component 12 to the substrate 14 . Referring in particular to FIG. 4A, like the first method, the electronic component 12 is placed on top of the substrate 14 such that the active surface 18 of the electronic component 12 is facing the surface 34 of the substrate 14 . The electronic component 12 is then heated to about 230° C. to about 260° C. The substrate 14 is also heated to about 75° C. to about 100° C. As the electronic component 12 is moved towards the substrate 14 as shown by arrows 50 , pressure is applied on the electronic component 12 . The amount of pressure applied in approximately 150 grams/bump such that the solder pad 22 penetrate the underfill material 46 (shown in FIG. 2A). As seen in FIG. 4B, the solder pad 22 is placed directly in contact with the top layer 44 of the substrate bond pads 36 . When the electronic component 10 is placed on top of the substrate 14 , a bond similar to the bond formed in the first method is first formed represented in FIG. 4B.
[0028] Referring in particular to FIG. 4C, the assembly 10 comprising the electronic component 12 on top of the substrate 14 is then heated to a temperature of about 300° C. Heating the assembly 10 at this temperature will cause the solder pad 22 to melt and reflow thereby forming a metallurgical bond between the solder pad 22 and the top layer 44 of the substrate bond pad 36 . In this method as shown in FIG. 1 and FIG. 4C, the top layer 44 is encapsulated by the reflowed solder pad 22 . Therefore, in this method the metallurgical bond is formed by vertical compression and horizontal expansion of the solder pad 22 . This result in more surface area contact thereby forming a strong bond between the electronic component 12 and the substrate 14 .
[0029] It should be noted that the method of attaching the electronic component 12 to a substrate 14 is not limited to the embodiments discussed above. With this invention because an underfill material 46 having a filler material is applied to the surface of the substrate before the attachment of the electronic component it accomplishes bonding of the electronic component 12 to the substrate 14 and the curing of the underfill material 46 occurs simultaneously. The bonding process therefore eliminates the need for an additional underfill step, thereby eliminating the additional cost of equipment and increasing the production output. Since the above discussed methods involve vertically compressing and laterally expanding solder pads 22 as they attach to the top layer 44 of the substrate bond pads 36 , it substantially eliminates the production of voids between the solder pad 22 and the substrate 14 . As a result the bonding method of the present invention results in a more reliable bond between the electronic component 12 and the substrate 14 to result in a more robust assembly 10 .
[0030] As any person skilled in the art will recognize from the previous description and from the figures and claims, modifications and changes can be made to the preferred embodiment of the invention without departing from the scope of the invention as defined in the following claims. | The present invention is generally directed towards a flip chip assembly. In particular a new bonding process for bonding an electronic component to the substrate is disclosed. The method comprises the steps of forming at least one solder pad on the electronic component and forming at least one bond pad on the substrate wherein the at least one bond pad has a top layer formed of a metal. Placing an underfill film on top of the at least one bond pad and heating the electronic component and the substrate. Moving the electronic component towards the substrate such that the at least one solder pad is aligned on top of the at least one bond pad and finally forming a bond between the at least one solder pad and the top layer of the at least one bond pad. | 7 |
CROSS-REFERENCES TO RELATED APPLICATIONS
This is a continuation-in-part of application Ser. No. 07/917,841 filed Jul. 21, 1992, now U.S. Pat. No. 5,471,811 which was a continuation-in-part of both: application Ser. No. 07/601,413 filed Oct. 22, 1990, now U.S. Pat. No. 5,131,786, which was a continuation-in-part of application Ser. No. 07/347,482 filed May 4, 1989, now U.S. Pat. No. 4,964,750; and application Ser. No. 07/675,503 filed Mar. 26, 1991, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
Applicant's invention relates to precast barrier systems and a method of construction. More specifically, the present invention relates to a precast retaining wall with precast concrete columns and panels, and a method of constructing such a wall on a foundation surface.
2. Description of the Prior Art
In recent years, many civil engineering construction projects have used concrete barriers in numerous different applications; such as a retaining wall or as a barrier to keep out intruding people, animals, vehicles, fire, wind, light, sound, heat and the like. For a concrete barrier to be selected for these different applications, the overall cost of the barrier must be lower when considering the manufacturing costs, manpower costs and construction, and the time required to construct the wall. The barrier must also be durable and maintenance free with the possibility of a wide variety of aesthetically pleasing surface finishing. Cast-in-place concrete has given way to the use of precast concrete barriers. Precast concrete barriers are preferred because they can be manufactured at a lower cost with a higher degree of uniformity not found in cast-in-place concrete barriers. The precast concrete barriers may also be erected in numerous configurations and are capable of self support without massive construction.
Another cost which must be considered in many municipal areas is the availability of costs of purchasing right-of-ways for the construction projects. Consideration of the right-of-way requirements is particularly important in highway construction near residential areas. If the roadway is constructed near the residences, then the noise from passing vehicles and the impact of the noise on nearby residences must be considered. Ideally, the highway would be built far enough away from the residences so that the noise would not bother the residents. However, due to a continued growth of urban sprawl and the need for more highways, many times there is just not enough land available. In these situations, sound abatement walls are constructed to minimize the noise reaching the residents. Unfortunately, many of the current barrier designs require more right-of-way land than that which is available.
The need to reduce right-of-way requirements and the need to reduce costs has created a need for an environmental barrier system in which the width of barrier construction is small and which may be straight, curved, angled, or which may follow a terrain of any contour. The straighter and narrower the barrier construction, the lower the overall construction costs since less land must be acquired.
Current column and panel barriers experience a variety of problems. One problem associated with column and panel barriers is the need to very precisely position adjacent columns if prefabricated panels are to be positioned in between. The positioning problem includes not only the column-to-column spacing but also the plumbness of the column, both to the wall face and the panel ridge. Once the panel dimensions arc selected, then the panels are fabricated, and the spacing between adjacent columns must correspond to the paneling for the full exposed length of the column. If precise column positioning is not maintained, then the panels will not fit between columns which are spaced too close, or the panels cannot be attached to columns which are spaced too far apart.
In typical precast concrete construction, tolerances of plus or minus one-quarter inch or more are common, depending upon the fabricators' experience and the cost of forms. Accumulation of such tolerances require that positioning and placement of columns be very precise in order to accommodate the precast panels there between. Precise tolerances on the lateral spacing between columns can be very difficult to maintain at construction sites. Consequently, accumulation of tolerances can lead to a loose joint between panels and columns. With a loose joint, vibration can occur and sounds and the like and other forces or energy can pass through the barrier. The present invention overcomes the problems with precise tolerances without any significant additional costs.
Another problem associated with column and panel barriers concerns thermally induced, linear expansion and contraction of the completed barrier. Thermal variations in the wall can lead to loose joints during contraction as discussed above, structural damage of columns and panels due to compressive stress developed during expansion, and construction difficulty when large thermal variations occur during construction. Thus, there is a need for a precast concrete barrier which overcomes problems of the type discussed above for column and panel barriers.
SUMMARY OF THE INVENTION
The present invention overcomes problems of the type discussed above by providing a precast concrete wall comprising a plurality of precast C-shaped wall segments with U-shaped members which when placed adjacent to another C-shaped wall segment forms a stay-in-place form for a structural column. Cast-in-place concrete is poured into the column and hardens and becomes an integral structural support column for the wall. The C-shaped wall segments have a panel to spread the force of impacting vehicles, to buttress against earth forces, and to abate noises. The precast concrete wall can be economically constructed from precast concrete elements which are adapted to be easily and rapidly stacked and joined in series to save on the cost of labor and materials. Expansion joints between the wall and the foundation allow the wall to move without damaging the structural support columns.
It is an object of the present invention to provide an efficient method of constructing a wall without the need for separate structural support columns.
Another object of the present invention is to provide a barrier which can withstand thermal variations without damaging the structural integrity of the barrier.
A further object of the present invention is to provide a barrier which can be constructed with reduced labor, material, and right-of-way costs.
Additional advantages, objects, and uses will be apparent from the description for those familiar with the relevant art.
The foregoing objectives are achieved in a precast C-shaped wall segment in accordance with the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a wall comprising a plurality of C-shaped wall segments, in accordance with this disclosure.
FIG. 2 is a perspective view of a C-shaped wall segment in accordance with this disclosure.
FIG. 3 is an expanded perspective view of a wall consisting of C-shaped wall segments constructed in accordance with this disclosure.
FIG. 4 is a top plan view of a structural support column for the C-shaped wall segments of the wall in FIG. 1.
FIG. 5 is a top plan view of a column for a relatively small degree of angle of curvature of the wall in FIG. 1.
FIG. 6 is a top plan view of a column for a small degree of angle of curvature of the wall in FIG. 1.
FIG. 7 is a top plan view of a column for a large degree of angle of curvature of the wall in FIG. 1.
FIG. 8 is a top plan view of an expansion joint column for the wall constructed in accordance with this disclosure.
FIG. 9 is a cross sectional view of a portion of the wall in FIG. 1.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Applicants incorporate by reference, as if rewritten herein in their entirety, the entire disclosures of application Ser. No. 07/917,841 filed Jul. 21, 1992, which was a continuation-in-part of both: application Ser. No. 07/601,413 filed Oct. 22, 1990, now U.S. Pat. No. 5,131,786, which was a continuation-in-part of application Ser. No. 07/347,482 filed May 4, 1989, now U.S. Pat. No. 4,964,750; and application Ser. No. 07/675,503 filed Mar. 26, 1991, now abandoned.
The preferred embodiment of the present invention is illustrated in FIG. 1. The wall (10) may be used in numerous situations where it is desirous to keep two areas separated; such as an attractive earth retaining wall or traffic barrier for roadways. It may also be used as a sound abatement wall, a security wall, a sea wall, or a free standing temporary wall. The height of the wall may be varied to meet the specific requirements of its intended use by stacking individual segments. The wall may be constructed out of any formidable material such as fiberglass, plastic, steel, galvanized iron, reformed shredded plastic, concrete, or other materials having suitable hardness and durability properties.
In the preferred embodiment, the wall (10) is comprised of a plurality of precast, reinforced concrete, C-shaped wall segments. The wall segments may be post-tensioned. The wall may be adapted to be in a straight line or in a curve to meet the specific geographic requirements of the location.
As shown in FIG. 2, each C-shaped wall segment (20) has a vertically disposed panel (22), a bottom horizontal surface (26), a top horizontal surface (28), and vertically extending U-shaped members (30, 38). U-shaped members (30, 38) are horizontally disposed at opposite ends of the panel (22) and projecting rearwardly therefrom. Bottom horizontal surface (26) is adapted for direct contact with either the ground, foundation, or stacked wall segment. The vertically disposed panel (22) is located in a horizontal plane which is described by the front leg (36) of U-shaped member (30) to the front leg (44) of U-shaped member (38).
The wall segment (20) normally has a length of about ten feet, but can vary from four feet to forty feet depending upon the specific requirements of the job. The wall segment (20) has an average normal height of ten feet, but may be adapted to any engineered height. In most uses, the wall segment will vary from three feet to thirty feet depending upon the specific requirements of the job.
The U-shaped members (30, 38) have a bottom (34, 42, respectively) and two legs (32, 36 and 40, 44, respectively). If the wall is to be constructed in a straight line, then the U-shaped members are precast with the sides having the same length. If the wall (10) requires a curvature, then U-shaped members may be precast with their sides having different lengths as shown in FIG. 6. Some curvature is possible in the wall (10) during construction by placement adjustments or by adding inserts as illustrated in FIGS. 5, 6 and 7, respectively.
The C-shaped wall segment (20) may be adapted to meet the specific load requirements of its use. The amount and strength of the embedded grid of vertical and horizontal reinforcement bars (not shown) may be varied. The thickness of the wall segment (20) may also be varied to meet specific requirements. If the wall segment (20) is to be used as a traffic barrier or in the bottom row of stacked wall segments, then the wall segment (20) may be precast with a thickness of 4 inches to 124 inches, although in the preferred embodiment it will be 8 inches thick with three-quarters of an inch exposed aggregate or other required surface material on the exposed face of the panel (20). The thickness of the wall segment (20) has no upper limit as the U-shaped members (30, 38) would also expand. The wall segments (20) are also easily transportable over existing roadways and railways.
An expanded perspective view of a portion of a wall with only two rows of stacked wall segments (220, 250 and 300, 310) is shown in FIGS. 3, 4 and 8. The C-shaped wall segment (220) is stable and self-supporting. When viewed from above wall segment (220) has a C-shaped configuration. The C-shape of wall segment (220) allows easier and quicker construction of a retaining wall because the contractor can stand upright a plurality of segments on-site in preparation for placement in the retaining wall. The wall segments will then be easily and quickly moved into place and stacked upon one another. The faster construction process allows the contractor to save on the cost of labor and materials. An inventive aspect of the preferred embodiment is that wall segment (220) is capable of being a free standing structure that relies on no other means of support other than that derived from its own stability.
Each C-shaped wall segment (220) has a vertically disposed panel (222), a bottom horizontal surface (223), a top horizontal surface (224), and vertically extending U-shaped members (230, 240). U-shaped members (230, 240) have a bottom (234, 244, respectively) and two legs (232, 236 and 242, 246 respectively). U-shaped member (260) of wall segment (250) has a bottom (264) and two legs (262, 266). The vertically disposed panel (222) is located in a horizontal plane which is described by the front leg (232) of U-shaped member (230) to the front leg (242) of U-shaped member (240).
The construction time is also reduced because when wall segments (220, 250) are placed adjacent to one another, as shown in FIGS. 3 and 4, their respective U-shaped members (240, 260) define four faces of a stay-in-place form for a structural column (270). Reinforcing rods (272) are attached to a drill pier in the foundation (not shown) and extend upwards a sufficient height to reinforce the column (270) and wall. Reinforcing material (274) may also be added to the column (270) for more reinforcement of the column (270). Cast-in-place concrete (276) is poured into the stay-in-place form encasing the reinforcing rods and material creating structural column (270). The hardened concrete (276) and rods (272) couple column (270) to the drill pier.
Another inventive aspect of the preferred embodiment is that column (270) ensures proper alignment between wall segments. This eliminates a common problem found in current column and panel walls. Current walls have imprecise lateral placement of panels due to accumulated variances in the panels and placement of the columns. Much construction time is wasted as contractors have to modify or add material to the panels or columns to obtain proper placement. If the placement is bad enough, then the columns may have to be re-built.
To support column (270) in its vertically upstanding position, any one of a multitude of suitable conventional supports may be used which would allow a round cage to extend from the support through the column. It is expected that either a drill shaft, a drill pier, cast-in-place spread footing, a caisson, or a steel piling encased in concrete may be used. If the ground underneath the column is hard and stable, then a ground anchor could even be used.
Thermally induced expansion and contraction of wall segment (220) may lead to cracking of the panel (222) unless some arrangement is established to relieve thermally induced expansions and contractions. Cracking can also be created by external forces applied to the barrier, such as wind forces, impact forces from vehicles, lifting or sinking forces from ground swell or collapse, and the like. The present invention uses an expansion joint column as illustrated in FIG. 8 as one method of relieving the thermally induced internal forces and external forces.
Expansion joint column (280) is formed by wall segment (282) being placed adjacent to wall segment (284). U-shaped members (283, 285) are placed adjacent to each other and over a drill pier or other support (not shown) and define the four faces of the stay-in-place form for expansion joint (280). Sufficient reinforcing steel (not shown) is inserted in the stay-in-place form to meet the design specifications. Cushioning material (286) is placed between U-shaped members (283, 285) and the support. Padding material (288) is placed on the inside of the stay-in-place form. Any material with sufficient padding and cushioning properties could be used as material (286, 288). However, in the preferred embodiment neoprene is used as cushioning material (286) and fiberboard is used as padding material (288). Seals (290) are placed between U-shaped members (283, 285). Cast-in-place concrete (292) is then poured into the stay-in-place form. Depending on the expected internal and external forces expansion joint column (280) could be used in place of column (270). In most situations, expansion joint columns will be used approximately every 100 feet of the retaining wall to provide for sufficient expansion and contraction of the barrier without cracking.
In certain situations, the wall will be constructed where it must follow the curve of the roadway or embankment being reinforced. FIG. 1 illustrates wall (10) being used as a wall in a straight line which gently curves in a clockwise direction. Wall (10) can be adapted to curve counter-clockwise or any other non-straight line to meet the needs of each particular job.
FIG. 5 illustrates construction of the wall if the desired angle of curve is relatively small, about 1° or less. Normally, gaps (54, 56) are the same, about three-quarters of an inch. When a relatively small degree of curve is required, the U-shaped members (30, 64) of wall segments (20, 60) are placed adjacent to each other so that the gap between one set of legs is less than the other set of legs, depending on the direction of curvature. For a clockwise curve (A), gap (54) between legs (72, 36) is less than gap (56) between legs (70, 32). This will result in a curvature of about 1° to the right when wall (10) is viewed from above. Seals (132) are placed in gaps (54, 56) to prevent cast-in-place concrete (138) from leaking out of stay-in-place form (139) prior to hardening.
FIG. 6 illustrates construction of the wall if the desired angle of curve is small, between about 1° and 10°. To obtain a small angle of curve, U-shaped members (62, 84) of panels (60, 80) are precast with different length legs. The legs may have an interior length which varies from 1 inch to 100 inches and an exterior length which varies from 2 inches to 120 inches. In the preferred embodiment, the legs are 7-1/2 inches long for the interior length and an exterior length which slopes from 13 inches to fourteen and 3/8 inches. To achieve a clockwise small angle of curve (A), leg (90) of wall segment (80) is precast longer than leg (92). Depending on the required angle, legs (90, 92) may vary as much as 24 inches in length. In the preferred embodiment, leg (90) will be about 3 inches longer than leg (92) to obtain a 10° angle of curve. Wall segment (60) has legs (66, 68) which are of the same length. If a counter-clockwise angle of curve is desired then leg (66) would be precast longer than leg (68) and legs (90, 92) would be precast the same length.
FIG. 7 illustrates construction of the wall if the desired angle of curve is large, greater than about 10°. In this situation, legs (86, 88) of U-shaped member (82) of wall segment (80) and legs (108, 110) of U-shaped member (104) of wall segment (100) are all of the same length. Precast spacer (112) with tic back rods (113) is inserted between legs (88, 108). The tie back rods keep spacer (112) in place while the cast-in-place concrete hardens. Another embodiment of the present invention uses a wedge shaped spacer (112) which has its wider face on the interior of the stay-in-place form. The adjoining legs are cast to complement the wedge design. Therefore, the pressure of the cast-in-place concrete actually presses the spacer against the adjoining legs ensuring that the spacer remains in place while the cast-in-place concrete hardens.
The length of spacer (112) can vary from 1 inch to 100 inches depending upon the required amount of clockwise curvature (A). Curvature (A) can be as great as 90° with spacer (112), if larger degrees of curvature is desired then spacer (112) could be modified and be precast in a curve. If a counter-clockwise curve is desired, then spacer (112) would be placed between legs (86, 110). Due to the larger column (130), support (118) could be expanded to properly support the column with spread footing (119).
FIGS. 5, 6, and 7 illustrate the independent use of varied gaps, varied length of legs, and a spacer. In actual use, all three methods could be used in any combination, or all at once, to adapt the wall to the specific requirements of the job.
As seen in FIG. 1, when wall (10) terminates, closure piece (114) is used to finish wall (10) in an aesthetically pleasing look. Closure piece (114) is U-shaped and is adapted to be placed adjacent to the U-shaped member (102) of the adjoining wall segment. The closure piece (114) and adjoining U-shaped member (102) create the stay-in-place form for column (130). Reinforcing bar extends from within closure piece (114) into the column (130) keeping closure piece (114) in its proper location once the cast-in-place concrete hardens. Sufficient reinforcing steel to adapt the closure piece to the design is also inserted in column (130) when the column is located at the end of wall (10).
If the design requirements for the location of wall (10) require fluid flow from one side of the wall segment to the other side, then drains (117) may be added as illustrated in FIG. 9. Drains (117) are precast in the wall segments. The amount of expected fluid flow will determine the number and size of drains (117).
FIG. 9 shows that wall (10) rests on, and is supported by, foundation or base (116) and drill pier or support (118). Foundation is built prior to the placement of the panels. The foundation can be made of any material having the necessary stability, strength, and durability properties including, but not limited to, concrete, crushed limestone, pea gravel, and the like. In some locations, the ground may be flat, stable, and solid enough so that the panel may rest directly on the ground. When resting directly on the ground, the reinforcing steel for the columns may be driven into the ground or be anchored by ground anchors including, but limited to, Dywidag anchors and the like.
If two rows of panels are used in the barrier, then reinforcing steel (134) may extend into both the bottom row of panels and second row of panels. In some situations reinforcing steel (134) may extend only into the bottom row of panels and reinforcing steel (136) extends from the bottom row of panels into the second. If more rows of panels are stacked, then the reinforcing steel is spliced into the lower levels to obtain the required strength and support for barrier (10).
Construction of the wall starts with a detailed analysis of the site and any special design requirements of the wall. The C-shaped wall segments are adapted to meet the specific requirements such as: drains, extra reinforcement of the bottom wall segments where potential for vehicle impact exists, conduits in the wall segments for running electrical cables for lights or other applications, and precasting the wall segments to adapt to the curvature of the location. The panels are then easily transported over existing highways and railways to the site location and placed in the vicinity of their final placement in the wall.
Any one of a multitude of suitable conventional foundations and supports may be used to support the C-shaped wall segments. For example, FIG. 1 illustrates drill piers (118) may be used to support the columns and a concrete base (116) may be used to support the panels themselves. The specifics for the foundation for the wall (10) is determined by the job site subsurface soil conditions and the use of the barrier. Factors which should be considered in determining specific foundation include, but are not limited to, thermal expansion, thermal contraction, broadside force, longitudinal force, weight from the barrier, frost heave, impact force, wind force, ground elevation, and soil stability.
A graded concrete foundation is constructed in the direction of the wall. If a stable surface exists, the foundation could be just the ground. In most normal applications, the foundation is constructed for support of the wall with a base and plurality of drill piers of sufficient depth for withstanding expected overturning and destructive forces which may be applied to the wall. The drill piers should be substantially lined with adjacent drill piers having a distance separating them which is substantially the same distance as the length of a wall segment. The depth of the drill piers may vary depending upon analysis of the above factors. Reinforcing material is placed through said drill pier extending upwards a sufficient height for reinforcing the wall. If leveling of the area around the drill pier is required, a cast rip-rap leveling pad may be poured around the drill pier.
A first precast C-shaped wall segment is positioned over the foundation so that it is aligned with a top surface of the foundation. Once aligned, the first precast C-shaped wall segment is lowered so that the C-shaped wall segment engages the top surface of the foundation by lengthwise contact thereagainst in a stacked relationship. The bottom surface and U-shaped members of the first precast C-shaped wall segment supports the wall segment in an upright position.
A second precast C-shaped wall segment is placed adjacent to the first precast C-shaped wall segment so that the U-shaped member of the second wall segment is removably coupled with the U-shaped member of the first wall segment, and defining the four faces of a stay-in-place form. The form surrounds the reinforcing material extending upward from the drill pier. The outer faces of the C-shaped wall segments form the relatively flat vertical outer face of the retaining wall. Shims may be used to assure that the wall segments are level and plumb.
After the stay-in-place form is formed, cast-in-place concrete is poured into the form in filling the drill pier and encasing the reinforcing material. An inventive aspect of the present disclosure is that the cast-in-place concrete can be poured into the stay-in-place form at any time after two C-shaped wall segments are placed adjacent to each other. In this manner, the columns can all be poured at one time when the entire wall has been aligned, or after each form is constructed, or when several forms are constructed.
After the cast-in-place concrete has reached its required strength in the stay-in-place form, the preceding steps could be repeated to the required height of the barrier so that a second row of C-shaped wall segments may be stacked on top of one another. If conditions allow, two C-shaped wall segments may be stacked on one another before pouring the cast-in-place concrete. Spliced vertical reinforcing bars may be inserted in the form as required for taller barriers. This splicing should be completed before setting of the upper C-shaped wall segments.
Although the invention has been described with reference to specific embodiments, this description is not meant to be construed in a limiting sense. Various modifications of the disclosed embodiments, as well as alternative embodiments of the invention, will become apparent to persons skilled in the art upon reference to the description of this invention. It is, therefore, contemplated that the appended claims will cover such modifications as fall within the true scope of the invention. | This invention relates to a precast concrete wall consisting of a plurality of precast concrete, retaining wall segments used as a retaining wall, used to buttress against earth forces, used to abate noises, and a method of constructing such a wall. The wall can be economically constructed from the precast wall segments which are adapted to be easily and rapidly stacked and joined in series to save on the cost of labor and materials. Each of the wall segments is capable of being varied in height, width or length, but having a generally similar cross-section. The wall segments also have members which form a stay-in-place form when two wall segments are placed end to end. Cast-in-place concrete is poured into the form and, upon hardening, becomes an integral structural support column for the wall. | 4 |
CROSS REFERENCE TO RELATED APPLICATION
The present application claims the benefit of and priority, under 35 U.S.C. §119(e), to U.S. Provisional Application Ser. No. 61/390,354, filed Oct. 6, 2010, the entire disclosure of which is incorporated by reference herein.
FIELD OF THE INVENTION
Embodiments of the present invention are generally related to selectively opening and closing one or more ports or access openings in a tubular string. More specifically, one embodiment allows selective access of a tubular annulus of a wellbore to provide a flow path between a tubular string positioned in the wellbore and a geologic formation that requires a treatment such as hydraulic fracturing.
BACKGROUND OF THE INVENTION
A wellbore used in recovering oil/gas typically includes a production string placed within a casing string. In some wellbore designs, the entire length of the wellbore is lined with the casing string, which is cemented within the wellbore. Alternatively, in open-hole designs, the casing string is limited to an upper portion of the wellbore and lower portions of the wellbore are open. In both open-hole and cased-hole designs, the production string is typically placed into the lower portions of the wellbore and mechanical or hydraulic packers are used to radially secure the production string in a predetermined location. The outside diameter of the production tubing is less than the diameter of the internal wellbore or production casing, thereby defining a tubular annulus.
To gain access to oil/gas deposits in the general area of the wellbore, selected portions of the production casing are perforated or, alternatively, sliding sleeves or other devices are used to provide a conduit to the oil and gas deposits. To enhance the flow of oil/gas into the tubular annulus, and to thus increase flow into the production tubing, hydraulic fracturing (i.e., “fracing”) of subterranean formations may be required, especially in low permeability formations. That is, in some instances subterranean formation that the wellbore penetrates does not possess sufficient permeability for the economic production of oil/gas so hydraulic fracturing and/or chemical stimulation of the subterranean formation is needed to increase flow performance.
Hydraulic fracturing consists of selectively injecting fracturing fluids into a subterranean formation in openhole or via perforations or other openings in the production casing of the wellbore at high pressures and rates to form a fracture. In addition, granular proppant materials, such as sand, ceramic beads, or other materials are injected into the formation with the fracturing fluids to hold the fracture open after the hydraulic pressure has been released. The proppant material prevents the fracture from closing and thus provides a more permeable flow path within the subterranean formation, resulting in increased flow capacity. In chemical stimulation treatments, permeability and thus flow capacity is improved by dissolving materials in the formation or otherwise chemically changing formation properties.
To gain access to multiple or layered reservoirs, or a very thick hydrocarbon-bearing formation by hydraulic fracturing, multiple fracturing zones are established and stimulated in stages. One technique currently being used with significant results utilizes the use of a directionally drilled well into a single reservoir. By drilling the well in a substantially horizontal orientation through the reservoir, the reservoir can be fractured in multiple locations to substantially improve the flow rate. To stimulate multiple fracturing zones, a target stimulation zone must be temporarily isolated from the already-stimulated zones to prevent injecting fluids into the already-stimulated zones. Various methods have been utilized to achieve zonal isolation, although numerous drawbacks to the current methods exist.
A common method currently used to isolate a fracturing zone in multistage fracturing utilizes composite bridge plugs. According to this method, the deepest zone in the wellbore (or most distal in horizontal wellbores) is stimulated. Then, the stimulated zone is isolated by a bridge plug that is positioned above the perforations associated with the stimulated zone. The process is repeated in the next zone up the wellbore. At the end of the stimulation process, a wellbore clean-out operation removes the bridge plug. The major disadvantages of using one or more bridge plugs to isolate a fracture stimulated zone are the high cost and risk of complications associated with multiple trips into and out of the wellbore to position the plugs. For example, bridge plugs can become stuck in the wellbore and need to be drilled out at great expense. A further disadvantage is that the required wellbore cleanout operation may block or otherwise damage some of the successfully fractured zones.
Another method used to isolate a fracturing zone utilizes frac baffles and balls. The first baffle, which contains the smallest inside diameter, is placed in the most distal portion of the wellbore. The succeeding baffles increase in diameter and are installed above the previous baffle. To achieve zonal isolation, a frac ball of a predetermined size is dropped that seats on the corresponding frac baffle at a specified depth or position to block a portion of the wellbore. The isolated zone is accessed by perforations or a sleeve is shifted then stimulated. After each stage, the process is repeated until all selected frac zones in the well are fracture stimulated. On the last day of operation, the frac balls typically are flowed back to the surface during the flow back of the fracturing fluids. The primary advantage of this method is that the frac baffles are installed within the casing and can be activated by dropping a ball from the surface, with little downtime between fracture stimulation stages. The disadvantages include the need to use progressively larger sized balls for subsequent fracturing stages, thus limiting the number of zones that can be treated for a given casing diameter. Additionally, the frac baffles and balls may need to be milled out of the casing string, which increases the number of wellbore operations and inherent risks and costs associated therewith.
One method for successfully isolating one or more production zones utilizes a sliding sleeve that is associated with a tubular string, which may include casing, liners, tubing, etc. Opening the sleeve permits zonal isolation and stimulation of the formation via the tubular string through the selected sleeve. The sleeve can be operated by using a mechanical/hydraulic shifting tool attached to coiled or jointed tubular or by using a ball-drop system. In a ball-drop system, a ball pumped down the tubular string engages a sliding sleeve and shifts the sleeve from a closed position to an open position, thereby opening a passageway to the tubular annulus. The ball also isolates the already-stimulated zones located beneath the open sleeve. The advantages of this method are that the tubular annulus can be accessed without requiring various tools or costly trips into the wellbore to isolate the various formations. However, the method is limited by the need to use progressively larger sized balls for subsequent fracturing stages, thus limiting the number of zones that can be deployed for a given tubing string diameter. This system inherently restricts the production flow rate due to the necessity of using progressively smaller balls to open and close the sleeves.
Accordingly, a need exists for an improved downhole tools and methods that efficiently isolates individual zones of a subterranean formation while (1) ensuring that stimulation fluids are directed to the desired location, (2) maintaining a desired inner diameter of the tubing string, (3) reducing the time between stimulations, and (4) is mechanically simplistic to operate and cost effective.
The following disclosure describes improved downhole tools and methods for selectively isolating downstream portions of a tubular string while simultaneously allowing access to the tubular annulus of a wellbore such that a selected zone may be stimulated. The improved downhole tools and methods do not limit the number of fracture stimulation stages created in a vertical or directional wellbore. As used herein, ‘downstream’ and ‘lower’ refers to the distal portions of a tubular string disposed toward the toe of the wellbore. Further, as used herein, ‘treatment fluid’ may comprise acid, proppant material, gels, or other stimulation fluids generally used in the art.
SUMMARY OF THE INVENTION
The downhole tools disclosed herein is designed for downhole well stimulation for oil and gas wells, but could be used for any downhole application where a shifting sleeve is used to selectively divert flow. Additionally, the downhole tools may be employed in either open or cased holes. Generally, a downhole tool is placed into a wellbore and provides for the opening of the tubular string to the geologic formation while simultaneously restricting the flow of fluid and proppant downstream of the downhole tool. Fluid with or without proppant is then pumped into the geologic formation through the openings to stimulate the rock through hydraulic fracturing (fracing) or other treatment processes. By progressing from the toe (bottom) of the well back toward the surface, it is possible to stimulate the subterranean formation in stages, thus improving the quality of the stimulation and/or minimizing fluid/proppant. The downhole tools disclosed herein improve upon existing shifting sleeve designs by 1) allowing for a very large number of stimulation stages (50-200), 2) minimizing the flow restrictions inherent in ball drop systems that rely on progressively smaller ball diameters, 3) providing a system that does not need to be drilled out in order to facilitate production, 4) using a single ball size for all stages, and 5) improving the speed and efficiency of the stimulation process.
It is thus one aspect of embodiments of the present invention to provide a downhole tool that seals a selected portion of a wellbore between geologic formations while simultaneously allowing access to a tubular annulus defined between the interior of a casing string or open-hole wellbore and a production string positioned therein. According to at least one embodiment, the downhole tool is integrated by a threaded connection, or any similar connection commonly practiced in the art, into a tubular production string that is positioned within the wellbore. The downhole tool provides a path for fluids or tools to enter the tubular annulus and simultaneously isolates downstream portions of the tubular production string from the high pressures exerted by a stimulation procedure, e.g., hydraulic fracturing. Additionally, with the use of packers or cement to isolate the tubular annulus, the downhole tool isolates non-targeted stimulation zones from the high pressures exerted by a stimulation procedure. As used herein, packers may be swellable, hydraulic, mechanical, inflatable, or any other alternative known in the art. The downhole tool in some instances eliminates the need to perforate various strings of pipe or position other tools into the wellbore, thus saving time, costs, and the inherent risk of trapping a tool. The downhole tool may be constructed of metallic or non-metallic materials, such as the composite materials currently used in composite bridge plugs, and typically combinations of both.
It is another aspect of embodiments of the present invention to provide a downhole tool that employs a flapper valve that is capable of moving between a first position and a second position to selectively open and close an axial bore and a lateral bore of the downhole tool. The axial bore of the downhole tool opens to and is in fluid communication with an internal bore of the tubular string. The lateral bore of the downhole tool opens to and creates a passageway to the tubular annulus. The flapper valve may be associated with a sealing element fabricated of an elastomeric, plastic, metallic, or any other sealing element known to one of ordinary skill in the art. In some embodiments, the flapper valve may be comprised of degradable materials. For example, after a predetermined period of time, the flapper valve may dissolve to allow production fluid to flow unrestricted through the axial and lateral bores of the downhole tool. A degradable flapper valve is disclosed in U.S. Pat. No. 7,287,596, which is incorporated herein by reference in its entirety.
When in the first position, the flapper valve seals the lateral bore of the downhole tool such that fluid may be pumped through the axial bore of the downhole tool. The axial bore of the downhole tool may also allow passage of solid elements, such as wireline tools, tubing, coiled tubing conveyed tools, cementing plugs, balls, darts, and any other elements known in the art. The sealing area of the first position may be irregular in shape and comprised of several sealing surfaces.
When in the second position, the flapper valve seals the axial bore of the downhole tool, thereby sealing the internal bore of the tubular string and allowing fluid to be pumped to the tubular annulus through the lateral bore of the downhole tool. The movement of the flapper from the first position to the second position effectively seals the downstream stimulation zone and opens a passageway to the tubular annulus, allowing the next stimulation zone to be immediately treated.
It is another aspect of embodiments of the present invention to provide a restraining mechanism for maintaining the flapper in the first position. The restraining mechanism may be a ring, finger, a tubular member, such as a sleeve, or any other restraining device. The restraining mechanism exerts a force against the flapper valve to prevent external forces acting upon the outside of the flapper valve, such as the external pressures associated with circulating a fluid in the tubular annulus, from unseating the flapper valve from its first position. When the restraining device is disengaged, the flapper valve is free to move to the second position. According to at least one embodiment, the restraining mechanism is disengaged by an actuating mechanism deployed on electric wireline, a slickline, coiled tubing, jointed tubing, solid rods, or drop members. Examples of drop members include balls, plugs, darts, or any other members commonly used in the art. As used herein, ‘ball’ refers to any shaped device that is feasible of being pumped down a tubular string and is not limited to a circular-shaped device. For example, a ‘ball’ may be circular, oval, oblong, or any other shape known in the art.
It is another aspect of embodiments of the present invention to provide a flapper valve that is biased toward the second position by a coiled spring, leaf spring band, or other similar energy storage system. The stored energy assists the movement of the flapper valve toward the second position. According to at least one embodiment, a spring is placed in the body of the downhole tool, and compressed, storing mechanical energy to aid in the movement of the flapper valve from the first position to the second position. Additionally, an explosive device may be used to assist the flapper valve movement. For example, cement located in the tubular annulus may interfere with flapper movement and the spring or explosive device would aid in breaking the flapper valve away from the cement. The activating tool used to move the flapper valve-restraining device also may assist in the movement of the flapper valve from the first position to the second position.
It is another aspect of embodiments of the present invention to provide a downhole tool that is activated with drop members from the surface using a multi-pressure activation system. The multi-pressure activation system exposes the downhole tool to a predetermined pressure to selectively actuate a sliding sleeve that receives a drop member. For example, in one embodiment, a first higher pressure does not actuate the sliding sleeve. Instead, the higher pressure causes the drop member to pass through the axial bore of the downhole tool, by use of a spring operated catch mechanism, and travel through the internal bore of the tubular string to the next tool or to the distal end of the wellbore. The higher pressure may either deform the drop member to allow it to pass through the axial bore of the downhole tool or actuate a ball catch mechanism, such as a collet slidable device, collet deformable fingers, or any other ball catch mechanism currently employed in the art. Collet slidable devices are disclosed in U.S. Pat. Nos. 4,729,432, 4,823,882, 4,893,678, 5,244,044, and 7,373,974, which are incorporated herein by reference in their entireties. Collet deformable fingers are disclosed in U.S. Pat. Nos. 4,292,988 and 5,146,992, which are incorporated herein by reference in their entireties.
In the above mentioned embodiment, a second lower pressure does not allow the drop member to pass through the axial bore of the downhole tool. Rather, the lower pressure keeps the drop member trapped, under pressure, in the axial bore of the downhole tool. The lower pressure is held for a period of time until the sliding sleeve moves, thereby allowing the flapper valve to move from the first position to the second position to block the axial bore of the tubular string and to open the lateral bore of the downhole tool.
In operation, the drop member would be inserted into the tubular string. Once the drop member lands and engages the sleeve of a downhole tool, a higher pressure would be exerted at the surface of the wellbore. The higher pressure would cause the drop member to pass through that downhole tool without sleeve actuation, and continue to pass through each tool distally in the wellbore until the desired tool is reached. The sleeve of the desired downhole tool would then be activated by applying the lower pressure, which would move the sleeve and allow the flapper valve to actuate from the first position to the second position. Fracture stimulation materials may then be selectively pumped through the internal bore of the tubular string, through the lateral bore of the downhole tool, and into the tubular annulus.
In another embodiment, utilizing hydraulics in the catch mechanism would allow a drop member to pass under a lower pressure; shifting would occur only under a higher pressure.
Another aspect of embodiments of the present invention is to provide a sliding sleeve associated with a reservoir of hydraulic oil or other fluid that allows the sliding sleeve to shift, thereby freeing the flapper valve to move from the first position to the second position. The hydraulic oil or other fluid bleeds through an orifice to a second reservoir allowing the sliding sleeve to move over a period of time from an initial position to a position that allows the flapper to move. The sliding sleeve may be moved back to its first position by means of a spring or other stored energy device, which would in turn transfer the hydraulic fluid back through the orifice to the first reservoir.
It is another aspect of embodiments of the present invention to provide a locking mechanism for securing a sliding sleeve in a shifted position. The locking mechanism prevents the sliding sleeve from shifting back to its initial position, thereby ensuring that the sliding sleeve does not disengage the flapper valve from its second position.
It is another aspect of embodiments of the present invention to provide a downhole tool that is activated by coiled tubing or small diameter jointed tubing. In this embodiment, the treatment for a given wellbore stimulation would be pumped in an annulus formed between the coiled tubing, solid rods, and the inner surface of a tubular string, thereby allowing the coiled tubing to function as a dead string to monitor down hole treating pressures. A tool located at the end of the coiled tubing engages a shifting sleeve associated with the tubing string that is held in place by shear pins or any other similar device. The use of coiled tubing as the actuating tool allows an unlimited number of treatment stages to be performed in a well, thus providing an advantage over frac baffles, for example, which require smaller actuation balls to be used to engage frac baffles in more distal positions in the wellbore. Additionally, using coiled tubing as the activation member removes the need for pressurizing fluid pumped from the surface as described above, and the coiled tubing may be used to cleanout proppant between fracing stages.
Another aspect of embodiments of the present invention is to provide a downhole tool utilizing a shifting sleeve that closes the tubular production string at a predetermined location and opens the annulus of the wellbore to allow fracing or other stimulation procedures in stages. In one embodiment a counter is embedded in the shifting sleeve and a uniform size ball is dropped into the well. Each shifting sleeve is preset with a unique counter number such that the counter locks in place after the proper number of balls have passed, catching and retaining the next ball. The ball then closes off the wellbore and shifts a sliding sleeve, opening the annulus and geologic formation to be treated at a predetermined depth or interval. The counter locking mechanism is designed to facilitate normal completion operations including flow back during screen out. As used herein, counting means refers to any form of counter that can increment and/or decrement. Sleeve activation means identifies any means that facilitates movement of an inner tubular member, such as a sleeve. For example, sleeve activation means include pressure activation, mechanical activation, and electronic activation techniques. Signal means identifies any form of electronic signal that is capable of conveying information.
Another aspect of embodiments of the present invention is to provide a swellable ball that is dropped into the well and a downhole tool utilizing a sliding sleeve. The ball is configured to swell after a predetermined period of time in a fluid, such as fracing fluid. In operation, the swellable ball is pumped quickly to the correct location. The location can be verified by counting pressure spikes, which result from the ball passing through a seat disposed in a sliding sleeve. Once the swellable ball is located in the tubular string proximal to the sleeve to be shifted, pumping is discontinued. Thus, the swellable ball would be allowed to swell to a size that would prevent the ball from passing through the selected sleeve. The operator would then continue pumping.
Another aspect of embodiments of the present invention is to provide a smart ball that is dropped into the well and a downhole tool utilizing a sliding sleeve. In one embodiment, the shifting sleeve has an embedded radio frequency identification (“RFID”) chip and the smart ball has an RFID reader built into it. When the ball passes the RFID chip, the RFID reader reads the number of the RFID chip. If the correct number is read, the ball releases a mechanism that expands the size of the ball. For example, the expansion could be a split in the middle of the ball that rotates part of the ball slightly. Alternatively, the top ⅓ of the ball may be hinged and would open upon the correct number being read. The larger ball would become stuck in the next seat. In another embodiment, the smart ball includes a timer that causes the ball to expand after a certain period of time. For example, in this embodiment, an operator would count the pressure spikes and stop pumping when the ball is in the right location and wait for the timer to go off. Pumping would then resume.
Another aspect of embodiments of the present invention is to provide a ball that is dropped into the well and a downhole tool utilizing a smart sleeve. In one embodiment, each sleeve has an RFID reader and the ball has an RFID chip. When the correct ball passes, the device releases a mechanism to catch the ball, plugging the orifice and shifting the sleeve. In another embodiment, each sleeve has a pressure transducer and circuit board with logic to understand pressure signals. The sleeve receives hydraulic pressure signals from a signal generator on the surface. The proper signal triggers the sleeve to shift, thus opening the annulus and creating a seat for the ball to land on. Then, a ball is dropped to close off the axial bore of the tubular production string.
It is another aspect of the present invention to provide a method for selectively treating multiple portions of a production wellbore, whether from the same geologic formation or different formations penetrated by the same wellbore. In one embodiment, a single sized ball is utilized multiple times to move a sleeve which isolates a lower portion of the wellbore, while providing communication to the annulus to treat the formation at a predetermined depth. After that zone is treated, subsequent balls of the same size are used to isolate and treat other zones at a shallower depth. After all the zones are treated, all of the balls may flow back to the surface, or disintegrate if manufactured from degradable materials. Dissolvable balls are disclosed in U.S. Patent Publication No. 2010/0294510, which is herein incorporated by reference in its entirety.
It is still yet another aspect of embodiments of the present invention to provide a downhole tool that employs an external cover associated with the lateral bore of the downhole tool. The external cover prevents debris, such as cement, from interfering with the movement of the flapper from the first position to the second position. The external cover may be removed or deformed by fluid pumped through the internal bore of the tubular string and the axial bore of the downhole tool. Coiled tubing carrying fluids alone or fluids with abrasive particles may also be used to remove or deform the external cover, which will also form a tunnel through the cement to the formation. It is another aspect of embodiments of the present invention to provide a downhole tool that is used with external tubular packers positioned within the tubular annulus to isolate a stimulation zone and to prevent clogging of the lateral bore. External casing packers, conventional packers, swellable packers, or any other similar devices may be employed. External tubular packers isolate the frac zone and/or prevent cement from contacting the external portion of the downhole tool and blocking the lateral bore.
Another aspect of embodiments of the present invention is to provide a downhole tool that facilitates tools exiting the tubular string through the lateral bore. According to at least one embodiment, the flapper valve may be longer in one axis such that when the flapper valve moves to the second position, it forms a whipstock slide that is angled with respect to a longitudinal axis of the tubular string. The whipstock slide guides drilling or workover tools to the lateral bore of the downhole tool. If the lateral bore is blocked by an external cover or by debris, the blockage may be removed by milling, drilling, acid, or other fluid, including abrasive particle laden fluids. Using the flapper valve as a whipstock slide may be particularly useful for short and ultra-short radius horizontal boreholes where the tubular string is the origin. The flapper valve may have an orienting mechanism, such as a crowsfoot's key that is commonly used to orient tools in a specified azimuth. When the flapper valve is in the second position, the orienting mechanism orients the tools to the lateral bore.
According to another aspect of embodiments of the present invention, the downhole tool may include several longitudinally spaced flapper valves. Additionally, numerous smaller flapper valves could be arranged around the circumference of the downhole tool. The smaller flapper valves could be activated by an activating member as described above to open one or more additional bores to the tubular annulus. After being released by an activating member, the smaller flapper valves would move toward a second position, which may be disposed in a recess about the body of the downhole tool so as not to block the axial bore of the downhole tool.
It is another aspect of embodiments of the present invention to provide a downhole tool that includes a flapper valve that does not open a lateral bore to the tubular annulus. In these embodiments, movement of an inner tubular member, such as a sleeve, opens ports to the annulus that allow fluid exchange between the axial bore of the tubular string and the subterranean formation. The movement of the inner tubular member allows the flapper valve to block the axial bore of the tubular string and thereby prevent fluid flow through the axial bore of the downhole tool to portions of the tubular string located downstream of the actuated flapper valve.
It is another aspect of embodiments of the present invention to provide a downhole tool that may be used as a blowout preventer that prevents a large volume of fluid from passing upward through the internal bore of the tubular string. According to at least one embodiment, a downhole tool includes a flapper valve and an inner tubular member. The flapper has two stationary positions, a first position and a second position. When the flapper valve is in the first position, fluid may be freely pumped through the axial bore of the downhole tool. When the flapper is in the second position, the internal bore of the tubular string is sealed such that fluids downstream of the flapper valve cannot flow upward through the axial bore of the downhole tool. In this embodiment, the inner tubular member is pressure activated and comprises a ball, a ball seat, a ball cage, and flow restriction orifices. The inner tubular member is held in place by shear pins or any other similar means known in the art that are responsive to axial force.
The inner tubular member allows fluid to be pumped from the surface in normal circulation and in reverse circulation. During normal circulation, fluid flows down the tubular string through the ball seat and the flow restriction orifices of the inner tubular member. The ball cage restricts the ball from moving distally in the tubular string. During reverse circulation, fluid flows up the tubular string causing the ball to seat in the ball seat, thus limiting the upward fluid flow by requiring the fluid to flow through flow restriction orifices. If a large volume of fluid attempted to pass upward through the downhole tool, such as in a blowout situation, the friction pressure through the orifices would overcome the shear pins, or any other similar means and shift the inner tubular member upwards. The upward shift of the inner tubular member allows the flapper valve to move from the first position to the second position. Once in the second position, the flapper valve seals the internal bore of the tubular member and fluid flow up the internal bore of the tubular string would be prevented. The flapper valve may have a sealing element fabricated of an elastomeric, plastic, metallic, or any other sealing elements customarily used in the art to prevent fluids from flowing up the inner bore of the tubular string. The sealing elements may be disposed on the flapper or on a flapper seat. Additionally, the downhole tool may include multiple flapper valves.
According to at least one embodiment of the present invention, a downhole tool is provided comprising: an upper end and a lower end adapted for interconnection to a tubular string; a catch mechanism positioned proximate to said lower end and adapted to selectively catch or release a ball traveling through said tubular string; a sleeve which travels in a longitudinal direction between a first position and a second position, and which is actuated based on an internal pressure in the tubular string, said sleeve preventing a flow of a treatment fluid in a lateral direction into an annulus of the wellbore while in said first position, and permitting the flow of the treatment fluid in the lateral direction through at least one port in said second position; and a flapper valve in operable engagement with said sleeve, wherein when said sleeve is in said second position, the treatment fluid cannot be pumped downstream of said flapper valve in the tubular string.
According to at least another embodiment of the present invention, a method for treating a plurality of hydrocarbon production zones is provided comprising: providing a wellbore with an upper end, a lower end and a plurality of producing zones positioned therebetween; positioning a string of production tubing in the wellbore, said string of production tubing having an upper end and a lower end; providing a plurality of selective opening tools in said production string, each of said selectively opening tools having a minimum internal diameter which are substantially the same; pumping a treatment fluid containing a first ball through the production tubing at a predetermined pressure until said first ball reaches a first selective opening tool positioned proximate to a predetermined portion of the hydrocarbon production zone; changing the internal pressure in said production tubing to retain said first ball in a catch mechanism in said first selective opening tool; retaining the pressure in said first selective opening tool for a predetermined time period to move a sleeve from a first position to a second position, wherein in said first position the treatment fluid is prohibited from traveling laterally into an annulus of the wellbore and in a second position a port is opened to allow the treatment fluid to flow into a wellbore annulus; closing a flapper valve to prevent the flow of treatment fluid downstream of said flapper valve in said production tubing; pumping the treatment fluid into a portion of at least one geologic formation; reducing the pressure in said production tubing; pumping the treatment fluid with a second ball having a diameter substantially the same size as a diameter of said first ball through said production tubing to a second selective opening tool positioned proximate to a second zone of the hydrocarbon production zone: retaining the pressure in said second selective opening tool for a predetermined time period to move a sleeve from a first position to a second position in said second selective opening tool, wherein in said first position the treatment fluid is prohibited from traveling laterally into an annulus of the wellbore and in a second position a port is opened to allow the treatment fluid to flow into the wellbore annulus; closing a flapper valve in said second selective opening tool to prevent the flow of treatment fluid downstream of said flapper valve in said production tubing; and pumping the treatment fluid into a second portion of at least one geologic formation.
According to yet another embodiment of the present invention, a subterranean tool is provided comprising: an axial bore in fluid communication with an internal bore of the tubular string; a lateral bore in fluid communication with a tubular annulus defined by an inner wall of the wellbore and the outer surface of the tubular string; a sliding sleeve which covers said lateral bore in a first position, and exposes said lateral bore in a second position to allow fluid communication between the inside of said tubular string and said tubular annulus; a catch mechanism adapted for selectively allowing the passage of a ball in a first position of use, and for retaining and sealing said ball in a second position of use, wherein in said second position of use said ball and said catch mechanism prevent the flow of fluid in said tubular string downstream of said catch mechanism; a counting means in operable communication with said catch mechanism, said counting means identifying how many of said balls have passed through said catch mechanism; and sleeve activation means interconnected to said sleeve, wherein when a predetermined number of balls are identified by said counting means, said sleeve selectively moves from said first position of use to said second position of use to allow fluid to flow through said lateral ports.
The Summary of the Invention is neither intended nor should it be construed as being representative of the full extent and scope of the present invention. Moreover, references made herein to “the present invention” or aspects thereof should be understood to mean certain embodiments of the present invention and should not necessarily be construed as limiting all embodiments to a particular description. The present invention is set forth in various levels of detail in the Summary of the Invention as well as in the attached drawings and the Detailed Description of the Invention and no limitation as to the scope of the present invention is intended by either the inclusion or non-inclusion of elements, components, etc. in this Summary of the Invention. Additional aspects of the present invention will become more readily apparent from the Detail Description, particularly when taken together with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate embodiments of the invention and together with the general description of the invention given above and the detailed description of the drawings given below, serve to explain the principles of these inventions.
FIG. 1 is a cross-sectional view of a fracture stimulation system according to one embodiment of the present invention;
FIG. 2 is a cross-sectional view of a well production system according to one embodiment of the present invention;
FIG. 3 is a cross-sectional view of a downhole tool that is actuated by a shifting tool according to one embodiment of the present invention;
FIG. 4 is another cross-sectional view of the embodiment of FIG. 3 ;
FIG. 5 is a cross sectional view of a horizontal well with multiple fracturing stages;
FIG. 6 is a cross-sectional view of a downhole tool that is actuated by a pressure activation system according to one embodiment of the present invention;
FIG. 7 is another cross-sectional view of the embodiment of FIG. 6 ;
FIG. 8 is yet another cross-sectional view of the embodiment of FIG. 6 ;
FIG. 9 is a cross-sectional view of a downhole tool that is actuated by a pressure activation system according to another embodiment of the present invention;
FIG. 10 is a cross-sectional view of the downhole tool shown in FIG. 9 in a non-shifted position;
FIG. 11 is a cross-sectional view of the downhole tool shown in FIG. 9 in a shifted position;
FIG. 12 is a cross-sectional view of the downhole tool shown in FIG. 11 during flow-back;
FIG. 13 is a cross-sectional view of a downhole tool that is actuated by a counter system according to yet another embodiment of the present invention;
FIG. 14 is a cross-sectional view of the downhole tool shown in FIG. 13 in a shifted position;
FIG. 15 is an end view of the downhole tool shown in FIG. 13 ;
FIG. 16 is a side view of the counter assembly shown in FIG. 13 ;
FIG. 17 is a top view of the counter assembly shown in FIG. 16 ;
FIG. 18 is a side view of a locking mechanism in a clockwise lock position;
FIG. 19 is a side view of the locking mechanism of FIG. 18 in a counterclockwise lock position;
FIG. 20 is a side view of a counter assembly according to another embodiment of the present invention;
FIG. 21 is another side view of the counter assembly shown in FIG. 20 ;
FIG. 22 is a cross-sectional view of a downhole tool that is employed as a whipstock slide according to one embodiment of the present invention;
FIG. 23 is another cross-sectional view of the embodiment of FIG. 22 ;
FIG. 24 is a cross-sectional view of a downhole tool that is configured to prevent a well blowout according one embodiment of the present invention;
FIG. 25 is another cross-sectional view of the embodiment of FIG. 24 ;
FIG. 26 is yet another cross-sectional view of the embodiment of FIG. 24 ;
FIG. 27 is a further cross-sectional view of the embodiment of FIG. 24 ; and
FIG. 28 is yet a further cross-sectional view of the embodiment of FIG. 24 .
In certain instances, details that are not necessary for an understanding of the invention or that render other details difficult to perceive may have been omitted. It should be understood, of course, that the invention is not necessarily limited to the particular embodiments illustrated herein.
To assist in the understanding of one embodiment of the present invention the following list of components and associated numbering found in the drawings is provided.
#
Components
2
Downhole tool
6
Wellbore
10
Subterranean formation
14
Tubular string
16
Packer
18
Axial bore
22
Lateral bore
26
Fracture ports
30
Flapper valve
34
Sliding sleeve
38
Stimulation fluid
42
Shifting tool
46
Production fluid
50
Shear pins
54
Hinge
58
Torsion spring
62
Compression spring
66
Fracturing zones
70
Sleeve
74
High pressure
78
Drop member
82
Catch mechanism
86
Lower pressure
88
Flange
90
Spring
94
Upper reservoir
98
Lower reservoir
102
Orifice
106
Radial port
110
Seals
114
Weep hole
118
Sleeve locking mechanism
122
Recess
126
Downhole tool
130
Shifting sleeve
132
Counter assembly
134
Counter mechanism
138
Counter locking mechanism
142
Rocker mechanism
146
Counter spring
150
Counter window
154
Perforations
158
Protrusion
162
Chamber
166
Pressure equalization device
170
Manual setting mechanism
174
Trip pin
178
Gears
180
Counter wheels
182
Inner shaft
186
Sliding lock
190
Anchor
192
Treatment fluid
194
Radial button
196
Rack
198
Gear
206
Fill material
210
Inner tubular member
214
Sealing element
218
Ball
222
Ball seat
226
Ball cage
230
Flow restriction orifices
DETAILED DESCRIPTION
FIGS. 1 and 2 show one embodiment of the present invention in which at least one downhole tool 2 and associated tubular string 14 is disposed in a wellbore 6 . According to this embodiment, the wellbore 6 is drilled through a subterranean formation. As shown in FIGS. 1 and 2 , three tools 2 are connected to a tubular string 14 . Each tool 2 is vertically disposed within a formation 10 A, 10 B, 10 C that has been selected to be fracture stimulated and/or produced. One of skill in the art will appreciate that packers, cement, or other sealants may be located on either side of the formation 10 A, 10 B, and 10 C to provide annular hydraulic isolation. As shown in FIG. 1 , packers 16 provide annular hydraulic isolation of formation 10 B. In this embodiment, each tool 2 has an axial bore 18 , a lateral bore 22 , fracture ports 26 , a flapper valve 30 , and a sliding sleeve 34 .
Referring now to FIG. 1 , a fracture stimulation of a multiple zone formation is shown. As illustrated, the lower formation 10 C has been fracture stimulated, the intermediate zone 10 B is currently being fracture stimulated, and the upper zone 10 A will be fracture stimulated in the future. Stimulation fluid 38 flows down the tubular string 14 (which includes downhole tools 2 A, 2 B and 2 C), through the downhole tool 2 A and into the downhole tool 2 B (identifying Tool 2 in formation B). As shown, the downhole tool 2 B has been actuated wherein the flapper valve 30 blocks the axial bore 18 of tool 2 B, thereby preventing fluid from entering a distal portion of the tubular string 14 below the flapper valve 30 of tool 2 B. The fluid 38 flows through the frac ports 26 and the lateral bore 22 of the downhole tool 2 B into the intermediate zone 10 B. Portions of the tubular string 14 not associated with the zone being stimulated may be isolated by cement, packers, etc.
After the fracture stimulation of the intermediate zone 10 B is completed, a shifting tool 42 is conveyed down the tubular string 14 to the downhole tool 2 A. The shifting tool 42 activates the downhole tool 2 A by shifting the sleeve 34 , thereby releasing the flapper valve 30 . Once released, the flapper valve 30 moves toward its second position and blocks the axial bore 18 of the downhole tool 2 A to fracturing zone 10 A prevent fluid from flowing distally in the tubular string 14 . The second position may be held in place by a variety of locking means that are well known to one of ordinary skill in the art. The shifting tool 42 is removed from the tubular string 14 or repositioned within the tubular string 14 to the next stimulation zone. Stimulation fluid 38 is then pumped down the tubular string 14 , through the activated tool 2 A, and into the fracturing zone 10 A. As will be appreciated by one skilled in the art, this fracture sequence can be repeated without limit in a wellbore. Additionally, more than one downhole tool 2 may be deployed within each formation 10 .
Referring now to FIG. 2 , production of a multiple zone formation is shown. As illustrated in FIG. 2 , three vertically displaced (or horizontally placed zones in a directional well) formations 10 are producing fluid and/or gas (hereinafter “fluid”). The three downhole tools 2 integrated into the tubular string 14 allow the production fluid 46 to enter and flow up the tubular string 14 . Flapper valves 30 open in response to fluid flow and pressure, allowing flow from both outside and below the downhole tool 2 . As shown, production fluid 46 is flowing from the stimulated zones 10 through the frac ports 26 and the lateral bore 22 of the vertically displaced tools 2 into the tubular string 14 . Once in the tubular string 14 , the production fluid 46 flows up the tubular string 14 . The flapper valve 30 in each respective tool 2 is moved between a first position, where the lateral bore 22 is blocked, and a second position, in which the flapper valve 30 blocks the axial bore 18 , in response to fluid flow and pressure from outside and below the respective tool 2 .
FIGS. 3 and 4 show a downhole tool according to another embodiment of the present invention. According to this embodiment, a sleeve 34 restrains a flapper valve 30 in its first position, thus closing a lateral bore 22 of the downhole tool 2 . A shifting tool shifts the sleeve 34 , thereby releasing the flapper valve 30 and allowing the flapper valve 30 to move toward its second position.
FIG. 3 shows the flapper valve 30 is restrained in its first position by the sleeve 34 . The sleeve 34 is held in place by shear pins 50 , which prevent the sleeve 34 from moving within the tubular string 14 . In this position, the axial bore 18 of the downhole tool 2 allows fluids and solid elements to pass through the downhole tool 2 into distal portions of the tubular string 14 , and the flapper valve 30 blocks access to a tubular annulus formed between the tubular string 14 and the wellbore. The sleeve 34 blocks the ports 26 and the flapper valve 30 blocks the lateral bore 22 .
Referring now to FIG. 4 , the sleeve 34 has been shifted in the downhole tool 2 , thereby releasing a flapper valve 30 from its first position. A hinge 54 connected to the bottom of the flapper valve 30 allows rotation. A torsion spring 58 connected to the bottom of the flapper valve 30 biases the flapper valve 30 towards its second position. A compressed spring 62 also may be included in the body of the downhole tool 2 to assist the movement of the flapper valve 30 from its first position toward its second position. As shown, the flapper valve 30 is in its second position to seal the axial bore 18 of the downhole tool 2 , thereby preventing fluid from flowing downward into distal portions of the tubular string 14 . Frac ports 26 and the lateral bore 22 of the downhole tool 2 create passageways to the annulus of the tubular string 14 . As will be appreciated by one of skill in the art, the lateral bore 22 is optional. Accordingly, in some embodiments, fluid exchange occurs solely through the frac ports 26 .
Referring now to FIG. 5 , a horizontal well with multiple producing zones is shown. As illustrated, a wellbore 6 is depicted which contains five fractured zones 66 . At least one downhole tool 2 but preferably five in this example may be disposed within the wellbore to isolate and allow production from the different zones in the geologic formation. Each of the downhole tools 2 may be activated by a sleeve 34 as discussed above or by a pressure activation system to allow the selective treatment of each zone and subsequent production simultaneously, thus optimizing economic performance of the producing formation. Although not shown, the fractured producing zones may be hydraulically isolated with packers or cement, for example, to isolate the annular space between the tubular string 14 and the wellbore or casing.
FIGS. 6-8 illustrate a downhole tool 2 according to another embodiment wherein the downhole tool 2 is actuated by a pressure activation system. More specifically, the sleeve 70 is pressure activated such that the flapper valve 30 is released depending on the pressure exerted into the tubular string 14 . In operation, a high pressure 74 applied to the tubular string 14 does not actuate a downhole tool 2 . Instead, the high pressure 74 causes a drop member 78 , such as a ball, to pass through a downhole tool 2 and travel to the next tool 2 in the tubular string 14 or to the distal portion of the wellbore 6 . The drop member 78 passes through the downhole tool 2 by deforming or by actuating a catch mechanism 82 , as shown in FIGS. 6-8 .
A lower pressure 86 actuates the downhole tool 2 by shifting the sleeve 70 , thereby releasing a flapper valve 30 and allowing it to move from its first position to its second position. More specifically, the lower pressure 86 acts upon the drop member 78 , which is lodged in the catch mechanism 82 , to slide the sleeve 70 away from the flapper valve 30 . Using a flange 88 , the sleeve contacts and compresses a spring 90 as it moves. The sleeve 70 is associated with an upper reservoir 94 , a lower reservoir 98 , and an orifice 102 for fluid passage. The outer surface of the sleeve 70 forms a boundary between the reservoirs 94 , 98 and the internal bore of the downhole tool 2 , and seals the reservoirs 94 , 98 from pressure in the tubular string. Sealing elements may be provided to enhance the seal between the sleeve 70 and the reservoirs 94 , 98 . Once the sleeve 70 is moved a predetermined distance, the flapper valve 30 is able to release. In one embodiment, a high pressure 74 of about 3000 psi causes the drop member 78 to pass through a downhole tool 2 , and a lower pressure 86 of about 1000 psi maintained in the tubular string 14 for roughly 15 seconds causes the drop member 78 to move the sleeve 70 . One of ordinary skill in the art would understand this embodiment uses a similar mechanism to that of a hydraulic fishing jar. As will be appreciated by one of skill in the art, the pressures may vary depending on design of the sleeve 70 , the drop member 78 , the catch mechanism 82 , and the spring 90 . Further design criteria include the depth of the wellbore, pressure from the producing formation, diameter of tubing string 14 , etc.
FIG. 8 shows a shifted sleeve 70 and a released flapper valve 30 in its second position. Once the sleeve 70 no longer abuts the flapper valve 30 , a torsion spring 58 will rotate the flapper valve 30 from its first position toward its second position, thereby blocking the axial bore 18 of the downhole tool and opening the lateral bore 22 of the downhole tool. An additional spring 62 may be used to assist the movement of the flapper valve 30 from its first position towards the second position.
FIGS. 9-12 illustrate a downhole tool 2 actuated by a pressure activation system according to another embodiment of the present invention. The downhole tool 2 shown in FIGS. 9-12 operates in a similar fashion as that described above in connection with FIGS. 6-8 . A flapper valve 30 is shown in FIGS. 9-12 ; however, in some embodiments, the flapper valve 30 is not included in the downhole tool 2 . In these embodiments, the sleeve 70 blocks access to the tubular annulus while in a non-shifted position. A drop member 78 shifts the sleeve 70 to allow access to the subterranean formation through openings formed in the circumference of the downhole tool 2 . The drop member 78 remains seated in the catch mechanism 82 during stimulation of the selected stage to isolate downstream portions of the tubular string from the stimulation fluid and/or proppant.
Referring to FIG. 9 , a sleeve 70 is disposed in an initial, non-shifted position. As shown, the sleeve 70 blocks access to the tubular annulus through a radial port 106 and restrains the flapper valve 30 in its first position, thereby blocking lateral bore 22 . Seals 110 provide a fluid tight engagement between the sleeve 70 and the downhole tool 2 , thus preventing fluid exchange between the tubular production string and the tubular annulus. The sleeve 70 is interconnected to a flange 88 , which is associated with an upper reservoir 94 and a lower reservoir 98 . The flange 88 has a weep hole 114 that allows fluid exchange between the upper and lower reservoirs. In operation, the weep hole 114 acts like a dashpot and resists motion of the sleeve 70 . The rate of fluid exchange between the upper and lower reservoirs increases once the flange 88 enters the larger cross-sectional reservoir area. Accordingly, in at least one embodiment, the sleeve 70 shifts at two different rates. Initially, the sleeve 70 shifts at a slow rate because of the restricted fluid flow through the weep hole 114 . However, once the sleeve has shifted to the point that the flange 88 enters the larger cross-section reservoir area, the sleeve shifts at an increased rate because of the increased fluid flow path between the upper reservoir 94 and the lower reservoir 98 .
As illustrated in FIG. 9 , a drop member 78 is seated in a catch mechanism 82 . At higher pressures, the drop member 78 passes through the catch mechanism 82 and travels to the next downhole tool 2 in the tubular production string, as shown in FIG. 10 . At lower pressures, the drop member 78 remains seated in the catch mechanism 82 and moves the sleeve 70 into a shifted position, as shown in FIG. 11 .
Referring to FIG. 10 , the sleeve 70 remains in a non-shifted position and the drop member 78 has passed through the catch mechanism 82 and is travelling through the tubular string toward a downstream tool 2 disposed in the tubular production string. Referring to FIG. 11 , the drop member 78 has shifted the sleeve 70 , thus allowing the flapper valve 30 to isolate the downstream portions of the tubular production string. A sleeve locking mechanism 118 prevents the sleeve 70 from shifting upward in the downhole tool 2 and unseating the flapper 30 from its second position. As shown, the sleeve locking mechanism 118 is spring loaded. Alternative actuation methods, as known in the art, may be used to activate the sleeve locking mechanism 118 . Additionally, the sleeve locking mechanism 118 may have the ability to reset to its original position, thereby allowing the sleeve 70 to reset to its initial non-shifted position.
FIG. 11 also depicts a recess 122 in the downhole tool 2 configured to receive the catch mechanism 82 . In one embodiment, the catch mechanism 82 has an undeformed outer diameter that is larger than the inner diameter of the downhole tool 2 . Accordingly, in this embodiment, the inner diameter of the downhole tool 2 constrains the outer diameter of the catch mechanism 82 . By providing a selectively positioned recess 122 in the downhole tool 2 , the catch mechanism 82 is allowed to expand into the recess 122 when the sleeve 70 is in a shifted position. This expansion allows the full inner diameter of the sleeve to be utilized for ball return during flow back operations. In one configuration, the catch mechanism 82 is a spring loaded collet assembly.
Referring to FIG. 12 , the downhole tool 2 is shown during flow back. As shown, the flapper valve 30 has rotated toward its first position, thereby allowing the drop member 78 to flow up the tubular string from distal portions of the wellbore. Additionally, the catch mechanism 82 has retracted into a recess 122 formed in downhole tool 2 . This retraction allows the full bore of the tubular string to be utilized and prevents the catch mechanism 82 from interfering with the return of the drop members 78 to the surface during flow back. In some configurations, the flapper valve 30 may be locked in its first position during flow back by a latching mechanism. Locking the flapper 30 in its first position would increase the flow up the axial bore 18 of the tubular production string while allowing flow from the stimulated zones to continue through the ports 106 . FIGS. 13-19 depict a downhole tool 126 that is actuated by a pressure activation system according to another embodiment of the present invention. Downhole tools 126 are selectively disposed within stimulation stages according to a predetermined stimulation process. Each downhole tool 126 utilizes a counter to actuate a sliding sleeve. Each counter is associated with a stimulation stage and is preset to a predetermined number. The counter indexes for every drop member 78 that passes through the downhole tool 126 . After the predetermined number is reached, the counter prevents subsequent drop members 78 from passing through the downhole tool 126 to downstream portions of the tubular production string. Accordingly, each drop member 78 that is dropped proceeds to a predetermined stage number. Once at the predetermined stage number, the drop member 78 seats in a catch mechanism and seals the axial bore of the tubular production string. Increased pressure in the tubular production string upstream of the predetermined stage number shifts the predetermined tool 126 and allows access to the subterranean formation through openings in the tubular production string.
Referring to FIG. 13 , a cross-sectional view of the downhole tool 126 in a pre-shifted position is illustrated. In the pre-shifted position, the downhole tool 126 allows fluid and/or proppant to pass through the downhole tool 126 to the stage being stimulated while restricting access to openings formed in the downhole tool 126 . The downhole tool 126 utilizes a shifting sleeve 130 that may be secured in a pre-shifted position by a shear pin 50 . The shifting sleeve 130 employs a counter assembly 132 to activate shifting of the sleeve 130 . The design of the counter assembly 132 may vary, as will be appreciated by one of skill in the art. As shown in FIG. 13 , the counter assembly 132 includes a counter mechanism 134 , a locking mechanism 138 , a rocker mechanism 142 , a counter spring 146 , and a catch mechanism, such as a protrusion 158 . In at least one embodiment, the counter assembly includes a manual setting mechanism 170 that allows the counter mechanism 134 to be incremented or decremented manually through buttons or levers. In an alternative embodiment, an electronic setting mechanism may be provided that allows an operator to remotely set the counter to a predetermined number. The preset number for the counter mechanism 134 may be revealed in a window 150 constructed of suitable transparent materials, such as Lexan or other similar materials. The window 150 may be viewed either from the sidewall of the pipe or by looking down the tubular before installation.
FIG. 14 depicts the downhole tool 126 in a shifted position, revealing perforations 154 in the tubular production string. In the shifted position, the downhole tool 126 allows fluid and/or proppant to pass through the perforations 154 while restricting access to downstream portions of the tubular production string. As illustrated in FIG. 14 , the drop member 78 remains lodged in the shifting sleeve 130 and restricts flow that might otherwise pass on to stages that have already been stimulated. After stimulation, the drop member 78 is no longer needed to seal the inner bore of the downhole tool 126 and thus is allowed to flow back to the surface. As shown, a sleeve locking mechanism 118 prevents the shifting sleeve 130 from shifting back into its pre-shift position.
FIG. 15 illustrates a simplified end view of the downhole tool 126 with a drop member 78 disposed therein. In FIG. 15 , the counter mechanism 134 , the locking mechanism 138 , and the counter spring 146 are not shown for simplicity reasons. As illustrated, the drop member 78 is seated on the protrusion 158 and substantially seals the inner bore of the downhole tool 126 . To prevent sand or other proppants from interfering with the gears of the counter assembly 132 and to ensure adequate lubrication thereof, the counter assembly 132 may be housed in a chamber 162 that is filled with oil or other fluid. A pressure equalization device 166 , such as a pressure regulator, may be used to ensure that the pressure inside the chamber 162 does not drop substantially below the pressure in the tubular production string, thus minimizing the likelihood of contaminants reaching the counter assembly and ensuring proper operation of the counter assembly 132 . The pressure equalization device 166 is in fluidic communication with the chamber 162 and the inner bore of the tubular production string, and isolates the fluid in the chamber 162 from the fluid and proppants in the tubular production string. In at least one embodiment the pressure equalization device is a piston and cylinder. Additionally, a sealing element may be provided between the counter assembly and the inner bore of the tubular string to further isolate the counter assembly 132 from contaminants.
FIGS. 16-19 illustrate in detail one embodiment of a counter assembly 132 . As shown in FIGS. 16-19 , the counter assembly 132 includes a counter mechanism 134 , a locking mechanism 138 , a rocker mechanism 142 , a counter spring 146 , and a manual setting mechanism 170 . Referring to FIGS. 16-17 , a catch mechanism, such as a protrusion 158 , interconnects with the rocker mechanism 142 . The rocker mechanism 142 interconnects to a counter mechanism 134 , a locking mechanism 138 , and a spring 146 . Upon contact with a drop member, the protrusion 158 rotates the rocker mechanism 142 and allows the drop member to pass through the internal bore of the downhole tool 126 . Upon rotation of the rocker mechanism 142 , the counter mechanism 134 indexes a running count number. Once the running count number reaches a predetermined number, the counter mechanism 134 moves a trip pin 174 which allows the locking mechanism 138 to shift, thereby preventing subsequent drop members from passing through the downhole tool 126 to downstream portions of the tubular string. In some embodiments, the counter mechanism generates an electronic signal to activate the locking mechanism. In these embodiments, once the predetermined number is reached, an electronic signal is sent to the locking mechanism, which shifts into a locked position upon receipt of the signal. In some embodiments, the counter mechanism also may generate an electronic signal to activate shifting of an inner tubular member, such as a sleeve. In these embodiments, the sleeve would not be activated by an internal pressure within the tubular string.
A manual setting mechanism 170 allows the counter mechanism 134 to be incremented or decremented manually through buttons or levers, thereby allowing the counter mechanism 134 to be preset to a predetermined number. As discussed above, an electronic setting mechanism may be provided that allows an operator to remotely set the counter to a predetermined number. Accordingly, the counter mechanism 134 is settable such that each tool 126 in the tubular production string will have a unique number and will lock out only after the proper numbers of balls have passed by it. The counter assembly 132 also includes a counter spring 146 that interconnects with the rocker mechanism 142 and restrains rotation of the rocker mechanism 142 . The counter spring 146 is configured to prevent the counter assembly 132 from counting when fracing fluid with or without proppant is passed through the downhole tool under typical fracing conditions. Accordingly, the counter spring 146 ensures that the rocker mechanism 142 will rotate only under the force of a drop member 78 seated on the catch mechanism. The counter spring 146 is illustrated as a linear spring; however, in some embodiments the counter spring 146 may be a torsion spring disposed on the shaft of the rocker mechanism 142 .
As depicted in FIGS. 16-17 , the counter assembly 132 incorporates a plurality of gears 178 and a plurality of counter wheels 180 to enable counting to a predetermined number, which in turn facilitates engagement of the locking mechanism 138 . The counter mechanism 134 may incorporate geneva gears or other incrementing/decrementing gears to facilitate proper counting. For example, the device may have a gear for 1's, 10's and 100's places and may use geneva gears or other incrementing gears to facilitate proper counting between these places.
As previously mentioned, the design of the counter assembly 132 may vary without departing from the scope of present disclosure. For example, in one embodiment, the counter is a disk that rotates to release the ball. In another embodiment, a button or section of the wall may move in the radial direction to allow the ball to pass and decrement the counter. As a further example, instead of utilizing a catch mechanism interconnected with a rocker mechanism 142 , the catch mechanism could translate in and out of the inner bore of the tubular production string to actuate a click counter. In this configuration, the motion of the protrusion 158 would be orthogonal to the central axis of the tubular production string. The orthogonal motion would actuate the counter mechanism 134 in a similar fashion as a hand-held clicker. Once the predetermined number is reached, the counter mechanism 134 would activate the locking mechanism 138 to prevent orthogonal movement of the protrusion. In this example, the protrusion 158 may have sloped surfaces to enable a drop member to force the protrusion 158 into the chamber 162 and to pass by the protrusion 158 .
FIGS. 18-19 depict an embodiment of the locking mechanism 138 . In FIGS. 18-19 , a trip pin 174 is disposed toward a lower, or downstream, end of the downhole tool 126 . Accordingly, during normal flow, the direction of fluid flow is from left to right in FIGS. 18-19 . Referring to FIG. 18 , the locking mechanism 138 is in a clockwise lock position. As illustrated, a sliding lock 186 prevents an inner shaft 182 of the rocker mechanism 142 from rotating clockwise, but allows the inner shaft 182 to rotate counterclockwise. A compression spring 62 biases the sliding lock 186 against a trip pin 174 and is disposed between the sliding lock 186 and an anchor 190 that is interconnected with the sleeve 130 . As shown in FIG. 17 , the trip pin 174 is interconnected with the counter mechanism 134 . Once a predetermined number of drop members passes by the counter assembly 132 , the counter mechanism 134 pulls the pin 174 . Accordingly, in the clockwise lock position, the locking mechanism 138 allows drop members, such as balls, to pass by the counter assembly 132 to distal portions of the tubular production string. However, the locking mechanism 138 prevents drop members from passing by the counter assembly 132 in a reverse direction toward the surface.
Referring to FIG. 19 , the trip pin 174 has been pulled by the counter mechanism 134 . As shown, the compression spring 62 has shifted the sliding lock 186 into a counterclockwise lock position. In this position, the sliding lock 186 prevents the inner shaft 182 from rotating counterclockwise, but allows the inner shaft to rotate clockwise. The compression spring 62 maintains the sliding lock 186 in this counterclockwise lock position. By preventing counterclockwise rotation, the lock mechanism 138 prevents drop members from passing to downstream portions of the tubular production string. Thus, once the lock mechanism 138 is in this lock position, a subsequent drop member will seat on the protrusion 158 and substantially seal the inner bore of the tubular production string. Internal pressure will build in the inner bore of the tubular production string, thus shifting the sleeve 130 associated with the counterclockwise locked counter assembly 132 into a shifted position. Accordingly, in the counterclockwise lock position, the locking mechanism 138 allows drop members, such as balls, to pass by the counter assembly 132 toward the surface. However, the locking mechanism 138 prevents drop members from passing by the counter assembly 132 to distal portions of the tubular production string.
FIGS. 20-21 depict a counter assembly according to another embodiment of the present invention wherein the counter assembly utilizes a button or section of the sleeve wall to allow a ball to pass and decrement the counter. In general, FIGS. 20-21 illustrate a linear actuation method of incrementing/decrementing a counter. Referring to FIGS. 20-21 , treatment fluid 192 is flowing toward distal portions of the tubular string. A button 194 has sloped surfaces and extends into an internal bore of a sleeve 130 . The button 194 is interconnected to a rack 196 , which is configured to intermesh with a gear 198 to increment/decrement a counter. The gear 198 may be, for example, a counter gear or a worm gear that is interconnected with a counter mechanism. A sliding lock 186 is interconnected with a spring 62 , an anchor 190 , and is in mechanical or electrical communication with a counter mechanism. Once a predetermined number of balls have passed by the button 194 , the counter mechanism will activate the sliding lock 186 to prevent subsequent balls from passing by the button 194 . As shown in FIG. 20 , a drop member 78 has contacted the button 194 . The sliding lock 186 is not engaged, and thus the ball may depress the button in a direction orthogonal to the fluid flow 192 and continue flowing toward distal portions of the tubular string. Referring to FIG. 21 , the drop member 78 has depressed the button 194 into the body of the sleeve 130 , and the rack 196 has engaged the gear 198 , thereby causing the gear 198 to rotate. The rotation of the gear 198 causes the counter mechanism to increment/decrement the running count number.
According to at least one embodiment of the present invention, a method is provided that selectively stimulates stages using a single-sized ball. Following the stimulation of a stage, a ball is dropped into the well and pumped down the center of the tubular production string. The ball passes through each downhole tool 126 in the system under the force of the fluid pressure. Because of the diameter of the inner bore of the tubular production string, the ball may pass through a downhole tool 126 only if it decrements a counter. In one embodiment, the counter is a disk that rotates to release the ball. In another embodiment, a button or section of the wall may move in the radial direction to allow the ball to pass and decrement the counter. When the counter reaches zero, a lock is engaged and the counter will no longer allow the ball to pass through the downhole tool 126 . With the ball prevented from passing, the flow through the tubular is greatly restricted and a pressure differential will be created. This pressure differential will create sufficient force to move the sleeve from a non-shifted position to a shifted position. The downhole tool may or may not incorporate shear pins to ensure that the sleeve only shifts when a predetermined force is applied. In the shifted position, the ball remains held by the locked counter and provides sufficient flow restriction to divert the bulk of the flow to radial openings in the tubular production string and for the stage to be fraced. Alternatively, the shifting mechanism may activate a flapper device to seal the axial bore of the tubular production string.
While in the non-shifted position, the downhole tool 126 will not allow balls to pass in the reverse direction. However, fluid will be allowed to pass by the ball relatively unimpeded because of the design of the tubular region. This feature allows the completions engineers to flow back in the event of a screen-out, but not accidently flow back beyond the next downhole tool. If this were to happen each ball would then decrement the counter as soon as fracing operations resumed and the sleeves would shift too soon. By preventing the ball from returning while in the downhole tool is in a non-shifted position, counting integrity is preserved. While in the shifted position, the reverse flow lock is removed and the downhole tool will allow relatively unrestricted flow of the balls through the downhole tool 126 .
The axial bore of the downhole tool may also allow passage of solid elements, such as wireline tools, tubing, coiled tubing conveyed tools, cementing plugs, balls, darts, and any other elements known in the art. When all of the stages have been fraced, the pressure is reduced and the flow reverses direction. In this flow back mode, the balls will pass back by the counter with very little resistance.
FIGS. 22-23 illustrate another embodiment wherein the flapper valve 30 is used as a whipstock slide. According to this embodiment, the flapper valve 30 is longer in one axis than in another, such that the flapper valve 30 forms a slide when in the second position. The angled flapper valve 30 assists the placement and extraction of tools through the lateral bore 22 of the downhole tool 2 . It is feasible that the lateral bore 22 of the downhole tool 2 may be filled with a fill material 206 , such as soft cast iron, cement, etc. that may need to be removed with a drilling apparatus or by chemical treatment. Additionally, an orienting key may be associated with the flapper valve 30 to orient and guide tools to the lateral bore 22 of the downhole tool 2 . In some embodiments, the orienting key is a separate member that is landed in a crowsfoot associated with the flapper valve 30 . The flapper valve 30 is restrained in its first position by a sleeve 34 , which is held in place by shear pins 50 . The flapper valve 30 may be held in place by other mechanisms described herein.
Referring to FIG. 23 , the sleeve 34 has been displaced vertically within the tubular string 14 by a shifting tool thereby allowing the flapper valve 30 to move from its first position to its second position. The shifting tool may be operated by wireline, slickline, coiled tubing, or jointed pipe as appreciated by one skilled in the art. A hinge 58 interconnects the lower end of the flapper valve 30 to the downhole tool and allows the flapper valve 30 to rotate. A torsion spring 58 biases the flapper valve 30 towards its second position. Another spring 62 may be provided to assist the movement of the flapper valve 30 from its first position to its second position.
FIGS. 24-28 illustrate yet another embodiment wherein a downhole tool 2 is utilized to prevent a well blowout. According to this embodiment, an inner tubular member 210 is operably interconnected to the axial bore of the downhole tool 2 by shear pins 50 or other connecting means known in the art. Additionally, a sealing element 214 may be placed around the inner tubular member 210 to provide a seal between the inner tubular member 210 and the downhole tool 2 . The sealing element 214 may be elastomeric, plastic, metallic, or any other sealing elements known to one of ordinary skill in the art. The inner tubular member 210 restricts the movement of the flapper valve 30 and holds the flapper valve 30 in its first position. The upper portion of the inner tubular member 210 forms a chamber that houses a ball 218 . The chamber is also defined by a ball seat 222 and a ball cage 226 .
FIG. 24 shows a condition where fluid is flowing down the tubular string 14 . As shown, the fluid flows into the inner bore of the downhole tool 2 and further into the inner tubular member 210 via a ball seat 222 and orifices 230 . The fluid flow and pressure forces the ball 218 to contact the ball cage 226 , which prevents the ball 218 from moving distally into the tubular string 14 . As illustrated, fluid flows around the ball 218 without unduly restricting the fluid flow. In this embodiment, the inner tubular member 210 is held in place within the downhole tool 2 by shear pins 50 . The annulus formed between the inner tubular member 210 and the downhole tool 2 is sealed by an o-ring 214 or other sealing elements commonly used in the art. As shown in FIGS. 24-25 , three sets of vertically displaced shear pins 50 and o-rings 214 are utilized. As will be appreciated by one of skill in the art, the number of shear pins and sealing elements may vary.
Referring to FIG. 25 , as fluid flows up the internal bore of the tubular string 14 , it enters the downhole tool 2 and the inner bore of the inner tubular member 210 . The fluid flow and pressure causes the ball 218 to seat in the ball seat 222 , thus restricting the fluid flow through the inner tubular member 210 by redirecting the fluid flow through orifices 230 in the inner tubular member 210 .
FIG. 26 shows an increased fluid flow associated by a well blowout that is represented by the dark arrows. The increased fluid flow flows through the orifices 230 , but in a restricted manner, which creates an upward force on the inner tubular member 210 .
In FIG. 27 , the increased fluid flow caused by the well blowout has sheared the shear pins 50 and thus the inner tubular member 210 has shifted upward in the downhole tool 2 . The upward movement frees the distal flapper valve 30 , which allows it to close the axial bore of the downhole tool 2 . The momentum of the fluid flow and the inner tubular member 210 causes the inner tubular member 210 to continue moving up the tubular string 14 , thus allowing a second proximal flapper valve 30 to close. The flapper valves 30 prevent fluid from flowing up the axial bore of the downhole tool 2 , thereby preventing the well blowout. As will be appreciated by one of skill in the art, more or less than two flapper valves 30 may be used without departing from the scope of the invention.
While various embodiments of the present invention have been described in detail, it is apparent that modifications and alterations of those embodiments will occur to those skilled in the art. Moreover, references made herein to “the present invention” or aspects thereof should be understood to mean certain embodiments of the present invention and should not necessarily be construed as limiting all embodiments to a particular description. However, it is to be expressly understood that modifications and alterations are within the scope and spirit of the present invention, as set forth in the following claims. | A downhole tool that selectively opens and closes an axial/lateral bore of a tubular string positioned in a wellbore used to produce hydrocarbons or other fluids. When integrated into a tubular string, the downhole tool allows individual producing zones within a wellbore to be isolated between stimulation stages while simultaneously allowing a selected formation to be accessed. The downhole tools and methods can be used in vertical or directional wells, and additionally in cased or open-hole wellbores. | 4 |
FIELD OF THE INVENTION
[0001] The present invention relates to a security panel, for example for use in a security barrier, and to a method of forming the security panel.
BACKGROUND
[0002] Security barriers are conventionally formed from straight sections of elongated metal tape having barbs formed at spaced intervals along the tape. The metal tape may be traditional barbed wire, which usually comprises two or more braided wires with regularly spaced intertwined wire barbs. Alternatively, the metal tape may be razor wire, which usually has a central wire with laterally extending planar barbs. An example of such razor wire is disclosed in U.S. Pat. No. 4,509,726.
[0003] It is known to form metal tape, and particularly razor wire, into a security mesh panel in order to provide a barrier which is both stronger and more secure than a barrier formed purely with elongate parallel strands of metal tape. One such security mesh is disclosed in patent document CA 1,190,433, which shows a security mesh panel formed from straight razor wire that is bent into a saw tooth pattern that interlinks with adjacent saw tooth bent razor wires. The mesh is then riveted or welded at the junctions.
[0004] Other types of security mesh panel formed from razor wire are disclosed in U.S. Pat. No. 4,666,129, GB 2,259,722 A, WO 00/65178 and 2,240,351 A, all of which are similar to CA 1,190,433 in that individual strands of razor wire are joined together by welding or riveting to form a security mesh panel.
[0005] A number of problems have been noted with such security mesh panels. First, a large number of individual strands of razor wire have to be formed and aligned relative to one another prior to fixing the strands together. In a production environment, this requires specially designed machinery both to manipulate and join the stands. Second, although in principle it is possible to make a weld or rivet as strong as the surrounding material, in practice each join is a potential source of weakness. For example, a weld may not have been formed in the optimum manner. Both welds and rivets are a potential source of corrosion, either from the use of differing types of metals in the same structure, or from damage done to a galvanized protective finish on the original razor wire.
[0006] One solution to the latter problem is to form the razor wire from stainless steel, but this is a prohibitively expensive material to use in many applications, particularly perimeter fencing formed from the security mesh panels.
[0007] It is an object of the present invention to provide a security mesh panel that deals with these issues.
SUMMARY OF THE INVENTION
[0008] According to the invention, there is provided security panel, comprising an expanded metal mesh, the mesh having apertures therethrough bounded by a plurality of sides, at least one of said apertures having at least one side to which is affixed a separate barbed structure, the barbed structure having at least one barb extending in a plane of the panel in towards another side of said aperture.
[0009] Because the security panel is formed from an expanded mesh, there is no need for welds or rivets at mesh nodes. The panel therefore has an inherent strength and durability beyond that which may be achieved with a security panel formed from individual lengths of razor wire. Furthermore, there is no need for there to be any welds or other joins between the barbed structures and the mesh at the mesh nodes. Such joins can be made entirely away from the mesh nodes. Therefore, the formation and performance of these joins cannot adversely affect the strength of the mesh at the nodes. Because any stresses on a security panel will tend to be concentrated at one or more of the mesh nodes, the overall strength of the security panel can readily be improved as compared with a security panel having joins between individual pieces of razor wire.
[0010] Preferably, the barbed structures are affixed to all sides of said at least one aperture. This helps to provide the maximum number of the barbs projecting into each aperture of the security panel, thereby improving the security of the panel. Furthermore, for the same reason the barbed structure may have a plurality of said barbs extending in the plane of the panel in towards another side of said aperture.
[0011] In one preferred embodiment of the invention, the barbed structure includes a plurality of barbed points grouped in threes, a first and a second one of said barbed points extending in opposite directions parallel with the corresponding side of said aperture, and the third one of said barbed points extending transversely away from the corresponding side of said aperture.
[0012] In general, each side of an aperture is formed from an elongate strip of metal, and each of the strips of metal is joined integrally to adjacent strips of metal at mesh nodes. In a preferred embodiment, the barbed structure is then affixed to just one corresponding strip of metal. So that the fixing of the barbed structure does not adversely affect the strength of the mesh nodes, the barbed structure is preferably affixed to this one corresponding strip of metal at one or more points lying between the mesh nodes. Similarly, the barbed structure preferably lies entirely between mesh nodes.
[0013] The invention further provides a security fence, comprising at least two upright fence supports, and a security panel, said security panel being supported by said fence supports, wherein the security panel is according to the invention.
[0014] Also according to the invention, there is provided a method of forming a security panel, comprising the steps of: making a plurality of non-intersecting cuts in a sheet of metal; expanding the cut sheet to form an expanded metal mesh, the mesh having apertures therethrough bounded by a plurality of sides; forming one or more barbed structures in metal separate from the expanded metal mesh, the or each barbed structure having at least one extending barb; and affixing at least one of said barbed structures to a side of at least one of said apertures so that at least one barb extends in a plane of the panel in towards another side of said aperture.
[0015] The method may also comprise the step of affixing the or each barbed structure between a pair of nodes of the metal mesh.
[0016] One way of affixing the barbed structure to the metal mesh is to form the barbed structure with at least one extending tab, and then wrap the or each tab around portions of the metal mesh bounding the aperture in order to affix the barbed structure to said side of said aperture.
[0017] Additionally or alternatively, the barbed structure may be affixed to the metal mesh by welding the barbed structure to the metal mesh at one or more points between nodes of the metal mesh.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] The invention will now be further described, by way of example only, and with reference to the accompanying drawings, in which:
[0019] FIG. 1 is a plan view of one side of a security mesh panel according to the invention;
[0020] FIG. 2 is an enlarged plan view of part of the opposite side of the security mesh panel of FIG. 1 ;
[0021] FIG. 3 is a cross-section view through the security mesh panel, taken along line III-III of FIG. 2 ; and
[0022] FIG. 4 is a view of a security fence, comprising upright fence supports that support the security panel of FIGS. 1 to 3 .
DETAILED DESCRIPTION
[0023] FIG. 1 shows a plan view of one side of a security mesh panel 1 . The security panel 1 is formed from a planar expanded metal mesh 2 to which individual elongate metal barbed structures 4 have been permanently affixed, for example by spot welding. The expanded mesh 2 is itself formed in a conventional manner from a metal sheet, for example 3 mm thick mild steel, galvanized steel or even stainless steel, through which a series of parallel non-overlapping slits have been punched. After the slits have been formed, a pair of opposite edges of the sheet is pulled apart to expand the sheet and form the mesh 2 . If the expanded metal sheet requires corrosion protection, then it may be galvanized.
[0024] Reference is now made also to FIGS. 2 and 3 , which show respectively an enlarged plan view of a side of the security mesh 2 opposite to that shown in FIG. 1 , and a cross section view through the security mesh. The mesh 2 consists of a series of adjacent strips of metal 6 , which in this example are essentially straight sections. Each straight section 6 is bounded by mesh nodes 8 at which each straight section merges integrally with adjacent straight sections 6 . Each mesh node 8 is therefore joined to four adjacent straight sections 6 in an X-pattern, except at an edge 10 of the mesh where each mesh node 8 is joined to two adjacent straight sections 6 in a V-pattern.
[0025] The metal mesh 2 therefore presents a number of diamond shaped apertures 9 , each of which is bounded by four adjacent sides 11 .
[0026] Each barbed structure 4 lies entirely between a pair of mesh nodes 8 , which are at opposite ends of a mesh straight section 6 . In the present example, there are three such barbed structures between 4 each mesh node 8 . There may, however, be one, two, four or any convenient number of such barbed structures 4 between the nodes 8 .
[0027] The barbed structures 4 are all punched from sheet metal, preferably galvanized steel or stainless steel and then folded along a central axis to form a square U-shaped channel 12 that extends the full length of each barbed structure 4 . As can be seen from FIG. 3 , each straight section 6 has a square cross-section. The cross section may, however, alternatively be rectangular. The cross-section of the straight section has a complementary shape with the U-shaped channel so that each barbed structure 4 is seated securely on a corresponding straight section 6 . Each straight section 6 is therefore seated in the channel 12 when the barbed structure 4 is affixed to the corresponding straight section 6 .
[0028] Each barbed structure 4 is formed with at least one, and preferably two or three barbs 14 along opposite sides of the barbed structure. Here, the barbs 14 are multi-pointed. The number and spacing of the barbs 14 will depend on the relative sizes of the barbs 14 and aperture 9 . The barbs 14 each have a pair of barbed points 15 , 16 that extend parallel with the length of the U-shaped channel 12 and at a distance from the straight section 6 . A third intermediate barbed point 17 extends transversely away from the channel 12 and straight section 6 . Each of the barbed points 15 , 16 , 17 is triangular in plan view and extends in the plane of the security mesh 2 towards another side 11 of the aperture 9 .
[0029] When the barbed structures 4 are being assembled with the metal mesh 2 , the complimentary square shapes of each straight section 6 and corresponding barbed structure 4 hell to align the barbed structure 6 with the plane of the metal mesh 2 . This greatly simplifies the manufacturing process, as it is not necessary to hold each barbed structure 4 in place prior to permanent affixing of the barbed structure 4 to the corresponding straight section 6 .
[0030] In order to make each barbed point 15 , 16 , 17 as sharp as possible, the barbed structure 4 is preferably stamped from relatively thin sheet metal, for example between 0.3 mm and 0.5 mm thick. The barbs 14 should, however, be difficult to bend back by hand, and in order to reinforce each barb 14 against such bending, each barb 14 has a corresponding base portion 18 that extends in the plane of the mesh panel 2 laterally away from the channel 12 . Each barb 14 has a central waist 20 from which the three barbed points 15 , 16 , 17 project and from which the base portion 18 flares outwards towards the channel 12 . This arrangement of base portion 18 and waist 20 therefore permits each barb 14 to be spaced at a sufficient distance from the straight section 6 to provide enhanced security, while at the same time diminishing the distance between the waist 20 and the barbed points 15 , 16 , 17 in order to reduce the amount of leverage that may be applied in an attempt to bend back a barbed point 15 , 16 , 17 .
[0031] The outwardly flared shape of the base portion 18 also makes the pair of parallel barbed points 15 , 16 more exposed, thus increasing the deterrent effectiveness of these barbed points 15 , 16 . For this reason, each base portion 18 is distinct from base portions of any adjacent barbs 14 .
[0032] The effectiveness of each barb 14 is also enhanced if there is a longitudinal spacing between adjacent parallel barbed points 15 , 16 at least as great as the lateral spacing of each of these points from the central channel 12 . Therefore, it is particularly preferred that each base portion 18 is separated by a gap 22 from adjacent base portions 18 .
[0033] Furthermore, this arrangement permits the barbed structure 4 to have one or more tabs 24 which wrap around the corresponding straight section 6 to which the barbed structure 4 is affixed. In the illustrated embodiment, there is a pair of such tabs 24 spaced along the length of the corresponding strip of metal 6 and which extend from opposite sides 25 , 26 of the channel 12 . The tabs 24 enhance the join between the barbed structure 4 and the corresponding straight section 6 , and may be wrapped around the straight section 6 prior to welding in order to ensure that each straight section 6 is held securely in place prior to permanent affixing of the barbed structure 4 to the straight section 6 .
[0034] The tabs 24 may be used to hold the barbed structures 4 to the corresponding straight section 6 prior to welding of the barbed structure to the straight section. In an alternative embodiment, not illustrated in the drawings, the barbed structures 4 have no tabs, but are crimped to the corresponding straight section 6 , the crimping being sufficient to hold the barbed structure in place prior to permanent fixing, for example by welding.
[0035] The security panel 1 described above may be used in various applications where a panel-type security barrier is needed. The security panel 1 may form only a portion of a security barrier, for example a security strip atop a wall or fence, or may form all or substantially all of a security barrier. An example of the latter application is illustrated in FIG. 4 , which shows a security fence 30 comprising at least two upright fence supports 32 , which may be secured in the ground 34 , with the security panel 1 being supported by the fence supports 32 . Because of the solid interconnection between the strips of metal 6 at integral mesh nodes 8 , such a security fence 30 is very strong compared with mesh structures in which initially separate strips have been subsequently secured together by welding or riveting.
[0036] In summary, there a number of advantages to forming the security panel 1 from an expanded metal mesh 2 to which a number of separate barbed structures 4 are affixed. First of all, the fixing of the barbed structures 4 and the mesh 2 does not adversely affect the strength of the mesh. Corrosion of a metal mesh 2 is a particular problem at mesh nodes, and because each mesh node 8 in the expanded metal mesh 2 is not subject to subsequent welding, riveting or the like, each mesh node 8 will tend to be less susceptible to corrosion. The security panel 1 of the invention therefore does not need to be formed in expensive materials such as stainless steel in order to form a durable security barrier.
[0037] The particular form of barbed structure 4 and mesh straight section 6 described above also provides significant advantages, both in terms of the assembly of the structure and the ultimate deterrent value of the security mesh structure.
[0038] The invention therefore provides an economical and convenient security panel that may be used in a range of different security applications. | The present invention relates to a security panel ( 1 ), for example for use in a security barrier, and to a method of forming the security panel. The security panel ( 1 ), comprises an expanded metal mesh ( 2 ), the mesh hating apertures ( 9 ) therethrough bounded by a plurality of sides ( 11 ), at least one of said apertures ( 9 ) having at least one side ( 11 ) to which is affixed a separate barbed structure ( 4 ), the barbed structure having at least one barb ( 14 ) extending in a plane of the panel ( 1 ) in towards another side ( 11 ) of said aperture ( 9 ). | 4 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates generally to a roof ridge ventilator assembly and method of fabricating such an assembly, and more particularly to a continuous in-line method of fabricating a roof ridge ventilator assembly which can be adjusted during installation to accommodate a variety of different roof pitches and modified on-site to different lengths, closes off the interior of the roof from the elements and insects and enables venting of the space beneath the roof.
2. Description of the Related Art
Roof ridge ventilators are installed overlying the open ridge and along the length of a building roof for exhausting air from an attic or other space beneath the roof. These ventilators typically are utilized in conjunction with soffit ventilators to provide a ventilation system in which air is exhausted from the attic through the roof ridge ventilator and is replenished through the soffit ventilators.
Since roofs are constructed with different pitches and lengths, roof ridge ventilators preferably are adjustable on-site to accommodate the different pitches and lengths with a single type of ventilator. An example of an adjustable roof ridge ventilator is disclosed in U.S. Pat. No. 5,122,095 which is assigned to the same assignee as the assignee herein. That ventilator is formed in one piece and is adjustable for different pitches by bending the ventilator at its apex and for different lengths merely by cutting the ventilator with snips or the like.
Another type of adjustable roof ridge ventilator is illustrated in U.S. Pat. No. 3,481,263 which discloses a ridge type ventilator device including a pair of metal lateral sections which are connected by a hinge mechanism. The hinge mechanism includes a pair of hinge elements integrally formed with the lateral sections and a separate elongate circular hinge element having a slot within which the hinge elements of the lateral sections extend and rotate. Each lateral section also includes a pair of discrete imperforate metal end walls, one each affixed to an opposite end thereof.
Although such a ventilator is adjustable on-site to accommodate different roof pitches, it is provided completely assembled including end walls secured to each opposite end and thus appears to be manufactured at the factory for a specific length of roof. Such a ventilator can be quite long which, combined with its substantial height, is difficult and expensive to store, ship and handle.
Additionally, the hinge mechanism substantially is rigid which inhibits ease of manufacturing, especially in an in-line roll forming process, does not provide a tight seal against the elements between the connected lateral sections and, since it includes end walls attached at the factory, cannot be cut to a desired length on-site to accommodate roofs of different lengths. The ventilator also provides an undesirable high profile and requires a substantial amount of material and labor to fabricate.
It therefore would be desirable to provide a roof ridge ventilator assembly which readily and inexpensively can be manufactured in a continuous in-line operation with a minimum amount of material and labor and in predetermined lengths, can be adapted on-site to a variety of roof lengths, readily is adjustable to accommodate a variety of roof pitches and provides a seal against the elements and insects.
SUMMARY OF THE INVENTION
The invention provides a continuous in-line method of fabricating a variable pitch roof ridge ventilator assembly and the assembly thereof including providing first and second elongate substantially rectangular panels and forming the panels into a predetermined configuration. The panels then are connected with a flexible connecting cap member that is roll formed into engagement with a longitudinal upturned edge of each of the first and second panels so that the flexible connecting member enables rotation between the first and second panels and provides a seal therebetween against infiltration of the elements or insects.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a length of a roof ridge ventilator assembly manufactured according to the method of the invention and mounted on a section of a roof;
FIG. 2 is a cross-sectional view of the ventilator assembly of FIG. 1 without a filter;
FIG. 3 is an enlarged fragmentary cross-sectional view of the ventilator assembly of the invention taken along line 3--3 of FIG. 1 and in the direction in dictated generally illustrating the ventilator assembly adjusted for use with a desired roof pitch;
FIG. 4 is an enlarged fragmentary cross-sectional view of the ventilator assembly of the invention, similar to FIG. 3, illustrating the ventilator assembly adjusted for use with a roof pitch less than that of FIG. 3;
FIG. 5 is a schematic block diagram illustrating the in-line continuous method of manufacturing the ventilator assembly of the invention;
FIG. 6 is an enlarged fragmentary cross-sectional view of the ventilator assembly of the invention illustrating the cap separate from the ventilator members and, in dotted outline, the cap initially assembled thereto; and
FIG. 7 is an enlarged fragmentary cross-sectional view of the ventilator assembly of the invention, similar to FIG. 6, illustrating the cap finally assembled to the ventilator members.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1, a roof ridge ventilator assembly embodying the invention generally is designated by the reference numeral 10. The assembly 10 typically is installed overlying an open ridge 12 of a building roof 14 having shingles 16 and is utilized in conjunction with a soffit ventilation system (not illustrated.) The ventilator assembly 10, however, can be utilized in a variety of roofing or similar venting applications if desired.
The assembly 10 includes two substantially identical ventilator members 18 which are rotatably interconnected by an enlongate flexible connecting cap 20. The ventilator members 18 preferably are formed from metal, such as aluminum, and have a predetermined length such as six, eight or ten feet, which can vary. The cap 20 preferably is formed from a flexible material, such as vinyl, rubber, plastic or any similar material so long as the desired connection, rotation and flexibility is provided.
A plurality of ventilator assemblies 10 typically are aligned end-to-end and connected to the roof 14 with fasteners 21, such as screws or the like, so that the entire length of the open ridge 12 is covered by ventilator assemblies 10. In order to inhibit infiltration of insects and the elements, a filter medium 22, such as a porous, nonwoven resilient fiberglass or similar material is secured to an inside surface of each of the ventilator members 18 prior to installation as will be described in detail hereinafter.
In order to match the shingles 16 of the remainder of the roof 14 and cover the seams between successive ventilator assemblies 10, the assemblies 10 can be shingled over with cap shingles 24. Thus, the low profile of the ventilator assembly 10 combined with the cap shingles 24 enables the ventilator assembly 10 to blend with the roof line to provide an aesthetically pleasing appearance. The cap shingles 24, however, can be omitted and the seams between successive assemblies 10 can be sealed in any desired way such as by overlapping a flange (not illustrated) between successive ventilator assemblies 10 or by including a separate cover or flashing member.
Briefly, in operation, a flow of air is established in the space beneath the roof 14, such as an attic 25 of a house. The ventilator assembly 10 enables heated air which rises within the attic 25 and through the open ridge 12 to escape through the ventilator assembly 10 to the exterior of the roof 14 while restricting the elements and insects from entering the attic 25 through the ventilator assembly 10. The escaping heated air from the attic 25 typically is replenished with outside air through soffit vents (not illustrated) installed within the soffit of the roof 14 or from any other air inlet source.
As FIGS. 1 and 2 illustrate, the ventilator members 18 are formed from aluminum, sheet metal or the like in an inline continuous operation to a predetermined length, width and shape. Each ventilator member 18 substantially is formed from a single panel or sheet 26 which can be embossed and includes an inside upturned longitudinal edge 28 which, as FIG. 6 illustrates, is formed into a substantially circular hook for cooperation with the cap 20.
Each panel 26 includes a top surface 29 and a bottom surface 29a and is bent longitudinally in four places to form the ventilator member 18. The first bend is positioned along a line 30 to form a first planar surface 32 and a second planar surface 34 formed at a first angle with respect to the first planar surface 32. The second bend is positioned along a line 36 to form a third planar surface 38 formed at a second angle with respect to the second planar surface 34. Preferably, the first and second angles approximately are thirty degrees, but can vary.
The third bend is positioned along a line 40 to form a fourth planar surface 42 formed approximately at a ninety degree angle with respect to the third surface 38. Finally, the fourth bend is positioned along a line 44 to form a fifth planar surface 46 formed approximately at a forty-five degree angle with respect to the fourth surface 42.
To provide venting of air from the attic 25 through the ventilator members 18 to ambient atmosphere, the second planar surface 34 includes a plurality of louvers or slots 48 extending therethrough. Preferably, the louvers 48 have a predetermined length and are provided in sets of eight louvers each at various positions along the length of each ventilator member 18. The number, placement, size and shape of the louvers 48 can vary.
As FIG. 2 illustrates, in order to partially shield and provide a low pressure area in the vicinity of the louvers 48 and enhance exhaustion of air through the louvers 48, the fourth and fifth surfaces 42 and 46 form an upturned edge or baffle member. The upturned edge is selectively spaced from the louvers 48 to provide the desired low pressure area.
In order to prevent water from building up between the third planar surface 38 and the fourth planar surface 42, a plurality of weep holes or drain apertures 50 (illustrated in FIG. 1) can be formed through the fourth planar surface 42 of each ventilator member 18 proximate the third bend line 40. The size, spacing and shape of the weep holes 50 can vary so long as the desired draining is provided.
As FIGS. 3 and 4 illustrate, the cap 20 substantially is "C" shaped in cross-sectional configuration and engages the hooked edges 28 of each ventilator member 18 to form the finished assembly 10. The cap 20 includes first and second opposite ends 52 and 54, each of which include a shoulder 56.
As FIGS. 6 and 7 illustrate, the particular design and materials of the cap 20 and the ventilator members 18 enables the cap 20 to be installed and the ventilator members 18 connected in an in-line roll forming operation. Such an operation enables automated assembly of the ventilator assembly 10 to substantially reduce manufacturing costs.
To install the cap 20, the cap 20 is fed into position above the hooked edges 2B of two ventilator members 18 that are positioned side by side as illustrated in FIG. 6. Upon initial movement of the cap 20 in the direction of arrow "A", the shoulders 56 of the first and second ends 52 and 54 simultaneously are rolled into engagement with the edges 28.
As FIG. 7 illustrates, upon further movement or pressure on the cap 20 by the roll forming machine in the direction of arrow "A", the circular hooked edges 28 of the ventilator members 18 are bent in the direction of arrows "B" into an oval configuration and lock the ends 52 and 54 of the cap 20 onto the edges 28. The ventilator members 18 then can be rotated with respect to each other without disengaging from the cap 20 to fit a relatively steep roof pitch, as illustrated in FIG. 3, or a relatively flat roof pitch, as illustrated in FIG. 4.
It is to be noted that flexibility of the cap 20 is important. As FIGS. 3 and 4 illustrate, adjustability between ventilator members 18 is provided in-part due to the flexibility of the cap 20. The motion between the cap 20 and the edges 28 is not purely rotational, but is a combination of rotation of the ventilator members 18 within the cap 20 and flexing of the cap 20.
For example, in rotating from the position illustrated in FIG. 3 to the position illustrated in FIG. 4, the oval shape of the hooked edges 28 tends to force the ventilator members 18 slightly apart. This movement is accommodated due to the flexibility of the cap 20.
Additionally, the roll forming operation utilized to bend the edges 28 as illustrated in FIG. 7 is possible due to the flexibility of the cap 20. If the cap 20 were made of a rigid material, such as metal, it would be difficult to bend the edges 28 through the rigid cap without also distorting the rigid cap and possibly limiting its effectiveness.
The flexibility of the cap 20 also is important in order to provide a tight seal against the elements, such as wind, rain and snow, as well as insects. The cooperation between the flexible cap 20, which preferably is made of vinyl, and metal ventilator members 18 provides the desired tight seal even if the ventilator members 18 are embossed.
FIG. 5 illustrates the in-line continuous method utilized to from the ventilator assembly 10. First, ventilator members 18 are punched in a press or the like to form the louvers 48, weep holes 50 and, if desired, apertures 58 for the fasteners 21. The ventilators 18 can be punched one at a time or two or more ventilators 18 can be punched simultaneously.
Next, the ventilator members 18 are bent to form the hook edges 28 and the bend lines 30, 36, 40 and 44 to inturn form the planar surfaces 32, 34, 38, 42 and 46. The bends 28, 30, 36, 40 and 44 can be performed individually or simultaneously and in any order.
Two ventilator members 18 then are aligned with their hook edges 28 facing each other and spaced a predetermined distance apart as illustrated in FIG. 6. The first and second ends 52 and 54 of the cap 20 then are rolled into initial engagement with the edges 28.
The edges 28 then are bent into the position illustrated in FIG. 7 to connect the cap 20 to the ventilator members 18. If desired, the initial engagement and bending of the edges 28 can be done simultaneously. To complete the assembly 10, the filter 22 then is adhered to the bottom or inside surface 29a of the ventilator member 18 to cover the louvers 48.
Modifications and variations of the present invention are possible in the light of the above teachings. A specific dimension, material or construction is not required so long as the assembled device functions as herein described. It therefore is to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described. | A continuous in-line method of fabricating a variable pitch roof ridge ventilator assembly and the assembly thereof including providing first and second elongate substantially rectangular panels formed into a desired configuration and connecting the panels by roll forming a flexible connecting cap member to a longitudinal upturned edge of each of the first and second panels where the flexible connecting member enables rotation between the first and second panels and provides a seal therebetween against infiltration of the elements or insects. | 5 |
TECHNICAL FIELD
[0001] The present invention relates to a knitted elastic lingerie article constituting a sheathing lower body garment, be it of the panties type or incorporated into a longer garment such as tights.
BACKGROUND
[0002] The purpose of sheathing garments is to provide comfort, well-being and pleasure when wearing them, while smoothing out unsightly bulges, smoothing and reshaping the body without restricting its movement.
[0003] In order to provide better support for the stomach at the front of the garment and buttocks at the back, it is known from the document U.S. Pat. No. 5,465,594 to knit (for example on circular loom) the part of the panties with different stitches and/or thread in particular at the plastron, leading to a certain complication of the knitting and a modification of the appearance of the knit which is not always desirable.
[0004] It is also known from the document EP 2181613, a lower body garment comprising a part of panties on which has been deposited a dense network of resin forming an elastic ring all around the pelvis for orthopedic or physical exercise purposes. On the one hand, it is not a sheathing garment. On the other hand, the network of resin lines considerably modifies the aspect of the garment, which is not necessarily suitable for users.
BRIEF SUMMARY
[0005] The purpose of the invention is to propose a sheathing lower body garment of modern appearance, smooth, and without a visible plastron.
[0006] The purpose of the invention is achieved by a lower body garment comprising panties with an elastic base knit engaging with a network of elastic resin applied on one surface of the knitted elastic base of the panties, in the front and/or at the back of the panties, characterized in that a knitted elastic lining lighter than the base knit is provided in order to be applied freely on said surface of the base knit at least at the place of said resin network, and preferably on the entire front or back surface, on which the resin network is deposited.
[0007] By elastic or elastomer resin network deposited on a surface of the garment, it is meant that the resin has been deposited so as to form lines that are more or less wide and more or less extended surfaces, which give a certain elastic compression in a preferential direction. These lines and surfaces form a network which may be more or less dense in places and absent in certain places of the garment surface. In any case, the resin is not uniformly disposed on the entire surface of the garment, but only on a part thereof.
[0008] The surface where the resin is applied is preferably the inner surface and the lining is therefore internal, but a stylish effect can also be created by depositing the resin network on the outer surface of the base knit and by covering it with an outer lining.
[0009] Thanks to this constitution, in particular in cases of internal lining, the garment retains a perfectly uniform appearance from the outside, the resin network not being directly visible. The purpose of the inner lining is not to hide the resin network but to considerably increase comfort and reduce the risk of allergy and irritation. This very light mesh lining, for example of a specific weight of around 85 g/m 2 , can even be translucent.
[0010] The inner or outer lining is advantageously applied with great freedom against the base knit layer, namely that it is not glued onto it over its entire surface, but simply attached substantially peripherally for example on a few points or lines, and for example preferably on the edges of the panties (waistband, leg openings).
[0011] Thanks to this lightweight lining, it is possible to use in a fairly significant manner resins that are usually avoided in the context of lingerie and in particular silicone rubbers of the rather tacky type. In fact, the silicone rubber is an interesting material due to its implementation and its natural elasticity; but until now, it's fairly large adherence made the use on the external surface of underwear undesirable in order to prevent snagging with the external garment, and the use on the internal surface of underwear also undesirable because of the unpleasant contact with the skin, allergy issues and sweating. The external or internal lining resolves these issues.
[0012] The resin network comprises a network of lines or surfaces of resin disposed on the front and/or at the back of the panties. In a particularly advantageous manner, when the network is only provided on one side (front or back) of the panties, it is completed on the other side by a compression band that allows creating around the panties a continuous ring of tension lines and obtaining interesting pulling and “push-up” effects. This compression band may advantageously be a heat-sealed textile band.
[0013] The lines of elastic resin disposed on a surface of the panties advantageously form a network which ends at the two lateral edges of said surface, at least in an (usually middle and/or upper) area of the edge; the ends of the band meet at the edges of the surface of the panties with the ending area of the resin lines disposed on the other surface. In this manner, the above-mentioned ring effect is obtained.
[0014] The elastic resin network lines are advantageously curved rather than straight.
[0015] On the front surface, the network of curved lines is composed of two symmetrical sets of lines going from the front of the thigh to the opposite hip, on the edge of the front surface, the two sets intersecting on the stomach.
[0016] On the back surface, the network of curved lines is composed of lines surrounding and enclosing the two inner zones of the gluteus maximus to join one edge with the other of the back surface of the panties.
[0017] The base knit of the article, at the panties, is made of a polyamide and elastane-based jersey mesh (preferably between 10% and 30% by weight of elastane with respect to the total weight of the knit). It advantageously exhibits an elongation of 15 Newtons (according to the BS 4952 standard) equal to or greater than 110%, at least in length. The specific weight of the knit at the panties is advantageously in the range of 150 to 200 g/m 2 (ISO 3801 standard).
[0018] The lining is advantageously a lightweight mesh of which the specific weight ranges between 60 and 100 g/m 2 and the elongation, at least in one direction, is equal to or greater than that of the base knit.
[0019] The silicone is advantageously a bicomponent HTV silicone. Its Shore A hardness advantageously ranges between 10 and 40.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] Other features and advantages of the invention will become apparent from the following description of two particular embodiment examples. Reference will made to the accompanying drawings in which:
[0021] FIGS. 1A and 1B are front and rear views of a first embodiment example of panties in accordance with the invention, the lines of resin and compression bands being represented visible as if the base knit was transparent.
[0022] FIGS. 2A and 2B are front and rear views of a second embodiment example of the panties in accordance with the invention, the lines of resin and compression bands being represented visible as if the base knit was transparent.
[0023] FIG. 3 is a schematic sectional view of the layers forming the panties of the invention.
DETAILED DESCRIPTION
[0024] FIGS. 1A and 1B show the front and back of panties 1 according to the invention, which typically includes an upper opening 2 for the torso and two lower openings 3 for passage of the thigh (or leg). The panties 1 can be knitted in a circular loom and can be seamless (except possibly at the crotch part 4 ); alternatively, it may comprise two front and back panels knitted in a rectilinear loom and sewn. The knit is elastic. The upper opening 2 comprises an elastic belt, not shown, which may itself be obtained in any known manner, for example by complete knitting or sewing, gluing, by heat-sealing an added elastic part, textile or otherwise, or by applying an elastic resin.
[0025] The panties 1 are for example knitted in a jersey mesh charmeuse with rows of polyamide thread wrapped with elastane alternating with rows of non-wrapped polyamide. The proportion of elastane in the knit is around 21% and the specific weight of the knit is 185 g/m 2 and its elongation is 130% in the direction corresponding to the width of the panties.
[0026] The front 5 of the panties is covered in places by a network of silicone rubber according to a particular geometry in which are substantially distinguished two intersecting sets of more or less wide curved lines 7 ranging from the upper and middle area of a lateral edge 8 of the panties 1 to the opposite thigh opening 3 , substantially towards the middle of the front of the thigh opening. These intersecting and oblique lines 7 may have several widths and both form a decorative pattern at the same time they provide some elastic compression. These lines 7 may possibly be complemented by an upper stomach panel 9 which extends under the belt between the two lateral edges 8 and falls to a point towards the middle.
[0027] In fact, these lines 7 and this panel 9 which have been represented visible on FIG. 1A are applied on the inner surface of the front 5 and are hence not visible from the outside of the panties. The figures represent in short panties which have been turned surface inside out.
[0028] The back 6 of the panties 1 comprises a band of compression material 10 that goes from edge 8 to edge 8 , at the same middle and upper part of the edge 8 at which end the intersecting lines 7 in the front and the upper panel 9 . This band of compression material 10 may be made from a deposited silicone rubber, but, in a more economical manner, it may be a band of textile compression material laminated on the surface 6 (for example with dots of polyamide adhesive).
[0029] Here again, the compression band 10 has been represented visible on FIG. 1B , but it is preferably applied on the inner surface of the back 6 and is not visible from the outside of the panties 1 . However, it is also possible to provide it on the external surface of the back 6 in as far as it is not likely to interfere with the garments if made of a textile band and not a silicone one.
[0030] In a particular embodiment example, the compression band 10 is made by heat bonding of a yoke made of the same material as the base knit, of which it hence comes to double the thickness.
[0031] The set of intersecting lines 7 and the back compression band 10 form a sort of elastic intersecting loop which acts effectively to maintain the abdomen. The lines 7 start from the left thigh, they rise towards the waist in a fluid curve to end at the right side. The lines 7 are lined mirrored in order to adopt the same disposition symmetrically from the right thigh to the waist on the left side. As represented, the lines 7 are preferably curved, for example downwardly concave, the curved lines being in fact more flexible and comfortable than straight lines. The curved lines 7 intersect on the stomach where they act to the maximum because the amount of silicone rubber deposited on the material is therefore more concentrated therein. The lines 7 are of different widths (4 mm to 40 mm) and spaced apart (from 2 to 6 mm), the widest line being in the example represented in the center of the lines 7 .
[0032] FIG. 3 schematically shows a section of the front of the panties 1 with the knit forming the front 5 on which are applied lines or surfaces 7 of silicone rubber, preferably on the internal surface of the front. These applications penetrate very slightly into the knit 5 and do not pass through it, so that they are not directly visible from the other side of the knit 5 . Above the base knit 5 , a lightweight internal lining 20 has been disposed free over most of the surface, in any case facing the network of intersecting lines 7 . The lining is attached to the base knit for example at the upper and lower borders corresponding to the torso opening 2 and leg opening 3 . The attachment can be done for example by bonding in a manner known per se, with a glued or stitched added collar 21 , and/or by topstitching 22 . Preferably, the lining 20 is provided over the entire front surface, on the inside, and can also be provided on the entire back surface although it not being technically essential where there is no silicone.
[0033] The lining is a mesh including 10% elastane for a specific weight of the knit of 85 g/m 2 . Its elongation is of 145% in the direction corresponding to the width of the panties.
[0034] The silicone rubber is in a particular example a silicone (polydimethylsiloxane with vinyl groups and auxiliaries) of the Elastosil® brand and of LR 3003/10 grade from Wacker, curable under heat, and bicomponent (A+B). The silicone is screen printed on one surface of the panties and heat polymerized (for example 175° C. for 30 seconds under infrareds, other heating methods being of course possible).
[0035] The thickness of deposited silicone is about 0.20 to 0.25 mm (a thickness in the range of that of the base knit), which for the various sizes of considered panties represents a total weight of 16 g to 23 g.
[0036] Various measurements of maximum elongation A were carried out (in the width direction of the panties, unless otherwise specified), of the return force F, as well as the return force F30 at 30% elongation for different combinations of layers including the base knit (T), the lining (D), the base knit+silicone (TS), the base knit+compression band (TC):
[0000]
T
A = 130%
F = 425 cN at 80%
F30 = 200 cN
D
A = 145%
F = 195 cN at 80%
F30 = 100 cN
TS
A = 61%
F = 1191 cN at 50%
F30 = 1000 cN
TS + D
A = 47%
F30 = 939 cN
TC
A = 40%
F30 = 828 cN
[0037] These measurements show that with the application of silicone, the base knit retains an elongation of 61% and has become five times more nervous (this is what F30 indicates). The material is hence far from rigid. Therefore, the article is easier to pull on and the material moves with the body while compressing the stomach and waist.
[0038] The impact of the addition of the lining on the elongation and nervousness of the raw material with the application of silicone is very small. However, as mentioned above, its protective role is essential.
[0039] The measurements of the elongation and nervousness of the complex on the back side at the waist and hips are in the continuity of those found on the front sides of the product. The draw starts from the left thigh, rises, crosses the stomach to the right side at the waist and joins the yoke on the back, which takes over and goes around the back. On the other side of the waist (left front) new lines of silicone take over to pull the stomach such an elastic bandage ending on the right thigh.
[0040] FIGS. 2A and 2B show another embodiment in which the silicone is applied to the back of the panties to obtain a buttocks lift effect. In this case, the back part 6 of the panties 1 comprises, on its internal surface a network of curved lines 7 ′ of silicone rubber which are here disposed so as to surround the area 12 in the shape of an ossicle or kidney, and substantially corresponding to the internal zone of the gluteus maximus. Some of the curved lines 7 ′ almost entirely surround the zone 12 , such as the line 7 ′ a , others border the zone more widely and join the opposite edges 8 , such as the lines 7 ′ b.
[0041] All the lines 7 ′ ending at the edges 8 end therein in a median zone of the edge 8 where the elastic tensile stresses are taken to the other side of the panties, that is to say, in the front 5 , by a compression band 10 ′ similar to the band 10 of FIG. 1B and possibly concave on its lower part in the same way. As in the previous embodiment, a lightweight lining is provided, intended to be disposed freely at least in front of the networks of lines 7 ′, that is to say, on the back part of the panties. The lining may also extend over the entire panties.
[0042] The zone 12 (at least its lower part) and the neighboring lines of silicone 7 ′ at the bottom of the zone 12 are advantageously disposed in a rounded thermoforming mold to give a shape to the back part of the panties. During this operation, only the fabric takes the curved form, the silicone retaining its memory of previous form.
[0043] Wearing tests were conducted with the two embodiments and have shown 100% satisfaction on the part of users.
[0044] It has been described here separate panties but the invention can be applied to the panties part of a longer garment and even tights. | The invention relates to a lower body garment comprising pants ( 1 ) with a knitted elastic base engaging with a network of rows of resin ( 7 ) applied to one surface of the elastic knit which forms the base of the pants, on the front and/or rear of the pants, characterised in that a knitted elastic lining ( 20 ) which is lighter than the base knit ( 5, 6 ) is provided in order to be applied freely to said surface of the base knit ( 5, 6 ) at least on said network of rows of resin ( 7 ). | 3 |
FIELD OF THE INVENTION
The present invention is generally directed to the field of power supplies. More specifically, the present invention is directed to providing adaptive digital control of the power factor correction front end of a switching mode power supply.
BACKGROUND OF THE INVENTION
A power supply unit converts main AC voltage to one or more regulated DC voltages supplied to one or more loads, such as the internal components of a computer, server, or other electrical device. A digitally controlled switching mode power supply unit typically includes a primary side for power factor correction (PFC) and AC-to-DC voltage conversion, and a secondary side for DC-to-DC voltage conversion. The primary side is under control of a first digital signal controller (DSC) and the secondary side is under control of a separate second DSC or a digital control chip.
Adaptive control is a control method used by a controller which must adapt to a controlled system with parameters which vary, or are initially not optimized. Applying adaptive control to switching mode power supplies improves system performance. However, due to the non-linearity of the power train circuitry to be controlled, designing control parameters used in such an adaptive control is challenging.
One conventional approach for designing a loop controller for a switching mode power supply is to initially design control loop parameters based on a small signal model and Bodeplot. There is a separate small signal model for the primary side and the secondary side. Small signal modeling is a common analysis technique used to approximate the behavior of nonlinear devices with linear equations. In this manner, the power supply can be modeled using a mathematical model. Stability theory is then applied to design the digital controller in order to ensure that the switched mode power supply operates with sufficient phase margin and gain margin. In other words, the loop controller is designed to ensure that the power supply can operate at both steady state condition and transient state condition. The designed control loop parameters are finalized by trial and error, which is extremely time consuming, such as ranging from a couple of days to a few weeks. Additionally, the system performance is still subject to temperature and environment changes, which result in changes to the control loop parameters. As such, optimized performance can not be achieved as operating conditions change.
Another approach for designing the loop controller for a switching mode power supply is based on a system identification technique. The system identification technique adds functionality to the second DSC on the secondary side of the power supply. The second DSC is configured to determine system characteristics of the switching mode power supply under the current operating condition and to then adjust the control loop parameters according to the determined system characteristics. Parameters of the secondary-side small signal model are identified and then the parameters of the secondary-side loop controller are adjusted accordingly. To determine the system characteristics, such as the transfer function of the small signal model, white noise is injected into the power supply. The second DSC calculates the variance and covariance resulting from the injected noise to determine the system characteristics. Proper control loop parameters are calculated using the determined system characteristics, and these calculated control loop parameters replace the previous control loop parameters in the small signal model used by the second DSC. However, it is impractical to implement the system identification technique in a functioning power supply since injecting white noise can impact the stability of the system and even damage the power supply. Further, implementation of the system identification technique results in significant signal processing burden which requires a more powerful and expensive second DSC.
SUMMARY OF THE INVENTION
A method is directed to providing adaptive digital control for the PFC stage or front-end of a switching mode power supply. The method uses an evaluation model to adjust the control loop parameters of the control algorithm used by a controller on the primary side of the power supply. The method performs a series of step adjustments of the control loop parameter values to determine optimized values. In some embodiments, the method determines and compares the line current THD corresponding to different control loop parameter values. The method provides simplified digital control loop design, optimizes PFC front-end performance, improves system efficiency by decreasing harmonic ripples, and reduces labor cost and time to market due to shorter research and development phase. System performance optimization is fully adaptive adjusted for changes in operating conditions due to, for example, environmental and temperature variations.
In an aspect, a method of adaptively controlling a power supply is disclosed. The method includes configuring a switching mode power supply to include a transformer having a primary side and a secondary side, a primary side circuit under control of a primary side controller and a secondary side circuit under control of a secondary side controller, wherein the primary side controller controls the primary side circuit using a control algorithm that includes control loop parameters. The method also includes setting the control loop parameters to default control loop parameter values, and determining line current total harmonic distortion corresponding to the default control loop parameter values. The method also includes adjusting the control loop parameters, and determining line current total harmonic distortion corresponding to the adjusted control loop parameters. The method also includes comparing the line current total harmonic distortion corresponding to the adjusted control loop parameters to the line current total harmonic distortion corresponding to the default control loop parameter values to determine a lowest line current total harmonic distortion. The method also includes setting optimized control loop parameters using the control loop parameters corresponding to the lowest line current total harmonic distortion, and executing the control algorithm using the optimized control loop parameters.
Determining line current total harmonic distortion can include measuring a line current and applying a Fast Fourier Transform to the measured line current. Determining line current total harmonic distortion can further include performing a power spectral density analysis on the Fast Fourier Transform result. Alternatively, determining line current total harmonic distortion can include passing a line current through a set of band pass filters. Adjusting the control loop parameters can include increasing or decreasing each control loop parameter by a predefined increment. The primary side circuit can be configured for power factor correction and AC-to-DC voltage conversion. The secondary side circuit can be configured for DC-to-DC voltage conversion.
In another aspect, another method of adaptively controlling a power supply is disclosed. The method includes configuring a switching mode power supply to include a transformer having a primary side and a secondary side, a primary side circuit under control of a primary side controller and a secondary side circuit under control of a secondary side controller, wherein the primary side controller controls the primary side circuit using a control algorithm that includes control loop parameters. The method also includes setting the control loop parameters to default control loop parameter values, and determining line current total harmonic distortion corresponding to the default control loop parameter values. The method also includes adjusting the control loop parameters, and determining line current total harmonic distortion corresponding to the adjusted control loop parameters. The method also includes comparing the line current total harmonic distortion corresponding to the adjusted control loop parameters to the line current total harmonic distortion corresponding to the default control loop parameter values to determine a lowest line current total harmonic distortion. The method also includes setting improved control loop parameters using the control loop parameters corresponding to the lowest line current total harmonic distortion. The method also includes performing one or more iterations of adjusting the improved control loop parameters for a present iteration, determining a resulting line current total harmonic distortion corresponding to the present iteration, comparing the resulting line current total harmonic distortion of the present iteration to the determined line current total harmonic distortion corresponding to the improved control loop parameters of a previous iteration, and resetting the improved control loop parameters using the control loop parameters corresponding to the lowest line current total harmonic distortion, wherein the one or more iterations are repeated until an optimized criteria is achieved and the improved control loop parameters are set as optimized control loop parameters. The method also includes executing the control algorithm using the optimized control loop parameters.
Determining line current total harmonic distortion can include measuring a line current and applying a Fast Fourier Transform to the measured line current. Determining line current total harmonic distortion can further include performing a power spectral density analysis on the Fast Fourier Transform result. Alternatively, determining line current total harmonic distortion can include passing a line current through a set of band pass filters. The optimized criteria can include determining that the determined line current total harmonic distortion is less than a line current total harmonic distortion minimum threshold value. Adjusting the improved control loop parameters for the present iteration can include increasing or decreasing each improved control loop parameter by a predefined increment. The optimized criteria can be achieved when a minimum line current total harmonic distortion is determined through successive incrementing and decrementing of the improved control loop parameters. Adjusting the control loop parameters can include increasing or decreasing each control loop parameter by a predefined increment. The primary side circuit can be configured for power factor correction and AC-to-DC voltage conversion. The secondary side circuit can be configured for DC-to-DC voltage conversion.
In yet another aspect, an apparatus for adaptively controlling a power supply is disclosed. The apparatus includes a switching mode power supply with a transformer having a primary side circuit and a secondary side circuit, and a primary side controller configured to control the primary side circuit using a control algorithm that includes control loop parameters. The control algorithm is configured to set the control loop parameters to default control loop parameter values, and to determine line current total harmonic distortion corresponding to the default control loop parameter values. The control algorithm is also configured to adjust the control loop parameters, and determine line current total harmonic distortion corresponding to the adjusted control loop parameters. The control algorithm is also configured to compare the line current total harmonic distortion corresponding to the adjusted control loop parameters to the line current total harmonic distortion corresponding to the default control loop parameter values to determine a lowest line current total harmonic distortion. The control algorithm is also configured to set optimized control loop parameters using the control loop parameters corresponding to the lowest line current total harmonic distortion, and execute the control algorithm using the optimized control loop parameters.
The apparatus also includes a secondary side controller configured to control the secondary side circuit. The control algorithm can be further configured to perform one or more iterations of adjusting the improved control loop parameters for a present iteration, determine a resulting line current total harmonic distortion corresponding to the present iteration, compare the resulting line current total harmonic distortion of the present iteration to the determined line current total harmonic distortion corresponding to the improved control loop parameters of a previous iteration, and reset the improved control loop parameters using the control loop parameters corresponding to the lowest line current total harmonic distortion, wherein the one or more iterations are repeated until an optimized criteria is achieved and the improved control loop parameters are set as optimized control loop parameters. The primary side controller can be configured to determine line current total harmonic distortion by measuring a line current and applying a Fast Fourier Transform to the measured line current. The primary side controller can be further configured to perform a power spectral density analysis on the Fast Fourier Transform result. Alternatively, the apparatus can also include a set of band pass filters and the primary side controller can be further configured to determine line current total harmonic distortion by passing a line current through the set of band pass filters. The primary side controller can be configured to adjust the control loop parameters by increasing or decreasing each control loop parameter by a predefined increment. The primary side circuit can be configured for power factor correction and AC-to-DC voltage conversion. The secondary side circuit can be configured for DC-to-DC voltage conversion.
BRIEF DESCRIPTION OF THE DRAWINGS
Several example embodiments are described with reference to the drawings, wherein like components are provided with like reference numerals. The example embodiments are intended to illustrate, but not to limit, the invention. The drawings include the following figures:
FIG. 1 illustrates a switching mode power supply unit under digital control for supplying power to a load according to an embodiment.
FIG. 2 illustrates a method of adaptively controlling the power supply unit through execution of the control algorithm by the first DSC, or other primary side controller, according to an embodiment.
DETAILED DESCRIPTION OF THE EMBODIMENTS
Embodiments of the present application are directed to a method of adaptive digital control of the power factor correction front end of a switching mode power supply. Those of ordinary skill in the art will realize that the following detailed description of the method is illustrative only and is not intended to be in any way limiting. Other embodiments of the method will readily suggest themselves to such skilled persons having the benefit of this disclosure.
Reference will now be made in detail to implementations of the method as illustrated in the accompanying drawings. The same reference indicators will be used throughout the drawings and the following detailed description to refer to the same or like parts. In the interest of clarity, not all of the routine features of the implementations described herein are shown and described. It will, of course, be appreciated that in the development of any such actual implementation, numerous implementation-specific decisions must be made in order to achieve the developer's specific goals, such as compliance with application and business related constraints, and that these specific goals will vary from one implementation to another and from one developer to another. Moreover, it will be appreciated that such a development effort might be complex and time-consuming, but would nevertheless be a routine undertaking of engineering for those of ordinary skill in the art having the benefit of this disclosure.
FIG. 1 illustrates a switching mode power supply unit under digital control for supplying power to a load according to an embodiment. The power supply unit includes a primary side for power factor correction (PFC) and AC-to-DC voltage conversion, and a secondary side for DC-to-DC voltage conversion. The primary side receives an AC input voltage, such as the main line AC voltage, and outputs a DC bus voltage, such as 400V. The secondary side converts the DC bus voltage output from the primary side to a desired DC voltage level that is used by a coupled load, such as 15V, 5V, or 3.3V. The PFC stage on the primary side is digitally controlled by a first DSC. The DC-to-DC stage on the secondary side is digitally controlled by a second DSC. There is bi-directional or unidirectional communication signals sent between the first DSC and the second DSC.
The first DSC includes a control algorithm which when executed provides a method of adaptive digital control of the PFC front end of the switching mode power supply unit. In some embodiments, the method optimizes system performance by minimizing line current total harmonic distortion (THD). FIG. 2 illustrates a method of adaptively controlling the power supply unit through execution of the control algorithm by the first DSC, or other primary side controller. The control algorithm includes control loop parameters having numerical values which are stored and retrieved by the first DSC when executing the control algorithm. At the step 10 , the control loop parameters are initialized to default values. At the step 20 , the power supply is operated under control of first DSC with the control loop parameters set at the default values. At the step 30 , while operating in normal, or steady-state, the line current is sampled by the first DSC. Normal state is that state where the power supply operates within predefined operating parameters, for example, no over voltage, no over current, and no over temperature.
At the step 40 , the sampled line current is processed by the first DSC to determine the line current THD. The line current THD determined at this step corresponds to the default values of the control loop parameters. The line current can be processed either in firmware or hardware. In some embodiments, a Fast Fourier Transform is applied to the sampled line current to generate the fundamental line current component and corresponding harmonics, referred to in whole as the line current THD. An additional power spectral density analysis can performed on the Fast Fourier Transform result, although typically the Fast Fourier Transform result is sufficient. Power spectral density, which represents a measurement of the energy at various frequencies by using complex conjugate, is analyzed after the Fast Fourier Transform for helping identify harmonics in cases of quite noisy environment. In other embodiments, a set of band pass filters are used and the line current is passed through the band pass filters to generate the line current THD. Setting the control loop parameters to the default values, sampling the line current, and determining the line current THD corresponding to the control loop parameter default values corresponds to a first iteration of the control algorithm. The control algorithm is configured as an evaluation model where the control loop parameters are systematically adjusted and the resulting line current THD is evaluated to arrive at optimized values. The control algorithm performs multiple iterations of setting the control loop parameter values, sampling the line current, and determining the line current THD corresponding to the set control loop parameter values for the present iteration. The line current THD for the present iteration is compared to the line current THD from the previous iteration to determine the better control loop parameter values. In some embodiments, the lower line current THD is considered to be the better configuration, and the corresponding control loop parameter values are considered to be the better values. Additional iterations determine better and better control loop parameter values until a defined criteria is reached or the lowest line current THD is found.
After the first iteration is completed at the step 40 , the control loop parameter values are adjusted at the step 50 . In order to avoid unstable operation of the power supply from adaptive control loop parameters, reasonable parameter boundaries are set for safe operation during parameter adjustments. Many different techniques can be used to systematically adjust the control loop parameter values until optimized values are determined. In some embodiments, each of the control loop parameter values is incremented and/or decremented by a defined interval value, such as in a mountain-climbing interval technique. In an exemplary implementation, each of the control loop parameter values is initially incremented by a predefined interval value. The interval value can be the same for each control loop parameter, or the interval value can be different from parameter to parameter. In this exemplary implementation, the initial adjustment is an increment. Alternatively, the initial adjustment for each control loop parameter value can be a decrement. Still alternatively, the initial adjustment can be an increment for some control loop parameters, and a decrement for other control loop parameters.
At the step 60 , the power supply is operated under control of first DSC with the control loop parameters set at the adjusted values, as set at the step 50 . At the step 70 , while operating in normal state, the line current is sampled by the first DSC. At the step 80 , the sampled line current is processed by the first DSC to determine the line current THD. The line current THD determined at this step corresponds to the adjusted values of the control loop parameters set during the present iteration, which at this stage is the second iteration.
At the step 90 , the first iteration line current THD determined at the step 40 is compared to the second iteration line current THD determined at the step 80 . The comparison determines which control loop parameter values result in the better configuration. In this exemplary implementation, the lower line current THD is considered to be the better configuration. If the line current THD corresponding to the first iteration is considered the better configuration, then the control loop parameter values are set at the default values. If the line current THD corresponding to the second iteration is considered the better configuration, then the control loop parameter values are set at the adjusted values, as in the step 50 . In this manner, the control loop parameter values are optimized to either the default values or the adjusted values. At the step 100 , one or more optional additional iterations can be performed to further optimize the control loop parameter values. Each additional iteration includes further adjusting the control loop parameter values, sampling the line current while operating in the normal state, determining the line current THD, and comparing the line current THD of the present iteration to the line current THD corresponding to the better configuration determined in the previous iteration.
If an additional iteration is to be performed, it is determined whether the control loop parameter values are to be incremented or decremented. If the most recent iteration, for example the second iteration, was determined to be the better configuration compared to the preceding iteration, for example the first iteration, then the control loop parameter values are adjusted in the same direction as the most recent iteration. For example, if the control loop parameter values were incremented in the second iteration, and the second iteration had the better configuration, then for the third iteration the control loop parameter values are again incremented. The line current is then sampled while the system operates in the normal state, the line current THD is determined and compared to the previous iteration. It is understood, that the “previous iteration” and the line current THD and control loop parameter values corresponding to the previous iteration refer to the determined better configuration, such that the present iteration is compared to the better configuration determined in the previous iteration. Subsequent iterations will continue to adjust the control loop parameter values in this same direction until the line current THD is not improved.
In the case where the second iteration does not result in an improved line current THD as compared to the first iteration, then for the third iteration the control loop parameter values are adjusted in the opposite direction as the adjustments made in the second iteration. For example, if the control loop parameter values were incremented in the second iteration, and the first iteration had the better configuration, then for the third iteration the control loop parameter values are decremented. The line current THD corresponds to the third iteration is compared to the line current THD of the first iteration, as in this case the better configuration from the “previous iteration” corresponds to the control loop parameter values and line current THD of the first iteration. If the line current THD corresponding to the third iteration is improved compared to the line current THD from the first iteration, then subsequent iterations will continue to adjust the control loop parameter values in this same direction, decrements in this case, until the line current THD is not improved.
In some embodiments, the additional iterations are performed with the increment or decrement adjustments made in the same direction, as described above, until a present iteration fails to result in an improved line current THD. At this point, the control loop parameter values from the previous iteration are determined to be optimized values. At the step 110 , the system commences normal operation under control of the primary side controller executing the control algorithm using the optimized control loop parameter values.
In other embodiments, further refinement of the control loop parameter values can be performed once a present iteration fails to result in an improved line current THD. In some embodiments, a spiral approach can be used. For example, if the control loop parameter values had most recently been incremented, and the resulting line current THD did not improve, then a subsequent iteration can be performed where the control loop parameter values are decremented, but by a small interval than the preceding increments. The resulting line current THD is compared to the previous best configuration as before. Further iterations can be performed where the control loop parameter values are adjusted as increments or decrements in smaller by smaller intervals, thereby spiraling in on optimized control loop parameter values. A predefined criteria is used to conclude the refinement loop. For example, a defined number of refinement iterations can be performed, a minimum increment/decrement interval size is reached, or a minimum inter-iteration improvement in the line current THD is achieved. It is understood that other criteria can be used. In some cases, use of the refinement methodology enables larger increment sizes in the first one or more adjustments.
It is understood that the control loop parameter values, line current THDs, and any other corresponding results and variables associated with each iteration can be stored in memory for look-up and comparison to determine the optimized control loop parameter values. It is also understood that criteria other than the lowest line current THD can be used to determine the better configuration.
The method can be implemented at any time to determine optimized control loop parameter values. For example, the method can be implemented at device power-up, at defined time periods or intervals, or in response to changing operating conditions such as changes in the load, line voltage, or environmental conditions.
The method described above utilizes an evaluation model for optimizing the control loop parameter values used within the control algorithm executed by the primary side controller. The evaluation model utilizes a series of step adjustment of the control loop parameter values to determine optimized values. In the exemplary implementation described above, the evaluation model determines and compares the line current THD corresponding to different control loop parameter values. The evaluation model does not use a small signal model for determining the control loop parameter values, and as such also does not inject white noise into the system for identifying the small signal model, as in conventional approaches.
The evaluation model can be implemented as firmware executed by the primary side controller, or the primary side controller can be have a dedicated design for implementing the evaluation model, or the evaluation model can be implemented through the use of additional or modified hardware. For cost effectiveness, the part of firmware code for processing adaptive parameters' adjustment can be executed in firmware background operation.
The present application has been described in terms of specific embodiments incorporating details to facilitate the understanding of the principles of construction and operation of the method. Many of the components shown and described in the various figures can be interchanged to achieve the results necessary, and this description should be read to encompass such interchange as well. As such, references herein to specific embodiments and details thereof are not intended to limit the scope of the claims appended hereto. It will be apparent to those skilled in the art that modifications can be made to the embodiments chosen for illustration without departing from the spirit and scope of the application. | A method is directed to providing adaptive digital control for the PFC front-end of a switching mode power supply. The method uses an evaluation model to adjust control loop parameters of a control algorithm used by a controller on the primary side of the power supply. The method performs a series of step adjustments of the control loop parameter values to determine optimized values. In some implementations, the method determines and compares the line current THD corresponding to different control loop parameter values. The method provides simplified digital control loop design, optimizes PFC front-end performance, improves system efficiency by decreasing harmonic ripples, and reduces labor cost and time to market due to shorter research and development phase. System performance optimization is fully adaptive adjusted for changes in operating conditions due to, for example, environmental and temperature variations. | 7 |
RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. patent application Ser. No. 11/293,888, which claims priority to Japanese Patent Application No. 2004-101447, filed on Dec. 3, 2004, both of which are incorporated by reference.
TECHNICAL FIELD
[0002] The present invention relates to a thin film transistor array substrate, and more particularly to a thin film transistor array substrate and a fabricating method thereof that are adaptive for minimizing a residual image to thereby improve picture quality.
DESCRIPTION OF THE RELATED ART
[0003] Generally, a liquid crystal display (LCD) controls light transmittance of a liquid crystal using an electric field to thereby display a picture. To this end, the LCD includes a liquid crystal display panel having liquid crystal cells arranged in a matrix, and a driving circuit for driving the liquid crystal display panel. 2. Background Information
[0004] The liquid crystal display panel includes a thin film transistor array substrate and a color filter array substrate opposed to each other, a liquid crystal injected between two substrates, and a spacer for keep a cell gap between two substrates.
[0005] The color filter array substrate consists of color filters formed for each liquid crystal cell, black matrices for dividing the color filters and reflecting external light, common electrodes for commonly applying reference voltages to the liquid crystal cells, and an alignment film coated thereon.
[0006] The liquid crystal display panel is completed by preparing the thin film array substrate and the color filter array substrate individually, joining them together, injecting liquid crystal between the joined substrates, and sealing the joined substrates.
[0007] FIG. 1 is a plan view illustrating a related art thin film transistor array substrate, and FIG. 2 is a section view of the thin film transistor array substrate taken along the I-I′ line in FIG. 1 .
[0008] Referring to FIG. 1 and FIG. 2 , the thin film transistor array substrate includes a gate line 2 and a data line 4 provided on a lower substrate 42 to intersect each other with the gate insulating film 44 therebetween, a thin film transistor 6 provided at each intersection, and a pixel electrode 18 provided at a cell area having a crossing structure. Further, the thin film transistor array substrate includes a storage capacitor 20 provided at an overlapped portion between the pixel electrode 18 and the pre-stage gate line 2 . The thin film transistor 6 includes a gate electrode 8 connected to the gate line 2 , a source electrode 10 connected to the data line 4 , a drain electrode 12 connected to the pixel electrode 18 , and an active layer 14 overlapping the gate electrode 8 and defining a channel between the source electrode 10 and the drain electrode 12 . The active layer 14 is provided to overlap with the data line 4 , the source electrode 10 and the drain electrode 12 , and further includes a channel portion between the source electrode 10 and the drain electrode 12 . On the active layer 14 , an ohmic contact layer 48 is deposited for making an ohmic contact with the data line 4 , the source electrode 10 , the drain electrode 12 .
[0009] The thin film transistor 6 allows a pixel voltage signal applied to the data line 4 to be charged into the pixel electrode 18 and kept in response to a gate signal applied to the gate line 2 .
[0010] The pixel electrode 18 is connected, via a first contact hole 16 passing through a protective film 50 , to the drain electrode 12 of the thin film transistor 6 . The pixel electrode 18 generates a potential difference with respect to a common electrode provided at an upper substrate (not shown) by the charged pixel voltage signal. This potential difference rotates a liquid crystal positioned between the thin film transistor array substrate and the upper substrate owing to dielectric anisotropy of the liquid crystal and transmits light inputted, via the pixel electrode 18 , from a light source (not shown) toward the upper substrate.
[0011] The storage capacitor 20 is formed by a pre-stage gate line 2 and a pixel electrode 18 . The gate insulating film 44 and the protective film 50 are located between the gate line 2 and the pixel electrode 18 . The storage capacitor 20 allows a pixel voltage signal charged in the pixel electrode 18 to be stably maintained until the next pixel voltage is charged.
[0012] Hereinafter, a method of fabricating the thin film transistor substrate will be described in detail with reference to FIG. 3A to FIG. 3D .
[0013] Firstly, a gate metal layer is formed on the lower substrate 42 by a deposition technique such as sputtering. Then, the gate metal layer is patterned by photolithography and etching using a first mask to thereby form gate metal patterns including the gate line 2 , the gate electrode 8 as shown FIG. 3A .
[0014] Next, the gate insulating film 44 , an amorphous silicon layer, a n+ amorphous silicon layer and a source/drain metal layer are sequentially provided on the lower substrate 42 provided with the gate metal patterns by deposition techniques such as plasma enhanced chemical vapor deposition (PECVD) and sputtering, etc.
[0015] Then, a source/drain pattern including the data line 4 , the source electrode 10 and the drain electrode 12 is formed on the source/drain metal layer by photolithography and etching using a diffractive exposure mask; and a semiconductor pattern 45 including the active layer 14 and the ohmic contact layer 48 is formed at the lower portion of the source/drain pattern.
[0016] Alternatively, the semiconductor pattern 45 may be provided individually with the source/drain pattern using a separate mask process.
[0017] The protective film 50 is entirely formed on the gate insulating film 44 provided with the source/drain pattern by a deposition technique such as PECVD, etc. Thereafter, the protective film 50 is patterned by photolithography and etching to thereby provide a contact hole 16 as shown FIG. 3C . The contact hole 16 passes through the protective film 50 and exposes the drain electrode 12 .
[0018] A transparent electrode material is entirely deposited onto the protective film 50 by a deposition technique such as sputtering, etc. Thereafter, the transparent electrode material is patterned by photolithography and etching to thereby provide the pixel electrode 18 as shown FIG. 3D . The pixel electrode 18 is electrically connected, via the first contact hole 16 , to the drain electrode 12 . Further, the pixel electrode 18 overlaps the pre-stage gate line 2 with the gate insulating film 44 and the protective film 50 therebetween, thereby providing the storage capacitor 20 .
[0019] In the TFT array substrate, as shown in FIG. 4 , the gate electrode 8 of the TFT 6 is supplied with a gate voltage (Vg) and the source electrode 10 thereof is supplied with a data voltage Vd. If a gate voltage more than a threshold voltage is applied to a gate voltage 8 of the TFT 6 , then a channel is formed between the source electrode 10 and the drain electrode 12 . In this case, the data voltage Vd is charged, via the source electrode 10 and the drain electrode 12 of the TFT 6 , into the liquid crystal cell Clc and the storage capacitor 20 Cst.
[0020] Herein, a feed-through Voltage ΔVp, that is, a difference between the data voltage Vd and a voltage Vlc charged in the liquid crystal cell Clc is defined by the following equation:
Δ Vp = Cgd Cgd + Clc + Cst Δ Vg ( 1 )
wherein Cgd is a parasitic capacitor formed between the gate terminal and the drain terminal of the TFT; and ΔVg is a difference voltage between a voltage Vgh and a voltage Vgl.
[0021] Such a feed-through voltage ΔVp causes a deterioration of picture quality such as a residual image, for example, a flicker. Accordingly, studies have been undertaken for reducing the deterioration of picture quality by maximizing the capacitance Cst of the storage capacitor 120 in order to minimize the feed-through voltage ΔVp as indicated in the above equation (1). However, as the capacitance Cst of the storage capacitor 120 increases, an area occupied by the storage capacitor 120 increases commensurately. This reduces the aperture ratio of the pixel. Furthermore, if a thickness of the protective film 50 and the gate insulating film 44 is reduced, then the amount of insulation provided by the gate insulating film 44 and the protective film 50 decreases.
SUMMARY
[0022] By way of introduction only, a thin film transistor array substrate according to one aspect of the present invention includes a gate line and a data line crossing each other; a thin film transistor provided at each intersection between the gate line and the data line; a storage capacitor including another gate line and/or a common line separated from the gate line; a protective film that covers the data line and the thin film transistor and the at least one of the other gate line or the common line in the storage capacitor, the protective film in the storage capacitor thinner than the protective film that covers the data line and the thin film transistor, the protective film having a contact hole exposing a drain electrode of the thin film transistor; and a pixel electrode connected, via the contact hole, to the drain electrode of the thin film transistor, the pixel electrode forming one electrode of the storage capacitor.
[0023] A method of fabricating a thin film transistor array substrate according to another aspect of the present invention includes forming a gate line and a common line and/or another gate line separated from the gate line on a substrate; forming a data line crossing the gate line and a thin film transistor provided at the intersection between the gate line and the data line; forming a protective film covering the thin film transistor; removing a portion of the protective film to form a contact hole exposing a drain electrode of the thin film transistor and at least thin the protective film in a storage capacitor area; and forming a pixel electrode connected, via the contact hole, to the drain electrode of the thin film transistor, a storage capacitor being formed that includes the pixel electrode and at least one of the common line or the other gate line
[0024] In another embodiment, a liquid crystal display includes a thin film transistor array substrate, a substrate that opposes the thin film transistor array substrate, and liquid crystal between the substrates. The thin film transistor array substrate includes: a first gate line and a data line crossing each other on a transparent substrate; a thin film transistor provided at an intersection of the first gate line and the data line; a protective film that covers the data line and the thin film transistor; a gate insulating film that covers the first gate line; and a pixel electrode connected to a drain electrode of the thin film transistor. The pixel electrode is separated from a conductive material by an insulator to form a storage capacitor in a storage capacitor area. The insulator includes the protective film and/or the gate insulating film. The thickness of the insulator in the storage capacitor area is thinner than a combined thickness of the protective film and the gate insulating film outside the storage capacitor area.
BRIEF DESCRIPTION OF THE DRAWINGS
[0025] The following detailed description of the embodiments of the present invention reference the accompanying drawings in which:
[0026] FIG. 1 is a plan view showing a portion of a related art thin film transistor array substrate;
[0027] FIG. 2 is a section view of the thin film transistor array substrate taken along the I-I′ line in FIG. 1 ;
[0028] FIG. 3A to FIG. 3D are section views illustrating a method of fabricating the thin film transistor substrate shown in FIG. 2 ;
[0029] FIG. 4 is a waveform diagram of a voltage applied to the liquid crystal panel;
[0030] FIG. 5 is a section view showing a portion of a thin film transistor array substrate according to a first embodiment of the present invention;
[0031] FIG. 6A to FIG. 7B are section views illustrating a method of fabricating the thin film transistor substrate according to a first embodiment of the present invention;
[0032] FIG. 8 is a section view showing a portion of a thin film transistor array substrate according to a second embodiment of the present invention;
[0033] FIG. 9A to FIG. 9C are section views illustrating a method of fabricating the thin film transistor substrate according to a second embodiment of the present invention; and
[0034] FIG. 10 is a plan view showing a film transistor array substrate according to a third embodiment of the present invention.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0035] Hereinafter, the preferred embodiments of the present invention will be described in detail with reference to FIG. 5 to FIG. 10 .
[0036] FIG. 5 is a section view showing a thin film transistor array substrate according to a first embodiment of the present invention.
[0037] Referring to FIG. 5 , the thin film transistor array substrate includes a gate line 102 and a data line 104 provided on a lower substrate 142 to intersect each other with a gate insulating film 144 therebetween, a thin film transistor 106 provided at each intersection, and a pixel electrode 118 provided at a cell area having a crossing structure. Further, the thin film transistor array substrate includes a storage capacitor 120 provided at an overlapped portion between the pixel electrode 118 and the pre-stage gate line 102 . The thin film transistor 106 includes a gate electrode 108 connected to the gate line 102 , a source electrode 110 connected to the data line 104 , a drain electrode 112 connected to the pixel electrode 118 , and an active layer 114 overlapping the gate electrode 108 and defining a channel between the source electrode 110 and the drain electrode 112 . The active layer 114 overlaps the data line 104 , the source electrode 110 and the drain electrode 112 and has a channel portion between the source electrode 110 and the drain electrode 112 . On the active layer 114 , an ohmic contact layer 148 is deposited for making ohmic contact with the data line 104 , the source electrode 110 , and the drain electrode 112 .
[0038] The thin film transistor 106 allows a pixel voltage signal applied to the data line 104 to be charged into the pixel electrode 118 and kept in response to a gate signal applied to the gate line 102 .
[0039] The pixel electrode 118 is connected, via a first contact hole 116 passing through a protective film 150 , to the drain electrode 112 of the thin film transistor 106 . The pixel electrode 118 generates a potential difference with respect to a common electrode provided at an upper substrate (not shown) by the charged pixel voltage signal. This potential difference rotates a liquid crystal positioned between the thin film transistor array substrate and the upper substrate owing to dielectric anisotropy of the liquid crystal and transmits light inputted, via the pixel electrode 118 , from a light source (not shown) toward the upper substrate. The storage capacitor 120 is formed by the storage electrode 118 and the pre-stage gate line 102 . The gate insulating film 144 is located between the gate line 102 and the pixel electrode 118 .
[0040] The protective film 150 is not located in the storage capacitor 120 . Thus, a feed-through voltage ΔVp is minimized. Accordingly, a residual image such as flicker is minimized to improve a picture quality.
[0041] Hereinafter, this will be described in more detail
[0042] Generally, a capacitance value of the capacitor is in proportion to a section area of the electrode while being in inverse proportion to a distance between the electrodes as indicated in the following equation:
C˜A/d (2)
wherein C represents a capacitance value of the capacitor; A represents an area of the capacitor; and d represents a distance between the electrodes of the capacitor.
[0043] In the first embodiment of the present invention, the protective film 150 is not present on the gate insulating film 144 in the storage capacitor 120 . Accordingly, since a distance between the pixel electrode 118 and the gate electrode 102 is reduced, a capacitance value Cst of the storage capacitor 120 is increased. The capacitance Cst of the storage capacitor 120 plays a role to reduce a feed-through voltage ΔVp as indicated in the following equation:
Δ Vp = Cgd Cgd + Clc + Cst Δ Vg ( 3 )
[0044] As a result, the feed-through voltage ΔVp is minimized. Thus, a residual image problem such as flicker can be minimized to improve the picture quality.
[0045] Hereinafter, a method of fabricating the thin film transistor substrate will be described in detail with reference to FIG. 6A to FIG. 6D .
[0046] Firstly, a gate metal layer is formed on the lower substrate 142 by a deposition technique such as sputtering. Then, the gate metal layer is patterned by photolithography and etching using a first mask to thereby provide gate metal patterns including the gate line 102 , the gate electrode 108 as shown FIG. 6A . The gate metal layer may be a single-layer or multiple-layer structure of chrome (Cr), molybdenum (Mo) or an aluminum group metal, etc.
[0047] The gate insulating film 144 is formed on the lower substrate 142 provided with the gate pattern by deposition techniques such as plasma enhanced chemical vapor deposition (PECVD) and sputtering, etc. The gate insulating film 144 is formed from an inorganic insulating material such as silicon oxide (SiOx) or silicon nitride (SiNx).
[0048] An amorphous silicon layer, an n+ amorphous silicon layer and a source/drain metal layer are sequentially provided on the lower substrate 142 provided with the gate insulating film 142 .
[0049] A photo-resist pattern is formed on the source/drain metal layer by photolithography using a mask. Herein, the mask has a diffractive exposure part at the channel portion of the thin film transistor 106 , thereby allowing the photo-resist pattern at the channel portion to have a lower height than at the source/drain regions.
[0050] Subsequently, the source/drain metal layer is patterned by wet etching using the photo-resist pattern to thereby provide source/drain patterns including the data line 104 , the source electrode 110 , and the drain electrode 112 , which is integral with the source electrode 110 .
[0051] Next, the amorphous silicon layer and the n+ amorphous silicon layer are simultaneously patterned by dry etching using the same photo-resist pattern to thereby provide the semiconductor pattern 145 including the ohmic contact layer 148 and the active layer 114 .
[0052] Further, the photo-resist pattern having a relatively low height at the channel portion is removed by ashing, and thereafter the source/drain pattern and the ohmic contact layer 148 at the channel portion is etched by dry etching. Thus, the active layer 114 at the channel portion is exposed to disconnect the source electrode 110 from the drain electrode 112 as shown FIG. 6B .
[0053] Then, the photo-resist pattern left on the source/drain pattern group is removed by stripping. Herein, the source/drain metal is selected from molybdenum (Mo), titanium (Ti), tantalum (Ta) or a molybdenum alloy, Cu, an aluminum group metal etc.
[0054] Alternatively, the semiconductor pattern 145 may be formed individually with the source/drain pattern using a separate mask process.
[0055] The protective film 150 is entirely formed on the gate insulating film 144 provided with the source/drain patterns by a deposition technique such as PECVD, etc. The protective film 150 is patterned by photolithography and etching using a mask to thereby define a contact hole 116 . The contact hole 116 passes through the protective film 150 and exposes the drain electrode 112 . The gate insulating film 144 is exposed at an area provided with the storage capacitor.
[0056] Hereinafter, a method of fabricating the protective film 150 will be described in detail with reference to FIG. 7A to FIG. 7B .
[0057] Referring to FIG. 7A , after the protective film 150 is formed on the entire lower substrate 142 , a photo-resist 190 a is entirely coated thereon. Then, after a mask 180 including a transmitting area 180 a and a shielding area 180 b is aligned, the photo-resist 190 a under the transmitting area 180 a is exposed to radiation.
[0058] Next, as shown in FIG. 7B , after a photo-resist pattern 190 b is formed by development of the photo-resist 190 a , the protective film 150 is patterned by utilizing the photo-resist pattern as a mask. Thus, as shown in FIG. 6C , a contact hole 116 is defined to expose the drain electrode 112 of the thin film transistor 106 . Also, the protective film 150 is removed at an area where the storage capacitor 120 is positioned, thereby exposing the gate insulating film 144 .
[0059] The protective film 150 is made from an inorganic insulating material identical to the gate insulating film 144 , or an organic insulating material such as an acrylic organic compound having a small dielectric constant, BCB (benzocyclobutene) or PFCB (perfluorocyclobutane), etc.
[0060] A transparent electrode material is entirely deposited onto the protective film 150 by a deposition technique such as sputtering, etc. Thereafter, the transparent electrode material is patterned by photolithography and etching using a fourth mask to thereby provide transparent electrode patterns including the pixel electrode 118 . The pixel electrode 118 is electrically connected, via a contact hole 116 , to the drain electrode 112 . Also, the storage capacitor 120 consists of a pixel electrode 118 overlapping a pre-stage gate line 102 with the gate insulating film 144 therebetween. The transparent electrode material is selected from indium-tin-oxide (ITO), tin-oxide (TO), indium-zinc-oxide (IZO) or the like.
[0061] As described above, in the first embodiment of the present invention, the protective film 150 is removed from the storage capacitor 120 to thereby increase a capacitance of the storage capacitor 120 . Accordingly, a feed-through voltage ΔVp is minimized. Thus, a residual image problem such as flicker can be minimized to improve the picture quality.
[0062] FIG. 8 is a section view showing a structure of a thin film transistor array substrate according to a second embodiment of the present invention.
[0063] The thin film transistor substrate shown in FIG. 8 has the same elements as the thin film transistor substrate shown in FIG. 5 except that the protective film 150 is partially removed within the storage capacitor 120 to have a low height. Therefore, the same elements in FIG. 8 are given the same reference numerals as those in FIG. 5 . Further, an explanation as to the same elements will be omitted. The protective film 150 includes a contact hole 116 for exposing the drain electrode 112 of the thin film transistor 106 , and has a lower height than the prior art within the storage capacitor 120 .
[0064] Accordingly, as a distance between the pixel electrode 118 and the gate electrode 102 is reduced, a capacitance value Cst of the storage capacitor 120 is increased. As a result, a feed-through voltage ΔVp is minimized. Thus, a residual image problem such as flicker can be minimized to improve the picture quality.
[0065] According to the second embodiment of the present invention, the height of the protective film 150 within the storage capacitor 120 can be adjusted by forming the protective film 150 using a diffractive exposure mask. Thus, it becomes possible to increase a capacitance Cst of the storage capacitor 120 . Also, it becomes possible to provide the storage capacitor 120 having a desired capacitance value. Herein, the height of the protective film 150 in the storage capacitor 120 is controlled by controlling the etching time.
[0066] FIG. 9A to FIG. 9C are views for explaining a thin film transistor array substrate and a fabricating method thereof according to the second embodiment of the present invention.
[0067] A method of fabricating the thin film transistor substrate according to the second embodiment of the present invention is identical to a method of fabricating the thin film transistor array substrate according to the first embodiment of the present invention as shown FIG. 6A to FIG. 6D except that the contact hole 116 for exposing the drain electrode 112 of the thin film transistor 106 is positioned and the partially removed protective film 150 is located within the storage capacitor 120 by forming the protective film 150 using a diffractive exposure mask. Therefore, an explanation as to the same elements will be omitted.
[0068] Referring to FIG. 9A , the protective film 150 and the photo-resist are sequentially provided on the lower substrate 142 provided with the thin film transistor etc. Thereafter, the photo-resist pattern 192 a is provided by exposure and development after a diffractive exposure mask 182 including a transmitting part 182 a , a shielding part 182 b and a semi-transmitting part 182 c was aligned. Herein, the protective film 150 is exposed at an area where the contact hole 116 is to be defined, and has a relatively low height (A area in the drawing) at an area where the protective film 150 having a low thickness in the storage capacitor 120 is to be positioned.
[0069] The protective film 150 is patterned by utilizing the photo-resist pattern 192 a as a mask to thereby provide a contact hole 116 exposing a drain electrode 112 of the thin film transistor 106 . Next, ashing is carried out to expose the protective film 150 to be included in the storage capacitor 120 through the remaining photo-resist pattern 192 b as shown in FIG. 9B . Further, the exposed protective film 150 is etched (dry etched) by utilizing the remaining photo-resist pattern 192 b as a mask to thereby leave the protective film 150 having a lower height than the protective film 150 at the area excluding the storage capacitor 129 as shown in FIG. 9C . Herein, the thickness of the remaining protective film 150 is adjusted by adjusting the etching time. Thereafter, the remaining photo-resist pattern 192 b is removed by stripping to thereby provide the partially removed protective film 150 .
[0070] FIG. 10 is a plan view showing a film transistor array substrate according to a third embodiment of the present invention;
[0071] The thin film transistor array substrate shown in FIG. 10 is a thin film transistor array substrate of storage on common type in which the storage capacitor 120 is provided in such a manner to cross the pixel electrode 118 .
[0072] Such a thin film transistor array substrate of storage on common type has the same elements as the thin film transistor array substrate shown in FIG. 5 except that it crosses the pixel electrode 118 and is parallel with the gate line 102 . In addition, a common line 125 supplied with a reference voltage is provided upon driving the liquid crystal. The storage capacitor 120 is defined by the common line 125 and the pixel electrode 118 . Therefore, the same elements will be given by the same reference numerals, and a detailed explanation as to the same elements will be omitted. The thin film transistor array substrate according to the third embodiment of the present invention has a storage capacitor 120 that crosses a pixel area, that is, an area at which the pixel electrode is positioned.
[0073] In the thin film transistor array substrate, the protective film 150 is completely or partially removed within the storage capacitor 120 to have a low height like the first and second embodiments of the present invention. In the third embodiment, the storage capacitor 120 is defined by the common line 125 and the pixel electrode 118 rather than the gate line 102 .
[0074] As described above, the storage-on-common type thin film transistor array substrate according to the third embodiment of the present invention is formed such that the protective film is completely or partially removed within the storage capacitor. Accordingly, a distance between the pixel electrode 118 and the gate electrode 102 is reduced to increase a capacitance Cst of the storage capacitor 120 . As a result, a feed-through voltage ΔVp is minimized. Thus, a residual image problem such as flicker can be minimized to improve the picture quality.
[0075] Herein, when the protective film 150 is partially removed within the storage capacitor 120 , the diffractive mask 182 is used. Accordingly, it becomes possible to increase a capacitance Cst of the storage capacitor 120 . Also, it becomes possible to provide a storage capacitor 120 having a desired capacitance value.
[0076] In the method of fabricating the thin film transistor substrate according to the third embodiment of the present invention, a gate pattern such as the gate line 102 is formed simultaneously with the common line 125 . When the protective film is completely removed from the storage capacitor 120 , the same method as shown in FIG. 7A to FIG. 7B is used. On the other hand, when the protective film 150 is partially removed from the storage capacitor 120 , the gate line 102 and the common line 125 are formed by the same method as the patterning process including photolithographic, ashing, etching processes, etc employing the diffractive exposure mask 182 shown FIG. 9A to FIG. 9C . Accordingly, the detailed description as to this will be omitted.
[0077] As described above, according to the present invention, the protective film within the storage capacitor is completely or partially removed, thereby increasing a capacitance of the storage capacitor. Accordingly, a feed-through voltage ΔVp is minimized. Thus, a residual image problem such as flicker can be minimized to improve the picture quality.
[0078] Although the present invention has been explained by the embodiments shown in the drawings described above, it should be understood to the ordinary skilled person in the art that the invention is not limited to the embodiments, but rather that various changes or modifications thereof are possible without departing from the spirit of the invention. Accordingly, the scope of the invention shall be determined only by the appended claims and their equivalents. | A thin film transistor array substrate and a fabricating method are disclosed. A gate line and a data line cross each other and a thin film transistor (TFT) is provided at the intersection between the gate and data lines. A protective film covers the data line and the thin film transistor and has a contact hole exposing a drain electrode of the TFT. A pixel electrode is connected, via the contact hole, to the drain electrode of the TFT. A storage capacitor includes a gate insulating film between the pixel electrode and the gate line and/or a common line. Some or all of the protective film within the storage capacitor is removed such that the storage capacitor contains no protective film or a layer of protective film that is thinner than the portion covering the TFT. | 6 |
BACKGROUND OF THE INVENTION
The present invention relates to a process for the production of polymers of ethylene and an apparatus for operating the process.
Processes for polymerizing ethylene under high pressure (about 400 to 3000 bars) by means of either a free radical initiator, as in U.S. Pat. No. 3,255,171, or a catalytic system of the Ziegler type comprising an organo-metallic activator and a transition metal halide, as in British Pat. No. 1,441,115 have long been known.
In the continuous ethylene polymerization processes, the polymer produced is separated from the reaction mixture in a first separation zone under a pressure generally between 100 and 500 bars, and then in a second separation zone is maintained at a pressure as close as possible to atmospheric pressure: 2 atmospheres according to the examples in U.S. Pat. No. 3,551,397.
In the known polymerization processes cited above, the ethylene fraction separated in the second separation zone--a fairly large fraction since it generally represents 20 to 50% of the production of polymer--has to be passed to a booster to be compressed to the pressure of the ethylene feed flow, mixed with this flow, and compressed with it to the pressure of the first separation zone. The resulting mixture is then mixed with the ethylene fraction separated in the first separation zone and compressed with it to the working pressure of the reactor.
The process of recycling of ethylene cited above has two main disadvantages. Firstly it is wasteful of energy because it leads to the expansion followed immediately by recompression of a relatively large flow of ethylene (separated in the second separation zone), the supplementary cost in energy of this operation being all the greater because the pressure of the second zone of separation is lower. Secondly it permits only an incomplete degassing of the polymer produced, which results in difficulties in storing the polymers. The presence of residual gas in the storage areas causes a disagreeable odor, risks of explosion, and stress on the workers engaged in storage and handling. The development of standards in force in many countries in relation to toxicology, hygiene, and safety makes it likely that the present processes will soon no longer conform to these standards because they do not ensure adequate degassing of the polymers produced.
British Pat. No. 1,313,836 describes a process for the polymerization of ethylene under a pressure of 700 to 5000 bars at a temperature of 100° to 400° C., characterized by the presence of one or more high pressure separators, at least one of which works at a pressure of 500 to 1000 bars. According to the description in this patent, "high pressure" means at least 250 bars. This process, in a manner emphasized by the very high pressure chosen, has the same disadvantages as the processes cited above.
SUMMARY OF THE INVENTION
The object of the present invention is thus to provide a solution to the two disadvantages cited above of the known polymerization processes.
Additional objects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.
To achieve the foregoing objects and in accordance with the purpose of the invention, as embodied and broadly described herein, the process of the invention for the production of polymers of ethylene in a continuously operating system under a pressure between about 400 and 3000 bars and a temperature between about 150° and 320° C. comprises separating the polymers formed from the reaction mixture in a first separation zone maintained at a pressure between about 100 and 500 bars, further separating the polymer from the first separation zone from residual gases in an intermediate separation zone maintained at a pressure between about 10 and 70 bars, mixing the residual gases separated in the intermediate separation zone with an ethylene feed stream, compressing the mixture of residual gases and ethylene feed to the pressure of the first separation zone, and further separating the polymer from the intermediate separation zone in a second separation zone maintained at a pressure between about 1 and 1.5 bars.
To further achieve the objects of the present invention and in accordance with its purpose, as embodied and broadly described herein, the invention also relates to an apparatus for operating the process described above, which comprises:
(a) a polymerization reactor;
(b) a first separation zone, whose inlet is connected to the outlet of the reactor;
(c) a hypercompressor, whose outlet is connected to the inlet of the reactor 1;
(d) a gas conduit extending from an outlet of the first separation zone to the inlet of the hypercompressor;
(e) an intermediate separation zone, whose inlet is connected to an outlet of the first separation zone by a polymer conduit;
(f) a monomer feed conduit connected to the inlet of the hypercompressor;
(g) a gas conduit extending from an outlet of the intermediate separation zone to the monomer feed conduit; and
(h) a second separation zone, whose inlet is connected to an outlet of the intermediate separation zone.
The accompanying drawing, which is incorporated in and constitutes a part of this specification, illustrates one embodiment of the invention and, together with the description, serves to explain the principles of the invention.
BRIEF DESCRIPTION OF THE DRAWING
The drawing is a flow diagram of a process and apparatus in accordance with the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Reference will now be made in detail to the presently preferred embodiments of the invention, an example of which is illustrated in the accompanying drawing.
The basic concept for achieving the object of the invention is to introduce in the process of separation and recycling of ethylene a supplementary separation zone maintained at an intermediate pressure between that of the first separation zone and that of the second separation zone. In spite of its apparent simplicity, this concept is not easy to implement in an industrially effective manner, because the intermediate pressure must be chosen as a function of three partly contradictory objectives and of a physico-chemical constraint on which there is no means of acting. The three objectives are on the one hand, as shown above, reduction in the consumption of energy of the process and reduction in the difficulties in storing the polymer, and on the other hand maintenance of the quality of the production of the polymer measured by the physical and mechanical properties of the latter. It has then been observed that the introduction of a supplementary separation zone kept at an intermediate pressure permits reduction in the energy consumption and reduction of the odor of stored polymer, while keeping the polymer in a separation zone at high pressure tends to degrade the properties of the polymer and consequently the quality of production. The physico-chemical restraint that there is no means of affecting constitutes a variation as a function of pressure of the solubilities of the oligomers, oils, and impurities in the ethylene, which shows a singular point at a pressure of about 15 bars.
The present invention thus constitutes a choice of an industrially effective means of introducing a supplementary separation zone, that is, in particular, the choice of the intermediate pressure and the pressure of the second separation zone to ensure a good compromise between the three objectives cited above, while taking the physico-chemical constraints into account. The process according to the invention is a process for producing polymers of ethylene continuously under a pressure between about 400 and 3000 bars and a temperature between about 150° and 320° C., comprising a first step of separating the polymers from the reaction mixture in a first separation stage maintained at a pressure between about 100 and 500 bars, then a second step of separating the previously separated polymers from residual gas in a second separation zone maintained at a pressure between about 1 and 1.5 bars, characterized in that it comprises in addition an intermediate step of separating the residual gases from the polymers separated in the first step, the intermediate separation step being carried out in an intermediate separation zone maintained at a pressure between about 10 and 70 bars, the polymers separated in this intermediate zone being then passed on to the second separation zone, while the residual gases separated in this intermediate zone are mixed, after compression if necessary, with the ethylene feed flow and compressed with it to the pressure of the first separation zone. As in the known processes, the mixture of residual gases and feed is then mixed with the ethylene separated in the first separation zone and compressed with it to the working pressure of the process.
By ethylene polymers in the sense of the present invention is meant both homopolymers of ethylene and copolymers of ethylene with comonomers such as α-olefins (propylene, butene-1, methyl-4-pentene-1, hexene-1, octene-1, etc.) or polar monomers (maleic anhydride, vinyl acetate, ethyl acrylate, etc.).
It should be understood that the conditions of polymerization do not constitute a distinctive part of the present invention and that the conditions proposed (pressure between about 400 and 3000 bars, temperature between about 150° and 320° C.) only represent the most usual conditions in practice. Polymerization conditions deviating slightly from those proposed, such as notably a pressure above 3000 bars or a temperature above 320° C. (in particular in a tubular reactor), will not therefore be sufficient to fall outside the scope of the invention. However, the choice of clearly differentiated pressure conditions in the second separation step on the one hand and in the supplementary separation step on the other constitutes the characteristic feature of the invention. As regards the pressure in the first separation stage, it does not constitute a further distinctive part of the invention and those possessing ordinary skill in the art know how to choose it in relation to the polymerization pressure.
The present invention is applicable to polymerization by means of a free racial initiator (oxygen, peroxides, peresters) as well as by means of a catalytic system of the Ziegler type comprising an organo-metallic activator and a transition metal halide.
As the invention relates only to a specific process of separation and recycling of the ethylene, it is intended that any means of affecting the course of the polymerization or any means of controlling the same, such as the introduction of inhibitors or regulating agents or complexing agents at any stage whatever of the process that have been or may be used within the scope of known processes, may be used with the scope of the process according to the invention with increased ease and flexibility, because a supplementary zone is available to act on the polymerization or to control it. By way of supplementary examples of such means of action, we may cite the processes of cooling the first separation zone described in British Pat. No. 1,540,894 and copending application Ser. No. 016,540 filed Mar. 1, 1979, and the process of deactivation of catalyst described in U.S. Pat. No. 4,105,609.
The results which can be achieved by the present invention conform to its objects. On the one hand, the quality of the production, i.e. the physical and mechanical properties of the polymer is maintained at an identical level to that of the production achieved by the known processes. On the other hand, a strong reduction in the odor of the stored polymer is observed, due to its almost complete degassing. The invention therefore to a significant extent eliminates the nuisance caused to workers responsible for storage and to a large extent eliminates the need for ventilation installations in the storage areas. Finally, a reduction in energy consumption of the process is found, which varies with a large number of parameters, but is generally about 50 kWh per metric ton of polymer. This reduction in energy consumption is also accompanied by a reduction in investment for the production of polymer, because the invention eliminates the booster for compressing the ethylene separated in the second separation zone to the pressure of the ethylene feed stream.
The apparatus of the present invention comprises:
(a) a polymerization reactor 1;
(b) a first separation zone 2 whose inlet is connected to the outlet of the reactor 1;
(c) a hypercompressor 3, whose outlet is connected to the inlet of the reactor 1;
(d) a gas conduit 4 extending from an outlet of the first separation zone 2 to the inlet of the hypercompressor 3;
(e) an intermediate separation zone 6, whose inlet is connected to an outlet of the first separation zone 2 by a polymer conduit 7;
(f) a monomer feed conduit 10 connected to the inlet of the hypercompressor 3;
(g) a gas conduit 9 extending from an outlet of the intermediate separation zone 6 to the monomer feed conduit 10; and
(h) a second separation zone 5, whose inlet is connected to an outlet of the intermediate separation zone 2.
The apparatus according to the invention may also comprise a compressor 11 interposed on the feed conduit 10 of the reactor between the point of connection of the gas conduit 9 originating from the intermediate separation zone 6 and the inlet of the hypercompressor 3 or the point of connection of the gas conduit 4 originating from the first separation zone 2. As proposed above, the apparatus according to the invention may also comprise means for cooling the first separation zone 2, such as an injector according to British Pat. No. 1,540,894 or a turbine according to French Pat. No. 78/06,030.
It will be apparent to those skilled in the art that various modifications and variations could be made in the process and apparatus of the invention without departing from the scope or spirit of the invention. | The energy efficiency of a high pressure, high temperature continuous process for the production of polyethylene is improved and residual gases are more completely removed from the product without detriment to product quality by employing an intermediate separator between the first and second separators. The intermediate separator is maintained at a pressure between about 10 and 70 bars, and the second separator is maintained at a pressure between about 1 and 1.5 bars. | 2 |
BACKGROUND OF THE INVENTION
1. Field of The Invention
The present invention relates to a portable drawer assembly for use with a four legged piece of furniture having a space between the legs.
2. Description Of The Prior Art
Drawer assemblies of this type are known in the prior art, but these assemblies have the disadvantage of having a fixed width and therefore of not being able to optimally use the effective space between the four legs of the piece of furniture and of not being able to be used with a wide range of sizes of furniture.
Among the known prior art drawer assemblies that have these disadvantages are those taught in U.S. Pat. Nos. 210,487; 1,295,043; 1,566,664; 1,928,890; 2,652,887; 2,692,007; 2,765,025; and 3,544,157.
Accordingly, in my prior U.S. Pat. No. 4,061,395, issued Dec. 6, 1977, I disclosed a portable drawer that may be adjusted in its width to fit between the four legs of a piece of furniture and be slidably mounted therebetween. This was achieved by forming the drawer from two slidably engageable telescoping sections, which together constitute an enclosure that can be selectively adjusted in width for positioning between the legs of the furniture. The enclosure is slidably mounted to rods clamped to the legs along the length of the enclosure, so the drawer can be pulled outwardly from between the legs of the furniture for use.
The drawer enclosure however, did not have a top, cover or closure which is desirable when storing certain articles nor was the drawer readily removable from its mounted position and self-supporting, whereby a user would gain greater access to the interior of the enclosure. Further, by being readily removable, the enclosure would be immediately portable for use at different locations on different furniture. This invention provides a portable drawer assembly having such improved features.
SUMMARY OF THE INVENTION
In accordance with the invention, a complementary shaped cover is provided on the drawer enclosure which is adjustable in width by telescopically connecting two relatively slidable sections. The drawer enclosure and cover are adjustable to fit the space between the legs of the furniture and are attached therebetween by a pair of spring-slat clamps extending along the sidewalls of opposite sides of the cover, whereupon twisting of the slats enables ready removal of the cover and drawer enclosure. The sidewalls of the drawer enclosure are provided with pivotable legs for supporting the drawer and cover above a surface when not clamped between the furniture legs. The drawer enclosure is slidable lengthwise relative to the cover along a pair of rods suspending its interior from the cover enabling the drawer to be uncovered or opened for access whether in its self-supported mode or furniture supported mode.
BRIEF DESCRIPTION OF THE DRAWINGS
Further objects and advantages of the invention will become apparent from the following description and claims, and from the accompanying drawings wherein:
FIG. 1 is a perspective view of the portable drawer assembly of the present invention mounted on a chair;
FIG. 2 is a partial cross-sectional view of the drawer assembly taken substantially along the plane indicated by line 2--2 of FIG. 1;
FIG. 3 is a cross-sectional view taken substantially along the plane indicated by line 3--3 of FIG. 2;
FIG. 4 is a side view of the drawer assembly of the present invention removed from a chair and supported on a plane surface; and
FIG. 5 is a partial top view of the drawer assembly of FIG. 2 with portions broken away and illustrated in section.
DETAILED DESCRIPTION OF THE INVENTION
Referring to the drawings in detail wherein like numerals indicate like elements throughout the several views, and particularly, to FIG. 1, a portable drawer assembly 10 is shown mounted to a chair 12.
The assembly 10 may be used with any four legged piece of furniture that has a space between the legs 13 which are disposed rectangularly. The assembly 10 permits selective adjustment of the width of the drawer 14 to suit the piece of furniture beneath which it is mounted. The drawer 14 or enclosure is closed at the top by a cover 15, and each of the drawer 14 and cover 15 is constructed of first and second sections 16, 16a, 17, 17a, respectively that are telescopingly-engageable to one another. Each section 16, 16a has a rectangular base 18, 18a and three side walls 20, 20a each disposed perpendicular to its respective base 18, 18a. Similarly, each section 17, 17a of the cover 15 includes two walls 19, 19a each having a top rectangular portion and a vertical portion, said portions configured as a right angle to form an L. The base 18 and two side walls 20 of the first section 16 have slots 22 machined therein along the edges thereof that define an open side of the first section 16. The top portion of wall 19 of cover section 17 is also machined with a slot 23. The base 18a and corresponding two side walls 20a of the second section 16a are configured to be slidably received in the slot 22, while the top portion of wall 19a of cover 15 is slidably received in slot 23. A screw 24 in one or both of walls 18, 19 is slidable in a slot 25 in walls 18,19 respectively, to guide and maintain the two sections 16, 16a of the drawer 14 and sections 17, 17a of the cover in a selected position corresponding to a desired width as shown in FIG. 2. A handle 26 is connected to one side wall 20 of the first section 16 for grasping to slide the drawer assembly 14 open or closed, as will be described hereinafter.
The drawer assembly 14 with its cover 15 is mounted between the four legs 13 of the chair 12 for sliding movement in the space between said legs 13. Connected to each pair of legs 13 is a clamping member 28.
Each clamping member 28, as shown in FIGS. 2, 3 and 5, includes an elongated slat 50 adapted to span the space between a pair of chair legs 13 connected by a flexible wire 52 to the adjacent ends of a pair of elongatable coil springs 54, 56, each housed within a cylinder 58 secured by a collar 60 to the interior surface of the top portion of wall 19, 19a of section 17, 17a, respectively, of cover 15. In lieu of flexible wire 52, a curved rigid rod (not shown) can be used to mount coil springs 54, 56. Each end of wire 52 passes through an opening 63 in the vertical portion of wall 19 of section 17 and is secured by a pair of spaced grommets 62 to the slat 50. Wire 52 allows a slat 50 to be twisted or pivoted relative to the vertical portion of wall 19 of each cover section 17, 17b so that the cover 15 and attached drawer 14 can be positioned between the front and rear legs 13 of chair 12 and slats 50 manipulated to engage about the outer surfaces of a pair of adjacent legs 13 expanding springs 54, 56 which hold the vertical portions of walls 19, 19a against the interior of legs 13 as shown clearly in FIG. 5.
Two first or fixed rods 30, 30a are each connected between two clamping collars 31 along the length of the cover 15. Two second or movable rods 32, 32a are connected at two sides 20, 20a of each section 16, 16a along the length of drawer 14. Two first or rear connecting members 34, 34a are affixed with set screws or the like to its respective movable rod 32, 32a and is slidably connected to its respective fixed rod 30, 30a as shown in FIG. 3 by an eye member 36. Two second or front connecting members 38, 38a are affixed with set screws or the like to their respective fixed rods 30, 30a and are slidably connected to their respective movable rods 32, 32a by an eye member 40.
As illustrated in FIGS. 1 and 3, the drawer 14 can be pulled by handle 26 to an open position 44 and then reclosed by sliding drawer 14 and interior movable rods 32, 32a forwardly in eye members 40. Eye members 36 slide on fixed rods 30, 30a secured to the cover 15.
Slats 50 can aid in holding sections 17, 17a of the cover in adjusted relation by being further secured to cover 15 by straps 42 connected to the ends of each slat 50. Each strap 42 has Velcro fasteners 46 which are matingly engaged with a similar fastener 46 on the cover 15. Upon opening each strap 42 and twisting of slats 50 relative to the cover 15 and drawer 14, the entire drawer assembly 10 can be removed from the legs 13 of chair 12. Velcro fasteners on straps 42 are also connected to bases 18, 18a so that the bases 18, 18a can be prevented from sliding relative to each other when the drawer is collapsed, removed from the chair, and relocated.
The assembly 10 can be supported on a plane surface by pivoting support legs 64 about a pin 66 connecting each support leg 64 to each corner of a vertical side wall 20, 20a of drawer 14 until the leg abuts a stop surface 68 on a block 70 provided at each corner of the vertical side walls 20, 20a. | A portable drawer assembly for use with a four legged chair or the like having a space between the legs. The assembly comprises an enclosure having a top cover, both of which have a width which is selectively adjustable to effect the positioning thereof in the space between the four legs. The cover and enclosure can be mounted on the four legs so the drawer can be slid into and out of the space between the four legs or alternatively, it can be supported on legs pivotably mounted on the enclosure. | 0 |
[0001] This application claims the benefit of U.S. Provisional Application No. 61/441,998 filed Feb. 11, 2011.
STATEMENT CONCERNING FEDERALLY SPONSORED RESEARCH
[0002] The invention was made with government support under NSF IIS-1017990 awarded by the National Science Foundation. The government may have certain rights in the invention.
FIELD OF THE INVENTION
[0003] The invention relates generally to computer databases hosted on untrusted servers, and more specifically, to a system and methods for ensuring transactional consistency and integrity, and assured provenance of a computer database running on an untrusted server, such as a cloud server.
BACKGROUND OF THE INVENTION
[0004] Ensuring the integrity and authenticity of data is of ever increasing importance as data are generated by multiple sources, often outside the direct control of fully trusted entities. Increasingly, data are subjected to environments which can result in invalid (malicious or inadvertent) modifications to the data. Such possibilities clearly arise when data are hosted in a cloud computing environment where complete control over the hardware and software running at the cloud servers is lacking. Invalid modifications can also arise when the data are maintained on trusted servers, but the data may get modified by a malicious insider or an intruder that manages to compromise the server or the communication channels. In these situations, it is desirous to be ensured that the data retrieved from an untrusted server are trustworthy (i.e., the data and retrieved values have not been tampered or incorrectly modified).
[0005] With the advent of Cloud Computing there is increasing interest to move operations, including databases, onto a cloud platform. Although Cloud Computing holds great promise, it raises a number of security and privacy concerns. It also raises concerns about the fidelity of the service. In particular, since the clients have little or no direct control over the software and hardware that is running at the servers, there is reluctance to blindly trust the server. For example, a server may be improperly configured, or inadvertently left open to hacker attacks. There is also the concern about the server being attacked by an external entity that can corrupt the outsourced data or service despite the best efforts of the server. Even though, the cloud service provider is likely to be honest, it may try to hide its failure. Currently, users have no recourse but to trust the server or rely on legal agreements. Even with such agreements, it is difficult for a user to discover, let alone prove, any foul play by the server.
[0006] For purposes of this application, the term “untrusted database” is used herein to refer to one or more of the of the following situations: (1) a database that is hosted on a cloud server, (2) a database that has been outsourced to a third party, or (3) a database running on a machine that could be compromised by insiders or hackers.
[0007] There are several challenges for ensuring the authenticity and integrity of databases primarily due to the ability to execute queries over this data—e.g., using SQL—and to make updates to parts of the database. The correctness of query results and validity of updates are crucial requirements for databases. In order to ensure authenticity, it is necessary for the database server to guarantee correctness, completeness and transactional consistency.
[0008] Correctness requires that all answers to a given query do indeed come from the authentic database. In other words, this implies that the values returned are not manufactured by the server or corrupted along the communication path.
[0009] Completeness requires that all tuples that should be present in a query answer are indeed part of the answer. In other words, the database host has evaluated the query correctly and has returned all tuples that are produced as a result without dropping any out.
[0010] Transactional consistency requires that the current consistent state is indeed the correct state corresponding to the initial state followed by the correct application of all previous valid transactions. Query freshness is part of transactional consistency.
[0011] Many applications may also require, e.g., due to regulatory compulsions, to keep the provenance of updates to the database. This can be particularly important to check if malicious activity occurred in the past. For purposes of this application, the term “provenance” refers to the order of changes to a database, the exact transactions that made those changes, and the authorization from an accessor that authorized the changes.
[0012] Existing solutions assume that the data being outsourced to a third-party are not modified at the outsourcing server. In other words, it is assumed that all updates are authenticated by the data owner and then sent to the database server such that the legitimacy of any data that is part of the outsourced database is established directly by the data owner. In an untrusted database setting (e.g., a cloud database setting), this assumption breaks down. A typical outsourced database usually supports large numbers of authorized clients that run transactions directly on the database. Updates to the data are made through these transactions. It is infeasible for the database owner to determine the correct updates for each transaction. The validity of these modifications made to the database is determined by the standard transactional semantics of databases. Thus, there is a need to assure the database owner that the (untrusted) server is indeed correctly executing all transactions.
[0013] In addition to these requirements from the data owner's perspective, there is a requirement from the outsource service provider's perspective. The server should be able to prove its innocence if it has faithfully executed all transactions, for example, indemnity for the server against false claims of malpractice.
[0014] Given that the goal of the outsourcing is to alleviate the burden on the data owner, satisfactory solutions need to minimize the overhead and role of the data owner in establishing the authenticity and integrity of the solutions. In this regard, existing solutions are inadequate as they require the data owner to play a significant role. In addition, existing solutions also place significant overhead on the service provider. While this may work for some applications, many outsourced databases are expected to have both a large size and high rate of querying and updates. Thus it is necessary to explore more efficient solutions with low overheads for all involved parties.
[0015] Therefore, there is a need for a novel solution to ensure authenticity and integrity of an untrusted database in the presence of transactional updates that runs directly on the untrusted database. There is also a need for an authentication mechanism to ensure correctness, completeness, and transactional consistency, including the assurance to the database owner that the (untrusted) server is indeed correctly executing all transactions. Furthermore, there is a need for providing indemnity of the server against false claims of incorrect operation. In addition, there is a need for implementing the aforementioned checks without excessive demand on the server resources or altering the internal structure of the outsourced database. The invention satisfies these needs. In addition, the invention provides assured provenance for all changes to the data—i.e., using the exact same mechanism for ensuring authenticity and integrity, the invention can provide incontrovertible evidence about all the modifications that have been made to the data.
SUMMARY OF THE INVENTION
[0016] The invention is a system and methods for providing guarantees about faithful execution of databases that run under the control of an untrusted entity such as a cloud computing service provider that is different than the owner of the data and applications being hosted at the untrusted server. Specifically, the invention establishes when an untrusted database server is being faithfully hosted. Furthermore, the invention provides indemnity for the service provider from false claims, enabling the server to prove its innocence against untrue claims of faulty operation. It also provides assured provenance for all changes made to the database. The untrusted database cannot fabricate assured provenance.
[0017] There are three main types of entities involved in an untrusted database: owner, host and accessor. The owner owns the database. More specifically, the owner owns the data and authenticates the accessors such that they can access the data from the server. The owner wants to host the database at the host and also wants to ensure that the changes sent to the host by the accessors (in the form of transactions) are applied correctly by the host. The host is the cloud service provider server that hosts the database. The accessor is the one or more clients that access this data from the server. It is contemplated that an accessor may include an owner. Clients are authorized by the owner and can independently authenticate themselves with the server.
[0018] In most cloud computing settings, the server is likely to be at least semi-honest. In other words, the server will not maliciously alter the data or query results. However, due to reasons such as poor implementation, failures, over-commitment of resources, some loss of data or updates may occur. Given the lack of direct control over the server, the owner should not assume that the host is infallible. Thus, assumptions about the host are minimal.
[0019] The owner and the accessor need to be ensured that the database is operated faithfully such that the host does not violate the integrity and authenticity of the data. The host is interested in hosting the owner's database (possibly in return for a fee) and makes efforts to ensure that the owner is convinced about the fidelity of the hosting service. The host controls the hardware and software that is used to host the database and has complete control over all the data. The host has unconditional read and write access to the data, and can intercept all queries posed to the database as well as the results of the query. It is also contemplated that the host may modify the stored data or the results sent back to the accessor.
[0020] For the purpose of this application, the term “consistent state” means the initial state of a database and any subsequent state. The correct—isolated, atomic—execution of a transaction over a consistent state takes the database to a new consistent state. It should be noted that a consistent state is a conceptual notion. In reality, multiple transactions may execute concurrently and can have various SQL isolation levels. Thus, in practice, the database is often in an inconsistent state represented by the partial execution of concurrent transactions.
[0021] In the case of strict isolation, each transaction sees a consistent, committed state of the database corresponding to the state produced after completing a set of earlier committed transactions. All its reads are from this consistent state. If the transaction is able to successfully execute and commit, it generates a set of updates which must all be installed atomically to produce the next consistent state. Thus, test for ensuring the integrity and authenticity of a transaction's execution can be divided into three sub-components: (1) establishing that all values read by the transaction come from a single consistent state (in particular, one that reflects the updates of all prior committed transactions, in correct order); (2) faithful execution of the transaction using these values—this includes correctness and completeness of all data read, and determination of the correct values of the transaction's updates, and (3) establishing that all updates generated by this execution have been applied to the database.
[0022] The term “faithful execution” means that: (1) only those transactions authorized by the data owner and authorized clients are executed; (2) all such transactions are executed; (3) each transaction is executed in the correct order; and (4) each transaction is correctly executed.
[0023] An assessment of “transactional consistency” (in addition to correctness and completeness) is required to ensure that the untrusted database achieves faithful execution. Transactional consistency requires that each transaction is run against a consistent database containing all, and only the changes of all previously committed transaction, in order of their commits. Consequently, the current consistent state is indeed the correct state corresponding to the initial state followed by the correct application of all previous valid transactions. Furthermore, any updates generated by the transaction are reflected in the updated database upon commitment. Query freshness is part of transactional consistency.
[0024] Transactional consistency is particularly important in situations where updates to the database results from modifications that are not known to the owner, but are determined by the correct evaluation of a transaction on the existing database. Many databases regularly operate this way such as a transaction that pays interest for each account in a banking application, or a transaction that transfers funds between two accounts. In each case, the correct value of the updated data is determined by the values read from the database, and the logic of the transaction.
[0025] To ensure transactional consistency, the owner or the accessor must have authorized the execution of the transaction. The owner needs to be ensured that the transaction was faithfully executed by the host without any tampering of the results. Furthermore, any subsequent queries should be answered against this resulting database following the transaction's commitment. Transactional consistency ensures that the database host does not: (1) drop a transaction—i.e., pretends to execute it, but does not; (2) add an invalid transaction not authorized by the owner or the accessor; (3) alter the order of execution of transactions; or (4) alter the data read by or modified by a transaction.
[0026] From the point of view of authentication, transactional consistency is at least guaranteed for “replayable transactions”. A “replayable transaction” is a transaction that is deterministic. Specifically, the outcome of the transaction—the outputs it generates, the values of its updates and its decision to commit or abort—is completely determined by the values that it reads from the database and its input parameters. This is a reasonable assumption for databases as it is used in most systems and research in databases. Under this assumption, the host does not need to prove all transactions are executed under faithful execution since this can be verified by a simple re-execution of the transaction over the same consistent state that was visible to the transaction when it was run by the host.
[0027] In one embodiment of the invention, a transaction can be specified either as: (i) an SQL statement, or (ii) the identity of a well-defined transaction, for example, a transfer, a withdrawal, a stored procedure, or some embedded code predefined by the owner, a host, and/or an accessor. This does not in any way limit the ability of the owner or the host to issue arbitrary queries—they can simply send an SQL command to the host—but it does obviate the need to send large pieces of transaction code to the host. Instead, a request to execute a transaction can simply specify the transaction by this identity or SQL statement without embedded code. For example, an accessor could ask a host to “transfer” $500 from one account to another. In the case of a stored procedure or embedded code, it is in the host's interest to impose this restriction so that the host can be protected from false claims. The stored procedure or embedded code would be authorized by the owner and immutable. Thus, if the accessor asks to run such a transaction, the host knows exactly what code is running and the owner or the accessor cannot question the outcome that the host has produced if the host faithfully runs the transaction. This restriction can be removed by allowing the owner or the accessor to submit arbitrary code as a transaction to be run at the server. The owner or accessor would have to sign this code for the host to accept it.
[0028] The present invention sets up a strict serializable transaction that sees a consistent database state corresponding to the atomic execution of earlier committed transactions. During the execution of a transaction, the state of the database may not be in a consistent state, for example, there may be uncommitted changes made by other concurrent transactions. However, if only strict serializable transactions are allowed, when a transaction is allowed to commit it is certain that its execution is equivalent to having run in isolation against the consistent state produced by the execution of all transactions that have committed earlier (in the order of commits). The sequence of commit operations in a database defines the progression of the committed state of the database. Even though two or more transactions can run concurrently, when they are committed, they become serialized.
[0029] In one embodiment of the invention, transactional consistency is ensured via a three-step process. First, the owner and the host perform an initialization step by confirming an initial consistent database state. Second, transactions are requested by the accessor and executed by the host. For every executed transaction, the host generates a commit sequence number, creates the verification object of the consistent database state before and after the transaction, and returns a proof of database states to the owner and the accessor for further confirmation. The accessor then passes the proof to the owner who then compares the proofs from the host and the accessor. Third, the accessor can arbitrarily verify a given (current or past) transaction, which is accomplished by retrieving the verification objects for all values read by the transaction, retrieving the proof of database states before and after the transaction from the owner, and confirming the outputs and updates of the transaction based on information supplied by the host and the owner. All signed messages are verified by the recipient. Those of skill in the art will appreciate that the execution and verification of a single transaction may be extended to multiple relations.
[0030] While it is certainly feasible for the owner to validate every single transaction, this results in a heavy burden on the owner. In practice, the owner will likely validate transactions randomly with a frequency that reflects the owner's distrust of the host.
[0031] It is an advantage of the present invention that the owner may identify any transaction that has been executed in the past and ask for it to be validated without any forewarning to the host during the execution of the transaction.
[0032] It is a further advantage of the present invention that once the owner (or the accessor) requests the validation of a transaction, it is impossible for the host to go back and “fix” any errors or omissions with respect to the execution of that transaction.
[0033] It is a further advantage of the present invention that provides an indemnity for the database host against false claims made by the owner or the accessor. In other words, if the database host faithfully executes the database, the host may prove its innocence without depending upon the owner or the accessor.
[0034] It is a further advantage of the present invention that makes it possible to detect failures on the host's part to faithfully host the owner's dynamic database. The host supports a transactional interface (e.g., SQL) to the data allowing the owner to view and update the owner's data.
[0035] It is a further advantage of the present invention that if the host makes any invalid changes to the database or the results of queries, the owner should be able to discover this and be able to prove this error.
[0036] It is a further advantage of the present invention that if the host does indeed faithfully operate the database, then the host should be able to establish innocence, for example, such that the host is indemnified against invalid claims by the owner or the accessor if the host faithfully executes the database.
[0037] It is a further advantage of the present inventions that the host can provide an authentic provenance for all changes made to the data. The host cannot fabricate false provenance. The invention and its attributes and advantages will be further understood and appreciated with reference to the detailed description below of presently contemplated embodiments, taken in conjunction with the accompanying drawings.
DESCRIPTION OF THE DRAWINGS
[0038] FIG. 1 illustrates a diagram of entities relating to an untrusted database system according to one embodiment of the invention.
[0039] FIG. 2 illustrates a simplified view of database consistency according to one embodiment of the invention.
[0040] FIG. 3 illustrates a structure of a Merkle Hash Tree according to one embodiment of the invention.
[0041] FIG. 4 illustrates a structure of a MB-Tree for completeness according to one embodiment of the invention.
[0042] FIG. 5 illustrates transaction execution steps according to one embodiment of the invention.
[0043] FIG. 6 illustrates the legends used in the experimental result graphs according to the invention.
[0044] FIG. 7 are graphs illustrating the effect of database size on (a) construction time and (b) storage cost according to the invention.
[0045] FIG. 8 are graphs illustrating (a) execution time, (b) 10 cost and (c) space cost as the number of insert transactions increases according to the invention.
[0046] FIG. 9 are graphs illustrating (a) execution time and (b) 10 cost for insert transactions with a varying number of clients according to the invention.
[0047] FIG. 10 are graphs illustrating the effect of insert transactions with increasing fractions of transactions on (a) execution time, (b) 10 cost and the effect of the increase in number of clients on execution time according to the invention.
[0048] FIG. 11 are graphs illustrating (a) execution time and (b) 10 cost of range queries with verification according to the invention.
[0049] FIG. 12 are graphs illustrating (a) execution time and (b) 10 cost of range queries with verification when history size is varied according to the invention.
[0050] FIG. 13 illustrates an exemplary cloud computing system that may be used to implement the methods according to the present invention.
DETAILED DESCRIPTION
[0051] As described herein, the preferred embodiments of the present invention provide a method for ensuring the transactional consistency of an untrusted database. Below are the details of certain embodiments, however, this does not limit other embodiments from using other suitable methods or materials. Those of skill in the art will appreciate that the following description is related to preferred and/or example embodiments of the present invention. Certain embodiments of the present invention are defined exclusively within the appended claims.
[0052] FIG. 1 illustrates a diagram of entities relating to an untrusted database system according to one embodiment of the invention. As shown in FIG. 1 , there are three main types of entities involved in an untrusted database system 100 : owner 102 , host 104 and accessor 106 . The owner owns the database including the data of the database and authenticates the accessors such that they can access the data from the server. The host is the untrusted server that hosts the database, e.g., a cloud service provider. The accessor is the one or more clients that access this data from the server. It is contemplated that an accessor may include an owner. Clients are authorized by the owner and can independently authenticate themselves with the server.
[0053] A list of symbols used in the specification and their descriptions are summarized in Table 1:
[0000]
TABLE 1
Symbol Table
Symbol
Description
t
a tuple in a relation
t i
the i th tuple of a relation
h(x)
the value of a one way hash function over x
Φ(x)
label of node x in MB-Tree
a||b
concatenation of a and b
VO
a verification object
T i
the i th committed transaction
DB i
the consistent DB state after the i th commit
MBT i
the proof structure after the i th commit
Proof i
the MB-tree root label after the i th commit
S User (M)
message M signed by User
[0054] FIG. 2 illustrates a simplified view of database consistency 200 according to one embodiment of the invention. As shown in FIG. 2 , each transaction 202 sees a consistent, committed state 204 of the database corresponding to the state produced after completing a set of earlier committed transactions. All its reads are from this consistent state. If the transaction is able to successfully execute and commit, it generates a set of updates which must all be installed atomically to produce the next consistent state.
[0055] In one embodiment of the invention, the database authentication process employs data securities tools including, inter alia, one-way hashing, hash trees such as Merkle Hash Trees (“MHT”) and Merkle Binary Trees (“MBT” or “MB-Tree”), and digital signatures, as described in detail below. Although the invention is discussed herein with respect to Merkle Trees, other hash trees are also contemplated, for example, a Markovian Binary Trees.
[0056] A one-way hash function is a function h, that takes as input a data item x and produces as output the hash of the data item y=h(x). Important requirements for a one-way hash function are (1) given a hash value y, and the details of the hashing function h, it is very difficult to find x such that h(x)=y and (2) the probability that h(x)=h(y) for x≠y is very low, for example, it is unlikely that two different input values will yield the same hash. Therefore, given a hashed value y, it is virtually impossible to discover any data value that yields y as its hash value. Also, given a value x, it is virtually impossible to generate a value z which yields the same hash value. There are many well-known and commonly used strong one-way hash functions such as SHA-256.
[0057] A Merkle Binary-Tree (“MBT” or “MB-Tree”), or simply Merkle Tree, is a binary tree with labeled nodes. For this application, φ(n) represents the label for node n. If n is an internal node with children n left and n right , then:
[0000] φ( n parent )= h (φ( n left )|φ( n right )) Equation 1
[0058] The function h is a one-way hash function. Labels for leaf nodes are commuted using data values depending upon the application. For example, in the case of a relation, each leaf represents a tuple, and the label is calculated as the hash of that tuple.
[0059] A digital signature serves a role similar to regular signatures in that: (1) it enables the recipient to ascertain without doubt the author of a message; (2) it prevents forgery—i.e., it is (computationally) infeasible for the owner to sign a message with the host's signature, and (3) the signature is not reusable, for example, a message signed by the owner cannot be used to generate a signature for another message. One possible scheme for signing documents involves public-key cryptography and one-way hash functions. In order to sign a message, M, the owner first produces a hash of the message and then encrypts the hash using a private key: S Owner (h(M)). The message M, and the signature, S Owner (h(M)) are referred together as a signed message, or S Owner (M). To verify a signed message, the host applies the same hash function to the message to get h(M). The host then decrypts the signature using the owner's public key. If the decrypted value matches the hash that the host computed, the host is certain that the owner has signed the message M.
[0060] In one embodiment of the invention, the correctness of a transaction may be verified using data securities tools. Those of skill in the art will appreciate that the following description is related to preferred and/or example embodiments of the present invention and does not limit other embodiments from using other suitable methods.
[0061] Merkle trees can be used to establish the correctness of query results from an untrusted database. Initially, when the data owner chooses to host a database table on an untrusted host, she computes a Merkle tree over the table as follows. The hash of each tuple's value is computed: had. These hash values represent the labels of the leaves of the Merkle tree. The labels for all the non-leaf nodes in the Merkle tree are computed using Equation. 1. The data owner saves only the value of the root label. The data are then sent to the host for servicing queries. The host computes the same Merkle tree structure over this data and then services queries from the data owner. FIG. 3 shows an example of the tree produced. The correctness of each tuple, t i , in the result of any query is established as follows: the data owner requests the Verification Object (VO) for tuple t i . Let x be the leaf node whose label was computed as the hash of t i . The VO for t i consists of all sibling nodes along the path from x to the root of the Merkle tree. In FIG. 3 , these nodes are shaded and are: a; b; c; d. The host returns to the data owner the VO for t i . The data owner uses the value of t i that she is trying to verify to compute the label of x. Then uses this label and the label for a from the VO to compute the label for x's parent, etc. all the way to the label for the root. If this value is the same as the label for the root that the data owner had computed before hosting the data, the data owner is convinced that t i must be part of the original table. If not, then the data owner is unconvinced that the database is uncompromised.
[0062] Note that the hash function has to be public. The label of the root saved by the data owner is known as the proof. Of course, it is also possible for the accessor to submit queries and verify the correctness of each answer similarly. All the accessor needs to know is the value of the root label initially computed by the owner. This can be obtained directly from the owner at any time.
[0063] The owner could sign the label for the root and publish it to the accessor. The signature ensures that the accessor does indeed have the correct label. If the verification of the correctness of individual attributes of tuples is desired, then it suffices to add one more level to the Merkle tree structure (a new leaf level). Instead of hashing an entire tuple to produce the label for a leaf, the leaf labels can be computed by hashing individual attributes. The next level up combines all the labels for a single tuple into a label for the parent of these nodes. This implies that the structure is no longer a binary tree, but that does not cause any problems. Individual attributes can now be verified in a manner similar to tuples as discussed herein.
[0064] Establishing completeness requires that the owner or the accessor are assured that all answers that should be in the result are indeed in the result. In one embodiment of the invention, the completeness of a transaction may be verified using data securities tools as described below. Those of skill in the art will appreciate that the following description is related to preferred and/or example embodiments of the present invention and does not limit other embodiments from using other suitable methods.
[0065] In one embodiment of the invention, Merkle Trees can be easily extended to use a B+-tree to establish completeness of a query. An MB-Tree behaves just like a regular B+-tree with its keys extended with child hash values. Similar to the Merkle Tree, the label of each non-leaf node is computed by hashing concatenation of labels of its children. Label of a leaf node is computed by hashing concatenation of hash values of each tuple entry in the node. A MB-Tree is used to establish the completeness of the results of a query. FIG. 4 shows an example tree 400 for establishing completeness. Consider a range query which returns tuples t 0 . . . t r . To establish the completeness of tuples satisfying a range, the VO consists the tuple just before the range (t —1 ) and the tuple just after the range (t r+1 ). VO then includes the path from those two tuples to the root. To establish completeness, the data owner computes the labels for all tuples in the results and the two surrounding values from the VO. She then computes the labels of ancestor nodes working her way up the tree. The VO contains the labels of nodes that she needs to compute the ancestor label and also which tuples belongs to the same leaf node. Finally, the data owner compares the label computed for the root with the root label she stored earlier to determine if indeed the result set contains all the tuples that should have been returned. If this is the case, the data owner is assured that all valid tuples were returned to her. The data owner verifies that t 0 and t r+1 are outside the query range, ensuring that the query results were indeed complete.
[0066] If the data owner wishes to update the data that she has previously hosted at the server, she can do so by simply sending the updates to the host after recomputing the Merkle Tree structure incorporating the updates. The host similarly applies the updates to the structure that he maintains. All subsequent queries are then answered using the updated database at the host server, and verifications are now based upon the newly generated structure. Thus, the data owner must use the new proof which is the value of the hash of the new root after incorporating the changes to the data.
[0067] This solution requires that (i) all updates have to be routed through the data owner and (ii) if the data owner wants to verify the update, she has to do it before executing further updates. A skilled person in the art will appreciate that other embodiment of the invention does not require the owner to know the new data values or to retain a copy of the original data, for verifying transaction updates not generated by the owner, as discussed in greater detail below.
[0068] In one embodiment of the invention, the step of initializing the database process is performed. In the beginning, the owner and the host independently compute MBT 0 —the MB-Tree structure over the initial state of the relation. The owner retains only the label of the root of this structure—this is the proof for the initial state, Proof 0 . The host sets up the database with this initial table, ready for processing transactions from the owner and the accessor. This process can be summarized as follows: (1) the owner sends the initial database, DB 0 to the host, (2) the host computes MBT 0 , and sends S Host (Proof 0 ) to the owner, (3) the owner independently computes Proof 0 and verifies what the host has sent; and (4) the owner retains Proof 0 .
[0069] In accordance with an embodiment of the invention, the commit operation and serialization of the transactions are exemplified below. For example, an initial database corresponding to consistent state DB 0 and if two transactions T 1 and T 2 run concurrently over this database, they begin to produce an inconsistent state corresponding to the partial execution of both transactions.
[0070] Without loss of generality, assume that T 1 commits first. This produces a new consistent state, DB 1 that incorporates only the changes of T 1 . The actual database may still reflect an inconsistent state containing uncommitted changes of T 2 . When T 2 attempts to commit, it will only be allowed to commit if its execution is consistent with being run after T 1 (i.e., against DB 1 ). This is the role of concurrency control and is achieved by locking or other means. If T 2 cannot be committed, there is no need to worry about its effects as they will not be in any consistent state. If T 2 is serializable after T 1 it will be committed and will now produce the new consistent state DB 2 . Any subsequently committed transaction will have to be correct with respect to DB 2 .
[0071] To establish that a given transaction, ran against a particular consistent state, DB i−1 , the host may produce the correct MBT structure corresponding to DB i−1 . Although the database at any time is in flux and contains inconsistent states, the MBT structures are only updated at the time of transaction commitment. The correctness and completeness of each transaction may be established by data tools security, as described further herein.
[0072] Thus, each new MBT reflects the commitment of exactly one transaction. In other words, a one-to-one correspondence between the conceptual consistent states and the proof structure is maintained—a new version of the structure is generated in one step only upon the commitment of a transaction. This new structure is computed from the previous structure by applying the changes made by exactly one transaction—the one that has just committed. The host has to declare this structure at the time of commitment of a transaction (by sending out a signed copy of the new root or Proof i beyond the host's control), and be able to use this structure when asked to verify the correct execution of the transaction, which will also involve the structure before the commitment of the given transaction.
[0073] In accordance with one embodiment of the invention, the transaction execution of a database process is performed. FIG. 5 illustrates transaction execution steps according to one embodiment of the invention including an owner 502 , a host 504 , and an accessor 506 . To execute a transaction, the accessor sends to the host a signed message containing the identity of the transaction (as discussed above), all necessary parameters (e.g., account numbers), and a unique transaction sequence number for each transaction submitted by the accessor (if there are multiple accessors, i.e., multiple authorized clients, the number needs to be unique for each such client, but not necessarily across all clients). The host verifies the signature to be that of the accessor and examines the message. The host rejects a transaction request from the accessor if the sequence number is not larger than the earlier request from the same client. The sequence numbers prevent replay attacks by the host. That is, the host will be prevented from reusing a transaction request to run that transaction multiple times.
[0074] The host then runs the requested transaction. The host keeps track of the data items and written by the transaction. If the transaction successfully commits, the host installs the updates produced by the transaction into the current proof structure. Since transactions are committed sequentially, i is the ordinal position of this transaction's commitment since the initial database state. This transaction is identified by the host as T i —i.e., the i th transaction to commit. Concurrency control will ensure that this transaction's reads were consistent with DB i−1 —the consistent state corresponding to all earlier committed transactions. If this is not the case, then the transaction will not be allowed to commit (assuming only strict, serializable executions). Once it commits, its changes will be included in the next conceptual consistent state, DB i . These changes are handled by the normal database processing. The host records the authorization message from the accessor along with the transaction's commit position, i.
[0075] The host needs to declare that T i was applied on DB i−1 and produced DB i . The host does this by computing the corresponding MBT structures MBT i−1 and MBT i . As part of the proof of the commitment of T i , the host sends to the accessor a signed message containing (1) the sequence number submitted by the accessor, (2) the transaction's commit sequence number, i, (3) the label of the root of MBT i−1 , i.e., Proof i−1 , (4) the label of the root of MBT i , i.e., Proof i , and (5) RSet, the result set produced by the transaction. The host also sends to the owner a signed message containing (1) Proof i−1 , (2) Proof i , and (3) the identity of the client that sent this transaction and the SID. Note that for a read-only transaction, the host does not need to send anything to the owner.
[0076] The owner uses the message from the host (after verifying the signature) to maintain the sequence of proofs: Proof 0 , Proof 1 , . . . Proof i that the host claims to be the sequence of consistent states that the database has gone through. The owner checks to see that Proof i−1 is currently the last value in its proof chain. If this is the case, the owner adds Proof i to the end of the chain. The owner also retains the client ID and SID sent by the host. The owner checks (every time, or randomly) to see that the SID has not been used by this client earlier and is in increasing order for the client. The accessor verifies the host's signature, and sends Proof i−1 and Proof i to the owner. The owner checks that Proof i−1 does indeed precede Proof i in the sequence received from the host. If this is not the case, the owner has detected a problem.
[0077] In accordance with one embodiment of the invention, the transaction execution process can be summarized as follows:
[0078] (1) the accessor sends S Accessor (TName; Params; SID) to the host with TName specifying one of the replayable transactions, Params specifying the parameters for the transaction, and SID specifying the unique transaction sequence number generated by the accessor,
[0079] (2) the host records this message after verifying the signature and executes the transaction,
[0080] (3) if the transaction successfully commits, the host computes MBT i and sends S Host (SID; i; Proof i−1 ; Proof i ;RSet) to the accessor, where i is the transaction's commit sequence number, and RSet are the values read by the transaction,
[0081] (4) the host also sends to the owner S Host (i, Proof i−1 ; Proof i ; S Accessor (TName, Params, SID)),
[0082] (5) the owner verifies the signature and then adds Proof i to its chain of proofs after verifying that Proof i−1 is at the end of the current chain,
[0083] (6) the accessor sends S Accessor (Proof i−1 ; Proof i ) to the owner, and
[0084] (7) the owner checks that Proof i−1 and Proof i are contiguous proofs in its chain and checks that the SID is larger than the largest SID the owner already had for this client.
[0085] In accordance with one embodiment of the invention, the transaction verification process is performed following the execution of a transaction. Following the execution of a transaction, the owner or the accessor can arbitrarily decide if the host should verify a given transaction (current or past). If the owner or accessor asks for verification of Transaction T i , the host needs to establish three requirements.
[0086] First, the host has to show that all values read by the transaction were indeed from DB i−1 . As is always the case, if T i updates a data value and subsequently reads it, it should be reading the value it wrote, not the one from DB i−1 . This may be accomplished during the verification of the execution. To do this, the host needs to produce the verification objects for the reads from MBT i−1 . For now, the host may maintain a copy of each MBT or alternative optimized structures. The accessor uses the correctness and completeness mechanisms discussed earlier to verify the reads.
[0087] Second, the accessor needs to know the correct values of all updates generated by the given (replayable) transaction when run on a database corresponding to DB i−1 . The validity of the values read by the transaction is achieved as discussed above. Given a replayable transaction and the values read by the transaction (as declared by the host and validated in the previous step), the values of its updates need to be determined. This verification is the onus of the owner or the accessor. Given a deterministic transaction, and the values that it reads, it is possible to determine the values of its output and updates. Those of skill in the art will appreciate that the verification may be performed in a number of ways including setting up a rudimentary database and running the query, manual inspection of the inputs, query, and outputs, or using a special-purpose tool.
[0088] Third, the owner or the accessor needs to establish that the updates of the transaction were faithfully recorded in the database and used for subsequent transactions. To do this, the host needs to show that MBT i differs from MBT i−1 by exactly the modifications of T i . The host can generate MBT i in a manner similar to the generation of MBT i−1 .
[0089] In accordance with one embodiment of the invention, the transaction execution process can be summarized as follows:
[0090] (1) the accessor asks the host to verify a transaction T i ,
[0091] (2) the host computes MBT i−1 and MBT i ,
[0092] (3) the accessor obtains Proof i−1 and Proof i from the owner,
[0093] (4) the host sends to the accessor the verification objects for all values read by T i based on MBT i−1 ,
[0094] (5) the accessor verifies the correctness and completeness for T i 's reads,
[0095] (6) the accessor determines the outputs and updates for T i (replays T i ) given these reads,
[0096] (7) the host sends to the accessor the verification objects for T i 's updates based on MBT i , and
[0097] (8) the accessor verifies that MBT i contains these updates.
[0098] In accordance with an embodiment of the present invention, failure on the part of the host may be detected. Detection happens when the owner or the accessor decide to verify a given transaction. While it is unlikely that most transactions will be verified, the model for untrusted hosts ensures that even if a single instance of infidelity is detected by the owner it will result in severe penalties for the host. These could include immediate loss of the owner's business, or a lawsuit. In order to increase the likelihood of being caught, it is desirable that any arbitrary transaction can be verified—even one executed a while back.
[0099] If the host drops a transaction, for example, a transaction is submitted by the accessor that the host pretends to execute (i.e., sends unauthentic responses to the accessor, but does not actually execute the transaction), the host will be unable to verify the correctness of that transaction if asked. The verification for this transaction will fail since the host will not be able to show that the state corresponding to Proof i for this transaction reflects the correct execution of T i .
[0100] If the host executes an unauthorized transaction, it will result in either (1) a discrepancy between the latest Proof i that the host has and that at the end of the owner's proof chain such that the host will be unable to verify future transactions, or (2) a message from the host to the owner with an unauthorized pair of proofs. If the owner asks the host to prove this link in the chain, the host will have to produce the original request from an authorized client for this transaction. The host will be unable to produce such a signed message. Replay attempts by the host such as when the host tries to execute an authorized transaction more than once will be caught when the owner receives the Client; SID values that do not show an increase in SID. The owner needs to periodically run verification checks to ensure that the host does not run unauthorized transactions. The owner does this by randomly identifying transactions and asking for them to be validated.
[0101] If the host does not run the transactions in the claimed sequence, the chain of proofs maintained by the owner prevents this from happening. The host informs the accessor of the commit sequence, i, for each transaction. The corresponding pair of proofs, Proof i−1 and Proof i must validate this transaction. If the host does not specify these correctly, verification fails.
[0102] If the host is honest and faithfully executes all transactions submitted by the owner or the accessor, then the host can prove his innocence via an indemnification process. In accordance with one embodiment of the invention, the indemnification process is performed as described below.
[0103] First described is the host's indemnity from the accessor. In order to verify a transaction submitted by the accessor, the host needs the following from the accessor: (1) the request for running the transaction including the transaction name, its parameters, and a sequence number, and (2) the accessor's ability to replay a transaction faithfully. The accessor cannot repudiate the request for running a transaction since the accessor signs the request with all the necessary information. If the accessor does not replay a transaction correctly, the host can check that by replaying it in order to implicate the accessor. This is possible because each transaction is known to each party. To strengthen this, the host may want the owner to sign each transaction's definition if it is not pure SQL. The parameters cannot be repudiated by the accessor, the values read from the database are known to the host such that they can be verified that they are consistent with the consistent state corresponding to the proof value the host sent to the accessor in response to the transaction request. Thus, it is not possible for the accessor to falsely implicate the host.
[0104] Second described is the host's indemnity from the owner. The host relies on the owner to maintain the chain of proofs and also to check that a given SID has not been used earlier for a given client. The owner cannot modify the chain with impunity. If the owner adds a proof that the host has not provided, the owner would have to produce a signed message from the host containing the old and new proofs. the owner cannot manufacture such a signed message. The owner cannot also delete any proof from the chain. If the owner deletes Proof i from the chain, the host can ask the owner to produce the host's message with Proof i−1 ; Proof i+1 (as they are now contiguous in the chain). Since the host never sent such a message, the owner would be unable to produce such a message signed by the host. If the owner claims that an SID value for a client is being reused by the host, the owner can once again be challenged to produce the prior message from the host containing this SID and client pair. If the host has never sent the owner such a message, the owner will be unable to produce it.
[0105] Thus, the host is protected from baseless claims of wrongdoing from either the owner or the accessor.
[0106] In accordance with an embodiment of the invention, the efficiency of the authentication process may be improved by several optimizations, as described below.
[0107] In the above protocol, the host has to maintain the details of which values are read and written by all transactions, and the information necessary to generate the MBT structures for any transaction in the past. The size of this information can grow to be very large. To avoid this, verification checkpoints may be introduced. A verification checkpoint corresponds to a statute of limitations for the owner. In other words, the owner is barred from verifying any transaction beyond a certain time in the past, for example, a month. Thus the owner has up to one month to challenge any transaction. After this point, if the transaction is not challenged, the host can assume that the owner accepts it and the host can discard any data necessary to verify that transaction.
[0108] The owner's burden is significantly reduced in the protocol since the owner can choose to do less frequent testing while still retaining the ability to verify any transaction. The owner is, however, involved in each transaction such that the owner has to maintain the chain of proofs and track the SIDs for each client. This burden can be reduced by involving a semi-honest third party that the owner trusts to handle these tasks. For purposes of this application, the third party is referred to herein as a tester. If the owner can be assured that the tester and the host do not collude, then the owner can be reasonably confident that the tester can maintain checks on the host. The owner could always ask for the verification of any transaction by the tester.
[0109] The host may maintain a copy of each successive MBT i corresponding to the commit of each transaction. This may be expensive and unnecessary. To reduce the cost of storage, each tuple in the database and each node in MB-Tree is assigned a unique id. Each tuple in the relation is also assigned a version number. A history stores each value that a tuple or a node takes as the database evolves. At the start, for each tuple and MB-Tree node, the history stores only one value—the value in the database or MB-Tree after the initialization step. Each initial tuple value is assigned version number 0. When a tuple or a node is modified, the version number is incremented by one and the new value is added to the history along with the transaction's sequence number which modified the value. As the database evolves, the history stores all the values that a particular tuple or MB-Tree node takes on consistent states. When an accessor wants to verify an old transaction, the host can use the history to generate the values that the server read when executing this transaction.
[0110] In accordance with one embodiment of the invention, a secure provenance of the data is provided using history. With history, the host can show which transactions modified a particular tuple. Since with each transaction, the data owner stores the Proof (root label when the transaction was executed), the data owner can verify the correctness of each past value of the tuple, proving the trustworthiness of provenance for that tuple. Since each transaction is signed by the accessor, and the data owner has the proof chain, the host cannot add false history values or drop a value. The data owner can also ask the complete provenance of the database and verify its trustworthiness.
[0111] When an accessor asks for the provenance of a tuple, the server responds with a set of provenance records. Each provenance record has three components: the id of the transaction that created that value; the version of the tuple; and the value of the tuple. The accessor can verify that the returned provenance has not been maliciously manufactured by the host.
[0112] An embodiment of the authentication data structures and protocols according to the present invention is implemented as described in detail below.
[0113] The authentication data structures and protocols are implemented in Oracle—commercial strength database management system that is popularly used by industries and researchers. The implementation is built on top of Oracle without making any modifications to the source code or internals. This demonstrates the applicability of the invention to an existing DBMS. The protocols are implemented in the form of database procedures using PI/SQL. Additional efficiency may be gained by modifying the database internals or exploiting the index frameworks. The data structures may also be created and managed for any generic DBMS.
[0000]
TABLE 2
Tables in the Database
Table
Description
uTable
TupleID, A, Version#
uTableHistory
TransactionID, TupleID, A, Version#
uTableMBT
id, level, Label, keys, children,
key_min, key_max
uTableMBTHistory
TransactionID, id, parentID, level, Tuple
ID, Label, childLabels, canAccomodate,
index
Transaction
id, query, finalLabel
[0114] A synthetic database is created with one table uTable of 1 million tuples. uTable is composed of a table with 2 attributes (TupleID and A). Table 2 describes different tables used in the prototype. An MB-Tree is created on attribute A (integer). The table is populated with synthetic data with random values of A between −10 7 and 10 7 . Three transactions are implemented as stored procedures, namely Insert, Delete, and Select. “Insert” creates a new tuple with a given value of attribute A. “Delete” deletes the tuples which have the given value of attribute A and “Select” is a range query over attribute A. In practice, transactions will be more complex than a single insert or delete. The solution can handle complex transactions as well. However, for simplicity, only simple transactions are considered. The experiments were run on an Intel Xeon 2.4 GHz machine, 12 GB RAM and 7200 RPM disk with a transfer rate of 3 Gb/s, running Oracle 11 g on Linux. Oracle is run with a strict serializable isolation level. A standard block size of 8 KB is used.
[0115] Now, the overhead of constructing (bulk loading) the present invention is examined. FIG. 6 illustrates the legends used in the experimental result graphs as shown in FIG. 7 through FIG. 12 . For the present invention, there is an extra cost for storing the history of the database, which increases the storage cost and construction time. FIGS. 7( a ) and 7 ( b ) show the effect of data size on construction time and storage overhead or cost, respectively. Both costs increase linearly with the size of the database. In addition to the MB-Tree, an extra copy of the MB-Tree and the database table is maintained in the history files. Hence, the solution incurs a 100% storage overhead. The construction time has two components; time to compute hashes and time for IO. The proposed protocol needs twice the amount of IO as compared to MB-Tree, however, the IO cost is superseded by hash computation. Hence, the construction time is not much higher than maintaining just an MB-Tree. In past work, the verification of a transaction was only allowed immediately after the execution of a transaction before any other transactions are executed. This restriction is removed to enable the verification of past transactions. This provides much greater flexibility and reduces the need to immediately verify transactions. Of course, the added functionality comes at an additional storage cost for the history tables.
[0116] Next, the cost of inserting and deleting tuples is examined. Since both operations show similar costs, only the results for insertion are presented. For this experiment no verification is performed. The first experiment studies the performance as the number of insert transactions increases. FIGS. 8( a ), 8 ( b ) and 8 ( c ) show the results. As expected, with a single accessor, the proposed protocol incurs a much higher overhead for storage and IO for maintaining the history information. These costs increase linearly with the number of transactions. However, this does not translate into a significant increase in the running time. This represents the computational overhead of hashing and concatenations which dominate the cost. A key advantage of the present invention comes to light as the number of concurrent clients increases, as seen in FIG. 8( a ) where the running time for our the protocol drops significantly.
[0117] In order to better study the impact of concurrent clients, another set of experiments was ran with 1000 insert transactions with a varying number of clients. The results are shown in FIGS. 9( a ) and 9 ( b ). The MB-Tree solution which needs to process all updates through a single node (the data owner) sees no gain in performance, whereas the proposed solution results in improved performance with greater concurrency (even though it is performing a much larger amount of IO).
[0118] Next, the overhead of transaction verification on the system is examined. One-thousand insert transactions with increasing fractions of transactions that are verified were executed. The percentage of transactions that are verified reflects the data owner's distrust of the host. FIGS. 10( a ) and 10 ( b ) show the results. As the verification percentage increases, it is observed that the execution time of the transactions increases. However, disk IO does not increase as rapidly since there is little extra IO for verification as compared to running the transaction itself. Verification also takes advantage of already cached MB-Tree nodes.
[0119] FIG. 10( c ) shows the effect of the increase in number of clients on execution time. For this experiment, 1000 insert transactions and each transaction is verified. As before, the proposed prototype scales much better to the increase in the number of clients. This is because verification can be done independent of transaction execution, hence, verification executes while other transactions are running. Whereas for the case of just an MB-Tree, the verification of a transaction prevents other transactions from running.
[0120] Next, the performance of the proposed solution for range queries (Search) is examined. This cost is influenced by both the size of the result (larger results will be more expensive to verify) and the size of the history that needs to be searched for generating the proof. Two experiments were conducted to study this behavior. In the first experiment, 1000 insert transactions were ran on the database to populate history. Then, 100 search transactions with 100% verification for different ranges (thereby with different result set size) were executed. FIGS. 11( a ) and 11 ( b ) show the results. As the result set size increases, execution time and the amount of IO increase. For verification, the server has to return the right and left most path of the range. Along with this, the server also has to return which tuples belong to which leaf nodes, as that is crucial information for the client to be able to verify the result set. Hence, as the result set size increases, the verification object size increases which results in increase in verification time. The performance of the solution is comparable to that of an MB-Tree alone.
[0121] In the second experiment, the history size is varied by executing varying numbers of insert transactions before running a fixed search and verification. FIGS. 12( a ) and 12 ( b ) show the effect of increase in history size. The x-axis in both graphs represents number of insert transactions executed before running the search transactions. As expected, increase in the history size increases the verification time for the solution. However, it does not increase rapidly. Note that the search time without verification for the solution and MB-Tree was the same, hence it is not reported separately.
[0122] It is contemplated that the proposed ideas can be easily implemented on top of an existing DBMS. Even with this simple implementation, the overhead for ensuring transactional consistency is reasonable over and above the cost of ensuring only correctness and completeness. Additional optimization methods will be apparent to those skilled in the art from consideration of the specification and practice of the embodiments disclosed herein.
[0123] FIG. 13 illustrates an exemplary cloud computing system 1100 that may be used to implement the methods according to the present invention. The cloud computing system 1100 includes a plurality of interconnected computing environments. The cloud computing system 1100 utilizes the resources from various networks as a collective virtual computer, where the services and applications can run independently from a particular computer or server configuration making hardware less important.
[0124] Specifically, the cloud computing system 1100 includes at least one client computer 1102 . The client computer 1102 may be any device through the use of which a distributed computing environment may be accessed to perform the methods disclosed herein, for example, a traditional computer, portable computer, mobile phone, personal digital assistant, tablet to name a few. The client computer 1102 includes memory such as random access memory (“RAM”), read-only memory (“ROM”), mass storage device, or any combination thereof. The memory functions as a computer usable storage medium, otherwise referred to as a computer readable storage medium, to store and/or access computer software and/or instructions.
[0125] The client computer 1102 also includes a communications interface, for example, a modem, a network interface (such as an Ethernet card), a communications port, a PCMCIA slot and card, wired or wireless systems, etc. The communications interface allows communication through transferred signals between the client computer 1102 and external devices including networks such as the Internet 1104 and cloud data center 1106 . Communication may be implemented using wireless or wired capability such as cable, fiber optics, a phone line, a cellular phone link, radio waves or other communication channels.
[0126] The client computer 1102 establishes communication with the Internet 1104 —specifically to one or more servers—to, in turn, establish communication with one or more cloud data centers 1106 . A cloud data center 1106 includes one or more networks 1110 a , 1110 b , 1110 c managed through a cloud management system 1108 . Each network 1110 a , 1110 b , 1110 c includes resource servers 1112 a , 1112 b , 1112 c , respectively. Servers 1112 a , 1112 b , 1112 c permit access to a collection of computing resources and components that can be invoked to instantiate a virtual machine, process, or other resource for a limited or defined duration. For example, one group of resource servers can host and serve an operating system or components thereof to deliver and instantiate a virtual machine. Another group of resource servers can accept requests to host computing cycles or processor time, to supply a defined level of processing power for a virtual machine. A further group of resource servers can host and serve applications to load on an instantiation of a virtual machine, such as an email client, a browser application, a messaging application, or other applications or software.
[0127] The cloud management system 1108 can comprise a dedicated or centralized server and/or other software, hardware, and network tools to communicate with one or more networks 1110 a , 1110 b , 1110 c , such as the Internet or other public or private network, with all sets of resource servers 1112 a , 1112 b , 1112 c . The cloud management system 1108 may be configured to query and identify the computing resources and components managed by the set of resource servers 1112 a , 1112 b , 1112 c needed and available for use in the cloud data center 1106 . Specifically, the cloud management system 1108 may be configured to identify the hardware resources and components such as type and amount of processing power, type and amount of memory, type and amount of storage, type and amount of network bandwidth and the like, of the set of resource servers 1112 a , 1112 b , 1112 c needed and available for use in the cloud data center 1106 . Likewise, the cloud management system 1108 can be configured to identify the software resources and components, such as type of Operating System (“OS”), application programs, and the like, of the set of resource servers 1112 a , 1112 b , 1112 c needed and available for use in the cloud data center 1106 .
[0128] The present invention is also directed to computer products, otherwise referred to as computer program products, to provide software to the cloud computing system 1100 . Computer products store software on any computer useable medium, known now or in the future. Such software, when executed, may implement the methods according to certain embodiments of the invention. Examples of computer useable mediums include, but are not limited to, primary storage devices (e.g., any type of random access memory), secondary storage devices (e.g., hard drives, floppy disks, CD ROMS, ZIP disks, tapes, magnetic storage devices, optical storage devices, Micro-Electro-Mechanical Systems (“MEMS”), nanotechnological storage device, etc.), and communication mediums (e.g., wired and wireless communications networks, local area networks, wide area networks, intranets, etc.). It is to be appreciated that the embodiments described herein may be implemented using software, hardware, firmware, or combinations thereof.
[0129] The cloud computing system 1100 of FIG. 11 is provided only for purposes of illustration and does not limit the invention to this specific embodiment. It is appreciated that a person skilled in the relevant art knows how to program and implement the invention using any computer system or network architecture.
[0130] While the invention has been described with reference to particular embodiments, those skilled in the art will recognize that many changes may be made thereto without departing from the scope of the invention. Each of these embodiments and variants thereof is contemplated as falling with the scope of the claimed invention, as set forth in the following claims. | A system and methods for providing guarantees about faithful execution of databases that run under the control of an untrusted entity—such as a cloud computing service provider—that is different than the owner of the data and applications being outsourced; or runs on a server that may be compromised by unauthorized users. Specifically, the system and methods establishes that an untrusted database is being faithfully hosted and provides indemnity for the service provider from false claims, enabling the server to prove its innocence against untrue claims of faulty operation. The invention also provides assured provenance for all changes made to the database. | 6 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention generally involves chemical lasers. More particularly, the present invention involves an improved chemical laser configuration for space and ground applications.
2. Description of the Related Art
Conventional linear lasers provide a single chemical laser gain region from a combustion chamber as shown in FIG. 1 . With this configuration, mass efficiency is limited by heat loss to the large surface area i.e., three sides of the combustion chamber. The high weight of the conventional laser is driven by the structural requirement to contain combustion gases at high pressure and high temperature. Finally, the medium quality of the conventional laser is degraded with increasing device length and power due to systematic optical path disturbances in gain medium that cannot be compensated.
The use of a chemical reaction to produce a continuous wave chemically pumped lasing action is well known. The basic concept of such a chemical laser is described, for example, in U.S. Pat. No. 3,688,215, the subject matter of which is incorporated herein by reference. As therein described, the continuous wave chemical laser includes a plenum in which gases are heated by combustion or other means to produce a primary reactant gas containing dissociated atoms of a reactant element such as fluorine mixed with diluting gases, such as helium or nitrogen. The resulting reaction between the hydrogen (or deuterium) and fluorine produces vibrationally excited HF or DF molecules. These molecules are unstable at the low temperature and pressure condition in the cavity and return to a lower vibrational state by releasing photons. Mirrors spaced in the cavity along an axis transverse to the flow field amplify the lasing action from the released photons within the optical cavity formed by the mirrors. The lasing action is of the continuous wave type, which is pumped by the high-energy vibrationally excited molecules formed in the optical cavity. The lasing action depends on producing vibrationally excited states in the HF or DF molecules. This in turn requires that the molecules be formed under conditions of low temperature and pressure. As the pressure and temperature increase, the number of vibrationally excited molecules decreases and more energy goes into translational movement of the molecules, defeating the lasing action.
Cylindrical lasers as illustrated in FIG. 2 provide compact packaging of the gain generator, but require large volumes for handling the radial outflow of laser exhaust gas. End domes are required to contain the combustion products with atomic fluorine in the chamber. The domes are large surface area, heavy structural members that reduce mass efficiency from heat loss effects. Gain medium optical path disturbances increase with cylinder length and cannot be compensated, thereby limiting length and power scaling. Cylindrical combustion devices and optics for power extraction require stringent tolerances during fabrication and alignment, resulting in very high costs for a fragile beam generator. Conventional linear and cylindrical lasers experience large temperature gradients in the structure resulting in time-varying medium quality and laser performance. The radial flow of laser gas lowers the mass flux at the entrance to the diffuser, resulting in lower pressure recovery than linear flow devices.
A low-pressure hydrogen fluoride (HF) laser is a chemical laser, which combines heated atomic fluorine (produced in a combustion chamber similar to the one in a rocket engine) with hydrogen gas to produce excited hydrogen fluoride molecules. The light beam that results radiates on multiple lines between 2.7 μm and 2.9 μm. These wavelengths transmit poorly through the atmosphere. Conventional HF lasers utilize primary nozzles, referred to as hypersonic low temperature or HYLTE nozzles, the surfaces of which are smooth, curved planes that result in nearly parallel flow of gases at the exit of the nozzle. Helium and hydrogen cavity fuel are injected at oblique angles from the nozzle sidewalls. Mixing, reaction and laser gain are produced internal to the primary nozzles and in the downstream optical cavity region. A large base region is formed between adjacent primary nozzles. In a process referred to as helium base purge, helium or other gas must be introduced into these base regions to prevent recirculation of laser gas with ground-state HF that would reduce laser gain and mass efficiency. Conventional HYLTE nozzle configurations wherein hydrogen is injected with wall-jets produces gain internal to the primary nozzle and the large base region between the adjacent primary nozzles is subsonic helium flow that produces no gain. Further, there are flow regions at the laser cavity exit with unmixed atomic fluorine, hydrogen rich regions, and a large subsonic base flow region. These attributes of the conventional HYLTE nozzle result in inefficiencies within the HF laser and a significant loss of power.
There is a need in the art for a laser and nozzle configuration that reduces the inefficiencies currently found in the conventional configurations.
SUMMARY OF THE INVENTION
Summary of the Problem
Available chemical lasers, including linear and cylindrical lasers, have limited mass efficiency due to heat loss and are structurally burdensome and heavy. Power is limited due to optical path disturbances resulting from the need for longer combustion chambers. Further, conventional chemical lasers experience large temperature gradients, which result in time-varying medium quality and reduced laser performance. Finally, available nozzle configurations are in efficient due to a number of non-gain regions resulting therefrom.
Summary of the Solution
An embodiment of the present invention includes a chemical combustion laser component comprising: a first and a second gain region, a combustion region, and a first and a second nozzle blade, wherein the first and second nozzle blades separate the combustion region from the first and second gain regions.
In a further embodiment, each of the first and second nozzle blades is comprised of a primary structure and a secondary structure, wherein the primary structure is formed from a first material and the secondary structure is formed of a second material.
In a yet a further embodiment of the present invention, the second material is able to withstand higher temperatures than the first material.
In yet a further embodiment of the present invention, the first material is aluminum and the second material is nickel.
In yet a further embodiment of the present invention, the first and second nozzle blades are self-cooling.
In still a further embodiment of the present invention a component for a combustion laser comprises: at least one inlet manifold for receiving and distributing combustion fuel; at least one upper manifold sheet having holes therein for receiving combustion fuel from the at least one inlet manifold and further distributing the combustion fuel; at least one pair of nozzle blade structures for receiving the combustion fuel from the at least one upper manifold sheet; and at least one lower manifold sheet, wherein the at least one inlet manifold, the at least one upper manifold sheet, the at least one pair of nozzle blade structures, and the at least one manifold sheet are stacked one on the other and affixed one to the other in a stacked relationship.
In still a further embodiment of the present invention, each of the nozzle blade structures includes a primary nozzle having a serrated tip.
These embodiments result in a combustion laser having lighter weight (e.g., per unit flow area), a more compact, flexible configuration for packaging in spacecraft, aircraft, or ground mobile vehicles, higher mass efficiency from lower heat loss and proven power extraction efficiency of linear lasers, superior output beam quality by incremental compensation of gain medium optical path disturbances and by reduction in time-dependent variations in structural and gain medium characteristics, lower cost and shorter fabrication time for modular dual flow laser and linear optics, more efficient pressure recovery with side-wall isolation nozzles and compact diffuser configurations, and increased small signal gains for more efficient extraction of overtone power.
BRIEF DESCRIPTION OF THE DRAWINGS
In the Figures:
FIG. 1 depicts a conventional linear combustion laser;
FIG. 2 depicts a conventional cylindrical combustion laser;
FIG. 3 depicts a dual-chamber combustion laser component according to an embodiment of the present invention;
FIG. 4 depicts a dual-chamber combustion laser component according to an embodiment of the present invention;
FIG. 5 depicts a dual-chamber combustion laser component according to an embodiment of the present invention;
FIG. 6 depicts a nozzle blade structure according to an embodiment of the present invention;
FIGS. 7 ( a ) and ( b ) depict a manifold assembly according to an embodiment of the present invention;
FIG. 8 depicts a nozzle blade according to an embodiment of the present invention; and
FIG. 9 depicts a combustion laser assembly according to an embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
According to an embodiment of the present invention, a chemical combustion laser is provided having a modular, aluminum design that produces two linear, supersonic gain regions from a single combustion chamber as shown in FIG. 3 . This structure results in a minimum surface area combustion chamber and a balanced thermal design. The laser module is referred to herein as a boxer laser module 1 . FIG. 3 is an end view of the boxer laser module that includes a combustion chamber 22 and on the left and the right sides, gain regions 28 . Gain is produced in the gain regions 28 by the out-flow of combustion products such as, deuterium fluoride, nitrogen, atomic fluorine, and heated helium and by the helium and hydrogen gases injected into the cavity which produce a chemical reaction.
As shown in FIGS. 4 and 5 , each boxer laser module consists of two nozzle blade structures 10 with combustor injectors 12 , cavity injectors 14 , combustor sidewalls 16 and cavity shrouds 18 with integral cavity isolation nozzles 20 . A combustion chamber 22 is formed between two nozzle blade structures 10 connected by combustor sidewalls 16 . The nozzle blade structures 10 are self-cooled by gaseous combustor reactants such as, nitrogen trifluoride, deuterium, and helium, which are injected and burned in the combustion chamber 22 to produce, for example, atomic fluorine, deuterium fluoride, nitrogen, and heated helium and by cavity injectant gases, hydrogen and helium. Boxer laser modules 1 are placed side-by-side to increase the length of the combustion chamber 22 and to form converging-diverging primary nozzles 26 between adjacent nozzle blade structures 10 . Combustion product gases, e.g., atomic fluorine, deuterium fluoride, nitrogen and helium, are expanded through these primary nozzles 26 from a high-pressure of approximately 0.5 atmospheres, a high-temperature of, e.g., approximately 1500K to 1700K condition to a low pressure of approximately 0.005 atmospheres, supersonic, e.g., Mach number of 3 to 5 condition, where cavity fuel, e.g., hydrogen and helium gas mixtures, is injected to produce laser gain. The heat is transferred to the combustor sidewalls 16 and by making the chamber length short, all of the heat that is transferred to the combustor sidewalls 16 , even in the case of a small quantity, can be conducted to the nozzle blade structures 10 and cooled. The nozzle blade structures 10 , combustor sidewalls 16 , and cavity shrouds 18 are designed to achieve dynamic and static thermal balance conditions. This thermal balance condition results in equal heating rates and nearly equal steady-state temperatures for nozzle blade structures 10 , combustor sidewalls 16 , and cavity shrouds 18 . Uniform heating and isothermal steady-state temperatures of the boxer modules 24 results in nearly time-constant combustor pressure and laser cavity flow conditions to maintain desired conditions for laser power and medium quality. According to this embodiment, all parts of the boxer laser module 1 can be heated at a nearly equal rate and operate at nearly equal steady state temperature, such that the throat gap of the primary nozzle 26 which is formed between side-by-side boxer laser modules 1 remains constant. If the throat gap remains constant, all of the properties in the laser gain region 28 remain time-independent and increase the efficiency of the gain regions 28 . This is important to efficient gain production, efficient power extraction, and the medium quality that is required for a high-power laser.
FIG. 5 is a side view of a boxer laser module 1 . The boxer laser module 1 incorporates isolation nozzles 20 in the cavity shrouds 18 downstream of the laser gain regions 28 . In an exemplary embodiment, helium is injected through the nozzles to energize flow along the cavity shrouds 18 to allow formation of strong shock waves just downstream of the laser gain regions 28 for efficient pressure recovery with compact diffuser configurations. Diffuser lengths can be factors of three to five times shorter than for conventional linear lasers when using the boxer laser modules 1 described above. The placement of the isolation nozzles 20 , ensures that the gain regions 28 are independent of their environment. Utilizing a boxer laser comprised of the boxer laser modules 1 having a single minimum surface area combustor region 22 which produces laser gain regions 28 described above, the structural weight to support the combustor is minimized, the heated surface area is minimized, and thereby heat loss to the combustor which drives mass efficiency is minimized. The boxer laser configuration described herein minimizes non-functional structure and facilitates incremental production of very long gain paths, such as those required for an overtone laser.
According to an embodiment of the present invention, FIG. 6 illustrates a nozzle blade structure 10 configuration for reducing heat loss. Combustor injector triplets 32 are incorporated into secondary structure 30 made of high temperature fluorine-compatible material such as nickel, stainless steel, or ceramics like lanthanum hexaboride or alumina. Referring to FIG. 6 , the secondary structure 30 fits into the primary structure 34 which is formed of a lightweight material such as aluminum. By making the secondary structure 30 out of high temperature fluorine-compatible material as opposed to aluminum, the secondary structure 30 can operate at significantly higher temperatures of e.g., 900K to 1300K, as compared to the safe operating temperature of 600K for aluminum. The secondary structure 30 is inserted into the primary structure 34 of the nozzle blade structure 10 in order to reduce heat transfer that would otherwise occur when operating with wall temperatures higher than allowed for an all aluminum nozzle blade structure. The secondary structure 30 is cooled by injected combustor reactants such as, nitrogen trifluoride, deuterium and helium and by conduction to the primary structure 34 that is cooled by the cavity injected hydrogen and helium. In a further embodiment of the present invention, the above-identified combustor reactants as well as cavity injectants hydrogen and helium are transferred from at least one boxer laser module 1 to at least one adjacent boxer laser module 1 for cooling and for injection into the combustor 22 and cavity flow.
In an embodiment of the present invention, the nozzle blade structures 10 and consequently, the boxer laser modules 1 , are connected by a thin, laminated manifold assembly 60 as shown in FIGS. 7 ( a ) and 7 ( b ). The thin manifold sheets 62 have flow channels 64 machined into their surfaces to provide gas flow passages from oxidizer inlet manifolds 66 to coolant and distribution passes (not shown) internal to the nozzle blade structures 10 . The manifold sheets 62 also contain and connect combustor fuel inlet manifolds 67 for facilitating the efficient conduction of fuel to the nozzle blade structures 10 . The manifold sheets 62 are joined together by brazing, diffusion bonding, or the like in order to form upper and lower manifold assemblies 60 and 68 on the top and bottom surfaces of the nozzle blades 10 . This configuration places parent material, e.g., aluminum, with no bond joints, between the oxidizer and the combustion fuels to eliminate the possibility of interpropellant leakage that could cause failure. This configuration also reduces the number of external connections that have to be made to the hardware.
In a further embodiment of the present invention, nozzle blade structures 10 as described in relation to FIG. 6 , increase laser chemical efficiency when used in, for example, HF (Helium Fluoride), HF-overtone, DF (Deuterium Fluoride), and gaseous iodine combustion driven lasers and increase the small signal gain for more efficient extraction of power. Referring to FIG. 8 , a nozzle blade 70 according to an embodiment of the present invention has serrated primary nozzle surfaces 72 to direct primary nozzle flow into the region 74 between primary nozzles. Cavity fuel, e.g., helium gas 76 and hydrogen gas 78 , is injected from the base region through pairs of nozzles that enhance molecular mixing and prevent recirculation of laser gas. Further, a secondary flow of atomic fluorine, is injected into the laser cavity between adjacent pairs of nozzles by means of the serrated primary nozzle surfaces in order to control the flow trajectory of the cavity fuel. This nozzle configuration eliminates the gas flow normally required for base purge, simplifies the design and fabrication of the nozzles, and increases overall mass efficiency of the laser by utilizing all of the cavity area 28 to produce gain. In this embodiment of the present invention, the placement of nozzle blades at the base, allows the laser to filly utilize a conventionally inactive zone that occupies approximately 40 percent of the length of gain region. By injecting the fuel internal to the nozzle, the expansion that the fuel will undergo in the cavity is limited. Referring to helium and hydrogen flow jet patterns 76 and 78 , respectively, complete use of the laser gain region 28 is illustrated.
In a further embodiment of the present invention, the components described above are assembled into a boxer laser 100 as shown in FIG. 9 . At least one boxer laser module is contained in a housing comprised of upper and lower manifold assemblies 160 and 168 surrounded by enclosed gain regions 128 . The at least one boxer laser module comprises the boxer laser 100 along with a surrounding optical train comprised of various optical elements (e.g., mirrors, reflectors, beamsplitters, lenses, switches, and the like) 180 . One skilled in the recognizes the necessity for optical elements and the many configurations of optical elements available for use within a combustion laser.
The embodiments described herein are intended to be exemplary, and while including and describing the best mode of practicing, are not intended to limit the invention. Those skilled in the art appreciate the multiple variations to the embodiments described herein, which fall within the scope of the invention. | The invention herein is directed to a dual-chamber combustion laser assembly having lighter weight (per unit flow area), a more compact, flexible configuration for packaging in spacecraft, aircraft, or ground mobile vehicles, higher mass efficiency from lower heat loss and proven power extraction efficiency of linear lasers, superior output beam quality by incremental compensation of gain medium optical path disturbances and by reduction in time-dependent variations in structural and gain medium characteristics, lower cost and shorter fabrication time for modular dual flow laser and linear optics, more efficient pressure recovery with side-wall isolation nozzles and compact diffuser configurations, and increased small signal gains for more efficient extraction of overtone power. | 8 |
[0001] This application is a continuation of pending International Application Number PCT/US00/00663, filed Jan. 11, 2001, entitled “Vapor Compression System and Method”, the disclosure of which is hereby incorporated by reference. International Application Number PCT/US00/00663 is a continuation-in-part of the following applications: pending U.S. patent application Ser. No. 09/228,696, filed Jan. 12, 1999, entitled “Vapor Compression System and Method”; issued U.S. Pat. No. 6,185,958, Ser. No. 09/431,830, filed Nov. 2, 1999, entitled “Vapor Compression System and Method”; and pending U.S. patent application Ser. No. 09/443,071, filed Nov. 18, 1999 entitled “Vapor Compression System and Method”, the disclosures of which are hereby incorporated by reference.
FIELD OF THE INVENTION
[0002] This invention relates, generally, to vapor compression systems, and more particularly, to mechanically-controlled refrigeration systems using forward-flow defrost cycles.
BACKGROUND OF THE INVENTION
[0003] In a closed-loop vapor compression cycle, the heat transfer fluid changes state from a vapor to a liquid in the condenser, giving off heat, and changes state from a liquid to a vapor in the evaporator, absorbing heat during vaporization. A typical vapor-compression refrigeration system includes a compressor for pumping a heat transfer fluid, such as a freon, to a condenser, where heat is given off as the vapor condenses into a liquid. The liquid flows through a liquid line to a thermostatic expansion valve, where the heat transfer fluid undergoes a volumetric expansion. The heat transfer fluid exiting the thermostatic expansion valve is a low quality liquid vapor mixture. As used herein, the term “low quality liquid vapor mixture” refers to a low pressure heat transfer fluid in a liquid state with a small presence of flash gas that cools off the remaining heat transfer fluid, as the heat transfer fluid continues on in a sub-cooled state. The expanded heat transfer fluid then flows into an evaporator, where the liquid refrigerant is vaporized at a low pressure absorbing heat while it undergoes a change of state from a liquid to a vapor. The heat transfer fluid, now in the vapor state, flows through a suction line back to the compressor. Sometimes, the heat transfer fluid exits the evaporator not in a vapor state, but rather in a superheated vapor state.
[0004] In one aspect, the efficiency of the vapor-compression cycle depends upon the ability of the system to maintain the heat transfer fluid as a high pressure liquid upon exiting the condenser. The cooled, high-pressure liquid must remain in the liquid state over the long refrigerant lines extending between the condenser and the thermostatic expansion valve. The proper operation of the thermostatic expansion valve depends upon a certain volume of liquid heat transfer fluid passing through the valve. As the high-pressure liquid passes through an orifice in the thermostatic expansion valve, the fluid undergoes a pressure drop as the fluid expands through the valve. At the lower pressure, the fluid cools an additional amount as a small amount of flash gas forms and cools of the bulk of the heat transfer fluid that is in liquid form. As used herein, the term “flash gas” is used to describe the pressure drop in an expansion device, such as a thermostatic expansion valve, when some of the liquid passing through the valve is changed quickly to a gas and cools the remaining heat transfer fluid that is in liquid form to the corresponding temperature.
[0005] This low quality liquid vapor mixture passes into the initial portion of cooling coils within the evaporator. As the fluid progresses through the coils, it initially absorbs a small amount of heat while it warms and approaches the point where it becomes a high quality liquid vapor mixture. As used herein, the term “high quality liquid vapor mixture” refers to a heat transfer fluid that resides in both a liquid state and a vapor state with matched enthalpy, indicating the pressure and temperature of the heat transfer fluid are in correlation with each other. A high quality liquid vapor mixture is able to absorb heat very efficiently since it is in a change of state condition. The heat transfer fluid then absorbs heat from the ambient surroundings and begins to boil. The boiling process within the evaporator coils produces a saturated vapor within the coils that continues to absorb heat from the ambient surroundings. Once the fluid is completely boiled-off, it exits through the final stages of the cooling coil as a cold vapor. Once the fluid is completely converted to a cold vapor, it absorbs very little heat. During the final stages of the cooling coil, the heat transfer fluid enters a superheated vapor state and becomes a superheated vapor. As defined herein, the heat transfer fluid becomes a “superheated vapor” when minimal heat is added to the heat transfer fluid while in the vapor state, thus raising the temperature of the heat transfer fluid above the point at which it entered the vapor state while still maintaining a similar pressure. The superheated vapor is then returned through a suction line to the compressor, where the vapor-compression cycle continues.
[0006] For high-efficiency operation, the heat transfer fluid should change state from a liquid to a vapor in a large portion of the cooling coils within the evaporator. As the heat transfer fluid changes state from a liquid to a vapor, it absorbs a great deal of energy as the molecules change from a liquid to a gas absorbing a latent heat of vaporization. In contrast, relatively little heat is absorbed while the fluid is in the liquid state or while the fluid is in the vapor state. Thus, optimum cooling efficiency depends on precise control of the heat transfer fluid by the thermostatic expansion valve to insure that the fluid undergoes a change of state in as large of cooling coil length as possible. When the heat transfer fluid enters the evaporator in a cooled liquid state and exits the evaporator in a vapor state or a superheated vapor state, the cooling efficiency of the evaporator is lowered since a substantial portion of the evaporator contains fluid that is in a state which absorbs very little heat. For optimal cooling efficiency, a substantial portion, or an entire portion, of the evaporator should contain fluid that is in both a liquid state and a vapor state. To insure optimal cooling efficiency, the heat transfer fluid entering and exiting from the evaporator should be a high quality liquid vapor mixture.
[0007] The thermostatic expansion valve plays an important role and regulating the flow of heat transfer fluid through the closed-loop system. Before any cooling effect can be produced in the evaporator, the heat transfer fluid has to be cooled from the high-temperature liquid exiting the condenser to a range suitable of an evaporating temperature by a drop in pressure. The flow of low pressure liquid to the evaporator is metered by the thermostatic expansion valve in an attempt to maintain maximum cooling efficiency in the evaporator. Typically, once operation has stabilized, a mechanical thermostatic expansion valve regulates the flow of heat transfer fluid by monitoring the temperature of the heat transfer fluid in the suction line near the outlet of the evaporator. The heat transfer fluid upon exiting the thermostatic expansion valve is in the form of a low pressure liquid having a small amount of flash gas. The presence of flash gas provides a cooling affect upon the balance of the heat transfer fluid in its liquid state, thus creating a low quality liquid vapor mixture. A temperature sensor is attached to the suction line to measure the amount of superheating experienced by the heat transfer fluid as it exits from the evaporator. Superheat is the amount of heat added to the vapor, after the heat transfer fluid has completely boiled-off and liquid no longer remains in the suction line. Since very little heat is absorbed by the superheated vapor, the thermostatic expansion valve meters the flow of heat transfer fluid to minimize the amount of superheated vapor formed in the evaporator. Accordingly, the thermostatic expansion valve determines the amount of low-pressure liquid flowing into the evaporator by monitoring the degree of superheating of the vapor exiting from the evaporator.
[0008] In addition to the need to regulate the flow of heat transfer fluid through the closed-loop system, the optimum operating efficiency of the refrigeration system depends upon periodic defrost of the evaporator. Periodic defrosting of the evaporator is needed to remove icing that develops on the evaporator coils during operation. As ice or frost develops over the evaporator, it impedes the passage of air over the evaporator coils reducing the heat transfer efficiency. In a commercial system, such as a refrigerated display cabinet, the build up of frost can reduce the rate of air flow to such an extent that an air curtain cannot form in the display cabinet. In commercial systems, such as food chillers, and the like, it is often necessary to defrost the evaporator every few hours. Various defrosting methods exist, such as off-cycle methods, where the refrigeration cycle is stopped and the evaporator is defrosted by air at ambient temperatures. Additionally, electrical defrost off-cycle methods are used, where electrical heating elements are provided around the evaporator and electrical current is passed through the heating coils to melt the frost.
[0009] In addition to off-cycle defrost systems, refrigeration systems have been developed that rely on the relatively high temperature of the heat transfer fluid exiting the compressor to defrost the evaporator. In these techniques, the high-temperature vapor is routed directly from the compressor to the evaporator. In one technique, the flow of high temperature vapor is dumped into the suction line and the system is essentially operated in reverse. In other techniques, the high-temperature vapor is pumped into a dedicated line that leads directly from the compressor to the evaporator for the sole purpose of conveying high-temperature vapor to periodically defrost the evaporator. Additionally, other complex methods have been developed that rely on numerous devices within the refrigeration system, such as bypass valves, bypass lines, heat exchangers, and the like.
[0010] In an attempt to obtain better operating efficiency from conventional vapor-compression refrigeration systems, the refrigeration industry is developing systems of growing complexity. Sophisticated computer-controlled thermostatic expansion valves have been developed in an attempt to obtain better control of the heat transfer fluid through the evaporator. Additionally, complex valves and piping systems have been developed to more rapidly defrost the evaporator in order to maintain high heat transfer rates. While these systems have achieved varying levels of success, the system cost rises dramatically as the complexity of the system increases. Accordingly, a need exists for an efficient refrigeration system that can be installed at low cost and operated at high efficiency.
SUMMARY OF THE INVENTION
[0011] The present invention provides a refrigeration system that maintains high operating efficiency by feeding a saturated vapor into the inlet of an evaporator. As used herein, the term “saturated vapor” refers to a heat transfer fluid that resides in both a liquid state and a vapor state with matched enthalpy, indicating the pressure and temperature of the heat transfer fluid are in correlation with each other. Saturated vapor is a high quality liquid vapor mixture. By feeding saturated vapor to the evaporator, heat transfer fluid in both a liquid and a vapor state enters the evaporator coils. Thus, the heat transfer fluid is delivered to the evaporator in a physical state in which maximum heat can be absorbed by the fluid. In addition to high efficiency operation of the evaporator, in one preferred embodiment of the invention, the refrigeration system provides a simple means of defrosting the evaporator. A multifunctional valve is employed that contains separate passageways feeding into a common chamber. In operation, the multifunctional valve can transfer either a saturated vapor, for cooling, or a high temperature vapor, for defrosting, to the evaporator.
[0012] In one form, the vapor compression system includes an evaporator for evaporating a heat transfer fluid, a compressor for compressing the heat transfer fluid to a relatively high temperature and pressure, and a condenser for condensing the heat transfer fluid. A saturated vapor line is coupled from an expansion valve to the evaporator. In one preferred embodiment of the invention, the diameter and the length of the saturated vapor line is sufficient to insure substantial conversion of the heat transfer fluid into a saturated vapor prior to delivery of the fluid to the evaporator. In one preferred embodiment of the invention, a heat source is applied to the heat transfer fluid in the saturated vapor line sufficient to vaporize a portion of the heat transfer fluid before the heat transfer fluid enters the evaporator. In one preferred embodiment of the invention, a heat source is applied to the heat transfer fluid after the heat transfer fluid passes through the expansion valve and before the heat transfer fluid enters the evaporator. The heat source converts the heat transfer fluid from a low quality liquid vapor mixture to a high quality liquid vapor mixture, or a saturated vapor. Typically, at least about 5% of the heat transfer fluid is vaporized before entering the evaporator. In one embodiment of the invention, the expansion valve resides within a multifunctional valve that includes a first inlet for receiving the heat transfer fluid in the liquid state, and a second inlet for receiving the heat transfer fluid in the vapor state. The multifunctional valve further includes passageways coupling the first and second inlets to a common chamber. Gate valves position within the passageways enable the flow of heat transfer fluid to be independently interrupted in each passageway. The ability to independently control the flow of saturated vapor and high temperature vapor through the refrigeration system produces high operating efficiency by both increased heat transfer rates at the evaporator and by rapid defrosting of the evaporator. The increased operating efficiency enables the refrigeration system to be charged with relatively small amounts of heat transfer fluid, yet the refrigeration system can handle relatively large thermal loads.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] [0013]FIG. 1 is a schematic drawing of a vapor-compression system arranged in accordance with one embodiment of the invention;
[0014] [0014]FIG. 2 is a side view, in partial cross-section, of a first side of a multifunctional valve in accordance with one embodiment of the invention;
[0015] [0015]FIG. 3 is a side view, in partial cross-section, of a second side of the multifunctional valve illustrated in FIG. 2;
[0016] [0016]FIG. 4 is an exploded view of a multifunctional valve in accordance with one embodiment of the invention;
[0017] [0017]FIG. 5 is a schematic view of a vapor-compression system in accordance with another embodiment of the invention;
[0018] [0018]FIG. 6 is an exploded view of the multifunctional valve in accordance with another embodiment of the invention;
[0019] [0019]FIG. 7 is a schematic view of a vapor-compression system in accordance with yet another embodiment of the invention;
[0020] [0020]FIG. 8 is an enlarged cross-sectional view of a portion of the vapor compression system illustrated in FIG. 7;
[0021] [0021]FIG. 9 is a schematic view, in partial cross-section, of a recovery valve in accordance with one embodiment of this invention;
[0022] [0022]FIG. 10 is a schematic view, in partial cross-section, of a recovery valve in accordance with yet another embodiment of this invention;
[0023] [0023]FIG. 11 is a plan view, partially in section, of valve body on a multifunctional valve or device in accordance with a further embodiment of the present invention;
[0024] [0024]FIG. 12 is a side elevational view of the valve body of the multifunctional valve shown in FIG. 11;
[0025] [0025]FIG. 13 is an exploded view, partially in section, of the multifunctional valve or device shown in FIGS. 11 and 12;
[0026] [0026]FIG. 14 is an enlarged view of a portion of the multifunctional valve or device shown in FIG. 12;
[0027] [0027]FIG. 15 is a plan view, partially in section, of valve body on a multifunctional valve or device in accordance with a further embodiment of the present invention; and
[0028] [0028]FIG. 16. is a schematic drawing of a vapor-compression system arranged in accordance with another embodiment of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0029] An embodiment of a vapor-compression system 10 arranged in accordance with one embodiment of the invention is illustrated in FIG. 1. Refrigeration system 10 includes a compressor 12 , a condenser 14 , an evaporator 16 , and a multifunctional valve 18 . Compressor 12 is coupled to condenser 14 by a discharge line 20 . Multifunctional valve 18 is coupled to condenser 14 by a liquid line 22 coupled to a first inlet 24 of multifunctional valve 18 . Additionally, multifunctional valve 18 is coupled to discharge line 20 at a second inlet 26 . A saturated vapor line 28 couples multifunctional valve 18 to evaporator 16 , and a suction line 30 couples the outlet of evaporator 16 to the inlet of compressor 12 . A temperature sensor 32 is mounted to suction line 30 and is operably connected to multifunctional valve 18 . In accordance with the invention, compressor 12 , condenser 14 , multifunctional valve 18 and temperature sensor 32 are located within a control unit 34 . Correspondingly, evaporator 16 is located within a refrigeration case 36 . In one preferred embodiment of the invention, compressor 12 , condenser 14 , multifunctional valve 18 , temperature sensor 32 and evaporator 16 are all located within a refrigeration case 36 . In another preferred embodiment of the invention, the vapor compression system comprises control unit 34 and refrigeration case 36 , wherein compressor 12 and condenser 14 are located within the control unit 34 , and wherein evaporator 16 , multifunctional valve 18 , and temperature sensor 32 are located within refrigeration case 36 .
[0030] The vapor compression system of the present invention can utilize essentially any commercially available heat transfer fluid including refrigerants such as, for example, chlorofluorocarbons such as R-12 which is a dicholordifluoromethane, R-22 which is a monochlorodifluoromethane, R-500 which is an azeotropic refrigerant consisting of R-12 and R-152a, R-503 which is an azeotropic refrigerant consisting of R-23 and R-13, and R-502 which is an azeotropic refrigerant consisting of R-22 and R-115. The vapor compression system of the present invention can also utilize refrigerants such as, but not limited to refrigerants R-13, R-113, 141b, 123a, 123, R-114, and R-11. Additionally, the vapor compression system of the present invention can utilize refrigerants such as, for example, hydrochlorofluorocarbons such as 141b, 123a, 123, and 124, hydrofluorocarbons such as R-134a, 134, 152, 143a, 125, 32, 23, and azeotropic HFCs such as AZ-20 and AZ-50 (which is commonly known as R-507). Blended refrigerants such as MP-39, HP-80, FC-14, R-717, and HP-62 (commonly known as R-404a), may also be used as refrigerants in the vapor compression system of the present invention. Accordingly, it should be appreciated that the particular refrigerant or combination of refrigerants utilized in the present invention is not deemed to be critical to the operation of the present invention since this invention is expected to operate with a greater system efficiency with virtually all refrigerants than is achievable by any previously known vapor compression system utilizing the same refrigerant.
[0031] In operation, compressor 12 compresses the heat transfer fluid, to a relatively high pressure and temperature. The temperature and pressure to which the heat transfer fluid is compressed by compressor 12 will depend upon the particular size of refrigeration system 10 and the cooling load requirements of the systems. Compressor 12 pumps the heat transfer fluid into discharge line 20 and into condenser 14 . As will be described in more detail below, during cooling operations, second inlet 26 is closed and the entire output of compressor 12 is pumped through condenser 14 .
[0032] In condenser 14 , a medium such as air, water, or a secondary refrigerant is blown past coils within the condenser causing the pressurized heat transfer fluid to change to the liquid state. The temperature of the heat transfer fluid drops about 10 to 40° F. (5.6 to 22.2° C.), depending on the particular heat transfer fluid, or glycol, or the like, as the latent heat within the fluid is expelled during the condensation process. Condenser 14 discharges the liquefied heat transfer fluid to liquid line 22 . As shown in FIG. 1, liquid line 22 immediately discharges into multifunctional valve 18 . Because liquid line 22 is relatively short, the pressurized liquid carried by liquid line 22 does not substantially increase in temperature as it passes from condenser 14 to multifunctional valve 18 . By configuring refrigeration system 10 to have a short liquid line, refrigeration system 10 advantageously delivers substantial amounts of heat transfer fluid to multifunctional valve 18 at a low temperature and high pressure. Since the fluid does not travel a great distance once it is converted to a high-pressure liquid, little heat absorbing capability is lost by the inadvertent warming of the liquid before it enters multifunctional valve 18 , or by a loss of in liquid pressure. While in the above embodiments of the invention, the refrigeration system uses a relatively short liquid line 22 , it is possible to implement the advantages of the present invention in a refrigeration system using a relatively long liquid line 22 , as will be described below.The heat transfer fluid discharged by condenser 14 enters multifunctional valve 18 at first inlet 22 and undergoes a volumetric expansion at a rate determined by the temperature of suction line 30 at temperature sensor 32 . Multifunctional valve 18 discharges the heat transfer fluid as a saturated vapor into saturated vapor line 28 . Temperature sensor 32 relays temperature information through a control line 33 to multifunctional valve 18 .
[0033] Those skilled in the art will recognize that refrigeration system 10 can be used in a wide variety of applications for controlling the temperature of an enclosure, such as a refrigeration case in which perishable food items are stored. For example, where refrigeration system 10 is employed to control the temperature of a refrigeration case having a cooling load of about 12000 Btu/hr (84 g cal/s), compressor 12 discharges about 3 to 5 lbs/min (1.36 to 2.27 kg/min) of R-12 at a temperature of about 110° F. (43.3° C.) to about 120° F. (48.9° C.) and a pressure of about 150 lbs/in 2 (1.03 E5 N/m 2 ) to about 180 lbs/in. 2 (1.25 E5 N/m 2 ).
[0034] In accordance with one preferred embodiment of the invention, saturated vapor line 28 is sized in such a way that the low pressure fluid discharged into saturated vapor line 28 substantially converts to a saturated vapor as it travels through saturated vapor line 28 . In one embodiment, saturated vapor line 28 is sized to handle about 2500 ft/min (76 m/min) to 3700 ft/min (1128 m/min) of a heat transfer fluid, such as R-12, and the like, and has a diameter of about 0.5 to 1.0 inches (1.27 to 2.54 cm), and a length of about 90 to 100 feet (27 to 30.5 m). As described in more detail below, multifunctional valve 18 includes a common chamber immediately before the outlet. The heat transfer fluid undergoes an additional volumetric expansion as it enters the common chamber. The additional volumetric expansion of the heat transfer fluid in the common chamber of multifunctional valve 18 is equivalent to an effective increase in the line size of saturated vapor line 28 by about 225%.
[0035] Those skilled in the art will further recognize that the positioning of a valve for volumetrically expanding of the heat transfer fluid in close proximity to the condenser, and the relatively great length of the fluid line between the point of volumetric expansion and the evaporator, differs considerably from systems of the prior art. In a typical prior art system, an expansion valve is positioned immediately adjacent to the inlet of the evaporator, and if a temperature sensing device is used, the device is mounted in close proximity to the outlet of the evaporator. As previously described, such system can suffer from poor efficiency because substantial amounts of the evaporator carry a liquid rather than a saturated vapor. Fluctuations in high side pressure, liquid temperature, heat load or other conditions can adversely effect the evaporator's efficiency.
[0036] In contrast to the prior art, the inventive refrigeration system described herein positions a saturated vapor line between the point of volumetric expansion and the inlet of the evaporator, such that portions of the heat transfer fluid are converted to a saturated vapor before the heat transfer fluid enters the evaporator. By charging evaporator 16 with a saturated vapor, the cooling efficiency is greatly increased. By increasing the cooling efficiency of an evaporator, such as evaporator 16 , numerous benefits are realized by the refrigeration system. For example, less heat transfer fluid is needed to control the air temperature of refrigeration case 36 at a desired level. Additionally, less electricity is needed to power compressor 12 resulting in lower operating cost. Further, compressor 12 can be sized smaller than a prior art system operating to handle a similar cooling load. Moreover, in one preferred embodiment of the invention, the refrigeration system avoids placing numerous components in proximity to the evaporator. By restricting the placement of components within refrigeration case 36 to a minimal number, the thermal loading of refrigeration case 36 is minimized.
[0037] While in the above embodiments of the invention, multifunctional valve 18 is positioned in close proximity to condenser 14 , thus creating a relatively short liquid line 22 and a relatively long saturated vapor line 28 , it is possible to implement the advantages of the present invention even if multifunctional valve 18 is positioned immediately adjacent to the inlet of the evaporator 16 , thus creating a relatively long liquid line 22 and a relatively short saturated vapor line 28 . For example, in one preferred embodiment of the invention, multifunctional valve 18 is positioned immediately adjacent to the inlet of the evaporator 16 , thus creating a relatively long liquid line 22 and a relatively short saturated vapor line 28 , as illustrated in FIG. 7. In order to insure that the heat transfer fluid entering evaporator 16 is a saturated vapor, a heat source 25 is applied to saturated vapor line 28 , as illustrated in FIGS. 7 - 8 . Temperature sensor 32 is mounted to suction line 30 and operatively connected to multifunctional valve 18 , wherein heat source 25 is of sufficient intensity so as to vaporize a portion of the heat transfer fluid before the heat transfer fluid enters evaporator 16 . The heat transfer fluid entering evaporator 16 is converted to a saturated vapor wherein a portion of the heat transfer fluids exists in a liquid state 29 , and another portion of the heat transfer fluid exists in a vapor state 31 , as illustrated in FIG. 8.
[0038] Preferably heat source 25 used to vaporize a portion of the heat transfer fluid comprises heat transferred to the ambient surroundings from condenser 14 , however, heat source 25 can comprise any external or internal source of heat known to one of ordinary skill in the art, such as, for example, heat transferred to the ambient surroundings from the discharge line 20 , heat transferred to the ambient surroundings from a compressor, heat generated by the compressor, heat generated from an electrical heat source, heat generated using combustible materials, heat generated using solar energy, or any other source of heat. Heat source 25 can also comprise an active heat source, that is, any heat source that is intentionally applied to a part of refrigeration system 10 , such as saturated vapor line 28 . An active heat source includes but is not limited to source of heat such as heat generated from an electrical heat source, heat generated using combustible materials, heat generated using solar energy, or any other source of heat which is intentionally and actively applied to any part of refrigeration system 10 . A heat source that comprises heat which accidentally leaks into any part of refrigeration system 10 or heat which is unintentionally or unknowingly absorbed into any part of refrigeration system 10 , either due to poor insulation or other reasons, is not an active heat source.
[0039] In one preferred embodiment of the invention, temperature sensor 32 monitors the heat transfer fluid exiting evaporator 16 in order to insure that a portion of the heat transfer fluid is in a liquid state 29 upon exiting evaporator 16 , as illustrated in FIG. 8. In one preferred embodiment of the invention, at least about 5% of the of the heat transfer fluid is vaporized before the heat transfer fluid enters the evaporator, and at least about 1% of the heat transfer fluid is in a liquid state upon exiting the evaporator. By insuring that a portion of the heat transfer fluid is in liquid state 29 and vapor state 31 upon entering and exiting the evaporator, the vapor compression system of the present invention allows evaporator 16 to operate with maximum efficiency. In one preferred embodiment of the invention, the heat transfer fluid is in at least about a 1% superheated state upon exiting evaporator 16 . In one preferred embodiment of the invention, the heat transfer fluid is between about a 1% liquid state and about a 1% superheated vapor state upon exiting evaporator 16 .
[0040] While the above embodiments rely on heat source 25 or the dimensions and length of saturated vapor line 28 to insure that the heat transfer fluid enters the evaporator 16 as a saturated vapor, any means known to one of ordinary skill in the art which can convert the heat transfer fluid to a saturated vapor upon entering evaporator 16 can be used. Additionally, while the above embodiments use temperature sensor 32 to monitor the state of the heat transfer fluid exiting the evaporator, any metering device known to one of ordinary skill in the art which can determine the state of the heat transfer fluid upon exiting the evaporator can be used, such as a pressure sensor, or a sensor which measures the density of the fluid. Additionally, while in the above embodiments, the metering device monitors the state of the heat transfer fluid exiting evaporator 16 , the metering device can also be placed at any point in or around evaporator 16 to monitor the state of the heat transfer fluid at any point in or around evaporator 16 .
[0041] Shown in FIG. 2 is a side view, in partial cross-section, of one embodiment of multifunctional valve 18 . Heat transfer fluid enters first inlet 24 and traverses a first passageway 38 to a common chamber 40 . An expansion valve 42 is positioned in first passageway 38 near first inlet 22 . Expansion valve 42 meters the flow of the heat transfer fluid through first passageway 38 by means of a diaphragm (not shown) enclosed within an upper valve housing 44 . Expansion valve 42 can be any device known to one of ordinary skill in the art that can be used to meter the flow of heat transfer fluid, such as a thermostatic expansion valve, a capillary tube, or a pressure control. Control line 33 is connected to an input 62 located on upper valve housing 44 . Signals relayed through control line 33 activate the diaphragm within upper valve housing 44 . The diaphragm actuates a valve assembly 54 (shown in FIG. 4) to control the amount of heat transfer fluid entering an expansion chamber 52 (shown in FIG. 4) from first inlet 24 . A gating valve 46 is positioned in first passageway 38 near common chamber 40 . In a preferred embodiment of the invention, gating valve 46 is a solenoid valve capable of terminating the flow of heat transfer fluid through first passageway 38 in response to an electrical signal.
[0042] Shown in FIG. 3 is a side view, in partial cross-section, of a second side of multifunctional valve 18 . A second passageway 48 couples second inlet 26 to common chamber 40 . A gating valve 50 is positioned in second passageway 48 near common chamber 40 . In a preferred embodiment of the invention, gating valve 50 is a solenoid valve capable of terminating the flow of heat transfer fluid through second passageway 48 upon receiving an electrical signal. Common chamber 40 discharges the heat transfer fluid from multifunctional valve 18 through an outlet 41 .
[0043] An exploded perspective view of multifunctional valve 18 is illustrated in FIG. 4. Expansion valve 42 is seen to include expansion chamber 52 adjacent first inlet 22 , valve assembly 54 , and upper valve housing 44 . Valve assembly 54 is actuated by a diaphragm (not shown) contained within the upper valve housing 44 . First and second tubes 56 and 58 are located intermediate to expansion chamber 52 and a valve body 60 . Gating valves 46 and 50 are mounted on valve body 60 . In accordance with the invention, refrigeration system 10 can be operated in a defrost mode by closing gating valve 46 and opening gating valve 50 . In defrost mode, high temperature heat transfer fluid enters second inlet 26 and traverses second passageway 48 and enters common chamber 40 . The high temperature vapors are discharged through outlet 41 and traverse saturated vapor line 28 to evaporator 16 . The high temperature vapor has a temperature sufficient to raise the temperature of evaporator 16 by about 50 to 120° F. (27.8 to 66.7° C.). The temperature rise is sufficient to remove frost from evaporator 16 and restore the heat transfer rate to desired operational levels.
[0044] While the above embodiments use a multifunctional valve 18 for expanding the heat transfer fluid before entering evaporator 16 , any thermostatic expansion valve or throttling valve, such as expansion valve 42 or even recovery valve 19 , may be used to expand heat transfer fluid before entering evaporator 16 .
[0045] In one preferred embodiment of the invention heat source 25 is applied to the heat transfer fluid after the heat transfer fluid passes through expansion valve 42 and before the heat transfer fluid enters the inlet of evaporator 16 to convert the heat transfer fluid from a low quality liquid vapor mixture to a high quality liquid vapor mixture, or a saturated vapor. In one preferred embodiment of the invention, heat source 25 is applied to a multifunctional valve 18 . In another preferred embodiment of the invention heat source 25 is applied within recovery valve 19 , as illustrated in FIG. 9. Recovery valve 19 comprises a first inlet 124 connected to liquid line 22 and a first outlet 159 connected to saturated vapor line 28 . Heat transfer fluid enters first inlet 124 of recovery valve 19 to a common chamber 140 . An expansion valve 142 is positioned near first inlet 124 to expand the heat transfer fluid entering first inlet 124 from a liquid state to a low quality liquid vapor mixture. Second inlet 127 is connected to discharge line 20 , and receives high temperature heat transfer fluid exiting compressor 12 . High temperature heat transfer fluid exiting compressor 12 enters second inlet 127 and traverses second passageway 123 . Second passageway 123 is connected to second inlet 127 and second outlet 130 . A portion of second passageway 123 is located adjacent to common chamber 140 .
[0046] As the high temperature heat transfer fluid nears common chamber 140 , heat from the high temperature heat transfer fluid is transferred from the second passageway 123 to the common chamber 140 in the form of heat source 125 . By applying heat from heat source 125 to the heat transfer fluid, the heat transfer fluid in common chamber 140 is converted from a low quality liquid vapor mixture to a high quality liquid vapor mixture, or saturated vapor, as the heat transfer fluid flows through common chamber 140 . Additionally, the high temperature heat transfer fluid in the second passageway 123 is cooled as the high temperature heat transfer fluid passes near common chamber 140 . Upon traversing second passageway 123 , the cooled high temperature heat transfer fluid exits second outlet 130 and enters condensor 14 . Heat transfer fluid in common chamber 140 exits recover valve 19 at first outlet 159 into saturated vapor line 28 as a high quality liquid vapor mixture, or saturated vapor.
[0047] While in the above preferred embodiment, heat source 125 comprises heat transferred to the ambient surroundings from a compressor, heat source 125 may comprise any external or internal source of heat known to one of ordinary skill in the art, such as, for example, heat generated from an electrical heat source, heat generated using combustible materials, heat generated using solar energy, or any other source of heat. Heat source 125 can also comprise any heat source 25 and any active heat source, as previously defined.
[0048] In one preferred embodiment of the invention, recovery valve 19 comprises third passageway 148 and third inlet 126 . Third inlet 126 is connected to discharge line 20 , and receives high temperature heat transfer fluid exiting compressor 12 . A first gating valve (not shown) capable of terminating the flow of heat transfer fluid through common chamber 140 is positioned near the first inlet 124 of common chamber 140 . Third passageway 148 connects third inlet 126 to common chamber 140 . A second gating valve (not shown) is positioned in third passageway 148 near common chamber 140 . In a preferred embodiment of the invention, the second gating valve is a solenoid valve capable of terminating the flow of heat transfer fluid through third passageway 148 upon receiving an electrical signal.
[0049] In accordance with the invention, refrigeration system 10 can be operated in a defrost mode by closing the first gating valve located near first inlet 124 of common chamber 140 and opening the second gating valve positioned in third passageway 148 near common chamber 140 . In defrost mode, high temperature heat transfer fluid from compressor 12 enters third inlet 126 and traverses third passageway 148 and enters common chamber 140 . The high temperature heat transfer fluid is discharged through first outlet 159 of recovery valve 19 and traverses saturated vapor line 28 to evaporator 16 . The high temperature heat transfer fluid has a temperature sufficient to raise the temperature of evaporator 16 by about 50 to 120° F. (27.8 to 66.7° C.). The temperature rise is sufficient to remove frost from evaporator 16 and restore the heat transfer rate to desired operational levels.
[0050] During the defrost cycle, any pockets of oil trapped in the system will be warmed and carried in the same direction of flow as the heat transfer fluid. By forcing hot gas through the system in a forward flow direction, the trapped oil will eventually be returned to the compressor. The hot gas will travel through the system at a relatively high velocity, giving the gas less time to cool thereby improving the defrosting efficiency. The forward flow defrost method of the invention offers numerous advantages to a reverse flow defrost method. For example, reverse flow defrost systems employ a small diameter check valve near the inlet of the evaporator. The check valve restricts the flow of hot gas in the reverse direction reducing its velocity and hence its defrosting efficiency. Furthermore, the forward flow defrost method of the invention avoids pressure build up in the system during the defrost system. Additionally, reverse flow methods tend to push oil trapped in the system back into the expansion valve. This is not desirable because excess oil in the expansion can cause gumming that restricts the operation of the valve. Also, with forward defrost, the liquid line pressure is not reduced in any additional refrigeration circuits being operated in addition to the defrost circuit.
[0051] It will be apparent to those skilled in the art that a vapor compression system arranged in accordance with the invention can be operated with less heat transfer fluid those comparable sized system of the prior art. By locating the multifunctional valve near the condenser, rather than near the evaporation, the saturated vapor line is filled with a relatively low-density vapor, rather than a relatively high-density liquid. Alternatively, by applying a heat source to the saturated vapor line, the saturated vapor line is also filled with a relatively low-density vapor, rather than a relatively high-density liquid. Additionally, prior art systems compensate for low temperature ambient operations (e.g. winter time) by flooding the evaporator in order to reinforce a proper head pressure at the expansion valve. In one preferred embodiment of the invention, vapor compression system heat pressure is more readily maintained in cold weather, since the multifunctional value is positioned in close proximity to the condenser.
[0052] The forward flow defrost capability of the invention also offers numerous operating benefits as a result of improved defrosting efficiency. For example, by forcing trapped oil back into the compressor, liquid slugging is avoided, which has the effect of increasing the useful life of the equipment. Furthermore, reduced operating cost are realized because less time is required to defrost the system. Since the flow of hot gas can be quickly terminated, the system can be rapidly returned to normal cooling operation. When frost is removed from evaporator 16 , temperature sensor 32 detects a temperature increase in the heat transfer fluid in suction line 30 . When the temperature rises to a given set point, gating valve 50 and multifunctional valve 18 is closed. Once the flow of heat transfer fluid through first passageway 38 resumes, cold saturated vapor quickly returns to evaporator 16 to resume refrigeration operation.
[0053] Those skilled in the art will appreciate that numerous modifications can be made to enable the refrigeration system of the invention to address a variety of applications. For example, refrigeration systems operating in retail food outlets typically include a number of refrigeration cases that can be serviced by a common compressor system. Also, in applications requiring refrigeration operations with high thermal loads, multiple compressors can be used to increase the cooling capacity of the refrigeration system.
[0054] A vapor compression system 64 in accordance with another embodiment of the invention having multiple evaporators and multiple compressors is illustrated in FIG. 5. In keeping with the operating efficiency and low-cost advantages of the invention, the multiple compressors, the condenser, and the multiple multifunctional valves are contained within a control unit 66 . Saturated vapor lines 68 and 70 feed saturated vapor from control unit 66 to evaporators 72 and 74 , respectively. Evaporator 72 is located in a first refrigeration case 76 , and evaporator 74 is located in a second refrigeration case 78 . First and second refrigeration cases 76 and 78 can be located adjacent to each other, or alternatively, at relatively great distance from each other. The exact location will depend upon the particular application. For example, in a retail food outlet, refrigeration cases are typically placed adjacent to each other along an isle way. Importantly, the refrigeration system of the invention is adaptable to a wide variety of operating environments. This advantage is obtained, in part, because the number of components within each refrigeration case is minimal. In one preferred embodiment of the invention, by avoiding the requirement of placing numerous system components in proximity to the evaporator, the refrigeration system can be used where space is at a minimum. This is especially advantageous to retail store operations, where floor space is often limited.
[0055] In operation, multiple compressors 80 feed heat transfer fluid into an output manifold 82 that is connected to a discharge line 84 . Discharge line 84 feeds a condenser 86 and has a first branch line 88 feeding a first multifunctional valve 90 and a second branch line 92 feeding a second multifunctional valve 94 . A bifurcated liquid line 96 feeds heat transfer fluid from condenser 86 to first and second multifunctional valves 90 and 94 . Saturated vapor line 68 couples first multifunctional valve 90 with evaporator 72 , and saturated vapor line 70 couples second multifunctional valve 94 with evaporator 74 . A bifurcated suction line 98 couples evaporators 72 and 74 to a collector manifold 100 feeding multiple compressors 80 . A temperature sensor 102 is located on a first segment 104 of bifurcated suction line 98 and relays signals to first multifunctional valve 90 . A temperature sensor 106 is located on a second segment 108 of bifurcated suction line 98 and relays signals to second multifunctional valve 94 . In one preferred embodiment of the invention, a heat source, such as heat source 25 , can be applied to saturated vapor lines 68 and 70 to insure that the heat transfer fluid enters evaporators 72 and 74 as a saturated vapor.
[0056] Those skilled in the art will appreciate that numerous modifications and variations of vapor compression system 64 can be made to address different refrigeration applications. For example, more than two evaporators can be added to the system in accordance with the general method illustrated in FIG. 5. Additionally, more condensers and more compressors can also be included in the refrigeration system to further increase the cooling capability.
[0057] A multifunctional valve 110 arranged in accordance with another embodiment of the invention is illustrated in FIG. 6. In similarity with the previous multifunctional valve embodiment, the heat transfer fluid exiting the condenser in the liquid state enters a first inlet 122 and expands in expansion chamber 152 . The flow of heat transfer fluid is metered by valve assembly 154 . In the present embodiment, a solenoid valve 112 has an armature 114 extending into a common seating area 116 . In refrigeration mode, armature 114 extends to the bottom of common seating area 116 and cold refrigerant flows through a passageway 118 to a common chamber 140 , then to an outlet 120 . In defrost mode, hot vapor enters second inlet 126 and travels through common seating area 116 to common chamber 140 , then to outlet 120 . Multifunctional valve 110 includes a reduced number of components, because the design is such as to allow a single gating valve to control the flow of hot vapor and cold vapor through the valve.
[0058] In yet another embodiment of the invention, the flow of liquefied heat transfer fluid from the liquid line through the multifunctional valve can be controlled by a check valve positioned in the first passageway to gate the flow of the liquefied heat transfer fluid into the saturated vapor line. The flow of heat transfer fluid through the refrigeration system is controlled by a pressure valve located in the suction line in proximity to the inlet of the compressor. Accordingly, the various functions of a multifunctional valve of the invention can be performed by separate components positioned at different locations within the refrigeration system. All such variations and modifications are contemplated by the present invention.
[0059] Those skilled in the art will recognize that the vapor compression system and method described herein can be implemented in a variety of configurations. For example, the compressor, condenser, multifunctional valve, and the evaporator can all be housed in a single unit and placed in a walk-in cooler. In this application, the condenser protrudes through the wall of the walk-in cooler and ambient air outside the cooler is used to condense the heat transfer fluid.
[0060] In another application, the vapor compression system and method of the invention can be configured for air-conditioning a home or business. In this application, a defrost cycle is unnecessary since icing of the evaporator is usually not a problem.
[0061] In yet another application, the vapor compression system and method of the invention can be used to chill water. In this application, the evaporator is immersed in water to be chilled. Alternatively, water can be pumped through tubes that are meshed with the evaporator coils.
[0062] In a further application, the vapor compression system and method of the invention can be cascaded together with another system for achieving extremely low refrigeration temperatures. For example, two systems using different heat transfer fluids can be coupled together such that the evaporator of a first system provide a low temperature ambient. A condenser of the second system is placed in the low temperature ambient and is used to condense the heat transfer fluid in the second system.
[0063] Another embodiment of a multifunctional valve or device 225 is shown in FIGS. 11 - 14 and is generally designated by the reference numeral 225 . This embodiment is functionally similar to that described in FIGS. 2 - 4 and FIG. 6 which was generally designated by the reference numeral 18 . As shown, this embodiment includes a main body or housing 226 which preferably is constructed as a single one-piece structure having a pair of threaded bosses 227 , 228 that receive a pair of gating valves and collar assemblies, one of which being shown in FIG. 13 and designated by the reference numeral 229 . This assembly includes a threaded collar 230 , gasket 231 and solenoid-actuated gating valve receiving member 232 having a central bore 233 , that receives a reciprocally movable valve pin 234 that includes a spring 235 and needle valve element 236 which is received with a bore 237 of a valve seat member 238 having a resilient seal 239 that is sized to be sealingly received in well 240 of the housing 226 . A valve seat member 241 is snuggly received in a recess 242 of valve seat member 238 . Valve seat member 241 includes a bore 243 that cooperates with needle valve element 236 to regulate the flow of refrigerant therethrough.
[0064] A first inlet 244 (corresponding to first inlet 24 in the previously described embodiment) receives liquid feed refrigerant from expansion valve 42 , and a second inlet 245 (corresponding to second inlet 26 of the previously described embodiment) receives hot gas from the compressor 12 during a defrost cycle. In one preferred embodiment multifunctional valve 225 comprises first inlet 244 , outlet 248 , common chamber 246 , and expansion valve 42 , as illustrated in FIG. 16 . In one preferred embodiment, expansion valve 42 is connected with first inlet 244 . The valve body 226 includes a common chamber 246 (corresponding to common chamber 40 in the previously described embodiment). Expansion valve 42 receives refrigerant from the condenser 14 which then passes through inlet 244 into a semicircular well 247 which, when gating valve 229 is open, then passes into common chamber 246 and exits from the multifunctional valve 225 through outlet 248 (corresponding to outlet 41 in the previously described embodiment).
[0065] A best shown in FIG. 11 the valve body 226 includes a first passageway 249 (corresponding to first passageway 38 of the previously described embodiment) which communicates first inlet 244 with common chamber 246 . In like fashion, a second passageway 250 (corresponding to second passageway 48 of the previously described embodiment) communicates second inlet 245 with common chamber 246 .
[0066] Insofar as operation of the multifunctional valve or device 225 is concerned, reference is made to the previously described embodiment since the components thereof function in the same way during the refrigeration and defrost cycles. In one preferred embodiment, the heat transfer fluid exits the condenser 14 in the liquid state passes through expansion valve 42 . As the heat transfer fluid passes through expansion valve 42 , the heat transfer fluid changes from a liquid to a liquid vapor mixture. The heat transfer fluid enter the first inlet 244 as a liquid vapor mixture and expands in common chamber 246 . In one preferred embodiment, the heat transfer fluid expands in a direction away from the flow of the heat transfer fluid. As the heat transfer fluid expands in common chamber 246 , the liquid separates from the vapor in the heat transfer fluid. The heat transfer fluid then exits common chamber 246 . Preferably, the heat transfer fluid exits common chamber 246 as a liquid and a vapor, wherein a substantial amount of the liquid is separate and apart from a substantial amount of the vapor. The heat transfer fluid then passes through outlet 248 and travels through saturated vapor line 28 to evaporator 16 . In one preferred embodiment, the heat transfer fluid then passes through outlet 248 and enters evaporator 16 at first evaporative line 328 , as described in more detail below. Preferably, the heat transfer fluid travels from outlet 248 to the inlet of evaporator 16 as a liquid and a vapor, wherein a substantial amount of the liquid is separate and apart from a substantial amount of the vapor.
[0067] In one preferred embodiment, a pair of gating valves 229 can be used to control the flow of heat transfer fluid or hot vapor into common chamber 246 . In refrigeration mode, a first gating valve 229 is opened to allow refrigerant to flow through first inlet 244 and into common chamber 246 , and then to outlet 248 . In defrost mode, a second gating valve 229 is opened to allow hot vapor to flow through second inlet 245 and into common chamber 246 , and then to outlet 248 . While in the above embodiments, multifunctional valve 225 has been described as having multiple gating valves 229 , multifunctional valve 225 can be designed with only one gating valve. Additionally, multifunctional valve 225 has been described as having a second inlet 245 for allowing hot vapor to flow through during defrost mode, multifunctional valve 225 can be designed with only first inlet 244 .
[0068] In one preferred embodiment, multifunctional valve comprises bleed line 251 , as illustrated in FIG. 15. Bleed line 251 is connected with common chamber 246 and allows heat transfer fluid that is in common chamber 246 to travel to saturated vapor line 28 or first evaporative line 328 . In one preferred embodiment, bleed line 251 allows the liquid that has separated from the liquid vapor mixture entering common chamber 246 to travel to saturated vapor line 28 or first evaporative line 328 . Preferably, bleed line 251 is connected to bottom surface 252 of common chamber 246 , wherein bottom surface 252 is the surface of common chamber 246 located nearest the ground.
[0069] In one preferred embodiment, multifunctional valve 225 is dimensioned as specified below in Table A and as illustrated in FIGS. 11 - 14 . The length of common chamber 246 will be defined as the distance from outlet 248 to back wall 253 . The length of common chamber 246 is represented by the letter G, as illustrated in FIG. 11. Common chamber 246 has a first portion adjacent to a second portion, wherein the first portion begins at outlet 248 and the second portion ends at back wall 253 , as illustrated in FIG. 1. First inlet 244 and outlet 248 are both connected with the first portion. The heat transfer fluid enters common chamber 246 through first inlet 244 and within the first portion of the common chamber 246 . In one preferred embodiment, the first portion has a length equal to no more than about 75% of the length of common chamber 246 . More preferably, the first portion has a length equal to no more than about 35% of the length of common chamber 246 .
TABLE A DIMENSIONS OF MULTIFUNCTIONAL VALVE Inches Millimeters (all dimensions not specified (all dimensions not speci- Dimensions are to be +/−0.015) fied are to be +/−0.381) A 2.500 63.5 B 2.125 53.975 C 1.718 43.637 D1 (diameter) 0.812 20.625 D2 (diameter) 0.609 15.469 D3 (diameter) 1.688 42.875 D4 (diameter) 1.312 (+/−0.002) 33.325 (+/−0.051) D5 (diameter) 0.531 13.487 E 0.406 10.312 F 1.062 26.975 G 4.500 114.3 H 5.000 127 I 0.781 19.837 J 2.500 63.5 K 1.250 31.75 L 0.466 11.836 M 0.812 (+/−0.005) 20.6248 (+/−0.127) R1 (radius) 0.125 3.175
[0070] In one preferred embodiment, the heat transfer fluid passes through expansion valve 42 and then enters the inlet of evaporator 16 , as illustrated in FIG. 16. In this embodiment, evaporator 16 comprises first evaporative line 328 , evaporator coil 21 , and second evaporative line 330 . First evaporative line 328 is positioned between outlet 248 and evaporator coil 21 , as illustrated in FIG. 16. Second evaporative line 330 is positioned between evaporative coil 21 and temperature sensor 32 . Evaporator coil 21 is any conventional coil or device that absorbs heat. Multifunctional valve 18 is preferably connected with and adjacent evaporator 16 . In one preferred embodiment, evaporator 16 comprises a portion of multifunctional valve 18 , such as first inlet 244 , outlet 248 , and common chamber 246 , as illustrated in FIG. 16. Preferably, expansion valve 42 is positioned adjacent evaporator 16 . Heat transfer fluid exits expansion valve 42 and then directly enters evaporator 16 at inlet 244 . As the heat transfer fluid exits expansion valve 42 and enters evaporator 16 at inlet 244 , the temperature of the heat transfer fluid is at an evaporative temperature, that is the heat transfer fluid begins to absorb heat upon passing through expansion valve 42 .
[0071] Upon passing through inlet 244 , common chamber 246 , and outlet 248 , the heat transfer fluid enters first evaporative line 328 . Preferably, first evaporative line 328 is insulated. Heat transfer fluid then exits first evaporative line 328 and enters evaporative coil 21 . Upon exiting evaporative coil 21 , heat transfer fluid enters second evaporative line 330 . Heat transfer fluid exists second evaporative line 330 and evaporator 16 at temperature sensor 32 .
[0072] Preferably, every element within evaporator 16 , such as saturated vapor line 28 , multifunctional valve 18 , and evaporator coil 21 , absorbs heat. In one preferred embodiment, as the heat transfer fluid passes through expansion valve 42 , the heat transfer fluid is at a temperature within 20° F. of the temperature of the heat transfer fluid within the evaporator coil 21 . In another preferred embodiment, the temperature of the heat transfer fluid in any element within evaporator 16 , such as saturated vapor line 28 , multifunctional valve 18 , and evaporator coil 21 , is within 20° F. of the temperature of the heat transfer fluid in any other element within evaporator 16 .
[0073] As known by one of ordinary skill in the art, every element of refrigeration system 10 described above, such as evaporator 16 , liquid line 22 , and suction line 30 , can be scaled and sized to meet a variety of load requirements.
[0074] In one preferred embodiment, the refrigerant charge of the heat transfer fluid in refrigeration system 10 , is equal to or greater than the refrigerant charge of a conventional system.
[0075] Without further elaboration it is believed that one skilled in the art can, using the preceding description, utilize the invention to its fullest extent. The following examples are merely illustrative of the invention and are not meant to limit the scope in any way whatsoever.
EXAMPLE I
[0076] A 5-ft (1.52 m) Tyler Chest Freezer was equipped with a multifunctional valve in a refrigeration circuit, and a standard expansion valve was plumbed into a bypass line so that the refrigeration circuit could be operated as a conventional refrigeration system and as an XDX refrigeration system arranged in accordance with the invention. The refrigeration circuit described above was equipped with a saturated vapor line having an outside tube diameter of about 0.375 inches (0.953 cm) and an effective tube length of about 10 ft (3.048 m). The refrigeration circuit was powered by a Copeland hermetic compressor having a capacity of about {fraction (1/3)} ton (338 kg) of refrigeration. A sensing bulb was attached to the suction line about 18 inches from the compressor. The circuit was charged with about 28 oz. (792 g) of R-12 refrigerant available from The DuPont Company. The refrigeration circuit was also equipped with a bypass line extending from the compressor discharge line to the saturated vapor line for forward-flow defrosting (See FIG. 1). All refrigerated ambient air temperature measurements were made using a “CPS Date Logger” by CPS temperature sensor located in the center of the refrigeration case, about 4 inches (10 cm) above the floor.
[0077] XDX System—Medium Temperature Operation
[0078] The nominal operating temperature of the evaporator was 20° F. (−6.7° C.) and the nominal operating temperature of the condenser was 120° F. (48.9° C.). The evaporator handled a cooling load of about 3000 Btu/hr (21 g cal/s). The multifunctional valve metered refrigerant into the saturated vapor line at a temperature of about 20° F. (−6.7° C.). The sensing bulb was set to maintain about 25° F. (13.9° C.) superheating of the vapor flowing in the suction line. The compressor discharged pressurized refrigerant into the discharge line at a condensing temperature of about 120° F. (48.9° C.), and a pressure of about 172 lbs/in 2 (118,560 N/m 2 ).
[0079] XDX System—Low Temperature Operation
[0080] The nominal operating temperature of the evaporator was −5° F. (−20.5° C.) and the nominal operating temperature of the condenser was 115° F. (46.1° C.). The evaporator handled a cooling load of about 3000 Btu/hr (21 g cal/s). The multifunctional valve metered about 2975 ft/min (907 km/min) of refrigerant into the saturated vapor line at a temperature of about −5° F. (−20.5° C.). The sensing bulb was set to maintain about 20° F. (11.1° C.) superheating of the vapor flowing in the suction line. The compressor discharged about 2299 ft/min (701 m/min) of pressurized refrigerant into the discharge line at a condensing temperature of about 115° F. (46.1° C.), and a pressure of about 161 lbs/in 2 (110,977 N/m 2 ). The XDX system was operated substantially the same in low temperature operation as in medium temperature operation with the exception that the fans in the Tyler Chest Freezer were delayed for 4 minutes following defrost to remove heat from the evaporator coil and to allow water drainage from the coil.
[0081] The XDX refrigeration system was operated for a period of about 24 hours at medium temperature operation and about 18 hours at low temperature operation. The temperature of the ambient air within the Tyler Chest Freezer was measured about every minute during the 23 hour testing period. The air temperature was measured continuously during the testing period, while the refrigeration system was operated in both refrigeration mode and in defrost mode. During defrost cycles, the refrigeration circuit was operated in defrost mode until the sensing bulb temperature reached about 50° F. (10° C.). The temperature measurement statistics appear in Table I below.
[0082] Conventional System—Medium Temperature Operation With Electric Defrost
[0083] The Tyler Chest Freezer described above was equipped with a bypass line extending between the compressor discharge line and the suction line for defrosting. The bypass line was equipped with a solenoid valve to gate the flow of high temperature refrigerant in the line. An electric heat element was energized instead of the solenoid during this test. A standard expansion valve was installed immediately adjacent to the evaporator inlet and the temperature sensing bulb was attached to the suction line immediately adjacent to the evaporator outlet. The sensing bulb was set to maintain about 6° F. (3.33° C.) superheating of the vapor flowing in the suction line. Prior to operation, the system was charged with about 48 oz. (1.36 kg) of R-12 refrigerant.
[0084] The conventional refrigeration system was operated for a period of about 24 hours at medium temperature operation. The temperature of the ambient air within the Tyler Chest Freezer was measured about every minute during the 24 hour testing period. The air temperature was measured continuously during the testing period, while the refrigeration system was operated in both refrigeration mode and in reverse-flow defrost mode. During defrost cycles, the refrigeration circuit was operated in defrost mode until the sensing bulb temperature reached about 50° F. (10° C.). The temperature measurement statistics appear in Table I below.
[0085] Conventional System—Medium Temperature Operation With Air Defrost
[0086] The Tyler Chest Freezer described above was equipped with a receiver to provide proper liquid supply to the expansion valve and a liquid line dryer was installed to allow for additional refrigerant reserve. The expansion valve and the sensing bulb were positioned at the same locations as in the reverse-flow defrost system described above. The sensing bulb was set to maintain about 8° F. (4.4° C.) superheating of the vapor flowing in the suction line. Prior to operation, the system was charged with about 34 oz. (0.966 kg) of R-12 refrigerant.
[0087] The conventional refrigeration system was operated for a period of about 24½ hours at medium temperature operation. The temperature of the ambient air within the Tyler Chest Freezer was measured about every minute during the 24½ hour testing period. The air temperature was measured continuously during the testing period, while the refrigeration system was operated in both refrigeration mode and in air defrost mode. In accordance with conventional practice, four defrost cycles were programmed with each lasting for about 36 to 40 minutes. The temperature measurement statistics appear in Table I below.
TABLE I REFRIGERATION TEMPERATURES (° F./° C.) XDX 1) XDX 1) Medium Low Conventional 2) Conventional 2) Temperature Temperature Electric Defrost Air Defrost Average 38.7/3.7 4.7/−15.2 39.7/4.3 39.6/4.2 Standard 0.8 0.8 4.1 4.5 Deviation Variance 0.7 0.6 16.9 20.4 Range 7.1 7.1 22.9 26.0
[0088] As illustrated above, the XDX refrigeration system arranged in accordance with the invention maintains a desired the temperature within the chest freezer with less temperature variation than the conventional systems. The standard deviation, the variance, and the range of the temperature measurements taken during the testing period are substantially less than the conventional systems. This result holds for operation of the XDX system at both medium and low temperatures.
[0089] During defrost cycles, the temperature rise in the chest freezer was monitored to determine the maximum temperature within the freezer. This temperature should be as close to the operating refrigeration temperature as possible to avoid spoilage of food products stored in the freezer. The maximum defrost temperature for the XDX system and for the conventional systems is shown in Table II below.
TABLE II MAXIMUM DEFROST TEMPERATURE (° F./° C.) XDX Conventional Conventional Medium Temperature Electric Defrost Air Defrost 44.4/6.9 55.0/12.8 58.4/14.7
EXAMPLE II
[0090] The Tyler Chest Freezer was configured as described above and further equipped with electric defrosting circuits. The low temperature operating test was carried out as described above and the time needed for the refrigeration unit to return to refrigeration operating temperature was measured. A separate test was then carried out using the electric defrosting circuit to defrost the evaporator. The time needed for the XDX system and an electric defrost system to complete defrost and to return to the 5° F. (−15° C.) operating set point appears in Table III below.
TABLE III TIME NEEDED TO RETURN TO REFRIGERATION TEMPERATURE OF 5° F. (−15° C.) FOLLOWING XDX Conventional System with Electric Defrost Defrost Duration (min) 10 36 Recovery Time (min) 24 144
[0091] As shown above, the XDX system using forward-flow defrost through the multifunctional valve needs less time to completely defrost the evaporator, and substantially less time to return to refrigeration temperature.
[0092] Thus, it is apparent that there has been provided, in accordance with the invention, a vapor compression system that fully provides the advantages set forth above. Although the invention has been described and illustrated with reference to specific illustrative embodiments thereof, it is not intended that the invention be limited to those illustrative embodiments. Those skilled in the art will recognize that variations and modifications can be made without departing from the spirit of the invention. For example, non-halogenated refrigerants can be used, such as ammonia, and the like can also be used. It is therefore intended to include within the invention all such variations and modifications that fall within the scope of the appended claims and equivalents thereof. | A vapor compression system includes an evaporator, a compressor, and a condenser interconnected in a closed-loop system. In one embodiment, a multifunctional valve is configured to receive a liquefied heat transfer fluid from the condenser and a hot vapor from the compressor. A saturated vapor line connects the outlet of the multifunctional valve to the inlet of the evaporator and is sized so as to substantially convert the heat transfer fluid exiting the multifunctional valve into a saturated vapor prior to delivery to the evaporator. The multifunctional valve regulates the flow of heat transfer fluid through the valve by monitoring the temperature of the heat transfer fluid returning to the compressor through a suction line coupling the outlet of the evaporator to the inlet of the compressor. Separate gated passageways within the multifunctional valve permit the refrigeration system to be operated in defrost mode by flowing hot vapor through the saturated vapor line and the evaporator in a forward-flow process thereby reducing the amount of time necessary to defrost the system and improving the overall system performance. | 5 |
BACKGROUND OF THE INVENTION
The present invention relates to a camera, and particularly to a camera having a barrier movable along a rail mechanism between a position over a photographing lens and a position retreated from the photographing lens.
A compact camera having a barrier movable along a rail mechanism has been conventionally known. The purpose of the barrier is to protect the optical system, such as the photographing lens and the finder, when the camera is carried, and to cover the projecting portion to make the camera compact.
A number of camera makers have proposed a type of camera which has a barrier capable of simply moving linearly along a rail, a so-called “full barrier”.
Further, a camera having a barrier, called “a flat barrier”, is known as a more compact camera. The barrier of this type is movable along a rail mechanism also in a direction substantially parallel to the optical axis of the photographing lens, so that the front surface of the camera is flat when the barrier is closed.
For example, Jpn. UM Appln. KOKAI Publication No. 58-163938 discloses a camera which achieves the aforementioned objects by means of a barrier movable along a rail mechanism not only in the horizontal direction but also in the direction substantially parallel to the optical axis of the photographing lens.
The conventional camera of this type has a structure in which a barrier rail branches in the horizontal direction in front of the camera. While the barrier is traveling, a plurality of pins (claws) of the barrier are slid along the rail.
With the barrier rail having the basic structure described above, however, when the user is to manually slide the barrier, a pin of the barrier may be removed from a predetermined route of the rail while sliding, particularly, at a branch point of the rail. Otherwise, the pin may erroneously enter into another route. Thus, the barrier is easily caught in the rail.
In this state, even if the user simply continues the manual operation, the barrier cannot be moved successfully.
In this case, the user must first remove the barrier from the caught position by, for example, returning the barrier in the opposite direction, and then try to move it in the forward direction.
The conventional camera as described above has a problem in operation that the barrier cannot be moved successfully in only a single smooth operation.
BRIEF SUMMARY OF THE INVENTION
The present invention has been made to overcome the problem of the conventional art as described above, and an object of the present invention is to provide a camera having a compact and simple rail mechanism which can realize a successful barrier slide operation by a single smooth operation.
To achieve the above object, according to a first embodiment of the present invention, there is provided a camera comprising:
a camera body including a photographing lens;
a barrier supported on the camera body so as to be movable between a cover position covering the photographing lens and a retreat position retreated from the cover position in a first direction substantially parallel to an optical axis of the photographing lens and a second direction substantially perpendicular to the first direction; and
a rail mechanism for guiding relative movement between the camera body and the barrier in the first and the second directions of the barrier,
the rail mechanism comprising:
a first slide projection having a predetermined projecting length for guiding movement of the barrier;
a second slide projection, having a projecting length longer than the first slide projection, for guiding movement of the barrier;
first cam means, slidably engaged with the first and the second slide projections, for guiding movement of the barrier in the second direction; and
second cam means, branched from the first cam means and slidably engaged with only the first slide projection, for guiding movement of the barrier in the first direction.
According to another embodiment of the present invention, there is provided a camera comprising:
a camera body including a photographing lens and a rail formed of a shallow groove and a deep groove connected to each other;
a barrier supported on the camera body so as to be movable along the rail between a cover position covering the photographing lens and a retreat position retreated from the cover position;
a long projection provided on the barrier so as to be slidable along the rail and engageable with only the deep groove;
a short projection provided on the barrier so as to be engageable with both the deep groove and the shallow groove; and
urging means, elastically deformed when one of both ends of the barrier along a direction of movement of the barrier is brought into contact with the camera body, for urging the barrier so that the short projection can be inserted and removed from the shallow groove.
According to still another embodiment of the present invention, there is provided a camera comprising:
a camera body including a photographing lens;
a barrier supported on the camera body so as to be movable between a cover position covering the photographing lens and a retreat position retreated from the cover position in a first direction substantially parallel to an optical axis of the photographing lens and a second direction substantially perpendicular to the first direction;
a first slide projection having a short length formed on the barrier;
a second slide projection having a long length formed on the barrier; and
a rail for guiding movement of the barrier,
the rail comprising:
a common rail portion formed in the camera body, engaged in common with the first and the second slide projections, when the barrier is moved;
a first rail portion branched from a middle portion of the common rail portion and engaged with only the first slide projection; and
a second rail portion continuous to the common rail portion in a region where only the second slide projection can move, and engaged with the second slide projection.
According to a further embodiment of the present invention, there is provided a camera comprising:
a camera body including a photographing lens;
a movable barrier movable between a first position covering a front of the photographing lens, where the movable barrier and a front surface of the camera body are substantially on a same plane, and a second position retreated from the front of the photographing lens and projected from the front surface of the camera body to expose the photographing lens;
a long pin and a short pin, arranged in line with an axis of movement of the movable barrier and crossing an optical axis of the photographing lens, the long pin being closer to the photographing lens than the short pin;
a first cam groove, engaged with the long pin and bent so that the movable barrier comes closer to the photographing lens via the long pin, when the movable barrier moves from the second position to the first position;
a contact portion brought into contact with a distal end portion of the movable barrier when the movable barrier approaches the first position along the first cam groove;
a second cam groove, shallower than the first cam groove and branched from the first cam groove, for guiding the short pin together with the long pin engaged with the first cam groove, so that the movable barrier can be positioned at the first position.
According to a still further embodiment of the present invention, there is provided a camera comprising:
a camera body including a photographing lens;
a movable barrier movable between a first position covering a front of the photographing lens, where the movable barrier and a front surface of the camera body form a substantially flat surface, and a second position retreated from the front of the photographing lens and projected from the front surface of the camera body to expose the photographing lens;
a guide surface for guiding side surfaces of the movable barrier;
a cam groove bent so that the movable barrier is movable with respect to the guide surface between the first position and the second position;
a long pin and a short pin, engaged with the cam groove and arranged in line with an axis of movement of the movable barrier, the long pin being closer to the photographing lens in the axis of movement of the movable barrier; and
a contact portion brought into contact with a distal end portion of the movable barrier when the movable barrier moves from the second position to the first position;
wherein the cam groove comprises:
a first groove portion engaged with the long pin, when the movable barrier moves from the second position to the first position; and
a second groove portion, having a depth smaller than a length of the long pin and branched from the first groove portion, provided to be engaged with the short pin when the movable barrier is brought into contact with the contact portion.
Additional objects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out in the appended claims.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate presently preferred embodiments of the invention, and together with the general description given above and the detailed description of the preferred embodiments given below, serve to explain the principles of the invention.
FIG. 1 is a perspective view of a camera according to a first embodiment of the present invention in which the barrier is closed;
FIG. 2 is a perspective view of a camera according to the first embodiment in which the barrier is opened;
FIG. 3 is an exploded perspective view of a camera according to the first embodiment;
FIG. 4 is a cross-sectional view of a main part of a case relating to the barrier;
FIG. 5 is an enlarged view of the main part relating to the barrier shown in FIG. 4;
FIG. 6 is a perspective view of a camera according to a second embodiment of the present invention in which the barrier is closed;
FIG. 7 is a perspective view of a camera according to the second embodiment in which the barrier is opened; and
FIG. 8 is an exploded perspective view of a camera according to the second embodiment.
DETAILED DESCRIPTION OF THE INVENTION
Reference will now be made in detail to the presently preferred embodiments of the invention as illustrated in the accompanying drawings, in which like reference characters designate like or corresponding parts throughout the several drawings.
First Embodiment
FIG. 1 is a perspective view of a camera according to a first embodiment of the present invention.
FIG. 1 shows a closed state of a barrier 30 seen obliquely from above the camera.
The camera has a wall member called “a flat barrier” slidably mounted on a front cover so as to be closed when the camera is not used. This barrier structure covers a main optical system of the camera, thereby forming a flat front surface which is safe and convenient to carry.
The camera comprises a front cover 10 , a barrier 30 , a barrier ornament 35 , a cover 40 , a rear cover 50 and a shutter button 80 . The front cover 10 covers a camera body 1 from the front. The barrier 30 is attached to the front surface of the camera body 1 so as to be movable in the directions indicated by the arrows, to shield an optical system such as a photographing lens 60 mounted on the camera body 1 . The barrier ornament 35 is attached to an end portion of the front surface of the barrier 30 along the vertical direction and projected forward, so that the user can slide the barrier 30 in the directions of the arrows by a finger. The cover 40 covers the front of, for example, a region held by the right hand of the user. The rear cover 50 covers the overall main portion of the camera from the side opposite to the front cover 10 . The shutter button 80 slightly projects upward above a right portion of the upper surface of the front cover 10 .
It is understood from FIG. 1 that, when the barrier 30 is closed, a front surface of the front cover 10 having a 90°-turned U shape, the cover 40 and the barrier 30 form a flat surface of the same level, as described above.
FIG. 2 is a perspective view of a camera according to the first embodiment in the case where the barrier 30 shown in FIG. 1 is opened.
When the barrier is slid by pressing the barrier ornament 35 leftward in the drawing, a power supply (not shown) is turned on in association with the slide movement, thereby supplying power to the camera body 1 . As a result, as shown in FIG. 2, a lens barrel of the photographing lens 60 hidden behind the barrier 30 projects forward along the optical axis and a finder 65 is exposed.
At this time, the barrier 30 is slid along barrier pin traveling grooves 15 , which are provided in upper and lower interior edge portions 17 of the front cover 10 . Each of the upper and lower barrier pin traveling grooves 15 has a predetermined form and predetermined two levels of depth.
A plurality of pins 31 , 32 , 33 and 34 are projected from inner portions of the barrier 30 (see FIG. 3 ). These pins are inserted in and travel along the barrier pin traveling grooves.
When the closed barrier 30 is slid to the left in the drawing, the barrier 30 is at first moved forward smoothly along the optical axis by a predetermined amount from the flat state, with the inner surface of the right end of the barrier 30 being kept in contact with a contact portion 16 .
Thereafter, the barrier 30 is moved parallel with the front surface of the camera body, keeping a predetermined distance from the initial flat state, and finally stopped at the left end of the camera body 1 so as to completely cover the front surface of the cover 40 .
Only after this state, the shutter button 80 can function to allow a photographing operation.
FIG. 3 is an exploded perspective view of a camera according to the first embodiment of the present invention.
Structures of the parts of the camera of the present invention will be described in detail with reference to FIG. 3 . The front cover 10 has a plurality of openings.
More specifically, the front cover 10 has an opening 11 for the photographing lens, through which the lens barrel of the photographing lens 60 is inserted so as to be movable along the optical axis. Further, it has an opening 12 for the finder corresponding to the position of the finder 65 , an opening 13 for a wall member (described later) to which a wall member 20 is attached, and an opening 14 for the shutter button through which the shutter button 80 is loosely inserted.
The barrier pin traveling groove 15 has two levels of depth, i.e., a shallower portion and a deeper portion. It further includes first and second branched cam means as will be described below. Thus, the barrier pin traveling groove 15 is constituted by four groove portions: grooves 15 a , 15 b , 15 c and 15 d.
In a plan view, the deep groove (the longest groove, hereinafter referred to as the parallel groove) 15 b extends parallel with the front surface of the cover 10 from an approximately left end of the camera body 1 to a middle portion of the lower interior edge portion 17 . The shallow groove (oblique groove) 15 a is branched from the parallel groove 15 b and extends obliquely backward. The deep groove (oblique groove) 15 c is branched from the right end of the parallel groove 15 b and extends backward parallel with the oblique groove 15 a . The deep groove (oblique groove) 15 d forms the distal end portion of the oblique groove 15 c.
The deep grooves and the shallow grooves have depths respectively corresponding to the lengths of the long pins 31 and 32 and short pins 33 and 34 of the barrier 30 . The short pins 33 and 34 constitute a first sliding projection and the long pins 31 and 32 constitute a second sliding projection, as will be described later.
The contact portion 16 is a slightly projected portion having a trapezoidal cross section. The surface of the contact portion 16 is smoothed.
Like the barrier pin traveling groove 15 formed in the lower interior edge portion 17 as described above, a branched barrier pin traveling groove 15 is also formed in the upper interior edge portion, as indicated by a broken line.
A side wall 10 a has two holes h 1 and h 2 . A partition wall 10 b is formed in the vertical direction between the upper and lower interior edge portions 17 of the front cover 10 to the left of the center of the camera in the drawing. The partition wall 10 b have two holes h 3 and h 4 . Thus, the two walls have the four holes h 1 to h 4 .
The four holes h 1 , h 2 , h 3 and h 4 respectively correspond to attachment holes 24 , 25 , 22 and 23 for attaching a wall member 20 (described below) to the walls 10 a and 10 b.
The wall member 20 has the attachment holes 22 to 24 in four corner portions and a boss hole 21 made through a portion near the central thereof.
In the wall member 20 , a rectangular region formed in a central portion thereof is thicker than edge portions in which the attachment holes are made.
The wall member 20 is attached from the rear side of the opening 13 for the wall member of the front cover 10 , so that the opening 13 is closed by the rectangular region of the wall member 20 .
The wall member 20 is fixed to the partition wall 10 b and the side wall 10 a by screwing fixing screws 72 a , 72 b , 73 a and 73 b (see FIG. 4) into the four holes h 3 , h 4 , h 1 and h 2 .
The partition wall 10 b and the side wall 10 a respectively have positioning holes 18 and 19 for determining the position of the cover 40 as will be described later.
The barrier 30 has a shape approximate to the U shape of the recess formed in the front surface of the front cover 10 . The length in the longitudinal direction of the barrier 30 plus the cover 40 is the same as the length of the recess.
Further, as shown in FIG. 3, the barrier 30 has four edge portions 30 a , 30 b , 30 c and 30 d slightly projecting in the thickness direction of the barrier. Long and short cylindrical barrier pins 33 , 34 , 31 and 32 are projected from the edge portions in the vertical direction. The barrier pins 33 and 34 constitute a first slide projecting portion and the barrier pins 31 and 32 constitute a second slide projecting portion.
The barrier 30 has the barrier ornament 35 projected forward in a left end portion of the surface.
When the barrier 30 is closed and fitted in the recess of the cover 10 , the surface of the camera body 1 is flat as a whole together with the front cover 10 and the cover 40 .
The cover 40 has a boss 41 near the center of the rear surface thereof. A bottomed small hole 41 a is formed in the center of the boss 41 .
Positioning pins 42 and 43 are projected from two end portions on a diagonal of the rear surface of the cover 40 , as shown in FIG. 3 .
The cover 40 is located at a portion usually held by the right hand of the user, and covers the front right portion of the camera body 1 , when the barrier 30 is closed. Therefore, it is preferable that the cross section of the cover 40 taken in the longitudinal direction be substantially trapezoidal, having obtuse corners.
FIG. 4 is a cross-sectional view of the front cover 10 having the above barrier 30 e.
When the elements described above are assembled, the barrier 30 is inserted in the opening 13 from the inner side of the front cover 10 so as to be in front of the front cover 10 , before the rear cover 50 shown in FIGS. 1 and 2 is fitted to the front cover 10 .
At this time, the barrier pins 31 and 32 are inserted in the barrier pin traveling grooves 15 , so that the barrier 30 is slid to the position in front of the opening 11 for the photographing lens. Further, the barrier pins 33 and 34 are inserted in the barrier pin traveling grooves 15 .
Then, the barrier 30 is completely closed. Thereafter, the boss 41 of the cover 40 is inserted in the boss hole 21 of the wall member 20 , such that the front cover 20 is sandwiched between the cover 40 and the wall member 20 .
At this time, the cover 40 is positioned with respect to the cover 10 by inserting the positioning pins 42 and 43 on the diagonal line of the rear surface of the cover 40 into the positioning holes 18 and 19 formed in the partitioning wall 10 b and the side wall 10 a of the front cover 10 .
A boss screw 71 , such as a self-tapping tight screw, is screwed into the bottomed small hole 41 a formed in the boss 41 of the cover 40 from the rear side. As a result, the wall member 20 and the cover 40 are fixed to each other with the front cover 10 sandwiched therebetween.
Thus, the front portion of the camera body 1 is assembled.
The barrier pin traveling grooves 15 formed in the front cover 10 will now be described in detail with reference to FIG. 4 .
The parallel groove 15 b extends, in the horizontal direction, from the neighborhood of the position where the wall member 20 is fixed by the fixing screws 73 a and 73 b to the position before the center of the opening 11 for the photographing lens. At this position, the deep parallel groove 15 b is continuous to the oblique groove 15 c of the same depth which forms an angle of about 300 to 45° with the groove 15 b , and then to the oblique end groove 15 d at the distal end of the same depth.
It is understood from the cross-sectional view of FIG. 4 that the oblique end groove 15 d reaches a portion near the center of the opening 11 for the photographing lens in the horizontal direction.
The oblique groove (shallow groove) 15 a , branched from the parallel groove 15 b , extends substantially parallel with the oblique groove 15 c from the neighborhood of the position where the wall member 20 is fixed by the fixing screws 72 a and 72 b . The length of the oblique groove 15 a is substantially the same as that of the oblique groove 15 c.
It is also understood from the cross-sectional view of FIG. 4 that the contact portion 16 is slightly projected in the direction along the optical axis.
As described above, when the wall member 20 and the cover 40 are attached to the front cover 10 from the front and the rear sides, gaps are formed between the front cover 10 and the upper and the lower sides of the cover 40 . The four edge portions projecting in the thickness direction of the barrier 30 can travel horizontally along the gaps.
At this time, the long pins 31 and 32 and the short pins 33 and 34 are slid in the barrier traveling grooves 15 .
FIG. 5 is an enlarged view of the characteristic part relating to the barrier 30 shown in FIG. 4 .
The following is a more detailed explanation of the barrier pin traveling groove 15 and the long pins 31 and 32 and the short pins 33 and 34 of the barrier 30 which travel along the barrier pin traveling grooves 15 .
The shallow oblique groove 15 a of the barrier pin traveling groove 15 is branched from a middle portion of the longest deep groove 15 b extending parallel with the front surface of the camera body 1 .
The parallel groove (deep groove) 15 b is continuous to the oblique groove 15 c of the same depth extending in the direction substantially parallel to the oblique groove 15 a . The oblique groove 15 c is continuous to the oblique end groove 15 d extending substantially parallel to the groove 15 b.
The barrier pin (long pin) 32 of the barrier 30 travels straight from the neighborhood of the partition wall in the parallel groove (deep groove) 15 b . It changes the direction of travel, proceeds into the oblique groove (deep groove) 15 c , and stops in the oblique end groove (deep groove) 15 d.
In the same manner, the barrier pin (long pin) 31 is slid along the barrier pin traveling groove 15 provided in the upper edge of the front cover 10 .
The barrier pin (short pin) 34 first travels in the parallel groove (deep groove) 15 b . After passing the partition wall, it enters into the oblique groove (shallow groove) 15 a branched from the parallel groove 15 b and stops at the distal end of the groove 15 a.
In the same manner, the barrier pin (short pin) 33 is slid along the barrier pin traveling groove 15 provided in the upper edge of the front cover 10 .
At this time, as indicated by the broken line in FIG. 5, the surface of the barrier 30 is slightly inclined to the direction substantially parallel to the optical axis of the photographing lens 60 (shown in FIG. 2 ), with the lowermost end of the barrier 30 being kept in contact with the contact portion 16 .
The pins 34 and 32 of the barrier 30 enter the corresponding oblique grooves 15 a and 15 c . At this time, the contact point in the contact portion 16 serves as a fulcrum for “a single-point support”.
As a result, the barrier 30 also moves in the direction substantially parallel to the optical axis of the photographing lens 60 (shown in FIG. 2 ). At the position where the barrier 30 finally stops, the front surface of the camera body 1 is flat.
In an actual barrier closing operation by a finger of the user, at the same time that lateral force F 1 for sliding the barrier in the lateral direction acts, pressing force F 2 for pressing the barrier in the direction of the optical axis acts.
The resultant force F at this time causes the barrier 30 to be pressed from the front so as to be integrated with the front surface of the cover 10 .
Thus, when the recess of the front cover 10 is completely closed by the barrier 30 , the front surface of the camera body 1 becomes flat.
As described above, according to the first embodiment of the present invention, the front cover has a rail structure having shallow and deep grooves continuous at a stepped branch point. Further, the first embodiment is characterized in that the barrier has long pins (inner pins) of such a length as to be prevented from entering the shallow groove at the stepped point and allowed to enter only in the deep groove, and short pins (outer pins) of such a length as to be allowed to enter both the deep and shallow grooves.
In the operation of closing the barrier by the combination of the front cover and the barrier, when the short pin is located at the branch point, force is applied so that the distal end of the barrier elastically functions as a spring, and the short pins smoothly enter the shallow grooves without fail.
As described above, the purpose of providing the distal end of the barrier with the elastic function is to insert the short pins in the shallow grooves without fail. However, the distal end of the barrier does not necessarily have the elastic function, if the dimensions are precise.
In short, the barrier has the combination of two kinds of pins different in length and the rail including two kinds of grooves different in depth. With this combination, it is possible to realize a camera in which the pins can travel smoothly along the grooves of the predetermined depths without being caught by the rails.
Although the above description mainly relates to the process of closing the barrier to be flat, the barrier 30 can be smoothly moved in the opposite direction to an open state. In the opening operation also, the combination of the characteristic barrier 30 and the barrier pin traveling grooves serving as rails and the elastic force of the distal end of the barrier function in the same manner as described above, that is, the correct barrier pins are selected at the branch points, so that the barrier can be moved smoothly in the direction along the optical axis and then travel along the rails smoothly without being caught by the rails.
As described above, according to the first embodiment of the present invention, it is possible to provide a camera having a compact and simple rail mechanism which can realize a successful barrier slide operation by a single smooth operation.
Second Embodiment
A second embodiment of the present invention will now be described.
The second embodiment is different from the first embodiment in the positions of the grooves and the positions of the pins. Since the other portions of the second embodiment are the same as those of the first embodiment, descriptions thereof will be omitted.
FIG. 6 is a perspective view of a camera according to the second embodiment, particularly showing a closed state of a barrier 30 seen obliquely from above the camera.
In the closed state, the camera of the second embodiment has substantially the same elements as those of the first embodiment. However, the second embodiment differs from the first embodiment in the following respects.
First, a barrier 30 movably attached in front of a camera body 1 has no barrier ornament, and the cross section taken along the vertical direction is channel-shaped.
Secondly, the front surface of the camera body 1 is completely flat.
FIG. 7 is a perspective view of the camera shown in FIG. 6 in the case where the barrier is opened.
In this case, when the barrier 30 is slid leftward in the drawing with the upper and the lower sides held between fingers of the user, the power supply (not shown) is turned on. As a result, as shown in FIG. 7, the lens barrel of a photographing lens 60 hidden behind the barrier 30 projects forward along the optical axis and the finder 65 is exposed.
At this time, the barrier 30 is slid along barrier pin traveling grooves 15 , which are provided in upper and lower interior edge portions 17 ′ of the front cover 10 .
As in the first embodiment, each of the upper and lower barrier pin traveling grooves 15 has a predetermined form and predetermined two levels of depth.
Two pairs of long and short pins are projected from inner portions of the barrier 30 (for details, see FIG. 8 ). The pins are inserted in and travel along the barrier pin traveling grooves 15 .
When the closed barrier 30 is slid to the left, the barrier 30 is at first moved forward smoothly along the optical axis by a predetermined amount from the flat state, with the inner surface of the right end of the barrier 30 being kept in contact with a contact portion 16 .
Thereafter, the barrier 30 is moved parallel, keeping a predetermined distance from the initial flat state, and finally stopped at the left end of the camera body 1 so as to completely cover the front surface of the cover 40 .
Only after this state, the shutter button 80 can function to allow a photographing operation.
FIG. 8 is an exploded perspective view showing the relationship between the barrier and the front cover 10 of the camera body 1 according to the second embodiment.
Referring to FIG. 8, as in the first embodiment, the front cover 10 has an opening 11 for the photographing lens, an opening 12 for the finder and an opening 14 for the shutter button, through which the lens barrel of the photographing lens 60 , the finder 65 , and the shutter button 80 are respectively inserted.
The projected contact portion 16 is arranged in the recess portion of the front cover 10 in the same manner as in the first embodiment.
In the second embodiment, the barrier pin traveling grooves 15 are arranged symmetrically in the upper and lower interior edge portions 17 ′.
The cover 40 is formed integrally with a front left portion of the front cover 10 as one piece.
As shown in FIG. 8, the barrier pin traveling groove 15 comprises an oblique groove (shallow groove) 15 a , a parallel groove (deep groove) 15 b , an oblique groove (deep groove) 15 c , and an oblique groove (deep groove) 15 d , as in the first embodiment.
The formal characteristic of the barrier 30 is understandable from FIG. 8 . The barrier pin (long pin) 31 and the barrier pin (short pin) 33 are projected downward from the upper edge portion of the barrier 30 . The barrier pin (long pin) 32 and the barrier pin (short pin) 34 are projected upward from the lower edge portion of the barrier 30 .
When a camera body is assembled, the barrier 30 is attached to the cover 40 so as to overlap it. At this time, the long pins 31 and 32 are first inserted in the barrier traveling grooves 15 . Thereafter, the short pins 33 and 34 are inserted therein following the long pins.
As a result, the barrier 30 can be freely slid along the grooves rightward in the drawing.
As described above, the second embodiment of the present invention has a simpler structure and a less number of members as compared to the first embodiment. For example, the positioning holes, the wall member, the boss hole, the attachment holes, the barrier ornament, etc., are not required in the second embodiment.
Further, the same effect and advantage as those of the first embodiment can be obtained by the barrier traveling grooves 15 formed in the upper and lower edge portions 17 ′ of the front cover 10 and the barrier having a channel-shaped cross section along the vertical direction.
Furthermore, the barrier and the cover can be worked easily due to the simple shape, and assembled easily and firmly by utilizing the elastic force of the material of the barrier.
If the barrier 30 is opened and closed reliably and smoothly without using the contact portion 16 in the front cover 10 , the contact portion 16 need not be formed.
Thus, according to the second embodiment, it is possible to provide a camera comprising a barrier which has a simple and compact rail structure.
Other Modifications
The limitations of the camera relating to “left and right”, “in and out”, and “upper and lower” are not necessarily restricted to those of the embodiments described above.
Further, the present invention is applicable not only to a compact camera but to any type of camera.
In the above description, the barrier pin grooves, the shallow grooves and the deep grooves are not necessarily bottomed grooves. It is easily conceivable that they may be replaced by cams or cam means with which a projecting member can be engaged.
As has been described above in detail, the present invention can provide a camera having a compact and simple rail mechanism which can realize a successful barrier slide operation by a single smooth operation.
Additional embodiments of the present invention will be apparent to those skilled in the art from consideration of the specification and practice of the present invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with the true scope of the present invention being indicated by the following claims. | A camera body includes a photographing lens. A barrier is supported on the camera body so as to be movable between a cover position covering the photographing lens and a retreat position retreated from the cover position in a first direction substantially parallel to an optical axis of the photographing lens and a second direction substantially perpendicular to the first direction. A rail mechanism is provided to guide relative movement between the camera body and the barrier in the first and the second directions of the barrier. The rail mechanism comprises a first slide projection, a second slide projection, a first cam portion and a second cam portion. The first slide projection has a predetermined projecting length and guides movement of the barrier. The second slide projection has a projecting length longer than the first slide projection and guides movement of the barrier. The first cam portion is slidably engaged with the first and the second slide projections and guides movement of the barrier in the second direction. The second cam portion, branched from the first cam means and slidably engaged with only the first slide projection, guides movement of the barrier in the first direction. | 6 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to Chinese Application No. CN201520065126.7, entitled “ABOVE GROUND POOL,” filed on Jan. 29, 2015, the disclosure of which is incorporated by reference herein in its entirety.
BACKGROUND INFORMATION
[0002] 1. Technical Field
[0003] The present invention relates to pools, and more specifically, to an above ground pool.
[0004] 2. Background
[0005] An above ground pool is a facility installed on a piece of vacant land for recreational usage. For example, it can be installed on the yard of a house or a piece of vacant land elsewhere for adults and children to play together. Due to its ease of installation and usage, above ground pools have become very popular.
[0006] Currently, above ground pools can be mainly categorized into two types: frame pools and inflatable pools. There are a variety of structures and forms for frame pools. A round frame pool is the most typical above ground pool, which mainly includes a series of horizontal support members, vertical support members and a pool liner. In these types of above ground pools, the horizontal support members are connected in sequence via connecting members to form a circular structure. The vertical support members support the circular structure so as to form a support frame, and then the pool liner is affixed to the support frame to form a pool body. The pool body forms an above ground pool or basin for holding water. When a frame pool of this structure is fully filled with water, the water can exert a significant amount of pressure on the pool body, thus the support frame must be sturdy enough to withstand extremely high pressure forces.
[0007] However, most horizontal support members, vertical support members, and connecting members used in the support frames of traditional round frame pools comprise tubes having a D-shaped cross-section. In practical applications, these “D-shaped tubes” have a number of disadvantages. For example, such tubes are difficult to manufacture and control their manufacturing process due to the asymmetric shape of the tubes' cross-section. These D-shaped tubes typically have a structure without a narrowed mouth at a tube end, so the clearance fit between the tube end and a corresponding connector is relatively large, resulting in poor overall stability. Since the shape of the D-shaped tube is asymmetric, it is more difficult to cut to form arcuate corners. Also, the manufacturing cost is fairly costly. All of these factors result in great difficulty in the machining of connector elbows.
[0008] In addition, the connection between corresponding D-shaped tubes is achieved by engagement at single point, such that the connection has a relatively poor firmness and strength. Therefore, support frames formed by the use of D-shaped tubes mentioned above have a lower bearing capacity, thus compromising the safety and performance of the above ground pool.
[0009] Overall, the bearing performance of the support frame of an above ground pool may have a direct impact on the stability of the entire above ground pool. Due to the factors discussed above, conventional above ground pools are prone to collapse and cause injury accidents. Thus, a need therefore exists for an above ground pool having a sturdy support frame that is easy to assemble.
SUMMARY
[0010] An above ground pool according to the present invention is provided in order to solve the technical problems present in support frames of conventional above ground pools, namely, the poor bearing capacity of existing above ground pool support frames.
[0011] One example of an above ground pool of the present invention includes a support frame and a pool liner. The support frame includes a series of horizontal support members and vertical support members. The horizontal support members and the vertical support members each include an elongated tube with an elliptical cross-section.
[0012] The pool liner is affixed to the support frame. The pool liner is supported by the support frame to form a body for holding water within the pool.
[0013] In some implementations, the support frame further includes a plurality of T-shaped connectors for coupling the horizontal support members and the vertical support members together. Each T-shaped connector includes a horizontal tubular member and a vertical tubular member transverse to the horizontal tubular member. The horizontal tubular member and the vertical tubular member each has an elliptical cross-section.
[0014] In some implementations, the T-shaped connectors couple two corresponding horizontal support members together in sequence to form a substantially circular ring-shaped structure. In some implementations, the ring-shaped structure may be oval in shape. In some implementations, the vertical tubular member is coupled to a corresponding vertical support member.
[0015] In some implementations, a first end of the horizontal tubular member is detachably connected to an end of a first corresponding horizontal support member and a second end of the horizontal tubular member is detachably connected to an end of a second corresponding horizontal support member. The first corresponding horizontal support member and the second corresponding horizontal support member may be connected to the first end of the horizontal tubular member and the second end of the horizontal tubular member by a retainer located proximal the respective points of attachment.
[0016] In some implementations, the retainer is a retaining pin configured to pass through a first set of positioning holes and a corresponding second set of positioning holes. The first set of positioning holes is formed at the first end of the horizontal tubular member and the second end of the horizontal tubular member. The corresponding second set of positioning holes is formed at ends of the corresponding horizontal support members. The retaining pin is configured to lock the horizontal tubular member and the corresponding horizontal support members together.
[0017] In some implementations, the vertical tubular member is detachably connected to a corresponding vertical support member by a spring-loaded latch coupled to an end of the vertical support member. The latch is configured to engage an aperture formed at an open end of the vertical tubular member.
[0018] In some implementations, the spring-loaded latch includes a pin boss that houses a spring element and detent pin. The pin boss is mounted inside one end of the vertical support member and configured such that the detent pin is outwardly biased by the spring element to engage the aperture. The detent pin is configured to lock the vertical tubular member and the vertical support member together.
[0019] In some implementations, the above ground pool further includes a plurality of tensioning devices coupled to an outer surface of the body of the pool and a tensioning belt. Each tensioning device is coupled to the outer surface of the body in-between two neighboring vertical support members. The tensioning belt may be alternately weaved about the outer surface of the body through the tensioning devices and over the vertical support members to retain the vertical support members close to the body. In some implementations, the tensioning belt is arranged about the body of the pool at a height equal to approximately one-third of the height of the body of the pool. In some implementations, the above ground pool further includes a plurality of support bases coupled to a bottom end of the vertical support members.
[0020] A second example of an above ground pool of the present invention is further provided. The above ground pool includes a support frame and a pool liner. According to this example, the support frame includes a series of horizontal support members, connectors, and U-shaped support members. The horizontal support members and connectors may each have a circular cross-section. The U-shaped support members may have an elliptical cross-section.
[0021] The pool liner is affixed to the support frame. The pool liner is supported by the support frame to form a body for holding water within the pool.
[0022] In some implementations, the horizontal support members are coupled together in series by the connectors to form a ring-shaped structure. In some implementations, the ring-shaped structure forms a rectangle, square, or other polygon shape. In some implementations, the connectors are each L-shaped.
[0023] In some implementations, the above ground pool further includes couplings coupled to free ends of the U-shaped support members. The couplings detachably connect the U-shaped support members to the ring-shaped structure to support the ring-shaped structure in an oblique fashion.
[0024] In some implementations, each free end of the U-shaped support member includes a reduced diameter portion. The reduced diameter portion includes a first set of latching holes spaced apart from a second set of latching holes.
[0025] In some implementations, the coupling further includes a flexible V-shaped pin and a hollow casing. The flexible V-shaped pin includes a first pair of studs spaced apart from a second pair of studs. The hollow casing includes a pair of orifices. The flexible pin is disposed within the reduced diameter portion of U-shaped support members such that the first pair of studs extends through the second set of latching holes to engage the pair of orifices, and the second pair of studs extends through the first set of latching holes.
[0026] In some implementations, the casing is a tube having an oval cross-section corresponding with the cross-section of the U-shaped support members.
[0027] In some implementations, the above ground pool further includes a plurality of support belts coupled to and arranged about a bottom portion of the body of the pool. Each support belt is coupled between the bottom portion of the body of the pool and a horizontal portion of a corresponding U-shaped support member.
[0028] In some implementations, each support belt includes a sleeve for passing the horizontal portion of the U-shaped support member therethrough.
[0029] A first example of a support frame for an above ground pool of the present invention is provided. The support frame includes a plurality of horizontal support members and a plurality of vertical support members, where a pool liner may be affixed to and supported by the support frame to form a body for holding water within the pool.
[0030] The horizontal support members may include an elongated tube with an elliptical cross-section. The vertical support members may be coupled to the horizontal support members. The vertical support members may include an elongated tube with an elliptical cross-section.
[0031] In some implementations, the support frame further includes a plurality of T-shaped connectors for coupling the horizontal support members and the vertical support members together. The T-shaped connector including a horizontal tubular member and a vertical tubular member transverse to the horizontal tubular member. The horizontal tubular member and the vertical tubular member each has an elliptical cross-section.
[0032] In some implementations, the T-shaped connectors couple two corresponding horizontal support members together in sequence to form a substantially circular ring-shaped structure. In some implementations, the ring-shaped structure may be oval in shape.
[0033] In some implementations, the vertical tubular member is coupled to a corresponding vertical support member. In some implementations, a first end of the horizontal tubular member is detachably connected to an end of a first corresponding horizontal support member and a second end of the horizontal tubular member is detachably connected to an end of a second corresponding horizontal support member. The first corresponding horizontal support member and the second corresponding horizontal support member are connected to the first end of the horizontal tubular member and the second end of the horizontal tubular member by a retainer located proximal the respective points of attachment.
[0034] In some implementations, the retainer is a retaining pin configured to pass through a first set of positioning holes formed at the first end of the horizontal tubular member and the second end of the horizontal tubular member, and a corresponding second set of positioning holes formed at ends of the corresponding horizontal support members. The retaining pin is configured to lock the horizontal tubular member and the corresponding horizontal support members together.
[0035] In some implementations, the vertical tubular member is detachably connected to a corresponding vertical support member by a spring-loaded latch coupled to an end of the vertical support member. The latch is configured to engage an aperture formed at an open end of the vertical tubular member.
[0036] In some implementations, the spring-loaded latch includes a pin boss that houses a spring element and detent pin. The pin boss is mounted inside one end of the vertical support member and configured such that the detent pin is outwardly biased by the spring element to engage the aperture. The detent pin is configured to lock the vertical tubular member and the vertical support member together.
[0037] In some implementations, the support frame further includes a plurality of tensioning devices coupled to an outer surface of the body of the pool and a tensioning belt. Each tensioning device may be coupled to the outer surface of the body in-between two neighboring vertical support members The tensioning belt may be alternately weaved about the outer surface of the body through the tensioning devices and over the vertical support members to retain the vertical support members close to the body.
[0038] In some implementations, the tensioning belt is arranged about the body of the pool at a height equal to approximately one-third of the height of the body of the pool. In some implementations, the above ground pool further includes a plurality of support bases coupled to a bottom end of the vertical support members.
[0039] A second example of a support frame for an above ground pool of the present invention is further provided. The support frame includes a plurality of horizontal support members, a plurality of connectors, and a plurality of U-shaped support members, where a pool liner may be affixed to and supported by the support frame to form a body for holding water within the pool.
[0040] The plurality horizontal support members each include an elongated tube with a circular cross-section. Each of the connectors that couple corresponding horizontal support members together comprise an L-shapes tube with a circular cross-section.
[0041] Each of U-shaped support members comprise a U-shaped tube with an elliptical cross-section. In some implementations, the horizontal support members are coupled together in series by the connectors to form a ring-shaped structure. In some implementations, the ring-shaped structure forms a rectangle, square or other polygon shape.
[0042] In some implementations, the above ground pool further includes couplings coupled to free ends of the U-shaped support members. The couplings detachably connect the U-shaped support members to the ring-shaped structure to support the ring structure in an oblique fashion.
[0000] In some implementations, each free end of the U-shaped support member has a reduced diameter portion, the reduced diameter portion having a first set of latching holes spaced apart from a second set of latching holes.
[0043] In some implementations, the coupling further includes a flexible V-shaped pin including a first pair of studs spaced apart from a second pair of studs and a hollow casing. The hollow casing includes a pair of orifices. The flexible pin is disposed within the reduced diameter portion of U-shaped support members such that the first pair of studs extends through the second set of latching holes to engage the pair of orifices, and the second pair of studs extends through the first set of latching holes. In some implementations, the casing includes a tube with an oval cross-section corresponding with the cross-section of the U-shaped support members.
[0044] In some implementations, the support frame further includes a plurality of support belts coupled to and arranged about a bottom portion of the body of the pool. Each support belt may be coupled between the bottom portion of the body of the pool and a horizontal portion of a corresponding U-shaped support member. In some implementations, each support belt includes a sleeve for passing the horizontal portion of the U-shaped support member therethrough.
[0045] Advantageously, support frames of above ground pools according to the present invention are at least partially composed of tubes with an elliptical cross-section. The symmetric shape of the cross-section reduces the difficulty in machining a tube bend, lowers the complexity in manufacturing the tubes, effectively improves the stability, and facilitates quality control. Meanwhile, a slight clearance fit between the tube end of the elliptical tubes and the connector may be achieved. This enables the support frame to withstand large mechanical stresses and provide stability and enhanced structural support. In addition, a bolt connection is utilized between the tube end of the elliptical tubes and the connector. Such bolt connection is secure and provides greater strength. Therefore, support frames formed by elliptical tubes provide better bearing performance, thereby improving the stability of the entire above ground pool and providing an excellent safety performance.
[0046] Other devices, apparatus, systems, methods, features and advantages of the disclosure will be or will become apparent to one with skill in the art upon examination of the following figures and detailed description. It is intended that all such additional systems, methods, features and advantages be included within this description, and be protected by the accompanying claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0047] The above-mentioned and other features, properties and advantages of the present invention will become more apparent from the following description of embodiments with reference to the accompany drawings, in which:
[0048] FIG. 1 is a perspective view illustrating one example of an implementation of a support frame of an above ground pool according to the teachings of the present invention.
[0049] FIG. 2 is a front view of the support frame illustrated in FIG. 1 .
[0050] FIG. 3 is a top view of the support frame illustrated in FIG. 1 .
[0051] FIG. 4 is a partial exploded view of the support frame of FIG. 1 , illustrating how corresponding horizontal support members are coupled with a vertical support member by a T-shaped connector.
[0052] FIG. 5 is another partial exploded view of the support frame of FIG. 1 , illustrating how corresponding horizontal support members are coupled with a vertical support member by a T-shaped connector.
[0053] FIG. 6 is a partial cross-sectional view of the support frame of FIG. 1 , illustrating how a horizontal support member is coupled to the T-shaped connector.
[0054] FIG. 7 is a perspective view of a spring-loaded latch for connecting a vertical support member and a T-shaped connector in the support frame of FIG. 1 .
[0055] FIG. 8 is a bottom view of the spring-loaded latch illustrated in FIG. 7 .
[0056] FIG. 9 is a side view of the spring-loaded latch illustrated in FIG. 7 .
[0057] FIG. 10 is a front view of the spring-loaded latch illustrated in FIG. 7 .
[0058] FIG. 11 is an exploded perspective view of the spring-loaded latch illustrated in FIG. 7 .
[0059] FIG. 12 is a perspective view illustrating an above ground pool incorporating the support frame illustrated in FIG. 1 .
[0060] FIG. 13 is a perspective view illustrating a second example of an implementation of a support frame of an above ground pool according to the teachings of the present invention.
[0061] FIG. 14 is a top view of the support frame illustrated in FIG. 13 .
[0062] FIG. 15 is a front view of the support frame illustrated in FIG. 13 .
[0063] FIG. 16 is a side view of the support frame illustrated in FIG. 13 .
[0064] FIG. 17 is a partial exploded view of the support frame of FIG. 13 , illustrating how corresponding horizontal support members are coupled with the U-shaped support members.
[0065] FIG. 18 is a perspective view of a horizontal support member of the support frame illustrated in FIG. 13 .
[0066] FIG. 19 is a side view of the horizontal support member illustrated in FIG. 18 .
[0067] FIG. 20 is a perspective view of a U-shaped support member of the support frame illustrated in FIG. 13 .
[0068] FIG. 21 is a front view of the U-Shaped support member illustrated in FIG. 20 .
[0069] FIG. 22 is a partial cross-sectional view of the support frame of FIG. 13 illustrating how the U-shaped support members are coupled to the horizontal support members.
[0070] FIG. 23 is a partial cross-sectional view of the support frame of FIG. 13 illustrating how the neighboring horizontal support members are coupled together.
[0071] FIG. 24 is a perspective view of a positioning member of the support frame illustrated in FIG. 13 .
[0072] FIG. 25 is a front view of the positioning member illustrated in FIG. 24 .
[0073] FIG. 26 is a top view of the positioning member illustrated in FIG. 24 .
[0074] FIG. 27 is a side view of the positioning member illustrated in FIG. 24 .
[0075] FIG. 28 is a perspective view illustrating an above ground pool incorporating the support frame illustrated in FIG. 13 .
[0076] FIG. 29 is a perspective view illustrating a third example of an implementation of a support frame of an above ground pool according to the teachings of the present invention.
[0077] FIG. 30 is an enlarged view of the portion A in FIG. 29 .
[0078] FIG. 31 is a front view of the support frame illustrated in FIG. 29 .
[0079] FIG. 32 is a side view of the support frame illustrated in FIG. 29 .
[0080] FIG. 33 is a top view of the support frame illustrated in FIG. 29 .
[0081] FIG. 34 is a perspective view illustrating an above ground pool incorporating the support frame illustrated in FIG. 29 .
[0082] FIG. 35 is a top view illustrating a fourth example of an implementation of a support frame of an above ground pool according to the teachings of the present invention.
DETAILED DESCRIPTION
[0083] The present invention will be further described below in conjunction with particular example implementations and the accompanying drawings. Further details are provided in the following description in order for the present invention to be fully understood. However, the present invention can be implemented in various ways other than those described herein. A person skilled in the art can make similar analogies and modifications according to practical applications without departing from the spirit of the present invention, and therefore the contents of the particular examples herein should not be construed as limiting to the scope of the present invention.
[0084] FIGS. 1-30 illustrate various implementations of a support frame for an above ground pool according to the teachings of the present invention. Referring now to FIGS. 1-3 , FIG. 1 is a perspective view illustrating one example of an implementation of a support frame 10 of an above ground pool according to the teachings of the present invention. FIG. 2 is a front view of the support frame 10 . FIG. 3 is a top view of the support frame 10 .
[0085] As shown, the support frame 10 includes a plurality of horizontal support members 11 and a plurality of vertical support members 12 . The horizontal support members 11 and the vertical support members 12 each include an elongated tubular member with an elliptical cross-section. The vertical support members 12 are coupled to the horizontal support members 11 . The support frame 10 may further include a plurality of T-shaped connectors 13 that are mainly used to couple the horizontal support members 11 and the vertical support members 12 together.
[0086] Referring now to FIGS. 4-6 , FIG. 4 is a partial exploded view of the support frame 10 illustrating how corresponding horizontal support members 11 are coupled with a vertical support member 12 by the T-shaped connector 13 . FIG. 5 is another partial exploded view of the support frame 10 illustrating how corresponding horizontal support members 11 are coupled with a vertical support member 12 by a T-shaped connector 13 . FIG. 6 is a partial cross-sectional view of the support frame 10 illustrating how a horizontal support member 11 is coupled to the T-shaped connector 13 .
[0087] As shown, the T-shaped connector 13 includes a horizontal tubular member 130 and a vertical tubular member 131 . The vertical tubular member 131 is transversely arranged on the horizontal tubular member 130 . In particular, the vertical tubular member 131 is transversely perpendicular to the horizontal tubular member 130 . The horizontal tubular member 130 and the vertical tubular member 131 each have an elliptical cross-section.
[0088] The T-shaped connectors 13 couple two neighboring horizontal support members 11 together in sequence by means of the horizontal tubular member 130 . In this way, the horizontal support members 11 may be coupled together to form a substantially circular ring structure (as best shown in FIG. 3 ).
[0089] Turning back to FIGS. 4 and 5 , a first end 132 of the horizontal tubular member 130 of each T-shaped connector 13 may be detachably coupled to an end 112 of a first corresponding horizontal support member 110 . A second end 133 of the horizontal tubular member 130 may, likewise, be detachably coupled to an end 113 of a second corresponding horizontal support member 111 . The first corresponding horizontal support member 110 and the second corresponding horizontal support member 111 may respectively be coupled to the first end 132 and the second end 133 of the horizontal tubular member 130 by a retainer, as discussed in further detail below. In order to ensure the stability and firmness of the coupling, the retainer should be located proximal the respective points of attachment between the horizontal support members 110 , 111 and the horizontal tube member 130 .
[0090] In some implementations, the retainer may include a retaining pin 14 . In other implementations, the retainer may include claps, threaded fasteners, or other suitable attachment means. As shown in FIG. 4-6 , a first set of positioning holes 134 is provided on the first end 132 and the second end 133 of the horizontal tubular member 130 . A corresponding second set of positioning holes 114 is provided on the end 112 of the first horizontal support member 110 and the end 113 of the second horizontal support member 111 . When the first end 132 and the second end 133 of the horizontal tubular member 130 of the T-shaped connector 13 are respectively butt-jointed to the end 112 of the first horizontal support member 110 and the end 113 of the second horizontal support member 111 , the first set of positioning holes 134 is correspondingly aligned with the second set of positioning holes 114 . In this alignment, the retaining pin 14 may be passed through the first set of positioning holes 134 and the corresponding second set of positioning holes 114 (as shown in FIG. 6 ), so that the horizontal tubular member 130 of the T-shaped connector 13 and the corresponding horizontal support members (i.e., the first horizontal support member 110 and the second horizontal support member 111 ) are, for example, snap-locked together. In some implementations, a bearing pad 140 may be provided between the retaining pin 14 and the horizontal tubular member 130 to reduce the wear between the retaining pin 14 and the horizontal tubular member 130 and increase robustness therebetween.
[0091] Similarly, the vertical tubular member 131 of the T-shaped connector 13 may be coupled to a corresponding vertical support member 12 . As shown in FIGS. 4 and 5 , the vertical tubular member 131 of each T-shaped connector 13 may be detachably connected to the corresponding vertical support member 12 by a spring-loaded latch 15 . During connection, the spring-loaded latch 15 is coupled to an end 121 of the vertical support member 12 . An aperture 122 is provided at an open end of the end 121 . The spring-loaded latch 15 is disposed in the end 121 of the vertical tubular member 131 and engages and is locked with the aperture 122 .
[0092] Referring to FIGS. 7-11 , FIG. 7 is a perspective view of one example of a spring-loaded latch 15 for coupling the vertical support member 12 with a T-shaped connector 13 . FIG. 8 is a bottom view of the spring-loaded latch 15 . FIG. 9 is a side view of the spring-loaded latch 15 . FIG. 10 is a front view of the spring-loaded latch 15 . FIG. 11 is exploded perspective view of the spring-loaded latch 15 .
[0093] As shown, the spring-loaded latch 15 includes a pin boss 150 . The pin boss 150 houses a spring element 151 and a detent pin 152 . The pin boss 150 includes a hollow circular annular outer wall 153 with an outwardly protruding, semi-circular accommodating cavity 154 coupled to an open end of the annular outer wall 153 . The spring element 151 may be mounted within the accommodating cavity 154 such that one end of the detent pin 152 passes through the interior of the accommodating cavity 154 and bears against the spring element 151 , while the other end is outwardly biased, such that a portion of the detent pin may extend out from the accommodating cavity 154 (as best shown in FIGS. 7 and 8 ).
[0094] The annular outer wall 153 may be shaped to match or otherwise complement the cross-section of the end 121 of the vertical support member 12 (as shown in FIGS. 4 and 5 ). When the spring-loaded latch 15 is fitted into the end 121 of the vertical support member 12 , the annular outer wall 153 of the pin boss 150 is embedded in the interior of the end 121 of the vertical support member 12 such that the detent pin 152 snap-fitted into the aperture 122 on the end 121 of the vertical support member 12 under the elastic force of the spring element 151 .
[0095] Turning back to FIG. 5 , an aperture 135 may be formed at an open end of the vertical tubular member 131 of the T-shaped connector 13 . The vertical tubular member 131 is butt-jointed to the end 121 of the vertical support member 12 . The aperture 135 on the vertical tubular member 131 may be aligned with the aperture 122 on the vertical support member 12 , so that the detent pin 152 passes through the apertures 122 and 135 to, for example, snap-lock the T-shaped connector 13 to the vertical support member 12 .
[0096] FIG. 12 is a perspective view of one example of an above ground pool 100 incorporating the support frame 10 . As shown in FIG. 12 , the above ground pool 100 includes the support frame 10 and a pool liner 16 . The pool liner 16 may be affixed to and supported by the support frame 10 to form a pool body for holding water. In some implementations, the upper part of the pool liner 16 may be sheathed on the horizontal support members 11 , and the periphery of the pool liner 16 may lie against the vertical support members 12 .
[0097] In order to further secure the poor liner 16 to the above ground pool 100 , the above ground pool 100 may further include a plurality of tensioning devices 17 and a tensioning belt 18 . The tensioning devices 17 include one or more straps or loops coupled to an outer surface of the pool body. Each tensioning device 17 may be coupled to the outer surface of the body in-between two neighboring vertical support members 12 . The tensioning belt 18 may be alternately weaved about the outer surface of the body through the tensioning devices 17 and over the vertical support members 12 to retain the vertical support members 12 close to the pool body, thereby increasing the tensioning force of the pool body. In some implementations, the tensioning belt 18 may be arranged about the pool body at a height equal to approximately one-third of the height of the pool body. The tensioning belt 18 serves to reinforce the lower structure of the pool body to impart a greater bearing capacity. In some implementations, the above ground pool 100 may further include a plurality of support bases 120 coupled to a bottom end of the vertical support members 12 for improving the overall robustness of the above ground pool 100 .
[0098] Referring to FIGS. 13-16 , FIG. 13 is a perspective view of a second example of a support frame 20 of an above ground pool according to the teachings of the present invention. FIG. 14 is a top view of the support frame 20 . FIG. 15 is a front view of the support frame 20 . FIG. 16 is a side view of the support frame 20 .
[0099] As shown, the support frame 20 includes a plurality of horizontal support members 21 , a plurality of connectors 22 , and a plurality of U-shaped support members 23 . Each horizontal support member 21 has a circular cross-section. The connectors 22 are used for to couple corresponding horizontal support members 21 together, and each connector 22 has a circular cross-section. Free ends of the U-shaped support members 23 are connected to the horizontal support members 21 and each U-shaped support member 23 has an elliptical cross-section. The horizontal support members 21 are coupled together in series by the plurality of connectors 22 to form a ring structure. In the present implementation, the connectors 22 may be L-shaped such that the ring structure forms a rectangle. In other implementations, the connectors 22 may have other shapes, such as V-shape, such that the ring structure may for a polygon or other geometric shape.
[0100] FIG. 17 is a partial exploded view of the support frame 20 , illustrating how corresponding horizontal support members 21 are coupled with the U-shaped support members 23 and L-shaped connectors 22 . As shown, when the ring structure forms a rectangle or polygon, the sides of the rectangle or polygon are formed by the horizontal support members 21 . Every two or corresponding horizontal support members 21 are connected in series successively. The corner parts of the sides of the rectangle are formed by the L-shaped connectors 22 connected between corresponding horizontal support members 21 .
[0101] Each horizontal support member 21 is further connected to a corresponding U-shaped support member 23 . The horizontal support members 21 may be affixed to each other via a positioning member 25 . The horizontal support member 21 and the connector 22 may likewise be affixed to each other via a positioning member 25 . However, a coupling 24 may be required to fixedly connect the U-shaped support member 23 and the horizontal support member 21 to each other.
[0102] FIG. 18 is a perspective view of the horizontal support member 21 , and FIG. 19 is a front view of the horizontal support member 21 . As shown in these figures, one end 211 of the horizontal support member 21 includes a reduced diametrical portion and a first aperture 212 in the reduced portion. A second aperture 215 is formed at an opposite end 213 of the horizontal support member 21 . One or more connection opening 214 are formed along a rod surface of the horizontal support member 21 for receiving free ends of a corresponding U-shaped support member 23 .
[0103] Referring now to FIGS. 20-22 , FIG. 20 is a perspective view of the U-shaped support member 23 . FIG. 21 is a front view of the U-shaped support member 23 . As shown in FIGS. 20 and 21 , the free end of the U-shaped support members 23 include a reduced diameter portion 231 having a first set of latching holes 232 spaced apart from a second set of latching holes 233 .
[0104] FIG. 22 is a partial cross-sectional view of the support frame 20 , illustrating how the free ends of U-shaped support members 23 are connected to the horizontal support members 21 . As shown in FIG. 22 , in conjunction with FIG. 17 , the coupling 24 is coupled in the reduced diameter portion 231 of the free ends of the U-shaped support members 23 , such that the U-shaped support member 23 is detachably connected to the ring structure via the coupling 24 . The U-shaped support members 23 support the ring structure in an oblique fashion; for example, the U-shaped support member 23 may be inclined outwardly along the ring structure by 30° or any other suitable angle.
[0105] The coupling 24 may include a flexible V-shaped pin 241 and a hollow casing 242 . The flexible V-shaped pin 241 may include a first pair of studs 243 spaced apart from a second pair of studs 244 .
[0106] The hollow casing 242 includes a pair of orifices 245 and the hollow casing 242 is sheathed outside the reduced diameter portion 231 of the U-shaped support member 23 such that the first set of latching holes 232 and the second set of latching holes 233 are respectively aligned with the orifices 245 . The flexible V-shaped pin 241 is positioned within the reduced diameter portion 231 of the U-shaped support member 23 such that the first pair of studs 243 extends through the second set of latching holes 233 to engage the corresponding orifices 245 . Likewise, the second pair of studs 244 extends through the first set of latching holes 232 . In this way, the U-shaped support member 23 and the horizontal support member 21 may be, for example, snap-locked together via the couplings 24 .
[0107] The hollow casing 242 includes a tube having an oval cross-section corresponding with the cross-section of the U-shaped support members 23 . As such, the connection between the U-shaped support members 23 and the horizontal support members 21 may be more robust.
[0108] FIG. 23 is a partial cross-sectional view of the support frame 20 , illustrating how neighboring horizontal support members 21 are coupled together a positioning member 25 . As shown in FIG. 23 , in conjunction with FIGS. 17-19 , the sides of the rectangle or polygon ring structure are formed by the horizontal support members 21 . Every two or corresponding horizontal support members 21 are connected in series successively via the positioning members 25 . The positioning member 25 is sheathed on the reduced diameter portion of end 211 of one of the horizontal support members 21 , and the other end 213 of the other neighboring horizontal support member 21 is sheathed outside the positioning member 25 , such that the two neighboring horizontal support members 21 are affixed to each other.
[0109] Turing now to the positioning member 25 , FIG. 24 is a bottom perspective view of the positioning member 25 . FIG. 25 is a front view of the positioning member 25 . FIG. 26 is a top view of the positioning member 25 . FIG. 27 is a side view of the positioning member 25 .
[0110] As shown in FIGS. 24-27 , in conjunction with FIG. 17-19 , the positioning member 25 includes a hollow sheathing member 251 comprising a tube with an oval cross-section corresponding to the cross-section of the reduced diameter portion of the horizontal support member 21 . One end of the positioning member 25 is provided with an annular stud 252 . The cross-section of the annular stud 252 corresponds to the cross-section of the horizontal support members 21 . The opposite end of the positioning member 25 is provided with a locking buckle 253 . When two neighboring horizontal support members 21 are connected, one end of the positioning member 25 is sheathed on the reduced diameter portion of one end 211 of one of the horizontal support members 21 , with the other end 213 of the other neighboring horizontal support member 21 is sheathed outside the positioning member 25 . In this way, the locking buckle 253 passes through the second aperture 215 of the other end 213 of the horizontal support member 21 so that the locking of two neighboring horizontal support members 21 can be achieved.
[0111] Likewise, the L-shaped connector 22 and corresponding horizontal support members 21 may also be fixedly locked with each other via the positioning member 25 . For example, one end of the positioning member 25 may be sheathed at one end of the L-shaped connector 22 , while the opposite end 213 of the horizontal support member 21 may be sheathed on the positioning member 25 , such that the locking buckle 253 passes through the second aperture 215 of the opposite end 213 of the horizontal support member 21 and the locking of the horizontal support member 21 and the L-shaped connector 22 can be achieved (not shown in the Figures).
[0112] FIG. 28 is a perspective view illustrating one example of an above ground pool 200 incorporating the support frame 20 . As shown, the above ground pool 200 includes the support frame 20 (as shown in FIG. 13 ) and a pool liner 26 . The pool liner 26 may be affixed to and supported by the support frame 20 to form a pool body for holding water. In some implementations, the upper part of the pool liner 26 may be sheathed on the horizontal support members 21 such that the periphery of the pool liner 26 lies against the U-shaped support members 23 .
[0113] In order to further secure the poor liner 26 , the above ground pool 200 may further include a plurality of support belts 27 . The support belts 27 may be coupled to and arranged about a bottom portion of the body of the pool. Each support belt 27 may be coupled between the bottom portion of the body of the pool and a horizontal portion of a corresponding U-shaped support member 23 . In particular, in order to increase the strength of support of the support belts 27 , each support belt 27 may include a sleeve 271 where the horizontal portion of the U-shaped support member 23 passes through the sleeve 271 of the support belt 27 to tension the support belt 27 .
[0114] Turning to FIGS. 29-34 , FIG. 29 is a perspective view illustrating a third example of an implementation of a support frame 30 an above ground pool according to the teachings of the present invention. FIG. 30 is an enlarged view of the portion A in FIG. 29 . FIG. 31 is a front view of the support frame 30 . FIG. 32 is a side view of the support frame 30 . FIG. 33 is a top view of the support frame 30 .
[0115] As shown in FIGS. 29-33 , the support frame 30 may include a plurality of horizontal support members 31 , a plurality of vertical support members 32 , and a plurality of U-shaped support members 34 . The horizontal support members 31 and the vertical support members 32 may each have an elliptical cross-section, and the vertical support members 32 may be coupled to the horizontal support members 31 .
[0116] The support frame 30 may further include a plurality of T-shaped connectors 33 which are used to couple the horizontal support members 31 and the vertical support members 32 together. As best shown in FIG. 30 , the T-shaped connectors 33 may include a horizontal tubular member 330 and a vertical tubular member 331 , where the vertical tubular member 331 is transversely arranged on the horizontal tubular member 330 . In particular, the vertical tubular member 331 is transverse and perpendicular to the horizontal tubular member 330 . Moreover, the horizontal tubular member 330 and the vertical tubular member 331 may each have an elliptical cross-section.
[0117] The T-shaped connectors 33 may be used to couple two neighboring horizontal support members 31 together in sequence via the horizontal tubular members 330 . At the same time, at least some of the neighboring horizontal support members 31 may be connected in series via the positioning members 35 . In this way, the T-shaped connectors 33 and the positioning members 35 together couple the plurality of horizontal support members 31 with one another to form a substantially elliptical ring structure.
[0118] As further shown in FIG. 30 , opposite ends 332 of the horizontal tubular member 330 of each T-shaped connector 33 may be detachably connected to ends of the corresponding horizontal support members 31 . The corresponding horizontal support members 31 may be respectively connected to opposite ends 332 of the horizontal tubular member 330 by a retainer. To ensure the stability and firmness of the coupling, the retainer may be located proximal the respective points of attachment between the horizontal tubular member 330 and the T-shaped connector 33 .
[0119] In like manner, the vertical tubular member 331 of the T-shaped connector 33 may be coupled to a corresponding vertical support member 32 . The vertical tubular member 331 of each T-shaped connector 33 may be detachably connected to the corresponding vertical support member 32 by a spring-loaded latch.
[0120] It should be noted that the structure of the T-shaped connector 33 in the present example is the same as that of the T-shaped connector 13 in the example above. In particular, the manner in which the T-shaped connectors 33 are coupled to the horizontal support members 31 and the vertical support members 32 is the same as that described the examples above. The structure of the positioning member 35 in the present example is also the same as that of positioning member 25 in the example above, and the manner in which the positioning member 35 is connected to the horizontal support member 31 is the same as that of the first example above, the detailed description of which is omitted for brevity.
[0121] The U-shaped support members 34 may be detachably connected to the ring structure via the couplings. The U-shaped support members 34 support the ring structure in an oblique fashion. For example, a U-shaped support member 34 may be inclined outwardly along the ring structure by angle of 30°. It is further noted that free ends of the U-shaped support members 34 are coupled to the corresponding horizontal support members 31 , and each U-shaped support member 34 has an elliptical cross-section. The structure of the U-shaped support member 34 in the present example is the same as that of the U-shaped support member 23 in the second example, and the manner in which the U-shaped support member 34 is coupled to the horizontal support member 31 is the same as that described in the second example, the detailed description of which is omitted for brevity.
[0122] FIG. 34 is a perspective view of illustrating one example of an above ground pool 300 incorporating the support frame 30 . As shown, the above ground pool 300 includes the support frame 30 (as shown in FIG. 29 ) and a pool liner 36 , where the pool liner 36 may be affixed to and supported by the support frame 30 to form a pool body for holding water. In some implementations, the upper part of the pool liner 36 may be sheathed on the horizontal support members 31 such that the periphery of the pool liner 36 lies against the vertical support members 32 .
[0123] In order to further secure the poor liner 36 , the above ground pool 300 may further include a plurality of tensioning devices 37 and a tensioning belt 38 . The tensioning devices 37 may be coupled to an outer surface of the pool body. In some implementations, each tensioning device 37 may be coupled to the outer surface of the body in-between two neighboring vertical support members 32 . The tensioning belt 38 may be alternately weaved about the outer surface of the body through the tensioning devices 37 and over the vertical support members 32 to retain the vertical support members 32 close to the pool body, thereby increasing the tensioning force of the pool body. In some implementations, the tensioning belt 38 may be arranged about the pool body at a height equal to approximately one-third of the height of the pool body to effectively reinforce the lower structure of the pool body to impart a greater bearing capacity. In some implementations, the above ground pool 300 may further include a plurality of support bases 320 , where the support bases 320 are coupled to a bottom end of the vertical support members 32 for improving the overall robustness of the above ground pool 300 .
[0124] The above ground pool 300 may further include a plurality of support belts 39 that may be coupled to and arranged about a bottom portion of the body of the pool. Each support belt 39 may be coupled between the bottom portion of the body of the pool and a horizontal portion of a corresponding U-shaped support member 34 . In particular, in order to increase the strength of support of the support belts 39 , each support belt 39 may include a sleeve 391 adapted to allow the horizontal portion of the U-shaped support member 34 to pass through the sleeve 391 of the support belt 39 to tension the support belt 39 .
[0125] FIG. 35 is a top view illustrating a fourth example of an implementation of a support frame 40 of an above ground pool according to the teachings of the present invention. As shown, the support frame 40 is substantially the same as that of the support frame 30 of the previous example, except that support frame 40 includes a plurality of horizontal support members 41 , a plurality of arcuate support members 42 , a plurality of vertical support members (not shown), and a plurality of U-shaped support members 44 . The horizontal support members 41 , the arcuate support members 42 , the U-shaped support members 44 and the vertical support members may each have an elliptical cross-section. The vertical support members may be coupled to the plurality of arcuate support members 42 in an upright or vertical fashion. The U-shaped support members 44 may be coupled to the horizontal support members 41 in an oblique fashion.
[0126] The support frame 40 may further include a plurality of T-shaped connectors 43 , each comprising a horizontal tubular member and a vertical tubular member. The vertical tubular member is transversely arranged on the horizontal tubular member. In some implementations, the vertical tubular member is transversely perpendicular to the horizontal tubular member.
[0127] The horizontal tubular member and the vertical tubular member may each have an elliptical cross-section. The connectors 43 couple two neighboring arcuate support members 42 together in sequence via the horizontal tubular members. At the same time, the horizontal support members 41 are connected in series via the positioning members 45 . In this way, the T-shaped connectors 43 and positioning members 45 couple the horizontal support members 41 and the arcuate support members 42 with one another to form an elliptical ring structure.
[0128] It should be noted that the structure of the T-shaped connector 43 in the present example is the same as that of the T-shaped connectors described in the previous examples, and the T-shaped connector 43 is coupled to the arcuate support member 42 and the vertical support member in the same manner as that described in the first example above. The structure of the positioning member 45 in the present example is the same as that of the positioning member 25 in the second example above. The positioning member 45 is, further, connected to the horizontal support member 41 in the same manner as that described in the first example above.
[0129] Further, the structure of the U-shaped support member 44 in the present example is the same as that of the U-shaped support member 23 in the second example. The U-shaped support member 44 may be coupled to the horizontal support member 41 in the manner as that described in the second example above, the detailed description of which is omitted for brevity.
[0130] In summary, by improving the structure of the support frame, a more robust above ground pool structure with a high bearing capacity may be achieved according to the teachings the present invention. The support frame is at least partially composed of tubes having an elliptical cross-section. Due to the symmetric shape of the cross-section of the elliptical tubes, difficulties in the manufacture of the tubes are reduced, thus effectively improving the support frame's stability. A slight clearance fit between the ends of the elliptical tubes and each connector enables the support frame to withstand large mechanical stresses and contributes to its enhanced stability. In addition, a tailored bolt connection is provided between the ends of the elliptical tubes and each connector, which is more secure and provides greater structural strength. Therefore, above ground pools according to the teachings of the present invention provide better bearing performance and the overall stability and safety performance than existing above ground pool designs.
[0131] The various components of the support frame of the present invention may be constructed from molded or machined stainless steel, aluminum, metal, iron, plastic, fiberglass, composite, polycarbonate, alloy, or other suitable materials. The pool liner, tensioning devices, tensioning belt, and support belt of the present invention may be constructed of flexible reinforced polyvinyl chloride (PVC), polyurethane (PU) cloth, plastic, canvas, tactical nylon webbing, or any other durable material. Above ground pools of the present invention may further incorporate other components not shown or described herein, such as water pumps, valves, piping, motors, or other pool components and accessories known in the art.
[0132] In general, terms such as “coupled to,” and “configured for coupling to,” and “secured to,” and “configured for securing to” and “in communication with” (for example, a first component is “coupled to” or “is configured for coupling to” or is “configured for securing to” or is “in communication with” a second component) are used herein to indicate a structural, functional, mechanical, electrical, signal, optical, magnetic, electromagnetic, ionic or fluidic relationship between two or more components or elements. As such, the fact that one component is said to be in communication with a second component is not intended to exclude the possibility that additional components may be present between, and/or operatively associated or engaged with, the first and second components.
[0133] While the detailed embodiments of the present invention have been described, a person skilled in the art should understand that these are merely illustrative, and that the scope of the present invention is defined by the appended claims. Various alterations or modifications can be made by a person skilled in the art to these embodiments without departing from the spirit of the present invention. However, these alterations and modifications shall all fall within the scope of the present invention. | An above ground pool is provided. The above ground pool includes a support frame and a pool liner. The pool liner is affixed to and supported by the support frame to form a body for holding water within the pool. The support frame includes a series of horizontal support members and vertical support members, each having an elliptical cross-section. The symmetric shape of the cross-section of the elliptical tubes reduces the difficulties inherent in machining tube bends, simplifies the manufacturing of the tubes, effectively improves the support frame's stability, and facilitates quality control. The horizontal support members and vertical support members are coupled together by one or more connectors to form an enclosed or ring structure. | 4 |
BACKGROUND OF THE INVENTION
This invention relates generally to a new roller-furling sail construction and to a method of using said sail on sailing vessels.
More particularly this invention relates to a roller furling sail with at least two different weight sail cloths in its construction and which when furled retains its desired flat shape and to the method of using such sails on various sailing vessels.
DESCRIPTION OF THE PRIOR ART
Sails have been powering vessels ever since the early days of ancient Egypt. Sails have been made of various types of construction. There have been mitered cuts, scotch-cuts commonly known in the art as reverse miter cut, vertical cuts, horizontal cuts as well as others. It has been a relatively recent development to have the main and the head sail furl on sail boats. This is done mostly to achieve a measure of safety in heavy weather sailing with a minimum of sail handling. Various United States Patents have been issued on roller-furling systems for sail boats.
These roller-furling Patents that are known are:
U.S. Pat. No. 3,938,460 issued Feb. 17, 1976 to Wales, et al, entitled, Sail-Raising System.
U.S. Pat. No. 3,958,523 issued May 25, 1976 to T. S. Holmes, entitled, Sail Hoisting, Supporting and Furling operating.
U.S. Pat. No. 3,980,036 issued Sept. 14, 1976 to D. H. Crall, entitled, Roller Furling Assembly.
U.S. Pat. No. 4,034,694 issued July 12, 1977 to N. B. Dismuker, entitled Jib Furler.
U.S. Pat. No. 4,080,917 issued Mar. 28, 1978 to Alter, et al, entitled Roller Furling Mechanism.
U.S. Pat. No. 4,196,687 issued Mar. 5, 1978 to R. C. Newick, entitled Roller Furling Sail.
U.S. Pat. No. 4,248,281 issued May 20, 1980 to F. E. Hood, entitled Sail Furling.
U.S. Pat. No. 4,267,791 issued May 19, 1981 to J. P. Ingoref, entitled Jib Roller System.
U.S. Pat. No. 4,267,790 issued May 19, 1981 to R. S. Hood, entitled, Sail Furling and Reefing opportunities.
While all of the above U.S. Patents constitute the body of art existing in the field of Roller-Furling none of them disclose or even suggest the roller-furling sail construction of the present invention.
Additional prior art related to but in no way anticapitory of the present invention are a number of patents that relate to the so-called scotch-cut jibs ranging from the Dec. 26, 1899 U.S. Pat. No. 639,916 entitled Sailing Vessel and including, U.S. Pat. No. 3,194,202 to P. K. Saunders July 13, 1965, U.S. Pat. No. 3,602,180 issued Aug. 31, 1971 to T. S. Holmes, and U.S. Pat. No. 3,828,711 issued Aug. 13, 1974 to Russel.
Even though these Patents show Scotch-cut jibs are old, none describe a scotch-cut roller-furling sail constructed with at least two different weight sail cloths.
U.S. Pat. No. 4,196,687 issued Mar. 5, 1978 to R. C. Newich entitled Roller-Furling Sail, describes a roller-furling jib that is designed to eliminate fullness. This patent does not anticipate the specific embodiment of the present invention which maintains the desirable flat sail shape when a roller-furling sail is partially furled.
SUMMARY OF THE INVENTION
The present invention relates to a roller furling sail construction that utilizes at least two different sail cloth weights, said sail being constructed so that as the sail is furled, it is predominently the lightest weight cloth that is the first cloth to be taken up leaving a greater percentage of the heavier weight cloth or cloths exposed to take the load of the heavier weather. At the same time the total sail area of the sail is reduced.
The present invention also envisions the additions to the roller-furling sail, a luff flattening panel which may be sewn, glued, taped or secured in any suitable manner to the luff of the sail, thereby taking up the draft of the sail as the sail is furled so the most desirable flat sail shape is not effected by reducing sail area in the process roller-furling.
Thus it is the object of the present invention to provide a single roller-furling sail that is effective in winds from up to 10 knots to over 40 knots.
Another object of the present invention is to provide a method of sail handling in varying wind conditions and eliminating the danger of sail changing in rough weather.
A further object of the present invention is to provide a roller-furling sail where the sail remains flat while reducing sail area.
These and other objects of the present invention will become evident by reading the following specification in connection with the accompanying drawings.
DETAILED DESCRIPTION OF THE INVENTION
Sailing has been part of the worlds transportation and sports for as long as recorded history. It has always been a problem for sailors to deal with varying wind conditions. There are various ways of dealing with this problem. The two principle ways of handling heavy air are reducing sail area and/or presenting a sail, usually a smaller sail, made of heavier sail cloth to the heavier air. At first, only reducing sail area was used and generally done only on main sails by what is known in the art as reefing. Reefing is accomplished by pulling the main sail down, to a predetermined point and tying it to the boom, whereas; furling is accomplished by rolling a sail up on itself in the manner of a window shade, but in a more vertical position.
In the early days, the only way to reduce sail area of the jib was to go forward to the fore deck and take down the working and genoa jib and put up a smaller, heavier head sail, such as a storm jib. In the mid part of this century roller-furling was introduced. Roller-furling is described in the United States Patents cited supra. While roller-furling reduces sail area, it has been still necessary to go forward to the fore deck put up a small heavy weight storm jib because the roller-furling said, while being able to be reduced in sail area, is made of a sail cloth weight that is too light for the heavy weather.
Safety as sea is always a major consideration. The most hazardous work on board a sail boat is done on the foredeck. As the wind increases white caps start to form and the deck begins to pitch just as it is necessary to venture forward to change to a small heavy storm jib. This situation represents a real danger.
The sail construction of the present invention eliminated this problem by allowing a sailor to reduce sail area from the cockpit and at the same time present, to the increasing wind a much increased percentage area of heavier sail cloth. In addition, this is accomplished without the usual problem of bulging draft, generally inherent in roller-furling sails, just when you need it least, that is, in heavy weather wind.
In the present invention, the sail is constructed in the reverse miter cut or as commonly known in the art as the Scotch-cut. This cut can be generally discribed as having sail cloth panels running parallel to both the leech and the foot of the sail. The miter seam generally bisects the clew angle formed by the leech panel and the foot panel of the sail. It is of course recognized that this bisect angle may be varied by a number of degrees either way but this variation in no way takes such a construction outside of the spirit of the present invention. The sail of the present invention is constructed of panels diagonal to the luff with one mitired center seam generally bicecting the clew angle.
The main body of the scotch-cut sail of the present invention is composed of a sail weight that is generally the proper weight for the area in which the boat is generally sailed. This weight is usually 5 to 6 ounce dacron, although the weight could vary from 3 to 8 ounce dacron and the material may also vary from the use of dacron. This limitation is only guided by the selection of the cloth such as nylon, cotton, kevlor, a registered trademark of Du Pont & Co., Inc. and Mylar also a registered trademark of Du Pont & Co. These and any other sail cloth material are all included within the scope of the present invention.
A luff flattening panel is secured to the luff of the sail of present invention, thereby providing for the flat shape of the sail to be maintained and eliminating unwanted bulging of a roller-furled sail as it is furled. The luff flattening panel is generally curved in shape, ranging generally from the head to the tack of the sail along the luff. The width of the luff flattening panel is generally determined by the length of the luff of the sail. The longer the luff the wider the curved flattening panel. It is recognized, of course, that the description of the dimensions are generally a guide for optimum shape. The actual selection of the dimensions does not take such a sail out of the scope of the present invention.
It should also be noted that the scotch-cut panels in the sail of the present invention reduces stress on the seams of the roller-furling sail thereby increasing longevity of the sail. In general roller-furling sails have horizontal panels and direct pressure is constantly being exerted on the seams as the sail is furled again and again and causes many seams to blow out within the first year of use.
In a preferred embodiment of the present invention a dacron roller-furling genoa sail is constructed in a reverse miter or Scotch-cut. The sail is constructed with the panels diagonal to the luff with one miter center seam bisecting the angle of the clew. The main body of the sail is made of 5 to 6 ounce dacron and the outer panel of the leech and the foot are made of 7 to 8 ounce dacron. A curved luff flattening panel is sewn into the luff of the sail. The genoa is rigged on the jib roller-furling system of a sailing yacht. As the wind increases the sail is furled and the lighter sail material area is reduced, as a result an overall higher percentage of heavier sail cloth area is presented to the wind and at the same time reducing the overall sail area of the sail. The sail is also maintained flat.
DISCUSSION OF MAIN SAIL
The present invention has been described supra with respect to head sails such a jibs. It is part of the present invention to construct a main sail in the same manner as the jibs are constructed and used with main sail roller-furling gear. The main sail is constructed in the Scotch-cut wherein the main body of the sail is made of lighter weight sail cloth dacron, the leech panel and the foot panel is made of a heavier weight sail cloth dacron in the same manner as the jib. A luff flattening panel is also sewn at the luff of the main sail. As with the jib, the size of the luff of main sail will determine the number of varying weight sail cloth panels that are used in the sail. The main sail is rigged on the main sail roller-furling system of a sailing yacht. As the wind increases the main sail is furled and the lighter sail material area is reduced, as a result, an overall higher percentage of heavier sail area is presented to the wind and at the same time reducing the overall sail area of the main sail. The sail is also maintained flat.
All of the foregoing and still further advantages of the present invention will become apparent from a study of the specification taken in connection with the accompanying drawing wherein like characters of reference designate corresponding parts through the several views and wherein:
FIG. 1 is a plain view of the roller-furling genoa jib fully entended.
FIG. 2 is a plain view of the roller-furling genoa jib furled to storm jib position.
FIG. 3 is a plain view of the roller-furling main sail fully extended.
FIG. 4 is a plain view of the roller-furling main sail furled to storm jib position.
In the drawings, a genoa jib sail is shown in FIG. 1 on roller-furling gear where the numeral 8 indicates a roller-furling drum and 9 is a roller-furling headswivel. In the sail itself 1 is the leech, 4 is the foot, 5 is the luff, 2 is the head, 7 is the tack and 3 is the clew. The construction of this new sail of the present invention which has a Scotch-cut design is shown, wherein the miter seam is indicated at 6, the heavier weight panels are shown at 10, the lighter weight main body of the sail is at 11 and the luff flattening panel is shown at 12. The sail shown in FIG. 1, for example, would have, in its fully unfurled position as shown therein, about 70 percent light weight panel cloth 11 and about 30 percent heavy weight panel cloth 10.
In the furled position example of the sail as shown in FIG. 2, 28 shows the roller-furling drum and 29 is the roller-furling head swivel. In the furled sail 21 is the leech, 24 is the foot, 25 is the newly formed luff, 22 is the new head, 27 is the newly formed tack and 23 is the clew. The results of the sail construction of the present invention are shown with the miter seam at 26, the heavier weight panels are at 34, the lighter weight panels are at 35 and the fattened sail shape as a result of luff flattening panel 12 of FIG. 1 is indicated at 36. In the furled sail shown in FIG. 2, as an example, it would have in a storm furled position as shown therein, about 60 percent heavy weight panel cloth 34 and 40 percent lighter weight panel cloth 35.
It is evident that as a sailor furls the sail further the heavy weight panel percentage increases and the light weight panel decreases with lesser total sail area exposed to the wind. Conversely, as the sail is unfurled the percentage of light panel increases and the percentage of the heavier panels decreases with the total sail area increases.
In FIG. 3 a furling main sail is shown on a mast 50 where the numeral 48 indicates a roller-furling drum and 49 is a roller-furling head swivel. In the sail itself 41 is the leech, 44 is the foot, 45 is the luff, 42 is the head, 47 is the tack and 43 is the clew. The construction of this new sail of the present invention has a Scotch-cut design wherein the miter seam is indicated at 46, the heavier weight panels are shown at 40, the lighter weight main body of the sail is at 51 and the luff flattening panel is shown at 52. The main sail shown in FIG. 3, for example, would have at its fully unfurled position, as shown therein, about 68 percent light weight panel cloth 51 and about 32 percent heavy weight panel cloth 40.
In the furled position example of the main sail as shown in FIG. 4, 68 shows the roller-furling drum and 69 is the roller-furling head swivel. In the furled sail 61 is the leech, 64 is the foot, 65 is the newly formed luff, 62 is the new head, 67 is the newly formed tack and 63 is the clew. The results of the sail construction of the present invention are shown with the miter seam at 66, the heavier weight panels are at 74, the lighter weight panels are at 75, and the flattened sail shape as a result of luff flattening panel 52 of FIG. 3 is indicated at 76. In the furled sail shown in FIG. 4, as an example, it would have in the furled position as shown therein, about 60 percent heavy weight panel cloth 74 and 40 percent lighter weight panel cloth 75.
It is evident that as a sailor furls the sail further the heavy weight panel cloth percentage increases and the light weight panel cloth decreases with lesser total sail area exposed to the wind. Conversly, as the sail is unfurled the percentage of light panel cloth increases and the percentage of the heavier panel cloth decreases with the total sail area increases.
Although several embodiments of the invention have been herein illustrated and described it will be evident to those skilled in the art that various modification may be made in the details of construction and method of use without departing from the spirit of the present invention as set forth and limited only by scope of the appended claims. | A Roller-furling sail both main sail and head sail, such as jibs or genoas, are constructed in the reverse miter cut or Scotch cut. The sails are constructed of sail cloth panels to the luff with one mitered seam bisecting the angle made by the panels that run parallel to the foot and the leech of the sail. The panels running adjacent to the foot and the leech are of a heavier weight cloth than the remaining body of the sail. As the sail is furled a greater portion of the lighter weight sail cloth is taken up thereby leaving an increased percentage of the heavier sail cloth exposed to the stronger winds. The sail may also be provided with a luff flattening panel that is seared to the luff of the sail in a generally curved shape from the area of the tack to the area of the head of the sail. The luff flattening panel allows the sail to be partially furled and maintain the desired flat shape. | 1 |
[0001] This application claims priority to U.S. Provisional Applications, U.S. Ser. Nos. 60/643,386 filed Jan. 12, 2005, and 60/695,967 filed Jul. 1, 2005.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to the treatment of allergic or inflammatory diseases or other Syk-mediated diseases or conditions. More particularly, the present invention relates to the topical or systemic administration of certain 3,6-substituted imidazol[1,2-b]pyridazine analogs for the treatment of such diseases or conditions.
[0004] 2. Description of the Related Art
[0005] Syk is a tyrosine kinase that plays a critical role in mast cell degranulation, eosiniphil activation, lipid mediator synthesis and cytokine production. Accordingly, Syk kinase is implicated in various inflammatory and allergic disorders in particular asthma.
[0006] It has been shown that Syk binds to the phosphorylated gamma chain of the high affinity IgE receptor (Fcε RI) signaling via N-terminal SH2 domains and is essential for downstream signaling [Taylor et al, Molecular and Cellular Biology 1995; 15:4149-4157]. Syk kinase is important in the intracellular propagation of signaling following the crosslinking of the high affinity IgG receptor (FcγRI) by IgG. Since the mediators released as the results of Fcε RI and FcγRI are responsible at least in part for adverse effects associated with allergic responses or inflammation, compounds that inhibit Syk kinase may be effective in inhibiting those adverse effects [Sirganian et. al. Molecular Immunology 2002, 38:1229-1233].
[0007] The term “Syk-mediated disease” or “Syk-mediated condition”, as used herein, means any disease or other deleterious condition in which Syk protein kinase is known to play a role. Such conditions include, without limitation, inflammation and allergic disorders, especially asthma.
[0008] As taught in WO 2004/014382 (Rigel Pharmaceuticals) certain 2,4-pyridinediamine compounds have Syk kinase inhibitory activity. Lai et. al. describe a series of oxindoles having Syk kinase activity [Biorganic and Medicinal Chemistry Letters 2003, 13:3111-3114. Cywin et. al. describe the activity of a series of [1,6]naphthyridine compounds that inhibit Syk kinase [Biorganic and Medicinal Chemistry Letters 2003, 13:1415-1418]. Yamamoto et. al. describe an orally available imidazo[1,2,c]pyrimidine Syk kinase inhibitor [Journal of Pharmacology and Experimental Theapeutics 2003, 306:1174-1181]. WO2004/085409 discloses 5-substituted 2,3-diaminopyrazines.
SUMMARY OF THE INVENTION
[0009] The present invention provides a method for treating an allergic or inflammatory disease or other Syk-mediated disease or Syk-mediated condition characterized by administering a formulation which contains a therapeutically effective amount of a 3,6-substituted imidazol[1,2-b]pyridazine compound of formula (I) or a pharmaceutically acceptable salt thereof. The compounds of formula (I) have Syk kinase inhibitory activity. In one embodiment, the compounds of formula (I) are administered topically to treat an allergic or inflammatory disease or other Syk-mediated disease or Syk-mediated condition of the eye, ear or nose. In a preferred embodiment, the compounds of the present invention are used to treat an allergic eye disease selected from the group consisting of allergic conjunctivitis; vernal conjunctivitis; vernal keratoconjunctivitis; and giant papillary conjunctivitis.
DETAILED DESCRIPTION OF THE INVENTION
[0010] The 3,6-substituted imidazol[1,2-b]pyridazine compounds useful in the methods of the present invention are defined by formula (I):
[0000]
[0000] wherein:
A=aryl or heteroaryl optionally substituted by F, Cl, Br, C 1 -C 6 alkyl, OR 2 , or OCF 3 ; R 1 ═H, C 1 -C 6 alkyl, heterocyclyl, or (CH 2 ) n —X; n=1-4; X=aryl, heteroaryl, OR 5 or NR 3 R 4 ; and R 2 , R 3 , R 4 , R 5 independently=H or C 1 -C 6 alkyl.
[0016] According to a preferred embodiment of the present invention, a compound of formula (I), or a pharmaceutically acceptable salt thereof, is topically administered to the eye. Examples of pharmaceutically acceptable salts of the compounds of formulas (I) include, but are not limited to, inorganic acid salts such as hydrochloride, hydrobromide, sulfate and phosphate; organic acid salts such as acetate, maleate, fumarate, tartrate and citrate; alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt and calcium salt; metal salts such as aluminum salt and zinc salt; and organic amine addition salts such as triethylamine addition salt (also known as tromethamine), morpholine addition salt and piperidine addition salt.
[0017] It is recognized that compounds of Formula (I) can contain one or more chiral centers. This invention contemplates all enantiomers, diastereomers, and mixtures thereof. In the above definitions, the total number of carbon atoms in a substituent group is indicated by the C i— C j prefix, where the numbers i and j define the number of carbon atoms; this definition includes straight chain, branched chain, and cyclic alkyl or (cyclic alkyl)alkyl groups.
[0018] The term “aryl” refers to a monocyclic, bicyclic or tricyclic ring system having a total of five to fourteen ring members, wherein at least one ring in the system is aromatic and wherein each ring in the system contains 3 to 7 ring members. The term “aryl” may be used interchangeably with the term “aryl ring”.
[0019] The term “heterocycle”, “heterocyclyl”, or “heterocyclic” as used herein means non-aromatic, monocyclic, bicyclic or tricyclic ring systems having three to fourteen ring members in which one or more ring members is a heteroatom, wherein each ring in the system contains 3 to 7 ring members.
[0020] The term “heteroaryl” reffers to monocyclic, bicyclic or tricyclic ring systems having three to fourteen ring members wherein at least one ring in the system is aromatic, at least one ring in the system contains one or more heteroatoms, and wherein each ring in the system contains 3 to 7 ring members.
[0021] The term “heteroatom” means nitrogen, oxygen, or sulfur and includes any oxidized form of nitrogen and sulfur, and the quarternized form of any basic nitrogen. Also the term “nitrogen” includes a substitutable nitrogen of a heterocyclic ring. As an example, in a saturated or partially unsaturated ring having 0-3 heteroatoms selected form oxygen, sulfur or nitrogen, the nitrogen may be N (as in 3,4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl) or NR (as in substituted pyrrolidinyl).
[0022] It is important to recognize that a substituent may be present either singly or multiply when incorporated into the indicated structural unit.
[0023] The compounds of this invention are commercially available (BioFocus Discovery, Ltd., United Kingdom).
[0024] The compounds of the present invention may be administered topically (i.e., local, organ-specific delivery) by means of conventional topical formulations, such as solutions, suspensions or gels for the eye and ear; nasal sprays or mists for the nose. The concentration of the 3,6-substituted imidazol[1,2-b]pyridazine compound of formula (I) in the formulations of the present invention will depend on the selected route of administration and dosage form, but will generally range from 0.00001 to 5% (w/v). For solutions intended for topical administration to the eye, the concentration of the 3,6-substituted imidazol[1,2-b]pyridazine compounds of formulas (I) is preferably 0.0001 to 0.5% (w/v). The topical compositions of the present invention are prepared according to conventional techniques and contain conventional excipients in addition to one or more 3,6-substituted imidazol[1,2-b]pyridazine compounds of formula (I). A general method of preparing eye drop compositions is described below:
[0025] One or more 3,6-substituted imidazol[1,2-b]pyridazine compounds of formula (I) and a tonicity-adjusting agent are added to sterilized purified water and if desired or required, one or more excipients. The tonicity-adjusting agent is present in an amount sufficient to cause the final composition to have an ophthalmically acceptable osmolality (generally about 150-450 mOsm, preferably 250-350 mOsm). Conventional excipients include preservatives, buffering agents, chelating agents or stabilizers, viscosity-enhancing agents and others. The chosen ingredients are mixed until homogeneous. After the solution is mixed, pH is adjusted (typically with NaOH or HCl) to be within a range suitable for topical ophthalmic use, preferably within the range of 4.5 to 8.
[0026] Many ophthalmically acceptable excipients are known, including, for example, sodium chloride, mannitol, glycerin or the like as a tonicity-adjusting agent; benzalkonium chloride, polyquaternium-1 or the like as a preservative; sodium hydrogenphosphate, sodium dihydrogenphosphate, boric acid or the like as a buffering agent; edetate disodium or the like as a chelating agent or stabilizer; polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, to polysaccharide or the like as a viscosity-enhancing agent; and sodium hydroxide, hydrochloric acid or the like as a pH controller.
[0027] According to the present invention, the 3,6-substituted imidazol[1,2-b]pyridazine compounds of formulas (I) are useful for treating an allergic or inflammatory disease or other Syk-mediated diseases or Syk-mediated conditions. Such disorders include, but are not limited to, septic shock, haemodynamic shock, sepsis syndrome, post ischaemic reperfusion injury, malaria, mycobacterial infection, meningitis, psoriasis, congestive heart failure, fibrotic diseases, cachexia, graft rejection, cancers such as cutaneous T-cell lymphoma, diseases involving angiogenesis, autoimmune diseases, skin inflammatory diseases, inflammatory bowel diseases such as Crohn's disease and colitiss, osteo and rheumatoid arthritis, ankylosing spondylitis, psoriatic arthritis, adult Still's disease, ureitis, Wegener's granulomatosis, Behcet's disease, Sjogren's syndrome, sarcoidosis, polymyositis, dermatomyositis, multiple sclerosis, radiation damage, hyperoxic alveolar injury, periodontal disease, HIV, non-insulin dependent diabetes mellitus, systemic lupus erythematosus, glaucoma, sarcoidosis, idiopathic pulmonary fibrosis, bronchopulmonary dysplasia, retinal disease, scleroderma, osteoporosis, renal ischemia, myocardial infarction, cerebral stroke, cerebral ischemia, nephritis, hepatitis, glomerulonephritis, cryptogenic fibrosing aveolitis, transplant rejection, atopic dermatitis, vasculitis, ophthalmic allergic disorders, otic allergic disorders, nasal allergic disorders, rhinitis, sinusitis, reversible airway obstruction, adult respiratory distress syndrome, asthma, chronic obstructive pulmonary disease, and bronchitis.
[0028] In a preferred embodiment the compounds of formula (I) are useful in treating ophthalmic allergic disorders, including allergic conjunctivitis, vernal conjunctivitis, vernal keratoconjunctivitis, and giant papillary conjunctivitis; nasal allergic disorders, including allergic rhinitis and sinusitis; and otic allergic disorders, including eustachian tube itching.
[0029] For ocular disorders, the eye drops produced by the above method typically need only be applied to the eyes a few times a day in an amount of one to several drops at a time, though in more severe cases the drops may be applied several times a day. A typical drop is about 30 μl.
[0030] Certain embodiments of the invention are illustrated in the following examples.
Example 1
Topical Ophthalmic Solution Formulation
[0031]
[0000]
Ingredient
Concentration (W/V %)
Compound of formula I
0.1
Dibasic Sodium Phosphate
0.5
(Anhydrous), USP
Sodium Chloride, USP
0.65
Benzalkonium Chloride
0.01
Sodium Hydroxide, NF
q.s. pH 7.0 ± 0.2
Hydrochloric Acid, NF
q.s. pH 7.0 ± 0.2
Purified Water
q.s. 100
Example 2
Topical Ophthalmic Gel Formulation
[0032]
[0000]
Ingredient
Concentration (W/V %)
Compound of formula I
0.1
Carbopol 974 P
0.8
Disodium EDTA
0.01
Polysorbate 80
0.05
Benzalkonium Chloride, Solution
0.01 + 5 xs
Sodium Hydroxide
q.s. pH 7.0 ± 0.2
Hydrochloric acid
q.s. pH 7.0 ± 0.2
Water for Injection
q.s. 100
Example 3
Syk Kinase Activity
[0033] In a final reaction volume of 25 μl, Syk (h) (5-10 mU) is incubated with 50 mM Tris pH 7.5, 0.1 EGTA, 0.1 mM Na 3 VO 4 , 0.1% β-mercaptoethanol, 0.1 mg/mL poly (Glu, Tyr) 4:1, 10 μM test agent, 10 mM MgAcetate and [γ- 33 P-ATP] (specific activity approximately 500 cpm/pmol, concentration as required). The reaction is initiated by the addition of the MgATP mix. After incubation for 40 minutes at room temperature, the reaction is stopped by the addition of 5 μl of a 3% phosphoric acid solution. 10 μl of the reaction is then spotted onto a Filtermat A and washed three times for 5 minutes in 75 mM phosphoric acid and once in methanol prior to drying and scintillation counting. Percent inhibition was calculated using the following formula:
[0000] % Control=((sample-mean no enzyme)/(mean plus enzyme−mean no enzyme))×100.
[0034] In the syk kinase inhibition assay described above, the compounds shown in Table 1 were tested and were found to inhibit syk kinase; the results are shown in Table 1 below.
[0000]
TABLE 1
Structure
% inhibition
81
77
42
38
33
27
26
24
23 | Methods for treating an allergic or inflammatory disease or other Syk-mediated disease or Syk-mediated condition characterized by administering a composition which contains a therapeutically effective amount of a 3,6-substituted imidazol[1,2-b]pyridazine compound. | 2 |
CROSS REFERENCE TO RELATED DOCUMENTS
This application claims priority to TAIWAN Application No. 093106057, filed on Mar. 8, 2004.
FIELD OF THE INVENTION
The present invention generally relates to a printed circuit board, and more specifically to a method for fabricating embedded thin film resistors of a printed circuit board.
BACKGROUND OF THE INVENTION
In general, besides using conventional discrete passive elements, a printed circuit board can also use a thick film or a thin film process to develop the resistors required. In the thick film process, the resistors of the printed circuit board are made of carbon paste printed on the printed circuit board. Then the resistances of the resistors are fine-tuned by the laser trimming. In the thin film process, on the other hand, a nickel-plated copper foil and the epoxy resin of the printed circuit board is pressed together during the fabricating process of the printed circuit board. The nickel-plated side of the copper foil faces toward the printed circuit board and the non-plated side of the copper foil faces outward. Then, in a subsequent photolithography process, an acid etching solution is first used to etch both the copper and nickel layers, and then an alkaline etching solution is used to etch away the copper layer. A number of nickel blocks with the required dimensions are thereby formed. Laser is then used to trim each of the nickel blocks to achieve the precise resistance required.
In addition, currently, there is an electroless deposition technology that can replace the foregoing thin film method for building the resistor blocks to form thin film resistors.
In conventional thick film resistor fabricating methods, using high curing temperature carbon paste for the resistors is rather simple, mature, and less costly. However, because the laminate of the printed circuit board is susceptible to high temperature, low curing temperature carbon paste is usually used. The macromolecular polymer contained in the low curing temperature carbon paste will remain in the formed resistors even after the curing and solidification processes of the resistors. The hydrophilic property of the macromolecular polymer is the major factor causing the resistances of the resistors to vary along with the environmental change. Therefore, resistors having constant and precise resistances are difficult to achieve. On the other hand, the conventional thin film methods use the same temperatures and solutions as the conventional printed circuit board fabrication methods. The fabricated embedded resistors also have better stability and accuracy than those made by thick film methods. However, because the nickel-plated copper foil is difficult to manufacture, there are only limited supply sources and therefore the price is high. Although there are methods using the electroless deposition technology, the fabricated thin film resistors have inadequate adherence due to certain process factors. The application of these methods for mass production is thereby limited. Accordingly, the present invention is aimed at overcoming problems and disadvantages of conventional methods for fabricating thin film resistors of printed circuit boards.
SUMMARY OF THE INVENTION
The method provided by the present invention can be applied to single-sided, double-sided, multi-layered, and build-up printed circuit boards. The present invention develops at least a resistor layer in at least any one layer of the printed circuit board. The resistor layer is then etched to form a number of resistor elements required by the circuit layout of the printed circuit board.
The embedded thin film resistors made by the present invention replace the bulky conventional discrete resistors. The printed circuit board can therefore have finer circuit layout and much smaller size. The capacitive reactance effect usually found at the connectors of conventional discrete resistors is also avoided. The signal transmission speed and quality of the printed circuit board is therefore significantly enhanced, especially for high frequency applications. The process for forming the resistor layer provided by the present invention is very similar to that used for ordinary printed circuit boards and can be carried out using the same equipment. Therefore there is no significant investment on new equipment. The process for forming the resistor layer provided by the present invention, just like the process for ordinary printed circuit boards, is applicable in mass production and contributes to a significant lower manufacturing cost.
The foregoing and other objects, features, aspects and advantages of the present invention will become better understood from a careful reading of a detailed description provided herein below with appropriate reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a flow chart showing the steps of forming embedded thin film resistors on a printed circuit board according to a first embodiment of the present invention.
FIGS. 2( a )– 2 ( f ) are schematic diagrams showing the various steps of FIG. 1 respectively.
FIG. 3 is a flow chart showing the steps of forming embedded thin film resistors on a printed circuit board according to a second embodiment of the present invention.
FIGS. 4( a )– 4 ( i ) are schematic diagrams showing the various steps of FIG. 3 respectively.
FIGS. 5( a )– 5 ( e ) are schematic diagrams showing the various steps of depositing multiple resistor layers respectively according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 is a flow chart showing the steps of forming embedded thin film resistors on a printed circuit board according to a first embodiment of the present invention. These steps are described sequentially as follows.
In step 101 , as shown in FIG. 2( a ), the conductive wires 21 with resistor wells 22 are formed on a substrate made of an insulating polymer according to layout requirement of circuitry.
The foregoing conductive wires 21 and resistor wells 22 can be formed using an ordinary printed circuit board fabrication process such as the subtractive, additive, or semi-additive process. The conductive wire 21 is made of copper, aluminum, other well conductive material, or an alloy of the above.
In step 102 , as shown in FIG. 2( b ), an activated layer 3 is coated on top of at least surface of each resistor well 22 so as to activate the insulating polymer of the substrate 1 exposed by each resistor well 22 .
The foregoing activated layer 3 is made of activated palladium (Pd) or other appropriate activator that can be used to form the activated layer using a printing, spraying, or dipping method.
In step 103 , as shown in FIG. 2( c ), the printed circuit board is immersed in an electroless nickel solution so that a resistor layer 4 with an expected thickness is plated on the activated layer 3 .
The foregoing resistor layer 4 can be made of a nickel-phosphorus, palladium-phosphorus, ruthenium-phosphorus, or other metallic material having considerable resistance characteristics.
In step 104 , as shown in FIG. 2( d ), an etching resist 5 is coated on the resistor layer 4 , based on the locations and dimensions of the resistors required by the printed circuit board.
The foregoing etching resist 5 is made of etching resistible dry film, wet film, ink, plastic film, or solder mask ink, and can be formed by a screen printing or photolithography process.
In step 105 , as shown in FIG. 2( e ), the resistor layer 4 is etched to form a number of resistor elements 41 and contact points 42 matching the locations and dimensions of the etching resist 5 . On two ends of each of the resistor elements 41 , contact points 42 are formed so that each resistor element 41 is connected to the conductive wires 21 .
In step 106 , as shown in FIG. 2( f ), the etching resist 5 on the resistor layer 4 is stripped away.
The foregoing etching resist 5 on the resistor layer 4 may not be stripped away if the etching resist 5 is made of solder mask ink.
In step 107 , the shape and dimension of each resistor element 41 of the resistor layer 4 is adjusted to obtain accurate resistance by laser trimming.
At the end of this step, each resistor element 41 of the resistor layer 4 can be coated with protective ink. The protective ink is then heated and solidified so that subsequent processes of the printed circuit board do not affect the resistance of each resistor element 41 . The coating and solidification of the protective ink can also be conducted before the laser trimming. In this way, undesirable influence of the ink coating and solidification on the resistances of the resistor elements 41 can be avoided after their resistances are adjusted by laser trimming.
FIG. 3 is a flow chart showing the steps of forming embedded thin film resistors on a printed circuit board according to a second embodiment of the present invention. These steps are described sequentially as follows.
In step 201 , as shown in FIG. 4( a ), a conductive layer 2 is formed on a substrate 1 made of an insulating polymer. The conductive layer 2 is then processed, based on the locations and dimensions of the resistors required by the printed circuit board, to form the corresponding resistor windows 23 .
The conductive layer 2 is made of copper, aluminum, other well conductive material, or an alloy of the above.
In step 202 , as shown in FIG. 4( b ), an activated layer 3 is coated on top of at least surface of each resistor window 23 of the conductive layer 2 so as to activate the insulating polymer of the substrate 1 exposed by each resistor window 23 .
The foregoing activated layer 3 is made of activated palladium (Pd) or other appropriate activator that can be used to form the activated layer 3 using a printing, spraying, or dipping method.
In step 203 , as shown in FIG. 4( c ), the printed circuit board is immersed in an electroless nickel solution so that a resistor layer 4 with an expected thickness is coated on the activated layer 3 .
The foregoing resistor layer 4 can be made of a nickel-phosphorus, palladium-phosphorus, ruthenium-phosphorus, or other metallic material having considerable resistance characteristics.
In step 204 , as shown in FIG. 4( d ), an etching resist 5 is coated on the resistor layer 4 , based on the locations and dimensions of the layout of the conductive wires and the resistor windows required by the printed circuit board.
The foregoing etching resist 5 is made of etching resistible dry film, wet film, ink, plastic film, or solder mask ink, and can be formed by a screen printing or photolithography process.
In step 205 , as shown in FIG. 4( e ), the resistor layer 4 and conductive layer 2 are etched together according to the locations and dimensions of the etching resist 5 so that the layout of conductive wires 21 of the conductive layer 2 and the resistor windows required by the printed circuit board are formed.
In step 206 , as shown in FIG. 4( f ), the etching resist 5 on the resistor layer 4 is stripped away.
In step 207 , as shown in FIG. 4( g ), an etching resistible etching resist 5 ′ is coated on the resistor layer 4 , based on the locations and dimensions of the resistors required by the printed circuit board.
In step 208 , as shown in FIG. 4( h ), the resistor layer 4 is etched to form a number of resistor elements 41 matching the locations and dimensions of the etching resist 5 ′. On two ends of the resistor elements 41 , contact points 42 are formed to connect with the conductive wires 21 of the conductive layer 2 .
In step 209 , as shown in FIG. 4( i ), the etching resist 5 ′ on the resistor layer 4 is stripped away.
The foregoing etching resist 5 ′ on the resistor layer 4 may not be stripped away if the etching resist 5 ′ is made of solder mask ink.
In step 210 , the shape and dimension of each resistor element 41 of the resistor layer 4 is adjusted to obtain accurate resistance by laser trimming.
In the foregoing steps 205 to 209 , the layout of conductive wires 21 is first formed by etching the conductive layer 2 and the resistor elements 41 is then formed by etching the resistor layer 4 . If higher degree of accuracy is required, the etching of the conductive layer 2 and resistor layer 4 can be conducted together so that the layout of conductive wires 21 and each of the resistor elements 41 are formed according to the locations and dimensions of the etching resist 5 . The etching resist 5 is then stripped away. Subsequently, the conductive layer 2 and resistor layer 4 is coated with another etching resist 5 ′ according to the locations and dimensions of the resistors required by the printed circuit board. Then the superfluous resistor layer 4 on the conductive layer 2 is etched away. Each individual resistor elements 41 has two contact points 42 connecting with the conductive wires 21 of the conductive layer 2 . The etching resist 5 ′ is then stripped away.
At the end of the foregoing process, each resistor element 41 of the resistor layer 4 can be coated with protective ink. The protective ink is then heated and solidified so that subsequent processes of the printed circuit board do not affect the resistance of each resistor element 41 . The coating and solidification of the protective ink can also be conducted before the laser trimming. In this way, undesirable influence of the ink coating and solidification on the resistances of the resistor elements 41 can be avoided after their resistances are adjusted by laser trimming.
The resistance of the resistor element 41 depends on the thickness and dimension of the resistor element 41 , and the volume resistivity of the material used for the resistor layer 4 . Since the thickness and volume resistivity of the resistor elements 41 are the same because they are all developed from the same deposition of resistor layer 4 , adjusting the dimension of the resistor elements 41 is the only way to differentiate the resistance among the resistor elements 41 . For resistor elements 41 having a large resistance, their shape would be much longer or narrower than those having a smaller resistance. Therefore there is a range limitation on the resistance achievable by varying the dimension of the resistor elements 41 . To overcome these disadvantages, multiple resistor layers 4 can be deposited. As shown in FIG. 5( a ), to form a number of resistor elements 41 having similar resistance, a resistor layer 4 having a specific volume resistivity and thickness is deposited first. Then the foregoing process is applied to form the required resistor elements 41 as shown in FIG. 5( b ). The resistor elements 41 all have identical thickness and volume resistivity. Their resistances are then fine-tuned by adjusting their dimensions. Then, as shown in FIG. 5( c ), a protective film is coated to protect the resistor elements 41 in subsequent operations. Then, for another set of required resistor elements 41 ′, another resistor layer 4 ′ having a specific volume resistivity and thickness is deposited as shown in FIG. 5( d ). The same process is repeated to form the required resistor elements 41 ′ as shown in FIG. 5( e ). The resistor elements 41 ′ all have identical thickness and volume resistivity. Their resistances are then fine-tuned by adjusting their dimensions. Similarly additional resistor layers can be deposited so that resistor elements can have a large variance in their resistances. The process can be conducted on the same layer or on different layers of a printed circuit board if the printed circuit board has more than one layer.
The resistor elements 41 and 41 ′ of the resistor layer 4 and 4 ′ respectively can have their dimensions etched or laser-trimmed simultaneously at the end so as to achieve the desired resistances.
In addition, the method provided by the present invention can be applied to single-sided, double-sided, multi-layered, and build-up printed circuit boards. In these printed circuit boards, at least a resistor layer 4 is formed in at least any one layer of these printed circuit boards and etched to obtain the resistor elements 41 required by the circuit layout of the printed circuit boards. Electrical connections are then established between the resistor elements 41 and the conductive wires 21 .
Although the present invention has been described with reference to the preferred embodiments, it will be understood that the invention is not limited to the details described thereof. Various substitutions and modifications have been suggested in the foregoing description, and others will occur to those of ordinary skill in the art. Therefore, all such substitutions and modifications are intended to be embraced within the scope of the invention as defined in the appended claims. | A method for fabricating the embedded thin film resistors of a printed circuit board is provided. The embedded thin film resistors are formed using a resistor layer built in the printed circuit board. Compared with conventional discrete resistors, embedded thin film resistors contribute to a smaller printed circuit board as the space for installing conventional resistors is saved, and better signal transmission speed and quality as the capacitive reactance effect caused by two connectors of the conventional resistors is avoided. The method for fabricating the embedded thin film resistors provided by the invention can be conducted using the process and equipment for conventional printed circuit boards and thereby saving the investment on new types of equipment. The method can be applied in the mass production of printed circuit boards and thereby reduce the manufacturing cost significantly. | 8 |
FIELD OF THE INVENTION
This invention relates to a distillation process and apparatus.
BACKGROUND OF THE INVENTION
U.S. Pat. No. 4,533,372 to Jaime A. Valencia and Robert D. Denton discloses a method and apparatus for separating carbon dioxide and other acid gases from methane by treating a feedstream in a controlled freezing zone. Such treatment is referred to as the "CFZ Process". The CFZ Process provides for the solidification of carbon dioxide in a distillation tower in a controlled manner and permits the thermodynamic separation by distillation of a feedstream mixture containing carbon dioxide and methane in a single distillation column. The present invention can be used to provide improved heat transfer in the CFZ Process.
SUMMARY OF THE INVENTION
Briefly, the invention includes a bubble cap tray having elongated caps. The elongated caps enable the formation of a sufficiently deep heat reservoir on the tray to be capable of melting any solids such as solid CO 2 formed above the tray that fall into it and provide stable unit operations. The warm vapors from beneath the tray flow up the risers and down between risers on the tray and the elongated caps and are released at the open end of the caps, near the bottom of the liquid layer on the tray. The warm vapor transfers heat to the liquid, and in turn to the solid carbon dioxide. The depth of the liquid layer provides a sufficiently long contact time of warm vapors, liquid, and solids to insure at least the substantial melting of the solids prior to the resultant liquid being discharged from the tray to the lower distillation section of the column. The tray also provides excellent mass transfer between all three phases present: vapor, liquid and solid.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a phase diagram of carbon dioxide and methane at 650 psia.
FIG. 2 illustrates, in schematic fashion, a process of separating carbon dioxide from methane using the CFZ Process.
FIG. 3 illustrates in a simplified manner, an elongated bubble cap tray according to one embodiment of the invention.
FIG. 4 is a side view of a portion of an elongated bubble cap tray according one embodiment of the invention.
FIG. 5 is a top view of an elongated bubble cap tray according to one embodiment of the invention as viewed along line 5--5 of FIG. 3.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Prior to U.S. Pat. No. 4,533,372 to Valencia et al., the phenomenon of carbon dioxide solids formation was considered a problem in performing the cryogenic distillation of carbon dioxide and methane. This phenomenon is thermodynamically illustrated in FIG. 1. This diagram is based on data from H. G. Donnelly, and D. L. Katz, Ind. Eng. Chem. 46, 511 (1954). The diagram shows regions for the various phases of carbon dioxide: liquid only, vapor only, vapor and liquid existing together, and regions having solids existing with either vapor or liquid.
FIG. 1 illustrates that the formation of carbon dioxide solids would be expected if separation of a carbon dioxide-methane mixture is attempted at 650 psia. For example, cooling a 30% methane/70% carbon dioxide mixture initially at 60° F., along line "A" in FIG. 1 will cause liquid to form beginning at about 15° F. At this point, vapor-liquid equilibrium distillation may take place. The vapor in equilibrium with the liquid would increase in methane content along line "B". As the temperature is lowered to about -80° F., solid carbon dioxide would begin to form. At these conditions, three phases coexist along line "C": solid, point "C s "; liquid, point "C 1 "; and vapor, point "C v ". Thus conventional vapor-liquid distillation could take place in the "Vapor-Liquid" region limited by the solidification line "C" and by pure CO2, point "D". However, at temperatures colder than -80° F., the formation of solid carbon dioxide would render conventional distillation tower internals inoperable. Therefore at 650 psia, the product methane stream in the illustration would have as much as 15% carbon dioxide remaining in it.
FIG. 2 illustrates, in schematic fashion, the concept of separating carbon dioxide from methane using the CFZ Process. Table I is an approximate material balance for one such application showing operating conditions at various points enumerated in FIG. 2. Table II shows an approximate characterization of the distillation tower 104. In a typical application, a dried gas stream from a wellhead containing methane, carbon dioxide and other components such as nitrogen, hydrogen sulfide, and other hydrocarbons, is introduced into the unit through line 10.
This feed stream may be first cooled in indirect heat exchanger 100 and then expanded through a turbine expander or a Joule-Thompson ("J-T") valve 102 as shown in FIG. 2. The function of pre-cooler 100 and J-T valve 102 is to drop the temperature to a level suitable for introduction of this stream into the methane-carbon dioxide distillation tower 104.
As shown in this diagram, the distillation tower 104 is separated into three sections: a lower distillation section 106, a middle controlled freezing zone 108, and an upper distillation section 110. However, the upper distillation section 110 can be located in a separate column or eliminated altogether depending on product purity requirements. The internals of upper section 110 and lower section 106 may include equipment suitable for vapor liquid distillation such as trays, random or structured packing, downcomers, and weirs, or other conventional equipment if desired. The tower feed, as mentioned above, is introduced into the lower distillation section 106 through line 10 where it undergoes typical distillation. Liquid carbon dioxide product leaving the bottom of the section is heated in reboiler 112 and a portion is returned to the tower as reboiled liquid. The remainder leaves the process as a product via line 24.
The lighter vapors leave distillation section 106 and enter the controlled freezing zone 108 via a bubble cap tray 130 having elongated caps. After bubbling through the liquid in the elongated bubble cap tray, at the bottom of zone 108, the rising vapors contact liquid spray (sprayed freezing zone liquid feedstream which as used here may also be referred to as spray liquid) emanating from nozzles or spray jet assemblies 120. The vapor then continues up through the upper distillation section 110. Reflux is introduced to the tower through lines 18 and if desired through 28. Vapor leaving tower 104 through line 14 can be partially condensed in reflux condenser 122 and separated into liquid and vapor phases in reflux drum 124. Liquid from reflux drum 124 can be returned to the tower via line 18. The vapor from the drum can be taken off as a product in line 16 for subsequent sale to a pipeline or condensation as LNG.
The liquid produced in upper distillation section 110 can be collected and withdrawn from the tower via line 20. Liquid in line 20 may be accumulated in vessel 126 and returned to the controlled freezing zone using pump 128 and spray nozzles 120. The vapor rising through bubble cap tray 130 meets the spray liquid emanating from nozzles 120. Solid carbon dioxide forms and falls to the bottom of controlled freezing zone 108, where a level of liquid is maintained on the tray 130.
Optimal operation of the CFZ Process requires that all the solids falling on the CFZ tray 130 be melted at the bottom of the controlled freeze zone 108 and that only a liquid phase stream 22 be passed from the controlled freeze zone 108 to the lower distillation zone 106.
FIG. 3 illustrates the operation of the bubble cap tray having elongated caps. Warm vapors from the lower distillation zone 106 rise through the vapor feed risers 134, then flow downward through the annular space between the vapor feed risers 134 and the caps 136, and are discharged near the bottom of the liquid layer 137 adjacent the upper surface of the tray base. The skirt of the cap is preferably nearly the same as the length of the riser. The invention can be carried out with only one riser if desired, but better results will be obtained when a plurality of risers are used. The risers will generally have a length in the range of about 0.5 to about 10 feet, usually in the range of about 1 to about 5 feet corresponding with the liquid depth on the tray. The risers in a preferred embodiment can have a length to inside diameter ratio in the range of about 2:1 to about 20:1, usually in the range of about 3:1 to about 10:1, although the invention can be carried out with risers not so constructed.
As the vapor rises through the liquid layer on the tray, it intimately and turbulently contacts the liquid and Solids mixture pooled on the tray and transfers heat to the liquid. The heat from the liquid layer is transferred in turn to the falling crystals of solid carbon dioxide, thus melting them. The turbulence in the liquid created by the rising vapor also facilitates the transfer of heat to the solids. The bubble cap tray having elongated caps allows the efficient melting of the solids formed in the CFZ section, significantly reducing and if desired, eliminating the need of all external heat source to melt the solids.
In addition, mass transfer also takes place between the liquid, vapor and solids present. Much like in conventional distillation, the light, more volatile component in the liquid phase, in this case methane, vaporizes to enrich the vapor above the tray in methane. Likewise, the heavier component, in this case carbon dioxide, condenses out of the vapor and enriches the liquid in carbon dioxide. The degree of separation effected in the bubble cap tray is further enhanced by the melting of pure carbon dioxide crystals. This results in a liquid stream highly enriched in carbon dioxide, much more so than if only vapor-liquid distillation were to take place without the heretofore troublesome formation of solid carbon dioxide.
The vertically elongated configuration of the tray enables a sufficient depth of liquid to be easily maintained. A sufficient depth is needed to provide enough contact time between the three phases for heat and mass transfer to take place. In one simple embodiment, liquid level is controlled by use of a downcomer having an inlet in the CFZ section and an outlet in the lower distillation section. Liquid level control can be accomplished by flowing over weir 138 and down downcomer 139 as shown in FIG. 3. However, more sophisticated, adjustable liquid level control methods, using level sensors, control valves and/or pumps can also be used. Optimal results would be anticipated by maintaining the liquid level in the proximity of the upper surface of the caps.
In the example configuration of FIG. 3 the downcomer entry is positioned near the periphery of the bubble cap tray. As shown in FIG. 5, the downcomer 139 entry can be defined between the weir 138 and the inside wall of the distillation column 150. The apparatus is provided with a deflecting cover or roof 140 to prevent solids from falling into the downcomer. A baffle 142 prevents solids which fall past the roof edge or too near the downcomer entrance from bypassing across the liquid surface and entering the downcomer.
The deflecting cover 140 and baffle 142 are not completely sealed to each other. A passage is left to provide for equalization of pressure of vapors above and below the cover 140. In a preferred embodiment, a slot is formed between the upper rim of the baffle and the lower lip of the roof for any vapor flow needed for pressure equalization. The opening to the downcomer is positioned under the eave of the roof. The baffle is positioned under the eave of the roof between the opening of the downcomer and the elongated caps and is formed by a wall structure oriented generally normally to the tray structure and spaced apart therefrom, so that liquid can flow under the baffle and upwardly over the top of the weir and into the downcomer opening. In a preferred embodiment, a slot is formed between a lower lip of the baffle and an upper surface of the tray. As is known to those skilled in the art, multiple liquid outlets, or multiple downcomers or a different location for the downcomer can be used to improve flow patterns, particularly in large towers.
The downcomer provides a means for transferring liquid from the CFZ section to the lower distillation section. A sufficient leg of liquid is maintained in the downcomer as a liquid seal to prevent vapors from flowing from the lower distillation section to the CFZ section effectively bypassing the elongated bubble cap tray. Other means can also be used to transfer liquid from the CFZ section to the lower distillation section such as an external line with a liquid level control valve.
FIGS. 4 and 5 illustrate a typical mechanical configuration for the bubble cap tray having elongated caps. The risers 134 are attached to the tray base plate 132 by welding, screwing or any other suitable means. The caps in turn are attached, in the illustration, to the risers via connecting posts 144 and to each other via connecting posts 146. Other arrangements can be employed if desired, such as attaching the caps 136 to the tray base plate 132 via support posts that are designed so as not to interfere with the vapor flow out of the caps.
The height of the elongated bubble caps and risers is to be tailored to specific applications. In general they should be no less than 6 inches and no larger than 10 ft. preferably between about 1 ft. and about 5 ft. The diameter of the caps should be such as to provide an annular cross sectional area for vapor flow approximately equal to the riser cross sectional area for vapor flow. In turn the diameter of the risers and the number of sets of risers is to be determined for each specific application so as to provide liquid residence times in the 10 seconds to 10 minutes range, preferably in the about 1/2 to about 5 minutes range given the above liquid depth guidelines. The riser diameter and number of riser/cap sets should also be consistent with generally accepted guidelines in the art for vapor flow passages of 5 to 25% of the tray area. | An elongated bubble cap tray allows three phases: solid, vapor and liquid, to come in contact at the bottom of a controlled freezing zone and transfer heat and mass amongst themselves. Complete melting of the solid phase may be achieved in this tray, significantly reducing or totally eliminating the need for an external source of energy as well as its associated heat transfer equipment. | 8 |
BACKGROUND
[0001] Software developers may wish to test various features and situations within a software application to determine whether the application is performing as specified. One technique is to perform manual testing, in which a developer or user causes the application to perform various functions, and observes or reports on the results. Based on those results, the application may be modified to perform differently. Manual testing techniques typically are laborious and relatively time consuming, and may not be effective in identifying every defect or other functionality that may need to be modified. Automated testing techniques, typically referred to as “test automation,” are used to automatically perform such testing. Test automation often involves developing other software applications or environments that can automatically execute the software application that is being tested. Automated tests typically may be performed relatively quickly more reliably than manual techniques.
[0002] Within test automation, significant time may be spent during setup and tear-down on individual test case runs, i.e., creating the specific situation or state of the software application that is to be tested. Setup often requires elaborate processes to reach a particular execution state that the test case is intended to validate.
BRIEF SUMMARY
[0003] The invention provides advantageous methods and systems for developing and executing automated testing using multiple test cases, without requiring conventional setup and tear-down, or cleanup steps before and after execution of each test case.
[0004] An embodiment of the disclosed subject matter may include obtaining a tree having a plurality of test case nodes that identify one of a plurality of test cases to be executed by a computer system. The method further includes identifying and executing a first test case, which causes the computer system to be in a first state, and logging a result of the execution. The method continues with identifying a second test case that proceeds from the first state and executing the second test case prior to changing the state of the computer system from the first state. The method concludes with logging a result of executing the second test case.
[0005] Another embodiment of the disclosure is a method including receiving a description of a plurality of test cases that may be executed by a computer system in a first state, which, upon execution, cause the computer system to be in a different state. The method further includes identifying a first test case for which the different state is suitable for execution of a second test case, and constructing a test case tree with nodes corresponding to the first and second test cases. Traversal of the tree allows a processor of the computer system to execute each of the first and second test cases without requiring a clean-up step to be performed between each execution.
[0006] Additional features, advantages, and embodiments of the invention may be set forth or apparent from consideration of the following detailed description, drawings and claims. Moreover, it is to be understood that both the foregoing summary of the invention and the following detailed description are exemplary and intended to provide further explanation without limiting the scope of the invention as claimed.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] The accompanying drawings, which are included to provide a further understanding of the disclosed subject matter, are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the detailed description serve to explain the principles of the disclosure. No attempt is made to show structural details of the disclosure in more detail than may be necessary for a fundamental understanding of the disclosure and various ways in which it may be practiced.
[0008] FIG. 1 shows a network configuration according to an embodiment of the disclosed subject matter.
[0009] FIG. 2 shows a computer system according to an embodiment of the disclosed subject matter.
[0010] FIG. 3 shows an example execution of three test cases in a software application in a conventional automated testing system.
[0011] FIGS. 4A-4C show the example test cases shown in FIG. 3 , after being integrated into a tree according to an embodiment of the present disclosure.
[0012] FIG. 5A shows an example test case tree according to an embodiment of the disclosure.
[0013] FIG. 5B shows an example execution order for the tree shown in FIG. 5A .
[0014] FIG. 6 shows an example process for executing a test case tree according to an embodiment of the disclosure.
[0015] FIG. 7 shows an example process for generating a test case tree according to an embodiment of the disclosure.
DETAILED DESCRIPTION
[0016] Conventional automation systems may not handle the setup and tear-down required for various test cases efficiently, requiring processing resources to perform setup and teardown before each test case. For example, many known test automation harnesses, such as Test Director available from Mercury Interactive Corporation and HPSoftware, or the Selenium web application testing system, operate based on a “single test case, single execution code path” principle. That is, each presumes that a developer will construct and test individual test cases, with each test case requiring its own setup and tear-down.
[0017] FIG. 3 shows an example execution of three test cases of a software application in a conventional automated testing system. Each node identifies an operation performable within a software application being tested, such as a button press, menu item selection, icon selection, or the like. In Test Case 1 , which validates results of operation or state 104 , operations 101 , 102 , and 103 are performed in order, at the end of which the system is in the state for operation 104 to be performed and tested. Operation 104 is then performed, the results are logged, and any necessary cleanup is performed. Cleanup may be necessary because the performance of a specific operation (such as operation 104 in Test Case 1 ) may influence, or pollute the state of the preceding operation (such as operation 103 in Test Case 1 ). Cleanup therefore includes removing any effects of the performance of prior operations, such as to uninstall and reinstall the software application being tested, for example. Next, Test Case 2 is performed. In the example, Test Case 2 is designed to test operation or state 105 , which occurs or is possible in the application after operations 101 , 102 , and 103 have been performed. Hence, Test Case 2 proceeds similarly to Test Case 1 , with operation 105 being performed after operation 103 instead of operation 104 . The results are logged, and any needed cleanup is performed. In Test Case 3 , operation or state 106 , which occurs or may be performed after operation 104 , is to be tested. Hence, operations 101 , 102 , 103 , and 104 are performed as a prerequisite to the testing of operation 106 . The results are again logged and any needed cleanup is performed.
[0018] Embodiments of the present invention may reduce the amount of time required to set up and/or run a particular test case or set of test cases. In addition, the test cases may be developed and executed without requiring duplicate code in the prerequisite. This may improve the maintainability and consistency of the test code.
[0019] According to an embodiment, multiple test cases may be created and arranged in a tree-like structure, with each node representing a separate test case. State management also may be performed at each node in the tree. Each node may be executed in a depth-first, serialized fashion which may remove or reduce the need for duplicate work, such as the cleanup and duplicative performance of operations necessary to re-establish a state that existed prior to a particular test. In some arrangements, a test case may require an exclusive execution of a given parent node or nodes. In this case, embodiments may provide for the ability to generate a virtual clone of earlier cases in the tree, after which the node may be executed in the normal order. State management may be handled at each node to assure that each appropriate component is present before execution of a particular test case, and to assure that the execution of other test cases has not polluted the test environment in a harmful way.
[0020] In an embodiment, each test case may be a structured entity containing relational information (e.g., parent and/or child information) for the tree, a unique identifier (GUID), a method of communicating with the state manager, pre and post execution steps (if needed), a reference to an ancestor from which an exclusive execution path is needed, a timeout value, execution steps, a human readable friendly name, or any combination thereof. When a test case is inserted into the tree, if it includes a reference to an exclusive ancestor reference, then clones of all ancestors between the test case and the identified case may be created and appended to the tree to force exclusive execution for execution of the test case. These may be marked as “volatile,” and may be discarded if or when the tree is unloaded.
[0021] During an execution phase, the top level node of the tree may be run first. Since it is the first entry into the test case, a state manager may be called to take a snapshot of the current target product. Any tasks that are required to run before the test can be run also may be performed. The test itself then may be run, along with any desired validation. Post-test processes may then be executed. The state manager may be called to verify that the state is still as expected when the test case was entered. For example, the state manager may be called to determine if a state variable contains a value within expected limits, such as confirmation that a text box within which text is required is not empty, or that a required checkbox has been checked, for example. If the state manager indicates a failure, further processing may be halted, and the test case marked as a failure. Otherwise, each child test case of the current test case may be executed in a depth-first recursive fashion. The state manager may be called to validate each test case before each execution.
[0022] In an embodiment, each test case may be relatively small, for example only one or two logical operations. As a specific illustrative example, a test case may include generating a click on a button or other action, such as to launch a wizard, select a file, open a directory, or the like. Because the functionality associated with each test case is limited, the system may readily adapt to new changes, such as a new panel in a wizard, a new file dialog, or the like, by inserting a small set of one or more of new cases for the added functionality. In general, test cases that exist further down the tree may need no alteration to account for the changes.
[0023] In an embodiment, the state manager may contain state information for each test case in an execution path. This may be useful since the failure of any one test case could pollute the environment and incorrectly influence the results of other test cases, such as those that depend from the failed test case. The failure is attributed to the offending test case, so remaining test cases can then be marked blocked and not run, thus reducing both test execution time and undue failures.
[0024] FIGS. 4A-4C show the example test cases shown in FIG. 3 , after being integrated into a tree according to an embodiment of the present invention. As shown in FIG. 4A , operations 101 , 102 , 103 , and 104 may be executed as described with respect to FIG. 3 . After executing operation 104 , the results of performing the test by executing operation 104 may be logged. As previously described, if a test case for operation 104 (also referred to generally as “test case 104 ”) fails or the state manager otherwise indicates a fault, execution may be halted. Otherwise, after execution of the test case 104 , the system is in a state suitable for execution of the test case 106 , which is then performed and the results logged.
[0025] The test system may then return to or otherwise obtain the state needed to perform test case 105 . For example, as described herein, a virtual copy of the application state being tested may be made at operation 103 . The virtual copy is a duplicate of the state resulting from execution of test case 103 , or the state of operation 103 . When the system needs to execute test case 105 , the virtual copy may be accessed to do so. Thus, any state changes resulting from execution of test case 106 will not impact execution of test case 105 . After execution, the virtual state may be discarded and other cleanup performed. Notably, only a single cleanup may be performed after the tree is executed, in contrast to the arrangement shown in FIG. 3 in which multiple setup and cleanup, or tear-down steps are required.
[0026] FIG. 4B shows a relational tree illustration of the arrangement shown in FIG. 4A . FIG. 4C shows the same tree with an “exclusive” execution of test case 103 , i.e., where execution of operation 103 causes a state change that renders the system unsuitable for execution of both test cases 104 and 105 . For example, execution of test case 103 may include deleting or modifying a file that is needed in its original state for execution of one or more subsequent test cases, such as test case 105 . As previously described, a virtual copy of the state in which test case 103 is to be executed, node 103 ′, shown by the dashed outline, may be created after execution of test case 102 . The virtual copy 103 ′ may then be used to execute test case 105 .
[0027] FIG. 4D shows an example execution order for the tree shown in FIG. 4A . As previously described, operations 101 , 102 , and 103 may be performed followed by test case 104 . The results of test case 104 may be logged as previously described, after which test case 106 may be executed and the results logged. A virtual copy of the state of operation 103 , 103 ′ may be created and used to execute test case 105 . The results of test case 105 may be logged. Once all test cases are complete, the system may perform any needed cleanup.
[0028] The virtual copy 103 ′ may be created at any convenient time. For example, where sufficient information is available regarding the relevant states of the system the virtual copy 103 ′ may be created prior to traversal of the tree, such as during construction of the test tree. As another example, the virtual copy 103 ′ may be created once a system such as the test system is in the appropriate state. More generally, embodiments of the disclosed subject matter allow for creation of virtual copies at any time prior to execution a test case that is associated with the virtual copy.
[0029] It will be understood that the simple tree shown in FIGS. 4A-4D is illustrative only, and that in general any number of test cases may be incorporated into a tree. FIG. 5A shows an example test case tree 500 according to an embodiment of the invention. FIG. 5B shows an example execution order 550 for the tree 500 shown in FIG. 5A . As previously described, the tree 500 may be traversed and each test case executed using, for example, a depth-first recursion of the tree 500 . An example procedure used to traverse the tree 500 is provided below. Generally any technique that reaches each test case in the tree that is to be executed may be used.
[0030] An example procedure to traverse the tree may include the following actions:
1. Test case 501 is run as it's the first node in the tree. 2. It is determined that test case 501 has a child, test case 502 , so test case 502 is run. 3. Test case 502 has two children, 503 and 507 . One child test case is selected and executed. In this example, test case 503 is selected; more generally, any child test case may be selected first. 4. Test case 503 is run. Test case 503 has two children. As with test case 502 , one child test case ( 504 in the example) is selected and run. 5. Test case 506 is run. It has no children, so test case 507 is selected as the nearest child of the nearest ancestor that has not yet been executed (test case 503 in the example). 6. Test case 507 is run. It has 2 children, so the first, test case 508 in the example, is selected. 7. Test case 508 is run. 8. Test case 508 has 1 child, test case 511 , so 511 is run. 9. Test case 511 has no children. As previously described, the nearest child of the nearest ancestor that has not yet been executed is selected. In the example, this is test case 509 . 10. Test case 509 is run. It has two children, so the first, test case 510 , is selected. 11. Test case 510 is run. It has a single child, test case 514 , which is selected. 12. Test case 514 is run. It has a single child, test case 515 , which is selected and run. 13. Test case 515 has no children, so the nearest child of the nearest ancestor that has not yet been executed is selected and run. In the example, this is test case 512 . 14. Test case 512 has 5 children, so the first, test case 516 , is selected and run. 15. Test case 516 has no children, so the nearest child of the nearest ancestor that has not yet been executed, test case 517 , is selected and run. 16. Similarly, each of test cases 517 , 518 , and 519 , has no children. For each, the test case is run and then the nearest child of the nearest ancestor that has not yet been executed is selected and run (test cases 518 , 519 , and 520 , respectively). 17. Test case 520 has no children, so the nearest child of the nearest ancestor that has not yet been executed is selected. In the example, this corresponds to virtual node 503 ″, which is shown with a dashed outline to indicate it is a “virtual” node as previously described. That is, node 503 ″ is a replica of the state at node 503 , following execution of operation 502 , to allow for test cases that require exclusive execution due to, for example, a change in state that renders the system unsuitable for subsequent test cases. 18. Node 503 ″ has a child 505 , so test case 505 is run. 19. Node 505 has no children, so the nearest child of the nearest ancestor that has not yet been executed, 502 ′, so is run. 20. Test case 502 ′ has a child 503 ′, so 503 ′ is run. 21. Similarly, 503 ′, 504 ′, 506 ′, and 513 ′ are run in turn. 22. After execution of test case 513 ′ there are no unexecuted nodes remaining, so the system exits the tree and performed any needed cleanup.
[0053] As previously described, after execution of each test case shown in FIG. 5A , the results of the test case may be logged. If any test case indicates a failure, the system may exit the node and perform cleanup without executing subsequent nodes if the failed test case may affect execution of subsequent test cases.
[0054] FIG. 6 shows an example process for executing test cases according to an embodiment. FIG. 6 may be used, for example, in conjunction with the example test case trees previously described. At 610 , a test case tree may be obtained. The test case tree may include multiple test case nodes, each of which identifies a test case to be executed. At 620 , a first test case to be executed may be identified. The first test case may be, for example, a node in the tree that does not have a parent node. As another example, where an error or other result caused a test case in the test case tree to be halted and/or traversal of the test case tree to halt previously, the first test case selected may be the test case that caused traversal to halt. This may be the case where an error associated with the test case node which caused the halt has been corrected and the test case is to be re-run, but the error does not affect other nodes in the tree.
[0055] At 630 the first test case may be run, and the results may be logged at 640 . When the first test case is run, it may place the system being tested into a state associated with completion of the first test case, which may be suitable for further test cases to be executed. At 650 , one or more subsequent test cases may be identified in the tree, such as those associated with child nodes of the first test case node. A subsequent test case may be executed at 660 and the results logged at 670 . The subsequent test case may be run without changing the state of the system being tested, for example, without performing any clean-up steps typically associated with a conventional test case. At 680 , the test system may determine whether there is an unexecuted test case represented in the tree and, if so, return to step 650 or 660 to identify and/or execute the unexecuted test case. As previously described, steps 650 - 680 may be performed repeatedly to traverse the entire tree, such as by using a depth-first traversal technique. When there are no unexecuted test cases represented in the tree, traversal of the tree and execution of test cases may end at 690 . If any cleanup is required, it may be performed at 690 , after execution of all test cases in the tree.
[0056] FIG. 7 shows an example process for constructing a test case tree according to an embodiment, such as for constructing the test case trees illustrated in FIGS. 4 and 5 . At 710 , a computer system may receive information about test cases to be included in the tree. The information may include, for example, a description of the start and end state of a test system before and after execution of the test case, an indication of which test cases may be executed before or after other test cases, an explicit execution order of one or more of the test cases, or any other relevant information.
[0057] At 720 an execution arrangement for the test cases may be determined and/or constructed. For example, the system may match start and end states of the test cases, such that a test case which may be executed from a state resulting from execution of another test case is placed into the test case tree as a child of the other test case. Similarly, those test cases requiring exclusive execution relative to other test cases may be identified, and the test cases placed into the tree appropriately as previously described. As another example, those points in the tree where a virtual test case should be created may be noted, and/or various data for generating the virtual test case may be stored with the tree. The test case tree may be arranged such that traversal of the tree by a processor allows the processor to execute each of the test cases without requiring a clean-up or equivalent step to be performed between each execution.
[0058] Embodiments of the invention may be implemented in and used with a variety of component and network architectures. FIG. 1 is an example computer 20 suitable for implementing embodiments of the invention. The computer 20 includes a bus 21 which interconnects major components of the computer 20 , such as a central processor 24 , a memory 27 (typically RAM, but which may also include ROM, flash RAM, or the like), an input/output controller 28 , a user display 22 , such as a display screen via a display adapter, a user input interface 26 , which may include one or more controllers and associated user input devices such as a keyboard, mouse, and the like, and may be closely coupled to the I/O controller 28 , fixed storage 23 , such as a hard drive, flash storage, Fibre Channel network, SAN device, SCSI device, and the like, and a removable media component 25 operative to control and receive an optical disk, flash drive, and the like.
[0059] The bus 21 allows data communication between the central processor 24 and the memory 27 , which may include read-only memory (ROM) or flash memory (neither shown), and random access memory (RAM) (not shown), as previously noted. The RAM is generally the main memory into which the operating system and application programs are loaded. The ROM or flash memory can contain, among other code, the Basic Input-Output system (BIOS) which controls basic hardware operation such as the interaction with peripheral components. Applications resident with the computer 20 are generally stored on and accessed via a computer readable medium, such as a hard disk drive (e.g., fixed storage 23 ), an optical drive, floppy disk, or other storage medium 25 .
[0060] The fixed storage 23 may be integral with the computer 20 or may be separate and accessed through other interfaces. A network interface 29 may provide a direct connection to a remote server via a telephone link, to the Internet via an internet service provider (ISP), or a direct connection to a remote server via a direct network link to the Internet via a POP (point of presence) or other technique. The network interface 29 may provide such connection using wireless techniques, including digital cellular telephone connection, Cellular Digital Packet Data (CDPD) connection, digital satellite data connection or the like. For example, the network interface 29 may allow the computer to communicate with other computers via one or more local, wide-area, or other networks, as shown in FIG. 2 .
[0061] Many other devices or components (not shown) may be connected in a similar manner (e.g., document scanners, digital cameras and so on). Conversely, all of the components shown in FIG. 1 need not be present to practice the present disclosure. The components can be interconnected in different ways from that shown. The operation of a computer such as that shown in FIG. 1 is readily known in the art and is not discussed in detail in this application. Code to implement the present disclosure can be stored in computer-readable storage media such as one or more of the memory 27 , fixed storage 23 , removable media 25 , or on a remote storage location.
[0062] FIG. 2 shows an example network arrangement according to an embodiment. One or more clients 10 , 11 , such as local computers, smart phones, tablet computing devices, and the like may connect to other devices via one or more networks 7 . The network may be a local network, wide-area network, the Internet, or any other suitable communication network or networks, and may be implemented on any suitable platform including wired and/or wireless networks. The clients may communicate with one or more servers 13 and/or databases 15 . The devices may be directly accessible by the clients 10 , 11 , or one or more other devices may provide intermediary access such as where a server 13 provides access to resources stored in a database 15 . The clients 10 , 11 also may access remote platforms 17 or services provided by remote platforms 17 such as cloud computing arrangements and services. The remote platform 17 may include one or more servers 13 and/or databases 15 .
[0063] More generally, various embodiments may include or be embodied in the form of computer-implemented processes and apparatuses for practicing those processes. Embodiments also may be embodied in the form of a computer program product having computer program code containing instructions embodied in non-transitory and/or tangible media, such as floppy diskettes, CD-ROMs, hard drives, USB (universal serial bus) drives, or any other machine readable storage medium, wherein, when the computer program code is loaded into and executed by a computer, the computer becomes an apparatus for practicing embodiments of the invention. Embodiments also may be embodied in the form of computer program code, for example, whether stored in a storage medium, loaded into and/or executed by a computer, or transmitted over some transmission medium, such as over electrical wiring or cabling, through fiber optics, or via electromagnetic radiation, wherein when the computer program code is loaded into and executed by a computer, the computer becomes an apparatus for practicing embodiments of the invention. When implemented on a general-purpose microprocessor, the computer program code segments configure the microprocessor to create specific logic circuits. In some configurations, a set of computer-readable instructions stored on a computer-readable storage medium may be implemented by a general-purpose processor, which may transform the general-purpose processor or a device containing the general-purpose processor into a special-purpose device configured to implement or carry out the instructions. Embodiments may be implemented using hardware that may include a processor, such as a general purpose microprocessor and/or an Application Specific Integrated Circuit (ASIC) that embodies all or part of the techniques according to various embodiments in hardware and/or firmware. The processor may be coupled to memory, such as RAM, ROM, flash memory, a hard disk or any other device capable of storing electronic information. The memory may store instructions adapted to be executed by the processor to perform the techniques disclosed herein.
[0064] The foregoing description, for purpose of explanation, has been described with reference to specific embodiments. However, the illustrative discussions above are not intended to be exhaustive or to limit the invention to the precise forms disclosed. Many modifications and variations are possible in view of the above teachings. The embodiments were chosen and described in order to best explain the principles of the invention and its practical applications, to thereby enable others skilled in the art to best utilize the invention and various embodiments with various modifications as may be suited to the particular use contemplated. | Systems and methods for generating and traversing test cases trees are provided. A test case tree indicates an order of execution for multiple test cases, where setup and tear down or equivalent steps are not required before and after execution of each test case in the tree. The tree may allow for generation of virtual test cases to encompass multiple test cases which ordinarily would have mutually exclusive execution requirements. | 6 |
PRIORITY
[0001] This application claims the benefit under 35 U.S.C. §119(a) of an application filed in the Korean Industrial Property Office on Jan. 25, 2006 and assigned Serial No. 2006-7981, the contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention generally relates to an apparatus and a method for transmitting/receiving data in a High Rate Packet Data (HRPD) system, and more particularly to a transmission/reception apparatus and method for supporting an Orthogonal Frequency Division Multiplexing (OFDM) scheme and a Multiple Input Multiple Output (MIMO) technology as well as an Evolution Data Only (EV-DO) transmission scheme in an HRPD system.
[0004] 2. Description of the Related Art
[0005] With rapid development of communication technology, current mobile communication systems are providing not only ordinary voice communication services but also high rate data services which enable transmission of large-capacity digital data, such as moving images, as well as transmission of an e-mail or a still image, by using a Mobile Station (MS).
[0006] Representative examples of mobile communication systems currently providing high rate data services include an EV-DO system, an OFDM system, etc. An EV-DO system uses one of the high rate data service standards proposed by the Qualcomm company of the United States for transmission of large-capacity digital data and has been one-step evolved from a conventional Code Division Multiple Access (CDMA) 2000 1× in order to provide a forward transmission speed of 2.4 Mbps. An EV-DO system is also called an “HRPD system.”
[0007] Further, one of representative wireless communication systems employing a multi-carrier transmission scheme is an OFDM system. According to an OFDM scheme, a serial symbol sequence is converted into parallel symbol sequences and the parallel symbol sequences are modulated with a plurality of mutually orthogonal sub-carriers before being transmitted. OFDM schemes have come into the spotlight since the beginning of the 1990's according to development of Very Large Scale Integration (VLSI) technology.
[0008] According to an OFDM transmission scheme, data is modulated with multiple sub-carriers, and the sub-carriers maintain orthogonality between them. Therefore, an OFDM transmission scheme is stronger against a frequency selective multi-path fading channel and is more proper for HRPD services, such as a broadcasting service, than a conventional single carrier modulation scheme.
[0009] A slot structure and a transmitter structure in a forward link of a typical HRPD system will now be briefly described.
[0010] A forward link of an HRPD system uses a Time Division Multiple Access (TDMA) technology for multiple access, and uses a Time Division Multiplexing (TDM)/Code Division Multiplexing (CDM) scheme for multiplexing.
[0011] FIG. 1 shows a slot structure of a forward link in a conventional HRPD system. One slot has a structure including repeated one-half slots. Each of the one-half slots includes a pilot signal 103 or 108 having an N pilot hip length, which is inserted at a center thereof and is used in channel estimation of the forward link in a receiver of an MS. Medium Access Control (MAC) signals 102 , 104 , 107 , and 109 , each of which has an N MAC chip length and includes reverse power control information and resource allocation information, are located at both sides of associated pilot signals 103 and 108 . Further, actual transmission data 101 , 105 , 106 , and 110 , each of which has an N Data chip length, are located at opposite outer sides of associated MAC signals 102 , 104 , 107 , and 109 . In an HRPD system as described above, a slot of a forward link has been multiplexed according to a TDM scheme in which a pilot, MAC information, data, etc. are transmitted at different time points.
[0012] In the slot structure shown in FIG. 1 , the MAC information and the data are multiplexed according to a CDM scheme using Walsh codes, and the pilot signal, the MAC signal, and a small block unit of data have been set to have sizes such that N pilot =96 chips, N MAC =64 chips, and N Data =400 chips, respectively, in the forward link of the HRPD system.
[0013] FIG. 2 shows a transmitter of a conventional HRPD system. Packet data of a data channel passes through a channel encoder 201 for channel-encoding the packet data, a channel interleaver 202 for interleaving the encoded data, and a modulator 203 for modulating the interleaved packet data. Data of a MAC channel passes through a channel encoder 204 . The pilot tone, the MAC signal, and the data pass through a TDM multiplexer (MUX) 206 and then forms a physical link having a slot structure of FIG. 1 . The data output from the TDM MUX 206 is transmitted to users through an antenna (not shown) after passing through a sub-carrier modulator 207 . Reference numeral 208 in FIG. 2 denotes an HRPD processor for compatibility with an HRPD system, which includes the channel encoder 204 , the TDM MUX 206 , and the sub-carrier modulator 207 .
[0014] However, an HRPD system having the above-described structure is insufficient for adequate support of wideband data transmission and efficient use of frequency resources, which are used by next generation systems, such as broadcasting service systems. In order to support wideband data transmission and efficient use of frequency resources, a need exists to provide a solution for high speed data transmission and efficient use of frequency resources by using multiple antennas and a proper data modulation scheme.
SUMMARY OF THE INVENTION
[0015] Accordingly, the present invention has been made to solve the above-mentioned problems occurring in the prior art, and an object of the present invention is to provide a transmission/reception apparatus and method for supporting an OFDM scheme and a MIMO technology as well as an EV-DO transmission scheme in an HRPD system.
[0016] It is another object of the present invention to provide a transmission/reception apparatus and method for supporting an OFDM scheme and an EV-DO transmission scheme and supporting the MIMO technology by allocating a position of a data symbol to a fixed interlace in an HRPD system.
[0017] In order to accomplish this object, there is provided a transmitter for transmitting packet data in a forward link of an HRPD system, the transmitter including a transmission unit for modulating physical layer packet data to a transmission signal according to a transmission scheme and transmitting the transmission signal to a wireless network; a MIMO signal inserter for inserting a MIMO signal for channel estimation in a receiver into a particular interlace of a slot in which the transmission signal is transmitted; and a MIMO interlace selector for controlling an operation of the MIMO signal inserter to insert the MIMO signal into the particular interlace.
[0018] In accordance with another aspect of the present invention, there is provided a method for transmitting packet data in a forward link of an HRPD system, the method including determining when a current interlace is a particular interlace in which a MIMO signal for channel estimation in a receiver is inserted; and inserting the MIMO signal into the particular interlace when the current interlace is the particular interlace and then transmitting the MIMO signal according to a transmission scheme.
[0019] In accordance with another aspect of the present invention, there is provided a receiver for receiving packet data in a forward link of an HRPD system, the receiver including a MIMO signal extractor for extracting a MIMO signal for channel estimation from a particular interlace of a slot in which a wireless signal is transmitted; and a reception unit for receiving the wireless signal according to a transmission scheme, performing channel estimation by using the MIMO signal, and demodulating the packet data from the wireless signal, wherein information about the particular interlace is included in at least one of information promised in advance between a transmitter for transmitting the packet data and the receiver and control information transmitted from the transmitter to the receiver
[0020] In accordance with another aspect of the present invention, there is provided a method for receiving packet data in a forward link of an HRPD system, the method including extracting a MIMO signal for channel estimation from a particular interlace of a slot in which a wireless signal is transmitted; receiving the wireless signal according to a transmission scheme, and performing channel estimation by using the MIMO signal; and demodulating the packet data from the wireless signal based on a result of the channel estimation wherein information about the particular interlace is included in at least one of information promised in advance between a transmitter for transmitting the packet data and a receiver and control information transmitted from the transmitter to the receiver.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] The above and other objects, features and advantages of the present invention will be more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which:
[0022] FIG. 1 illustrates a slot structure of a forward link in a conventional HRPD system;
[0023] FIG. 2 illustrates a structure of a transmitter of a conventional HRPD system;
[0024] FIG. 3 illustrates a slot structure of a forward link in an HRPD system according to the present invention, in which OFDM symbols are inserted in data transmission periods;
[0025] FIG. 4 illustrates a structure of a transmitter in an HRPD system according to the present invention;
[0026] FIG. 5A illustrates an example of arrangement of MIMO pilot tones when using an OFDM transmission scheme supporting the MIMO in a forward link of an HRPD system according to the present invention;
[0027] FIGS. 5B and 5C illustrate examples of arrangement of MIMO pilots when using the EV-DO transmission scheme supporting the MIMO in a forward link of an HRPD system according to the present invention;
[0028] FIG. 6A is a view in order to illustrate the reason why interlaces for the MIMO users are fixedly allocated in the forward link of an HRPD system according to the present invention;
[0029] FIG. 6B illustrates an example in which interlaces are fixedly allocated exclusively for the MIMO in the forward link of an HRPD system according to the present invention;
[0030] FIG. 7 is a flow diagram of a transmission process when MIMO interlaces have been allocated in the forward link of an HRPD system according to the present invention;
[0031] FIG. 8 is a block diagram illustrating a structure of a receiver when using a non-MIMO EV-DO transmission scheme in a forward link of an HRPD system according to the present invention;
[0032] FIG. 9 is a block diagram illustrating a structure of a receiver when using a MIMO EV-DO transmission scheme in a forward link of an HRPD system according to the present invention;
[0033] FIG. 10 is a block diagram illustrating a structure of a receiver when using a non-MIMO OFDM transmission scheme in a forward link of an HRPD system according to the present invention; and
[0034] FIG. 11 is a block diagram illustrating a structure of a receiver when using a MIMO OFDM transmission scheme in a forward link of an HRPD system according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0035] Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. In the following description, a detailed description of known functions and configurations will be omitted when it may make the subject matter of the present invention rather unclear.
[0036] FIG. 3 shows a slot structure of a forward link in a High Rate Packet Data (HRPD) system according to the present invention, in which Orthogonal Frequency Division Multiplexing (OFDM) symbols are inserted in data transmission periods.
[0037] In an HRPD system according to the present invention, locations and sizes of a pilot signal and a Medium Access Control (MAC) signal for maintaining compatibility with a forward link are the same as those in the slot structure of the conventional forward link shown in FIG. 1 . Therefore, a pilot signal 303 or 308 having an N pilot chip length is located at a center of each one-half slot, and MAC signals 302 , 304 , 307 , and 309 each having an N MAC chip length are located at both sides of associated pilot signals 303 and 308 . Therefore, even a typical HRPD Mobile Station (MS), which does not support an OFDM transmission scheme, can perform channel estimation through the pilot signals 303 and 308 and can receive the MAC signals 302 , 304 , 307 , and 309 . In the remaining regions, that is, in the data transmission periods, OFDM symbols 301 , 305 , 306 , and 310 are inserted.
[0038] In the forward link of an ordinary HRPD system, a data transmission period is set to have a size so N Data =400 chips. According to an OFDM transmission scheme, a Cyclic Prefix (CP) is attached to the front of an OFDM symbol to be transmitted, in order to prevent self-interference of a time-delayed incoming signal through a multi-path. That is, one OFDM symbol includes a CP 301 b and OFDM data 301 a obtained through Inverse Fast Fourier Transform (IFFT) of packet data information.
[0039] The CP 301 b has a size of N CP chips and is obtained by copying a signal as much as the N CP chips from the rear portion of the OFDM data and the attaching the copied signal to the front of the OFDM data. Therefore, the OFDM data has a size of (N Data -N CP ), wherein N CP is determined according to how much the time delay causing self-interference will be allowed. When N CP is large, more delayed incoming signals can be demodulated without causing interference. However, the size of the OFDM data is reduced just as much, thus the quantity of information to be transmitted is also reduced. In contrast, when N CP is small, the information to be transmitted can be increased. However, the probability of occurrence of self-interference in an environment having a severe multi-path fading increases, thereby degrading the reception quality.
[0040] All of N Data number of tones cannot be used in the data symbol transmission. Some tones located in the periphery of a used frequency band should be used as guard tones in order to reduce the influence by the interference of signals out of the used frequency band. The pilot signals 303 and 308 used in the forward link of the conventional HRPD system are also used for the channel estimation of the OFDM symbol. However, dedicated signals are additionally necessary for the channel estimation of a multi-antenna system for Multiple Input Multiple Output (MIMO) users. To this end, some tones may be used in order to transmit signals for use in channel estimation. As used herein, such tones will be called “MIMO pilot tones.”
[0041] FIG. 4 shows a transmitter in an HRPD system according to the present invention. The transmitter includes a channel encoder 401 for channel-encoding packet data, a channel interleaver 402 for interleaving the encoded packet data, a modulator 403 for modulating the interleaved packet data, a guard tone inserter 404 for inserting guard tones in order to reduce the influence of interference by the signals out of the band, and a MIMO pilot tone inserter 405 for inserting MIMO pilot tones for channel estimation of a multi-antenna in a receiver mobile station of a MIMO user.
[0042] The transmitter shown in FIG. 4 also includes a spreader 406 , an IFFT processor 407 for converting a time-domain signal into a frequency-domain signal, a CP inserter 408 for inserting a CP into a front part of OFDM data, an HRPD processor 415 for compatibility with a transmission scheme of the HRPD system, an EV-DO transmitter 411 , and a MIMO pilot inserter 410 for inserting a MIMO pilot for an HRPD system. The spreader 406 may be, for example, a Quadrature Phase Shift Keying (QPSK) spreader.
[0043] The transmitter shown in FIG. 4 also includes a MIMO interlace selector 412 and an OFDM/EV-DO selector 413 . The MIMO interlace selector 412 selects and operates the MIMO pilot tone inserter 405 in order to transmit a MIMO pilot tone by a dedicated pilot when an OFDM transmission scheme supporting the MIMO is used, and selects and operates the MIMO pilot inserter 410 in order to transmit a MIMO pilot by a dedicated pilot when an Evolution Data Only (EV-DO) transmission scheme supporting the MIMO is used. The OFDM/EV-DO selector 413 controls a multiplexer (MUX) 409 so the MUX 409 outputs an OFDM signal or EV-DO signal according to the transmission scheme, thereby selecting transmission of the OFDM signal or EV-DO signal.
[0044] When the MIMO is not supported for a non-MIMO interlace, the MIMO interlace selector 412 controls the operation of the MIMO pilot tone inserter 405 and the MIMO pilot inserter 410 to prevent the MIMO pilot tone or the MIMO pilot from being inserted into the pilot dedicated for the MIMO. The transmitter shown in FIG. 4 follows a typical OFDM transmission scheme or EV-DO transmission scheme. Therefore, in a system including both users of the OFDM or EV-DO transmission schemes using the MIMO or users of the OFDM or EV-DO transmission schemes not using the MIMO, it is preferable to fixedly locate an interlace for allocation of the MIMO pilot or a MIMO pilot tone for support of the MIMO.
[0045] Further, a controller 414 controls the operation of the MIMO interlace selector 412 by checking whether the MIMO interlace has been allocated, and controls the operation of the OFDM/EV-DO selector 413 by checking whether the current slot is for the transmission for the OFDM users or the EV-DO users.
[0046] Hereinafter, a process of transmission by a Base Station (BS) for the OFDM transmission scheme or MIMO-OFDM transmission scheme according to the present invention will be described.
[0047] Physical layer packet data generated in a higher layer is input to and encoded by the channel encoder 401 , and the channel-encoded bit stream is interleaved by the channel interleaver 402 in order to obtain a diversity gain. The interleaved bit stream is input to and modulated into a modulation signal by the modulator 403 . The modulation signal is located at the data tone of the data transmission period in the slot construction shown in FIG. 3 .
[0048] Further, the guard tone inserter 404 places the guard tones at the band periphery of the signal output from the modulator 403 . For a MIMO-OFDM transmission scheme, the MIMO interlace selector 412 of the transmitter inserts a MIMO pilot tone into an allocated interlace by controlling the operation of the MIMO pilot tone inserter 405 . For a typical OFDM transmission scheme, the insertion of the MIMO pilot tone is omitted. When using a typical OFDM transmission scheme, the HRPD processor 415 inserts and transmits only the pilot signal of a typical EV-DO system.
[0049] When signals to be transmitted have been allocated to all tones according to the operation described above, the spreader 406 performs, for example, QPSK spreading, through which different complex Pseudo Noise (PN) streams of BS signals transmitting different information are multiplied by each other. The complex PN streams refer to a complex number stream in which both the real number components and the imaginary number components are PN codes. The modulation signals having been subjected to the QPSK spreading are IFFTed by the IFFT processor 407 , so they are located at the positions of desired frequency tones. Further, the CP inserter 408 generates an OFDM symbol by inserting a CP into the IFFTed OFDM data in order to prevent self-interference due to the multi-path fading. The OFDM symbol having the MIMO pilot tone inserted therein is transferred through the MUX 409 to the HRPD processor 415 under the control of the OFDM/EV-DO selector 413 .
[0050] Further, the HRPD processor 415 performs the compatibility processing of the HRPD system in order to multiplex the pilot signals 303 and 308 and the MAC signals 302 , 304 , 307 , and 309 together with the transmission data by the TDM scheme according to the slot structure shown in FIG. 3 . Therefore, the wireless signal finally transmitted through the transmitter shown in FIG. 4 has the slot structure as shown in FIG. 3 .
[0051] Hereinafter, a process of transmission by a base station for a typical EV-DO transmission scheme or an EV-DO transmission scheme supporting the MIMO according to the present invention will be described.
[0052] When an EV-DO transmission scheme supporting the MIMO is used, the MIMO interlace selector 412 of the transmitter inserts a MIMO pilot into an allocated interlace by controlling the operation of the MIMO pilot tone inserter 405 having received a transmission signal from the EV-DO transmitter 411 . The signal having the MIMO pilot inserted therein is transferred through the MUX 409 to the HRPD processor 415 under the control of the OFDM/EV-DO selector 413 . Further, the HRPD processor 415 performs the compatibility processing of the HRPD system in order to multiplex the pilot signals 303 and 308 and the MAC signals 302 , 304 , 307 , and 309 together with the transmission data by the TDM scheme according to the slot structure shown in FIG. 3 . When a typical OFDM transmission scheme is used, the insertion of the MIMO pilot tone by the MIMO pilot tone inserter 405 is omitted. That is, when using a typical OFDM transmission scheme, the HRPD processor 415 inserts and transmits only the pilot signal of a typical EV-DO system.
[0053] Meanwhile, it is possible to construct a transmitter, which has a fixed interlace in which, for example, a MIMO pilot tone or a MIMO pilot is inserted, further to the transmitter structure shown in FIG. 4 , and uses one of the MIMO OFDM scheme and MIMO EV-DO scheme as a transmission scheme dedicated for the MIMO.
[0054] Hereinafter, a scheme for arranging MIMO pilot tones and MIMO pilots in the case of using an EV-DO transmission scheme and an OFDM transmission scheme supporting the MIMO in an HRPD system according to the present invention will be described with reference to FIGS. 5A to 5 C.
[0055] FIG. 5A shows an example of arrangement of MIMO pilot tones when using an OFDM transmission scheme supporting the MIMO in a forward link of an HRPD system according to the present invention.
[0056] When using a typical EV-DO or OFDM transmission scheme, the pilot signals inserted by the HRPD processor 415 can be used as they are, as described above. However, when a Mobile Station (MS) supports the MIMO, since it is impossible to estimate the channel of a multi-antenna by the existing pilot signal 502 , the present invention places a MIMO pilot tone 504 dedicated for the MIMO in the data transmission region in which is the data tone 503 is located. The MIMO pilot tone 504 can be used in various forms in the time domain and the frequency domain within one slot.
[0057] The arrangement shown in FIG. 5A is intended to improve the frequency diversity. However, it is possible to arrange the MIMO pilot tones 504 in various forms in the time domain and the frequency domain. The present invention may also be applied to arrangements where the pilot tones are exclusively arranged for the MIMO.
[0058] FIGS. 5B and 5C show examples of arrangement of MIMO pilots when using the EV-DO transmission scheme supporting the MIMO in a forward link of an HRPD system according to the present invention. FIG. 5B corresponds to an arrangement in which the MIMO pilots 505 are inserted in the existing pilot signal region 502 after being subjected to the Code Division Multiplexing (CDM), and FIG. 5C corresponds to an arrangement in which the MIMO pilots 507 are inserted in the existing pilot signal region 506 after being subjected to the CDM.
[0059] FIG. 6A shows a reason why interlaces for the MIMO users are fixedly allocated in the forward link of an HRPD system according to the present invention.
[0060] In the HRPD system according to the present invention in which an OFDM system and EV-DO system supporting the MIMO and a typical OFDM system and EV-DO system co-exist, it is possible to use feedback (Channel Quality Information (CQI)) information 601 for the multi-antenna, which is transmitted to a BS from an MS of a MIMO user, as shown in FIG. 6A . By receiving the feedback (CQI) information 601 from the MS, the transmitter of the BS can control the power of the MIMO pilot and the MIMO pilot tone in the next transmission.
[0061] When fixedly allocated interlaces are used for transmission of the MIMO pilots and the MIMO pilot tones, the BS can support the MIMO user in an easy and simple manner without using a complex higher control signal. That is, the BS can inform the MS of the interlace to be exclusively used for the MIMO through the control signal, and the BS transmits data of the MIMO user by using the dedicated fixed interlace. Further, the MS receives data through an interlace allocated to the MS itself by using the received control signal from the BS.
[0062] FIG. 6B shows an example in which interlaces are fixedly allocated exclusively for the MIMO in the forward link of an HRPD system according to the present invention. Interlace # 0 602 has been allocated exclusively for the MIMO, and the other interlaces # 1 , # 2 , and # 3 603 , 604 , and 605 have been allocated for data transmission for typical OFDM users using the existing pilot signals transmitted by the TDM, for example, typical EV-DO rev. A/B users or typical OFDM users. Therefore, through interlace # 0 602 , it is possible to transmit data of the OFDM or EV-DO user supporting the MIMO.
[0063] In FIG. 6B , reference numerals 606 to 608 denote slot structures transmitted through interlace # 0 602 , in which the MIMO pilot tones or MIMO pilots are inserted according to the arrangements shown in FIGS. 5A to 5 C, respectively. Further, in FIG. 6B , reference numerals 609 and 610 denote slot structures in which the pilot signals for a typical OFDM user and EV-DO user are transmitted by the TDM as in the existing structure, respectively.
[0064] FIG. 7 shows a transmission process according to whether MIMO interlaces have been allocated in the forward link of an HRPD system according to the present invention. In step 710 , the controller 414 of the transmitter determines whether the current slot to be transmitted is a MIMO interlace slot. When the current slot to be transmitted is a MIMO interlace slot, the controller 414 determines in step 702 whether the transmission is for a MIMO-OFDM user or a MIMO EV-DO user, in order to perform an operation according to a corresponding transmission scheme. When the transmission has been determined as transmission for the EV-DO user in step 702 , the transmitter proceeds to step 703 in which the transmitter performs general EV-DO transmission. Then, in step 704 , under the control of the controller 414 , the MIMO interlace selector 412 operates the MIMO pilot inserter 410 in order to insert a MIMO pilot into a transmission signal. The MIMO interlace selector 412 may insert the MIMO pilot 505 in the existing pilot signal region 502 after code division multiplexing the pilot or may insert the MIMO pilot 507 in the existing data region 506 according to a CDM scheme. Thereafter, under the control of the OFDM/EV-DO selector 413 , the MUX 409 outputs a signal in which the MIMO pilot has been inserted, and the HRPD processor 415 of the transmitter performs compatibility processing in order to TDM transmit a data channel, a MAC channel, and a pilot channel as designated by reference numeral 208 of FIG. 2 for the compatibility with the HRPD system in step 705 , and then transmits the TDMed signal by a sub-carrier to a radio network in step 706 .
[0065] Meanwhile, when it is determined in step 702 that the transmission is for the OFDM user, the transmitter proceeds to step 707 in which the transmitter encodes, interleaves, and modulates data to be transmitted, thereby generating a data tone. Thereafter, the guard tone inserter 404 of the transmitter inserts a guard tone into a portion near to a band periphery of the modulation signal in step 708 , and the MIMO pilot tone inserter 405 inserts the MIMO pilot tone in the interlace allocated under the control of the MIMO interlace selector 412 , for example, as shown in FIG. 5A . Then, when signals to be transmitted have been allocated to all tones, the spreader 406 performs, for example, QPSK spreading in step 710 , so the modulation signals having been subjected to the spreading are placed at desired locations of desired frequency tones through IFFT by the IFFT processor 407 . Then, in step 711 , the CP inserter 408 inserts a CP into the IFFTed OFDM data in order to prevent the self-interference, thereby generating an OFDM symbol. Thereafter, under the control of the OFDM/EV-DO selector 413 , the MUX 409 outputs an OFDM signal having a MIMO pilot tone inserted therein, and the HRPD processor 415 of the transmitter performs compatibility processing in order to TDM transmit a data channel, a MAC channel, and a pilot channel for the compatibility with the HRPD system in step 712 , and then transmits the TDMed signal by a sub-carrier to a radio network in step 713 .
[0066] Meanwhile, when it is determined in step 701 that the current slot to be transmitted is not a MIMO interlace slot, the transmitter of the BS determines in step 714 whether the transmission is for an OFDM user or an EV-DO user, in order to perform an operation according to a corresponding transmission scheme. The operation in steps 718 to 723 corresponding to a transmission process for a non-MIMO OFDM user is the same as the operation the operation in steps 707 to 713 except for the operation of MIMO pilot tone insertion in step 709 of FIG. 7 , and the operation in steps 715 to 717 corresponding to a transmission process for a non-MIMO EV-DO user is the same as the operation in steps 715 to 717 except for the operation of MIMO pilot insertion in step 704 of FIG. 7 , so detailed description will be omitted.
[0067] Hereinafter, a structure of a receiver according to the present invention will be described with reference to FIGS. 8 to 11 for each transmission scheme. The receivers shown in FIGS. 8 to 11 correspond to receivers using a non-MIMO EV-DO scheme, a MIMO EV-DO scheme, a non-MIMO OFDM scheme, and a MIMO OFDM scheme, respectively. When an actual MS is implemented, at least one of the four types of receivers can be implemented within the MS. Then, the MS can receive a forward signal through a corresponding receiver according to a transmission scheme indicated by a control signal of a BS or according to a transmission scheme promised in advance between the MS and the BS.
[0068] FIG. 8 shows a receiver in the case of using a non-MIMO EV-DO transmission scheme in a forward link of an HRPD system according to the present invention. An HRPD processor 801 operates in a process inverse to the operation of the HRPD processor 415 of FIG. 4 . Specifically, the HRPD processor 801 demultiplexes TDMed data channel, MAC channel, and pilot channel signals and then transfers the demultiplexed signals. An EV-DO demodulator 802 receives the data channel from among the demultiplexed signals from the HRPD processor 801 and demodulates the data according to, for example, an EV-DO rev. A/B scheme. The EV-DO demodulator 802 is well-known in the art, so a detailed description will be omitted.
[0069] FIG. 9 shows a receiver when using a MIMO EV-DO transmission scheme in a forward link of an HRPD system according to the present invention. An HRPD processor 901 operates in a process inverse to the operation of the HRPD processor 415 of FIG. 4 . Specifically, the HRPD processor 901 demultiplexes TDMed data channel, MAC channel, and pilot channel signals and then transfers the demultiplexed signals. A MIMO pilot extractor 902 performs channel estimation by using a MIMO pilot inserted in the data channel region or pilot channel region from among the demultiplexed signals as shown in FIG. 5B or 5 C and outputs a signal corresponding to the data. Further, the EV-DO demodulator 903 demodulates the received data according to, for example, an EV-DO rev. A/B scheme.
[0070] FIG. 10 shows a receiver when using a non-MIMO OFDM transmission scheme in a forward link of an HRPD system according to the present invention. An HRPD processor 1001 operates in a process inverse to the operation of the HRPD processor 415 of FIG. 4 . Specifically, the HRPD processor 1001 demultiplexes TDMed data channel, MAC channel, and pilot channel signals and then transfers the demultiplexed signals. From among the transferred demultiplexed signals, a pilot signal is transferred to a channel estimator 1007 and a data signal is transferred to a CP remover 1002 . The CP remover 1002 eliminates the CP contaminated due to the propagation delay, the multi-path, etc., from the received signal. An FFT processor 1003 converts the input time domain signal to a frequency domain signal, and a QPSK de-spreader 1004 de-spreads the frequency domain signal and outputs tones of each signal. This is based on an assumption that the signal transmitted by the transmitter is spread before being transmitted. Therefore, when the transmitter uses a different spreading scheme, the receiver is equipped with a de-spreader corresponding to the used spreading scheme.
[0071] The de-spread tones of each signal are transferred to the data tone extractor 1006 , which extracts data tones from the received signal tones. Meanwhile, the channel estimator 1007 estimates the channel from the received pilot signal, and transfers the channel-estimation value to a demodulator 1008 . The demodulator 1008 performs demodulation of the data tones by using the received channel estimation value, and the demodulated signal is de-interleaved by a de-interleaver 1009 and is then input to a decoder 1010 . The decoder 1010 decodes the input signal, thereby restoring the originally transmitted signal.
[0072] FIG. 11 shows a receiver in the case of using a MIMO OFDM transmission scheme in a forward link of an HRPD system according to the present invention. The same components of the receiver shown in FIG. 11 as those of the receiver shown in FIG. 10 have the same functions as those of latter, so detailed description will be omitted.
[0073] In the receiver of FIG. 11 , an HRPD processor 1101 operates in a process inverse to the operation of the HRPD processor 415 of FIG. 4 . Specifically, the HRPD processor 1101 demultiplexes TDMed data channel, MAC channel, and pilot channel signals and then transfers the demultiplexed signals. From among the transferred demultiplexed signals, a pilot signal is transferred to a channel estimator 1108 and a data signal is transferred to a MIMO interlace selector 1102 . The MIMO interlace selector 1102 determines whether the received signal corresponds to a fixedly allocated interlace, and then transfers the received signal to a CP remover 1103 . Then, the CP remover 1103 eliminates the CP contaminated due to the propagation delay, the multi-path, etc. from the received signal. An FFT processor 1104 converts the input time domain signal to a frequency domain signal, and a QPSK de-spreader 1105 QPSK de-spreads the frequency domain signal and outputs tones of each signal. This is based on an assumption that the signal transmitted by the transmitter is QPSK spread before being transmitted. Therefore, when the transmitter uses a different spreading scheme, the receiver is equipped with a de-spreader corresponding to the used spreading scheme.
[0074] The receiver of FIG. 11 is equipped with a MIMO pilot extractor 1106 for channel estimation, and the de-spread tones of each signal are transferred to the MIMO pilot extractor 1106 . The MIMO pilot extractor 1106 extracts a MIMO pilot tone inserted in a data channel region as shown in FIG. 5A from the interlace allocated exclusively for the MIMO-OFDM and transmits the extracted MIMO pilot tone to the channel estimator 1108 . 1107 k extracts data tones except for the MIMO pilot tone from the data region and transfers the extracted data tones to a demodulator 1109 for restoration of the originally transmitted signal.
[0075] As described above, the present invention uses an HRPD system and a transmission technology based on an EV-DO scheme and an OFDM scheme while maintaining compatibility between them and transmits a MIMO-only pilot/pilot tone by a fixedly allocated MIMO interlace. Therefore, according to the present invention, it is possible to effectively use the MIMO in a system in which EV-DO users, MIMO EV-DO users, OFDM users, MIMO-OFDM users co-exist.
[0076] While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. For example, the arrangement of the MIMO pilot tones or MIMO pilots shown in FIG. 5A to 5 C is only an example, and the present invention is applicable various types of different arrangements. Further, in allocation of the interlaces, the identifications and the number of fixedly allocated interlaces may become different according to the number of MIMO-OFDM users within a base station. Therefore, the scope of the present invention should not be limited to the described embodiments and should be determined by the attached claims and equivalents thereof. | An apparatus and method for allocating dedicated pilots for supporting MIMO and setting MIMO-only interlace slots in a CDMA 2000 Nx-EV-DO compatible system. The method includes determining whether a current interlace is a particular interlace in which a Multiple Input Multiple Output (MIMO) signal for channel estimation in a receiver is inserted; and inserting the MIMO signal into the particular interlace when the current interlace is the particular interlace and then transmitting the MIMO signal according to a predetermined transmission scheme. By the apparatus and method, it is possible to effectively use the MIMO in a system in which EV-DO users, MIMO EV-DO users, OFDM users, MIMO-OFDM users co-exist. | 7 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of our prior application, Ser. No. 434,259, filed Oct. 14, 1982 which is incorporated herein by reference.
FIELD OF THE INVENTION
The present invention generally relates to the monitoring and control of a single zone HVAC unit which enables it to independently control conditions in a plurality of zones with each zone including a thermostat and damper interfaced with the monitor control in a manner to enable the single zone HVAC unit to be utilized in a multiple zone arrangement.
DESCRIPTION OF THE PRIOR ART
Various control systems have been provided for maintaining occupant comfort in a single zone or plurality of zones. Our prior copending applications, Ser. No. 362,142, filed Mar. 26, 1982 and Ser. No. 434,259, filed Oct. 14, 1982, each for Temeprature Control System disclose a temperature control system employing a damper and thermostat arrangement associated with a single zone for controlling the conditions in that zone, these also being exemplary of the air prior to this application. The prior art cited in the aforementioned copending applications is also included in this application as being relevant to the subject matter of the invention.
As is known, a single zone HVAC unit may supply conditioned heated or cooled air to more than one distinct zone or room. Each room or zone may have different comfort requirements due to occupancy differences, individual preferences, exterior load differences, or perhaps different zones may even be on different levels, thereby creating different heating or cooling requirements. As is also known, a single zone HVAC unit is named such because it is normally controlled from one thermostat controller. In a building which has more than one zone and whose zones have different heating and cooling requirements, it becomes difficult to choose a good representative location for the controlling thermostat.
Several attempts to solve the problems of controlling the different needs of more than one zone which is provided heating and cooling from a single zone HVAC unit have been tried. Among those tired is control of the air into each zone by a zone damper and a thermostat arrangement with said damper and thermostat opening and closing the air into said zone in response to said thermostat requirements. These dampers suffered many drawbacks, not the least of which is how to coordinate the change from a heating mode to a cooling mode or vice versa when the HVAC control thermostat changes modes of the HVAC unit. Another drawback of using independent zone control dampers and thermostats is that, even though the damper can control the air into each respective zone, it still is at the mercy of the thermostat that is controlling the HVAC unit. This creates a situation in which either some zones require more conditioning but cannot become satisfied because the HVAC unit has cycled off, or the HVAC unit ran needlessly after the zone dampers had satisifed their respective zone requirements prior to the HVAC thermostat having been satisfied. In essence, even though each zone may have its own thermostat, there is still only one thermostat controlling the HVAC unit.
The prior art has not disclosed a system which controls both the HVAC unit and the air distribution of that respective HVAC unit from two or more thermostats, creating a control system which allows a single zone HVAC unit to become a multiple zone HVAC system.
SUMMARY OF THE INVENTION
In accordance with the present invention, there is provided the ability to control a single zone HVAC unit and its air distribution system from a common set of thermostats in two or more zones with each thermostat controlling both the single zone HVAC unit through a monitor control and its own respective zone damper which controls the air flow in its zone which is provided from the HVAC unit, thereby creating an automatic heating and cooling variable air volume and variable temperature control system for single zone HVAC units.
Briefly, the above is accomplished by providing a thermostat, damper and damper control system of the type disclosed in our above noted copending applications in each zone to be controlled. The thermostat controls the damper in its respective zone in the manner set forth in our copending applications noted above. In addition, a signal related to the temperatures sensed by each thermostat and the damper position in each zone is sent to a central monitor system in which the monitor considers the needs of the individual zones, the damper position in each zone, the amount of demand in the zone, mode of the zone dampers and other factors which affect the comfort of zone occupants and control the HVAC unit to provide a desired comfort level in a plurality of zones by the use of a single zone HVAC unit so that it in effect becomes a multiple zone system.
The monitor includes a microprocessor system which assesses various information obtained from each damper thermostat such as the set point of the thermostat, the minimum and maximum stop settings of the damper, the position of the dampers which the thermostat is controlling, the mode (heating or cooling) which the thermostat is in, the room temperature or zone temperature at the thermostat, the duct temperature at the damper assembly which is controlled by the thermostat, the exiting air temperature of the HAVC unit, with all of this information being assessed and stored in the memory of the monitor so that such information can be compared from all of the governor zone thermostats with the switch settings on the monitor and then properly control the HVAC unit.
The monitor can change the HVAC unit from one mode to another with a time delay being provided and information instruction sent to the zone thermostats to enable the individual thermostats to position their respective zone dampers to the positions which will be in harmony with the type of conditioned air the HVAC under control of the monitor is preparing to send through the duct system, with the monitor then energizing the appropriate heating or cooling circuits.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagrammatic view illustrating the monitor and its assocation with the HVAC unit and its interface with the zone thermostats and zone dampers or governors;
FIG. 2 is a schematic illustration of a typical installation illustrating the mechanical components and the electrical components of the monitor and its association with the zones, damper and HVAC unit;
FIG. 3 is a plan view of the control panel incorporated into a cabinet structure forming a portion of the monitor of the present invention;
FIG. 4 is a schematic wiring diagram of one of the dampers and other components associated with the monitor;
FIGS. 5A1-5A4 and 5b-5b3 are a circuit and diagram of the governor monitor circuit;
FIGS. 6A and 6b is a circuit diagram of the monitor sensor probe circuit.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now specifically to FIGS. 1, 2 and 4, the monitor of the present invention is generally designated by reference numeral 10 and has an electrical connection to each of eight thermostats 12 and damper assemblies or governors 14 with the aforementioned copending applications disclosing the details of the thermostats 12 and the dampers or governors 14. The monitor is electrically connected to a time clock for night setback through line 16, to a transformer of a power supply through line 18 and to a sensor on the HVAC through line 20. Also, the monitor is connected to the HVAC unit generally designated by numeral 22 through a plurality of conductors generally designated by the numeral 24. The monitor is electrically connected for external communication through line 19.
FIG. 2 illustrates the monitor 10 schematically associated with an air supply duct 26 having a branch duct 28 extending into a room or zone 30 with a damper assembly or governor 14 (governor 1 of FIG. 1 as an example) being incorporated therein whih is controlled by a thermostat 12 as illustrated so that the thermostat is also connected to the monitor 10 through line 32. This arrangement discloses the interface between the monitor 10, the HVAC unit and the governor and thermostats with the system including a monitor sensor probe 34 connected to the HVAC unit by lines 20 and a bypass system 36 for the HVAC unit. The bypass system 36 is more specifically described in applicants' copending U.S. application Ser. No. 470,331, filed Feb. 28, 1983.
FIG. 3 discloses a control panel 38 of a cabinet or the like which is shown as part of the monitor 10 including a designated connection for each governor or damper assembly 14 other connection locations as shown in FIG. 2 and various indicator lights 40 and switches 42. The switches 42 include a power switch 44 for turning the power on and off, a cool switch 46 which can be turned off or set on automatic, a heat switch 48 which can be turned off or set on automatic, a pair of fan switches 50 and 52 with the switch 50 having an "on" position and an "automatic" position and the switch 52 having a cool or heat/cool position. Priority switch 54 is provided with a cool or heat position and the GOV. LOCK switch 56 has a lock or unlock position. The light assemblies 40 include an indicator light for the power 90, an indicator light for each governor status 88 and indicator lights 92 to 106 for other conditions as illustrated in the drawing of the control panel 38 as illustrated in FIG. 3.
FIG. 4 illustrates schematically the electrical association between the monitor 10, the thermostat 12 and a governor or damper 14.
The monitor 10 is provided with a power supply (not shown) from a separate 24 VAC transformer through the power supply line 18, as illustrated in FIGS. 1 to 4 and as disclosed in this application. The monitor 10 has the capability of inerfacing with eight governors or dampers 14 and thermostats 12 which are disclosed in detail in the aforementioned copending application with the monitor 10 being wired to the three lower terminals on the thermostat 12, as illustrated in FIG. 4, which are color coded with these wires being connected to the designated areas 14 of the monitor 10 along the top edge thereof. In FIG. 4, the monitor 10 includes terminals 58 to which the power supply is connected through the wiring 18, terminals 60 for external communication, terminals 62 connected to the time clock for night setback through wiring 16, terminals 64 connected to the monitoring sensor probe 34 through wiring 20 and terminal 66 connected to the HVAC unit through wiring 24 with the wiring 24 including a connection to the reversing valve, fan, second heat, first heat, second cool, first cool and a 24 volt control ine as schematically illustrated in FIGS. 1 and 4.
As indicated, each governor or damper location is identified by number and a chart may be provided on the inside of the monitor cabinet door for recording the location of the governors 14 and the governor thermostats 12 are connected to the governors or dampers 14 and connected to the monitor as illustrated in FIGS. 1 through 4. The night setback terminal 62 has a two position terminal strip provided with a jumper wire which, when in place, the monitor set point temperatures are established at the governor thermostats 12. When continuity between the night setback terminals is broken, the monitor will automatically go into the setback mode and the set point temperatures are automatically readjusted to energize the first stage heating at 65° F.; second stage heating at 63° F.; first stage cooling at 85° F.; and second stage cooling at 87° F. The night setback terminal strip 62 is connected to a time clock so that the monitor may be automatically switched from an occupied mode to a night setback mode. This is accomlished by merely running the contacts of the time clock through the two position terminal strip 62 on the monitor panel 38. The time clock may be incorporated into the panel 38 or oriented in any desired location.
The monitor sensor probe 34 is located where it will sense the temperature of both the heating and cooling circuits. In heat pump installations, the probe 34 is located where it can sense the refrigeration circuit only without sensing the resistance heater in the heat pump installation and the probe 34 is electrically connected to the terminal strip 64 which is a three position terminal strip that is also color coded. The HVAC unit is connected to the terminal strip 66 which is a seven position terminal strip which is also color coded with the wiring varying with the HVAC unit and the options used. The external communication terminal 60 and lines 19 therefrom are for use when the monitor is connected to a computer or other optional peripheral control which does not form part of the present invention.
The power switch 44 is used to energize or de-energize the monitor 10. The cool switch 46 can be moved to an "off" position in which a call for cooling will not energize the cooling relay in the monitor but when the switch 46 is in the "auto" position, a call for cooling will energize the cooling relay or relays in the monitor. A call for first stage cooling occurs when the temperature at a governor thermostat 12 is 2° F. above set point and second stage cooling is called for when the temperature at a governor thermostat is 3° F. above set point.
The switch 48 can be set at the "off" position where a call for heating will not energize the heating relays or it can be moved to an "auto" position where a call for heating will energize the heating relays. A call for first stage heating is when the room temperature at a governor thermostat 12 is 2° F. below set point and second stage heating is when the room temperature at a governor thermostat is 3° F. below set point. When both the cool switch 46 and heat switch 48 are in the "auto" position, the monitor 10 will operate with automatic heating/cooling changeover.
The fan switches 50, 52 can be oriented with the switch 50 in the "on" position in which the fan relay will be energized continuously and in the "auto" position in which the fan relay will be energized on a call for cooling only or on a call for heating or cooling depending upon the setting of the switch 52 which can be moved from a cool position or a heat/cool position. When the switch 52 is in the "cool" position and the switch 50 is in the "auto" position, the fan will run only on a call for cooling. When the switch 52 is in the "heat/cool" position and the switch 50 is in the "auto" position, the fan will run on a call for heating or a call for cooling.
The priority switch 54 determines whether the system operates in a cooling or heating mode when an equal number of governor themostats call for cooling and heating at the same time. For example, if two governor thermostats call for cooling and two call for heating and the priority switch 54 is in the "cool" position, the operating mode of the system will be cooling, whereas, if an equal number of governor thermostats call for cooling and heating and the priority switch 54 is in the "heat" position then the system will be in a heating mode. After the priority mode has been satisfied, the monitor may operate in the opposite mode if there is sufficient demand.
The governor lock switch 56 can be set in the "locked" position in which all set point temperatures at the governor thermostats 12 are locked and cannot be changed and they will remain at the temperature as set. When the switch 56 is in the "unlocked" position, the set point temperatures of the governor thermostats 12 may be adjusted within the temperature range of the thermostat (68° F. to 81° F.).
The monitor panel 38 is also provided with a plurality of switches 68 as illustrated in FIG. 3 with eight switches being incorporated into the group and including a reverse valve switch 70, a time delay switch 72, an energy saver switch 74, demand switch A 76, demand switch B 78, a monitor sensor probe switch A 80, a monitor sensor probe switch B 82 and an emergency heat switch 84. These switches coordinate the function of the HVAC unit with the particular installation requirements and each of these switches is numerically identified and can be moved between an "up"-and-"down" position. The reverse valve switch 70 may be used in heat pump applications with external reversing valve circuits. The switch 70 determines the mode in which the reversing valve relay is energized. With the switch 70 in the "up" position, the reversing valve relay is energized in the heat mode and in the "down" position, the reversing valve relay is energized in the cool mode. The time delay switch 72 is a protective switch which prevents short-cycling of the equipment in that it provides for a five minute delay when the monitor is first energized on initial start-up, after a power interruption or during normal operation after each stage of a mode has been de-energized. When the time delay switch 72 is in the up or cool position, the delay occurs only in the cooling mode and when the switch 72 is in the down, heat/cool position, the delay occurs in both the heating and the cooling mode.
The energy saver switch 74 is used only with night setback options and when it is in the up, cool position, second stage cooling, only, is not energized for 20 minutes after the night setback time clock returns to the day mode of operation. When the switch 74 is in the down, cool/heat position, both second stage cooling and second stage heating are not energized for 20 minutes after the night setback time clock returns to the day mode of operation. The down position is used for heat pump applications where electric heat is used to provide second stage heating.
The demand switches 76 and 78 determine the number of governors that have to be calling for heating or for cooling at the same time before heating or cooling is energized at the HVAC. If both demand switches 76 and 78 are down, one governor must be calling for heating or cooling in order to energize the heating or cooling operation. When switch 76 is in the up position and switch 78 is in the down position, two governors must demand heating or cooling in order to energize the heating and cooling operation. When switch 76 is down and switch 78 up, three governors are required and when both switches are up, four governors are required to demand heating or cooling before the heating and cooling operation will be energized. The monitor sensor probe switches 80, 82 are associated with the sensor probe 34 which is a limit control that provides high and low temperature limit protection for the HVAC unit and is applicable only when the monitor sensor probe option is being used. The use of this feature makes it possible to vary the limit settings, thereby making it possible to use the monitor sensor probe with various HVAC equipment or vary the method of sensing, such as air temperature or refrigerant gas temperature. If the sensor probe 34 is not connected to the monitor, both of the sensor probe switches 80, 82 must be in the down position. The monitor will automatically de-energize all HVAC circuits if the monitor sensor probe is not attached with either of the monitor sensor probe switches in an up position. When the temperature limits are exceeded at the monitor sensor probe, the monitor will turn off the relay which corresponds to the trip temperatures found on a monitor sensor probe table and when the temperature returns to within the limit setting, a five minute delay is initiated before that particular stage may be re-energized.
When the probe 34 is used to sense air temperature in a heat pump installation, the switch 80 is up and switch 82 is down with the trip temperatures in the heating system being 108° F. in the first stage and a cooling trip temperature being 45° F. in the first stage and 50° F. in the second stage. When used with a heat pump for sensing refirgerant temperature, both switches are up and the trip temperature for the first stage of heating is the same and the cooling temperature trip points are 32° F. in the first stage and 38° F. in the second stage. In a gas/electric system and when sensing air temperature, the switch 80 is down and the switch 82 up and in this mode, the trip temperature in heating is 160° F. in the first stage and 140° F. in the second stage and in the cooling stages, the trip temperature is 45° F. in the first stage and 50° F. in the second stage.
The emergency heat switch 84 provides for normal function of the first and second stage heating when in the down position. When in the up position, first stage heating is locked out and only second stage heating will operate normally.
The monitor panel 38 is also provided with a reset button 86 which, when depressed, will reduce the time delay function from five minutes to approximately one and one-half minutes and automatically reset all functions of the monitor.
As illustrated in FIG. 3, the light array 40 includes governor status lights 88 which are numerically numbered for identification and are a distinguishable color such as green so that when any one of the lights 88 is off, that particular governor is not connected or is not functioning properly. When a particular green light 88 is on continuously, the governor thermostat is not calling for heating or cooling. If the light 88 is blinking slowly, the governor thermostat is calling for cooling, and if the light 88 is blinking rapidly, the governor thermostat is calling for heating. Alongside but spaced from the governor status lights 88 is a power light 90 which indicates that the unit is energized when it is on. Located above the power light 90 and the governor status lights 88 is a red high/low temperature light 92 which will be illuminated when a monitor sensor probe 34 is attached to the monitor. When the sensor probe senses a temperature above the high set point limit as established by the probe switches 80, 82, the light 92 will blink rapdily. When the probe senses a temperature below the low set point limit as established by the switches 80, 82, the light 92 will blink slowly. Alongside the light 92 is a night setback light 94 which is illuminated when the monitor is operating in the night setback mode. HVAC indicator lights 96, 98, 100 and 102 are illuminated when first stage cooling, second stage cooling, first stage heating and second stage heating are energized. Also fan light 104 and reversing valve light 106 are illuminated when the fan or reversing valve circuits are energized. All of the lights except for the governor status lights are red so that they may be distinguishable from the governor status lights which are green.
As set forth previously, the monitor permits up to eight individual computerized zone control thermostats to control the HVAC unit thereby providing a zone control system which is economical in cost and easy to use and install. As disclosed, the system provides control of a single zone HVAC unit and renders it feasible to control up to eight different zones or locations in which each zone is continuously air balanced by the thermostat and damper assembly associated with each zone as disclosed in detail in the aforementioned applications which are incorporated herein by reference thereto. The monitor considers individual zones as to its needs, damper position, demand in the zone, mode of the zone damper and other factors which affect the comfort of the zone occupants with the monitor deciding how and when to control the HVAC unit so that the single zone HVAC unit actually becomes a multiple zone system. The monitor in each given time increment, such as 10 seconds, will communicate with up to eight governor thermostat assemblies and will access six pieces of information including (1) the set point of the governor thermostat; (2) the minimum and maximum damper stop settings at the governor thermostat; (3) the position of the dampers which the governor thermostat is controlling; (4) the mode, heating or cooling, which the governor thermostat is in currently; (5) the ambient (room) temperature at the governor thermostat; and (6) the duct temperature at the damper assembly which the governor thermostat is controlling. This information is stored in the memory of the monitor system. The monitor then compares the information which has been received from the governor thermostats with the switch settings on the monitor and appropriate action or actions are taken. If there is sufficient demand at the governor thermostats to initiate the cooling or heating circuits, the monitor will first change the mode, if necessary, (heating or cooling) of the governor thermostats to the mode which the monitor is preparing to energize before actual energization takes place. After the monitor changes the mode of the governor thermostats, there is a time delay which gives the governor thermostats time to position their respective zone dampers to the positions which will be in harmony with the type of conditioned air the monitor is preparing to send through the duct system. After this delay, the monitor then energizes the heating or cooling circuits.
For example, the monitor will recognize that enough governor thermostats call for cooling in accordance with the previous explanation. The monitor will change the mode of all of the governor thermostats to the cooling mode and provide a one minute delay in order to give the dampers time to be positioned after which the appropriate stages of cooling are energized.
The foregoing arrangement provides for appropriate control of a single zone HVAC unit from a plurality of zones with each zone including a damper assembly (governor) and a thermostat with each governor thermostat controlling the HVAC unit in accordance with the switch positions and other predetermined parameters of operation.
The above is accomplished utilizing the electronic circuits described hereinbelow in conjunction with the monitor firmware.
Referring now to FIG. 5, there is shown the electronic circuitry contained in the monitor which is connected to the lines entering the monitor as shown in FIGS. 1, 2 and 4 and which operates under control of the switches shown in FIG. 3 which are disposed on the front face of the monitor in the preferred embodiment. The circuitry includes a microprocessor device U1 and a program memory U2 which stores the programmed memory therein in the form of instruction codes to be executed by the microprocessor U1. In the preferred embodiment, the program stored in the memory U2 is in machine language. A latch U3 is positioned to transfer address data from the microprocessor U1 to memory U2. During an instruction fetch, microprocessor U1 will place the lower address bits on the data buss corresponding to pins 12 through 19 thereon and will place the upper address bits on the lower nibble of port 2 which comprises pins 21 through 24. The lower address bits will appear at the input of the octal latch U3. When microprocessor U1 strobes ALE on pin 11 thereof, the address bits will be latched into latch U3. Microprocessor U1 will then restore the data buss pins 12 through 19 of microprocessor U1 and all address bits will appear at the inputs of memory U2. When microprocessor U1 then strobes PSEN on pin 9 thereof, the address instruction located in the memory U2 will be placed on the data busses composed of pins 9 through 17 of the memory U2. This instruction is transmitted to pins 12 through 19 of microprocessor U1 and, once the instruction is stored internally in microprocessor U1, the microprocessor will restore the data busses and port 2 to its original condition. The microprocessor U1 provides a clock frequency of 6 MHz, this being determined by the crystal Y1 and the capacitors C1 and C2 which are connected to pins 2 and 3 of the microprocessor and provide the clock frequency. Also shown connected to pin 6 of the microprocessor U1 is a reset switch S16 which is connected to the interrupt input. Operation of this switch makes possible different system behavior after a user reset and power-up reset. Switch S16 corresponds to the reset button 86 in FIG. 3.
Referring again to FIG. 5, there are shown a plurality of panel switches S1 through S7 which correspond to the even numbered switches 46 through 56 in FIG. 3. Also shown are dip switches S8 through S15 which correspond to the even numbered switches 70 through 84 of FIG. 3. Further shown is the night set-back terminal TS5 of FIG. 5 which corresponds to the night set-back switch 62 in FIG. 3 and the HLTL sensor terminal TS6 of FIG. 5 which corresponds to the sensor probe terminal 64 of FIG. 3. These inputs corresponding to switches S2 through S15, night set-back terminal TS5 and sensor terminal TS6 are selected and read one at a time by two C-MOS one of eight data selector units U11 and U12. Selector U11 selects the dip switches addressed by a three bit code which microprocessor U1 places on selector U11 inputs 9, 10, 11 from terminals 27, 28 and 29 of the microprocessor. If microprocessor U1 places a low signal on inhibit terminal 6 of selector U11 from terminal 33 of the microprocessor, the status of the select switch will appear at terminal 38 of microprocessor U1, having been transmitted from I/O terminal 3 of selector U11.
Selector U12 shares the same address bits as selector U11, receiving them on terminals 9, 10 and 11 thereof and therefore selects one of the panel switches S2 through S7, the night set-back input or the sensor probe input, depending upon the address. When the inhibit input 6 of selector U12 is brought low, selector U12 will send the status of the selected switch/input to the T1 input at pin 39 of microprocessor U1 from the I/O terminals at pin 3 of the selector U12.
An open circuit at the night set-back input TS5 will cause transistor Q3 and transistor Q11 to be turned off. This allows night set-back status LED 16 corresponding to lamp 94 in FIG. 3 to be turned on and the pin 2 input of selector U12 to be low. Closing the input circuit of night set-back TS5 will cause both transistors Q3 and Q11 to conduct, turning off the LED 16 and causing the input at pin 2 of selector U12 to go high. The sensor probe connected at TS6 provides a constant current pulse output whose width is determined by the probe temprature. Resistor R7 serves as a load to convert the current into voltage. When the pulse is high, transistor Q2 conducts and brings the pin 4 of selector U12 low. When selected and enabled, the pulse from the sensor will appear at the T1 input at pin 39 of microprocessor U1 which then measures the pulse width and establishes the temperature of the probe therefrom.
The input signals from the governors GOV 1 through GOV 8 at the monitor 38 as shown in FIGS. 1 through 4 correspond to the inputs labelled GOV 1 through GOV 8 shown in FIG. 5. The operation on signals received from the governors or thermostats and signals transmitted thereto from the monitor in conjunction with the electronic circuit of the monitor will now be discussed. The circuit includes a level translator U10, a transmit multiplexer U7, a receive multiplexer U8, and a line driver U9 and thereby interfaces the eight governor communication ports to the microprocessor U1. The translator U10 has its input pins to the left thereof connected to pins 27 through 32 of microprocessor U1. Translator U10 inverts the outputs of the microprocessor which swing from zero to five volts and makes the signals swing from zero to twelve volts for compatability with the driver U9 output ports at the right of U9. At the output pins of translator U10, the lowest order bits at pins 8, 6 and 10 are the complement of the governor to thermostat to be selected. Pin 4 of the translator provides the serial data to the selected governor whereas pin 12 of the translator disables the line driver U9 when appropriately energized. Pin 2 of the translator goes low to enable both multiplexers U7 and U8. Since the address is complemented, the order of connection to the multiplexers has been mirror imaged to compensate therefor. To send data to a governor or thermostat, the address of the governor is provided from microprocessor U1 followed by a multiplexer enable and line driver enable signals on lines 12 and 2 of the translator U10. A low signal on pin 30 of the microprocessor U1 causes the selected "COM" Data line on TS4 to go high whereas a high signal on pin 30 causes the selected "COM" Data line to go low. After the data has been sent from the translator U10, microprocessor U1 disables the line driver and allows a response to return over the same wire. With the address and multiplexer enable signals still intact, the response data is routed through multiplexer U8 and is attenuated by a diode network composed of diodes D1 through D3 and resistor R2. This network shifts logic levels from twelve volts back to five volts. The data is then fed to pin 39 of the multiplexer U1.
A sixteen bit port expander U4 provides the microprocessor U1 with more output capability. Pins 13 through 20 of port expander U4 drive the eight governor status LEDs 1 through 8 which correspond to the governor status lamps 88 shown in FIG. 3 via a Darlington array U6 and one Darlington from U5. Pin 21 of port expander U4 drives the high-low temperature status LED 15 through transistor Q1. Port expander U4 pins 1 through 5 and pin 23 drive the six HVAC control relays and relay status LEDs 9 through 14 through the remaining Darlington circuits of U5. Pin 9 of Darlington circuit U5 is connected to the power source of the relays K1 through K6. The Darlington circuits are internally connected to suppression diodes which are part of U5 (not shown) and serve to limit transient voltages developed when the magnetic field of a relay collapses as it is de-energized. Metal oxide varistors MV1 through MV6 shunt the relay contacts and provide protection against voltage kick-back from external inductive loads.
An electrically isolated serial data communication, "COM", port TS4 is made up of transistors Q6 and Q7 and optical isolator circuits U15 and U16. A high from the "COM" Data line on the center terminal of TS4 turns on isolator U16 and causes the TO input at pin 1 of the microprocessor U1 to go low. The "COM" Data line returning to low turns off isolator U16 and makes input TO at pin 1 of microprocessor U1 to return high. To respond, microprocessor U1 will pull pin 34 thereof low which turns on transistor Q7 and isolator U15 and transistor Q6, forcing the "COM" Data line high. Returning pin 34 of microprocessor U1 to high level returns the "COM" Data line low.
Power is supplied by external twenty-four VAC source connected to terminal TS3. Capacitor C15 bypasses line noise to chassis ground. Power is rectified by the diodes D4 through D7 and filtered by capacitor C13 which is shown following the power switch S1 which corresponds to switch 44 on the panel 38 of FIG. 3. Power switch S1 interrupts current flow when it is turned off. The filtered DC voltage at capacitor C13 is dropped by resistors R26 and R27 and presented to the input of regulator VR2. Regulator VR2 provides plus twelve volts DC to the governor interface and to the input of voltage regulator VR1 which supplies plus five volts DC to the remaining logic. Filter capacitor C13 also supplies the status LEDs and the relays through dropping resistor R25 with voltages labelled as V1 and V2. Operational amplifier U14 is connected to detect insufficient input voltage caused by brownouts at the regulators, power glitches, power up, etc. When amplifier U14 triggers, it will reset the microprocessor U1 by temporarily discharging reset capacitor C8 at pin 4 of the microprocessor U1 through the power fail output from amplifier U14 and transistors Q4 and Q5. Amplifier U14 also resets port expander U4 by removing power therefrom through transistors Q8 and Q9. This ensures that the relays K1 through K6 will be off during a brownout or power interruption. Also, during this condition, transistor Q10 will remove plus twelve volts from the governor interface circuitry.
Referring now to FIG. 6, there is shown the details of the monitor sensor probe 34 as shown in FIG. 2. The monitor sensor probe circuitry measures temperature and provides an output compatible with the microprocessor U1. Basically, the monitor sensor probe is a pulse width modulator controlled by the voltage developed across a thermistor (not shown). The thermistor is connected to a resistor network composed of resistors R2' and R3'. The resistor network provides a voltage output that is a function of the thermistor temperature. Monostable multivibrator U2', comparator U1', transistor Q1' and capacitor C3' and charging resistors R4', R5' and R6' form an astable multivibrator circuit. When multivibrator U2' is inactive, transistor Q1' allows capacitor C3' to be charging at a rate determined by calibrated potentiometer R4' and resistors R5' and R6'. When the voltage at capacitor C3' equals the thermistor network voltage, comparator U1' output goes low, triggering multivibrator U2' into the active state. Therefore, the length of time that multivibrator is not active depends on the thermistor temperature. The exponential nature of the charging curve of capacitor C3' tends to cancel the logarithmic characteristic of the network voltage function over the target temperature range. Output buffer Q2' is tied through resistor R9' to the discharge pin 7 of the multivibrator U2'. Transistor Q2' is off when multivibrator U2' is active and on when multivibrator U2' is inactive. Diode D2' serves to isolate the base drive current from timing component composed of resistor R8' and capacitor C4'. The length of time that the collector of transistor Q2' pulls high is determined by the thermistor temperature and the length of time that it is in the hi-2 state depends upon the value of the dead time components composed of capacitor C4' and resistor R8' which are set at about 1.1 milliseconds. In actual use, the output buffer transistor Q2' will drive a current sink or load resistor reference to ground, thus providing a pulse with an amplitude of five volts. The circuit is calibrated by adjusting resistor R4' so that the pulse width will be equal to 9.00 milliseconds plus or minus 7.5 microseconds at 77° F. The pulse output of this device is fed into and tested by input line T1, pin 39 of the microprocessor U1. The particular processor selected to interface with the monitor sensor probe has a cycle time of 2.5 microseconds. A pulse width counter routine is implemented utilizing increment, test and jump instructions for a total of 7.5 microseconds per count.
To find the number of counts, simply divide the pulse width by 7.5 microseconds. In order to determine the pulse width, however, it will first be necessary to find the thermistor network voltage (Vnet). This may be done by reading the expected thermistor resistance (Rt) from the resistance vs. temperature chart for a curve 1 NTC device and plugging it into the network equation:
Vnet=Vcc/[R3[1/Rt+1/R2]+1]
where:
Vcc =Supply voltage (+5 Volts)
R3=4.99k ohms
R2=8.87K ohms
Rt=Thermistor resistance
Once the voltage has been established, the pulse width (tpw) can be found using:
tpw=LOG n[1/[[1-Vnet/Vcc]↑RC]]
where:
Vnet=thermistor network voltage
Vcc=supply voltage (+5 Volts)
C=0.1 microfarad
R=135.601K ohms (the normalized value of R4, 5 and 6)
Combining the two above expressions yields:
tpw=LOG n[1/[1-[Vcc/[R3[1/Rt+1/R2]+1]/Vcc]]↑RC]
Cancelling out two redundant terms brings forth:
tpw=LOG n[1/[[1-1/[R3[1/Rt+1/R2]+1]]↑RC]]
From here it can be seen that in a theoretical sense the supply voltage has no effect on the output pulse width. Although in reality small dissipation factors may become involved making it desirable to maintain a constant supply voltage. This is done with regulator VR-1.
Other support components include capacitor C2' which rejects normal mode noise picked up by the thermistor connection wires. Capacitor C5' is a power supply bypass capacitor and stabilizes the five volt source at comparator U1' and multivibrator U2'. Capacitor C6' shunts common road noise to chassis ground. Resistor R1', diode D1' and capacitor C1' form an input power filtering network with protection against accidental polarity reversal.
Though the invention has been described with respect to a specific preferred embodiment thereof, many variations and modifications will immediately become apparent to those skilled in the art. It is therefore the intention that the appended claims be interpreted as broadly as possible in view of the prior art to include all such variations and modifications. | A monitoring and control system for a heating, ventilating and air conditioning (HVAC) unit which provides zone control in plural zones in which each zone includes a control thermostat that is interfaced with the monitoring system so that each zone thermostat controls the HVAC unit as well as a damper unit for that particular zone thereby enabling independent zonal control in a multiple zone system which uses a single zone HVAC unit. The monitor considers individual zone needs, damper positions, amount of demand in the zone, mode of the zone damper and other factors which affect the comfort of zone occupants and, in response to signals from the thermostats, decides how and when to control the HVAC unit so that, in effect, a single zone HVAC unit becomes a multiple zone system. The system is comprised of two or more computerized thermostats which control both the HVAC unit through the monitoring control and the air distribution system of each zone through the damper for each zone, creating a heating, cooling, variable air volume and variable temperature control system. The thermostats also operate under control of signals received from the monitor. | 5 |
BACKGROUND OF THE INVENTION
The present invention relates to a centrifugal casting machine, and in particular to a machine for molding parts by means of the centrifugal casting of metals, or metallic alloys, with a low melting point, or of synthetic materials, such as for example polyester- or polyurethane-based resins.
Machines are known which perform the casting of metals, or metallic alloys, with a low melting point or of synthetic materials in molds made of vulcanized rubber which are rotated during the introduction of the molten metal.
More particularly, said types of machine comprise a main framework which supports, so that it can rotate about a generally vertical main axis, a carousel on which a mold is arranged; said mold is composed of two half-molds which are substantially disk-shaped, face one another and are arranged so that their axes coincide with the main axis. The casting cavities are defined on the two faces of the half-molds which face one another, and are connected, by means of appropriate ducts defined in said half-molds, to a feed duct which extends axially in at least one of the two half-molds. During the casting step, the two half-molds are pressed against one another and the molten metal is poured into the feed duct, while the carousel, together with the mold, is rotated about the main axis so that the molten metal can fill the casting cavity by exploiting the centrifugal force.
An electric motor which is connected to the carousel by means of a transmission, generally of the belt type, is used for the rotary actuation of the carousel.
Said known types of machine have some disadvantages.
In fact, due to the arrangement of the motor, which is located laterally and is spaced from the main axis in order to allow the interposition of the transmission, relatively bulky overall volume occupation occurs.
Furthermore, since the transmission is generally used as a speed variator by using, in the case of a belt, an expanding pulley, it also requires the possibility of adjusting the position of the motor when the transmission ratio is changed.
SUMMARY OF THE INVENTION
The aim of the present invention is to obviate the above described disadvantages by providing a machine for molding parts by means of the centrifugal casting of metals, or metallic alloys, with a low melting point, or of synthetic materials, which has a modest volume occupation with respect to conventional machines.
Within the scope of this aim, an object of the invention is to provide a machine which is very simple in design and execution.
Another object of the invention is to provide a machine which, despite having great flexibility in use, is structurally simple.
A further object of the invention is to provide a machine which is highly reliable in operation although it requires reduced maintenance interventions.
This aim, these objects and others which will become apparent hereinafter are achieved by a centrifugal casting machine as defined in the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
Further characteristics and advantages will become apparent from the detailed description of a machine according to the invention, illustrated only by way of non-limitative example in the accompanying drawings, wherein:
FIG. 1 is a sectional elevation view of a portion of the machine according to the invention; and
FIG. 2 is a lateral elevation view of a portion of the machine according to the invention, wherein the various elements for its actuation are schematically indicated.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
With reference to the above figures, the machine according to the invention, generally indicated by the reference numeral 1, comprises a main framework 2 which supports, so that it can rotate about a main vertical axis 3, a carousel 4 on which a mold 5 of the type made of vulcanized rubber is mounted in a per se known manner.
More particularly, the carousel 4 is constituted by a flat bottom 6 from which four uprights 7 extend perpendicularly and are arranged along an ideal cylindrical surface the base whereof is the bottom 6. A supporting plate 8 is arranged on the carousel 4 between the uprights 7, and the mold 5 is arranged above said supporting plate 8 and is constituted, in a known manner, by two disk-shaped half-molds 9a and 9b the axes whereof coincide with the axis 3. The casting cavities are defined on the faces of the half-molds 9a and 9b which face one another, and are connected, by means of appropriate channels, to a central hole which is defined at the center of the upper half-mold 9a.
Above the mold 5 there is a contrast disk 10 which is arranged parallel to the supporting plate 8 and can be locked axially by means of tabs 11 to be inserted within seats 12 defined in the uprights 7 proximate to their upper end.
A cylindrical fluid activated presser element is defined wherein a body 13 is rigidly connected to the lower face of the bottom 6, and a chamber 14 is defined inside said body and accommodates, so that it can slide along the axis 3, a piston 15 which passes through a passage 16 defined in the bottom 6 and engages against the supporting plate 8.
A covering element 17 is provided around and above the carousel 4 and is traversed, along the axis 3, by a central hole 18 into which the molten material is poured.
The carousel 4 can be actuated with a rotary motion about the axis 3 by means of a motor 19 which, according to the invention, is arranged so that the axis of its output shaft 20 coincides with the axis 3. The motor 19 is conveniently constituted by a three-phase asynchronous electric motor, the speed whereof can be varied in a per se known manner and which is equipped with a known braking device which is not illustrated for the sake of simplicity.
The motor 19 might also be constituted by a direct-current electric motor or by a single-phase asynchronous electric motor.
More particularly, the output shaft 20 is fixed, with its upper end, to the cylindrical body 13, so as to be rigidly associated with the carousel 4, and the motor 19 is supported by the main framework 2.
Conveniently, an axial duct 21 is defined in the output shaft 20 and is connected, by means of a known rotating coupling 22 which is coupled to the lower end of the output shaft 20 and by means of a controllable electric valve 34, to a source of pressurized fluid, for example air. The duct 21 is connected to the chamber 14 for the actuation of the piston 15.
The machine according to the invention furthermore comprises lifting means 23 which controllably act upon the covering element 17 to transfer it from a closure position to an opening position in order to allow access to the mold 5 at the end of casting.
The covering element 17, which has a substantially cylindrical hollow configuration which is open at the lower base, is pivoted with its lower edge to the main framework 2, and the lifting means are constituted by a fluid-activated jack 24 which is pivoted to the framework 2 with its body and to a portion of the covering element 17 with the end of the stem 24a of its piston.
The fluid-activated jack 24 is of the single-action pneumatic type, and is actuated through a feed line 25 on which an electric valve 26 is arranged; said electric valve 26 can be controlled by means of an electronic control element 27 which supervises the operation of the machine and also includes an electronic device for braking and varying the rotation rate of the motor 19.
More particularly, the valve 26 is arranged on a feed duct 28 of the jack 24 and can be controlled so as to connect said duct 28 to a source of pressurized air, in order to lift the covering element 17, or to the atmosphere, or with a discharge, to allow its lowering by gravity.
Advantageously, a flow regulator 29 is provided in the duct 28 and controls the discharge of the jack 24, adjusting the closure speed of the covering element 17.
The chamber of the jack 24, inside which its piston slides, is connected, on the side opposite to the inlet of the duct 28 with respect to the piston, to a one-way valve 33 which is also provided with a flow regulator which, in the case of pneumatic actuation, discharges into the atmosphere. In this manner it is possible to adjust the lifting speed of the covering element 17 in order to obtain a lifting speed which differs from the lowering speed.
Means for detecting the position of the covering element 17 are provided between the covering element 17 and the framework 2. Said detection means comprise a first microswitch 30 supported by a support which is fixed to the framework 2 and is arranged laterally to the covering element 17, which is provided with a pin 35 making contact with the microswitch 30 when the covering element 17 is in the closure position. The microswitch 30 is connected to the control element 27 so as to indicate thereto the closure position of the covering element 17.
The means for detecting the position of the covering element 17 furthermore comprise a second microswitch 32 arranged on the framework 2 behind the covering element 17, which is provided with a protrusion 36 making contact with said microswitch 32 when the covering element 17 is fully raised and is in an equilibrium condition. The microswitch 32 controls the electric valve 34, as will become apparent hereinafter.
Advantageously, there are also safety means for preventing the accidental opening of the covering element 17 during the operation of the machine. Said safety means comprise a pawl 37 which is arranged proximate to the microswitch 30 and engages the pin 35 when the covering element is in the closure position. The pawl 37 is actuated by a single-action fluid-activated jack 38 which is fed by a branch 28a of the duct 28 so that the pawl 37 releases the pin 35 only when the cylinder 23 is activated, as will become apparent hereinafter. A delay device, for example a choke, is provided on the duct 28 so that the pawl 37 releases the pin 35 before the jack 23 starts to lift the covering element 17. The disengagement of the pawl 37 from the pin 35 is biased by a spring 39.
For the sake of completeness in description, it should be noted that a manostat 31 is arranged on the feed line 25.
The operation of the machine according to the invention is as follows.
After placing the mold 5 on the carousel 4 and after fixing the contrast disk 10 to the carousel 4, the operator acts on the covering element 17 so as to move it from its equilibrium position and cause only the separation of the protrusion 36 from the microswitch 32. This separation causes the actuation of the valve 34 which connects the axial duct 21 to the source of compressed air so as to press the mold 5 against the contrast disk 10.
Meanwhile, the covering element 17 descends by gravity with a controlled speed, as explained above, and when the pin 35 makes contact with the microswitch 30 the electronic control element 27 actuates the motor 19 which rotates the carousel 4.
The molten material is poured through the central hole 18 and fills the casting cavities of the mold. Once molding has occurred, the control element 27 stops the motor 19 and, by switching the position of the valve 26, causes the release of the pawl 37 from the pin 35 and the opening of the covering element 17, thus indicating the end of the molding cycle to the operator, who can promptly act in order to extract the mold 5 and unload the molded parts.
After the operator has repositioned the mold 5 and the contrast disk 10 on the carousel, the operating cycle resumes as already described.
In practice it has been observed that the machine according to the invention fully achieves the intended aim, since the particular arrangement of the motor allows to reduce the overall volume occupation of the machine, considerably simplifying its design and execution.
A further advantage, which arises from the automatic opening of the covering element, is that the work of the operator is reduced and the end of the molding cycle is indicated.
In practice, the materials employed, as well as the dimensions, may be any according to the requirements and to the state of the art. | The centrifugal casting machine for molding parts by centrifugal casting of metals, or metallic alloys, with a low melting point, or of synthetic materials, includes a main framework which supports a carousel which can rotate about a main axis and supports a mold. The carousel is actuated with a rotary motion about the main axis by a motor which is arranged so that the axis of its output shaft substantially coincides with the main axis. | 1 |
FIELD OF THE INVENTION
The invention herein relates to improved doilies and a method of manufacturing the same, such that the doilies are provided to the consumer in an easily separated stack.
BACKGROUND OF THE INVENTION
Paper doilies are manufactured by passing paper stock between a die roller and one or more backer rollers. The die roller includes cutting dies which cut the exterior shape of the doily from the paper stock and also cut openings in the doily to simulate the appearance of crocheted lace. The die roller often includes an embossing portion, which operates against a cooperating backing roller to impart texture to the doily, thereby further simulating the appearance of cloth and, in some instances, embroidery.
To achieve efficiencies of manufacture, several sheets of paper stock are superimposed or layered and are passed together as a multi-layer web between the die roller and the cooperating backer rollers. Thus, the die roller operates to create a stacked plurality of doilies. The die roller generally contains several individual die portions deployed across the width of the roller, so that several stacks of doilies may be cut and embossed simultaneously from the entire width of the web.
Substantial pressure is required to cut and emboss the layered paper web in order to form stacks of the doilies, and, of course, higher pressures are required for higher numbers of layers. The pressures involved can cause the stack of doilies to stick together to the point where the consumer cannot separate them easily. The problem is exacerbated in doilies having a substantial number of cut out areas, in that when the thin strips of paper located between the cut out areas stick to the corresponding thin strips of the adjacent doily, the strips often tears upon attempted separation. There are four levels of this phenomenon, namely: level 1, wherein the doilies are stuck together and cannot be separated without substantial damage; level 2, wherein the consumer through careful manipulation can separate the doilies without tearing or with minimal tearing; level 3, wherein the doilies adhere to each other but can be readily separated with ordinary care in doing so; and level 4, wherein the doilies freely fall from each other upon handling of the stack of doilies. Level 4 is somewhat undesirable from a manufacturing standpoint, as it is difficult to package doilies that separate too easily.
Also, the tendency of the layered paper web to stick together as a result of the cutting and embossing process creates multi-layered chips from the cut out portions of the doilies. These chips have a tendency not to disperse from the stack of doilies until the consumer separates the doilies, leaving a confetti effect in the vicinity of the separation and sometimes leaving unsightly chips stuck in the open area of the doily.
The problem of adjacent doilies sticking together can be minimized through the use of certain papers having relatively long fibers and hard surface finishes, but such paper is expensive for use in the manufacturing of the doilies and can also be difficult to cut. There are other conditions which affect the tendency of the doilies to stick to each other, including the humidity at the time of production, the moisture content of the paper (for instance, if it has been stored for a period of time under high humidity conditions), the type of paper, any coating thereon and whether the coating is on one side or two sides, and the specific pattern of the doily. The problem is clearly exacerbated with respect to doilies having a large number of cut out areas and a deeply embossed texture.
Mineral oil has been applied to surfaces of the paper stock, in an effort to lubricate the interface between adjacent layers of paper and thereby reduce the tendency of the doilies to stick together. Using mineral oil, it is generally possible to produce doilies in pluralities of three layers, and sometimes four layers, with a level 2 or level 3 degree of separation, i.e., separable with care and sometimes readily separable. However, Level 2 is not very desirable. Therefore, manufactureability varies between three and four layers. Some manufacturing runs are somewhat more successful than others, e.g., because of the factors noted above, and problems with separability are not uncommon in four layer stacks of doilies.
It should now be apparent that efficiency of manufacture would be improved if more than three layers of doilies could be produced reliably, and the doilies themselves could be improved if they demonstrated consistent ease of separation.
SUMMARY OF THE INVENTION
It is an object of the invention herein to improve efficiency in manufacturing doilies.
It is an additional object of the invention herein to facilitate manufacturing doilies in multiple layers.
It is a further object of the invention herein to utilize existing equipment in the efficient manufacture of improved doilies.
It is another object of the invention herein to achieve improved disbursal of chips in the manufacture of open pattern doilies.
It is also an object of the invention herein to provide improved doilies.
It is an additional object of the invention herein to provide doilies in multiple layers with ease of separation.
In accomplishing these and other objects of the invention, there is provided a method of manufacturing doilies including dissolving or mixing a release agent in a lubricous liquid carrier to form a lubricous release fluid and applying the lubricous release fluid to selected surfaces of a plurality of sheets of paper stock. The sheets of paper stock are superimposed into a multiple layer paper web, and the layered web is passed between a die roller and at least one backer roller. The die roller cuts a plurality of stacked doilies from the layered web, including any desired openings in the doilies forming a pattern. The die roller also embosses any desired texture thereon.
According to certain aspects of the invention, the liquid carrier is mineral oil and the release agent is selected from the group consisting of silicone, surface active fluorocarbons, polytetrafluoroethylene metallic stearates, and platelet micro-crystalline structures, such as mica.
Further aspects of the invention reside in a lubricous release fluid consisting of 21/2 to 50% silicone in mineral oil. A deposition rate of 0.059 pounds wet of the fluid per 475,000 square inches of paper stock surface is contemplated by the invention. This results in from 0.0013 lb. to 0.0295 lb. of dry-equivalent silicone per 475,000 square inches. Variances in the wet deposition rate may be employed to provide application of dry-equivalent silicone in the same range to the paper stock.
According to further aspects of the invention, the lubricious release fluid is applied to all or some surfaces of the paper stock, as required for ease of separation of the plurality of stacked doilies. It is contemplated that up to six sheets of paper stock may be coated and cut into doilies.
The invention also resides in a stacked plurality of paper doilies, wherein the adjacent surfaces of the doilies have a lubricous release fluid applied thereto, the fluid including a lubricious liquid carrier and a release agent, as discussed above. According to additional aspects of the invention, the doilies have cut out openings and embossed surface texture.
The various features of novelty which characterize the invention are pointed out with particularity in the claims annexed to and forming a part of this specification. For a better understanding of the invention, its operating advantages, and specific objects attained by its use, reference is made to the accompanying drawings and description preferred embodiments of the invention set forth below.
DRAWINGS
FIG. 1 is an enlarged segmental plan view of a stack of doilies according to the invention herein, manufactured according to the processes of the invention;
FIG. 2 is a schematic view of the apparatus and process for manufacturing the doilies of FIG. 1;
FIG. 3 is an exploded perspective view of an applicator used in the manufacturing process of FIG. 2;
FIG. 4 is a sectional view of the applicator of FIG. 3;
FIG. 5 is an enlarged segmental sectional view of a cutting die used in the manufacturing process of FIG. 2;
FIG. 6 is a schematic plan view of a layered web of paper stock illustrating plural stacks of doilies formed therefrom; and
FIG. 7 is an enlarged sectional view, partially cut away, of the stack of doilies of FIG. 1, taken along the lines 7--7 of FIG. 1.
The same reference numerals refer to the same elements throughout the various figures.
DESCRIPTION OF PREFERRED EMBODIMENT
FIG. 1 is a segmental plan view of a stack of doilies 10, including a top doily 12 according to the invention herein, the doily 12 and stack of doilies 10 all being manufactured in accordance with the process of the invention herein. The doily 12 is fabricated of paper, and more particularly, is cut from a sheet of paper such that it has a cut periphery 14. The doily 12 further includes a plurality of cut out openings, such as openings 16 and 18, the openings being arranged in a pattern to simulate lace. The doily 12 is also embossed with ridges, such as the ridges 20 and 21 best seen in FIG. 7, the embossed ridges further imparting the appearance of fabric to the paper doily 12.
FIG. 2 illustrates the apparatus and process of manufacturing the stack of doilies 10, which in the embodiment shown consists of five individual doilies. Accordingly, there are provided five sheets of paper stock 22-26 which are delivered from supply rolls, not shown. Associated with each of the five sheets of paper stock, respectively, are five feed rollers 28-32 which direct the sheets to a main collection roller 34. At the collection roller 34, the sheet stock is superimposed into a multi-layered web 36 which passes sequentially between a die roller 38 and a first backer roller 40, and thereafter between the die roller 38 and a second backer roller 42. The layered web 36 exits the die roller and backer rollers as web 36a, having a plurality of stacks 10 of doilies cut therefrom as illustrated in FIG. 6. This general process of making doilies is well known in the art, and will not be discussed in further detail for that reason.
The sheet stock in the embodiment described is 40 lb. tablet grade paper, approximately 0.003 inches thick. The paper is uncoated. It will be appreciated that different grades, weights and thicknesses of paper may also be used.
Prior to collecting the sheet stock 22-26 into the multi-layer web 36, the surfaces of the sheet stock are coated with a lubricous release fluid 60. The lubricous release fluid is applied by oilers, such as oiler 44 illustrated in FIGS. 3 and 4. The oiler 44 consists of an applicator pad 46 in a reservoir 48. The reservoir 48 consists of a housing 50 including a trough 52 extending laterally outwardly beyond an upper side wall 54, thereby defining a trough opening 56. The applicator pad 46 is closely received in the trough 52, and extends upwardly to lie against the upper sidewall 54. The lubricous release fluid 60 is supplied to the reservoir 48, and maintained at a level sufficient to soak the lower portion 62 of the applicator pad 46.
The oiler 44 is provided with a roller 64, and paper sheet stock 22 is fed between the roller 64 and the applicator pad 46. The pad 46 absorbs the fluid 60 and wicks it throughout the pad. Therefore, when the roller 64 biases the sheet stock 22 against the applicator pad 46, the applicator pad 46 being supported by the upper side wall 54, the surface of the sheet stock 42 adjacent to the applicator pad 46 receives an application of the lubricous release fluid 60.
With reference to FIG. 2, the oiler 44 and oilers 66-74 together apply lubricous release fluid 60 to all the surfaces of the sheet stock 22-26 prior to collecting the sheet stock into the multi-layer web 36. It is also contemplated that other means of applying the lubricious release fluid may be used, such as spraying.
It will be appreciated that certain operating conditions may not require an application of fluid to all the surfaces, and an experienced operator may be able to delete an application of fluid to one or more surfaces with successful results. Because of the number of variables involved, such as the temperature, humidity, type of paper stock, humidity content of the paper stock, particular doily pattern and its intricacy, conditions of the dies, pressure adjustment of the die and backer rollers, and the like, withholding the application of fluid to a particular surface is more a matter of operating experience than predictable operating procedure. The most important consideration is the design of the doily pattern itself. Patterns with more cut out areas and/or deeper embossing separate with significantly more difficulty than patterns with less cut out areas and/or flatter embossing. However, as a matter of generalization, if the application of fluid is withheld from a surface, it is generally possible to withhold it from one of the upper sheets of stock rather than one of the lower sheets.
The preferred lubricous release fluid is silicone dissolved in mineral oil carrier. The percentage of silicone in the solution varies between about 21/2% to about 50%, depending upon the sticking tendency of the doilies, which is a function of the factors discussed above.
Mineral oil is the preferred carrier fluid because silicone is readily dissolvable therein, and also because mineral oil is colorless, odorless, tasteless, and ingestible. It is considered a "food grade" material, so that food which has contacted a doily treated with mineral oil may be eaten safely. Although vegetable oils such as olive oil and corn oil also have many of these advantages, mineral oil is also stable, i.e., it does not spoil or become rancid over time.
Solvents such as 1-1-1 trichloroethane are also suitable for the ability to accept silicone in solution, but tend to give off vapors which require care in manufacturing and the finished doilies also can have lingering odor from residual release of those vapors.
The release agent is preferably silicone, as it also enjoys the advantages of being colorless, odorless, tasteless, ingestible and stable. However, the release agent can also be selected from the group consisting of silicone, surface active fluorocarbons, metallic stearates including zinc stearate and calcium stearate, and platelet micro-crystalline structures such as mica. The preferred lubricous release fluid is available from Camie-Campbell, Inc. of St. Louis, Mo., Product L-7067. Various percentage solutions of silicone are available under that product number.
The oilers 44 and 66-74 apply approximately 0.059 pounds wet of the mineral oil and silicone solution to 475,000 square inches (one ream) of the sheet stock surface. Therefore, at 21/2% silicone and 971/2% mineral oil, the amount of silicone applied is 0.0013 pounds per 475,000 square inches of sheet stock. Given relatively ideal conditions, such as low humidity and low to normal pressures in the die and backer roller process, there is detectable improvement in separation of doilies made from such sheet stock, as compared to sheet stock with no lubricant applied and to sheet stock with just mineral oil applied.
Using 50% silicone and 50% mineral oil solution, the application of 0.059 pounds of solution wet per 475,000 square inch results in the application of 0.0295 pounds of silicone per 475,000 square inches of sheet stock. There is a substantial improvement in ease of separation at this percentage; however, at percentages of 50% or more, the doilies become so easily separable that they are difficult to handle for packaging, the economics become unrealistic (the cost of silicone is substantially higher than the cost of mineral oil alone), and the application by the oilers is increasingly more difficult. Further, at the high level of silicone, the manufactured doilies become quite slippery to the point of being unacceptable for retaining food items and dishes.
Excellent results are obtained with a lubricous release fluid consisting of 30% silicone and 70% mineral oil. With the oilers described above, this results in 0.0177 pounds of silicone applied to 475,000 square inches of sheet stock. The range of 15% to 40% silicone is believed to be the preferred range, resulting in from 0.009 to 0.0236 pounds of silicone per 475,000 square inches of stock. The amount of silicone deposited is expressed separately from the amount of fluid in that different oilers or other applications devices having a different application rate may require higher or lower concentrations of silicone as a percentage of fluid to achieve the same application of silicone per unit of area. It will further be recognized that the aforementioned results are for a doily design considered average in complexity and degree of embossing.
With reference to FIG. 5, the die roller 38 is seen to consist of a plurality of cutters 76, 78 and 80 operating against the first backer roller 40. As shown in FIG. 5, the cutters 76, 78 and 80 have cut through the upper sheet stock 22 and part way through the next layer of sheet stock 23, with the advance pressure the cutters beginning to deform the underlying layers of sheet stock 24-26. As noted above, the layers of sheet stock together for the multiple layer web 36. The first backers roller 40 accepts minimal contact with the cutters 76, 78 and 80 at the conclusion of their cut through the web 36 so as not to dull the cutters. The cutters form the cut peripheries of the stack of doilies 10 as well as the openings in the doilies, as illustrated by the periphery 14 and openings 16 and 18 in the segment of doily 12 shown in FIG. 1.
To keep the doilies from sticking together, it is preferred that the cutters pass cleanly through the paper sheet stock with a minimal amount of tearing. Tearing of the paper develops ragged edges, which tend to mesh together and cause the doilies to stick together, as well as creating difficulty in removing chips from the cut out openings. The lubricous release fluid 60 is believed to provide lubrication to the cutters 76, 78 and 80, permitting them to pass more readily through the sheet stock and provide cleaner cuts and therefore less sticking chips.
The die roller 38 also has an embossing pattern, not shown because it is well known in the art, which is applied to the web 36 as it passes between die roller 38 and backer roller 42. With reference to FIG. 7, the result of the embossing are apparent in the ridges 20 and 21 imparted to the finished stack of doilies 10. The pressure from embossing is a significant factor in causing the doilies to stick together, a tendency which is substantially reduced by the application of lubricous release fluid as described above.
With reference to FIG. 7, the stack of doilies 10 manufactured in accordance with the foregoing process characterized by the application of a lubricous release fluid to the sheet stock from which the doilies are formed, results in a stack of doilies which separates easily and without tearing of the doily pattern. The ease of separation that can be achieved in a greater number of layers of sheet stock in the multi-layered web 36 and FIG. 7 indicates a plurality of five doilies which may be readily and easily separated by the consumer.
Accordingly, the preferred embodiments of a process for manufacturing doilies and doilies that manufactured by that process have been described which admirably achieve the objects of the invention herein. With reference to the description of the preferred embodiments, those skilled in the art will appreciate that modifications may be made without departing from the spirit of the invention. Therefore, it is not intended that the scope of the invention be limited to the specific embodiment illustrated and described. Rather, it is intended that the scope of the invention be determined by the appended claims and equivalents thereof. | A method of producing doilies includes coating sheets of paper stock with a lubricious release fluid, collecting the sheets into a multi-layered web, and cutting and embossing doilies from the web. The fluid is preferably a solution of mineral oil and silicone, and results in the doilies being more easily separable after being adhered by the cutting and embossing process. A solution of mineral oil and 15%-40% silicone is disclosed. | 8 |
FIELD OF THE INVENTION
This invention relates to computer systems and, more particularly, to a multiprocessor computer system which is fault tolerant to processor siphon cache storage errors.
BACKGROUND OF THE INVENTION
One of the major challenges that traditional mainframe vendors face as personal computers and workstations become more and more powerful is in differentiating their midrange systems from the rapidly advancing smaller machines. One significant area in which mainframe machines can be made distinguishable from the smaller machines is in the area of fault tolerance.
The problem of processor cache storage errors has been a nuisance throughout the history of the use of cache memories in mainframe systems. These errors, as is true with main memory errors, can be caused by either alpha particle impact or transient (or hard) storage element failures. In the exemplary system in which the invention finds application, main memory single bit failures are masked from the system's visibility by specialized hardware in the memory controller that corrects the bit in error before the word associated with the flaw is sent to the requesting unit. However, processor cache failures are not corrected during the cache read activity because correction hardware has not been designed into the processor for a number of reasons such as the limited integrated circuit area available on the VLSI chips.
The advantages of processor cache memories greatly outweigh the complications that arise when they fail. Cache memories offer high-speed access to data and instructions that the processor would have to otherwise fetch from memory on every reference. A cache memory typically takes between 10% to 25% of the time required to access main memory, hence cache memories have gained a permanent position in system data storage hierarchy design.
Any computer design effort that incorporates a cache memory into its central processor unit architecture must address the following progressively more difficult challenges:
1. It is imperative that the processor detect a cache error condition; otherwise data corruption would result. The least expensive solution to this problem is to do nothing more than hang or crash the system when this type of error occurs, but this approach is, as a practical matter, completely unacceptable as a mainframe response.
2. A sophisticated machine should support the deconfiguration of a failing cache storage element. By merely deconfiguring an isolated failing element, the processor can continue to execute without substantial performance loss. Cache memories are divided into blocks that encompass many cache storage elements. In the exemplary machine, the block size is 16 words (64 bytes). Cache memories can also be divided into coarser subdivisions such as levels which, in this context, means a full column of blocks. The exemplary machine has been designed with logic that permits its cache blocks and cache levels to be individually deconfigured.
3. A truly sophisticated machine should ensure that if a processor cache error occurs, either the most recent copy of the block in error can be retrieved from main memory or the block in error can somehow be corrected. In the exemplary machine, an error correction code for correcting cache block single bit errors, invoked only during writes to main memory, has been implemented. But the design of this machine did not address explicit, "unnatural", correction of a specific cache block or restarting of the affected instruction. (The term "unnatural" is used in this context to indicate that it is required that the block be exchanged for correction even though the natural replacement algorithms would not dictate such an event at the time of the error.)
4. Store-into cache machines, such as the exemplary apparatus, are capable of operating extremely efficiently, but their characteristic of delaying writes to main memory which makes them performant is a liability when other processors are added to the system to further improve throughput. The multiple processor configuration leads to the ultimate challenge in cache error processing, that of handling cache operand block errors where the block in error resides in one processor's cache and is required by one or more processors and an "updated" copy of the block does not exist in the system's main memory. This problem, to which the present invention is addressed, is commonly referred to as the siphon error predicament. (Siphon is a term of art used to define the transfer of a cache block from one processor of a multi-processor system to either another processor or to an input/output unit.) The similar problem encountered in single processor systems is addressed by a related invention covered by U.S. patent application Ser. No. 07/708,420, filed on even date herewith, entitled FAULT TOLERANT COMPUTER SYSTEM, by David S. Edwards et al.
Some store-into cache prior art systems have handled the problem of processor cache errors by adding error correction hardware into each cache to correct an error as the data containing the error is read from cache. This is an effective, but expensive, solution to the problem.
A second prior art approach to solving the cache data correction and retry predicament incorporated a technique which masked the problem by implementing a store-through cache. (In store-through designs, when a cache block is updated, it is written to both the cache and immediately to main memory.) With this approach, whenever a fetch from cache is in error, the processor forces a cache bypass and issues a read-to-memory for the block which it will use both in instruction execution and to update (restore) the cache. The advantage of this solution is that the fetch from memory is identical to the cache miss condition such that the affected instruction is not impacted; therefore, all such errors can be recovered. This solution took advantage of the store-through design, which by definition provides the benefit of having main memory always up to date.
Store-into cache designs (commonly known as copy-back caches) are favored for performance oriented systems over store-through designs because they result in less processor-to-memory write activities, hence less main memory traffic which leads to less bottlenecking at the system bus when a bus design is implemented. The store-into characteristic that leads to enhanced performance necessarily results in the cache often containing the only valid copy of a particular block of data in the system. That is, when a cache block has been modified, it is not written back to main memory. Instead it is held by the cache until requested by a second active unit (CPU or I/O Unit) or until the block must be replaced at which time it is written back to main memory to make room in cache for a new block.
It will be apparent to those skilled in the art that it would be highly desirable to achieve, in an alternative approach, the advantages of these prior art solutions to the processor cache error predicament without resorting to the expense and complexity associated with the prior art solutions.
OBJECTS OF THE INVENTION
It is therefore a broad object of this invention to provide a solution to the processor cache error predicament which is straightforward and economic to implement.
It is a more specific object of this invention to provide a solution to the processor cache error predicament in the context of the problem as it applies to a system incorporating multiple processors which undertake to access one another's individual processor cache memories.
SUMMARY OF THE INVENTION
Briefly, these and other objects of the invention are achieved by a fault tolerant computer system including a plurality of Central Processing Units, each having a cache memory unit with a cache memory and a parity error detector adapted to sense parity errors in blocks of information read from and written to the cache memory unit and to issue a read or write cache parity error flag if a parity error is sensed. A system bus couples the CPU to a System Control Unit having a parity error correction facility, and a memory bus couples the SCU to a main memory. An error recovery control feature distributed across the CPU, a Service Processor and the operating system software, is responsive to the sensing of a read parity error flag in a sending CPU and a write parity error flag in a receiving CPU in conjunction with a siphon operation for transferring the faulting block from the sending CPU to main memory via the SCU (in which the given faulting block is corrected) and for subsequently transferring the corrected memory block from main memory to the receiving CPU when a retry is instituted.
DESCRIPTION OF THE DRAWING
The subject matter of 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, may best be understood by reference to the following description taken in conjunction with the subjoined claims and the accompanying drawing of which:
FIG. 1 is a very high level block diagram of the central system structure of an information processing system in which the subject invention finds application;
FIG. 2 is a general block diagram of a central processing unit of the central system structure of FIG. 1;
FIG. 3 is a block diagram similar to FIG. 1 showing certain data movements which take place during the practice of the subject invention; and
FIG. 4 is a flow chart effecting an alternative disclosure of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Attention is first directed to FIG. 1 which illustrates an exemplary Central Subsystem Structure (CSS) within which the subject invention may be incorporated. The System Control Unit (SCU) 1 centralizes and controls the system bus 2 and the memory bus 3 scheduling. More particularly, the SCU 1: A) performs memory control, single bit error correction and double bit error detection; B) controls the memory configuration of which there are one per Memory Unit (MU) 4; C) manages 64-byte block transfers between the Central Processing Units (CPUs) 5 and the MUs in conjunction with the store-into-cache feature of the CPUs; D) corrects single bit errors found in modified blocks of a CPU's cache or on a data transfer from a CPU, MU or Input/Output Unit (IOU) 6; and E) contains the system calendar clock.
The system bus 2 interconnects 1 to 4 CPUs and 1 to 4 IOUs with each other and with the SCU. The system bus includes a 16-byte bidirectional data interface, a bidirectional address and command interface, an SCU status interface monitored by all CPUs and IOUs, and a small number of control lines between the SCU and each individual CPU and IOU. Data is exchanged on the system bus in 16, 32 or 64-byte groups, and data exchanges can be between a CPU and an MU, an IOU and an MU, two CPUs and a CPU and an IOU. The operations through the system bus 2 are:
Read: 16, 32 or 64 bytes;
Read with exclusivity: 64 bytes;
Write from IOU: 16, 32 or 64 bytes;
Write from CPU (swapping): 64 bytes;
Interrupts and Connects;--Read/Write registers.
Every system bus operation consists of an address phase and a data phase, and an address phase can start every two machine cycles. Consecutive 16-byte data transfers within a group can occur on consecutive machine cycles. An IOU or CPU can wait for the data phase of up to two requests at the same time. The data blocks are transferred in the same order as the requests are received.
The memory bus 3 interconnects 1 to 8 MUs with the SCU. The memory bus includes a 16-byte bidirectional data interface, an address and command interface from the SCU to all MUs and a small number of control lines between the SCU and each individual MU. Data is exchanged on the memory bus in 16, 32 or 64-byte groups. The operations through the memory bus 3 are:
Read: 16, 32 or 64 bytes;
Write: 16, 32 or 64 bytes.
The main memory is composed of up to eight MUs. (A ninth slot, MU 4A, may be provided for ease of reconfiguration and repair in case of failure.) A single bit correction, double bit detection code is stored with every double word; i.e., 8 code bits for every 72 data bits. The code is arranged so that a 4-bit error within a single chip is corrected as four single bit errors in four different words. Data in an MU is addressed from the SCU in 16 byte (four word) increments. All bytes within any one MU are consecutively addressed; i.e., there is no interlace between MUs which operate in parallel. A memory cycle may start every machine cycle, and a memory cycle, as seen from a CPU, is ten machine cycles--assuming no conflicts with other units. An MU 4 contains 160 Dynamic Random Access Memory (DRAM) circuits, each of which has n by 4 bit storage elements where n=256, 1024 or 4096.
The IOUs 6 each provide a connection between the system bus 2 and two Input/Output Buses (IOBs) 7 such that each IOB interfaces with a single IOU. Thus, an IOU manages data transfers between the CSS and the I/O subsystems, not shown in FIG. 1.
A Clock and Maintenance Unit (CMU) 8 generates, distributes and tunes the clock signals for all the units in the CSS, provides the interface between the service processor(s) (SP) 9 and the central processing, input/output and power subsystems, initializes the units of the CSS and processes errors detected within the CSS units. The CSS employs a two-phase clock system and latched register elements in which the trailing edge of clock 1 defines the end of phase 1, and the trailing edge of clock 2 defines the end of phase two, each phase thus being one-half of a machine cycle.
The SP(s) 9 may be a commodity personal computer with an integrated modem for facilitating remote maintenance and operations, and large systems may include two SPs through which the system can be dynamically reconfigured for high availability. The SP performs four major functions:
monitors and controls the CSS during initialization, error logging and diagnostic operations;
serves as the primary operating system console during system boot or on operator command;
serves as console and data server for the input/output subsystems Maintenance Channel Adaptor (MCA);
provides a remote maintenance interface.
Attention is now directed to FIG. 2 which is a general block diagram of one of the CPUs 5 of FIG. 1. The Address and Execution Unit (AX unit) is a microprocessing engine which performs all address preparation and executes all instructions except decimal arithmetic, binary floating point and multiply/divide instructions. Two identical AX chips 10, 10A perform duplicate actions in parallel, and the resulting AX chip outputs are constantly compared to detect errors. The main functions performed by the AX unit include:
effective and virtual address formation;
memory access control;
security checks;
register change/use control;
execution of basic instructions, shift instructions, security instructions, character manipulation and miscellaneous instructions.
The cache unit 11 includes a data part of 64K bytes (16K words) and a set associative directory part which defines the main memory location of each 64-byte (16-word) block stored in the cache data part. Physically, the cache unit is implemented in an array of ten DT chips, a cache directory (CD) chip 12 and a duplicate directory (DD) chip 13.
The specific functions performed by the cache unit 11 include:
combined instruction and operand data storage;
instruction and operand buffering and alignment;
data interface with the system bus 7 (FIG. 1);
CLIMB safestore file.
The cache write strategy is "store into". If a longitudinal parity error is detected when reading a portion of a modified block from the cache, the block will be swapped out of the cache, corrected by the SCU and written into main memory. The corrected block will then be refetched from main memory upon retry.
Two copies of the cache directory information are respectively maintained in the CD and DD chips which perform different logic functions. The two directory copies allow interrogation of the cache contents from the system bus in parallel and without interference with instruction/operand access from the CPUs and also provide for error recovery. Functions performed by the CD chip 12 include:
cache directory for CPU accesses;
instruction, operand and store buffer management;
virtual-to-real address translation paging buffer.
Functions performed by the DD chip 13 include:
cache directory for system accesses;
system bus control;
distributed connect/interrupt management;
cache directory error recovery.
Efficient scientific calculation capability is implemented on the Floating Point (FP) chips 15, 15A. The identical FP chips execute all binary floating point arithmetic in duplicate. These chips, operating in concert with the duplicate AX chips 10, 10A, perform scalar scientific processing.
The FP chip 15 (duplicated by the FP chip 15A):
executes all binary and fixed and floating point multiply and divide operations;
computes 12 by 72-bit partial products in one machine cycle;
computes eight quotient bits per divide cycle;
performs modulo 15 residue integrity checks.
Functions performed by the FP chips 15, 15A include:
executes all floating point mantissa arithmetic except multiply and divide;
executes all exponent operations in either binary or hexadecimal format;
preprocesses operands and postprocesses results for multiply and divide instructions;
provides indicator and status control.
Two special purpose random access memories (FRAM 17 and XRAM 18) are incorporated into the CPU. The FRAM chip 17 is an adjunct to the FP chips 15, 15A and functions as an FP control store and decimal integer table lookup. The XRAM chip 18 is an adjunct to the AX chips 10 10A and serves as a scratchpad as well as providing safestore and patch functions.
The CPU also employs a Clock Distribution (CK) chip 16 whose functions include:
clock distribution to the several chips constituting the CPU;
shift path control;
maintenance;
interface between CMU and CPU;
provision of clock stop logic for error detection and recovery.
The DN chip 14 (in parallel with the DN chip 14A) performs the execution of the decimal numeric Extended Instruction Set (EIS) instructions. It also executes the Decimal-to-Binary (DTB), Binary-to-Decimal (BTD) conversion EIS instructions and Move-Numeric-Edit (MVNE) EIS instructions in conjunction with the AX chip 10. The DN chip both receives operands from memory and sends results to memory via the cache unit 11.
The AX, DN and FP chips, collectively, are sometimes referred to as the Basic Processing Unit (BPU). It was previously noted that the AX, DN and FP chips are duplicated with the duplicate units operating in parallel to obtain duplicate results which are available for integrity checking. Thus, master and slave results are obtained in the normal operation of these chips. The master results are placed onto a Master Result Bus (MRB) 20 while the slave results are placed onto a Slave Result Bus (SRB) 21. Both the master and slave results are conveyed, on the MRB and SRB respectively, to the cache unit 11. In addition, a COMTO bus 22 and a COMFROM bus 23 couple together the AX unit, the DN unit and the FP unit for certain interrelated operations.
The following discussion relates to the events that occur when a cache storage error is detected in a multiprocessor system and the data flow is from a first CPU's cache to a second CPU's BPU/cache. This is the more complex of the two cache operand data error scenarios and is the problem to which the subject invention is directed.
The preconditions that must exist for this error to arise are:
1. A CPU must have read a block of data into its cache due to a BPU request.
2. A second (or third or fourth) CPU must request the same block while it is still owned by the first CPU and after the block has had a single bit unexpectedly altered while residing in the first CPU's cache. (Unlike the single processor cache to BPU case, it does not matter if the word in error is the target word; i.e., any error in the cache block leads to the siphon predicament.)
When the CPU that owns the block in error (the sending CPU) enters its data transfer phase in response to the siphon request, the subject process for handling the error is invoked. It includes the following steps:
1. The sending CPU will detect the error when the requested block is read from cache storage. When the first quarter block is transferred to the requesting (receiving) CPU (data flow 28A, 28C in FIG. 3), an error signal will also be sent. The sending CPU will set a flag that specifically identifies this error type and notify its cache control logic (DD chip) of the error. The sending CPU's DD will set the BPU suspend directive and save the row and level information that identifies the defective cache block in the siphon history entry of its cache history register bank. The sending CPU's BPU will then be placed into a hard suspend state.
2. The receiving CPU will receive the error signal from the sending CPU and enter a BPU hard suspend state. This CPU will set an alarm with an error status, for the SP to evaluate, that specifies that it received the error signal from the sending CPU. It will also save information relating to the cache storage row and level that the block was targeted for in its cache history register bank for later SP reference.
3. The SCU will also note the error signal and force the faulting block, with bad parity, into memory (data flow 28A, 28B in FIG. 3). This will result in an alarm to the SP with the page address written into a register reserved specifically for this error type. The SCU will return a bad status signal to the sending CPU which will already be in a hard suspension state.
4. The SP must analyze these events; i.e., it must note that since an SCU alarm was reported in conjunction with a siphon/DT error from one CPU in conjunction with an alarm with a cache parity error indication set from a second CPU that a siphon error has occurred. The SP must then fetch the row and level information that pertains to the cache block in error from both the sending and receiving CPUs via an issuance of a Read DD Error Report directive to each. Next, the SP will use this information to invalidate the block held by the receiving CPU. (The SP will effectively ignore the SCU report although this must be read to ensure that the SCU is unlocked.)
5. The SP will force the correction of the cache block in error which is held by the sending CPU via the issuance of a swap directive, or swap command while specifying the destination memory address of the block being swapped. The swap will result in the failing cache block being written to memory (data movement 29A, 29B in FIG. 3). It is during this write that the SCU will correct the single bit failure. The SP will disable the storage elements in the cache associated with the failing block by disabling its level after the swap completes.
6. When the swap is complete, the SP must extract a certain amount of information from the BPU of the sending CPU. This information is required by the operating system software to increase the likelihood of its instruction retry routines creating a retryable machine state for the failing instruction,
7. The SP will write the failure symptoms and register data of the sending CPU into dedicated storage in main memory to be available for the operating system software to access later.
8. The SP will issue a Resume with Fault directive to command the sending CPU to restart from its suspended state with a parity fault. When the CPU restarts, it will push its state (safestore) from the XRAM 18 into cache and enter the fault handling/instruction retry routines of the operating system software.
9. The operating system software will note the parity fault and examine the information saved in dedicated memory to determine the type of fault. When it is found to be a cache operand error, the operating system software will evaluate the faulting instruction and determine whether it can be retried. The operating system software will use, in some cases, the sending CPU register information that was obtained by the SP to set preexecution states to increase the chances for a successful retry.
10. If the operating system software determines that the instruction associated with the failure is retryable, it will adjust the state that was pushed onto the safestore stack and restart the failed instruction by instructing the sending CPU to pop the stack entry.
11. While the operating system is performing steps 9 and 10, the SP will begin the task of restarting the receiving CPU from its halted state. The SP must extract a certain amount of information from the BPU of the receiving CPU. This information is required by the operating system software to increase the likelihood of its instruction retry routines creating a retryable machine state for the failing instruction.
12. The SP will write the failure symptoms and register data of the receiving CPU into dedicated storage in main memory to be available for the operating system software to access later.
13. The SP will issue a Resume with Fault directive to command the receiving CPU to restart from its suspended state with a parity fault. When the receiving CPU restarts, it will push its state (safestore) from the XRAM 18 into cache and enter the fault handling/instruction retry routines of the operating system software.
14. The operating system software will note the parity fault and examine the information saved in dedicated memory to determine the type of fault. When it is found to be a cache operand error, the operating system software will evaluate the faulting instruction and determine whether it can be retried. The operating system software will use, in some cases, the receiving CPU register information that was obtained by the SP to set preexecution states to increase the chances for a successful retry.
15. If the operating system software determines that the instruction associated with the failure is retryable, it will adjust the state that was pushed onto the safestore stack and restart the failed instruction by instructing the requesting CPU to pop the stack entry. This restart will result in the corrected block being fetched from main memory (FIG. 3, data movement 30A, 30B). The net result is that the affected process is resumed and is completely oblivious to the error.
If a second or third CPU request the same block and received the error signal from the sending CPU, steps 11-15 above would be repeated for each such receiving CPU.
The partitioning of the responsibilities between the CPU, SP and the operating system software is an important consideration in the exemplary implementation, and was determined first upon absolute necessity and then upon component strengths and weaknesses.
Some modest support had to be implemented into the hardware of the exemplary system which must provide the following functionality:
A) Detect the error;
B) Provide information relating to the error (including the identity of the associated cache block);
C) Freeze (halt) the affected BPU in a predictable manner;
D) Alarm the SP;
E) Support directives for:
1) Swapping the cache block;
2) Disabling the cache block (or larger cache subdivision such as a level in the exemplary machine); and
3) Restarting the CPU; and
F) Continue servicing system bus requests throughout the error processing (in order to avoid halting the entire system).
It would at first seem that the CPU hardware should be designed to handle all of these roles without SP intervention. That is, ideally, the CPU itself would automatically swap the block to memory for correction, refetch the corrected block and resume the affected instruction. But those skilled in the art will understand that such an approach is fraught with design error potential and also would sap much of the resources (i.e., designer's time and silicon space) of the system design effort. By distributing the responsibilities among the CPU, the SP and the operating system software, the overall design, development and production costs of the exemplary system, in terms of the commercial physical implementation of the hardware and also in terms of the development effort (the design/implementation responsibilities were not concentrated on one key individual) were significantly reduced. Furthermore, those skilled in the art will readily understand that it is easier to modify software, should bugs be found during early system testing, than to produce new versions of hardware VLSI components. This added flexibility gives the partitioned approach an advantage over concentrating the process in silicon.
The responsibilities of the SP include:
A) Alarm handling;
B) Supervising error processing and correction including:
1) Issuing a directive to determine the block to swap;
2) Issuing a directive to swap the block in error;
3) Handling exceptions that may occur during the swap; i.e., if the error is uncorrectable (e.g., a double bit failure), the SP is programmed to pass this information/status on to the operating system software;
C) Extracting registers from the affected BPU for instruction retry software; and
D) Ensuring that the CPU is in a state that it can be restarted via the issuance of a directive to do so.
It will be noted that the responsibility of the SP does not include determining whether the instruction associated with the failure can be retried. Several factors prohibit it from doing so. First, the algorithms that are required to determine whether some of the more complex instructions in the CPU assembly language instruction set are retryable are extremely complex (and this translates into an extremely large program). Because of expected storage capacity limitations, it was determined that no further storage demands on the SP should be made. In addition, the SP is slow in comparison to the mainframe computer that it supports; therefore with the retry software resident on the mainframe, this processing is much more performant.
The responsibility of the operating system software is primarily that of determining whether or not the affected instruction can be retried. This functionality is enabled after the affected CPU has been restarted with a fault. The operating system software interprets the fault type, and when it is determined to be of the class of error to which the subject invention is directed, it enters its parity fault processing procedure.
The analysis that the operating system software must perform to determine if an instruction can be retried depends on the type of instruction that failed. Essentially, the assembly language instruction set that the exemplary CPU supports consists of instructions that:
1) Load registers from cache;
2) Write to cache;
3) Modify registers;
4) Read, alter, then write into the same cache word;
5) Move cache data from one location to another; and/or
6) Transfer control.
The operating system software instruction retry components analyze these classes of instructions and determine whether a given instruction can be retried in a given circumstance. Superficially, this may seem to be a simple enough task; for example, if a simple "load A-register" (LDA) instruction fails because the data received during the siphon had bad parity, it would be expected that the LDA could be reexecuted following the correction of the cache block. But consider, merely by way of example, what would happen if the LDA had indirect and tally effective address modification associated because the programmer had intended to use this feature to ease implementation of a list search. Then, the operating system software must detect this situation and restore the tally word to its preexecution state. This LDA example is given to illustrate the well known fact that it is the exceptions to the instruction set that make retry algorithms complex.
In the exemplary system, the hardware provides some nontrivial support for recovering from these errors. The hardware provides some register shadowing so that a preexecution value for some registers can be found and used for retry. The truly complex cases (for example, double precision operations) benefit the most from this shadowing. In these complex cases, the operating system software can determine where the preexecution registers reside and use them for the retry. Essentially, the shadowing permits instructions that modify registers to be optimized to the extent that the operation completes, even when corrupt data is read, because a preexecution copy of the registers is available for retry. Without this feature, either these instructions would be deemed unretryable or the CPU's execution would have to be slowed to ensure that, when the corrupt data is detected, the operation is cancelled.
When an instruction can be retried, the operating system software returns control to the affected process, and the process is oblivious to the hardware error. If the instruction cannot be retried or the cache block failure is uncorrectable, then the affected process is terminated.
Attention is now directed to the flow chart of FIG. 4. This flow chart is an alternative disclosure of the invention which will be particularly useful to programmers in practising the invention in an environment similar to that of the exemplary system.
Thus, while the principles of the invention have now been made clear in an illustrative embodiment, there will be immediately obvious to those skilled in the art many modifications of structure, arrangements, proportions, the elements, materials, and components, used in the practice of the invention which are particularly adapted for specific environments and operating requirements without departing from those principles. | A fault tolerant computer system includes at least two central processing units each having a cache memory and a parity error detector adapted to sense parity errors in blocks of information read from and write to cache and to issue a cache parity read or write error flag if a parity error is sensed. A system bus couples the CPU to a System Control Unit having a parity error correction facility, and a memory bus couples the SCU to a main memory. An error recovery control feature distributed across the CPU, including a Service Processor and the operating system software, is responsive to the sensing of a read parity error flag in a sending CPU and a write parity error flag in a receiving CPU in conjunction with a siphon operation for transferring the faulting block from the sending CPU to main memory via the SCU (in which given faulting block is corrected) and for subsequently transferring the corrected memory block from main memory to the receiving CPU when a retry is instituted. | 6 |
BACKGROUND OF THE INVENTION
[0001] The present invention relates to hydrocarbon production treatments. More particularly, the present invention relates to methods and compositions for delaying the release of treatment chemicals. Even more particularly, the present invention is directed toward encaged treatment chemicals and methods of using them in subterranean applications. The term “encaged treatment chemical” refers to a “treatment chemical” that is encaged within a three-dimensional “polymer carrier” so that its release may be delayed.
[0002] In hydrocarbon exploration and production, a variety of treatment chemicals may be used to facilitate the production of the hydrocarbons. These include gel breakers, dispersing agents, and defoamers, among others. Unfortunately, many treatment chemicals may be adversely affected by exposure to the well bore environment before the chemicals reach their desired destinations in the subterranean formation. This can result in the reaction of the treatment chemical within the well bore, which, depending on the treatment chemical, could affect negatively the production potential of the well. The functionality of a particular fluid system may be adversely affected if a treatment chemical is released prematurely.
[0003] To combat these potential production setbacks, a variety of chemical or mechanical methods have been used to inhibit the interaction of the treatment chemical with the well bore environment. Some methods involve physically isolating the treatment chemicals from the well bore environment by injecting the chemicals into the reservoir through coiled tubing or a similar material. Other methods have used porous media to absorb the treatment chemical and then allow it to diffuse out of the media over time. Still other methods have encapsulated the treatment chemical within a degradable coating that degrades down hole to release the treatment chemical at a desired time or place. Several problems exist with conventional encapsulation techniques. For instance, in applications using latexes, rubbers, plastics, or zeolite materials to coat or encapsulate a treatment chemical, inadequate control over the size of pore throats and/or the surface areas of exposed surfaces has prevented consistent, reliable applications. FIG. 1A is an illustration of an encapsulated treatment chemical for a comparative illustration. Shown at 100 is a treatment chemical that is coated by coating 102 . FIG. 1B illustrates some of the problems that can exist with encapsulated treatment chemicals. For example, coating 102 has imperfections 104 . Also, treatment chemical 100 is not completed coated with coating 102 , and therefore, may not be protected from diffusion to the extent necessary to achieve the desired purpose.
[0004] Another conventional method that has been suggested to delay the release of a treatment chemical involves the use of “clathrates,” which is a unique class of chemical compounds in which a rigid, open network of bonded host molecules enclose, without directly chemically bonding to, appropriately-sized guest molecules of another substance. However, development clathrate-based treatment chemicals has been problematic. For example, the release rate is typically such that the treatment chemical is released too slowly to be used as an effective delivery mechanism, if the chemical is released at all. Thus, unable to reliably release the treatment chemical, clathrate-based delivery mechanisms have proven inadequate for hydrocarbon production treatments to date.
SUMMARY OF THE INVENTION
[0005] The present invention relates to hydrocarbon production treatments. More particularly, the present invention relates to methods and compositions for delaying the release of treatment chemicals. Even more particularly, the present invention is directed toward encaged treatment chemicals and methods of using them in subterranean applications.
[0006] In one embodiment, the present invention provides a method comprising: providing at least one encaged treatment chemical that comprises a treatment chemical and a polymer carrier; placing the encaged treatment chemical into a portion of a subterranean formation; and allowing the treatment chemical to diffuse out of the encaged treatment chemical and into a portion of the subterranean formation or an area adjacent thereto.
[0007] In one embodiment, the present invention provides an encaged treatment chemical for use in a subterranean application comprising a subterranean treatment chemical and a polymer carrier.
[0008] The features and advantages of the present invention will be apparent to those skilled in the art. While numerous changes may be made by those skilled in the art, such changes are within the spirit of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] These drawings illustrate certain aspects of some of the embodiments of the present invention, and should not be used to limit or define the invention.
[0010] FIG. 1A is an illustration of an encapsulated treatment chemical for a comparative illustration.
[0011] FIG. 1B illustrates some of the problems that can exist with encapsulated treatment chemicals.
[0012] FIG. 2 is a “cartoon” illustration (e.g., a pictorial representation of an idea) of an embodiment of an encaged treatment chemical of the present invention wherein a monomer is used to form the polymer carrier (shown two-dimensionally to represent a three-dimensional structure).
[0013] FIG. 3 is a “cartoon” illustration of an embodiment of an encaged treatment chemical of the present invention wherein a polymer is used to form the polymer carrier (shown two-dimensionally to represent a three-dimensional structure).
[0014] FIG. 4 illustrates some viscosity data.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0015] The present invention relates to hydrocarbon production treatments. More particularly, the present invention relates to methods and compositions for delaying the release of treatment chemicals. Even more particularly, the present invention is directed toward encaged treatment chemicals and methods of using them in subterranean applications. Because the treatment chemical is encaged within a polymer carrier, the release of the treatment chemical may be delayed so that, inter alia, the treatment chemical is able to be delivered to a specific, desired portion of a subterranean formation before the treatment chemical is substantially released. In preferred embodiments, once the treatment chemical has been delivered to an appropriate location, the treatment chemical is able to interact with components in a subterranean formation, e.g., by diffusing out of the polymer carrier.
[0016] The term “encaged treatment chemical” refers to a “treatment chemical” that is encaged within a three-dimensional “polymer carrier” so that its release may be delayed. The term “encaged” does not imply a particular degree of enclosure of the treatment chemical within the polymer carrier. Both the degree of encagement and the concentration of the treatment chemical in the polymer carrier affect the rate at which the treatment chemical will ultimately be released. Thus, to provide an optimal release, the degree of encagement and the concentration of the treatment chemical in the polymer carrier should be considered. In some embodiments, the treatment chemical may be soluble in the polymeric carrier (e.g., homogeneous); in other embodiments, the treatment chemical may be insoluble (e.g., heterogeneous). In some embodiments, a heterogeneous mixture may have a longer associated delay time for the treatment chemical, depending on, inter alia, the salts present in the mixture. The primary considerations in determining what degree of encagement is appropriate include, but are not limited to: the treatment chemical and its reactivity in the subterranean formation; the treatment chemical and its reactivity in the particular treatment fluids to which it is exposed; the desired delay period before release of the treatment chemical; and the compositions of the treatment chemical and polymer carrier (e.g., vis-à-vis each other).
[0017] The term “treatment chemical” does not imply any particular action by the chemical or a component thereof. A “treatment chemical” may be any component that is to be placed downhole to perform a desired function, e.g., act upon a portion of the subterranean formation, a tool, or a composition located downhole. Any treatment chemical that is useful down hole and that does not adversely react with the polymer carrier may be used as a treatment chemical in the present invention. Suitable treatment chemicals include, but are not limited to, chelating agents (e.g., EDTA, citric acid, polyaspartic acid,), scale inhibitors, gel breakers, dispersants, paraffin inhibitors, wax inhibitors, corrosion inhibitors, de-emulsifiers, foaming agents, tracers, defoamers; delinkers; scale inhibitors, crosslinkers, surfactants, derivatives and/or combinations thereof. For instance, a treatment chemical may be a boron-based crosslinking agent that will be used to crosslink a gelling agent downhole.
[0018] According to the present invention a polymer carrier encages a treatment chemical to form an encaged treatment chemical. The term “polymer carrier” refers to a three-dimensional organic, inorganic or hybrid structure composed of repeat units of a desired chemical functional group that possesses mechanical, chemical and physical properties commiserate with the use of the encaged treatment chemical. The number of the repeat units of the material is not critical, e.g., oligomers may be suitable in some embodiments. In certain embodiments, a polymer carrier may be a three-dimensional polymeric structure that is at least partially capable of encaging a treatment chemical. The polymer carrier may penetrate the treatment chemical. The molecular chains of the polymer carrier may react with themselves so as to entrap the treatment chemical within the resultant three-dimensional polymeric carrier structure. In some embodiments, the polymer carrier may be a three-dimensional hydrated structure that supports a treatment chemical. In other embodiments, the encaging polymer carrier may be dehydrated so that the pockets of polymer collapse around the treatment chemical so that the treatment chemical is released more slowly and only as the polymer rehydrates and slowly swells. The treatment chemical is then likely released at a rate of diffusion generally commiserate to the rate of diffusion of the polymer around the treatment chemical.
[0019] Any method known in the art may be used to create the encaging polymer carrier of the encaged treatment chemicals of the present invention. In some embodiments, a suitable monomer is mixed with a suitable treatment chemical and then the monomer is allowed to polymerize so as to encage the treatment chemical (referred to herein as the “monomer embodiments”). In such monomer embodiments, any known suitable polymerization method (including, but not limited to, free radical polymerization, condensation polymerization, vinyl polymerization, emulsion polymerization, etc.) may be used. In other embodiments of the present invention, a polymer may be mixed with a treatment chemical and then crosslinked around the treatment chemical. In embodiments of the present invention wherein a monomer is made to polymerize to substantially surround a treatment chemical, a mixture comprising the monomer and the treatment chemical are combined along with a polymerization activator such that the monomer polymerizes to eventually form a polymer carrier around the treatment chemical. In some embodiments, a crosslinking agent may also be added to the mixture to cause the formed polymer to have crosslinks. The choice of monomer, polymerization activator, and crosslinking agent (when used) should be made in such a way that the chosen compounds will not negatively interact with the chosen treatment chemical. In that way, the treatment chemical may be at least partially physically trapped within the polymer carrier. In some alternative embodiments of the present invention the treatment chemical may be covalently or otherwise weakly reversibly bonded to the treatment chemical.
[0020] FIG. 2 is a “cartoon” illustration (e.g., a pictorial representation of an idea to convey a point) of an embodiment of an encaged treatment chemical of the present invention wherein a monomer is used to form the polymer carrier. Although it is illustrated two-dimensionally, the structure is actually a three-dimensional structure. In FIG. 2 , A shown by 202 is a treatment chemical, M (at 204 ) denotes a monomer, and XL (at 206 ) denotes a crosslinking agent. The treatment chemical, monomer, and an optional crosslinking agent are placed into a solution, which is shown generally at 208 . A suitable polymerization activator is added, and an encaged treatment chemical (shown generally at 210 ) is produced. As illustrated in a cartoon fashion at 210 , the treatment chemical A is embedded within pockets of the three-dimensional polymer carrier formed by the interactions and polymerizations of M and XL. Note that the pockets may be interpolymer pockets or intrapolymer pockets. The term “pocket” as used herein refers to an opening between molecular chains.
[0021] In the monomer embodiments, a variety of monomers may be suitable. Examples include, but are not limited to, acrylamide; styrene; butadiene; methacrylate; N-isopropyl acrylamide; N,N-dimethyl acrylamide; methacrylamide; and, methylacrylate. Acrylamide is a preferred monomer. Other monomers known in the art that are capable of being polymerized also may be suitable for use in the present invention. Examples include anionic monomers (such as sodium acrylate) or cationic polymers (such as trimethyl allyl ammonium chloride and dimethyl diallyl ammonium chloride). One should be mindful that ionic attraction between the monomer/polymer and the treatment chemical may affect the diffusion rate of the treatment chemical. Selection of an appropriate monomer may be based, at least in part, on the environment in which the encaged treatment chemical is to be used. For example, it may be important to consider whether the treatment chemical will be released into an oil-based or water-based environment. Moreover, the choice of a monomer may depend on the treatment chemical. For example, a hydrophobic monomer may be used with a water-soluble treatment chemical, while a hydrophilic monomer may be preferred for an oil-soluble treatment chemical. In other cases, hydrophobic monomers may be combined with hydrophilic monomers to tune the release of the encaged treatment chemical through the resultant polymer carrier. For example, creating polymer gels whose surface is more hydrophobic, thereby slowing the hydration with water, may slow the diffusion rate. With the benefit of this disclosure, it should be within the ability of one skilled in the art to select an appropriate monomer. In some embodiments of the present invention the monomer is present in the mixture used to create the encaged treatment chemical in an amount ranging from about 10% to about 60% of the mixture. In some embodiments of the present invention the monomer is present in the mixture in an amount ranging from about 15% to about 35% of the mixture.
[0022] In some embodiments, a variety of polymerization activators may be used in the monomer embodiments of the methods of the present invention. In one embodiment, wherein the monomer is to be polymerized using free-radical polymerization, the polymerization activator may comprise a free-radical source. Generally, suitable free-radical sources are thermal free-radical initiators. Some suitable free-radical sources include, but are not limited to, sodium persulfate, sodium, potassium or organic peroxides, and sodium or potassium perborate bis azo compounds (“AIBN”). In other embodiments, a suitable polymerization activator may be a physical catalyst such as heat, time, or mechanical shear. In embodiments wherein the polymerization activator is a free radical source, a chain-transfer agent may be used to make the free-radical source more active. Generally, the chain-transfer agent forms an N-oxide that is capable of reacting with a free-radical source to form a stabilized free radical, thus lengthening the lifetime of the free radical. Any water soluble amine may be used as a suitable chain-transfer agent, including triethanolamine, spermidine, pyridine, and N-methylmorpholine.
[0023] In the monomer embodiments, optionally, a suitable crosslinking agent may be included so that crosslinks between polymeric molecules are incorporated within the three-dimensional structure of the polymer carrier. Suitable crosslinking agents typically comprise at least one ion that is capable of crosslinking at least two polymer molecules. Examples of suitable crosslinking agents include, but are not limited to, boric acid, disodium octaborate tetrahydrate, sodium diborate, pentaborates, ulexite and colemanite, compounds that can supply zirconium IV ions (such as, for example, zirconium lactate, zirconium lactate triethanolamine, zirconium carbonate, zirconium acetylacetonate, zirconium malate, zirconium citrate, and zirconium diisopropylamine lactate); compounds that can supply titanium IV ions (such as, for example, titanium lactate, titanium malate, titanium citrate, titanium ammonium lactate, titanium triethanolamine, and titanium acetylacetonate); aluminum compounds (such as, for example, aluminum lactate or aluminum citrate); antimony compounds; chromium compounds; iron compounds; copper compounds; zinc compounds; or a combination thereof. An example of a suitable commercially available zirconium-based crosslinking agent is “CL-24” available from Halliburton Energy Services, Inc., Duncan, Okla. An example of a suitable commercially available titanium-based crosslinking agent is “CL-39” available from Halliburton Energy Services, Inc., Duncan Okla. When used, the crosslinking agent is generally included with the treatment chemical and monomer in an amount ranging from about 10% to about 40% of the total mixture. In some embodiments, the crosslinking agent is included with the treatment chemical and monomer in an amount ranging from about 15% to about 35% of the total mixture.
[0024] In alternative embodiments, rather than starting with a monomer to form an encaged treatment chemical, a polymer may be used (referred to as the “polymer embodiments.”) FIG. 3 is a “cartoon” illustration of such an embodiment. Suitable polymer molecules are marked as G and shown at 302 . These molecules may be mixed with an (optional) crosslinking agent (XL) and a treatment chemical (A) to form an encaged treatment chemical shown generally at 304 . The treatment chemical A shown at 306 is embedded within pockets of the three-dimensional polymer carrier formed by the interactions and polymerizations of the polymer molecules (G) and the crosslinking agent (XL).
[0025] In the polymer embodiments, a variety of polymers may be suitable. Suitable polymers typically comprise polymers, synthetic polymers, or a combination thereof. Examples include, but not limited to, hydratable polymers that contain one or more functional groups such as hydroxyl, cis-hydroxyl, carboxylic acids, and derivatives of carboxylic acids, sulfate, sulfonate, phosphate, phosphonate, amino, or amide. In certain exemplary embodiments, the polymers may comprise polysaccharides, and derivatives thereof that contain one or more of the following monosaccharide units: galactose, mannose, glucoside, glucose, xylose, arabinose, fructose, glucuronic acid, and pyranosyl sulfate. Examples of suitable polymers include, but are not limited to, guar gum and derivatives thereof, such as hydroxypropyl guar and carboxymethylhydroxypropyl guar, and cellulose derivatives, such as hydroxyethyl cellulose. Additionally, synthetic polymers and copolymers that contain the above-mentioned functional groups may be used. Examples of such synthetic polymers include, but are not limited to, polyacrylate, polymethacrylate, polyacrylamide, polyvinyl alcohol, and polyvinylpyrrolidone. In other exemplary embodiments, the polymer may be somewhat depolymerized. The term “depolymerized,” as used herein, generally refers to a decrease in the molecular weight of the polymer. Depolymerized polymers are described in U.S. Pat. No. 6,488,091 issued Dec. 3, 2002 to Weaver, et al., the relevant disclosure of which is incorporated herein by reference.
[0026] In the polymer embodiments, optionally a crosslinking agent may be used. A variety of crosslinking agents may be suitable. Examples of suitable crosslinking agents include, but are not limited to, boric acid, disodium octaborate tetrahydrate, sodium diborate, pentaborates, ulexite and colemanite, compounds that can supply zirconium IV ions (such as, for example, zirconium lactate, zirconium lactate triethanolamine, zirconium carbonate, zirconium acetylacetonate, zirconium malate, zirconium citrate, and zirconium diisopropylamine lactate); compounds that can supply titanium IV ions (such as, for example, titanium lactate, titanium malate, titanium citrate, titanium ammonium lactate, titanium triethanolamine, and titanium acetylacetonate); aluminum compounds (such as, for example, aluminum lactate or aluminum citrate); antimony compounds; chromium compounds; iron compounds; copper compounds; zinc compounds; or a combination thereof. An example of a suitable commercially available zirconium-based crosslinking agent is “CL-24” available from Halliburton Energy Services, Inc., Duncan, Okla. An example of a suitable commercially available titanium-based crosslinking agent is “CL-39” available from Halliburton Energy Services, Inc., Duncan Okla. When used, the crosslinking agent is generally included with the treatment chemical and polymer in an amount ranging from about 10% to about 40% of the total mixture. In some embodiments, the crosslinking agent is included with the treatment chemical and polymer in an amount ranging from about 15% to about 35% of the total mixture.
[0027] In alternative embodiments, the treatment chemical may be impregnated into a polymer carrier. In an example of such an embodiment, a polymeric bead (e.g., polystyrene bead) may be swelled with a suitable solvent so that the pores of the bead are enlarged. A treatment chemical may then be added to the mixture. The treatment chemical should become trapped in the pores of the polymeric carrier. The polymeric carrier may then be collapsed so that the pores shrink. When added to a well bore, the polymeric carrier may swell so as to release the treatment chemical from its pores. Any polymers mentioned above may be used in these embodiments of the present invention. Examples of suitable polymeric materials include, but are not limited to, latexes, polystyrenes, polyvinyl chlorides, polyesters, polyolefins, polycarbonates, and polybutadienes. Some specific examples include, but are not limited to, Wang resins (4-benzyloxybenzyl alcohol, polymer bound), Janda Jel-NH2 resins (polystyrene cross-linked with a tetrahydrofuran linker (Aldrich Chemical Company, St. Louis, Mo.)), and Merrifeld resins (chloromethylated polystyrene). Preferred cross-linked polystyrene derivatives for use in the present invention include halomethyl, amino, or hydroxy derivatives. Each of these are specific examples of crosslinked polystyrene derivatives with preferable derivatives being the halomethyl, amino or hydroxy groups, and copolymers or terpolymers thereof.
[0028] In any of the above mentioned embodiments, the rate of diffusion of the treatment chemical from an encaged treatment chemical may be tailored through the addition of a salt to the polymer carrier. Generally, the more endothermic the chosen salt, the longer it takes for the resulting polymer carrier to release the treatment chemical. Thus, salts having an endothermic heat of dilution in water may be suitable. Such suitable salts include, but are not limited to, potassium chloride, cesium chloride, and ammonium chloride. Further details on the effect of a chosen salt on the rate of diffusion can be found in the examples, below. Others skilled in the art, with the benefit of this disclosure, should be able to identify other suitable salts.
[0029] Some embodiments of the encaged treatment chemicals of the present invention may also include other additives such as a pH adjusting agent (such as a buffer like potassium carbonate or ammonium acetate) or a caustic agent (like sodium hydroxide, potassium hydroxide, ammonium hydroxide). Generally, a caustic agent may react with the treatment chemical to generate a form of the treatment chemical suitable for release from the polymer carrier. For example, in the case of a boron treatment agent, a high concentration of caustic agent results in the formation of sodium tetraborate, which should equilibrate with the solution upon release, further contributing to the delay of the treatment chemical reacting with the formation. Also for example, in the case of ethylenediaminetetraacetic acid (“EDTA”), the caustic agent forms tetracarboxylate, which may be used for chelating and delinking fluids with zirconium or titanium crosslinks. Suitable caustic agents include, but are not limited to, sodium hydroxide, potassium hydroxide, and ammonium hydroxide. Further details on the effect of pH on the rate of diffusion can be found in the examples, below.
[0030] Once an encaged treatment chemical has been formed by any suitable method, it may be used in that form or, alternatively, it may be dehydrated and ground to a suitable size for use down hole. Generally, the dehydration process involves vacuum drying. The grind size provides a further variable through which to control the diffusion of the treatment chemicals out of the polymer carrier. Where the mixture is dried and ground, the selected grind size may range from about 4 to about 100 mesh U.S. Sieve Series. For example, in embodiments wherein the treatment chemical is a boric acid crosslinker, a larger grind size of about 8 to about 10 mesh standard U.S. Sieves may be selected. In certain embodiments, the size of particles separated with sieves may be selected based on the desired crosslink time (for further detail, see Table 6 in the examples). In other embodiments, the cage material may be added without dehydration (therefore no grinding is necessary). In such embodiments the material may be added to the treatment fluid as an emulsion or slurry.
[0031] In particular embodiments of the present invention, computer simulation software may be used to select the proper mixture of chemicals used to form an encaged treatment chemical and its associated polymer carrier so that the encaged treatment chemical exhibits or demonstrates the desired characteristics. An example of one such piece of simulation software is Formulation Assisted Software Toolkit (“FAST”) available from Accelrys, Inc., of San Diego, Calif., which includes algorithms for statistically optimizing and planning new formulations that exhibit specific measurable properties, such as time to crosslink or delink a given formulation, among others.
[0032] To facilitate a better understanding of the present invention, the following examples of certain aspects of some embodiments are given. In no way should the following examples be read to limit, or define, the scope of the invention.
EXAMPLES
[0033] The following examples involve encaging a treatment chemical (in this case, specifically a boron crosslinking agent) inside a polymer carrier according to the present invention. The experiments below, inter alia, looked at the amount of time it took the boron crosslinking agent to diffuse from the polymer carrier and crosslink a fluid.
[0034] Viscosified treatment fluid samples were prepared and the viscosities of the samples were measured over time with increasing temperatures using a Nordman Instruments Model 5004 viscometer equipped with a B5X bob. The samples included either crosslinked gelling agents crosslinked with mineral salts of boric acid (which is commercially available from Halliburton Energy Services, Duncan, Okla. as CL-28) or boric acid trapped within a polymer carrier of the present invention. Comparative test samples were prepared such that the active concentration of CL-28 and the polymer carrier contained substantially identical active boron concentrations.
Example 1
Crosslinking with Encaged Boric Acid
[0035] A sample of a boron crosslinked gelling agent viscosified treatment fluid was prepared by adding the following to tap water: 40 lb/MGAL guar gum; 2.25 gal/MGAL sodium hydroxide; and 1 gallon of a nonionic surfactant. As a control, 1.4 gal/MGAL CL-28, a conventional mineral based, slow dissolving boric acid, was used to crosslink the fluid. For comparison, the cage trapped boric acid (2 g/L boric acid in polymer carrier) was used to crosslink an identical fluid.
[0036] The temperatures of the samples were increased to 225° F., and their viscosities were measured. The results appear in FIG. 4 , below, which illustrates the change in viscosity of the two fluids. The delayed action of the encaged boric acid can be seen by comparing the crosslinked viscosities of the two fluids. In particular, a review of FIG. 1 at about 4 minutes and about 15 minutes is interesting. For the control sample, a viscosity of 669 cP was obtained after only four minutes. For the encaged boric acid sample, a viscosity of 669 cP was only obtained after 15 minutes. These results illustrate a delay in the encaged boric acid sample. Moreover, surprisingly the encaged boric acid sample showed a steady increase in viscosity with time, contrasting this with the control sample, which achieved a peak viscosity and then immediately began to reduce viscosity to less than half of that peak before rebuilding.
Example 2
Demonstration of Changing Static Crosslink Time at 120° F.
[0037] To form an encaged treatment chemical (in this case, specifically a boron crosslinking agent) the following general procedure was followed:
[0038] A brine was selected and mixed with a monomer (specifically, acrylamide), a crosslinking agent (specifically, N,N methylenebisacrylamide), a treatment chemical (specifically, boric acid), and a chain transfer agent (specifically, triethanolamine). Next, the pH was adjusted to a desired level (in all cases except those illustrated in Table 4) the pH was adjusted to about 8. A polymerization activator (sodium persulfate) was added, then placed in a temperature controlled water bath (in all cases except those illustrated in Table 6, the temperature was adjusted to about 120° F.).
[0039] Each of the tables below describes the results of modifying the polymer carrier by changing one or more variables. Altering one or more of the conditions in Tables 1 through 7 may permit optimization of the system to the desired application. Cage samples were screened using static crosslink time tests. The crosslink time was measure in seconds and is shown in
TABLE 1 Crosslink Time by Changing Alkali Metal Cation N,N Boric Sodium Salt Crosslink Acrylamide, methylenebisacrylamide, Acid, Persulfate, Salt Loading, Time, (moles) (moles) (moles) (moles) Type (moles) (sec) 0.25 0.02 0.24 0.0042 LiCl 0.23 648.00 0.25 0.02 0.24 0.0042 KCl 0.23 662.00 0.25 0.02 0.24 0.0042 CsCl 0.23 716.00
[0040]
TABLE 2
Crosslink Time by Changing KCl Concentration
N,N
Boric
Sodium
Acrylamide,
methylenebisacrylamide,
Acid,
Persulfate,
KCl,
Crosslink Time,
(moles)
(moles)
(moles)
(moles)
(moles)
(sec)
0.25
0.016
0.24
0.0042
0.5635
712
0.25
0.016
0.24
0.0042
0.3756
592
0.25
0.016
0.24
0.0042
0.2348
648
0.25
0.016
0.24
0.0042
0.1878
861
0.25
0.016
0.24
0.0042
0.1409
488
0.25
0.016
0.24
0.0042
0.0470
891
0.25
0.016
0.24
0.0042
0.0094
838
[0041]
TABLE 3
Crosslink Time by Changing Sodium Persulfate Concentration
N,N
Boric
Sodium
Acrylamide,
methylenebisacrylamide,
Acid,
Persulfate,
KCl,
Crosslink Time,
(moles)
(moles)
(moles)
(moles)
(moles)
(sec)
0.25
0.02
0.24
0.0252
0.19
264
0.25
0.02
0.24
0.0168
0.19
503
0.25
0.02
0.24
0.0084
0.19
753
0.25
0.02
0.24
0.0042
0.19
663
0.25
0.02
0.24
0.0021
0.19
786
[0042]
TABLE 4
Crosslink Time by Changing pH of Cage Solution
N,N
Boric
Sodium
Acrylamide,
methylenebisacrylamide,
Acid,
Persulfate,
KCl,
Crosslink
pH
(moles)
(moles)
(moles)
(moles)
(moles)
Time, (sec)
8
0.27
0.0065
0.24
0.0042
0.02
44
4
0.27
0.0065
0.24
0.0042
0.02
440
12
0.27
0.0065
0.24
0.0042
0.02
978
[0043]
TABLE 5
Crosslink Time by Changing Grind Size
N,N
boric
sodium
crosslink
Grind size,
Acrylamide,
methylenebisacrylamide,
acid,
persulfate,
KCl,
time,
(microns)
(moles)
(moles)
(moles)
(moles)
(moles)
(sec)
53
0.25
0.02
0.24
0.0042
0.56
433
106
0.25
0.02
0.24
0.0042
0.56
426
250
0.25
0.02
0.24
0.0042
0.56
102
420
0.25
0.02
0.24
0.0042
0.56
274
850
0.25
0.02
0.24
0.0042
0.56
324
1000
0.25
0.02
0.24
0.0042
0.56
369
1400
0.25
0.02
0.24
0.0042
0.56
649
2000
0.25
0.02
0.24
0.0042
0.56
854
[0044]
TABLE 6
Crosslink Time by Changing the Cage Synthesis Temp
Cage
N,N
boric
sodium
crosslink
Synthesis
acrylamide,
methylenebisacrylamide,
acid,
persulfate,
KCl,
time,
Temp, (° F.)
(moles)
(moles)
(moles)
(moles)
(moles)
(sec)
80
0.13
0.0084
0.13
0.0022
0.30
739.00
90
0.13
0.0084
0.13
0.0022
0.30
784.00
100
0.13
0.0084
0.13
0.0022
0.30
715.00
110
0.13
0.0084
0.13
0.0022
0.30
744.00
120
0.13
0.0084
0.13
0.0022
0.30
792.00
140
0.13
0.0084
0.13
0.0022
0.30
750.00
150
0.13
0.0084
0.13
0.0022
0.30
761.00
160
0.13
0.0084
0.13
0.0022
0.30
736.00
170
0.13
0.0084
0.13
0.0022
0.30
800.00
180
0.13
0.0084
0.13
0.0022
0.30
713.00
190
0.13
0.0084
0.13
0.0022
0.30
682.00
200
0.13
0.0084
0.13
0.0022
0.30
641.00
[0045]
TABLE 7
Changing Monomer (moles), Crosslink Time (seconds)
N,N
boric
sodium
crosslink
methylenebisacrylamide,
acid,
persulfate,
time,
Monomer #1
Monomer #2
(moles)
(moles)
(moles)
(sec)
acrylic acid,
none
0.008
0.128
0.002
289
0.128 moles
acrylamide,
sodium acrylate,
0.008
0.128
0.002
451
0.101 moles
0.021 moles
acrylamide,
N,N-
0.015
0.128
0.002
476
0.104 moles
dimethylacrylamide,
0.017 moles
acrylamide
none
0.008
0.128
0.002
556
(not
dehydrated),
0.129 moles
acrylamide,
none
0.013
0.192
0.006
607
0.196 moles
acrylamide,
N,N-
0.013
0.192
0.006
632
0.157 moles
dimethylacrylamide,
0.032 moles
acrylamide,
none
0.008
0.128
0.002
642
0.129 moles
acrylamide,
N,N-
0.013
0.192
0.006
646
0.157 moles
isoproplyacrylamide,
0.029 moles
acrylamide,
methylmethacrylate,
0.013
0.192
0.006
672
0.157 moles
0.032 moles
acrylamide,
methyl acrylate,
0.008
0.128
0.002
681
0.100 moles
0.024 moles
acrylamide,
N,N-
0.008
0.128
0.002
681
0.100 moles
isoproplyacrylamide,
0.019 moles
acrylamide,
methyl acrylate,
0.013
0.192
0.006
682
0.157 moles
0.039 moles
acrylamide,
none
0.008
0.128
0.002
692
0.129 moles
acrylic acid,
none
0.008
0.128
0.002
753
0.155 moles
[0046] Therefore, the present invention is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. While numerous changes may be made by those skilled in the art, such changes are encompassed within the spirit of this invention as defined by the appended claims. The terms in the claims have their plain, ordinary meaning unless otherwise explicitly and clearly defined by the patentee. | A method comprising: providing at least one encaged treatment chemical that comprises a treatment chemical and a polymer carrier; placing the encaged treatment chemical into a portion of a subterranean formation; and allowing the treatment chemical to diffuse out of the encaged treatment chemical and into a portion of the subterranean formation or an area adjacent thereto. | 2 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional Patent Application No. 60/527,275 filed Dec. 8, 2003.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates generally to physical connectivity of Ethernet device, and more particularly, to the ability to communicate over the Ethernet using 10 Mbps or 100 Mbps transmission rates over distances that are 5 to 10 times longer then the current standards.
[0004] 2. Prior Art
[0005] Ethernet connectivity based on the 10BASE-T and 100BASE-TX standards (known as IEEE standard 802.3) is one of the most important technologies in the networking industry today. These standards enable Ethernet communication at 10 Mega bits per second (Mbps) and 100 Mbps respectively. To enable this connectivity, a device transferring the generally digital signaling to signals that can be transmitted over larger distances is used. This device is responsible for the physical layer, which is the first layer of the standard communication model, and is often referred to as the PHY device, which is considered to be one of the key components in the Ethernet solution. It is the characteristics of the PHY that determine the system's capabilities to communicate over the distances mandated by the various Ethernet standards.
[0006] In the past decade, due to the rapid increase in the use of the Internet, 10/100 Mbps installations of Ethernet ports have increased exponentially, and the trend continues. With Ethernet being for all practical purposes the network solution of choice for enterprises, campus LAN, small offices and home offices as well as other networked industry applications, this trend is even stronger. In turn, these lead to the tremendous demands for 10BASE-T and 100BASE-TX Ethernet PHY devices, both single port and multi-port.
[0007] However, it is not only a numbers game for the 10BASE-T and 100BASE-TX, i.e., the number of ports actually installed. There is a strong trend for a demand for new and higher requirements from features and performance. For example, new features like Power-over-Ethernet, automatic cable diagnostics, polarity and medium dependent interface (MDI) and MDI crossover (MDIX) automatic correction, and so on, as well as higher performance requirements on power consumption, footprint, reliability, tolerance on temperature and power supply, surge and electrostatic discharge (ESD) protection, and the like, are commonly required in new Ethernet deployment.
[0008] Another important requirement is that of connectivity distance, a challenge facing a significant problem. Due to the fact that 10BASE-T and 100BASE-TX Ethernet standard (IEEE 802.3) was developed almost twenty years ago, the PHY devices developed based on that standard have a driving distance of 100 to 150 meters (without using a repeater), over a shielded or unshielded twisted pair. At that time this was considered a long enough distance for all the foreseeable and practical applications. However, as 10/100 Mbps Ethernet is used in more and more types of environments and scenarios, and the cost and ease of deployment is getting more and more important, the originally specified encoding schemes and the driving distances are hindering efficient deployment in an increasing number of situations. With requirements of up to 300 meters for 100BASE-TX and up to 500 meters for 10BASE-T for Ethernet connectivity, it can easily be shown that the IEEE standard (802.3) cannot support these driving distance requirements.
[0009] It would therefore be advantageous to provide a PHY that would be fully backward compatible with the existing 10BASE-T and 100BASE-TX PHY devices, but provide a significantly extended driving distance using a shielded or unshielded twisted pair. It would be further advantageous if such new PHY device would be capable of an auto-negotiation protocol to enable automatic switching between normal and long-range operation.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 is a schematic block diagram of an extended range PHY in accordance with the disclosed invention.
[0011] FIG. 2 is a timing diagram of various bit encoding schemes.
[0012] FIG. 3 is an exemplary signal chart for the operation of the pre-emphasis function.
[0013] FIG. 4 is an exemplary flowchart of the range detection portion for the setting of the PHY.
[0014] FIG. 5 is a distance chart comparing standard Ethernet distances to distances achieved in a system in accordance with the disclosed invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0015] Reference is first made to FIG. 1 where a non-limiting exemplary block diagram 100 of an extended range physical layer device (PHY) is shown. The PHY 100 comprises several blocks that are commonly used in the industry as well as certain unique or modified blocks that enable an extended range beyond the original definitions of the 10BASE-T and 100BASE-TX standards as defined by IEEE 802.3 for transmission over a shielded or unshielded twisted pair.
[0016] Block 110 comprises the interface between the physical layer, i.e., the actual wires that transmit the physical signals, and the media access device (commonly referred to as MAC). In addition, the block contains first-in first-out (FIFO) buffers to handle the traffic between the PHY and MAC devices. Traffic is bi-directional, i.e., data may be sent from the PHY to the MAC when data is received on the wires, as well as data may be sent from the MAC to the PHY for the purpose of transmitting such data over the physical wires. An auto crossover polarity and energy detector 190 is used to ensure that the polarity of the connectivity corresponds to the correct direction of communication over the twisted pair. This avoids the need to have a separate uplink port, and has become a standard unit in modern PHY implementations. The energy detector provides further indication of the energy provided by a signal received by PHY 110 , and may be further used by the DSP of block 170 as explained in more detail below.
[0017] Blocks 120 and 150 handle the transmit and receive functions for both 10 and 100 Mega bits per second (Mbps) transmission. For 10 Mbps, transmission and reception blocks 120 and 150 implement all the functionalities in the physical link signaling (PLS) unit and some of the functionalities in the media access unit (MAU) sub-layer. These include Manchester encoding, Manchester decoding, Input and Data Valid function, Error Sense function, Carrier Sense function, Collision Presence function, Input and Output function, Jabber function, SQE Message Test function, Loop-back function, and Clock and Data Recover function. For 100 Mbps transmission and reception blocks 120 and 150 implement all the functionalities in the physical coding sub-layer (PCS) such as 100BASE-TX, 100BASE-FX and 10/100BASE-LR, including the 4-bit/5-bit (4 b/5 b) encoding/decoding functions. Furthermore, they implement the state diagrams of Transmit Bits, Transmit, Receive Bits, Receive and Carrier Sense.
[0018] Blocks 130 and 160 handle the transmit and receive, respectively, of the physical medium attachment (PMA) and the physical medium dependent (PMD) sub-layer functions. These blocks implement functions such as scrambling and de-scrambling, MLT-3 encoding and decoding for 100 Mbps, 1:2 multiplexing and 2:1 multiplexing for 10 and 100 Mbps modes, converting the PCS sub-layer's non-return to zero (NRZ) format data to PMA sub-layer's NRZI format data. It also implements the Far End Fault Indication (FEFI) function that includes the Far End Fault Generate state diagram and Far End Fault Detect state diagram.
[0019] In order to extend the transmit distance when the device works in the regular 100BASE-TX mode, a digital signal processor (DSP) is integrated with the digital to analog converter (DAC) 140 for the purpose of performing a pre-emphasis function. A DSP is also integrated as part of the receiver analog to digital converter (ADC) and equalizer 170 . Based on information processed by the DSP of ADC 170 , the DSP of DAC 140 and the specific settings, discussed in more detail below, a decision is made on the specific use of the pre-emphasis function of DAC 140 . Once the DSP pre-emphasis setting is changed such as a new setting or from no pre-emphasis to pre-emphasis, auto-negotiation takes place if this function is enabled; otherwise, a procedure of forcing the link down for 1200 to 1500 milliseconds and then transmit idle takes place. This takes place in order to make the link partner recognize the link down event and re-start the linkup procedure from the beginning. A more detailed explanation of the pre-emphasis function is provided below. In a preferred embodiment of this invention, devices on both ends of the link have long-range capabilities and therefore the DSP of ADC 170 is capable of detecting these capabilities and allowing a greater distance of operation.
[0020] Reference is now made to FIG. 2 where a timing diagram of bit coding schemes is shown. A stream of input bits 210 must be first serialized and then transmitted over the transmission lines. Over time, various schemes have been developed in order to obtain better signal-to-noise ratios (SNR). It is desirable to have a high as possible SNR to guarantee a high quality of communication, i.e., reducing the bit error rate (BER) that requires re-transmission of data, effectively reducing the network bandwidth. For 10 Mbps and 100 Mbps, the coding commonly used are those of non-return to zero (NRZ) 220 , non-return to zero inverted (NRZI) 230 , Manchester coding 240 and multi-level transmit-3 levels (MLT3) 250 . The NRZ scheme is commonly used in low-speed communications but has the problem of long sequences of ‘0’s or ‘1’s that would cause the clock extraction to be practically impossible, as it is quite common to have long series of zeros or ones. Therefore it is common to find the use of the Manchester encoding instead. In the Manchester coding there will always be a transition at the center of the bit to indicate its value, for example, transition from ‘1’ to ‘0’ denoting a logical ‘0’ value and a ‘0’ to ‘1’ transition to denote a ‘1’ value. Manchester encoding guarantees transitions on both “1” and “0”, however, this naturally causes the system to operate at a higher frequency as seen in the example. The MLT3 introduces three levels to transmit the data over the lines. For MLT3 Encoding scheme, a bit “ 0 ” is encoded as no transition (keeping the same signal level); a bit “ 1 ” is encoded as a signal level transition of low to middle, or middle to high, or high to middle, or middle to low, depending on the previous transition. Both MLT3 and NRZI guarantee transition on “1”, but MLT3 is favorable due to electromagnetic interference (EMI) considerations.
[0021] In high-speed Ethernet, such as 1 Giga bit per second (Gbps) and above, another coding scheme is used, commonly referred to as pulse amplitude modulation, and for short PAM4 or 4PAM. According to this coding scheme a symbol is sent each clock and a symbol consists of two bits at a time. As can be seen in the example signal 260 in FIG. 2 , each symbol, i.e., ‘00’, ‘01’. ‘10’, and ‘11’, has its unique level in the transmission. This effectively halves the frequency of symbols to achieve the same data rate. While normally PAM4 is used for its superior SNR qualities for high bit rate systems, the inventors have found that applying this coding scheme on 10 and 100 Mbps Ethernet, extends significantly the range in which a 10 Mbps and 100 Mbps systems can operate. Specifically, the delta achieved in signal to noise ratio (SNR), is used to achieve a longer transmission distance.
[0022] Initially it is necessary for a device designed in accordance with this invention to detect whether the other device is capable of supporting long-range capabilities. IEEE 802.3 defines an auto-negotiation procedure so that two link partners are able to automatically negotiate a commonly acceptable link speed (e.g., 10 Mbps or 100 Mbps), duplex modes (half duplex or full duplex) and other features. By extending the protocol, for example through the use of the DSP units in DAC 140 and ADC 170 , it is possible to detect the distance between the two units. While the distance could be determined in various ways, one method is to measure the energy of the signal to estimate the distance it has traveled. While not very accurate, it is also not necessary to be a very accurate measurement, but rather good enough for the purposes of deciding which of the communication algorithms to use. By having simulations of typical signal energy patterns for various distances, the system can estimate that distance and the algorithm may decide which of the transmission protocols to select.
[0023] If the two units are at a distance that is above the standard but below a first range, then the pre-emphasis may be used to reach the higher distance. This will commonly occur if on one side, the device is designed in accordance with the disclosed invention, while the other device is a standard PHY. If the distance is longer than such first range then it can be assumed, and thereafter confirmed, that the other side also has a PHY designed in accordance with the disclosed invention, or otherwise is PAM4 enabled, and therefore setting for PAM4 communication should take place. With PAM4 encoding, the system is capable of communication in ranges of 500 meters and above.
[0024] Reference is now made to FIG. 3 where a signal diagram of an NRZ signal before ( 310 , 315 ) and after ( 320 , 325 ) the pre-emphasis process is shown. When the DSP of the receiver analog to digital converter (ADC) and equalizer 170 indicates that a certain level of transmit pre-emphasis is needed, the DSP of DAC 140 performs a pre-emphasis on the data to be transmitted by the analog transmitter. Signals 310 and 315 are the signals sent before pre-emphasis is performed. If pre-emphasis is necessary, signals 310 and 315 are modified by the pre-emphasis process and output as signals 320 and 325 respectively. As can be seen in FIG. 3 , pre-emphasis effectively modifies the signal levels of adjacent bits (two or more) having the same value, i.e., a certain emphasis to the signal is added bringing it above the absolute value of the originally to be transmitted signal. The number of bits and the magnitude of changes in the levels may be determined by the distances between the two link partners which are provided by the DSP of the receiver analog to digital converter (ADC) and equalizer 170 . The pre-emphasis itself is implemented using a finite impulse response (FIR) type filter such as:
y ( n )= a 0 x ( n )+ a 1 x ( n− 1)+ a 2 x ( n− 2)+ . . . + a k x ( n−k )
where y(n) is the output of the pre-emphasis block and x(n) is the input to the pre-emphasis block.
[0027] In a preferred embodiment, the pre-emphasis level is programmable. Therefore it is possible to have a signal with pre-emphasis that is not necessarily beyond the spec. Also, the signal only needs to be within the specification requirements as received by the link partner. Thus momentary pre-emphasis above specification limits for the purpose of decreasing the rise time of the signal as received by the link partner within specification limits can be implemented. Also, in FIG. 3 , pre-emphasis for an entire bit time is indicated, though this is not a limitation of the invention. Pre-emphasis may be longer, or more likely, shorter in duration as desired.
[0028] Reference is now made to FIG. 4 where a non-limiting exemplary flowchart 400 of the range detection portion of the setting of the PHY designed in accordance with the disclosed invention is shown. In step S 410 the distance between the PHY devices is detected. This can be initiated by a master PHY device that is responsible for the determination of the distance. In step S 420 it is determined whether the distance is within the distances supported by the IEEE 802.3 standard for either 10BASE-T or 100BASE-TX, and if it is not, special setting is required, as the default setting is for the standard operation mode; otherwise, execution continues with step S 430 . In steps S 430 it is determined if the range is above a predetermined value, for example 500 meters. If the range is below that threshold distance, i.e., above the range defined by IEEE 802.3 but less then the predetermined extended range, the execution continues with step S 440 where the device is set to activate the pre-emphasis function, as explained above; otherwise, execution continues with step S 450 . In step S 450 the device is set to enable the PAM4 coding and encoding which allows for operation beyond the predetermined extended threshold and to a long-range of 500 meters or more. A person skilled-in-the-art would appreciate that it would be possible, for example, to enable PAM4 coding and encoding if the transmission originally was detected as requiring only pre-emphasis but still fails to communicate properly. Further, if when NRZ coding with pre-emphasis is called for, it is determined that the other device is not enabled for NRZ coding with pre-emphasis, a check can then be made for possible PAM4 coding enablement of the other device, and if found, both devices switched to PAM4 coding.
[0029] Referring to FIG. 5 , there is shown a table of distances comparing the distance advantage of the disclosed invention over prior art solutions. For 10 Mbps data rate the standard requires operation up to the range of 150 meters. By using the PAM4 encoding, the disclosed system is capable of reaching at least a distance of 500 meters. For 100 Mbps data rate the standard 150 meters is extended to at least 200 meters by the use of the disclosed pre-emphasis technique, and to at least 300 meters when PAM4 coding is used.
[0030] The foregoing disclosure is of a preferred embodiment of the invention. It should be understood that other embodiments will be apparent to those skilled in the art, and that the various aspects of the invention may be practiced in sub-combinations as desired. Thus while a preferred embodiment of the present invention has been disclosed and described herein for purposes of illustration and not for purposes of limitation, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention. | Signaling and coding methods and apparatus for long-range 10 and 100 mbps Ethernet transmission. In accordance with the method, a physical layer (PHY) device is provided that includes the long-range capabilities. In operation, the PHY measures the distance to a companion PHY, and if it is within the specification limits, communicates with the companion device in the normal way. If the distance is above the specification limits, the PHY checks to see if the companion PHY is similarly enabled, and if so, switches to a long-range signaling method. In a preferred embodiment, NRZ coding with pre-emphasis on the first bit of two or more bits of the same value is used for a first range exceeding the specification limit, and PAM4 coding is used for a second range exceeding the first range. Various embodiments are disclosed. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to bait dispensers, and more particularly, to a bait dispenser which is formed in cooperation with a bait container and is capable of dispensing live bait through the end of the dispenser by manipulation of dispenser jaws. The dispenser may be used to contain and dispense substantially any variety of bait such as crickets, grasshoppers and the like, one at a time, without damaging the bait in the dispensing operation.
Fishing is a sport which is enjoyed by many persons who object to the actual handling of the bait necessary to attract and take the particular type of fish sought. For example, when fishing for bream, particularly in southern waters, a common bait is the cricket, which many people object to handling. Furthermore, such live bait as crickets and grasshoppers are quite easily dropped or lost when retrieved from conventional bait containers because of the natural propensity of the bait to move suddenly and elude the grasp of the handler. Additionally, such bait has a tendency to escape from conventional containers and closures when the lids are removed as the handler reaches for the bait.
2. Description of the Prior Art
Heretofore, bait containers and dispensing apparatus have been generally limited to wire cages or alternative containers such as the bait holder and dispenser disclosed in U.S. Pat. No. 2,948,986 to C. S. Williamson. This bait dispenser includes a box having sides constructed of wire mesh, with apertures around the periphery of the top, and pincher means fitted with a sponge or similar soft interior coating to grasp the bait and hold it in position for hooking.
Another prior art bait dispenser apparatus is the fishing bait container disclosed in U.S. Pat. No. 3,308,570 to E. Horton. The container disclosed in this patent is characterized by a tubular mesh container having a splined end member capped by a removable stopper, which end member is large enough to accommodate a cricket, grasshopper or other live bait. When the bait is located inside the splined member, a hook may be inserted in one of the parallel apertures formed in the splined member and thrust through the bait; the stopper may then be removed from the end of the splined member and the bait removed while embedded in the hook.
Yet another prior art bait dispenser is disclosed in U.S. Pat. No. 2,857,705 to J. Woodcock, which dispenser includes a cylindrically shaped container having a conical shaped member on one end with a slot and a hole on the dispensing end of the cone. The cone end also includes a clamp member mounted on the cone adjacent the hole to permit trapping a cricket, grasshopper or other bait as the bait attempts to exit the cone through the hole. The bait may then be hooked through the slot as it is held motionless by the clamp, thereby eliminating the necessity of handling the bait during the hooking operation.
Accordingly, it is an object of this invention to provide a bait dispenser which is capable of carrying and dispensing a quantity of live bait one at a time through a slotted dispensing mechanism located at one end of the container without the necessity of handling the bait.
Another object of the invention is to provide a new and improved bait dispenser which prevents the inadvertent loss of bait as bait is dispensed.
A still further object of the invention is to provide a bait dispenser which is capable of quickly and easily segregating a single bait entity and securely positioning the bait in a configuration to be easily pierced by a fish hook prior to dispensing the bait.
Yet another object of the invention is to provide a bait dispenser which is capable of holding individual items of bait substantially motionless and in a configuration to be easily hooked while the hook is inserted therein, and which subsequently permits dispensing of the bait without damaging the bait.
Yet another object of this invention is to provide a new and improved bait dispenser for dispensing live bait, which dispenser is capable of selectively dispensing a single bait entity in the discretion of the handler without the necessity of touching the bait during the dispensing operation and without releasing other bait in the dispensing process.
A still further object of the invention is to provide a new and improved bait dispenser which is characterized by a slotted, blunt dispensing end which defines a pair of dispensing jaws or mandibles, each having a manipulating lever for selectively widening or narrowing the slot, and further including a plunger member for blocking the passageway defined by the bait dispenser to insure capture and hooking of a single bait entity at a time.
Another object of the invention is to provide a bait dispenser which includes a closed, slotted end member having a pair of cooperating levers for manipulating the size of the slot and a plunger positioned adjacent and to the rear of the slot for blocking the exit of a bait entity to insure positive hooking of a single bait entity through the slot as the bait entity is confined in a limited space.
Another object of the invention is to provide a bait dispenser which is characterized by a container for carrying a supply of live bait and a dispensing means in cooperation with the container which includes a pair of mandibles or jaws separated and defined by a slot and having a plurality of vertically oriented, spaced and flexible bands across the ends of the jaws to permit controlled exit of bait from the container one at a time.
SUMMARY OF THE INVENTION
These and other embodiments of the invention are provided in a bait dispenser which includes a bait container for carrying a quantity of live bait; a cooperating bait dispenser tube having a closed end; a slot cut through the closed end of the dispenser tube to define a pair of adjacent dispenser jaws; a pair of jaw levers in cooperation with each of the dispenser jaws for manipulating the jaws to provide a selective widening or narrowing of the slot; and a plunger positioned to the rear of and adjacent the slot and communicating with the interior of the dispenser tube to prevent retreat of a bait entity toward the container after the bait entity has been positioned forward of the plunger and adjacent the slot and dispenser jaws in the dispenser tube.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood in view of the following description presented with reference to the accompanying drawing:
FIG. 1 of the drawing is a perspective view of the bait dispenser of this invention;
FIG. 2 is a front elevation of the bait dispenser illustrated in FIG. 1 with the dispenser jaws in closed configuration and the plunger extended;
FIG. 3 is a front elevation of the bait dispenser illustrated in FIG. 1 with the dispenser jaws in open configuration and the plunger depressed;
FIG. 4 is a right side elevation of the bait dispenser illustrated in FIG. 1;
FIG. 5 is a top elevation of the bait dispenser illustrated in FIG. 1 of the drawing;
FIG. 6 is a perspective view, partially in section, of the dispensing end of the bait dispenser illustrated in FIG. 1, further illustrating depression of the plunger and the position of the bait in the bait dispenser immediately prior to insertion of a hook in the bait;
FIG. 7 is a top elevation of the bait dispenser illustrated in FIG. 1 with the dispenser jaw levers depressed, and more particularly illustrating the removal of a hooked bait entity from the interior of the bait dispenser;
FIG. 8 is a top elevation of the front portion of the bait dispenser illustrated in FIG. 1 illustrating an adaptation of the dispenser jaw levers which includes a pair of springs to insure closing of the dispenser jaws after an insect or other bait entity is removed from the bait dispenser;
FIG. 9 is a front elevation of the bait dispenser of this invention illustrating an alternative dispenser jaw configuration; and
FIG. 10 of the drawing is a sectional view along lines 10--10 of FIG. 8 of the drawing, illustrating the plunger and collar lock tab and slot of the bait dispenser illustrated in FIG. 1.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to FIGS. 1-3 of the drawing, the bait dispenser of this invention is generally illustrated by reference numeral 1 and includes container 2, which communicates with dispenser tube 4 by means of container neck 3. Dispenser tube 4 is split at the terminal end thereof by slot 14, which defines first dispenser jaw 5 and second dispenser jaw 6. First jaw lever 7 and second jaw lever 8 are carried by first dispenser jaw 5 and second dispenser jaw 6, respectively, as illustrated, to permit selective widening and narrowing of slot 14. Fulcrums 21 are provided on first dispenser jaw 5 and second dispenser jaw 6 to facilitate opening of first dispenser jaw 5 and second dispenser jaw 6, respectively, when first jaw lever 7 and second jaw lever 8 are depressed.
Plunger 9 is disposed in collar 25 and in tube dispenser 4 immediately behind slot 14, and includes plunger cap 10, plunger body 11, plunger foot 12, which serves to constrain plunger 9 to remain in the wall of dispenser tube 4 and in collar 25, and plunger spring 13, which effects a bias of plunger 9 in the extended position, as illustrated in FIGS. 1 and 2. FIG. 3 particularly illustrates the manipulation of first dispenser jaw 5 and second dispenser jaw 6 by pressure (indicated by the arrows) applied to first jaw lever 7 and second jaw lever 8 to cause a levering action on first dispenser jaw 5 and second dispenser jaw 6 and effect a widening of slot 14. Plunger 9 is illustrated in depressed configuration with plunger spring 13 compressed between plunger cap 10 and collar 25 which is formed on dispenser tube 4, and plunger body 11 communicates with the interior of dispenser tube 4 to block the passage of the bait either from container 2 to the dispensing end of tube dispenser 4 or from the dispensing end of the tube back into container 2.
Referring now to FIGS. 4 and 5 of the drawing, and FIG. 4 in particular, it will be appreciated that cap 15 may be unscrewed from threads 16 located on the end of container 2 opposite dispenser tube 4 in order to permit the loading or unloading of bait in the interior of container 2 and/or the cleaning of container 2. It will also be appreciated that alternative closure means can be used to gain access into the interior of container 2 according to the knowledge of those skilled in the art. For example, container 2 may be formed in the same diameter dimension as dispenser tube 4 and may be fitted with a plug which fits the end of container 2 in a relatively tight fit. It will also be appreciated that container 2 may be formed in substantially any shape or size, as desired, although it is preferred to shape the container from plastic, and to provide air holes 24, as illustrated in FIG. 5 of the drawing for ventilation. Eyelet 23 is also preferably provided on container 2 in order to accommodate a string or sling to support container 2 on the shoulders of the user in order to free the hands for operation of bait dispenser 1, as hereinafter described.
Referring now to FIGS. 6, 7 and 10 of the drawing and to FIG. 6 initially, the bait dispenser of this invention is used in the following manner. When live bait such as crickets or grasshoppers are placed in container 2 by unscrewing cap 15 from threads 16, the bait has a natural tendency to move toward the darkest area of bait dispenser 1. Accordingly, it is preferable to form container 2 of a clear plastic or wire material and dispenser tube 4 of a dark material. The bait will therefore have a natural tendency to move from the area of light in container 2 toward dispenser tube 4. Since a small amount of light comes into dispenser tube 4 through slot 14, the bait see this limited light as a means of escape, and move one by one into the area forward of plunger 9 and adjacent first dispenser jaw 5 and second dispenser jaw 6, as illustrated in the case of the cricket 19, shown in FIG. 6. The diameter of dispenser tube 4 adjacent first dispenser jaw 5 and second dispenser jaw 6 is not sufficiently large to accommodate more than one cricket or other bait at a time. Accordingly, at any given point in time there is generally a single cricket 19 or alternative bait entity in this compartment, which is defined by plunger 9, first dispenser jaw 5 and second dispenser jaw 6. When it is desired to remove the cricket from this area, plunger cap 10 is first depressed against the bias of plunger spring 13 to cause lock tab 26 to engage lock tab slot 27 as illustrated in FIG. 10, and place plunger body 11 in position blocking the interior of dispenser tube 4, as illustrated in FIG. 6. This compressive force is illustrated by the arrow shown in FIG. 6 adjacent plunger cap 10, and the depressed position of plunger 9 operates to prevent cricket 19 from moving rearwardly and retreating from the dispensing end of dispenser tube 4. Cricket 19 is thus effectively confined and substantially immobilized in this area of dispensing tube 4, and hook 20 can easily be inserted through slot 14 and into cricket 19 as illustrated. Referring now to FIG. 7 of the drawing, after cricket 19 is secured on hook 20 as illustrated, pressure is exerted on first jaw lever 7 and second jaw lever 8 across fulcrums 21 as indicated by the arrows, to cause first dispenser jaw 5 and second dispenser jaw 6 to move outwardly and slot 14 to expand, as illustrated. This expansion of slot 14 permits easy retrieval of cricket 19, which is impaled on hook 20, from the interior of dispenser tube 4 with no danger of inadvertently releasing additional bait from container 2 and no necessity of touching or handling cricket 19.
Referring now to FIG. 8 of the drawing, it will be appreciated that in an alternative embodiment of this invention, first jaw lever spring 17 and second jaw lever spring 18 are positioned between first jaw lever 7, second jaw lever 8, and dispenser tube 4, respectively, in order to bias first dispenser jaw 6 into position as illustrated, when pressure is removed from first jaw lever 7 and second jaw lever 8. Thus, first jaw lever spring 17 and second jaw lever spring 18 serve to help prevent inadvertent escape of bait from container 2 and dispenser tube 4 when plunger 9 is in extended position and bait dispenser 1 is not in use.
As heretofore discussed, it will be appreciated that bait dispenser 1 can be formed of metal with a wire mesh portion included to form container 2. Alternatively, and in a preferred embodiment of the invention, container 2 may be formed of an easily moldable plastic, and dispenser tube 4 is preferably formed of plastic with first dispenser jaw 5 and second dispenser jaw 6 formed of flexible plastic to permit easy manipulation by first jaw lever 7 and second jaw lever 8. First jaw lever 7 and second jaw lever 8 should be made of a relatively rigid material such as metal or plastic to facilitate easy manipulation of first dispenser jaw 5 and second dispenser jaw 6. Plunger 9 may be formed of metal or plastic, as desired, but is preferably also formed of an easily moldable plastic material. While plastic as a material of construction is generally preferred, it will be appreciated that alternative materials such as fiberglass may be used to construct container 2, while other flexible materials such as rubber and other materials known to those skilled in the art can be used to form first dispenser jaw 5 and second dispenser jaw 6.
Referring to FIG. 9 of the drawing, another alternative embodiment of the invention is illustrated, in which the extremities of first dispenser jaw 5 and second dispenser jaw 6 do not converge to form a blunt dispenser end. Rather, the jaws are sharply clipped and flexible bands 22 are provided to span the gap between the top and bottom of first dispenser jaw 5 and second dispenser jaw 6 and form a barrier to prevent the exiting of bait from dispenser tube 4. In operation, a single cricket 19 or other live bait entity is trapped in the compartment between flexible bands 22 and plunger body 11 when plunger 9 is depressed as heretofore described, and the squeezing of first jaw lever 7 and second jaw lever 8 causes flexible bands 22 to stretch and produce a gap large enough to extricate an impaled cricket 19 and the carrying hook 20 from within dispenser tube 4, as heretofore described. It will be recognized that flexible bands 22 can be positioned horizontally instead of vertically as illustrated in FIG. 9, to serve a similar function in providing better visibility at the dispensing end of dispenser tube 4. One end of each of the flexible bands 22 is attached to the dispenser jaws, respectively, while the other end operates to define slot 14. In this embodiment, flexible bands 22 must have enough structural integrity to resist exit of the bait, but sufficient flexibility to bend when first jaw lever 7 and second jaw lever 8 are depressed.
Referring again to FIG. 3 of the drawing, it will be appreciated that plunger foot 12 is formed on plunger body 11 to retain plunger 9 in slidable relationship in collar 25 and in the wall of dispenser tube 4 against the bias of plunger spring 13. Furthermore, plunger body 11 may be as wide as desired in order to effectively block the internal passageway formed by dispenser tube 4 to prevent movement of the bait to and from the dispensing end of dispenser tube 4 when plunger 9 is depressed. | A bait dispenser for use by fishermen which includes a container for carrying live bait to be dispensed and a cooperating dispenser tube having a slot cut in the end thereof to form a pair of jaws with levers attached which levers facilitate a widening of the slot when depressed. The bait dispenser also includes a spring-loaded plunger on the dispenser tube which communicates with the interior of the tube to block the passage of live bait through the tube. | 0 |
BACKGROUND OF INVENTION
This invention relates to internal combustion engines and more particularly to an improvement in valve mechanism to direct intake and exhaust flow in and out of the engine.
Poppet type valves are most widely used valves to open and close combustion chamber. A conventional engine uses at least two individual poppet valves, one for the intake and another for exhaust, to control the engine gas exchange process. They operate in timed relation to the rotation of the engine crank shaft. Other types of valves such as rotary or sleeve valves, and in some instance a single poppet valve is also used to control the flow. There are advantages and disadvantages with any of these systems. Obtaining a positive sealing for the rotary and sleeve type valve for different speed range is still a challenge. Poppet type valves ensure positive sealing, however when individual poppet valve is used for intake and exhaust, it reduces the size of the gas passage, increases weight, and requires more energy to drive, to name a few. The use of single poppet valve is advantageous from the aspect of lightness and simplicity of construction, valve temperature control, and combustion chamber design.
The idea of an internal combustion engine having a single poppet type valve to control intake and exhaust flow of the combustion chamber is very well recognized. It dates back to as early as Jun. 16, 1895, U.S. Pat. No. 5,428,46 to Diesel, to the present time Pub. Date. Jul. 7, 2011, Pub. No. US2011/0162607 A1 to Joel et al. Most of these inventions are adaptable for use under constant speed condition where it is not necessary to control the intake and exhaust flow and timing in relation to the speed change. A few of the inventions, such as U.S. Pat. No. 2,107,389 and U.S. Pat. No. 40,755,986, provide mechanics to control the intake and exhaust flow before they enter the combustion chamber through the poppet valve. However, the intake timing and the size of gas flow passage directly depends on the timing and the size of the exhaust, hindering the optimization of valve timing. There are other limiting factors of single poppet type valve, such as the placement of the spark plug and the fuel injector system using conventional poppet type valves.
It is therefore an object of the invention to provide a combination of poppet type and unique plate type of valve system to minimize drawbacks of a current valve system and improve upon it.
Another object of our invention is to provide scavenging of the intake flow and simultaneously provide cooling of the poppet valve and the exhaust means, employing a common air chamber.
A further object of our invention is to provide a poppet type valve engine which is mechanically similar to standard practice and thus variable valve timing can be employed.
It is a general object of the present invention to improve internal combustion engine design.
SUMMARY OF INVENTION
The invention involves internal combustion engine, generally characterized by two-stroke or four-stroke principle, comprising intake, compression, power, and exhaust cycle of operation. The engine includes a piston cylinder having a combustion chamber and a piston mounted therein sealingly engaged with the walls of the combustion chamber. Air and combustible fuel, such as gasoline or diesel, are drawn into or injected into the combustion chamber, commonly known as intake. The charged combustible mixture is compressed by the piston and ignited, known as compression and power. Once energy is extracted from the combust mixture, a valve between the combustion chamber and the exhaust path opens to release the products of combustion out of the combustion chamber, known as exhaust.
With this innovation, both the intake and exhaust gas exchange process of the combustion chamber is collectively controlled using poppet type valves. A single poppet type valve on top of the combustion chamber permits larger gas passage area and a better intake swirl for better combustion characteristic. When it is desired to place the spark plug of spark ignition engine or the fuel injector of diesel engine on top of the combustion chamber, more than one poppet valve can be used where they all open and close collectively to control the gas exchange of the combustion chamber. In a single poppet type valve engine configuration the spark plug or the fuel injector can be placed through the center of the poppet using modified poppet valve to position them on top of the combustion chamber.
For both combustion chamber designs, a common transfer port adjacent to the combustion chamber communicates between the chamber and the intake and exhaust ducts, which are communicably aligned with the transfer port. A rotary or reciprocating plate type valve opens and closes the intake and exhaust ducts to and out from the transfer port in order to guide the gas flow. According to the innovation in an embodiment, the plates operate with sufficient mechanical clearance so no lubrication is required.
During the normal combustion process, the exhaust plate valve opens to allow the exhaust gases to escape at the end of power stroke. Then the poppet valve system open to allow the cylinder gases to exhaust into the transfer port and then out past the exhaust plate. At the end of the exhaust cycle, the poppet valve remains open and the intake plate opens to allow the exhaust to fully evacuate. The ejector effect caused by the intake air flow through the transfer port to the exhaust plate will draw a vacuum inside the cylinder. The exhaust plate closes and diverts the intake air into the cylinder.
Accordingly, one embodiment is directed to a flow control mechanism for an internal combustion reciprocating piston engine. The engine includes a combustion chamber, a common transfer port adjacent to the combustion chamber, an intake duct directly communicating with the transfer port and an exhaust duct extending out from the transfer port to communicate flow into and out of the transfer port, a first valve positioned inside the combustion chamber for controlling flow between the transfer port and the combustion chamber, a second valve for controlling flow between the intake duct and the transfer port, and a third valve for controlling flow between the exhaust duct and the transfer port, wherein the second valve and the third valve are independently controlled.
Other objects and features of the invention will be more fully understood from reading the drawings and description hereinafter.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is the sectional view of a prototypical poppet valve, cam, plate valves, and drive system mounted within a prototypical housing according to the instant invention.
FIG. 2 is a section view along the line L 1 of FIG. 1 showing the prototypical valve plate and poppet valve position in relation to the transfer port and combustion chamber.
FIG. 3 shows an exploded view of FIG. 1 without the housing.
FIG. 4 shows an exemplary timing of the exhaust and intake plate relative to the prototypical cam of the instant invention.
FIG. 5 is a side view of the prototypical valve plate configuration.
FIG. 6 is a side view of the prototypical cam configuration used for the poppet valve actuation.
FIG. 7A —is fragmented view showing the poppet and plate valve positions during end of a power phase operation cycle of the engine with an exhaust plate open.
FIG. 7B is fragmented view showing the poppet and plate valve positions during end of an exhaust cycle, the poppet valve remains open and intake plate opens through open exhaust plate to allow the exhaust to fully evacuate an exhaust operation cycle of the engine.
FIG. 7C is fragmented view showing the poppet and plate valve positions during an intake operation cycle of the engine with exhaust plate closed.
FIG. 7D is fragmented view showing the poppet and plate valve positions during a compression power phase operation cycle of the engine.
FIG. 8 shows another exemplary configuration of the combustion chamber with multiple poppet valves.
FIG. 9 is a cross section view similar to FIG. 1 showing substitute modification of the rotating plate valve mechanism with an exemplary reciprocating plate valve mechanism.
FIG. 10 shows an exemplary configuration of the reciprocating plate valve.
FIG. 11 is a side view of an exemplary cam configuration to actuate the reciprocating plate valve.
DETAILED DESCRIPTION
The following detail description with appended drawings helps explain the invention further. Same numerals present identical elements of the embodiments. Terms such as top, bottom, horizontally and vertically describes an orientation relative to the drawings only and do not necessarily correspond to an actual engine plane in which these parts may be incorporated.
Referring to the drawings, a first embodiment of an internal combustion engine of the invention is seen in FIGS. 1-6 and is generally designated by the numeral 10 . A second embodiment the engine of invention is seen in FIG. 8 and is designated by the numeral 10 ′. A third embodiment the engine of invention is seen in FIG. 9-11 and is designated by the numeral 10 ″. For the present invention, engine frame and crank shaft structures are conventional and therefore not shown. Unique aspects of the invention reside the engine head structure which incorporates an unconventional structure and method to control the intake and exhaust flow in and out of the engine 10 , 10 ′, and 10 ″.
The engine 10 includes a central valve housing member 12 having a recessed intake face 14 and a recessed exhaust face 16 . A non-centrally disposed transverse port 18 extends from the intake face 14 to the exhaust face 16 of the central valve housing member 12 . A piston cylinder 26 is positioned within the central valve housing member 12 and operably in communication with transfer port 18 . Upper end of the cylinder 26 forms a combustion chamber 24 inside which combusted fuel discharges in a conventional systems. A reciprocating piston 28 is operably disposed in the cylinder 26 .
The combustion chamber 24 is opened and closed to the transfer port 18 by means of a single poppet valve 36 constructed with a head 38 and a shaft 40 . The valve head 38 seats against a valve seat 34 in the piston cylinder 26 . In accordance with the invention, the poppet valve 36 opens and closes the combustion chamber 24 by means of a cam 20 in operable connection with shaft 40 and stays close throughout combustion and power stroke by means of a spring 52 connected to the shaft 40 of the poppet valve 36 . A central transverse opening 42 extends from the intake face 14 through to the exhaust face 16 of the housing 12 and serves to receive a cam shaft 32 and sealed using sealing element 66 and 67 connected to hub 64 and 65 , respectively. It is to be understood that the poppet valve 36 can be actuated using means other than a spring and cam mechanism such as desmodromic, solenoid, or electrical actuation.
Two separate rotary plate valves of similar structure, intake plate valve 46 and exhaust plate valve 56 , control the intake and exhaust flow through the transfer port 18 . In the rotary form, the semicircular plate valves 46 and 56 are preferably thin and lightweight, and have a radial peripheral opening 62 and 63 ( FIG. 4 ), respectively, to communicate with the transfer port 18 as seen in FIG. 2 . The plate valves 46 and 56 are mounted on the camshaft 32 using two rotary hubs, intake rotary hub 48 and exhaust rotary hub 58 . The cam shaft 32 and the hubs 48 and 58 can include complementary keyed structure to maintain relationship to the cam 20 . This also helps to prevent single valve rotation due to vibration. In this configuration, the axis of rotation of the plate valves 46 and 56 is in the same line with the axis of rotation of the cam 20 . A mechanical or electrical mechanism can be incorporated into the hubs 48 and 58 , to change the timing of the intake plate 46 and exhaust plate 56 in accordance with timing of the poppet valve 36 . Other structures are contemplated to adjust or set the timing of operation of the engine. Changing the timing based on the speed of the engine or other sensor controls can improve efficiency of the engine. For example, a centrifugal mechanism can be used to the change the plate timing as the engine speed changes. With this invention, the camshaft 32 axis of rotation is spaced parallel to the crankshaft axis of rotation.
Two separate housing mating plates of similar structure, an intake housing mating plate 44 , and an exhaust housing mating plate 54 , are configured to enclose the intake valve plate 46 and exhaust valve plate 56 . Both include a central annular bearing 64 and 65 , respectively, connected therein to rotatably receive the cam shaft 32 therein. Each of the housing mating plates 44 and 54 has a respective non central port 50 and 60 . When the intake housing mating plate 44 connects to the central valve housing 12 in a way that are communicably aligned with the transverse port 18 , they collectively create intake flow path into the combustion chamber 24 . Similarly, when the exhaust housing mating plates 54 connects to the central valve housing 12 in a way that are communicably aligned with the transverse port 18 , they collectively create exhaust flow path out of the combustion chamber 24 .
To describe the timing sequence of the intake and exhaust flow, as shown in FIG. 7 A-D, start with the piston 28 positioned at 90 degrees before the upper end of the cylinder 26 , commonly refer as top dead center. In this piston 28 position, as shown in FIG. 7A , the poppet valve 36 is open to exhaust the combusted gases out of the chamber 24 . At this time in the cycle, the exhaust plate valve 56 is open to clear the exhaust gases out of the transfer port 18 . The intake plate valve 46 is closed to prevent any exhaust transfer to the intake duct 50 . As shown in FIG. 7B , the intake plate opens to start intake flow and to assist the exhaust evacuation from the transfer port 18 . As it is shown in FIG. 4 , there is an overlap between the intake plate 46 opening 62 (opening position) and exhaust plate 56 opening 63 (closing position) to completely clear the exhaust out of the combustion chamber 24 and the transfer port 18 . The flow and the position of the plate valves 46 and 56 and the poppet valve 36 during this cycle are seen in FIG. 7B .
As shown in FIG. 7C , intake cool air passes through the intake port 50 into the transfer port 18 and finally to the combustion chamber 24 . The expelling of cool air passing the poppet valve 36 and contacting the exhaust plate valve 56 in area of the transfer port 18 reduces the temperature of the components. This cooling effect reduces detonation on the poppet valve 36 and the incidence of nitrogen oxide formation. Consequently, the temperature increase of the intake air help to achieve better combustion characteristics.
The poppet valve 36 starts to close as the volume of air in the combustion chamber 24 reaches a required amount. An amount of fuel is injected into the combustion chamber 24 by conventional means. The piston 28 starts traveling towards top dead center and the charge of air begin to compress. The position of the plate valves 46 and 56 and the poppet valve 36 during this cycle are shown in FIG. 7D . Once compresses, the charge of combustible mixture is ignited in conventional way. Using single poppet type valve system gasoline type of engine, the ideal position of the ignition system is in the center of the poppet valve head 38 . For diesel type of engine with single poppet valve system, the ideal location of the fuel injection point is in the center of the poppet valve head 38 .
The ignition of the combustible mixture produces hot gases of combustion that expand rapidly and push the piston 28 back towards bottom dead center. The poppet valve is valve 36 is sealed during the compression, ignition, and expansion of the combustible mixture, against the valve seat 34 . The poppet valve 36 starts to open once the volume of the combustion mixture reaches the maximum. Consecutively, the burnt gases are exhausted through the transfer port 18 . The piston 28 returns to the beginning of its cycle at top dead center. The poppet valve 36 is fully open on the exhaust stroke and remains fully open during the air intake stroke and only closes when it is desired to initiate compression, ignition and expansion. This is achieved by using a special cam 20 profile as shown in FIG. 6 . The opening and closing position and duration of the poppet valve 36 is determined by the requirement of air and speed of the engine. Since the plate valves 46 and 56 and the poppet valve 36 mechanism follows a traditional cam system, conventional variable valve timing mechanism can be incorporated.
In the embodiment seen in FIG. 8 , the engine 10 ′ shows an exemplary alternative design with two poppet valves 36 instead of one, nested within the housing 22 . In accordance with the invention, both poppet valves 36 collectively open and close the combustion chamber 24 by means of cam 30 and stay close throughout the combustion and power stroke by means of springs 52 . The cam 30 can have exact same timing profile to open and close both poppet valves simultaneously or they can vary slightly depending on the design need. The other operations of engine 10 ′ is similar to engine 10 .
In the embodiment seen in FIGS. 9-11 , the engine 10 ″ shows an exemplary alternative design using an intake slide valve 70 and exhaust slide valve 80 instead of the rotating plate valves 46 and 56 . In accordance with the invention, plate valves 70 and 80 open and close the intake and exhaust duct 50 and 60 respectively by means of cams 72 and 82 and stay close throughout the compression, ignition, and expansion strokes by means of springs 78 . In this embodiment, the intake housing mating plate 74 and the exhaust housing mating plate 84 are configured with opening 76 and 86 , respectively to house the cam and spring actuating mechanism. The actuation mechanism is typical of cam actuation mechanism and allows the flexibility of incorporating variable valve timing if desired.
The automotive industry is under mandates to increase the fuel efficiency of the internal combustion engine. The purpose of the instant invention design is to develop an engine that has higher fuel efficiency while maintaining the power output. One way of achieving this would be increasing the engine's thermal and volumetric efficiency. Our analysis suggest that using single poppet type valves to control the air in and out of the cylinder through the transfer port will significantly increases the engines volumetric efficiency.
For both instance of single or multiple poppet valves, where the poppet valves open and close collectively, the exhaust evacuates much more efficiently while the poppet valve stays open for longer period of time. In conventional engine the exhaust valve starts to close about 60 degrees before the intake starts to open leaving some exhaust gas in the cylinder. When a single poppet valve or multiple poppet valves are used collectively, the system increases the air flow area for the exhaust, thus overcoming the normal situation where the exhaust valves are generally smaller than the intake, which is a limiting factor of efficiently exhausting the combusted gases. The benefit of a single valve design is that it creates a chamber that is more hemispheric and the intake charge has high swirl to initiate better combustion.
When complete exhaust is desired, the intake plate valve can open slightly before the exhaust plate valve closing so there is an overlap of flow between the intake and the exhaust duct. The incoming fresh air scoops out any remaining exhaust in the combustion chamber through the transfer port and out through the exhaust. Alternatively, to control the nitrogen oxide formation, it is sometime desirable to have some exhaust gas inside the combustion chamber. Separate intake and exhaust control and the ability to vary the timing make it easier to achieve that. Using the plate type valve in the intake and exhaust duct, the timing can be varied so the exhaust closes before the intake opens and thus some of the intake air gets mixed with the exhaust gas trapped in the transfer port.
The above described embodiments are set forth by way of example and are not for purpose of limiting the present invention. It will be readily apparent to those skilled in the art that obvious modifications, derivations and variations can be made to the embodiment without departing from the scope of the invention. Accordingly, the claims appended hereto should be read in their full scope including any such modifications, derivations and variations. | This invention presents a method to improve the volumetric efficiency of a reciprocating internal combustion engine using a common transfer port between the exhaust and intake port. The engine employs a poppet valve as part of the intake and exhaust valve to control the flow from the transfer port into the combustion chamber. Two plate type valves outside of the combustion chamber are located at both ends of the transfer port to control the flow coming from the intake and out the exhaust. The timing for opening and closing of the poppet type valve is regulated to remain open for a longer duration which provides complete evacuation of air in the exhaust stroke. The ejector effect from the exhaust flow through the transfer port draws a vacuum into the cylinder. When the exhaust plate closes, the vacuum diverts the intake into the cylinder. | 5 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] Benefit of U.S. Provisional Application for Patent Ser. No. 61/136,792, filed on Oct. 3, 2008, is hereby claimed.
FIELD OF THE INVENTION
[0002] The present invention relates to an artificial attachment for use in attaching a synthetic element to vegetation or rod member. For example, the element may be in the form of a piece of foliage and the vegetation may be for example stems, stalks, twigs and the like, the combination creating a decorative effect. Such vegetation or rod member may be living or non-living.
[0003] The present invention has further reference to an artificial attachment for use in attaching a synthetic element to vegetation, wherein the synthetic element is a part of for example an entomological creature and a combination of such elements creates an artificial representation of the creature. Other creatures, animals or insects may be composed using specially formed synthetic elements according to the invention.
[0004] In a still further proposal of the invention the synthetic element is a part of a well-known character, a combination of parts representing the complete character, for example a cartoon character. Other applications of the present invention include but are not limited to miniature houses, mobile structures etc.
BACKGROUND OF THE INVENTION
[0005] The production of artificial flowers and arrangements thereof has existed for many years and embraces a wide field extending from children's toys to artificial flower structures including co-ordinated floral arrangement assemblies, and to kits for creating for example easy care-free instant yard beautification.
[0006] One such kit is disclosed in U.S. Pat. No. 6,861,108 to Potoroka who proposes various means of attaching artificial flowers and foliage to stems or stalks, such means including inter alia pins, clips or ties or any combination thereof. A disadvantage of such attachment means is that they are separate from the particular piece of foliage requiring attachment and further such small attachment means represent a hazard for children.
[0007] Accordingly, there is a need for an improved artificial attachment to enable and facilitate the attachment of synthetic elements to vegetation or rod member.
SUMMARY OF THE INVENTION
[0008] It is therefore a general object of the present invention to provide an improved artificial attachment for vegetation or rod member.
[0009] A further object of the present invention is to provide such an artificial attachment that is integral therewith, therefore affording an advantage in terms of a unitary piece.
[0010] A still further object of the present invention is to provide an artificial attachment for attaching a synthetic element to vegetation directly without the need to thread the element onto the vegetation.
[0011] According to the invention there is provided an artificial attachment formed integrally in a synthetic element, the attachment comprising a slot providing an entry for an elongate member to which the synthetic element is to be attached, said slot providing along at least part of its marginal edges a clamping zone which upon flexure of the element is openable and upon release is closable to clamp and thereby attach the element to the elongate member.
[0012] The slot or slot means may advantageously be of ‘figure-of-eight’ shape providing enlarged and rounded end portions and a restricted middle portion at the clamping zone, the restricted middle portion may be of relatively narrow dimension in comparison to the end portions. An alternative shape for the slot means may be an ‘hourglass’ shape and thus similar to the figure-of-eight shape giving a restricted middle portion for the clamping zone widening into the end portions.
[0013] Other alternative forms of slot may be employed and may be constituted by two spaced-apart apertures connected by a slit in the element the slit defining the clamping zone. The length of the slit may be of a size predetermined by the magnitude of the foliage to which the element is to be attached.
[0014] The synthetic element may conveniently be in the form of foliage, e.g. a leaf.
[0015] In the alternative, the synthetic element may be in the form of a representation of a part of an insect or other creature.
[0016] In a still further alternative, the synthetic element may be in the form of a part of famous characters, particularly cartoon characters, the assembled elements with the suitable vegetation combining to make the whole character.
[0017] Although the vegetation does not constitute a feature of the invention and generally will not be provided therewith when commercially available, it will usually consist of a twig, stem or stalk or similar element of relatively slender elongate form.
[0018] The invention may extend to a kit including but not limited to a plurality of flower parts, for example petals, stamens and other parts for assembly by interengagement one with the other by means of interleaving with a central opening of variable dimension for accommodating vegetation, such as generally represented by a twig, stem, stalk or similar element the end of which passes through the opening when assembly is completed, the whole to constitute an artificial flower. The kit would also include the synthetic element attachment herein described and claimed. Accordingly, a selection of synthetic elements may be included in the kit, for example leaves, insects parts and/or cartoon character parts. The object of providing such a kit would be to enable the user, for example a child, to create complete versions of flowers, insects, cartoon characters etc.
[0019] Other objects and advantages of the present invention will become apparent from a careful reading of the detailed description provided herein, with appropriate reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] Further aspects and advantages of the present invention will become better understood with reference to the description in association with the following Figures, in which similar references used in different Figures denote similar components, wherein:
[0021] FIG. 1 is a perspective front view of a synthetic element in the form of a leaf incorporating the artificial attachment of the present invention, the leaf being mounted on and attached to a piece of vegetation in the form of a twig;
[0022] FIG. 2 is a view of the leaf shown in FIG. 1 incorporating the attachment in accordance with an embodiment of the present invention;
[0023] FIG. 3 is a perspective scrap view 3 in FIG. 2 of the artificial attachment;
[0024] FIG. 4 is an enlarged perspective taken along line 3 of FIG. 2 shown in flexure with the attachment ready for application to the vegetation, viz. a twig also shown in this figure;
[0025] FIG. 5 is a perspective view of an assembled kit of synthetic elements attached to vegetation and combining to create a model of an animal, for example a dog; and
[0026] FIG. 6 is a diagrammatic representation of three different forms of slot means according to the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0027] With reference to the annexed drawings the preferred embodiment of the present invention will be herein described for indicative purpose and by no means as of limitation.
[0028] FIGS. 1 and 2 illustrate a synthetic element in the form of an ovate leaf 10 having at its root end an attachment referenced generally at 14 and comprising a slot 16 or slot means of ‘figure-of-eight’ shape with two end holes 18 separated by an open central clamping zone 20 of restricted dimension relative to the two holes 18 . In FIG. 1 the leaf 10 is shown attached to a piece of vegetation or rod member in the form of a twig 22 .
[0029] In FIGS. 3 and 4 the leaf 10 is shown in flexure, i.e. bent over in the region of the clamping zone 20 (as shown in FIG. 3 ), or slit, to give an opening for receiving vegetation in the form of the twig 22 of slender elongate form. In use, the application of the leaf 10 to the twig 22 is achieved by passing the twig 22 into the clamping zone 20 with the twig being accommodated in the end holes 18 . The leaf 10 is then allowed substantially to reassume its unflexed state thus clamping the leaf to the twig 22 . It will be appreciated that the attachment of the leaf to the twig is secured without the need to thread the leaf over the twig along its length to the desired position.
[0030] Referring now to FIG. 5 , like parts have been assigned the same numerals of reference as used in the foregoing figures. This figure represents an animal 30 such as a dog having four legs 23 represented and constituted by pieces of vegetation, for example twigs 22 with a spinal column 28 also comprised of a twig 22 with a trifurcated rear end 28 ′, the legs and the column being conjoined by a synthetic element forming the main body part 31 of the dog 30 . The main body part 31 of the dog 30 includes a number of attachment 14 shown engaging the legs 23 , the application of the attachment 14 to the legs 23 being as previously described in relation to FIG. 4 . The attachments 14 are formed in extensions 32 of the body part 31 , adjacent extensions 32 being spaced apart as at 34 . The body part 31 further has two holes 35 , only one of which can be seen in the figure, longitudinally aligned therein to receive the spinal column 28 as shown. A head 40 for the dog is illustrated with two frontal apertures representing eyes 42 , with an attachment 14 provided in the occipital region of the head to engage with and attach to the spinal column 28 . A stellar-shaped hole 44 is formed at the front of the head 40 to depict the mouth of the dog and also to function in the assembly of the kit parts to receive the end of the spinal column 28 .
[0031] Referring now to FIG. 6 , the three representations of the slot are designated A, B and C. ‘A’ shows a ‘figure-of-eight’ formation 16 , whilst ‘B’ shows a slot 16 ′ comprising the holes 18 interconnected by a slit 50 merging into the holes. ‘C’ illustrates a slot 16 ″ comprising holes 18 interconnected by a longer slit 50 than that of ‘B’, the clamping zone thus being sharper than for ‘A’ and ‘B’. The particular type of slot selected will depend upon the materials and the manufacturing techniques being employed.
[0032] The synthetic elements may be made of plastics material that may be recyclable, as indeed may the other parts, which may be commercially available as a kit.
[0033] The present invention may be utilized in all manner of applications in which synthetic elements are combined to create an artificial representation of real flora or fauna, insects, cartoon characters or indeed other structures.
[0034] The invention may be provided for use by children in view of its inherent safety, in terms of it obviating the need for several separate and potentially dangerous parts. In the alternative, the invention may be available for adult usage in terms of creating an artificial effect of natural growth giving colour and form to an otherwise drab environment.
[0035] Although the present invention has been described with a certain degree of particularity, it is to be understood that the disclosure has been made by way of example only and that the present invention is not limited to the features of the embodiments described and illustrated herein, but includes all variations and modifications within the scope and spirit of the invention as hereinafter claimed. | An artificial attachment includes a ‘figure-of-eight’ slot, or similar shape, which upon flexure permits clamping application to vegetation or rod member, for example a twig, thereby to effect attachment thereto upon reflexure to its original shape. | 8 |
BACKGROUND OF THE INVENTION
The present invention relates to a rotatable machinery system. The present invention more particularly relates to a rotatable machinery system including a rotatable cross member, a drive shaft coupled to the cross member, drive means for rotating the drive shaft and having a bearing forming a circumferential bearing junction with the drive shaft, and a washer for protecting the junction. The invention further relates to a washer for use with such a rotatable machinery system.
In a rotatable machinery system, a drive means provides power to rotate a drive shaft. The drive shaft, in turn, is coupled to other elements to perform work. For example, the drive shaft may be coupled to a crossbar for turning the crossbar. Generally, the drive means and drive shaft are coupled through a bearing, which provides reduced friction and shock absorption.
Rotatable machinery systems include both rotating and stationary components. Rotating components include drive shafts and crossbars. Stationary components include gearbox housings and bearings. In the environment in which many rotatable machinery systems are used, it is a frequent occurrence for debris to wrap around both rotating and stationary components. Both stationary and rotating components may be damaged by such debris.
One example of such a rotary equipment system is a rotary cutter for use in agricultural applications or as a mower. In such a system, a drive means such as an engine, motor or gearbox rotates a drive shaft. The drive shaft is coupled to a crossbar and the crossbar is in turn coupled to a cutting blade. As a result, when the drive shaft is rotated, the cutting blade is also rotated to cut grass, weeds or crops. The cutting blade may be covered by a deck plate or housing to prevent operator injury and to prevent the throwing of stones and other debris. The deck plate has an open bottom to allow the cutting blades to contact the grass, weeds or crops.
In such an environment, some debris may not be cut but may instead wrap around the rotary cutter. Debris such as wires, vines, string and plastic may be drawn into the housing or deck plate. This debris may wrap tightly about stationary components, such as the drive means, as well as rotating components such as the crossbar. Thus wrapped tightly, the debris may be rotated by the crossbar and dragged around stationary surfaces. The resulting friction and buildup of heat may cause damage to the drive means. Also, breakable components such as bearings may be damaged.
Therefore, there is a need in the art for a rotary machinery system immune to damage from debris wrapped around both rotary and stationary elements. Further, there is a need for an anti-wrap washer for use in conjunction with such a rotary machinery system for preventing debris which becomes wrapped around rotating elements from contacting stationary elements. The present invention provides such a rotary machinery system and washer by providing a system having a washer including flange means for keeping debris from contacting both rotating and stationary elements.
SUMMARY OF THE INVENTION
The present invention provides a rotatable machinery system. The rotatable machinery system includes a rotatable cross member, a drive shaft coupled to the cross member, drive means for rotating the drive shaft, the drive means including a bearing forming a circumferential junction with the drive shaft, and a washer, the washer having a substantially planar, ring-shaped body coaxial with the drive shaft and rotating responsive to the drive shaft, and flange means extending from the body for covering at least a portion of the junction.
The invention further provides a rotary cutter. The rotary cutter includes a rotatable member including a cutting blade, a rotatable drive shaft for rotating the member, drive means for rotating the drive shaft, the drive means being coupled to the drive shaft through a bearing coaxial with the drive shaft, and a washer for protecting the bearing, the washer including an annular disk coupled to and coaxial with the drive shaft and rotating with the drive shaft, the annular disk having a proximate face adjacent the drive means and an outer perimeter, and flange means extending from the outer perimeter toward the drive means for covering the bearing.
The invention still further provides a washer for use in rotatable machinery, the rotatable machinery having a rotatable member, a rotatable drive shaft for rotating the member, and drive means for rotating the drive shaft, the drive shaft being coupled to the drive means through a bearing coaxial with the drive shaft. The washer includes an annular disk for being coupled to and coaxial with the drive shaft and rotating with the drive shaft, the annular disk having a proximate face adjacent the drive means and an outer perimeter, and flange means extending from the outer perimeter toward the drive means for covering the bearing.
BRIEF DESCRIPTION OF THE DRAWINGS
The features of the present invention which are believed to be novel are set forth with particularity in the appended claims. The invention, together with further objects and advantages thereof, may best be understood by making reference to the following description taken in conjunction with the accompanying drawings, in the several figures of which like reference numerals identify identical elements, and wherein:
FIG. 1 is an exploded perspective view of a rotary machinery system, in partial cutaway, embodying the present invention;
FIG. 2 is a perspective view, in partial cutaway, of the assembled rotary machinery system of FIG. 1;
FIG. 3 is a perspective view of a first embodiment of an anti-wrap washer in accordance with the present invention;
FIG. 4 is a perspective view of a second embodiment of an anti-wrap washer in accordance with the present invention;
FIG. 5 is an assembled perspective view of a rotary machinery system embodying the present invention; and
FIG. 6 is an elevation view of an intermediate subassembly of the anti-wrap washer of FIG. 2 prior to the completion of its manufacture in accordance with the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to FIG. 1, it is an exploded perspective view in partial cutaway, illustrating a rotary machinery system 10 embodying the present invention. The system 10 generally includes a bearing housing 12, a drive shaft 14, a washer 16, a rotatable member or crossbar 18 and cutting blade 19. The system 10 further includes a bolt 20 having a threaded end which passes through the crossbar 18 and the washer 16 to engage a threaded socket 22 at the end of the drive shaft 14. The system 10 may further include washers 24 and 26 for securing the crossbar 18 to the drive shaft 14.
The drive shaft 14 may be driven by a drive means (not shown in FIG. 1). The drive means may be an electric motor or an engine for rotating the drive shaft 14. Further, the drive means may include a gearbox or differential or any other equipment in the drive train between the motor or engine and the drive shaft 14, forming a means for rotating the drive shaft.
The drive shaft 14 rotates supported by a bearing 28 within the bearing housing 12. The bearing 28 is preferably coaxial with the drive shaft 14 and provides low-friction support for the drive shaft 14. As shown in FIG. 1, the drive shaft 14 has a circular cross-section 13. The drive shaft 14 has a maximum cross-section length or dimension 15. However, it will be understood by those skilled in the art that the drive shaft 14 may have a cross-section other than that illustrated which may include any number of straight sides, to define a square, hexagonal or octagonal cross-section, for example. Without regard to the cross-sectional shape of the drive shaft 14, a circumferential junction 29 is formed between the drive means 12 and the drive shaft 14.
As shown in FIG. 1, the crossbar 18 includes a hole 30 for receiving the bolt 20 for coupling the crossbar 18 to the drive shaft 14. As will be understood by those skilled in the art, the hole 30 may be such as to receive the end of the drive shaft 14 for coupling the crossbar 18 to the drive shaft 14. Thus, the crossbar 18 is preferably rotatably coupled to the end of the drive shaft 14. The crossbar 18 may further be configured for coupling to other equipment, not shown, for performing work. For example, the system 10 may form a rotary cutter, wherein one or more cutting blades 19 are attached to the crossbar 18. The crossbar 18 includes mounting means 32 and 34 for mounting equipment such as cutting blade 19 to the crossbar for performing work. The crossbar 18 may further include a reinforcing brace 36 for assuring the crossbar 18 is securely coupled to the drive shaft 14.
The washer 16 preferably includes one or more legs 38. As shown in FIG. 1, the legs 38 of the washer 16 are configured for fitting over and around the reinforcing brace 36. The legs 38 thus form a means for engaging the cross member 18. When the cross member 18 rotates responsive to the drive shaft 14, the legs 38 engage the reinforcing brace 36 of the crossbar 18, causing the washer 16 to rotate in response to the rotation of the crossbar 18.
Referring now to FIG. 2, it illustrates a perspective view, in partial cutaway, of the assembled rotary machinery system of FIG. 1. FIG. 2 shows the crossbar 18 coupled to the end of the drive shaft 14, which passes through the crossbar 18 and is secured to the crossbar 18 by bolt 20. FIG. 2 further shows the bearing housing 12 forming the junction 29 with the drive shaft 14. At least a portion of the junction 29 is covered by the flange sections 46 and 48 of the washer 16. The washer 16 also includes legs 38 which engage the reinforcing brace 36 of the crossbar 18 to cause the washer 16 to rotate.
Referring now to FIG. 3, it illustrates a first embodiment of a washer 16 in accordance with the present invention. The washer 16 includes a body 40 in the form of an annular disk having a proximate or upper face 41 and a distal or lower face 43. The body 40 has a hole 42 adapted for receiving the bolt 20 for coupling the crossbar 18 to the drive shaft 14 (FIG. 1). The body 40 further has an outer perimeter 44. Extending from the outer perimeter 44 are flange sections 46 and 48. Also extending from outer perimeter 44, in a direction opposite the flange sections 46 and 48, is a leg 38. Not visible in FIG. 3 is a second leg analogous to the first leg 38 extending from the outer perimeter 44 in a direction opposite flange sections 46 and 48.
The flange sections 46 and 48 preferably extend from the outer perimeter 44 normal to the surface of the body 40. However, in accordance with the present invention, flange sections 46 and 48 may extend at an angle from the body 40.
Referring now to FIG. 4, it is a view of a second embodiment of an anti-wrap washer in accordance with the present invention. In FIG. 4, flange sections 46 and 48 (FIG. 3) have been replaced with a single continuous flange 50.
Referring now to FIG. 5, it shows an assembled perspective view of a rotary machinery system 10 in accordance with the present invention In FIG. 5, the rotary machinery system 10 includes a gearbox 50 driven by a horizontal drive shaft 52 for rotating the crossbar 18. The horizontal drive shaft 52 and the gearbox 50 form part of a drive system for rotating the drive shaft 14 (not visible in FIG. 5) and crossbar 18. In FIG. 5, crossbar 18 is coupled to the drive shaft 14. The legs 38 of the washer 16 engage the reinforcing brace 36 of the crossbar 18. The flange sections 46 and 48 of the washer extend upwardly from the washer body for covering at least a portion of the junction formed between the bearing housing 12 and the drive shaft 14, not visible in FIG. 5.
As the drive means rotates the drive shaft 14, the crossbar 18 also rotates. With the legs 38 engaging the reinforcing brace 36 of the crossbar 18, the washer 16 rotates responsive to rotation of the crossbar 18. As the washer 16 rotates, the flange sections 46 and 48 create a barrier to debris such as wire, vines, string and plastic. This barrier prevents rotating debris, caught on the crossbar 18, from contacting stationary components, such as the bearing housing 12. Further, the barrier formed by flange sections 46 and 48 prevents debris from penetrating this junction and damaging internal components, such as bearing 28 (FIG. 1).
Referring now to FIG. 6, it shows a plan view of the anti-wrap washer of FIG. 2 prior to the completion of its manufacture in accordance with the present invention. Figure 6 shows the washer 16 having a body 40 in the form of an annular disk about a hole 42, and having bendable tabs for forming flange sections 46 and 48 and first leg 38 and second leg 52. FIG. 6 thus shows how the washer 16 can be manufactured from sheet steel. As will be recognized by those skilled in the art, the washer 16 could also be molded from material such as plastic, eliminating the need for forming bendable tabs to form the flange sections and legs. FIG. 6 shows the hole 42 having a diameter 54. In addition, the bendable tabs which form flange sections 46 and 48 have a chord length 56. In accordance with the present invention, the chord length 56 is preferably greater than the diameter 54. Also, the chord length 56 is preferably greater than the major cross-section dimension of the drive shaft (FIG. 1). This insures that any debris wrapped around the flange sections 46 and 48 and rotating with the washer 16 will not contact and rub against stationary components of the rotatable machinery system.
As can be seen from the foregoing, the present invention provides a rotatable machinery system, and an anti-wrap washer for use therewith, having improved resistance to damage from rotating debris. The rotatable machinery system includes an anti-wrap washer having one or more flanges or flange sections for protecting stationary components of the system as well as breakable components of the system. While the present invention has been discussed in relation to one embodiment as a rotary cutter, it will be understood that the present invention can be effectively used with any rotatable machinery system wherein a drive shaft rotates a cross member in the vicinity of stationary components for rotating the drive shaft and in the presence of debris.
While particular embodiments of the present invention have been shown and described, modifications may be made, and it is therefore intended to cover in the appended claims all such changes and modifications which fall within the true spirit and scope of the invention. | A rotatable machinery system including a washer, the washer including a flange for keeping debris from contacting both rotating and stationary elements. The rotatable machinery system includes a rotatable cross member, a drive shaft coupled to the cross member, a bearing including a bearing housing, and a drive device for rotating the drive shaft. The bearing housing and drive shaft form a circumferential junction. The flange of the washer covers at least a portion of the junction, the washer turning responsive to the drive shaft. | 0 |
FIELD OF THE INVENTION
This invention relates to certain new electrostatographic toners and developers containing new quaternary ammonium salts as charge-control agents. More particularly, the new salts are thermally stable compounds that can be well-dispersed in typical toner binder materials to form the inventive toners having good charging properties without unacceptable interactions with other developer or copier components.
BACKGROUND
In electrostatography an image comprising an electrostatic field pattern, usually of non-uniform strength, (also referred to as an electrostatic latent image) is formed on an insulative surface of an electrostatographic element by any of various methods. For example, the electrostatic latent image may be formed electrophotographically (i.e., by imagewise photo-induced dissipation of the strength of portions of an electrostatic field of uniform strength previously formed on a surface of an electrophotographic element comprising a photoconductive layer and an electrically conductive substrate), or it may be formed by dielectric recording (i.e., by direct electrical formation of an electrostatic field pattern on a surface of a dielectric material). Typically, the electrostatic latent image is then developed into a toner image by contacting the latent image with an electrostatographic developer. If desired, the latent image can be transferred to another surface before development.
One well-known type of electrostatographic developer comprises a dry mixture of toner particles and carrier particles. Developers of this type are commonly employed in well-known electrostatographic development processes such as cascade development and magnetic brush development. The particles in such developers are formulated such that the toner particles and carrier particles occupy different positions in the tribolectric continuum, so that when they contact each other during mixing to form the developer, they become triboelectrically charged, with the toner particles acquiring a charge of one polarity and the carrier particles acquiring a charge of the opposite polarity. These opposite charges attract each other such that the toner particles cling to the surfaces of the carrier particles. When the developer is brought into contact with the latent electrostatic image, the electrostatic forces of the latent image (sometimes in combination with an additional applied field) attract the toner particles, and the toner particles are pulled away from the carrier particles and become electrostatically attached imagewise to the latent image-bearing surface. The resultant toner image can then be fixed in place on the surface by application of heat or other known methods (depending upon the nature of the surface and of the toner image) or can be transferred to another surface, to which it then can be similarly fixed.
A number of requirements are implicit in such development schemes. Namely, the electrostatic attraction between the toner and carrier particles must be strong enough to keep the toner particles held to the surfaces of the carrier particles while the developer is being transported to and brought into contact with the latent image, but when that contact occurs, the electrostatic attraction between the toner particles and the latent image must be even stronger, so that the toner particles are thereby pulled away from the carrier particles and deposited on the latent image-bearing surface. In order to meet these requirements for proper development, the level of electrostatic charge on the toner particles should be maintained within an adequate range.
The toner particles in dry developers often contain material referred to as a charge agent or charge-control agent, which helps to establish and maintain toner charge within an acceptable range. Many types of charge-control agents have been used and are described in the published patent literature.
One general type of known charge-control agent comprises a quaternary ammonium salt. While many such salts are known, some do not perform an adequate charge-control function in any type of developer, some perform the function well in only certain kinds of developers, and some control charge well but produce adverse side effects.
A number of quaternary ammonium salt charge-control agents are described, for example, in U.S. Pat. Nos. 4,684,596; 4,394,430; 4,338,390; 4,490,455; and 4,139,483. Unfortunately, many of those known charge-control agents exhibit one or more drawbacks in some developers.
For example, some of the known quaternary ammonium salt charge agents lack thermal stability and, thus, totally or partially decompose during attempts to mix them with known toner binder materials in well-known processes of preparing toners by mixing addenda with molten toner binders. Such processes are often referred to as melt-blending or melt-compounding processes and are commonly carried out at temperatures ranging from about 120° to about 200° C. Thus, charge agents that are thermally unstable at temperatures at or below 200° C. can exhibit this decomposition problem.
Also, some of the known quaternary ammonium salt charge-control agents have relatively high melting points. During melt-blending, a molten charge agent can be more quickly, efficiently, and uniformly dispersed in the molten toner binder than can a solid charge agent. Non-uniform dispersion can result in poor or inconsistent charge-control performance from toner particle to toner particle (among other undesirable effects discussed below). Therefore, it is a drawback to have a charge agent with a melting point higher than 120° C., because such a charge agent will be slowly, inefficiently, and non-uniformly dispersed in the toner binder during some melt-blending processes.
Furthermore, some of the known quaternary ammonium salt charge agents have relatively high electrical conductivity, which can lead to poor performance of some developers.
Also, some known quaternary ammonium salt charge agents exhibit high sensitivity to changes in environmental relative humidity and/or temperature, which can lead to erratic performance of the charge agents under changing environmental conditions.
Additionally, some of the known quaternary ammonium salt charge agents will adversely interact chemically and/or physically with other developer or copier components. For example, some will interact with carrier or carrier coating materials (e.g., fluorohydrocarbon polymer coatings such as poly(vinylidene fluoride)) and lead to premature carrier aging and shortened useful developer life. Some will interact with certain toner colorants to cause unacceptable hue shifts in the toner. Some will interact with copier fuser rollers (e.g., rollers coated with fluorohydrocarbon polymers such as poly(vinylidene fluoride-co-hexafluoropropylene)) to cause premature failure of the copier's toner fusing system.
Also, poor dispersibility of some of the known quaternary ammonium salt charge agents in some of the known toner binder materials, either because the charge agent has a high melting point (as discussed above) or because it is incompatible with or otherwise poorly dispersible in the binder, can lead to worsening of some of the problems mentioned above. Non-uniform dispersion of charge agent means that higher concentrations or agglomerations of charge agent will exist in some portions of the toner binder mix, compared to others. In typical melt-blending processes, the toner mixture is cooled and ground down to desired particle size after melt-blending. Agglomerations of charge agent provide sites in the mixture where fracture is more likely to occur during grinding. The new surfaces created by such fracture will have a higher concentration of charge agent then will internal sites. Thus, the final toner particles will have a higher surface concentration of charge agent then internal concentration. It should be readily appreciated that if a charge agent tends to adversely interact with the environment, copier components, or other developer components, higher surface concentrations of charge agent on the toner particles will lead to a greater degree of such interaction, thus exacerbating problems such as high conductivity, high environmental sensitivity, and premature failure of carrier and fuser roll materials.
It would, therefore, be desirable to provide new dry electrographic toners and developers containing quaternary ammonium salts that could perform the charge-controlling function well, while avoiding or minimizing all of the drawbacks noted above. The present invention does this.
SUMMARY OF THE INVENTION
The invention provides new dry, particulate electrostatographic toners and developers containing new charge-control agents comprising quaternary ammonium salts having the structure ##STR2## wherein R is alkyl having 12 to 18 carbon atoms.
The inventive toners comprise a polymeric binder and a charge-control agent chosen from the salts defined above. The inventive developers comprise carrier particles and the inventive particulate toner defined above.
The salts provide good charge-control in the inventive toners and developers. The inventive toners and developers do not exhibit unacceptably high conductivity or environmental sensitivity. The salt have decomposition points well above 200° C. and melting points well below 120° C. and are quickly, efficiently and uniformly dispersed and structurally intact in the inventive toners prepared by melt-blending the salts with appropriate polymeric binders. In the inventive toners and developers, the salts have not been found to interact unacceptably with commonly utilized toner colorants, carrier materials, or copier components such as fuser rolls.
It should be noted that the salts employed in the toners and developers of this invention and other new quaternary ammonium salts, and also other inventive toners and developers, different from those of the present invention, but devised to serve similar purposes, are described in copending U.S. patent application Ser. Nos. 134,285, 134,336, 134,344, 134,347, 134,399, 134,409, 134,411, 134,427, 134,478, 134,479, and 134,488, all filed Dec. 17, 1988.
DESCRIPTION OF PREFERRED EMBODIMENTS
The new quaternary ammonium salts employed in the toners and developers of the invention can be conveniently prepared from readily available starting materials, such as a halide salt of the appropriate benzyldimethyl(C12-18)alkylammonium monohydrate and an alkali metal salt of 3,5-dimethoxycarbonylbenzenesulfonate. For example, benzyldimethyloctadecyl ammonium chloride monohydrate is commercially available from Onyx Chemical Co., USA, under the trademark Ammonyx-4002, and sodium 3,5-dimethyoxycarbonylbenzenesulfonate is commercially available from the Aldrich Chemical Company, USA. Aqueous solutions of these materials, in proportions to give a slight stoichiometric excess of the alkali metal salt of 3,5-dimethoxycarbonylbenzenesulfonate, are mixed together and spontaneously react to yield a precipitate of the desired new quaternary ammonium salt.
To be utilized as a charge-control agent in the electrostatographic toners of the invention, the quaternary ammonium salt is mixed in any convenient manner (preferably by melt-blending as described, for example, in U.S. Pat. Nos. 4,684,596 and 4,394,430) with an appropriate polymeric toner binder material and any other desired addenda, and the mix is then ground to desired size to form a free-flowing powder of toner particles containing the charge agent.
Toner particles of the invention have an average diameter between about 0.1 μm and about 100 μm, a value in the range from about 1.0 to about 30 μm being preferable for many currently used machines. However, larger or smaller particles may be needed for particular methods of development or development conditions.
Generally, it is has been found desirable to add from about 0.05 to about 6 parts and preferably 0.05 to about 2.0 parts by weight of the aforementioned quaternary ammonium salts per 100 parts by weight of a polymer to obtain the improved toner composition of the present invention. Although larger or smaller amounts of a charge control agent can be added, it has been found that if amounts much lower than those specified above are utilized, the charge-control agent tends to exhibit little or substantially no improvement in the properties of the toner composition. As amounts more than about 6 parts of charge-control agent per 100 parts of polymeric binder are added, it has been found that the net toner charge exhibited by the resultant toner composition tends to be reduced. Of course, it must be recognized that the optimum amount of charge-control agent to be added will depend, in part, on the particular quaternary ammonium charge-control agent selected and the particular polymer to which it is added. However, the amounts specified hereinabove are typical of the useful range of charge-control agent utilized in conventional dry toner materials.
The polymers useful as toner binders in the practice of the present invention can be used alone or in combination and include those polymers conventionally employed in electrostatic toners. Useful polymers generally have a glass transition temperature within the range of from 50° to 120° C. Preferably, toner particles prepared from these polymers have relatively high caking temperature, for example, higher than about 60° C., so that the toner powders can be stored for relatively long periods of time at fairly high temperatures without having individual particles agglomerate and clump together. The melting point of useful polymers preferably is within the range of from about 65° C. to about 200° C. so that the toner particles can readily be fused to a conventional paper receiving sheet to form a permanent image. Especially preferred polymers are those having a melting point within the range of from about 65° to about 120° C. Of course, where other types of receiving elements are used, for example, metal plates such as certain printing plates, polymers having a melting point and glass transition temperature higher than the values specified above can be used.
Among the various polymers which can be employed in the toner particles of the present invention are polycarbonates, resin-modified maleic alkyd polymers, polyamides, phenol-formaldehyde polymers and various derivatives thereof, polyester condensates, modified alkyd polymers, aromatic polymers containing alternating methylene and aromatic units such as described in U.S. Pat. No. 3,809,554 and fusible crosslinked polymers as described in U.S. Pat. No. Re. 31,072.
Typical useful toner polymers include certain polycarbonates such as those described in U.S. Pat. No. 3,694,359, which include polycarbonate materials containing an alkylidene diarylene moiety in a recurring unit and having from 1 to about 10 carbon atoms in the alkyl moiety. Other useful polymers having the above-described physical properties include polymeric esters of acrylic and methacrylic acid such as poly(alkyl acrylate), and poly(alkyl metharylate) whrein the alkyl moiety can contain from 1 to about 10 carbon atoms. Additionally, other polyesters having the aforementioned physical properties are also useful. Among such other useful polyesters are copolyesters prepared from terephthalic acid (including substituted terephthalic acid), a bis(hydroxyalkoxy)phenylalkane having from 1 to 4 carbon atoms in the alkoxy radical and from 1 to 10 carbon atoms in the alkane moiety (which can also be a halogen-substituted alkane), and an alkylene glycol having from 1 to 4 carbon atoms in the alkylene moiety.
Other useful polymers are various styrene-containing polymers. Such polymers can comprise, e.g., a polymerized blend of from about 40 to about 100 percent by weight of styrene, from 0 to about 45 percent by weight of a lower alkyl acrylate or methacrylate having from 1 to about 4 carbon atoms in the alkyl moiety such as methyl, ethyl, isopropyl, butyl, etc. and from about 5 to about 50 percent by weight of another vinyl monomer other than styrene, for example, a higher alkyl acrylate or methacrylate having from about 6 to 20 or more carbon atoms in the alkyl group. Typical styrene-containing polymers prepared from a copolymerized blend as described hereinabove are copolymers prepared from a monomeric blend of 40 to 60 percent by weight styrene or styrene homolog, from about 20 to about 50 percent by weight of a lower alkyl acrylate or methacrylate and from about 5 to about 30 percent by weight of a higher alkyl acrylate or methacrylate such as ethylhexyl acrylate (e.g., styrene-butyl acrylate-ethylhexyl acrylate copolmer). Preferred fusible styrene copolymers are those which are covalently crosslinked with a small amount of a divinyl compound such as divinylbenzene. A variety of other useful styrene-containing toner materials are disclosed in U.S. Pat. Nos. 2,917,460; Re. 25,316; 2,788,288; 2,638,416; 2,618,552 and 2,659,670.
Various kinds of well-known addenda (e.g., colorants, release agents, etc.) can also be incorporated into the toners of the invention.
Numerous colorant materials selected from dyestuffs or pigments can be employed in the toner materials of the present invention. Such materials serve to color the toner and/or render it more visible. Of course, suitable toner materials having the appropriate charging characteristics can be prepared without the use of a colorant material where it is desired to have a developed image of low optical density. In those instances where it is desired to utilize a colorant, the colorants can, in principle, be selected from virtually any of the compounds mentioned in the Colour Index Volumes 1 and 2, Second Edition.
Included among the vast number of useful colorants are such materials as Hansa Yellow G (C.I. 11680), Nigrosine Spirit soluble (C.I. 50415), Chromogen Black ET00 (C.I. 45170), Solvent Black 3 (C.I. 26150), Fuchsine N (C.I. 42510), C.I. Basic Blue 9 (C.I. 52015). Carbon black also provides a useful colorant. The amount of colorant added may vary over a wide range, for example, from about 1 to about 20 percent of the weight of the polymer. Particularly good results are obtained when the amount is from about 1 to about 10 percent.
To be utilized as toners in the electrostatographic developers of the invention, toners of this invention can be mixed with a carrier vehicle. The carrier vehicles, which can be used with the present toners to form the new developer compositions, can be selected from a variety of materials. Such materials include carrier core particles and core particles overcoated with a thin layer of film-forming resin.
The carrier core materials can comprise conductive, non-conductive, magnetic, or non-magnetic materials. For example, carrier cores can comprise glass beads; crystals of inorganic salts such as aluminum potassium chloride; other salts such as ammonium chloride or sodium nitrate; granular zircon; granular silicon; silicon dioxide; hard resin particles such as poly(methyl methacrylate); metallic materials such as iron, steel, nickel, carborundum, cobalt, oxidized iron; or mixtures or alloys of any of the foregoing. See, for example, U.S. Pat. Nos. 3,850,663 and 3,970,571. Especially useful in magnetic brush development schemes are iron particles such as porous iron particles having oxidized surfaces, steel particles, and other "hard" or "soft" ferromagnetic materials such as gamma ferric oxides or ferrites, such as ferrites of barium, strontium, lead, magnesium, or aluminum. See, for example, U.S. Pat. Nos. 4,042,518; 4,478,925; and 4,546,060.
As noted above, the carrier particles can be overcoated with a thin layer of a film-forming resin for the purpose of establishing the correct triboelectric relationship and charge level with the toner employed. Examples of suitable resins are the polymers described in U.S. Pat. Nos. 3,547,822; 3,632,512; 3,795,618 and 3,898,170 and Belgian Pat. No. 797,132. Other useful resins are fluorocarbons such as polytetrafluoroethylene, poly(vinylidene fluoride), mixtures of these and copolymers of vinylidene fluoride and tetrafluoroethylene. See, for example, U.S. Pat. Nos. 4,545,060; 4,478,925; 4,076,857; and 3,970,571. Such polymeric fluorohydrocarbon carrier coatings can serve a number of known purposes. One such purpose can be to aid the developer to meet the electrostatic force requirements mentioned above by shifting the carrier particles to a position in the triboelectric series different from that of the uncoated carrier core material, in order to adjust the degree of triboelectric charging of both the carrier and toner particles. Another purpose can be to reduce the frictional characteristics of the carrier particles in order to improve developer flow properties. Still another purpose can be to reduce the surface hardness of the carrier particles so that they are less likely to break apart during use and less likely to abrade surfaces (e.g., photoconductive element surfaces) that they contact during use. Yet another purpose can be to reduce the tendency of toner material or other developer additives to become undesirably permanently adhered to carrier surfaces during developer use (often referred to as scumming). A further purpose can be to alter the electrical resistance of the carrier particles.
A typical developer composition containing the above-described toner and a carrier vehicle generally comprises from about 1 to about 20 percent by weight of particulate toner particles and from about 80 to about 99 percent by weight carrier particles. Usually, the carrier particles are larger than the toner particles. Conventional carrier particles have a particle size on the order of from about 20 to about 1200 microns, preferably 30-300 microns.
Alternatively, the toners of the present invention can be used in a single component developer, i.e., with no carrier particles.
The toner and developer compositions of this invention can be used in a variety of ways to develop electrostatic charge patterns or latent images. Such developable charge patterns can be prepared by a number of means and be carried for example, on a light sensitive photoconductive element or a non-light-sensitive dielectric-surfaced element such as an insulator-coated conductive sheet. One suitable development technique involves cascading the developer composition across the electrostatic charge pattern, while another technique involves applying toner particles from a magnetic brush. This latter technique involves the use of a magnetically attractable carrier vehicle in forming the developer composition. After imagewise deposition of the toner particles, the image can be fixed, e.g., by heating the toner to cause it to fuse to the substrate carrying the toner. If desired, the unfused image can be transferred to a receiver such as a blank sheet of copy paper and then fused to form a permanent image.
The following preparations, measurements, tests, and examples are presented to further illustrate some preferred embodiments of the toners and developers of the invention and the charge agent salts employed therein, and to compare their properties and performance to those of salts, toners, and developers outside the scope of the invention.
Preparation 1--Benzyldimethyloctadecylammonium 3,5-dimethoxycarbonylbenzenesulfonate
Benzyldimethylocatdecylammonium chloride monohydrate from Onyx Chemical Co. (68.2 g, 0.154 mole) was dissolved in hot water (1.5 l), and a solution of sodium 3,5-dimethoxycarbonylbenzene-sulfonate from Aldrich Chemical Co. (50.2 g, 0.169 mole) in warm water (1.5 l) was added. A gummy precipitate formed, which was extracted with dichloromethane, dried, and treated with anhydrous diethyl ether to crystallize as fine white needles, which were collected by filtration, washed with additional ether, and dried in a vacuum oven (70° C.). The product, benzyldimethyloctadecylammonium 3,5-dimethoxycarbonylbenzenesulfonate, was characterized by a combination of nuclear magnetic resonance spectroscopy, infrared spectroscopy, combustion analysis, melting point, and thermogravimetric analysis.
Yield: 94.7 g (0.143 mole, 93.0%); mp: 79.5°-81.5° C.; 'H NMR (CDCl 3 ): δ0.87 (t, 3H), 1.25 (m, 30H), 1.79 (m, 2H), 3.22 (s, 6H), 3.42 (m, 2H), 3.91 (s, 6H), 4.82 (s, 2H), 7.4-7.7 (m, 5H), 8.68 (s, 1H), and 8.80 ppm (s, 2H); IR (KBR): ν1738, 1725, 1233, 1223, 760, 734, and 623 cm -1 ; TGA (10° C./min, air: stable to 233° C. Atomic analysis calculated for C 37 H 59 NO 7 S (661.94): 2.1% N, 67.1% C, 9.0% H, and 4.8% S. Found: 2.0% N, 67.4% C, 8.9% H, and 4.8% S.
The other salts useful in toners within the scope of the invention are prepared similarly, with similar yields.
Measurements of Salt Melting Point and Decomposition Point
The quaternary ammonium salt of Preparation 1 was measured in comparison to similar salts useful in toners outside the scope of the present invention, in regard to melting point and decomposition point. Decomposition temperatures were measured in a DuPont Thermal Gravimetric Analyzer 1090. Results are presented in Table I.
TABLE I______________________________________ Useful in Toners Decom- Of the Melting positionSalt Invention? Point (°C.) Point (°C.)______________________________________benzyldimethylocta- yes 80-82 233decylammonium 3,5-di-methoxycarbonylbenzenesulfonatebenzyldimethylocta- no 145-146 160decylammoniumchloridep-nitrobenzyldimethyl no 189-190 189octadecylammoniumchloridebenzyldimethylocta- no 154-155 287decylammoniumbenzenesulfonatebenzyldimethylocta- no 173-174 272decylammonium p-chlorobenzenesulfonatebenzyldimethylocta- no 172-174 218decylammonium p-toluenesulfonate______________________________________
The data in Table I show that the salt useful in toners of the invention has a decomposition point well above 200° C. and a melting point well below 120° C., whereas the salts not useful in the inventive toners have a decomposition point below 200° C. (indicating likely decomposition during some toner melt-blending processes) and/or a melting point above 120° C. (indicating likely slow, inefficient, and non-uniform dispersion in toner binder during some toner melt-blending processes.
Carrier Coating Interaction Test
A salt useful in toners of the invention and non-inventive salts not useful in toners of the invention were tested for possible adverse interaction with a typical carrier material. Carrier samples were prepared as in U.S. Pat. No. 4,546,060, comprising strontium ferrite core material coated with a thin film of poly(vinylidene fluoride). The salts to be tested were coated from a dichloromethane solution onto the polymer-coated carrier samples to give a concentration of 4% salt and 96% polymer-coated carrier. A control for comparison purposes contained no salt on the polymer-coated carrier. All samples were exercised for 24 hours by placing them in vials on top of a typical, normally rotating, magnetic brush development apparatus. The salts were then extracted from the coated carriers with dichloromethane, and the carriers were dried. The charging capabilities of the carriers after this treatment were determined by mixing the carriers with a standard particulate toner and measuring the toner charge generated thereby in microcoulombs per gram (μc/g). In cases where no salt or a completely non-interactive salt were used, one would expect no change in charging capability after the treatment. Results are presented in Table II.
TABLE II______________________________________ Useful in Charge % decrease Toners after in charge Of the treatment because ofSalt Invention? (μc/g) treatment______________________________________none (control) no 29.7 0 (control)benzyldimethyloctadecyl- yes 26.0 12.5ammonium 3,5-dimethoxy-carbonylbenzenesulfonatebenzyldimethyloctadecyl- no i5.8 46.8ammonium 2,4 dimethyl-benzenesulfonatebenzyldimethyloctadecyl- no 8.l 72.7ammonium 2,5-dimethyl-benzenesulfonatebenzyldimethyloctadecyl- no 17.4 41.4ammonium p-chloro-benzenesulfonatebenzyldimethyloctadecyl- no 17.5 41.1ammonium p-toluene-sulfonatebenzyldimethyloctadecyl- no 13.6 54.2ammonium 2,4,5-tri-chlorobenzenesu1fonatephenethyldimethyloctadecyl- no 14.1 52.5ammonium p-toluene-sulfonate______________________________________
The data in Table II indicate that the salt useful in toners of the invention interacted minimally with the coated carrier, producing a minimal decrease in charging capability; while the salts not useful in the inventive toners decreased the charging capability of the carrier by much larger percentages, indicative of significant adverse interaction with the coated carrier.
Fuser Roll Cover Interaction Test
A salt useful in toners of the invention and various salts which could be employed in toners outside the scope of the invention were tested for possible adverse interaction with a typical fuser roll cover material. Plaques of poly(vinylidene fluoride-co-hexafluoropropylene) containing some carbon filler were compression molded to about 1.9 mm thickness to represent typical fuser roll covers. The salts to be tested were placed on the plaques in 100 mg portions (dry, no solvent). A control plaque had nothing placed on it. The plaques were baked at about 190° C. for 24 hours in air to simulate heat fusing conditions and were allowed to cool to room temperature. The salts or their residues were removed from the plaques by rinsing with dichloromethane. Any visible cracks in the plaques were noted. Areas of the plaques contacted by the salts were subjected to thermogravimetric analysis to determine their decomposition points. Results are presented in Table III.
TABLE III______________________________________ Decom- Useful in position Toners point of Of the Observed treatedSalt Invention? Cracking? cover (°C.)______________________________________none (control) no no 404.2benzyldimethylocta- yes no 383.4decylammonium 3,5-di-methoxycarbonylbenzenesulfonatebenzyldimethylocta- no no 377.3decylammonium p-toluenesulfonatephenethyldimethylocta- no no 329.3decylammonium p-toluenesulfonatebenzyldimethylocta- no yes 400.8decylammoniumchloride______________________________________
The data in Table III indicate that contact with a salt useful in toners of the invention under heat fusing conditions produced minimal effect on the fuser cover material, while contact with salts useful in toners outside the scope of the invention either produced cracks in the cover material or lowered its thermal stability more significantly. The lack of adverse lowering of decomposition point in the sample contacted with benzyldimethyloctadecylammonium chloride (although cracking did occur) may be because significant decomposition of that salt occurs at temperatures well below that used in the test. (See Table I).
EXAMPLE
TONERS AND DEVELOPERS
The salt of Preparation 1 was employed and evaluated as a charge agent in two different concentrations in inventive toners and developers.
Inventive toner samples were formulated from 30 g toner binder comprising a crosslinked vinyl-addition polymer of styrene, butyl acrylate, and divinylbenzene (weight ratio: 77/23/1.35); 1.8 g. of a carbon black pigment; and 0.3 and 0.9 g of the salt of Preparation 1. The formulations were melt-blended on a two-roll mill at 130° C., allowed to cool to room temperature, and ground down to form inventive toner particles. Inventive developers were prepared by mixing the toner particles (at a weight concentration of 13% toner) with carrier particles comprising strontium ferrite cores coated with poly(vinylidene fluoride). Toner charges were then measured in microcoulombs per gram of toner (μc/g). Previous experience has shown that a toner with well-dispersed charge agent will show increased charge as charge agent concentration is increased, but a toner with poorly dispersed charge agent will show decreased charge as charge agent concentration is increased. Results are presented in Table IV.
TABLE IV______________________________________Charge Agent Toner ChargeConcentration (g) in Toner (μc/g)______________________________________0.3 13.10.9 18.3______________________________________
The data in Table IV indicate that the charging properties of the inventive toners and developers were good, and that the charge agents were well dispersed in the inventive toner particles (since the toner charge increased with increased charge agent concentration).
Similarly good results are achieved when the inventive toners contain a charge agent comprising benzyldimethyldodecylammonium 3,5-dimethyoxycarbonylbenzenesulfonate.
The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it should be appreciated that variations and modifications can be effected within the spirit and scope of the invention. | New electrostatographic toners and developers are provided containing new charge-control agents comprising quaternary ammonium salts having the structure ##STR1## wherein R is alkyl having 12 to 18 carbon atoms. | 8 |
BACKGROUND OF THE INVENTION
The invention relates generally to a hollow door construction employing a structural void filler for augmenting door strength. More specifically, the door panel herein includes a "honeycomb", multi-cellular void filler utilizing variable cell size to provide greater door strength than known prior art constructions.
Applicants are aware of the following references generally pertaining to door, or panel construction: U.S. Pat. Nos. 2,765,056, 10/02/56, Tyree; 2,824,630, 2/25/58, Tolman; 2,827,670, 3/25/58, Schwindt; 2,833,004, 5/06/58, Johnson et al.; 2,980,573, 4/18/61, Clifford; 4,130,682, 12/19/78, Lauko.
These references disclose a consistent or repeated cell configuration throughout the structural void filler. The Schwindt patent discloses and discusses a preferred construction using a higher concentration of cellular material in the vicinity of the longitudinal edges of the door, but this is accomplished by compressing the uniformly sized cells into a smaller volume than the remaining cells. As will become more apparent from the detailed description of the invention, the purpose, placement, and manner of accomplishing variable cell size in Schwindt is far removed from similar considerations of the invention herein.
Reference is also made to U.S. Pat. No. 4,372,717, issued to us on Feb. 8, 1983, disclosing a cellular void filler particularly adapted for filling voids within a container carrying articles of freight. This patent discloses a honeycomb cell construction designed to be manually expanded from a flat stack of strips into a relatively thick, structural void filler. The patented structure is further adapted to maintain an expanded configuration when freely suspended under its own weight. It is not directed towards a thin, rigid door panel construction designed for hinge suspension from a longitudinal frame edge.
SUMMARY OF THE INVENTION
A door panel construction includes a rectangular door panel frame enclosing and reinforced by a structural void filler formed from elongated corrugated paperboard strips of the same width as the frame thickness. The strips are folded and connected to each other to form a plurality of quadrangular cells, a first type characterized as brace cells and a second type characterized as lateral cells.
The brace cells are apex connected to form a series or line of brace cells disposed along the longitudinal center line of the door frame, extending from the top end to the bottom end of the door frame. The brace cells are also formed to have shorter cell walls than those of the lateral cells, and consequently exhibit greater resistance to edge applied compressive forces than the lateral cells.
The lateral cells are attached to the brace cells, and fill the remaining voids within the door enclosure, on either side of the brace cells.
A pair of sheet panels is preferably glued both to the faces of the door frame and to the exposed edges of the quadrangular cells to form a rigid door panel.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an isometric perspective view of a conventional door panel construction, using uniform cell wall dimensions, the front sheet panel being removed for clarity;
FIG. 2 is an isometric perspective view of the present door panel construction, employing variable cell wall dimensions for additional strength along the longitudinal axis of the door, the front sheet panel being removed for clarity; and,
FIG. 3 is a tabulation of two compression tests, comparing prior art structural void filler with the present invention, Test A corresponding to a 12" thick structure and Test B corresponding to a 11/8" thick structure.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Making reference now to FIG. 1, there is afforded an outside frame 6, preferably constructed from lumber elements, including a pair of generally parallel upper and lower end pieces 7 and 8, respectively, as well as a pair of longitudinally extending side pieces 9 and 11, joined to the end pieces at right angled corners to form a rectangular, open center frame. Since all of the pieces of the frame are substantially of the same thickness, the frame defines a rectangular interior void, having a uniform thickness. The frame 6 usually includes between its ends a pair of short blocks 13 and 14, secured to the side pieces 9 and 11, providing a mounting base for a door handle and locking assembly.
In the FIG. 1 arrangement, the interior void is occupied by a conventional "honeycomb" structural void filler 15, assembled from a number of elongated corrugated paperboard strips 16, fastened together at various intersections 17. It is evident that the individual cells 18 within the filler 15 do not assume the same configuration, but rather appear somewhat distorted in various aspects. It is of interest to note that while the cells 18 in FIG. 1 are of different shapes, the cell wall dimension between adjacent intersections 17 is identical throughout the filler 15.
The cell distortion stems primarily from the inherent inability of the strips 16 to withstand even slightly excessive stretching forces when the filler is initially expanded to fill the void. Consequently, uneven and unpredictable distribution of the strips 16 throughout the interior void is a common problem associated with such a strip construction.
The door 19 is completed by affixing a front sheet panel (not shown) and a rear sheet panel 20 over the opposite, front and rear faces of the frame 6 and the parallel, outer edges of the strips 16.
In FIG. 2, the preferred construction of the present invention is disclosed. In this instance, there is a generally rectangular frame 21 comprised of a pair of parallel side members 22 and 23 joined at their ends to a pair of transversely extending upper end member 24 and lower end member 26, also parallel to each other. End members 24 and 26 meet side members 22 and 23 in right angle corners, affording a rectangular frame enclosing a central void. The thickness of all of the end and side members is substantially the same so that the frame 21, in effect, defines a pair of parallel, planar faces. The frame 21 also includes a pair of opposing, internally mounted blocks 27 and 28 for the mounting of locks and other hardware.
The void embraced by the frame 21 is largely filled by a structural void filler 29, formed by a plurality of strips 31. Constructed preferably from corrugated paperboard material, the strips 31 have elongated parallel edges spaced the same dimension as the distance between the opposite faces of the frame. Accordingly, the depth of the structural void filler 29 corresponds to the thickness of the surrounding frame 21.
As shown in FIG. 2, each strip 31 extends from the side member 22 to the opposing side member 23, and is folded and attached to the upper and lower adjacent strips 31 to form a plurality of quadrangular cells 32, including brace cells 33 and lateral cells 34. Each of the quadrangular cells 32 has apexes 36 and corners 37.
The apexes of the brace cells 33 are arranged to form a centrally positioned line of brace cells, extending longitudinally from the upper end member 24 to the lower end member 26. It is important to note that the apex to corner dimension of the brace cells 33 is characteristically shorter than the apex to corner dimension of the lateral cells 34. As the void filler 29 reaches a fully expanded state as shown in FIG. 2, the diamond-shaped brace cells are unable to stretch any farther longitudinally and act as a limit stop. In effect, this prevents the lateral cells 34 from distorting and causing the unequal and unpredictable distribution of supportive strip material shown in FIG. 1.
A second consequence of the reduced apex to corner dimension, or cell wall size, is a significant increase in the concentration of edgewise strip material along the longitudinal line of the brace cells 33. As will become more apparent herein, the series of short walled brace cells 33 affords in effect a strong, stiff or rigid backbone which supports the weakest portion of the structure.
In addition, lateral cells 34 are positioned on either side of a respective brace cell 33. Each lateral cell 34 has an inner corner connected to the adjacent corner of the brace cell, and the upper and lower apexes of each lateral cell are attached to respective apexes of superjacent and subjacent lateral cells. As illustrated in FIG. 2, the two lines of lateral cells 34 extend longitudinally from the upper end member 24 to lower end member 26.
Completing the door 38, a rear sheet panel 39 and a front sheet panel (not shown) abut and are secured to the opposite faces of the frame 21 and to the parallel edges of the strips 31. The corrugated paperboard used to construct the strips 31 has flutes oriented in a direction normal to the planes of the front and rear sheets, and therefore provides the desired degree of strength and rigidity to resist compressive or impact forces imposed upon the door panels. However, it is the strategic distribution of supportive strip material in the present invention which provides improved door strength over known prior art designs.
As has been mentioned previously, the largely unsupported central portion of a hollow door is the region least able to withstand destructive blows. By providing a line of relatively stronger brace cells within this weak region, the present invention largely overcomes the strength deficiencies of prior art designs. This additional cell strength is attained by reducing the apex to corner cell wall dimension in the brace cells, thereby increasing the amount of edgewise paperboard supporting a given surface area of panel sheeting. While compression tests have confirmed that brace cells so designed and strategically placed will increase the overall strength of a structural panel, the increase in strength for a thin panel or door construction is greater than would normally be expected.
Making reference to FIG. 3, the conditions and the results of compression tests conducted for two structural void fillers of different thicknesses are shown. In Test A, two 3' square structural void fillers, each 12" deep, and constructed from 8 ply corrugated paperboard, were tested for maximum compressive strength. The filler thickness and material correspond generally to that employed for structural void fillers used as dunnage while shipping articles of freight. The prior art filler used a standard honeycomb cell construction, in which each cell had an identical apex to corner, or cell wall dimension of 9". The other void filler, constructed in accordance with the teachings of the present invention, used the combination of strategically placed brace cells having a 7.25" cell wall, and lateral cells having a 10.25" cell wall dimension.
The filler using the brace cell construction exhibited a 6% increase in strength over the filler using the conventional, uniform cell construction. Since the compressive force was applied over the entire 9' square surface area, the smaller and stronger brace cells were able to withstand a greater amount of force before collapsing than were the 9" cells.
In Test B, a similar comparison was conducted using 3' square structural void fillers, each 11/8" deep and constructed from 18 ply corrugated paperboard. The thickness and the material of the panels in Test B agree with those normally associated with fillers for hollow doors. In this instance, the prior art filler also used the conventional honeycomb cell construction, but the cell wall dimension of each cell was only 5.5", the standard cell wall size for the structural filler in a hollow door. The remaining void filler used a centrally positioned line of brace cells having 4" cell walls, straddled on either side by lateral cells having 6" cell walls.
The filler construction making use of the 4" brace cells showed a 28% improvement in strength over the conventional, prior art construction. In other words, in going from a void filler construction for dunnage to a void filler construction for hollow doors, the use of brace cells affords an increase in strength over prior art construction which escalates from 6% to 28%. It is believed that this unexpected and beneficial result stems from the substantial reduction in brace cell size when comparing Test B (4" brace cell) to Test A (7.25" brace cell).
It is also significant to note that the increase in strength of the fillers using brace cells was achieved without using more corrugated paperboard material than that used in the conventional construction. Thus, the present invention affords higher resistance to compressive forces through reducing cell wall dimensions within a strategic region, rather than resorting to the costlier alternative of merely adding more structural material. | A hollow door panel construction includes a rectangular frame of predetermined thickness assembled from side and end members defining an elongated enclosure. Within the enclosure are corrugated paperboard strips, having a width equal to the predetermined thickness. The strips are variously formed and attached to define a plurality of horizontal cell rows, vertically stacked to fill the framed volume. Each cell row spans the internal width of the frame, and includes a centrally positioned short-walled brace cell straddled on either side by a long-walled lateral cell. To complete the panel construction, thin sheets abut and are secured to the opposite faces of the frame and to the outer edges of the strips. | 8 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is based upon and claims the benefit of priority from prior Japanese Patent Application No. 2009-049371, filed Mar. 3, 2009, the entire contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to an electronic apparatus, and more particularly to a cooling system for the electronic apparatus.
[0004] 2. Description of the Related Art
[0005] An electronic apparatus such as a television transmitter provided in a base station includes heat generating electronic circuits such as a power amplifier. The electronic circuits may be attached to or removed from a case of the electronic apparatus. When a large amount of heat is generated by driving of the circuits, performance characteristics of the electronic apparatus are decreased. Thus, various cooling mechanisms to cool the electronic circuits maintaining desired performance characteristics have been introduced.
[0006] For example, Jpn. Pat. Appln. KOKAI Publication No. 2007-243728 discloses a cooling mechanism provided with an exhaust fan to assure cooling reliability. According to the cooling mechanism, the external air is taken in the case of the electronic apparatus, circulated therein, and discharged from the case by the exhaust fan. The electronic circuits are controlled so that the heat generated by the electronic circuits is forced to be expelled from the case. Such forced cooling method is employed to achieve the desired performance characteristics.
[0007] However, higher-power outputs from recent electronic circuits generate a larger amount of heat to increase an exhaust heat temperature and a temperature of a room, in which the electronic apparatus is placed. Thus, thermal control for the electronic circuits can be difficult without improving air conditioning performance for the room to decrease the temperature of the air taken into the case.
[0008] In view of power-saving, which is strongly required in these days, it is considered to be important addressing a rise in air conditioning performance.
BRIEF SUMMARY OF THE INVENTION
[0009] According to an embodiment of the present invention, an electronic apparatus comprises:
[0010] a case configured to house an electronic circuit unit and comprising an air intake, through which external air is taken into the case, and an exhausting opening, from which the air is ejected;
[0011] an circulator provided in the case and configured to take the external air into the case through the air intake and supply the air to the electronic circuit unit;
[0012] an evaporation unit provided in the case and configured to cool the air by thermal exchange between the air and a working medium and guide the air to the exhausting opening, the working medium being vaporized as a result of the thermal exchange; and
[0013] a condenser provided out of the case and configured to liquidize the working medium and supply the working medium to the evaporation unit.
[0014] According to another embodiment of the present invention, a cooling system for an electronic apparatus comprising an electronic circuit unit, the cooling system comprises:
[0015] an circulator configured to take external air into a case of the electronic apparatus and supply the air to the electronic circuit unit;
[0016] an evaporation unit configured to cool the air by thermal exchange between the air and a working medium and guide the air to be ejected from the case of the electronic apparatus, the working medium being vaporized as a result of the thermal exchange; and
[0017] a condenser provided out of the case and configured to liquidize the working medium and supply the working medium to the evaporation unit.
[0018] Additional objects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out hereinafter.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
[0019] The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate embodiments of the present invention and, together with the general description given above and the detailed description of the embodiments given below, serve to explain the principles of the present invention.
[0020] FIG. 1 is a view showing a rear face of an electronic apparatus according to an embodiment of the present invention;
[0021] FIG. 2 is a view showing a cooling mechanism arrangement for an electronic circuit housed in the electronic apparatus shown in FIG. 1 ;
[0022] FIG. 3 is a view showing an arrangement of power amplifiers, exhausting fans, evaporation units, and outdoor units according to the embodiment;
[0023] FIG. 4 is a view showing a cooling cycle provided by an evaporation unit and an outdoor unit according to the embodiment;
[0024] FIG. 5 is a view showing a setting of a case of the electronic apparatus, according to an embodiment; and
[0025] FIG. 6 is a view showing another setting of the case of the electronic apparatus, according to an embodiment.
DETAILED DESCRIPTION OF THE INVENTION
[0026] An embodiment of the present invention will now be described with reference to the accompanying drawings.
[0027] FIG. 1 shows an electronic apparatus according to an embodiment of the present invention. A case 10 is provided with an air intake 11 which is vertically elongated along a substantially middle portion on a front face of the case 10 , for example. On both sides of a rear face of the case 10 , exhaust openings 12 are also provided, which are vertically elongated. The air intake 11 is located between the exhaust openings 12 . A filter member 13 is provided on the air intake 11 as shown in FIG. 2 . The air for cooling an exterior is taken into the case 10 through the filter member 13 .
[0028] Electronic circuits including power amplifiers 14 are stacked in two columns in the case 10 . The air intake 11 is located between the columns. One column of the power amplifiers 14 is communicated with one of the exhaust openings 12 via a duct 15 , which provides an exhaust channel. The other column of the power amplifiers 14 is also communicated with the other of the exhaust openings 12 via another duct 15 , which provides another exhaust channel.
[0029] It should be noted that another configuration of the air intake 11 and the exhaust openings 12 is possible in the case 10 .
[0030] In the ducts 15 , exhaust fans 16 are provided in association with the power amplifiers 14 . In one exhaust channel, evaporation units 17 are positioned between an exhaust opening 12 and an exhausting side of an exhaust fan 16 . Also in another channel, evaporation units 17 are positioned between an exhaust opening 12 and an exhausting side of an exhaust fan 16 . The evaporation units 17 in one channel are opposed to the evaporation units 17 in another channel. Each of the evaporation units 17 is individually configured. An internal air is discharged from the ducts 15 through the exhaust fans 16 and blown on the evaporation units 17 . The evaporation units 17 cause thermal exchange between the internal air and a circulating working medium to cool the internal air. The evaporation units 17 guide the internal air to be discharged from the exhaust openings 12 .
[0031] For example, as shown in FIG. 3 , outdoor units 18 which include condensing units are connected to the evaporation units 17 via pipelines 19 . The outdoor units 18 are driven by inverter control. According to the inverter control, an effective voltage and a frequency of an alternating-current power output can be arbitrarily controlled. When the inverter control is conducted at a low frequency, power consumption of the outdoor units 18 can be suppressed. Each of the outdoor units 18 includes a compressor 181 , a condenser 182 , and a pressure reducing valve 183 , as shown in FIG. 4 . The working medium is vaporized in the evaporation unit 17 and supplied to the compressor 181 via the pipeline 19 . The compressor 181 compresses the working medium to raise the pressure, and the condenser 182 liquidizes the working medium. The pressure reducing valve 183 reduces the pressure in the working medium, and then, the working medium is circularly supplied to the evaporation unit 17 .
[0032] Thus, the evaporation unit 17 causes the thermal exchange between the internal air, which is blown from the exhaust fans 16 , and the working medium, the pressure of which is reduced by the pressure reducing valve 183 , to cool the internal air. The wind power of the exhaust fans 16 ejects the cooled internal air through the evaporation units 17 and the exhaust openings 12 . In the present embodiment, the inverter control is employed in order that cooling the air is driven at a high frequency to assure a high cooling performance and at a low frequency to provide a lower cooling performance. Cooling operation at a low frequency allows the power consumption to be reduced. The cooling operation may be performed at a high frequency as well to provide a higher cooling performance, if necessary.
[0033] In the above configuration, the case 10 is provided in a room 20 such as a base station. As shown in FIG. 5 , the front face of the case 10 is opposed to a stationary air conditioner 21 . The power amplifiers 14 are used for a desired operation. The air conditioner 21 ejects air having a temperature (28° C., for example) which is lower than the temperature of the room 20 from an ejection opening 211 . The ejected air is mixed with the air in the room 20 , and the temperature of the room 20 is adjusted. The exhaust fans 16 are driven to take the air conditioned by the air conditioner 21 into the air intake 11 of the case 10 . The air is guided to the power amplifiers 14 and absorbs heat which is generated by driving of the power amplifiers 14 . Thus, the air rises in temperature up to 45° C., for example. Accordingly, the power amplifiers 14 are cooled down.
[0034] The temperature of the air which has absorbed the heat from the power amplifiers 14 comes to rise up. The air is blown on the evaporation units 17 by the wind power of the exhaust fans 16 . The evaporation units 17 cool the air down (to 33° C., for example) by the thermal exchange with the working medium which is circularly supplied form the outdoor units 18 . The air is ejected from the exhaust openings 12 to the room 20 .
[0035] A suction opening 212 of the air conditioner 21 sucks the cooled air (33° C., for example) which is expelled from the exhaust openings 12 . The air conditioner 21 further cools the air down toward 28° C. The air is ejected from the ejection opening 211 to the room 20 , to condition the temperature of the room 20 . Thus, when the electronic apparatus is provided with the evaporation units 17 and the outdoor units 18 having a small air conditioning performance, and when the air conditioner 21 is provided with cooling availability which cools the air by 5 degrees, the high-efficiency thermal control is possible and a cooling mechanism which assumes low power can be achieved. The cooling mechanism may be preferable to the electronic apparatus system. The temperature of the air taken in the case 10 is maintained at about 30° C. due to air conditioning by the air conditioner 21 . Therefore, in comparison with the case where the air is not conditioned, the thermal control for the power amplifiers 14 can be performed with the low cooling performance by the evaporation units 17 and the outdoor units 18 .
[0036] The air taken in the case 10 is warmed up by the power amplifiers 14 , passes through the evaporation units 17 to be subjected to the thermal exchange, and is cooled. The humidity of the air is also reduced and the air is ejected from the exhaust openings 12 to the room 20 . The air conditioner 21 takes in the low humidity air from the room 20 and performs latent heat cooling and sensible heat cooling to condition the air in the room 20 . If the humidity of the air taken in the air conditioner 21 is low, the heat processing is performed under a condition where necessity of the latent heat cooling is decreased and the air conditioner 21 mainly performs sensible heat cooling. Therefore, the cooling performance is improved. Thus, the latent heat cooling need not to be performed and requirement for the cooling performance is relieved. Therefore, the lower cooling performance can sufficiently condition the air in the room 20 .
[0037] That is, the electronic apparatus is configured as follows. The air intake 11 in the case 10 takes in air from the room 20 that is conditioned by the air conditioner 21 by the exhausting fans 16 . The air absorbs heat generated by driving of the power amplifiers 14 . The air is cooled by the thermal exchange with the working medium of the evaporation units 17 . The cooled air is forced to be ejected from the exhaust openings 12 by the wind force of the exhaust fans 16 .
[0038] The conditioned air is taken in the air intake 11 and warmed up by the heat emitted from the power amplifiers 14 . The wind power of the exhaust fans 16 guides the air to the evaporation units 17 . The air is cooled by the evaporation units 17 and ejected out of the case 10 . Thus, minimum temperature control for the internal air of the room 20 which is to be taken in the air intake 11 realizes the high-efficient thermal control for the power amplifiers 14 housed in the case 10 . As a result, the air-conditioning performance required to condition the air in the room 20 where the case 10 is set need not be so high. Power-saving in the electronic apparatus system can be improved.
[0039] For example, in the case of maintaining the electronic apparatus system including repairing the compressor 181 and condenser 182 in any of the outdoor units 18 , a cooling system required to be checked is stopped, while keeping the thermal control for the power amplifiers 14 to be in operation utilizing other cooling systems (or other combinations of the evaporation units 17 and the outdoor units 18 ). Thus, the electronic apparatus system can operate continuously. Therefore, the outdoor units 18 , which require frequent maintenance, can be readily maintained while continuing the operation of the electronic apparatus system.
[0040] In addition, when the air conditioner 21 breaks down, for example, only the evaporation units 17 and outdoor units 18 may be used to provide a higher cooling performance by the inverter control. Thus, thermal control for the power amplifiers 14 is continuously conducted, and also the electronic apparatus system can operate continuously.
[0041] According to the embodiment, the evaporation units 17 share the exhausting fans 16 having a long durable period, as a wind power source, which work as the forced cooling means to force heat emission. The exhausting fans 16 compulsory blows wind on the power amplifiers 14 which are continuously driven. Thus, the thermal exchange system is configured.
[0042] Accordingly, while keeping the case 10 to be in a small size, a durable period of the thermal exchange system utilizing the evaporation units 17 can be prolonged so that the thermal exchange system can be continuously used for substantially the same durable period as the exhausting fans 16 . For example, the exhausting fans 16 are produced, in general, to be operational for a long period which is corresponding to the durable period of the power amplifiers 14 . When the thermal exchange system is established using the evaporation units 17 , which share the exhausting fans 16 that is improved in durability, the thermal exchange system which is durable for a period corresponding to the power amplifiers 14 can be provided readily.
[0043] In the above embodiment, the exhausting fans 16 of the forced cooling means are provided on the side where the exhausting openings 12 are attached in the case 10 . However, the invention is not so limited. The exhausting fans 16 may be arranged on the side where the air intake 11 is provided, and similar effect to the above embodiment will be achieved.
[0044] In the above embodiment, the evaporating units 17 are provided in association with the exhausting fans 16 . However, the invention is not so limited. For example, a plurality of evaporating units 17 may be arranged in association with an exhausting fan 16 , and similar effect to the above embodiment will be achieved.
[0045] In the above embodiment, the evaporating units 17 are housed in the case 10 . However, the invention is not so limited. The evaporation units 17 may be arranged outside of the exhausting openings 12 .
[0046] In the above embodiment, the air intake 11 in the case 10 is opposed to the ejection opening 211 and the suction opening 212 of the air conditioner 21 which is placed in the room 20 . However, the arrangement is not so limited. For example, as shown in FIG. 6 , the exhausting openings 12 in the case 10 may be opposed to the ejection opening 211 and the suction opening 212 of the air conditioner 21 . In addition, the air conditioner 21 is not limited to the stationary type. Another configuration of air conditioning devices may be employed to present similar effect.
[0047] Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative embodiments shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents. | An electronic apparatus comprises a case configured to house an electronic circuit unit and includes an air intake, through which external air is taken into the case, and an exhausting opening, from which the air is ejected, an circulator provided in the case and configured to take the external air into the case through the air intake and supply the air to the electronic circuit unit, an evaporation unit provided in the case and configured to cool the air by thermal exchange between the air and a working medium and guide the air to the exhausting opening, the working medium being vaporized as a result of the thermal exchange, and a condenser provided out of the case and configured to liquidize the working medium and supply the working medium to the evaporation unit. | 7 |
BACKGROUND OF THE INVENTION
The present invention relates to an apparatus for heating an object having a circular cross-section, and more particularly to such an apparatus for heating a CRT (cathode ray tube) neck and sealing a glass stem wafer or electron gun mount therein.
A CRT comprises three major glass sections, namely a panel, a funnel, and a neck. The neck comprises at its end remote from the panel an electron gun that is mounted on a glass wafer with lead wires for the gun electrodes projecting through the wafer.
During manufacture, the CRT is held in the vertical panel-up position of a "carrousel" and the wafer with the gun mounted thereon is upwardly inserted into the neck by a mount pin or socket. Heat from burners is then applied to the outside of the neck proximate the wafer, i.e. at the "seal plane", and the CRT and the wafer are rotated as they are indexed to various stationary fire positions around the carrousel. The fires are positioned around the vertical central axis of the CRT neck so that the neck softens, thins, and then seals to the wafer. Also, excess neck material that is lower than the wafer (cullet) is cut off and therefore falls away from the neck.
Presently, there is a trend towards larger CRTs. This means that the carrousel and the rotating machinery, including two vertical support bars for the CRT, must be relatively large and heavy, and therefore expensive. Further, the two vertical bars interfere with the placement of an electrical resistance oven around the CRT neck for a preferred preheat step before the wafer sealing operation and an annealing step after sealing. Thus additional burners are required to perform these steps instead of the resistance oven. This requires additional carrousel positions and the heating provided by the burners is not as uniform as that provided by the resistance oven. The present invention overcomes the above problems.
SUMMARY OF THE INVENTION
Apparatus, in accordance with the invention, for heating a non-rotating hollow object having a circular cross-section and for sealing a wafer therein comprises a plurality of non-rotating burner nozzles disposed completely around the periphery of the object non-radially with respect to the circular cross-section. A method, in accordance with the invention, comprises substantially uniformly heating completely around the object approximately in the plane of the wafer by creating a rotating hot gas flow around the object without rotating said object or burners.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a top view of a heat sealing apparatus; and
FIG. 2 is a cross-sectional view taken along line 2--2 of FIG. 1.
DETAILED DESCRIPTION
FIG. 2 best shows a CRT bulb 10 comprising a panel 12 sealed to a funnel 14, which in turn is attached to a neck 16. The CRT bulb 10 is held by a cradle 19, which as explained below need not be capable of rotary motion. In the neck 16 is disposed at the seal plane an electron gun mount or wafer 18 that supports an electron gun 20 by way of lead wires 22. A mount pin 24 supports the wafer 18.
As shown in both FIGS. 1 and 2, a novel heat sealing apparatus comprises a metal manifold 26 having an L-shaped top plate 28 and an L-shaped bottom plate 30, which are sealed together with a sodium silicate cement. Two chambers 32 and 34 are defined by the plates 28 and 30. A plurality of burner tips 36, such as burner No. P-1 manufactured by J & P Machine and Tool Co., Clifton, N.J., communicate with one or the other of the chambers 32 or 34. In the embodiment of FIGS. 1 and 2, twenty burner tips 36 are shown but another number of such burners can be used. The burner tips 36 are in a non-radial configuration with respect to the circular cross-section of the neck 16, i.e. the center line of the burner tips forms an angle θ with respect to a radius line from the center of the neck 16. In the particular embodiment shown, which is for a standard size 29 mm outside diameter neck, the angle θ is 9 degrees and the ends of the burner tips are 7 mm from the neck periphery. In general, the burner tips 36 are aimed at the halfway point 39 between the outside diameter of the neck 16 and the outside diameter of the wafer 18. This is a compromise angle between the optimum angle for softening the neck 16, which would place the flames from the burner tips 36 at the outside diameter of the neck 16, and the optimum angle for cutting off and sealing the neck 16, which would place the flames at the outside diameter of the wafer 18.
Two pipes 40 and 42 respectively receive oxygen and a fuel, such as natural gas, and apply these gases to a gas premixing manifold 44. The combustible gas mixture from the manifold 44 is applied by a pipe 46 to the chamber 32 and by a pipe 48 to the chamber 34. The use of a single manifold 44 and the dual feed provided by the indentical in length and inside diameter pipes 46 and 48 and the chambers 32 and 34 results in a uniform temperature distribution around the neck 16.
In operation, the burner tips 36 are initially lower than the seal plane and a "clamshell" type electrical resistance oven (not shown) is brought to a temperature of 550° C., which is above the strain point for the particular neck glass used. The oven is then placed around the neck 16 for approximately 200 seconds for the preheating step. This can be done since the present invention allows support of the CRT 10 by the cradle 19 without any vertical bars near the neck 16 that would interfere with the placement of such an oven. This type of oven, in contradistinction to flame preheating, is easy to position and control and provides heat over a large area, thereby minimizing strain in the glass during the preheating step. Also, oxidation of the socket pins 24 is reduced.
Then the oven is withdrawn and the manifold 26 is raised so that the burner tips 36 are slightly above the seal plane. The burner tips 36 receive a combustible gas mixture, which is ignited to provide a temperature at the neck 16 in excess of 630° C., which is the softening point of the neck glass. Due to the angle θ, hot gas rotates around the neck 16 so that uniform heating of the neck 16 results. This eliminates the need for any rotation or back and forth oscillatory motion of the CRT 10 to provide uniform heating of the neck 16. In general, the combustible gas flow rate must be sufficient to provide the hot gas rotation, but not too great to avoid turbulent flow, which does not produce the gas rotation. The exact values of gas flow rate and pressure depend upon the energy content of the natural gas, orifice diameter of the burner tips 36, the angle θ, and the distance of the burner tips 36 from the neck 16. The neck 16 softens due to the hot gases and "necks-in" (becomes thinner and moves towards the wafer 18). Cullet (the excess neck material below the seal plane) beings to drop.
The manifold 26 and the burner tips 36 then are lowered to a position slightly below the seal plane. The oxygen flow rate is increased so that the temperature at the neck 16 is raised above 975° C. (the melting point of the neck and wafer glass) so that the cullet is quickly cut off. Surface tension draws the thinned neck up and around the stem button.
The burners 36 next are raised to the seal plane and the temperature at the seal plane is maintained at about 975° C. The neck glass and the wafer glass flow together to seal the neck 16 to the wafer 18.
Thereafter, the entire burner assembly is lowered and the glass temperature at the seal plane begins falling. the clamshell oven is re-positioned over the neck 16 for 50 seconds for an annealing step, which begins at about 600° C. due to the falling seal plane temperature, but gradually lowers to 525° C. due to a redistribution of heat in the neck 16. The oven then can be removed and the neck 16 placed in an insulated chamber (not shown) for further cooling. This results in a relatively strain free neck-to-wafer seal despite the fact that the oven is removed before the glass goes below its strain point temperature because of the redistribution of heat through the neck 16 by the oven.
Thus the entire mount-sealing operation is done in a single stationary position, and therefore no carrousel or rotating mechanism is needed.
It will be appreciated that there may be many other embodiments within the spirit and scope of the invention. For example, other temperatures than those given may be used in accordance with the type of glass used. Other types of seals can be performed, such as on camera tubes, gas lasers, splicing glass, etc. | The method for sealing a glass stem wafer into the neck of a CRT has a plurality of burner tips disposed completely around the neck. The burner tips are angled such as to create rotating hot gases around the neck. This eliminates the need to rotate the CRT bulb, the wafer or the burner tips, to achieve a uniform seal. | 2 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Application No. 61/983,213, filed on Apr. 23, 2014, which is incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
[0002] This invention relates to aspiration needle devices and uses therefore, particularly their applications in the biopsy procedures to obtain biological samples.
BACKGROUND OF THE INVENTION
[0003] Biopsy devices for fine needle aspiration (FNA) are widely used for screening diagnostic procedures and are useful for obtaining cytological specimens for examination, for example, to confirm the diagnosis of a suspected medical condition. Typical specimens collected include liquids or cell samples. Such devices are generally useful in sampling tissue from breast, head and neck, lymph nodes, and for some gynecologic conditions. Other applications include lung, prostate, and other soft tissue biopsies.
[0004] Generally, biopsy devices of this type extract samples of tissue through a small needle in the range of 25-18 gauge. The needle is inserted, typically through the skin, so that the tip of the needle is in the suspect tissue mass. A vacuum force is applied by withdrawing the plunger of a standard syringe attached to the needle. To aid in harvesting an adequate sample size, the needle is optionally moved in and out of the puncture site a plurality of times. This reciprocating motion causes cellular material to be scraped from the tissue and drawn into the needle. This procedure draws up a small amount of tissue fluid, together with loose cells, into the syringe, and the collected specimen can be directly placed on a slide for pathological analysis.
[0005] Most existing FNA biopsy procedures use the regular needle-syringe systems, which are designed for the purpose of injection instead of aspiration biopsy, and therefore, have many limitations. After the procedure is done with a regular needle-syringe system, the specimen usually spreads all over the needle, needle-syringe joint, and/or inside of the syringe. Only a small fraction of the collected specimen could be directly placed on a slide usable for pathological analyses, and a major portion of the specimen is left in the needle and syringe. For additional analysis, the specimen has to be transferred into different containers through an extra procedure such as washing, which would cause substantial loss of the precious specimen as well as possible damages to the fresh specimen. Often, with the existing FNA needles, the procedure has to be repeated multiple times in order to obtain enough samples for the required analyses.
[0006] On the other hand, multiple biomarker identifications have become more and more important in the modern personalized medicines, especially in cancer diagnosis and treatment. Effective uses of a small quantity of biopsy specimen for multiple tests are highly desirable and often required. Therefore, aspiration and biopsy devices and methods capable of collecting maximally usable biological samples are in great need.
SUMMARY OF THE INVENTION
[0007] The present invention provides new aspiration/biopsy needle devices to meet the foregoing need, which can overcome the various shortcomings of the conventional sample collection methods mentioned above.
[0008] The fine needle aspiration biopsy devices described here are novel useful tools for the FNA biopsy procedures, which can be readily used to minimize the loss of and/or damages to the specimen collected, yet are suitable for use in the normal operations of the conventional procedures.
[0009] In one aspect the present invention provides an aspiration or biopsy device comprising: a body, a cannula needle, and a sample collection container, wherein:
[0010] the body comprises a vacuum channel and a plurality of ports;
[0011] the cannula needle comprises an inlet end positioned at a first port of the body, an outlet end positioned at a second port of the body, and a middle portion enclosed inside the body; and
[0012] the vacuum channel of the body comprises a first opening end positioned at the second port of the body and a second opening end positioned at a third port of the body in communication with a vacuum source; and
[0013] the sample collection container is coupled with the second port of the body, enclosing both of the outlet end of the cannula needle and the first opening end of the vacuum channel;
[0014] wherein the inlet end of the cannula needle is capable of aspirating a sample from a target when vacuum is applied on the second opening of the vacuum channel.
[0015] In another aspect the present invention provides a needle apparatus comprising a body and a cannula needle, wherein:
[0016] the body comprises a vacuum channel and a plurality of ports;
[0017] the cannula needle comprises an inlet end positioned at a first port of the body, an outlet end positioned at a second port of the body, and a middle portion enclosed inside the body; and
[0018] the vacuum channel of the body comprises a first opening end and a second opening end, wherein the first opening end is positioned at the second port of the body so that the first opening end of the vacuum channel and the outlet end of the cannula needle can be contained in a same sample collection container coupled to the second port of the body, and the second opening end is positioned at a third port of the body, which can be in communication with a vacuum source.
[0019] In another aspect the present invention provides an aspiration device comprising a needle apparatus according to any one of the embodiments disclosed herein.
[0020] In another aspect the present invention provides a biopsy device comprising a needle apparatus according to any one of the embodiments disclosed herein.
[0021] In another aspect the present invention provides a method of extracting a biological sample from a subject, comprising: (1) providing a needle apparatus, an aspiration device, or a biopsy device according to any embodiment disclosed herein; (2) contacting the inlet end of the cannula needle of the device with a target of a desired biological sample; (3) applying a vacuum on the vacuum channel so that a desired biological sample is transferred through the cannula needle to a sample collection container.
[0022] In another aspect the present invention provides an aspiration method comprising:
[0023] a) providing an aspiration or biopsy device of any embodiment disclosed herein, or attaching a needle apparatus according to any embodiment disclosed herein to a sample collection container and a vacuum source; and b) aspirating a specimen through the needle inlet from a sample target into the sample collection container by applying a vacuum on the vacuum channel of the needle apparatus.
[0024] In one particular embodiment, the invention provides a fine needle aspiration (FNA) biopsy device for improved cell harvesting and a method of using the device. In one embodiment, the integrated fine needle aspiration (FNA) device comprises a detachable vial. In another embodiment, the integrated fine needle aspiration (FNA) device comprises a needle for penetration; an attached vial for receiving the specimen; and a syringe hub connector for attaching a vacuum source. In one embodiment, the syringe hub connector is a standard one. In another embodiment, the syringe hub connector is one having a specific size or shape to meet the need. In one embodiment, the vacuum source is a syringe, which can be a standard commercial one or a specifically designed one. In another embodiment, the vacuum source is a vacuum line optionally controlled by a vacuum gauge.
[0025] Among many other advantages, the aspiration needle system and the aspiration or biopsy devices of the present invention are easy to manufacture; convenient to assemble, dissemble, handle, and use, with each part easy to sterilize; and readily adaptable to different uses. All the parts of the apparatus or devices disclosed herein can be manufactured to fit the commercially readily available syringes, sample vials, needles, etc. manufactured according to the existing industrial standards. More importantly, the aspiration or biopsy methods using the system or devices of the present invention enable efficient extraction and use of biological samples while minimizing loss and damages to the specimens and preserving integrity of the specimens. The aspiration/biopsy devices capable of collecting maximally usable specimens will greatly benefit the clinical practices and the patients. Such devices are especially useful for extracting biological samples for early diagnosis of diseases, such as tumors, because the availability of samples is limited, and extraction of samples is difficult, at the early stage of the diseases.
[0026] These and other aspects of the present invention and advantages will become more apparent in view of the following drawings, detailed descriptions, and claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] FIG. 1 illustrates a fine needle aspiration device of the present invention that can be connected with a syringe.
[0028] FIG. 2 illustrates a fine needle aspiration device that can be connected with a vacuum line.
[0029] FIG. 3 illustrates a main center piece of the fine needle aspiration device.
[0030] FIG. 4 illustrates a fine needle aspiration device without attachments.
[0031] FIG. 5 illustrates an example of receiving vial for the fine needle aspiration device.
[0032] FIG. 6 illustrates the fine needle aspiration devices in various example shapes.
[0033] FIG. 7 illustrates various example dimensions of the fine needle aspiration devices.
[0034] FIG. 8 illustrates example dimensions of receiving vials for the fine needle aspiration devices.
[0035] FIG. 9 illustrates an example of the fine needle aspiration device with a detachable penetration needle.
[0036] FIG. 10 illustrates an example of the fine needle aspiration device connected with a detachable penetration needle.
[0037] FIG. 11 illustrates example dimensions of a detachable needle suitable for the fine needle aspiration devices.
DETAILED DESCRIPTION OF THE INVENTION
[0038] This invention, in one aspect, relates to fine needle aspiration (FNA) biopsy devices for improved cell harvesting and methods of using the devices, including but not limited to integrated fine needle aspiration (FNA) devices with detachable vials. For example, an integrated fine needle aspiration (FNA) device comprises a needle for penetration; an attached vial for receiving the specimen; and a standard syringe hub connector for attaching the vacuum source, such as a syringe. During the FNA biopsy procedure, the needle is inserted into a suspect tissue, a vacuum is created by a syringe or other vacuum sources, and cells and tissue from the targeted tissue mass are sucked through the needle into the attached vial. After the sample is obtained, the vial with the specimen sample can be detached from the device, and the sample is ready for examination.
[0039] Thus, in one aspect the present invention provides an aspiration or biopsy device comprising: a body, a cannula needle, and a sample collection container, wherein:
[0040] the body comprises a vacuum channel and a plurality of ports;
[0041] the cannula needle comprises an inlet end positioned at a first port of the body, an outlet end positioned at a second port of the body, and a middle portion enclosed inside the body; and
[0042] the vacuum channel of the body comprises a first opening end positioned at the second port of the body and a second opening end positioned at a third port of the body in communication with a vacuum source; and
[0043] the sample collection container is coupled with the second port of the body, enclosing both of the outlet end of the cannula needle and the first opening end of the vacuum channel;
[0044] wherein the inlet end of the cannula needle is capable of aspirating a sample from a target when vacuum is applied on the second opening of the vacuum channel.
[0045] In one embodiment of this aspect, the middle portion of the cannula needle is in airtight or substantially airtight contact with internal walls of the body surrounding the cannula needle.
[0046] In another embodiment of this aspect, the inlet and outlet ends of the cannula needle are two distinct pieces connected with each other through a connection means at the first port of the body.
[0047] In another embodiment of this aspect, the inlet end of the cannula needle comprises a detachable needle.
[0048] In another embodiment of this aspect, the inlet end piece comprises a needle of a commercially standard size and/or dimensions.
[0049] In another embodiment of this aspect, the inlet end of the cannula needle comprises a tip having a shape and dimension suitable for aspiration of a biological sample from an internal organ of a mammalian animal.
[0050] In another embodiment of this aspect, the second port of the body comprises a connection means to couple the body and the sample collection container.
[0051] In another embodiment of this aspect, the connection means is airtight or substantially airtight so that when a vacuum is applied on the vacuum channel, a sample can be aspirated by the inlet end of the cannula needle to the sample collection container.
[0052] In another embodiment of this aspect, the connection means fits a commercial sample collection container of standard size and/or dimensions.
[0053] In another embodiment of this aspect, the connection means is a clip mechanism, a screw mechanism, or a combination thereof.
[0054] In another embodiment of this aspect, the sample collection container is a disposable commercial sample vial.
[0055] In another embodiment of this aspect, the sample collection container is a centrifugation tube.
[0056] In another embodiment of this aspect, the inlet end of the cannula needle is protected by a cover.
[0057] In another embodiment of this aspect, the protection cover of the inlet end of the cannula needle comprises a plastic sheath.
[0058] In another embodiment of this aspect, the vacuum source comprises a means for generating a vacuum.
[0059] In another embodiment of this aspect, the means for generating a vacuum is selected from a vacuum pump, a syringe, an adaptor to connect with a vacuum line, or a combination thereof.
[0060] In another embodiment of this aspect, the vacuum source comprises a syringe.
[0061] In another embodiment of this aspect, the syringe is connected with the third port of the body through a connecting means so that the syringe can directly apply vacuum on the second opening end of the vacuum channel.
[0062] In another embodiment of this aspect, the connecting means is airtight or substantially airtight.
[0063] In another embodiment of this aspect, the connecting means is selected from clip mechanisms, screw mechanisms, and combinations thereof. In a preferred embodiment, the connection means is a standard syringe hub connector.
[0064] In another embodiment of this aspect, the connecting means is a standard screw that fits with a commercial syringe of standard size and dimensions.
[0065] In another embodiment of this aspect, the syringe is a disposable one.
[0066] In another embodiment of this aspect, the vacuum channel further comprises a vacuum duct enclosed inside and attached to the internal wall of the channel.
[0067] In another embodiment of this aspect, the vacuum duct comprises two opening ends extending outside the channel, wherein one opening end extends to the sample collection container, and the other opening end is in communication with a vacuum source.
[0068] In another embodiment of this aspect, the vacuum duct is a cannula needle, a metal tubing, or a plastic tubing.
[0069] In another embodiment of this aspect, the opening end of the vacuum duct in the sample collection container is at a distance from the opening of the outlet end of the cannula needle so that they are not in proximity with each other to prevent the sample collected from entering the vacuum duct.
[0070] In another embodiment of this aspect, the portion of the vacuum duct in the sample collection container is shorter than the outlet end of the cannula needle in the sample collection container.
[0071] In another embodiment of this aspect, the vacuum duct comprises a cannula needle having a sharp tip at the opening end in the sample collection container so that it can penetrate a rubber cap or stopper of a sample collection container.
[0072] In another embodiment of this aspect, at least one or two of the sample inlet needle piece, the sample collection container, and the vacuum source are provided separately in sterilized containers, respectively, from the body, and the device can be assembled right before use.
[0073] In another embodiment of this aspect, the device is pre-assembled and stored in a sterilized container ready for use.
[0074] In another embodiment of this aspect, all the parts of the aspiration device are disposable after a single use.
[0075] In another embodiment of this aspect, the aspiration device is a fine needle aspiration (FNA) device.
[0076] In another aspect the present invention provides a needle apparatus comprising a body and a cannula needle, wherein:
[0077] the body comprises a vacuum channel and a plurality of ports;
[0078] the cannula needle comprises an inlet end positioned at a first port of the body, an outlet end positioned at a second port of the body, and a middle portion enclosed inside the body; and
[0079] the vacuum channel of the body comprises a first opening end and a second opening end, wherein the first opening end is positioned at the second port of the body so that the first opening end of the vacuum channel and the outlet end of the cannula needle can be contained in a same sample collection container coupled to the second port of the body, and the second opening end is positioned at a third port of the body, which can be in communication with a vacuum source.
[0080] In one embodiment of this aspect, the middle portion of the cannula needle is in airtight or substantially airtight contact with internal wall of the body surrounding the cannula needle so that the inlet end of the cannula needle can extract a sample from a target when a sample collection container is coupled to the second port of the body, enclosing both of the outlet end of the cannula needle and the first opening end of the vacuum channel, and a vacuum is applied on the second opening end of the vacuum channel at the third port.
[0081] In another embodiment of this aspect, the vacuum channel further comprises a vacuum duct enclosed inside and attached to the internal wall of the channel.
[0082] In another embodiment of this aspect, the vacuum duct comprises two opening ends extending outside the channel, wherein one opening end extends to the sample collection container, and the other opening end is in communication with a vacuum source.
[0083] In another embodiment of this aspect, the vacuum duct is a cannula needle, a metal tubing, or a plastic tubing.
[0084] In another embodiment of this aspect, the opening end of the vacuum duct in the sample collection container is at a distance from the opening of the outlet end of the cannula needle so that they are not in proximity with each other to prevent the sample collected from entering the vacuum duct.
[0085] In another embodiment of this aspect, the portion of the vacuum duct in the sample collection container is shorter than the outlet end of the cannula needle in the sample collection container.
[0086] In another embodiment of this aspect, the vacuum duct comprises a cannula needle having a sharp tip at the opening end in the sample collection container so that it can penetrate a rubber cap or stopper of a sample collection container.
[0087] In another embodiment of this aspect, the inlet and outlet ends of the cannula needle comprise two distinct pieces connected with each other through a connecting means between the inlet end needle and the first port of the body.
[0088] In another embodiment of this aspect, the inlet end piece of the cannula needle is a replaceable needle.
[0089] In another embodiment of this aspect, the inlet end piece is a commercial needle of standard size and dimensions for aspiration of biological samples.
[0090] In another embodiment of this aspect, the inlet end of the cannula needle comprises a sampling tip of a size and shape suitable for aspiration of a biological sample from a mammalian subject.
[0091] In another embodiment of this aspect, the second port of the body comprises a connection means to couple with a sample collection container.
[0092] In another embodiment of this aspect, the connection means is airtight or substantially airtight so that when a vacuum is applied on the vacuum channel, a biological sample can be aspirated by the inlet end of the cannula needle.
[0093] In another embodiment of this aspect, the connection means fits a standard commercial sample vial.
[0094] In another embodiment of this aspect, the airtight connection means comprises a clip mechanism, a screw mechanism, or a combination thereof.
[0095] In another embodiment of this aspect, the sample collection container is a disposable commercial sample vial.
[0096] In another embodiment of this aspect, the sample collection container is a centrifugation tube.
[0097] In another embodiment of this aspect, the apparatus further comprises a cover to protect the inlet end of the cannula needle.
[0098] In another embodiment of this aspect, the protection cover at the inlet end of the cannula needle is a plastic sheath.
[0099] In another embodiment of this aspect, the vacuum source is selected from a vacuum pump, a syringe, and an adapter connected with a vacuum line, or a combination thereof.
[0100] In another aspect the present invention provides an aspiration/biopsy device comprising a needle apparatus according to any one of the embodiments disclosed herein.
[0101] In one embodiment of this aspect, the aspiration device further comprises a sample collection container, wherein said sample collection container is coupled to the second port of the body of the needle apparatus and encloses the outlet end of the cannula needle and the first opening end of the vacuum channel.
[0102] In another embodiment of this aspect, the aspiration device further comprises a vacuum source connected to the second opening end of the vacuum channel.
[0103] In another embodiment of this aspect, the vacuum source is a syringe.
[0104] In another embodiment of this aspect, the syringe is connected to the third port of the body through a connecting means.
[0105] In another embodiment of this aspect, the connecting means is a clip mechanism, a screw mechanism, or a combination thereof. In a preferred embodiment, the connection means is a standard syringe hub connector.
[0106] In another aspect the present invention provides an aspiration/biopsy device comprising a needle apparatus according to any one of the embodiments disclosed herein.
[0107] In one embodiment of this aspect, the biopsy device further comprises a sample collection container, wherein said sample collection container is coupled to the second port of the body of the needle apparatus and encloses the outlet end of the cannula needle and the first opening end of the vacuum channel.
[0108] In another embodiment of this aspect, the biopsy device further comprises a vacuum source connected to the second opening end of the vacuum channel.
[0109] In another embodiment of this aspect, the vacuum source is a syringe.
[0110] In another embodiment of this aspect, the syringe is connected to the third port of the body through a connecting means.
[0111] In another embodiment of this aspect, the connecting means is a clip mechanism, a screw mechanism, or a combination thereof. In a preferred embodiment, the connection means is a standard syringe hub connector.
[0112] In another aspect the present invention provides a method of extracting a biological sample from a subject, comprising: (1) providing a needle apparatus, an aspiration device, or a biopsy device according to any embodiment disclosed herein; (2) contacting the inlet end of the cannula needle of the device with a target of a desired biological sample; (3) applying a vacuum on the vacuum channel so that a desired biological sample is transferred through the cannula needle to a sample collection container.
[0113] In one embodiment of this aspect, the method further comprises (4) rinsing the cannula needle with a liquid to transfer the residue of the sample from the cannula needle to the sample collection container.
[0114] In another embodiment of this aspect, the sample collection container is a glass or plastic vial or a glass or plastic centrifugation tube.
[0115] In another embodiment of this aspect, the target of the biological sample is an organ of a subject or another biological sample.
[0116] In another embodiment of this aspect, the biological sample is a block of cells, a solid tissue, or a fluid.
[0117] In another embodiment of this aspect, the solid tissue is a tumor tissue.
[0118] In another embodiment of this aspect, the sample target is an internal organ or a mammalian animal, such as a human, a dog, a cat, a horse, or the like.
[0119] In another aspect the present invention provides an aspiration method comprising:
[0120] a) providing an aspiration or biopsy device of any embodiment disclosed herein, or attaching a needle apparatus according to any embodiment disclosed herein to a sample collection container and a vacuum source; and b) aspirating a specimen through the needle inlet from a sample target into the sample collection container by applying a vacuum on the vacuum channel of the needle apparatus.
[0121] In one embodiment of this aspect, the step b) further comprises rinsing residue of the biological sample from the cannula needle into the sample collection container by contacting the inlet end of the cannula needle with a rinsing liquid and applying a vacuum on the vacuum channel of the needle apparatus in a controlled amount.
[0122] In another embodiment of this aspect, the method further comprises c) detaching the sample collection container from the body of the aspiration or biopsy device or the needle apparatus.
[0123] In another embodiment of this aspect, the sample collection container is an analytical sample vial ready for analysis.
[0124] In another embodiment of this aspect, the sample collection container is a centrifugation tube, and the method further comprises d) concentrating the sample solution by centrifugation.
[0125] The needle apparatus and devices thereof according to the present invention are versatile and adaptable for different uses, for example, aspiration of fluid samples and biopsy of soft tissues, by varying design of the needle. For example, fluid biological samples can be readily extracted using regular disposable needle; and using a needle having a tip suitable for scraping soft tissues or even bone samples, the devices can be used for biopsy of those solid samples. The flexibility makes the devices especially useful for bone marrow aspiration or biopsy procedures as well as biopsy of various solid tumors, such as breast, head and neck, prostate, lung, stomach, liver, and brain cancers, and melanomas, etc.
[0126] The dimensions and specifications of the devices and apparatus disclosed herein can be adjusted to suit any particular use for extraction of biological samples, as a person skilled in the art will be able to do based on the disclosure and known practice in the medical field. For example, thickness, internal diameter, and lengths of the middle portion and the inlet and outlet ends of the needles can be adjusted based on the need and procedures in which the device or apparatus is used, as well as conditions under which the procedure takes place, which may include, but are not limited to, the source of the biological sample to be extracted, the nature and property of the biological sample to be extracted, and the amount to be extracted, etc.
[0127] In the present invention, the same device or apparatus may be suitable for use in both aspiration of liquid samples and biopsy of soft tissue or solid tissue samples by altering dimensions and/or shape of the specifications, for example, in particular, the tip of the inlet end of the cannula needle, as would be grasped by those skilled in the art. In this aspect, the detachable needle in the inlet end is particular desirable so that it can be changed readily, sterilized, and reused.
[0128] In some embodiments, the terms “aspiration” and “biopsy” may be interchangeable for the purpose of the present invention, and thus they may be collectively called “extraction” of a biological sample. The term “target” or “source”, or the like, of a biological sample in a “subject”, as used herein refers to an organ, tissue, blood, or any body part of a mammalian animal, preferably a human.
[0129] Although it would be preferable to have all or most of the connection means mentioned in the application meet the existing industrial standards so that they would be convenient to use and can avoid unnecessary special manufacturing costs, nevertheless, in principle, they can be manufactured customarily for different purposes without any specific limitations.
EXAMPLES
[0130] The following non-limiting examples of certain embodiments are provided to further illustrate certain aspects of the present invention.
[0131] Some needle aspiration devices for obtaining tissue samples are illustrated in FIG. 1 and FIG. 2 . These devices may be used in substantially all procedures employing conventional FNA devices and further increase the efficiency of FNA procedures with minimum loss of the collected specimen.
[0132] As illustrated in FIG. 3 , the invention of the integrated fine needle aspiration (FNA) device comprises a cannula penetration needle 101 with one sharp end for the penetration of the targeted tissue, and the other end inside the attached receiving vial 104 . During the procedure, the sharp tip of the penetration needle 101 penetrates into the target tissue mass and extracts a small amount of the tissue and cells by utilizing an in-and-out motion. The tissue fluid, together with loose tiny pieces of tissues and cells, is drawn directly into the attached receiving vial 104 through the cannula penetration needle 101 .
[0133] As illustrated in FIG. 3 , the invention of the integrated fine needle aspiration (FNA) device comprises also a vial holder with 108 , such as a click lock, through which, a receiving vial 104 is attached. The receiving vial 104 can be the common centrifuge vials with cap 110 that has a hole and a penetrable PTFE/silicone seal septum 109 as illustrated in FIG. 4 . The vial holder 108 has two needle outlets. The first needle outlet is the other end of the cannula of the penetration needle 101 , through which the specimen is guided into the receiving vial 104 . The second needle outlet is the end of the cannula of the vacuum needle 107 . Or in other embodiments, the second needle outlet is connected to a vacuum line through a tubing, duct, or the like. During the procedure, vacuum is generated inside the receiving vial 104 through the vacuum needle 107 by either a syringe 111 as illustrated in FIG. 1 , or by other vacuum sources such as vacuum line 112 as illustrated in FIG. 2 . The vial holder 108 has also a build-in click lock, which holds the receiving vial 104 in place during the procedure. The receiving vial 104 can be easily detached from the vial holder 108 with release of the click lock after the procedure. The specimen in the receiving vial 104 can be directly used for analysis. If desired, the specimen trapped inside the cannula of the penetration needle 101 can be washed into the receiving vial 104 by drawing a small quantity of proper washing buffer solution through the penetration needle 101 before detaching the receiving vial 104 .
[0134] As illustrated in FIG. 3 , the invention of the integrated fine needle aspiration (FNA) device comprises also a syringe connector 103 , which can be of a standard or non-standard size. For economic and convenience reasons, in some preferred embodiments, the syringe connector is of standard sizes so as to fit different standard sizes of syringes. A common standard syringe 111 can connected to the universal connector 103 as illustrated in FIG. 1 , and the biopsy procedure can be performed in the same way as the conventional FNA biopsy. Furthermore, through this universal standard syringe connector 103 , various vacuum sources, such as a standard syringe-needle connector 106 with a tube linked to the in-house vacuum port, can be connected to the FNA device of the current invention as illustrated in FIG. 2 . The biopsy procedure can be performed easily by directly handling the device without withdrawing the plunger of the syringe.
[0135] During the FNA biopsy procedure, the needle is inserted into the suspect tissue, a vacuum is created by the syringe or other vacuum sources, and cells and tissue from the targeted mass are sucked through the needle into the attached vial. When the sample is obtained, the vial with the specimen sample is detached from the device and ready for examination.
[0136] As illustrated in FIG. 6 , the receiving vial can be orientated to different angles to fit different biopsy positions for easy handling and preventing the sample from being sucked into the vacuum needle.
[0137] As illustrated in FIG. 7 , the penetration needle 101 can vary in size from 30-16 gauge, and 1 to 12 inch long to meet different needs for the different type of the target tissue and organs. The main body 113 of the device can also vary in size, such as from 1 inch to 3 inches. The smaller size, such as 1 inch, is for the device that is connected to a syringe as illustrated in FIG. 1 . The larger size, such as 3 inches, is for the device that is connected to a vacuum line as illustrated FIG. 2 for easy manual handling. The size of the vial holder 108 can be ¼ to 1 inches in diameter and ¼ to ¾ inches in depth to fit the most commonly used receiving vials 104 . The size of the receiving vial 104 can range from 0.5 ml to 5 ml depend on the sample types and sizes. Small sized receiving vial is for the biopsy of small quantity of solid tissue samples, while the larger receiving vial is for the fluid samples, which is frequently in relative larger volume.
[0138] As illustrated in FIG. 9 , the invention of the integrated fine needle aspiration (FNA) device can be modified to comprise also a detachable penetration needle 115 . The detachable penetration needle 115 has a flat head connector, which can be tightly connected to the flat bottom needle connector of the main FNA body 114 . The connectors were designed with tightly matched flat head/bottom connection to eliminate the dead space inside the connectors as illustrated in FIG. 10 .
[0139] As illustrated in FIG. 11 , the detachable penetration needle 115 can vary in size from 30-16 gauge, and 1 to 12 inch long to meet different needs for the different type of the target tissue and organs.
[0140] The foregoing examples and description of certain embodiments should be taken as illustrating, rather than as limiting the present invention as defined by the claims. As will be readily appreciated, numerous variations and combinations of the features set forth above can be utilized without departing from the present invention as set forth in the claims. All such variations are intended to be included within the scope of the following claims. | This application discloses aspiration/biopsy needle apparatus, devices containing these needle apparatus, and methods using these needle apparatus and devices for aspiration or biopsy of samples, in particular biological samples from mammalian subjects. The novel aspiration/biopsy needle systems can find wide applications in the manufacture of fine needle aspiration (FNA)/biopsy devices for convenient cell harvesting and tissue sampling and analysis. | 0 |
FIELD OF THE INVENTION
[0001] The present invention relates to a method and apparatus for temporarily storing at least one item of media at a storage location. In particular, but not exclusively, the present invention relates to the temporary storage of currency notes on a rotating support structure in a self-service terminal or teller assist unit or cash recycler unit or the like.
BACKGROUND TO THE INVENTION
[0002] As the bank branch becomes a primary delivery channel for financial institutions, there is a constant need to improve operational efficiency and provide users with an improved quality of service. Most financial institutions have in the past had a defined system in place determining how currency notes were physically handled in a branch. Typically, there has been a secure vault where bulk currency notes are stored and these are distributed after multiple counts to tellers who can then perform necessary cash transactions with customers. Likewise, when cash has been received from customers, this has been counted many times and eventually returned as incoming cash to a vault. It has thus not been uncommon for currency notes to be counted by hand many times on a journey through a branch. Such cash handling procedures have decreased employee efficiencies and increased customer wait times. There has thus been a need to reduce exposed currency notes in a branch.
[0003] As technology has improved, attempts have been made to automate certain aspects of the currency note handling process. Such technology allows for remote note imaging or check imaging, signature capture and other such verification steps. The development of such technology has led to the introduction of media depositories used in automated teller machines (ATMs) and other such self-service terminals. Media depositories are used to receive media items from a customer. One common type of media depository is a sheet media depository for receiving items of media in sheet form. For example, such items of media can be currency notes, checks, tickets, gyros or the like. Some sheet depositories are capable of receiving a bunch of sheet items of media in a loading area and then picking individual sheets from a bunch so that each sheet can then be identified and validated individually prior to storage of a validated sheet within a depository or returned to a customer.
[0004] Another type of automated unit is the currency recycler. In such devices, customers may deposit items of media such as currency notes, checks, vouchers or the like, and these are processed separately one-by-one and stored in various storage modules within a terminal. For example, a storage unit can be an escrow storage unit in which, instead of being deposited directly into a storage module, once counted and verified, currency notes or checks input by a user are held temporarily until a teller negotiating with a user completes a transaction. If a customer decides to cancel a transaction or asks for the items to be recounted, the original deposited bank currency notes can be returned. This function allows any disputes to be resolved promptly. The temporarily stored items are held in a roll storage module (RSM) in the escrow module.
[0005] Cash recyclers and other such units also include one or more roll storage modules (RSMs). Such RSMs are provided for each of the possible currency notes or checks or other such vouchers which may be presented at a recycler unit. For example, an RSM dedicated to a £10 note will be provided as well as an RSM dedicated to a £20 note as well as an RSM dedicated to a £50 note or the like.
[0006] When a customer presents a bunch of items, these do not need to be manually counted by a teller, but are instead fed into an input slot on the recycler unit. Each presented item is counted and verified within a recycler and once it has been decided to make a permanent deposit of the presented items, the items are separated and stored in a respective RSM. For example, all £20 notes presented in a bunch are stored in the £20 RSM etc.
[0007] A cash recycler thus helps automate acceptance, authentication and validation of currency notes. Another advantage of such units is that the deposited items which are stored in respective RSMs can subsequently be dispensed when another user attends at a teller and requests currency notes. A cash recycler thus enables previously deposited currency notes to be instantly available for dispensing to customers.
[0008] Cash recyclers also help reduce transaction times and time taken for start and end-of-day cash balancing. Average wait times for customers can thus be reduced and overall branch security is improved.
[0009] It is understood that there are other self-service terminals and other item storage devices where sheet items of media are stored on a semi-permanent basis for subsequent dispensation of the stored items to a user requesting them. On many occasions the rolled storage units utilized can store items for many hundreds, if not thousands, of hours in a curved state. This is because such storage units typically utilize a storage drum having a substantially cylindrical cross-section. Currency notes or checks or the like are stored by being wrapped around the drum and kept in place and duly located by one or more tape windings which are wound around the drum. A problem with such storage mechanisms is that when the items are dispensed, because they may have been stored for some time, they may retain part of the curved shape generated by being wrapped on a cylindrical drum. This effect can be worsened if the stored item was already badly curved prior to being stored. Such curled items of media have a tendency to increase a risk of jams occurring within a storage unit. Also, within the transport system utilized to move items of media around in a self-service terminal or the like, the risk of such jams is increased with curled or curved items.
SUMMARY OF THE INVENTION
[0010] It is an aim of the present invention to at least partly mitigate the above-mentioned problems.
[0011] It is an aim of certain embodiments of the present invention to provide an apparatus and method which can temporarily store one or more items of media in a way which prevents stored items acquiring a curved shape.
[0012] It is an aim of certain embodiments of the present invention to provide a method and apparatus for temporarily storing one or more items of media in a way which helps flatten incoming items of media which have a crumpled or already curved shape.
[0013] It is an aim of embodiments of the present invention to provide a method and apparatus that eliminates a returned curved shape of items of media stored on a rotating item support.
[0014] According to a first aspect of the present invention there is provided an apparatus for temporarily storing at least one item of media, comprising:
a rotatable item support member arranged to rotate about a support member axis of rotation and comprising an outer support surface; and a pair of drive tape members each arranged along a respective tape pathway, each tape pathway comprising a pathway portion in which the tape members extend in a co-operating relationship supported by said outer support surface; wherein the outer support surface comprises at least one support region that supports the tape members and an item located therebetween in a flat orientation.
[0018] The support region preferably stores media items without imparting a kink, curve, or bend to the media items either during storage or once they are removed from the support region. This may be achieved using a generally planar surface.
[0019] As used herein, the words “flat” and “generally planar” are used in a practical sense (rather than in a purely geometrical sense) and are intended to cover (i) regions that are planar, and also (ii) regions that have some surface profiling (for example small bumps, ridges, and/or stipples) provided that the surface profiling does not impart a kink, curve, or bend to the item.
[0020] Aptly, said at least one planar support region comprises a plurality of planar support regions arranged circumferentially around the outer support surface.
[0021] Aptly, each planar support region comprises a smooth planar area at least large enough to support an entire item of media.
[0022] Aptly, each support region has a planar area of about around 105 cm 2 or about around 135 cm 2 .
[0023] Aptly, the pair of drive tape members comprises only one tape element secured at a central region thereof to the item support member, each belt member comprising a respective portion of the tape element extending away from the central region, or the pair of drive tape members comprises two tape elements each secured at a respective first end region to the item support member.
[0024] Aptly, the apparatus further includes at least one driven reel element at a second end of each tape member.
[0025] Aptly, in a deposit mode of operation, each reel element is driven at a reel speed slower than a support speed at which the support member is driven and in a dispense mode of operation each reel element is driven at a reel speed faster than a support speed at which the support member is driven.
[0026] Aptly, at least one tape member comprises an indicator element that identifies a pre-determined position on the respective tape member.
[0027] Aptly, the apparatus further includes a plurality of guide pulleys that locate each tape pathway.
[0028] Aptly, the item support member and the tape members are selectively driven simultaneously and synchronously.
[0029] Aptly, the apparatus further includes a drive motor and at least one clutch element, wherein the drive motor and clutch element drive the support member and the tape members in a dispense mode of operation or a deposit mode of operation.
[0030] According to a second aspect of the present invention, there is provided a self-service terminal which comprises apparatus for temporarily storing at least one item of media, comprising:
a rotatable item support member arranged to rotate about a support member axis of rotation and comprising an outer support surface; and a pair of drive tape members each arranged along a respective tape pathway, each tape pathway comprising a pathway portion in which the tape members extend in a co-operating relationship supported by said outer support surface; wherein the outer support surface comprises at least one support region that supports the tape members and an item located therebetween in a flat orientation, and wherein each item of media comprises a currency note.
[0034] According to a third aspect of the present invention, there is provided a teller assist unit, comprising apparatus for temporarily storing at least one item of media, comprising:
a rotatable item support member arranged to rotate about a support member axis of rotation and comprising an outer support surface; and a pair of drive tape members each arranged along a respective tape pathway, each tape pathway comprising a pathway portion in which the tape members extend in a co-operating relationship supported by said outer support surface; wherein
[0037] 1 the outer support surface comprises at least one support region that supports the tape members and an item located therebetween in a flat orientation, and wherein each item of media comprises a currency note.
[0038] According to a fourth aspect of the present invention, there is provided a cash recycler unit comprising which comprises apparatus for temporarily storing at least one item of media, comprising:
a rotatable item support member arranged to rotate about a support member axis of rotation and comprising an outer support surface; and a pair of drive tape members each arranged along a respective tape pathway, each tape pathway comprising a pathway portion in which the tape members extend in a co-operating relationship supported by said outer support surface; wherein the outer support surface comprises at least one support region that supports the tape members and an item located therebetween in a flat orientation, and wherein each item of media comprises a currency note.
[0042] According to a fifth aspect of the present invention, there is provided a method for temporarily storing at least one item of media, comprising:
rotating an item support member comprising an outer support surface about an item support axis of rotation; driving tape members along respective tape pathways each comprising a respective pathway portion in which the tape members extend in a co-operating relationship supported on said outer support surface; and supporting the tape members and at least one item of media located therebetween in a flat orientation on at least one support region of the outer support surface.
[0046] Aptly, the method further comprises collecting a plurality of items of media one-by-one as the item support rotates by supporting consecutive items of media on consecutive planar support regions as the item support member rotates.
[0047] Aptly, the method further comprises rotating the item support media and driving the belt member simultaneously and synchronously.
[0048] Aptly, the method further comprises, for each supported item of media, supporting the entire item of media on a flat surface of a respective one support region of the item support member.
[0049] Aptly, the method further comprises driving the belt member by driving at least one driven reel element at each of a first and further respective end region of the belt member.
[0050] According to a sixth aspect of the present invention, there is provided a product which comprises a computer program comprising program instructions for:
rotating an item support member comprising an outer support surface about an item support axis of rotation; driving tape members along respective tape pathways each comprising a respective pathway portion in which the tape members extend in a co-operating relationship supported on said outer support surface; and supporting the tape members and at least one item of media located therebetween in a flat orientation on at least one support region of the outer support surface.
[0054] Certain embodiments of the present invention provide the advantage that a rolled storage module can be provided in which items of media such as currency notes, checks or the like are stored in a substantially planar orientation. As such, the items may be stored for a considerable time without risk of acquiring a curved shape. Thus, the risk of jams when such items are subsequently dispensed is eliminated or at least greatly reduced.
[0055] Certain embodiments of the present invention provide the advantage that very many items of media may be stored in an RSM in a substantially flat orientation. For example, many hundreds or even thousands of separate items may be stored in a single RSM.
BRIEF DESCRIPTION OF DRAWINGS
[0056] Embodiments of the present invention will now be described hereinafter, by way of example only, with reference to the accompanying drawings in which:
[0057] FIG. 1 is a schematic diagram of a teller assist unit according to an embodiment of the present invention;
[0058] FIG. 2 illustrates a rotatable item support according to a first embodiment of the present invention having planar support regions and co-operating tapes;
[0059] FIG. 3 illustrates a support member according to a second embodiment of the present invention which includes multiple planar support regions; and
[0060] FIG. 4 illustrates a rotatable item support according to a third embodiment of the present invention including multiple planar support regions.
DESCRIPTION OF EMBODIMENTS
[0061] In the drawings like reference numerals refer to like parts.
[0062] FIG. 1 illustrates a teller assist unit 100 according to an embodiment of the present invention. It will be understood that certain embodiments of the present invention are not restricted to storage units within a teller assist unit but optionally may be used in automated teller machines (ATMs), cash recyclers, vending machines or the like wherever sheet items of media such as currency notes, checks, vouchers, pages or the like are to be stored and/or deposited. The teller assist unit 100 includes a secure housing 101 which includes a top wall 102 and floor standing wall 103 , together with a back wall 104 and a front fascia wall 105 . The front fascia includes a bill, entry/exit slot 106 at which a user can present a bunch of currency notes or checks or single currency notes or checks or other such items of media for deposit. The bill entry/exit slot 106 is also the outlet slot whereby items of media such as currency notes and/or checks are returned or are dispensed to a user dependent upon a user requirement. In the instance of a teller assist unit, the user is a teller of a bank branch or other such authorized user who acts as an interface with a bank customer. Currency notes or checks deposited are validated by a bill validator 107 , as will be understood by those skilled in the art. A bill transport path 108 which includes one or more rollers and/or endless belts is used to locate items of media one-by-one at a desired roll storage module 120 .
[0063] In addition to handling deposits the teller assist unit can be utiliutilizedispense currency notes which are stored in the roll storage modules. For example, if a teller requires £120 worth of currency notes, this information may be input at a user interface (not shown) on the front fascia 105 of the teller assist unit and then a central processing unit (not shown) initiates selection of currency notes from one or more roll storage modules. For example, to dispense £120, the roll storage module (RSM) which holds £20 notes may be placed in a dispense mode of operation in which six previously stored £20 notes are dispensed from the RSM onto the bill transport path 108 . A bill return path module 125 is utilized to locate dispensing items from the bill transport path 108 to the exit slot 106 . It will be understood that rather than dispensing six £20 notes from a single RSM, the teller assist unit may be selectively operated to dispense two £50 notes from a £50 note RSM and two £10 notes from a £10 note RSM. Other combinations are of course possible.
[0064] FIG. 2 illustrates parts of an RSM 120 . Each RSM includes a secure box formed from a back plate 200 which is spaced apart from, and substantially parallel with, a front wall 201 (not shown). The front and back walls are closed by opposed end walls and top and bottom walls (also not shown).
[0065] Multiple shafts 205 extend between the front and back plates. Eight such shafts are shown in FIG. 2 , although the specific number will be determined by the particular layout in a particular RSM. Each shaft 205 extends from a first end 206 thereof, which is secured to the back plate 200 to a second end 207 thereof, which is secured to the front plate (not shown). The shafts are fixed in place and carry a rotatable sleeve 210 or a driven reel 211 a, 211 b. Each reel 211 includes a cylindrical body having a disc at each end thereof. Each reel is thus like a cotton reel-shaped body. A resilient tape is wound around the reels and the shafts.
[0066] Each RSM also includes a rotatable item support 250 which rotates about a longitudinal axis defined by a support shaft 255 . The drive shaft 255 is driven by a drive system which may optionally also drive the rotation of the reels 211 a , 211 b. As shown in FIG. 2 , according to a first embodiment of the present invention, the rotatable item support has a substantially rounded rectangular cross-section and extends along a longitudinal axis. A top surface 260 of the support is substantially planar and smooth and flat. This area provides a resting surface on which tape and/or currency notes may be supported in a flat configuration. The cross-sectional area of each planar support region is sized so as to be at least as large as a largest currency note or check or the like, which is predicted to be deposited and stored in the RSM. Aptly, each support region has a planar area of about around 105 cm 2 or more or less. Aptly, the support region has a planar area of about around 135 cm 2 . Aptly, each support region has a planar area of about around 155 cm 2 . As illustrated in FIG. 2 , the support member shown has a further planar support region 265 on the lower surface of the support member 250 . The planar support regions are joined together by curved, smooth surfaces at the outer surface of the support member.
[0067] As illustrated in FIG. 2 , each RSM includes an inlet slot 270 at which items of media transported by the bill transport system 108 are periodically presented one-by-one. This slit 270 is also used as an outlet slit whereby items of media previously stored on the support member may be unwrapped and dispensed through the exit slit 270 to the bill transport system 108 and the bill return path 125 for exit via exit slot 106 to a teller.
[0068] When a teller presents one or more currency notes at a bill entry slot 106 of the teller assist unit, these are transported one-by-one subsequent to bill validation via the bill transport system 108 and presented one-by-one at the inlet slit 270 . The storage support 250 is rotated in an anti-clockwise direction by a drive motor. Simultaneously, the drive motor system drives the reels of tape 211 a , 211 b. In a deposit mode of operation the item support 250 is rotated more quickly than the rotation of the tape reels. This keeps each tape relatively taut as incoming items of media are wrapped around the item support.
[0069] In the embodiment shown in FIG. 2 , two tapes are provided. One tape 260 is secured at a first end to the item support and is wrapped there around and extends across the pulley system to the upper reel 211 a. The further tape 261 is also attached at a first end thereof to the item support and then extends to the second lower reel 211 b . It will be appreciated that instead of utilizing two separate tapes, one long tape could be utilized which is fixed at a central position to the item support.
[0070] Incoming items of media are located between opposed upper and lower surfaces of the two tapes at an incoming region 280 . The two tapes at this region co-operate so that an incoming item of media is sandwiched there between. Rotary motion of the support winds the two tapes together with an item of media located there between onto the support member. The rotation of the support and the tapes is timed together with the presentation point of an item of media so that the item of media, such as a currency note, is stored wholly on a single flat surface of a planar support region of the item support. As the item support rotates further, items of media are deposited one-by-one on consecutive planar support regions. The net effect is that after a period of time, multiple currency notes are stored with intervening tape windings on each of the two planar support surfaces of the item support.
[0071] In a dispense mode of operation, currency notes previously stored on the item support must be removed and thereafter transferred to a bill exit slot 106 on the teller assist unit. Depending upon a number of currency notes which are needed, the upper reel 211 a and lower reel 211 b are driven so as to pull the tapes (and the currency notes stored therewith) off the also rotating item support. In the dispense mode of operation the item support shown in FIG. 2 is driven in a clockwise direction. One-by-one currency notes which are bound together between the opposed tape sections are carried with the tape off the item support to the region 280 where the two tapes are closely juxtaposed and thereafter ejected through the exit slot 270 .
[0072] Because the currency notes and tape are stored on planar, smooth, flat surfaces, there is no inclination for the currency notes to acquire a curved shape despite, perhaps, being stored for many hundreds or thousands of hours on a support surface.
[0073] There will of course be a limit to the number of items of media which can be stored on any single item support. This will in many respects be determined by the length of tape available and wrapped around each of the upper and lower reels 211 . At least one of the reels (shown in the upper tape section of FIG. 2 ) includes a marking line 295 which is carried on the tape. A detector (not shown) continually monitors for identification of this line or other such indicator which indicates that the reel is becoming empty and thus that a maximum storage capacity has almost been reached.
[0074] FIG. 3 illustrates an alternative embodiment of the present invention, in which the item support 350 is substantially triangular in cross-section. As such, the item support includes three planar surfaces, each of which is substantially smooth and flat and which is sized so as to wholly support a currency note that is to be stored in that particular RSM. As illustrated in FIG. 3 , the item support includes three spaced apart substantially planar walls 351 which are secured to a central sleeve 352 by respective connecting plates 353 . The smooth, flat walls 351 are connected together by curved regions 354 to prevent the tapes which are wrapped around the item support from being abraded. As the central shaft 255 rotates, the item support rotates. The item support rotation is driven in a deposit mode of operation slightly more quickly than the speed of rotation of the storage reels. In a dispense mode of operation, the reels are rotated slightly more quickly than the speed of rotation of the item support. This maintains the tapes in a taut state at all times so that items of media can be duly deposited or dispensed or dispensed as appropriate.
[0075] FIG. 4 illustrates an alternative item support 450 , according to another embodiment of the present invention, which includes six substantially flat surfaces 460 , spaced apart substantially circumferentially around a central drive shaft 255 . Other parts similar to those shown in FIGS. 2 and 3 are not illustrated in FIG. 4 for convenience.
[0076] It will be understood that an item support may have one, two or more planar surfaces. The number of support surfaces is only limited by the practical size of a storage module and the fact that each planar support region must be large enough to support a whole item.
[0077] It will be appreciated that certain embodiments of the present invention are not restricted to the location of a single item of media on a single planar storage surface. For example, as shown in FIG. 4 , when planar regions are adjacent and not angled too much with respect to one another, a single item of media could be bent in one or possibly two locations and stored in a substantially flat manner on multiple adjacent planar support surfaces. This would introduce a possible risk of creasing where an item is held across a joint between adjacent planar regions but would nevertheless provide an improvement upon current systems which produce curved items of media.
[0078] Throughout the description and claims of this specification, the words “comprise” and “contain” and variations of them mean “including but not limited to” and they are not intended to (and do not) exclude other moieties, additives, components, integers or steps. Throughout the description and claims of this specification, the singular encompasses the plural unless the context otherwise requires. In particular, where the indefinite article is used, the specification is to be understood as contemplating plurality as well as singularity, unless the context requires otherwise.
[0079] Features, integers, characteristics or groups described in conjunction with a particular aspect, embodiment or example of the invention are to be understood to be applicable to any other aspect, embodiment or example described herein unless incompatible therewith. All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of the features and/or steps are mutually exclusive. The invention is not restricted to any details of any foregoing embodiments. The invention extends to any novel one, or novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.
[0080] The reader's attention is directed to all papers and documents which are filed concurrently with or previous to this specification in connection with this application and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference. | An apparatus and method are disclosed for temporarily storing at least one item of media. The apparatus includes a rotatable item support member arranged to rotate about a support member axis of rotation and comprising an outer support surface. The apparatus also includes a pair of drive tape members, each arranged along a respective tape pathway, each tape pathway comprising a pathway portion in which the tape members extend in a co-operating relationship supported by said outer support surface. The outer support surface includes at least one support region that supports the tape members and an item located therebetween in a flat orientation. | 1 |
FIELD OF THE INVENTION
[0001] The present invention refers generally to water heating equipment with an ionized system that provides a constant water supply. The water heater of the present invention is a versatile piece of equipment that can be used both in pipe equipment and in fin equipment.
BACKGROUND OF THE INVENTION
[0002] To meet the constant demand for hot water with the maximum possible fuel economy, an electronic system was integrated with a set of gas valves that gradually lights the water heater burner in a direct way by means of an electric spark, and a flame detector, like the one cited in PCT patent application WO/2007/057864, however, the water heater described in the aforementioned patent does not adapt itself fully to most hydraulic installations existing in the country, and therefore in many cases it is necessary to adapt or integrate other elements for its operation, increasing the equipment and maintenance cost of the entire system.
[0003] The water heating system has an ignition system of the ionized type such as the one described in Patent No. WO/2007/057864, with the difference that the system of the present invention only works when the electronic card gives the order to ignite under the following conditions:
[0004] a) When the low pressure flow detector indicates a water demand to the system and the bimetallic detector, located 5.08 cm (2 inches) below the top lid of the heater, detects a temperature 4° C. lower than the temperature programmed onto the card by the user, and to turn off when it detects a temperature higher than the programmed temperature, eliminating the flow or water pressure detector which limits the equipment to having a minimal pressure in the residential hydraulic system.
[0005] b) It will also ignite when the day and hour programming in the card is actuated and when the bimetallic detector is 4° C. below the temperature programmed onto the electronic card by the user.
[0006] c) Similarly, the water heater will ignite when the wired remote control is actuated and when the bimetallic detector is 4° C. below the temperature programmed onto the electronic card.
[0007] In this way the water heater will only ignite when hot water is needed, according to the instructions programmed onto the electronic card by the user, which works with a power source that operates with four alkaline batteries of 1.5 V, lasting for a minimum for eight months.
[0008] Because on occasion the pressure of the water flow is not constant in residential hydraulic installations which are not regulated, there is need for a water heater, such as the one described in the previous paragraph, which uses any type of gas fuel, to achieve greater fuel economy, that is appropriate for the various diverse hydraulic installations already existing or which could be built in the future, to satisfy a constant demand for water at a comfortable temperature.
SUMMARY OF THE INVENTION
[0009] The water heater of the present invention has been designed in such a way that it has a power input between 10 kW and 40 kW, and a set of seven steel tubes forming a heat transfer collector where the length and diameter of the tubes are specified according to the hot water needs of the user, with the capacity to transfer from 82% to 90% of the input power (heater efficiency) using a corrugated coil with a set of fins that delays the gas outflow and allows for maximum utilization of the energy generated by the burner, at a temperature no greater than 250° C. The entire set of components of the present invention allows the backup heater to operate without a permanently lit pilot light.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 is a general view of the heater of the present invention, showing its main components which are: set of electrovalves, drainage stopcock, electronic card, heat exchanger tubes, burner, and plastic or metallic cover.
[0011] FIG. 2 is a partial view of the top part of the heater.
[0012] FIG. 3 is a partial view of the lower part of the heater.
[0013] FIG. 4 is a view of the wired or wireless remote control installed in a bathroom.
DETAILED DESCRIPTION OF THE INVENTION
[0014] The heater ( 1 ) of the present invention is designed to have only between 15 dm 3 (15 liters) and 40 dm 3 (40 liters) of internal volume and to withstand a pressure greater than 0.45 MPa. The entire tank ( 7 ) is made of steel and the areas in contact with water are porcelainized, depending on the capacity and the needs of the user.
[0015] The water feed is located at the posterior and lower part of tank ( 7 ); likewise, the water outlet is located at the upper lateral part of the tank. Additionally, on the lower part of the tank there is a coupling which connects the exterior with the water contained in the tank ( 7 ) to place a stopcock or plug ( 2 ) allowing for drainage and cleaning of the tank ( 7 ).
[0016] Power must be supplied to the water heater by means of a burner ( 5 ) with nine multi-burners ( 5 ) and with a variable nozzle diameter to supply between 10 kW and 40 kW for different types of gases.
[0017] Fuel gas is supplied by means of a system of electrovalves ( 9 ), connected to a cast aluminum or ZAMAC alloy body. This set of valves ( 9 ) connected to the cast body comprises the gas feed valve system ( 9 ), and said valve system ( 9 ) is located inside a plastic cover that protects the gas feed valve ( 9 ) (usually, the plastic cover thickness ranges between 1.5 and 3.5 mm), the connections to the bimetallic cables ( 10 ) and the electronic card ( 3 ) from the atmosphere. The gas feed valve ( 9 ) is connected to the burner ( 5 ) by means of an aluminum or copper tube of 9.525 mm (0.375 inches) in diameter and brass or bronze connections of 15.875 mm (0.625 inches) in diameter which normally must be closed until the electronic card ( 3 ) gives the signal to open. The gas feed connection to the gas feed valve ( 9 ) is 1.27 cm (0.5 inches) in diameter and must be calibrated between 1.7 kPa and 3.2 kPa depending on the type of gas to be used.
[0018] The bimetallic cable ( 10 ) is connected to a connection of brass, bronze, tropicalized steel or other corrosion resistant material in such a way that it is introduced into the connection and a neoprene seal is added to prevent water leakages.
[0019] The end that is in contact with the water must be tied between themselves, in order to detect the temperatures for turning on and off the ignition of the burner ( 5 ), and the opposite end is connected to the electronic card ( 3 ) as well as to the gas feed valve ( 9 ). The bimetallic cable ( 10 ) connection must be hidden by the metallic or plastic cover and located 5.08 cm (2 inches) below the top lid of the tank ( 7 ) to prevent overheating in the hydraulic network. Next to the bimetallic cable ( 10 ) another connection will be added that contains another bimetallic cable ( 11 ) for safety, the second cable only acting as a safety system in case there is overheating in the system. The heater ( 1 ) will only restart when the temperature detected by the bimetallic cable ( 10 ) is 4° C. lower than the temperature defined by the user.
[0020] The electronic card ( 3 ), upon receiving a water demand signal sent by the flow detector ( 12 ) checks the temperature, and if this temperature is 4° C. lower than the temperature programmed by the user, the card sends a direct current electric spark through a ceramic spark plug connected to the electronic card ( 3 ) by means of a cable covered with silicone and to an extension of reinforced cable to turn on the system.
[0021] The spark plug is attached, at a distance not greater than 4 mm, onto one of nine multi-burners ( 5 ) comprising the burner ( 5 ) of the water heater ( 1 ). After 1.0 second and with the electrical spark in operation, the electronic card ( 3 ) sends a signal to the gas feed valve ( 9 ) for the gradual and successive opening of the electrovalves ( 9 ) to allow for the gradual flow of gas to the burner ( 5 ), thus avoiding any excessive gas accumulation in the combustion chamber and preventing possible accidents. Once the burner ( 5 ) is lit, another spark plug attached at a distance not greater than 20 mm onto one of the nine multi-burners ( 5 ) detects the flame by means of an ionization process in which the spark generated by the other spark plug changes from direct current to alternating current. This current change is sent to the electronic card ( 3 ) by means of a reinforced cable and is followed by a silicone covered cable. If the change-of-current signal is not detected by the card ( 3 ) within five seconds or the signal appears intermittently in the same period of time, or if the burner goes out or the change-of-current signal appears intermittently while the heater ( 1 ) is operating, the electronic card ( 3 ) sends a signal to the gas feed valve ( 9 ) for the immediate closing of the electrovalves ( 9 ) for 10 to 15 seconds to carry out an electronic review of the components connected to card ( 3 ).
[0022] Once the aforementioned period of 10 to 15 seconds has elapsed, another attempt is made to turn on the heater ( 1 ) until a clear signal of the current change in burner ( 5 ) is obtained; if no change-of-current signal is detected after three attempts, the card ( 3 ) will show an error by means of a visual signal shown as a red light on the screen, which will indicate that as a precaution the system has been temporarily blocked.
[0023] Once the change-of-current signal is detected by the electronic card ( 3 ), the water inside the tank ( 7 ) will be heated until the bimetallic cable ( 10 ) sends a signal to the electronic card ( 3 ) indicating that the temperature has reached the temperature programmed by the user for the water contained inside tank ( 7 ). When the card ( 3 ) translates the signal sent by the bimetallic cable ( 10 ), which indicates that the programmed temperature has been reached, or when the flow detector ( 12 ) sends a signal to the electronic card ( 3 ) that the water demand has ended, the electronic card ( 3 ) in turn sends a signal to close the electrovalves ( 9 ) of the gas feed valve.
[0024] The ignition cycle will [not] be reactivated until there is again demand for water and bimetallic cable ( 10 ) sends a signal indicating that the water temperature in the tank ( 7 ) is 4° C. lower than the temperature programmed by the user.
[0025] The electronic card ( 3 ) is electrically fed by a power source which comprises a set of four alkaline batteries of 1.5 V or by a set of four rechargeable batteries in turn connected to the 110/220 VAC, with an output of 6 VDC. In turn the electronic card ( 3 ) distributes the electricity feed to the different components to which it is connected, administering it in the most efficient way to obtain a useful life for the batteries of approximately eight months according to the usage of the heater, these batteries acting only as backup since the equipment is connected to the electrical installation.
[0026] Between the power source and the electronic card ( 3 ) there are two ON/OFF switches ( 13 ), the first energizing or de-energizing the electronic system when it is working with batteries, giving priority to the 110 V electric connection, and the second to be used with alkaline or rechargeable batteries. The card ( 3 ) has two visual indicators, a blue one indicating that the heater ( 1 ) is in operation. [A red one] will indicate on the screen that the heater ( 1 ) is in error or conducting a failure analysis.
[0027] The tank ( 7 ) is supported upon a combustion chamber of 26 cm (10¼ inches) in height and of a diameter less than the external diameter of the tank, but strong enough to withstand the weight of the heater when full of water. Inside the combustion chamber are located the burner ( 5 ) and the spark plugs attached to it and connected to electronic card ( 3 ). The combustion chamber is attached to a round base which has a series of openings to provide the air flow necessary for combustion to take place and said openings are 40 mm high to allow for the airflow to circulate toward the burner ( 5 ). The combustion chamber is insulated with ceramic fiber of 26 cm (2 to 3 [sic] inches) in thickness and only the burner gate is left free of lining to have access to the chamber when it is necessary to conduct maintenance. The rest of the tank ( 7 ) is insulated with thermal fiberglass from 60 cm to 80 cm (2 to 3 [sic] inches) in thickness.
[0028] The insulated tank ( 7 ) and combustion chamber are placed inside of an external body comprising a laminate ( 14 ), which is coated with corrosion resistant electrostatic paint. This external body ( 14 ) is attached to the base of the combustion chamber and covered with a laminate lid. As was the case with the external body ( 14 ), the lid and the external base must be protected with corrosion and temperature resistant electrostatic paint. The external body ( 14 ) has three openings of different sizes, the largest one, located near the burner ( 5 ), provides an exit for the spark plug cables, as well as the tube connecting the system of gas feed valves to the burner ( 5 ) and allows for the unobstructed maintenance of the burner ( 5 ). This opening is later covered with a lid on which ceramic fiber insulation is deposited with a thickness from 5.08 to 7.62 cm (2 to 3 inches), allowing the spark plug cables and the gas feeding tube to pass through. This lid is attached by means of screws to have an easy access to burner ( 5 ) when maintaining water heater ( 1 ). The lid must be covered with corrosion and temperature resistant electrostatic paint.
[0029] The 2 smallest openings located in the posterior front part of the external body ( 14 ) allow the bimetallic cable ( 10 ) and the connection to pass through. Also the gas feeding valve ( 9 ) and the electronic card ( 3 ) are attached to the posterior part of external body ( 14 ), together with the power source where the batteries are located. This set is covered with a plastic cover covered with a corrosion resistant electrostatic paint leaving visible the indicators on the information screen ( 17 ) of card ( 3 ) as well as the equipment ignition button ( 17 ).
[0030] On the other hand, the information screen ( 17 ) contains a series of buttons with which the user will be able to make the different programmings earlier mentioned.
[0031] The last opening is located on the anterior part of the external body ( 14 ) at the level of the drainage coupling where a drainage stopcock ( 2 ) is placed for tank ( 7 ) maintenance.
[0032] The water heater ( 1 ) thus described is connected to the hydraulic installation through which the hot water flows in 1.90 cm (0.75 inches) corrosion resistant metal pipes. Water heater ( 1 ) will ignite only when the electronic card ( 3 ) gives the ignition order under the following conditions:
[0033] a) When the low pressure flow detector ( 12 ) indicates a water demand to the system and the bimetallic detector ( 10 ), located 5.08 cm (2 inches) below the top lid of the heater, detects a temperature 4° C. lower than the temperature programmed onto the card by the user, and to turn off when it detects a temperature higher than the programmed temperature, thus eliminating the flow detector or water pressure detector and limiting the equipment to a minimal pressure in the residential hydraulic system.
[0034] b) It will also ignite when the day and hour programming on the card ( 3 ) is actuated and when the bimetallic detector ( 10 ) is 4° C. below the temperature programmed onto electronic card ( 3 ) by the user.
[0035] c) Similarly, the water heater ( 1 ) will ignite when the wired or wireless remote control ( 16 ), which may be installed in the bathroom as shown in FIG. 4 , is actuated as soon as the bimetallic cable ( 10 ) measures 4° C. below the temperature programmed onto the electronic card ( 3 ) by the user.
[0036] In this way, water heater ( 1 ) will only ignite when hot water is needed, under the instructions programmed by the user onto the electronic card ( 3 ), which will operate with a power source of four 1.5 V alkaline batteries or rechargeable batteries (and/or a connection to the 110/220 VAC electric grid) lasting for a minimum of eight months, and when there is a demand for water and the bimetallic cable ( 10 ) detects a temperature 4° C. lower than the temperature programmed by the user, and it will turn off when the programmed temperature is reached or when the flow detector ( 12 ) indicates that there is no longer a demand for water.
[0037] It will also ignite when the day and hour programming is activated, turning on the heater ( 1 ) on the desired days and at the time programmed by the user, and it will turn off when the bimetallic cable ( 10 ) detects a temperature higher than the temperature programmed by the user. | A water heater is controlled by an electronic system that initiates the operation of the heater when a flow detector sends a demand signal for hot water flow to the electronic card, which ignites a burner as function of a temperature programmed by the user. The burner is lit gradually by an electrical spark emitted by a spark plug connected to the electronic card, which in turn controls gas feed to the burner. As soon as the burner is lit, the electric current generated by the first spark plug is transformed by the ionization effect, changing the polarization of the current, which is detected by another spark plug that emits the change signal to the electronic card for further control of the heater. The heater operates without a permanently lit pilot light. | 5 |
FIELD OF THE INVENTION
The invention relates to a shovel particularly useful for snow removal. The shovel is characterized by dual ground contacting edges allowing the shovel to be self-supporting and which allows the shovel to be used in an ergonomically efficient manner for removing snow from a surface.
BACKGROUND OF THE INVENTION
Snow removal shovels are well known. Various types of shovels have been used and developed over the years for particular uses or applications. For example, shovels having specialized handles and blades have been developed for lifting snow whereas other shovels have specifically been developed for pushing or plowing snow. In other shovels, particular aspects of the handles or blades have been designed in an attempt to improve the ergonomics and/or efficiencies of using the shovel.
While particular shovels have been designed with improved ergonomics and/or efficiencies of use, for particular applications, such as the clearing of walkways or driveways, shovels have not always enabled ergonomically efficient methodologies for the clearing of snow from a surface. In particular, past shovels have required either the lifting of a snow-laden shovel from the surface and carrying or throwing the snow away or pushing the snow in a manner that is ergonomically inefficient. These inefficiencies are particularly relevant to physically weaker persons, such as the elderly, who as a result of these inefficiencies may cause harm to themselves through the use of a shovel thereby giving themselves back problems, muscle strains or increasing the risk of heart attack through over-exertion. Such risks of harm may cause these people to be hesitant to make the effort to clear snow from their driveways or walkways which may lead to dangerous accumulations of snow and the resulting risk of slip and fall injuries.
Furthermore, past shovels are not self-supporting during non-use. That is, in order for a user to retrieve a shovel for use that is lying flat on the ground requires the user to bend over to lift the shovel or, alternatively retrieve the shovel from against a wall that the shovel may have been leaned against. Similarly, after use, past shovels must be returned to a supporting wall and carefully balanced against the wall or allowed to drop to the ground. Leaning shovels against a wall is often unstable with the result that the shovel may slip causing other shovels or similarly positioned implements to crash to the floor of a garage, shed or storage room. This is not only inconvenient but may also result in damage to cars or other stored equipment.
Still further, in snowy regions, shovels are often jammed into a snowbank by a user in order to support the shovel during or after use. Very often, the shovel will fall over and become lost beneath new snow as it falls thereby increasing the risk of damage by a vehicle running it over or simply inconveniencing a user by it not being available when needed.
Accordingly, there has been a need for a shovel which allows for the pushing of snow in an ergonomically efficient manner and which is self-supporting.
Examples of past shovels which provide various operational features are described. For example, U.S. Pat. No. 6,053,548 discloses a manually operable combination shovel and plow; U.S. Pat. No. 5,829,808 discloses an adjustable angle snow plow; U.S. Pat. No. 2,919,153 discloses a combination snow shovel and plow tool; U.S. Pat. No. 4,199,181 discloses a snow shovel having a diagonal curve; U.S. Pat. No. 2,896,993 discloses a snow shovel having an adjustable blade; U.S. Pat. No. 5,159,769 discloses a combination snow shovel and plow; U.S. Pat. No. 5,159,769 discloses a shovel having shovel and plow characteristics and; U.S. Pat. No. 5,511,328 discloses a snow plow having adjustable blades. In particular, none of the devices described in these patents is self-supporting.
SUMMARY OF THE INVENTION
In accordance with the invention, there is provided a shovel comprising:
a blade having first and second ground contacting edges;
a handle operatively connected to the blade
wherein the handle and blade allow pushing operation of the shovel with either of the first or second ground contacting edges in contact with the ground.
In a more specific embodiment, the invention provides a self-supporting shovel comprising:
a blade having first and second ground contacting edges and any one of or a combination of a semi-circular, semi-elliptical -or parabolic cross-section;
a handle operatively connected to and angled with respect to the blade
wherein the handle and blade allow pushing operation of the shovel with either of the first or second ground contacting edges in contact with the ground.
DESCRIPTION OF THE DRAWINGS
These and other features of the invention are described with reference to the drawings wherein;
FIG. 1 is an isometric view of the shovel in accordance with one embodiment of the invention;
FIG. 2 is a plan view of the shovel in accordance with one embodiment of the invention;
FIG. 3 is a side view of the shovel in accordance with one embodiment of the invention;
FIG. 3 a is a partial side view of one blade of the shovel having reinforcement;
FIG. 4 is a perspective view of a shovel in accordance with one embodiment of the invention in a stored and upright position;
FIG. 5 is a side view of a shovel in accordance with one embodiment of the invention wherein the radius of curvature of the blade is different across the width of the blade;
FIG. 6 is a side view of an alternate embodiment of the handle in accordance with one embodiment of the invention;
FIG. 7 is a plan view of a shovel in accordance with one embodiment of the invention wherein the position of the handle is variable with respect to the blade.
DETAILED DESCRIPTION OF THE INVENTION
With reference to the Figures, a shovel 10 having a blade 12 and handle 14 is described. The shovel 10 is particularly adapted for pushing material such as snow in a manner similar to that of a snowplow. While the shovel is particularly adapted for pushing snow, it is understood that other materials may be pushed by the shovel and, accordingly, reference to snow is not meant to be limiting to the scope of interpretation of the uses of the shovel.
The blade 12 of the shovel 10 is generally semi-cylindrical as shown in FIGS. 1, 3 and 4 with the blade 12 having first and second ground contacting edges 16 and 18 . In other embodiments, the blade 12 may be semi-elliptical or parabolic in cross-section. As shown, it is preferred that the handle projects outwardly from the convex surface of the blade 12 midway between the first and second ground contacting edges 16 and 18 and midway between a leading end 20 and trailing end 22 of the blade 12 . As shown in FIG. 2, it is also preferred that the handle is angled with respect to the blade 12 as denoted by θ.
The shovel 10 is particularly adapted to clear snow on surfaces such as driveways and walkways. In normal operation, the user would initiate the snow clearing routine at one edge or in the middle of the driveway or walkway. By engaging the first ground contacting edge 16 against the driveway or walkway and by pushing the handle in a desired direction x (normally parallel to one edge of the driveway or walkway), snow is collected by the blade and ejected from the blade at trailing end 22 in a direction y. The ejection of the snow is a result of the angle θ between the blade and the handle and the forward motion of the shovel 10 . More specifically, as snow encounters the inner concave surface of the blade 12 , it rises up the inner surface of the blade 12 to a position at which gravity causes the rising snow to fall and be deflected towards the trailing end 22 at which position it exits the shovel 10 . The ejected snow results in a berm 24 of snow generally parallel to the direction of travel x and the area of the driveway or walkway beneath the blade has been cleared of snow. The handle would typically be held by the user at an angle of approximately 30-60 degrees with respect to the horizontal as shown in FIG. 3 .
The user, upon reaching the end of the driveway or walkway would reverse the direction of travel and by rotating the blade of the shovel in a direction z (FIG. 3) would place the second ground contacting edge 18 against the driveway or walkway. With both ground contacting edge 16 and ground contacting edge 18 on the driveway/walkway surface 26 , the shovel 10 would be in a self-supporting position. By stepping over or around the shovel 10 , the handle 14 would be continued to be rotated in the direction z in order to lift the first ground contacting edge 16 from the surface 26 . Thereafter, and by orienting the handle in order that it is parallel to the berm 24 and the leading end 20 is adjacent and aligned with the berm 24 , the user pushes the shovel in a direction parallel to the berm 24 so as to continue the ejection of snow from the trailing end 22 . By successively repeating passes as described above, the user can effectively cause the movement of snow from the driveway or walkway to a location lateral to the driveway or walkway without lifting the shovel 10 from the surface. It is understood that the actual use of the shovel will depend on snow conditions with the specific actions of the user being modified to the specific conditions.
During non-use or storage, the shovel is self-supporting when placed on its first and second ground contacting edges 16 , 18 as shown in FIG. 4 .
In order to maximize the efficiency of the use of the shovel 10 , the first and second ground contacting edges 16 , 18 of the blade 12 are provided with a bevelled edge 30 , 30 ′ to promote the blade's snow lifting or scraping action close to the ground. That is, by providing a bevel, the edge of the shovel 10 is made sharper in order to promote dislodging compacted snow or ice from the ground. The angle of bevel, γ, is preferably in the order of 45 degrees in order to correspond to the average angle of the handle 14 with respect to the horizontal during use.
In another embodiment, the first and second ground contacting surfaces are provided with a reinforced edge 32 of metal or plastic to provide a sharper or reinforced edge as shown in FIG. 3 a.
Further still, it is preferred that the blade 12 is provided with rounded corners 40 at the leading corner of both the first and second ground contacting surfaces to facilitate the shovel's ability to ride over imperfections in the ground which might otherwise cause the blade 12 to catch on the ground.
Still further, it is also preferred that the leading end 20 and trailing end 22 are parallel to the handle 14 to enable the blade to be placed tightly against a vertical surface at the edge of a driveway or walkway.
In another embodiment, the blade is provided with a different or varying radius of curvature between the leading end 20 and trailing end 22 of the blade 10 as shown in FIG. 5 . The radius of curvature of either a fixed or variable curvature blade will typically be in the range of 4-12 inches although these dimensions are not intended to be limiting.
In a still further embodiment of the blade, the leading edge of the blade 20 may be provided with a cap 55 to minimize spillage of snow from the leading edge during use as shown in FIG. 7 .
The handle 14 of the shovel 10 may have various embodiments including a straight or a bent shaft. Specific embodiments of the handle 14 may include an auxiliary handle 50 or handles to promote the ergonomics of using the shovel 10 . In particular, an auxiliary handle as shown in FIG. 6 may be provided wherein the auxiliary handle 50 may rotate about the main handle 14 . Other embodiments may provide one or more auxiliary handles in a fixed position.
In one embodiment as shown in FIG. 7, the angle of the blade 12 with respect to the handle 14 is adjustable (FIG. 7) enabling the user to set a particular angle for optimization of the use of the shovel depending upon the depth and characteristics of the snow. That is, in the event that the snow is deeper and/or heavier, the user may select a smaller angle θ, so as to effectively reduce the width of the blade 12 as it is pushed through the snow.
In another embodiment, the handle may be selectively offset with respect to the blade 14 by moving the handle along a track 60 on the blade 12 as shown in FIG. 7 .
The shovel 10 may be manufactured from materials known to those skilled in the art including various woods, metals and plastics. | The invention relates to a shovel particularly useful for snow removal. The shovel is characterized by dual ground contacting edges allowing the shovel to be self-supporting and which allows the shovel to be used in an ergonomically efficient manner for removing snow from a surface. | 4 |
TECHNICAL FIELD
The present invention relates generally to semiconductor fabrication, and more particularly to methods for fabricating improved ultra-large scale integration (ULSI) semiconductor devices such as ULSI metal oxide silicon field effect transistors (MOSFETs).
BACKGROUND OF THE INVENTION
Semiconductor chips are used in many applications, including as processor chips for computers, and as integrated circuits and as flash memory for hand held computing devices, wireless telephones, and digital cameras. Regardless of the application, it is desirable that a semiconductor chip hold as many circuits or memory cells as possible per unit area. In this way, the size, weight, and energy consumption of devices that use semiconductor chips advantageously is minimized, while nevertheless improving the memory capacity and computing power of the devices.
A common circuit component of semiconductor chips is the transistor. In ULSI semiconductor chips, a transistor is established by forming a polysilicon gate on a silicon substrate, and then forming a source region and a drain region in the substrate beneath the gate by implanting appropriate dopant materials into the areas of the substrate that are to become the source and drain regions. The gate is insulated from the substrate by a thin gate oxide layer, with small portions of the source and drain regions, referred to as “extensions”, extending toward and virtually under the gate.
Between the source and drain regions and under the gate oxide layer is a source/drain extension (SDE) region, which is doped. The SDE region typically is doped early in the fabrication process, with the SDE dopant usually being implanted during the steps of forming the gate and source and drain regions. This generally-described structure cooperates to function as a transistor.
To suppress deleterious “short channel” effects such as threshold voltage roll-off (i.e., transistor operation at below intended voltages), it is important that the lateral dopant profile of the source/drain extensions be steep. Stated differently, it is important that virtually all of the dopant be concentrated within a relatively small area that is to function as the source/drain extension, with little or no dopant being located outside this relatively small doped region.
The present invention recognizes that the dopant gradient is deleteriously affected by high thermal budgets and particularly by high temperatures, such as those typically required during annealing to activate the dopant. Stated differently, exposing dopant in a source/drain extension to high temperatures can cause the dopant to thermally diffuse and, hence, can cause the dopant profile undesirably to spread. Nonetheless, the dopant must be activated for the device to function properly. The present invention has considered the above problem and has provided the solutions disclosed herein.
BRIEF SUMMARY OF THE INVENTION
A method for establishing at least one transistor on a semiconductor device includes providing a semiconductor substrate, and implanting deep dopants into the substrate to establish a source region and a drain region. Then, the method includes heating the substrate to activate the deep dopants. After activation, a neutral ion species is implanted in the substrate between the source and drain regions to define an amorphous extension region. Also, a source/drain extension (SDE) dopant is implanted in the amorphous extension region and is activated by heating the amorphous extension region.
In a preferred embodiment, the substrate is heated to more than nine hundred fifty degrees Celsius (950° C.) to activate the deep dopants, and the amorphous extension region is heated to no more than nine hundred fifty degrees Celsius (950° C.), and more preferably is heated to no more than six hundred fifty degrees Celsius (650° C.). With this process, the SDE dopant is substantially not thermally diffused.
As disclosed in greater detail below, the substrate defines a surface, and the neutral ion species preferably is implanted in the substrate by directing a beam of the neutral ion species onto the surface at an oblique angle to the surface. If desired, a halo dopant can also be implanted in the amorphous extension region. The amorphous extension region defines a depth, and the halo dopant is implanted to a halo depth of about one-half the depth of the amorphous extension region, with the SDE dopant in turn being implanted to a depth of about one-half the halo depth.
In another aspect, a method for making an ultra-large scale integration (ULSI) semiconductor device includes forming source and drain regions in a semiconductor substrate using a first activation temperature, then forming a doped source/drain extension (SDE) region between the source and drain regions using a second activation temperature less than the first activation temperature.
In yet another aspect, a semiconductor device includes a semiconductor substrate, at least one transistor gate on the substrate, and source and drain regions in the substrate below the gate. A source/drain extension (SDE) region is located between the source region and the drain region under the gate, and a recrystallized preamorphization substance is in the SDE extension region.
Other features of the present invention are disclosed or apparent in the section entitled “DETAILED DESCRIPTION OF THE INVENTION”.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a schematic diagram of a semiconductor device made according to the present invention, shown in combination with a digital processing apparatus;
FIG. 2 is a flow chart showing the steps of the present invention;
FIG. 3 is a side view of the device during deep source/drain junction dopant implant;
FIG. 4 is a side view of the device after deep source/drain junction dopant implant;
FIG. 5 is a side view of the device during preamorphization substance implanting;
FIG. 6 is a side view of the device during halo dopant implanting;
FIG. 7 is a side view of the device during SDE dopant implanting; and
FIG. 8 is a side view of the device after SDE dopant and halo dopant activation.
DETAILED DESCRIPTION OF THE INVENTION
Referring initially to FIG. 1, a semiconductor device embodied as a chip 10 is shown incorporated into a digital processing apparatus such as a computer 12 . The chip 10 is made in accordance with the below disclosure.
Now referring to FIGS. 2 and 3, as indicated at block 14 in FIG. 2 and as shown in FIG. 3, a transistor gate stack 16 is formed on a semiconductor substrate 18 , with a gate oxide layer 20 being sandwiched therebetween. Regions that are to become source and drain regions 22 , 24 are implanted with appropriate dopant, indicated by arrows 26 . Also, the dopant is implanted into the gate stack 16 , as indicated in FIG. 3 . Prior to implanting the dopant, a silicon nitride or other dielectric spacer 28 is formed on the side walls of the gate stack 16 as shown, to shield the region directly under the gate stack 16 from the source and drain dopants. A thin oxide layer 30 is disposed between the spacer 28 and the gate stack 16 , and isolation trenches 31 can be established on either side of the above-described MOSFET structure to isolate it from other MOSFETs.
Proceeding to block 32 in FIG. 2 and now referring to FIG. 4, the spacer 28 is removed by, e.g., hot H 3 PO 4 acid etch, and then the dopant in the source and drain regions 22 , 24 is activated using high temperature annealing. The annealing is undertaken at a temperature of at least nine hundred fifty degrees Celsius (950° C.) and more preferably at a temperature in excess of 1000° C. In one preferred embodiment, the depth of the source and drain regions can be between eight hundred Angstroms to twelve hundred Angstroms.
Moving to block 34 and now referring to FIG. 5, a preamorphization substance such as a neutral ion species, e.g., ionic Silicon or Germanium, is implanted into the substrate 18 as indicated by the arrows 36 between the source and drain regions 22 , 24 to define an amorphous extension region 38 that extends laterally under the gate stack 16 on both sides of the stack. The amorphous extension region 38 defines a depth D A from the surface 40 of the substrate 18 of about sixty nanometers to eighty nanometers (60 nm-80 nm).
In the preferred embodiment, the preamorphization substance is directed onto the substrate 18 at an oblique angle relative to the substrate surface 40 . More particularly, the preamorphization substance is directed onto the substrate 18 at an angle α relative to the normal to the surface 40 of between twenty degrees and forty degrees (20°-40°) to control the distance by which the amorphization extension region 38 extends under the gate stack 16 .
Proceeding to block 42 and now referring to FIG. 6, a halo dopant, represented by arrows 44 , is implanted into the substrate 18 partially under the gate stack 16 to establish a halo extension region 46 . The halo dopant can be established by Phosphorous, Arsenic, or Antimony for n-channel MOSFETs or Boron or Boron Fluoride (BF 2 ) for p-channel MOSFETs, and can be implanted at a peak concentration of, e.g., between 1×10 19 atoms/cc and 1×10 19 atoms/cc. Also, the halo dopant is implanted down to a halo depth of D H from the surface 40 of the substrate, with the preferred halo depth D H being about one-half the depth D A of the amorphous extension region 38 . If desired, the halo dopant can also be implanted at an oblique angle into the substrate 18 , as indicated by the arrows 44 .
Now moving to block 48 and referring to FIG. 7, a source/drain extension (SDE) dopant, represented by arrows 50 , is implanted into the substrate 18 partially under the gate stack 16 to establish an SDE extension region 52 that extends laterally under the gate stack 16 as shown. The SDE dopant can be established by Phosphorous, Arsenic, or Antimony for p-channel MOSFETs or Boron or Boron Fluoride (BF 2 ) for n-channel MOSFETs, and can be implanted at a peak concentration of, e.g., between 1×10 18 atoms/cc and 1×10 18 atoms/cc. Also, the SDE dopant is implanted down to an SDE depth of D S from the surface 40 of the substrate, with the preferred SDE depth D S being about one-half the halo depth D H . Although FIG. 7 shows that the SDE dopant is directed normally down on the substrate 18 during implantation, it can alternatively be directed at an angle after the manner of the preamorphization and halo implanting described above.
In accordance with the present invention, thanks to the preamorphization substance implanting, at block 54 the SDE dopant and halo dopant are activated using low temperature annealing. In one embodiment, the annealing at block 54 is undertaken at a temperature of no more than nine hundred fifty degrees Celsius (950° C.), and more preferably at a temperature of no more than six hundred fifty degrees Celsius (650° C.), such that the SDE dopant is substantially not thermally diffused, as shown in FIG. 8 . The annealing temperature preferably is maintained for a period sufficiently long to ensure that the preamorphization species fully recrystallizes. Processing, including the forming of contacts and interconnects, is completed at block 56 .
While the particular METHOD FOR REDUCING LATERAL DOPANT GRADIENT IN SOURCE/DRAIN EXTENSION OF MOSFET as herein shown and described in detail is fully capable of attaining the above-described objects of the invention, it is to be understood that it is the presently preferred embodiment of the present invention and is thus representative of the subject matter which is broadly contemplated by the present invention, that the scope of the present invention fully encompasses other embodiments which may become obvious to those skilled in the art, and that the scope of the present invention is accordingly to be limited by nothing other than the appended claims, in which reference to an element in the singular is not intended to mean “one and only one” unless explicitly so stated, but rather “one or more”. Indeed, although a single transistor structure is shown in the drawings for clarity, the skilled artisan will appreciate that the chip 10 can include plural transistors, each substantially identical to that shown, as well as other circuit components. All structural and functional equivalents to the elements of the above-described preferred embodiment that are known to those of ordinary skill in the art are expressly incorporated herein by reference and are intended to be encompassed by the present claims. Moreover, it is not necessary for a device or method to address each and every problem sought to be solved by the present invention, for it to be encompassed by the present claims. Furthermore, no element, component, or method step in the present disclosure is intended to be dedicated to the public regardless of whether the element, component, or method step is explicitly recited in the claims. No claim element herein is to be construed under the provisions of 35 U.S.C. §112, sixth paragraph, unless the element is expressly recited using the phrase “means for”. | A method for reducing lateral dopant gradient diffusion in the source/drain extension (SDE) region of a MOSFET includes forming the deep source and drain using high temperature dopant activation annealing, and then implanting a preamorphization species in an amorphized extension region that is to become the SDE region. Then, both SDE dopant and, if desired, halo dopant are implanted into the amorphized extension region and activated using relatively low temperature annealing, thereby reducing the thermal budget of the process and concomitantly reducing unwanted dopant thermal diffusion. | 7 |
BACKGROUND OF THE INVENTION
This invention relates to miniature two degree of freedom fluid bearing angular rate sensors for use primarily in tactical applications, i.e. for inertially guiding a missile or the like from launch to target.
Angular rate sensors, for the purposes described must be small, rugged and inexpensive to manufacture. For purposes of example, specifications for a particular two degree of freedom tactical angular rate sensor require the instrument to provide two axes of angular rate information in a package one inch in diameter and one and one-quarter inches in length. The instrument must be designed for constant angular rates up to 300 degrees per second. The sensor rotor bearing suspension must be able to sustain 40 g's of linear acceleration without degradation of performance. To best serve the purposes intended, the sensor should have a minimum number of components.
The present invention achieves the aforementioned requirements by featuring a miniature tactical angular rate sensor having a spherical hydrodynamic fluid bearing rotor component, a permanent magnet motor/torquer component and an optical pick-off component. The arrangement is such that each component can be preassembled as a sub-assembly, tested and stocked for final assembly, the same being recognized as advantageous.
SUMMARY OF THE INVENTION
This invention contemplates a miniature two degree of freedom, simple, economical angular rate sensor capable of surviving severe environments. The sensor provides two axes of analog outputs corresponding to sensed angular rate.
A spherical hydrodynamic fluid bearing rotor component includes two parts, i.e. a rotor bearing and a cylindrical, two pole permanent magnet having a reflective surface. The magnet is used for both torquer and spin motor operation, as well as providing a reflective surface for an optical pick-off.
A single permanent magnet rotor and an ironless stator containing the sensor spin motor and torquer windings are the main features of a motor/torquer (magnetic) component.
An optical pick-off component includes a light emitting diode (LED) light source, an optical beam splitter, a lens, the reflective surface on the rotor magnet and an optical quadrant detector.
The hydrodynamic bearing, the spin motor and torquer, and the optical pick-off are configured as three separate components for providing simplicity in design and a minimal number of parts resulting in an easily assembled, inexpensive instrument, and otherwise satisfying the intended requirements of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional diagrammatic view generally showing the several components of the invention.
FIG. 2 is an isometric diagrammatic representation showing the spin motor and torquer component.
FIG. 3 is an isometric diagrammatic representation showing the optical pick-off component.
FIG. 4 is an electrical schematic/block diagram showing the electrical features of the spin motor and torquer component.
FIG. 5 is a diagrammatic representation showing the hydrodynamic bearing rotor.
FIG. 6 is a diagrammatic representation showing the hydrodynamic bearing component and the fluid flow characteristics thereof.
DETAILED DESCRIPTION OF THE INVENTION
With reference first to FIG. 1, the miniature tactical angular rate sensor of the invention is supported within members 2, 4 and 5. Members 2, 4 and 5 provide a suitable evacuated and hermetically sealed case or housing for the sensor.
The sensor includes three basic components: a hydrodynamic bearing component 6; a spin motor and torquer component 8 and a signal generator or pick-off component 10.
Hydrodynamic bearing component is configured in accordance with the theory of hydrodynamic lubrication for fluid bearings, and to this end includes a spherical rotor 12 having an external spiral grooved pattern designated generally by the numeral 13, as particularly shown in FIG. 5. With reference to FIG. 5, groove pattern 13 may include a plurality of V-shaped grooves 14. In the preferred embodiment of the invention twenty-three such grooves (only one is shown) are equally spaced within 0.003 inches at any given latitude. The groove widths are tapered and the grooves have the same longitudinal width within 0.003 inches at any given latitude. The grooves are 0.000180 to 0.000220 inches deep and are of the same depth within 0.000020 inches.
Rotor 12, when rotating, generates a pressurized layer of gas which suspends the rotor within its housing 15 as particularly shown in FIGS. 1 and 6. Housing 15 includes a spherical cavity 16. Thus, with the arrangement described, rotor 12 is supported within cavity 16 on a fluid cushion, and which fluid may be a suitable gas, so that the rotor is free to rotate about X and Y pick-off axes and a rotor spin axis Z (FIG. 6), resulting in a two degree of freedom arrangement as is desired.
With continued reference to FIG. 6, the hydrodynamic characteristics of spherical rotor 12 supported in matching spherical cavity 16 in housing 15 are illustrated. Thus, gas flows through a hole 20 perpendicular to rotor spin axis Z and through and around the rotor as indicated by the arrows to provide the required rotor suspension.
Spin motor and torquer component 8 includes a single permanent magnet 22 (FIGS. 1, 2, 3 and 6) and an ironless stator 23 supporting windings 24 for the spin motor and windings 26 for the torquer (FIG. 1).
With particular reference to FIG. 2, magnet 22 is a two pole, cylindrical, permanent magnet mounted on rotor 12 through the center thereof (FIG. 1). Magnet 22, which has a reflective surface 21, is surrounded by torquer windings 26 which, in turn, are surrounded by motor windings 24 which are actually four separate winding arrangements. A suitable magnetic shield 28 surrounds motor windings 24.
A pair of Hall elements 30 and 32 are embedded in motor stator windings 24. Hall elements 30 and 32 provide outputs relating to the location of the poles of magnet 22 for continuous two phase closed loop operation as will hereinafter become evident. As will be further described with reference to FIG. 4, a commutator arrangement is driven by a processed feedback signal from the Hall elements and applies a drive signal to provide proper rotor polarity and synchronization. This signal is suitably amplified and provides the required power to accelerate and maintain the rotor at a particular commanded speed.
Torquer windings 26 in cooperation with magnet 22 maintain rotor 12 properly positioned in cavity 16 of housing 15. This is achieved by the torquer arrangement including magnet 22 and windings 26 applying the proper force required to null out the output signals from pick-off component 10. The output signals provide continuous information of the position of magnet 22 while Hall elements 30 and 32 provide the commutation angle relative to the rotor housing.
The output signals, along with the commutation signals, are processed by a conventional feedback loop 48 (FIG. 4) to provide a current output to the torquer arrangement aforenoted. The magnitude and phase of this current output is applied to the torquer arrangement to generate an axial field of the desired strength and timing, such that a net desired torque is provided to correct the rotor position of rotor magnet 22. The current is resolved through conventional resolver circuitry (not otherwise shown) to determine the applied rate information for each of the X and Y axes.
With particular reference to FIG. 3, pick-off 10 is utilized to sense the relative precession of rotor 12 as a result of rates applied to the sensor about its input axes. Thus, pick-off 10 includes a light emitting diode (LED) light source 34, an optical beam splitter 36, a lens 38, reflective surface 25 of rotor magnet 22 and an optical quadrant detector 40.
Optical quadrant detector 40 is a four cell photodiode quadrant detector, and reacts to light energy for generating a proportional current output. The current from each quadrant is summed and differentially amplified by conventional pick-off electronics (not otherwise shown). At pick-off null, the light reflected from reflective surface 25 of magnet 22 equally illuminates all four quadrants of detector 40. This occurs when rotor 12 is centered in cavity 16 of housing 15.
Off null, i.e. when the sensor rotor has precessed, the reflected beam differentially illuminates the four quadrants. Thus, some quadrants receive more illumination while opposite quadrants receive less. This results in a differential electrical output which is converted by conventional processing electronics (not otherwise shown) to linear output signals proportional to the precessed angular position of the rotor. These output signals are utilized by the aforementioned feedback loop as will be hereinafter described The construction of optical quadrant 40 on a common substrate as is the case provides two axes of rate information and tends to be self-compensating for temperature sensitivity effects.
Beam splitter 36 redirects the reflected light beam so that light source 34 and quadrant detector 40 need not be co-linear In the absence of beam splitter 36, a central hole through quadrant detector 40 would be necessary and an alternate mechanization would be provided.
Beam splitter 36 is configured to reflect fifty percent of the beam at the diagonal interface at each pass. The remaining fifty percent is transmitted, without reflection. Lens 38 is used to properly focus the reflected light beam.
With reference now to FIG. 4, the output of Hall element 30 providing information as aforenoted is applied to a commutator 42, and the output from Hall element 32 likewise providing the aforenoted information is applied to a commutator 44. The output from Hall element 32 is applied to a phase locked loop 46.
The outputs from phase locked loop 46 and from pick-off 10 are applied to feedback loop 48 which provides controlling outputs to commutators 42 and 44. The output from commutator 42 is applied to a driver arrangement 49 which drives phase A of the two-phase sensor motor which includes windings 24 and magnet 22. The output from commutator 44 is applied to a driver arrangement 50 which drives phase B of the two-phase motor.
Thus, as illustrated in FIG. 4, Hall elements 30 and 32 are effective for providing magnetic pole location information for continuous two phase closed loop operation of the sensor motor. Commutators 42 and 44 are driven by a processed feedback signal from the Hall elements to switch a drive signal to provide proper motor rotor polarity and synchronization. The drive signal is amplified via driver arrangements 49 and 50, as the case may be, to provide the required power to drive, i.e. to accelerate and maintain the motor rotor at a commanded speed.
It will thus be seen from the aforenoted description of the invention that a miniature two degree of freedom fluid bearing sensor, primarily for tactical applications, has been provided. The sensor includes a spherical hydrodynamic fluid bearing rotor, a permanent magnet motor/torquer, and an optical pick-off, whereby two axes of rate information are provided in a small package as is the intended purpose of the invention. The spherical hydrodynamic fluid bearing rotor heretofore described provides a suspension which sustains the aforenoted 40 g's of linear acceleration at a rotational speed of 24,000 RPM. The aforenoted packaging results in a minimum number of parts which tends to reduce static and dynamic balance effects as is desirable. The spherical rotor arrangement described provides the ruggedness necessary to survive severe shock levels without degradation in performance, as will now be understood.
With the foregoing description of the invention in mind, reference is made to the claims appended hereto for a definition of the scope of the invention. | A miniature two degree of freedom fluid bearing angular rate sensor used primarily for tactical applications includes a spherical hydrodynamic fluid bearing rotor, a permanent magnet motor/torquer, and an optical pick-off, all of which are arranged to provide two axes of rate information in a small package. The individual components can be pre-assembled as sub-assemblies, and individually stocked and tested for final assembly. | 6 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of Ser. No. 714,390, filed August 16, 1976, now abandoned, and Ser. No. 800,623, filed May 26, 1977, now abandoned.
BACKGROUND OF THE INVENTION
This invention provides novel compositions of matter. This invention further provides novel processes for producing these compositions of matter. This invention further provides novel chemical intermediates useful in the above processes.
This invention is specifically concerned with novel bicyclic nitrogen-containing compounds which are analogs of the prostaglandins, e.g., ##STR2## Included within the scope of this invention, in addition to such 9α, 11α-azo-9,11,15 -trideoxy-PGF-type compounds, are 9α,11α-epoxyimino-9,11,15 -trideoxy-PGF-type compounds and N,N'-dialkyl-9α,11α-hydrazino-9,11,15-trideoxy-PGF-type compounds, e.g., ##STR3## respectively.
Accordingly, the present invention is concerned with biheterocyclic, nitrogen-containing analogs of the prostaglandins, e.g., 9α, 11α-azo-, 9α-11α-epoxyimino, 11α-9α-epoxyimino-, and N,N'-alkyl or alkylcarbonyl-hydrazino-. Thus each of the above compounds is a derivative of prostane which has the following structure and carbon atom numbering ##STR4## For a discussion of the use of the corresponding C-1 carboxylic acid derivatives, i.e., the prostaglandins, see, for example, Bergstrom et al., Pharmacol. Rev. 20, 1 (1968), and references cited therein. A systematic name for prostanoic acid, the above-mentioned C-1 carboxylic acid, is 7-[2β-octyl)-cyclopen-1α-yl]-heptanoic acid.
In the above formulas, as well as in the formulas hereinafter given, broken line attachments to the cyclopentane ring indicate substituents in alpha configuration i.e., below the plane of the cyclopentane ring. Heavy solid line attachments to the cyclopentane ring indicate substituents in beta configuration, i.e., above the plane of the cyclopentane ring. The use of wavy lines (˜) herein will represent attachment of substituents in either the alpha or beta configuration or attachment in a mixture of alpha and beta configurations.
Molecules of the known prostaglandins each have several centers of asymmetry, and can exist in racemic (optically inactive) form and in either of the two enantiomeric (optically active) forms, i.e. the dextrorotatory and levorotatory forms. As drawn, the above formulas each represent the particular optically active form of the prostaglandin as is obtained from mammaliam tissues, for example, sheep vesicular glands, swine lung, or human seminal plasma, from carbonyl and/or double bond reduction of the prostaglandin so obtained. See, for example, Bergstrom et al., cited above. The mirror image of ech of these formulas, represents the other enantiomer of that prostaglandin. The racemic form of a prostaglandin contains equal numbers of both enantiomeric molecules, and one of the above formulas and the mirror image of that formula is needed to represent correctly the corresponding racemic prostaglandin. For convenience hereinafter, use of the term, prostaglandin or "PG" will mean the optically active form of that prostaglandin thereby referred to with the same absolute configuration as PGE 1 obtained from mammalian tissues. When reference to the racemic form of one of those prostaglandins is intended, the work "racemic" or "dl" will precede the prostaglandin name.
The term "prostaglandin-type" (PG-type) product, as used herein, refers to any bicyclic cyclopentane derivative which is useful as an antiinflammatory agent, as indicated herein.
The term prostaglandin-type intermediate, as used herein, refers to any cyclopentane derivative useful in preparing a prostaglandin-type product.
The formulas as drawn herein, which depict a prostaglandin-type product or an intermediate useful in preparing a prostaglandin-type product, each represent the particular stereoisomer of the prostaglandin-type product which is of the same relative stereochemical configuration as a corresponding prostaglandin obtained from mammalian tissues, or the particular stereoisomer of the intermediate which is useful in preparing the above stereoisomer of the prostaglandin-type product.
The term "prostaglandin analog", as used herein, represents that stereoisomer of a prostaglandin-type product which is of the same relative stereochemical configuration as a corresponding prostaglandin obtained from mammalian tissues or a mixture comprising that stereoisomer and the enantiomer thereof. In particular, where a formula is used to depict a prostaglandin-type compound herein, the term prostaglandin analog refers to the compound of that formula, or a mixture comprising that compound and the enantiomer, thereof.
See U.S. Pat. Nos. 3,950,363 and 4,028,350 for a description of 9α,11α-or 11α-9α-epoxymethano-9,11,15 -trideoxy-PGF compounds corresponding to certain compounds of the present invention. See also E. J. Corey, et al., Biochemistry, 72:3355-3358 (1975) for a disclosure of 9,11-dideoxy-9α--azo-PGF 2 .
SUMMARY OF THE INVENTION
The present invention particularly and especially provides a prostaglandin analog of the formula ##STR5## wherein W 1 is ##STR6## wherein R 2 is alkyl of one to 4 carbon atoms, inclusive or alkylcarbonyl of one to 4 carbon atoms, inclusive;
wherein Y 1 is
(1) trans--CH═CH--CH 2 --
(2) -- (ch 2 ) 3 --,
(3) --c.tbd. c-- ch 2 --,
(4) trans--CH 2 --CH═ CH--, or
(5) cis--CH═C--Ch 2 --
wherein L 1 is ##STR7## or a mixture of ##STR8## wherein R 3 and R 4 are hydrogen, methyl, or fluoro, being the same or different, with the proviso that one of R 3 and R 4 is fluoro only when the other is hydrogen or fluoro;
wherein Z 1 is
(1) cis--CH═CH--CH 2 --(CH 2 ) g --CH 2 --,
(2) cis--CH═ CH--CH 2 --(CH 2 ) g --CF 2 ,
(3) cis--CH 2 --CH═ CH--(CH 2 ) g --CH 2 --,
(4) --(ch 2 ) 3 --(ch 2 ) g --CH 2 --,
(5) --(ch 2 ) 3 --(ch 2 ) g --CF 2 --,
(6) --ch 2 --o--ch 2 --(ch 2 ) g --CH 2 --, ##STR9## wherein g is one, 2, or 3;
wherein R 7 is
(1) - (CH 2 ) m -CH 3 , ##STR10##
wherein h is zero to 3, inclusive,
wherein m is one to 5, inclusive, T is chloro, fluoro, trifluoromethyl, alkyl of one to 3 carbon atoms, inclusive, or alkoxy of one to 3 carbon atoms, inclusive and s is zero, one, 2, or 3, the various T's being the same or different, with the proviso that not more than two T's are other than alkyl, with the further proviso that R 7 is ##STR11## wherein T and s are as defined above, only when R 3 and R 4 are hydrogen or methyl, being the same or different;
wherein X 1 is
(1) -COOR 1 wherein R 1 is hydrogen; alkyl of one to 12 carbon atoms, inclusive; cycloalkyl of 3 to 10 carbon atoms, inclusive, aralkyl of 7 to 12 carbon atoms, inclusive; phenyl; phenyl substituted with one, two, or three chloro or alkyl of one to 3 carbon atoms; phenyl substituted in the para position by ##STR12## wherein R 25 is methyl, phenyl, acetamidophenyl, benzamidophenyl, or -NH 2 ; R 26 is methyl, phenyl, -NH 2 , or methoxy; and R 27 is hydrogen or acetamido; inclusive, or a pharmacologically acceptable cation;
(2) --CH 2 OH;
(3) --COL 4 , wherein L 4 is
(a) amido of the formula --NR 21 R 22 , wherein R 21 and R 22 are hydrogen; alkyl of one to 12 carbon atoms, inclusive; cycloalkyl of 3 to 10 carbon atoms, inclusive; aralkyl of 7 to 12 carbon atoms, inclusive; phenyl; phenyl substituted with one, 2, or 3 chloro, alkyl of one to 3 carbon atoms, inclusive; hydroxy, carboxy, alkoxycarbonyl of one to 4 carbon atoms, inclusive, or nitro; carboxyalkyl of one to four carbon atoms, inclusive; carbamoylalkyl of one to four carbon atoms, inclusive; cyanoalkyl of one to four carbon atoms, inclusive; acetylalkyl of one to four carbon atoms, inclusive; benzoylalkyl of one to four carbon atoms, inclusive; benzoylalkyl substituted by one, 2, or 3 chloro, alkyl of one to 3 carbon atoms, inclusive; hydroxy, alkoxy of one to 3 carbon atoms, inclusive; carboxy, alkoxycarbonyl of one to 4 carbon atoms, inclusive; or nitro; pyridyl; pyridyl substituted by one, 2, or 3 chloro, alkyl of one to 3 carbon atoms, inclusive; or alkoxy of one to 3 carbon atoms, inclusive; pyridylalkyl of one to 4 carbon atoms, inclusive; pyridylalkyl of one to 4 carbon atoms, inclusive; pyridylalkyl substituted by one, 2, or 3 chloro, alkyl of one to 3 carbon atoms, inclusive; hydroxy, alkoxy of one to 3 carbon atoms, inclusive; hydroxyalkyl of one to 4 carbon atoms, inclusive; dihydroxyalkyl of one to 4 carbon atoms, and trihydroxyalkyl of one to 4 carbon atoms; with the further proviso that not more than one of R 21 and R 22 is other than hydrogen or alkyl;
(b) cycloamido selected from the group consisting of ##STR13## wherein R 21 and R 22 are as defined above;
(c) carbonylamido of the formula --NR 23 COR 21 , wherein R 23 is hydrogen or alkyl of one to 4 carbon atoms and R 21 is as defined above;
(d) sulphonylamido of the formula --NR 23 SO 2 R 21 , wherein R 21 and R 23 are as defined above; or
(e) hydrazino of the formula --NR 23 R 24 , wherein R 24 is amido of the formula --NR 21 R 22 , as defined above, or cycloamido, as defined above; or
(4) --CH 2 NL 2 L 3 , wherein L 2 and L 3 are hydrogen or alkyl of one to 4 carbon atoms, inclusive, being the same or different; and the pharmacologically acceptable acid addition salts thereof when X 1 is not -COOR 1 , and R 1 a cation.
Those prostaglandin analogs herein wherein Z 1 is cis--CH═CH--CH 2 --(CH 2 ) g --CH 2 -- or cis--CH═CH--CH 2 --(CH 2 ) g --CF 2 -- are named as "PG 2 " compounds. The latter compounds are further characterized as "2,2-difluoro" PG-type compounds. When g is 2 or 3, the prostaglandin analogs so described are "2a-homo" or "2a,2b-dihomo" compounds, since in this event the carboxy terminated side chain contains 8 or 9 carbon atoms, respectively, in place of the 7 carbon atoms contained in PGE 1 . These additional carbon atoms are considered as though they were inserted between the C-2 and C-3 positions. Accordingly, these additional carbon atoms are referred to as C-2a and C-2b, counting from the C-2 to the C-3 position.
Further when Z 1 is --(CH 2 ) 3 --(CH 2 ) g --CH 2 -- or --(CH 2 ) 3 --(CH 2 ) g --CF 2 , wherein g is as defined above, the compounds so described are "PG 1 " compounds. When g is 2 or 3, the "2a-homo" and "2a,2b-dihomo" compounds are described as is discussed in the preceding paragraph.
When Z 1 is --CH 2 --O--CH 2 --(CH 2 ) g --CH 2 -- the compounds so described are named as "5-oxa-PG 1 " compounds. When g is 2 or 3, the compounds so described are "2a-homo" or "2a,2b-dihomo" compounds, respectively, as discussed above.
When Z 1 is cis--CH 2 --CH═CH--(CH 2 ) g --CH 2 --, wherein g is as defined above, the compounds so described are named "cis-4,5-didehydro-PG 1 " compounds. When g is 2 or 3, the compounds so described are further characterized as "2a-homo" or "2a,2b-dihomo" compounds, respectively, as discussed above.
For the novel compounds of this invention wherein Z 1 is ##STR14## there are described, respectively, 3-oxa-3,7-inter-m-phenylene-4,5,6-trinor- or 3,7-inter-m-phenylene-4,5,6-trinor-PG-type compounds, when g is one. When g is 2 or 3, the above compounds are additionally described as "2a-homo" or "2a,2b-dihomo" PG-type compounds, respectively.
The novel prostaglandin analogs herein which contain a --(CH 2 ) 3 --, cis--CH═CH--CH 2 --, or --C.tbd.C--CH 2 -- moiety as the Y 1 moiety, are accordingly, referred to as "13,14-dihydro," "cis-13", or "13,14-didehydro" compounds, respectively.
When Y 1 is trans-CH 2 --CH═CH--, the compounds so described are named as "13,14-dihydro-trans-14,15- ##STR15## wherein T and s are as defined above, only when R 3 and R 4 are hydrogen or methyl, being the same or different; compounds so described are further characterized as "2a-homo" or "2a,2b-dihomo" compounds, respectively, as discussed above.
For the novel compounds of this invention wherein Z 1 is ##STR16## there are described, respectively, 3-oxa-3,7-inter-m-phenylene-4,5,6-trinor- or 3,7-inter-m-phenylene-4,5,6-trinor-PG-type compounds, when g is one. When g is 2 or 3, the above compounds are additionally described as "2a-homo" or "2a,2b-dihomo" PG-type compounds, respectively.
The novel prostaglandin analogs herein which contain a --(CH 2 ) 3 --, cis--CH═CH--CH 2 --, or --C.tbd.C--CH 2 -- moiety as the Y 1 moiety, are accordingly, referred to as "13,14-dihydro," "cis-13", or "13,14-didehydro" compounds, respectively.
When Y 1 is trans--CH 2 --CH═CH--, the compounds so described are names as "13,14-dihydro-trans-14,15-didehydro" compounds.
When R 7 is --(CH 2 ) m --CH 3 , wherein m is as defined above, the compounds so described are named as "19,20-dinor", "20-nor", "20-methyl" or "20-ethyl" compounds when m is one, 2, 4, or 5, respectively
When R 7 is ##STR17## wherein T and s are as defined above, and neither R 3 nor R 4 is methyl, the compounds so described are named as "16-phenyl-17,18,19,20-tetranor" compounds, when s is zero. When s is one, 2, or 3, the corresponding compounds are named as "16-(substituted phenyl)-17,18,19,20-tetranor" compounds. When one and only one of R 3 and R 4 is methyl or both R 3 and R 4 are methyl, then the corresponding compounds wherein R 7 is as defined in this paragraph are named as "16-phenyl or 16-(substituted phenyl)-18,19,20-trinor" compounds or "16-methyl-16-phenyl- or 16-(substituted phenyl)-18,19,20-trinor" compounds, respectively.
When R 7 is ##STR18## wherein T and s are as defined above, the compounds so described are named as "17-phenyl-18,19,20-trinor" compounds, when s is 0. When s is one, 2, or 3, the corresponding compounds are named as "17-(substituted phenyl)-18,19,20-trinor" compounds.
When R 7 is ##STR19## wherein T and s are as defined above, the compounds so described are named as "18-phenyl-19,20-dinor" compounds, when s is 0. When s is one, 2, or 3, the corresponding compounds are named as "18-(substituted phenyl)-19,20-dinor" compounds.
When R 7 is ##STR20## wherein T and S are as defined above, the compounds so described are named as "19-phenyl-20-nor" compounds, when s is 0. When s is one, 2, or 3, the corresponding compounds are named as "19-(substituted phenyl)-20-nor" compounds.
When R 7 is ##STR21## wherein T and s are as defined above, and neither R 3 nor R 4 is methyl, the compounds so described are named as "16-phenoxy-17,18,19,20-tetranor" compounds, when s is zero. When s is one, 2, or 3, the corresponding compounds are named as "16-(substituted phenoxy)-17,18,19,20-tetra-nor" compounds. When one and only one of R 3 and R 4 is methyl or both R 3 and R 4 are methyl, then the corresponding compounds wherein R 7 is as defined in this paragraph are named as "16-phenoxy or 16-(substituted phenoxy)-18,19,20-trinor" compounds or "16-methyl-16-phenoxy- or 16-(substituted phenoxy)-18,19,20-trinor" compounds, respectively.
When at least one of R 3 and R 4 is not hydrogen then (except for the 16-phenoxy or 16-phenyl compounds discussed above) there are described the "16-methyl" (one and only one of R 3 and R 4 is methyl), "16,16-dimethyl" (R 3 and R 4 are both methyl), "16-fluoro" (one and only one of R 3 and R 4 is fluoro), "16,16-difluoro" (R 3 and R 4 are both fluoro) compounds. For those compounds wherein R 3 and R 4 are different, the prostaglandin analogs so represented contain an asymmetric carbon atom at C-16. Accordingly, two epimeric configurations are possible: "(16S)" and "(16R)". Further, there is described by this invention the C-16 epimeric mixture: "(16RS)".
When X 1 is -CH 2 OH, the compounds so described are named as "2-decarboxy-2-hydroxymethyl" compounds.
When X 1 is -CH 2 NL 2 L 3 , the compounds so described are named as "2-decarboxy-2-aminomethyl or 2-(substituted amino)methyl" compounds.
When X 1 is --COL 4 the novel compounds herein are named as PG-type, amides. Further when X 1 is -COOR, the novel compounds herein are named as PG-type, esters and PG-type, salts where R 1 is not hydrogen.
Finally, the NOMENCLATURE TABLE herein describes the convention by which trivial names are further assigned for the novel compounds herein:
NOMENCLATURE TABLE______________________________________W.sub.1 R.sub.2 Compound Type______________________________________(1) ##STR22## 9,11,15-trideoxy-9α,11α-azo- PGF-type(2) ##STR23## 9,11,15-trideoxy-11α,9α- epoxyimino-PGF-t ype(3) ##STR24## 9,11,15-trideoxy-9α,11α- epoxyimino-PGF-t ype(4) ##STR25## alkyl N,N'-dialkyl-9,11,15- trideoxy-9α,11α-hyd razino- PGF-type alkyl- N,N'-bis(alkylcarbonyl)- carbonyl 9,11,15-trideoxy-9α,11α- hydrazino-PGF-type(5) ##STR26## alkyl N-alkyl-9,11,15-trideoxy- 11α,9α-epoxyimi no- PGF-type alkyl- N-(alkylcarbonyl)-9,11,15- carbonyl trideoxy-11α,9α-epoxyimino- PGF-type(6) ##STR27## alkyl alkyl- carbonyl N-alkyl-9,11,15-trideoxy-9α, 11α-epoxyimi no-PGF-type N-(alkylcarbonyl)-9,11,15- trideoxy-9.alp ha.,11α- epoxyimino-PGF-type(7) ##STR28## alkyl 9,11,15-trideoxy-9α,11α- alkylhydrazino-P GF-type alkyl- 9,11,15-trideoxy-9α-11α- carbonyl (alkylcarbonyl)hydrazino- PGF-type (8) ##STR29## alkyl 9,11,15-trideoxy-11α,9α- alkylhydrazino-P GF-type alkyl- 9,11,15-trideoxy-11α,9α- carbonyl (alkylcarbonyl)hydrazino- PGF-type______________________________________
Examples of phenyl esters substituted in the para position (i.e. X 1 is --COOR 1 , R 1 is p-substituted phenyl) include p-acetamidophenyl ester, p-benzamidophenyl ester, p-(p-acetamidobenzamido)phenyl ester, p-(p-benzamidobenzamido)phenyl ester, p-amidocarbonylamidophenyl ester, p-acetylphenyl ester, p-benzylphenyl ester, p-amidocarbonylphenyl ester, p-methoxycarbonylphenyl ester, p-benzoyloxyphenyl ester, p-(p-acetamidobenzoyloxy)phenyl ester, and p-hydroxybenzaldehyde semicarbazone ester.
Examples of novel amides herein (i.e., X 1 is COL 4 ) include the following:
(1) Amides within the scope of alkylamido groups of the formula -NR 21 R 22 are methylamide, ethylamide, n-propylamide, n-butylamide, n-pentylamide, n-hexylamide, n-heptylamide, n-octylamide, n-nonylamide, n-decylamide, n-undecylamide and n-dodecylamide, and isomeric forms thereof. Further examples are dimethylamide, diethylamide, di-n-propylamide, di-n-butylamide, methylethylamide, methylpropylamide, methylbutylamide, ethylpropylamide, ethylbutylamide, and propylbutylamide. Amides within the scope of cycloalkylamido are cyclopropylamide, cyclobutylamide, cyclopentylamide, 2,3-dimethylcyclopentylamide, 2,2-dimethylcyclopentylamide, 2-methylcyclopentylamide, 3-tert-butylcyclopentylamide, cyclohexylamide, 4-tert-butylcyclohexylamide, 3-isopropylcyclohexylamide, 2,2-dimethylcyclohexylamide, cycloheptylamide, cyclooctylamide, cyclononylamide, cyclodecylamide, N-methyl-N-cyclobutylamide, N-methyl-N-cyclopentylamide, N-methyl-N-cyclohexylamide, N-ethyl-N-cyclopentylamide, N-ethyl-N-cyclohexylamide, dicyclopentylamide, and dicyclohexylamide. Amides within the scope of aralkylamido are benzylamide, 2-phenylethylamide, 2-phenylethylamide, N-methyl-N-benzylamide, and dibenzylamide. Amides within the scope of substituted phenylamido and p-chloroanilide, m-chloroanilide, 2,4-dichloroanilide, 2,4,6-trichloroanilide, m-nitroanilide, p-nitroanilide, p-methoxyanilide, 3,4-dimethoxyanilide, 3,4,5-trimethoxyanilide, p-hydroxymethylanilide, p-methylanalide, m-methylanilide, p-ethylanilide, t-butylanilide, p-carboxyanilide, p-methoxycarbonylanilide, o-carboxyanilide and o-hydroxyanilide. Amides within the scope of carboxyalkylamido are carboxyalkylamido are carboxymethylamide, carboxyethylamide, carboxypropylamide, and carboxybutylamide. Amides within the scope of the carbamoylalkylamido are carbamoylmethylamide, carbamoylethylamide, carbamoylpropylamide, and carbamoylbutylamide. Amides within the scope of cyanoalkylamido are cyanomethylamide, cyanoethylamide, cyanopropylamide, and cyanobutylamide. Amides within the scope of acetylalkylamido are acetylmethylamide, acetylethylamide, acetylpropylamide, and acetylbutylamide. Amides within the scope of benzoylalkylamido are benzoylmethylamide, benzoylethylamide, benzoylpropylamide, and benzoylbutylamide. Amides within the scope of substituted benzoylalkylamido are p-chlorobenzoylmethylamide, m-chlorobenzoylmethylamide, 2,4-dichlorobenzoylmethylamide, 2,4,6-trichlorobenzoylmethylamide, m-nitrobenzoylmethylamide, p-nitrobenzoylmethylamide, p-methoxybenzoylmethylamide, 2,4-dimethoxybenzoylmethylamide, 3,4,5-trimethoxybenzoylmethylamide, p-hydroxymethylbenzoylmethylamide, p-methylbenzoylmethylamide, m-methylbenzoylmethylamide, p-ethylbenzoylmethylamide, t-butylbenzoylmethylamide, p-carboxybenzoylmethylamide, m-methoxycarbonylbenzoylmethylamide, o-carboxybenzoylmethylamide, o-hydroxybenzoylmethylamide, p-chlorobenzoylethylamide, m-chlorobenzoylethylamide, 2,4-dichlorobenzoylethylamide, 2,4,6-trichlorobenzoylethylamide, m-nitrobenzoylethylamide, p-nitrobenzoylethylamide, p-methoxybenzoylethylamide, p-methoxybenzoylethylamide, 2,4-dimethoxybenzoylethylamide, 3,4,5-trimethoxybenzoylethylamide, p-hydroxymethylbenzoylethylamide, p-methylbenzoylethylamide, m-methylbenzoylethylamide, p-ethylbenzoylethylamide, t-butyl-benzoylethylamide, p-carboxybenzoylethylamide, m-methoxycarbonylbenzoylethylamide, o-carboxybenzoylethylamide, o-hydroxybenzoylethylamide, p-chlorobenzoylpropylamide, m-chlorobenzoylpropylamide, 2,4-dichlorobenzoylpropylamide, 2,4,6-trichlorobenzoylpropylamide, m-nitrobenzoylpropylamide, p-nitrobenzoylpropylamide, p-methoxybenzoylpropylamide, 2,4-dimethoxybenzoylpropylamide, 3,4,5-trimethoxybenzoylpropylamide, p-hydroxymethylbenzoylpropylamide, p-methylbenzoylpropylamide, m-methylbenzoylpropylamide, p-ethylbenzoylpropylamide, t-butylbenzoylpropylamide, p-carboxybenzoylpropylamide, m-methoxycarbonylbenzoylpropylamide, o-carboxybenzoylpropylamide, o-hydroxybenzoylpropylamide, p-chlorobenzoylbutylamide, m-chlorobenzoylbutylamide, 2,4-dichlorobenzoylbutylamide, 2,4,6-trichlorobenzoylbutylamide, m-nitrobenzoylmethylamide, p-nitrobenzoylbutylamide, p-methoxybenzoylbutylamide, 2,4-dimethoxybenzoylbutylamide, 3,4,5-trimethoxybenzoylbutylamide, p-hydroxymethylbenzoylbutylamide, p-methylbenzoylbutylamide, m-methylbenzoylbutylamide, p-ethylbenzoylbutylamide, t-butylbenzoylbutylamide, p-carboxybenzoylbutylamide m-methoxycarbonylbenzoylbutylamide, o-carboxybenzoylbutylamide, o-hydroxybenzoylmethylamide. Amides within the scope of pyridylamido are α-pyridylamide, β-pyridylamide, and γ-pyridylamide. Amides within the scope of substituted pyridylamido are 4-methyl-α-pyridylamide, 4-methyl-β-pyridylamide, 4-chloro-α-pyridylamide, and 4-chloro-β-pyridylamide. Amides within the scope of pyridylalkylamido are α-pyridylmethylamide, β-pyridylmethylamide, γ-pyridylmethylamide, α-pyridylethylamide, β-pyridylethylamide, γ-pyridylethylamide, α-pyridylpropylamide, β-pyridylpropylamide, γ-pyridylpropylamide, α-pyridylbutylamide, β-pyridylbutylamide, and γ-pyridylbutylamide. Amides within the scope of substituted pyridylalkylamido are 4-methyl-α-pyridylmethylamide, 4-methyl-β-pyridylmethylamide, 4-chloropyridylmethylamide, 4-chloro-β-pyridylmethylamide, 4-methyl-α-pyridylethylamide, 4-methyl-β-pyridylethylamide, 4-chloropyridylethylamide, 4-chloro-β-pyridylethylamide, 4-methyl-α-pyridylpropylamide, 4-methyl-β-pyridylpropylamide, 4-chloro-pyridylpropylamide, 4-chloro-β-pyridylpropylamide, 4-methyl-β-pyridylbutylamide, 4-methyl-α-pyridylbutylamide, 4-chloropyridylbutylamide, 4-chloro-β-pyridylbutylamide, 4-methyl-β-pyridylbutylamide. Amides within the scope of hydroxyalkyl are hydroxymethylamide, α-hydroxyethylamide, β-hydroxyethylamide, α-hydroxypropylamide, β-hydroxypropylamide, γ-hydroxypropylamide, 1-(hydroxymethyl)ethylamide, 1-(hydroxymethyl)propylamide, (2-hydroxymethyl)propylamide, and α,α-dimethyl-β-hydroxy ethylamide. Amides within the scope of dihydroxyalkylamido are dihydroxymethylamide, α,α-dihydroxyethylamide, α,β-dihydroxyethylamide, β,β-dihydroxyethylamide α,α-dihydroxypropylamide, α,β-dihydroxypropylamide, α ,γ-dihydroxypropylamide, β,β-dihydroxypropylamide, β,γ-dihydroxypropylamide, γ,γ-dihydroxypropylamide, 1-(hydroxymethyl)2-hydroxyethylamide, 1-(hydroxymethyl)-1-hydroxyethylamide, α,α-dihydroxybutylamide, α,β-dihydroxybutylamide, α,γ-dihydroxybutylamide, α,δ-dihydroxybutylamide, β,β-dihydroxybutylamide, β,γ-dihydroxybutylamide, β,δ-dihydroxybutylamide, γ,γ-dihydroxybutylamide, γ,δ-dihydroxybutylamide, δ,δ-dihydroxybutylamide, and 1,1-bis(hydroxymethyl)ethylamide. Amides within the scope of trihydroxyalkylamino are tris(hydroxymethyl)methylamide and 1,3-dihydroxy-2-hydroxymethyl-propylamide.
(2) Amides within the scope of the cycloamido groups described above are pyrrolidylamide, piperidylamide, morpholinylamide, hexamethyleneiminylamide, piperazinylamide, pyrrolinylamide, and 3,4-didehydropiperidinylamide.
(3) Amides within the scope of carbonylamido of the formula --NR 23 COR 21 are methylcarbonylamide, ethylcarbonylamide, phenylcarbonylamide, and benzylcarbonylamide. Amides within the scope of sulfonylamido of the formula --NR 23 SO 2 R 21 are methylsulfonylamide, ethylsufonylamide, phenylsulfonylamide, p-tolylsulfonylamide, benzylsulfonylamide,
(4) Hydrazines within the scope of the above hydrazino groups are hdyrazine, N-aminopiperidine, benzoylhydrazine, phenylhydrazine, N-aminomorpholine, 2-hydroxyethylhydrazine, methylhydrazine, 2,2,2-hydroxyethylhydrazine and p-carboxyphenylhydrazine
Examples of alkyl of one to 12 carbon atoms, inclusive, are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and isomeric forms thereof.
Examples of cycloalkyl of 3 to 10 carbon atoms, inclusive, which includes alkyl-substituted cycloalkyl, are cyclopropyl, 2-methylcyclopropyl, 2,2-dimethylcyclopropyl, 2,3-diethylcyclopropyl, 2-butylcyclopropyl, cyclobutyl, 2-methylcyclobutyl, 3 -propylcyclobutyl, 2,3,4-triethylcyclobutyl, cyclopentyl, 2,2-dimethylcyclopentyl, 2-pentylcyclopentyl, 3-tert-butylcyclopentyl, cyclohexyl, 4-tert-butylcyclohexyl, 3-isopropylcyclohexyl, 2,2-dimethylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl.
Examples of aralkyl of 7 to 12 carbon atoms, inclusive, are benzyl, 2-phenethyl, 1-phenylethyl, 2-phenylpropyl, 4-phenylbutyl, 3-phenylbutyl, 2-(1-naphthylethyl), and 1-(2-naphthylmethyl).
Examples of phenyl substituted by one to 3 chloro or alkyl of one to 4 carbon atoms, inclusive, are p-chlorophenyl, m-chlorophenyl, 2,4-dichlorophenyl, 2,4,6-trichlorophenyl, p-tolyl, m-tolyl, o-tolyl, p-ethylphenyl, p-tertbutylphenyl, 2,5-dimethylphenyl, 4-chloro-2-methylphenyl, and 2,4-dichloro-3-methylphenyl.
Examples of ##STR30## wherein T is alkyl of one to 3 carbon atoms, inclusive, fluoro, chloro, trifluoromethyl, or alkoxy of one to 3 carbon atoms, inclusive; and s is zero, one, 2, or 3, with the proviso that not more than two T's are other than alkyl, are phenyl, (o-, m-, or p-)tolyl, (o-, m-, or p-)-ethylphenyl, 2-ethyl-tolyl, 4-ethyl-o-tolyl, 5-ethylm-tolyl, (o-, m-, or p-)propylphenyl, 2-propyl-(o-, m-, or p-)tolyl, 4-isopropyl-2,6-xylyl, 3-propyl-4-ethylphenyl, (2,3,4-, 2,3,5-, 2,3,6-, or 2,4,5-)trimethylphenyl, (o-, m-, or p-)fluorophenyl, 2-fluoro-(o-, m-, or p-)tolyl, 4-fluoro-2,5-xylyl, (2,4-, 2,5-, 2,6-, 3,4-, or 3,5-)difluorophenyl, (o-, m-, or p-)-chlorophenyl, 2-chloro-p-tolyl, (3-,4-, 5-, or 6-)chloro-o-tolyl, 4-chloro-2-propylphenyl, 2-isopropyl-4-chlorophenyl, 4-chloro-3,5-xylyl, (2,3- 2,4-, 2,5-, 2,6-, 3,4,or 3,5-)dichlorophenyl, 4-chloro-3-fluorophenyl, (3- or 4-)chloro-2-fluorophenyl, o-, m-, or p-trifluoromethylphenyl, (o-, m-, or p-)methoxyphenyl, (o-, m-, or p-)ethoxyphenyl, (4- or 5-)chloro-2methoxyphenyl, and 2,4-dichloro-(5-or 6-)methylphenyl.
The acid addition salts of the 2-decarboxy-2-aminomethyl- or 2-(substituted aminomethyl)-PG analogs provided by this invention. are the hydrochlorides, hydrobromides hydriodides, sulfates, phosphates, cyclohexanesulfamates, methanesulfonates, ethanesulfonates, benzenesulfonates, toluenesulfonates and the like, prepared by reacting the PG-analog with the stoichiometric amount of the acid corresponding to the pharmacologically acceptable acid addition salt.
The novel prostaglandin analogs of this invention are highly active as inhibitors of the thromboxane synthetase enzyme system. Accordingly, these novel compounds are useful for administration to mammals, including humans, whenever it is desirable medically to inhibit this enzyme system. For example, these novel compounds are useful as anti-inflammatory agents in mammals and especially humans, and for this purpose, are administered systemically and preferably orally. For oral administration, a dose range of 0.05 to 50 mg. per kg. of human body weight is used to give relief from pain associated with inflammatory disorders such as rheumatoid arthritis. They are also administered intravenously in aggravated cases of inflammation, preferably in a dose range 0.01 to 100 μg. per kg. per minute until relief from pain is attained. When used for these purposes, these novel compounds cause fewer and lesser undesirable side effects than do the known synthetase inhibitors used to treat inflammation, for example, aspirin and indomethacin. When these novel compounds are administered orally, they are formulated as tablets, capsules, or as liquid preparations, with the usual pharmaceutical carriers, binders, and the like. For intravenous use, sterile isotonic solutions are preferred.
The novel prostaglandin analogs of this invention are useful in the treatment of asthma, are useful, for example, as broncodilators or as inhibitors of mediators, such as SRS-A, and histamine which are released from cells activated by an antigen-antibody complex. Thus, these compounds control spasm and facilitate breathing in conditions such as bronchial asthma, bronchitis, bronchiectasis, pneumonia, and emphysema. For these purposes, the compounds are administered in a variety of dosage forms, e.g., orally in the form of tablets, capsules, or liquids; rectally in the form of suppositories, parenterally; subcutaneously; or intramuscularly; with intravenous administration being preferred in emergency situations; by inhalation in the form of aerosols or solutions for nebulizers; or by insufflation in the form of powder. Doses in the range of about 0.01 to 5 mg. per kg. of body weight are used 1 to 4 times a day, the exact dose depending on the age, weight, and condition of the patient and on the frequency and route of administration. For the above use these prostaglandins can be combined advantageously with other anti-asthmatic agents, such as sympathomimetics (isoproterenol, phenylephrine, epinephrine, etc.); xanthine derivatives (theophylline and aminophylline); and corticosteroids (ACTH and prednisolone. Regarding use of these compounds see M. E. Rosenthale, et al., U.S. Pat. No. 3,644,638.
The novel prostaglandin analogs of this invention are useful in mammals, including man, as nasal decongestants are used for this purpose, in a dose range of about 10 μg. to about 10 mg. per ml. of a pharmacologically suitable liquid vehicle or as an aerosol spray, both for topical application.
These prostaglandins are useful whenever it is desired to inhibit platelet aggregation, reduce the adhesive character of platelets, and remove or prevent the formation of thrombi in mammals, including man, rabbits, and rats. For example, these compounds are useful in the treatment and prevention of myocardial infarcts, to treat and prevent post-operative thrombosis, to promote patency of vascular grafts following surgery, and to treat conditions such as atherosclerosis, arteriosclerosis, blood clotting defects due to lipemia, and other clinical conditions in which the underlying etiology is associated with lipid imbalance or hyperlipidemia. For these purposes, these compounds are administered systemically, e.g., intravenously, subcutaneously, intramuscularly, and in the form of sterile implants for prolonged action. For rapid response especially in emergency situations, the intravenous route of administration is preferred. Doses in the range about 0.005 to about 20 mg. per kg. of body weight per day are used, the exact dose depending on the age, weight, and condition of the patient or animal, and on the frequency and route of administration.
These compounds are further useful as additives to blood, blood products, blood substitutes, or other fluids which are used in artificial extracorporeal circulation or perfusion of isolated body portions, e.g., limbs and organs, whether attached to the original body, detached and being preserved or prepared for transplant, or attached to a new body. During these circulations and perfusions, aggregated platelets tend to block the blood vessels and portions of the circulation apparatus. This blocking is avoided by the presence of these compounds. For this purpose, the compound is added gradually or in single or multiple portions to the circulating blood, to the blood of the donor animal, to the perfused body portion, attached or detached, to the recipient, or to two or all of those at a total steady state dose of about 0.001 to 10 mg. per liter of circulating fluid. It is especially useful to use these compounds in laboratory animals, e.g., cats, dogs, rabbits, monkeys, and rats, for these purposes in order to develop new methods and techniques for organ and limb transplants.
When X 1 is --COOR 1 , the novel PG analogs so described are used for the purposes described above in the free acid form, in ester form, in pharmacologically acceptable salt form. When the ester form is used, the ester is any of those within the above definition of R 1 . However, it is preferred that the ester be alkyl of one to 12 carbon atoms, inclusive. Of the alkyl esters, methyl and ethyl are especially preferred for optimum absorption of the compound by the body or experimental animal system; and straight-chain octyl, nonyl, decyl, undecyl, and dodecyl are especially preferred for prolonged activity in the body or experimental animal.
Pharmacologically acceptable salts of the novel prostaglandin analogs of this invention compounds useful for the purposes described above are those with pharmacologically acceptable metal cations, ammonium, amine cations, or quaternary ammonium cations.
Especially preferred metal cations are those derived from the alkali metals, e.g., lithium, sodium, and potassium, and from the alkaline earth metals, e.g., magnesium and calcium, although cationic forms of other metals, e.g., aluminum, zinc, and iron are within the scope of this invention.
Pharmacologically acceptable amine cations are those derived from primary, secondary, or tertiary amines. Examples of suitable amines are methylamine, dimethylamine, trimethylamine, ethylamine, dibutylamine, triisopropylamine, N-methylhexylamine, decylamine, dodecylamine, allylamine, crotylamine, cyclopentylamine, dicyclohexylamine, benzylamine, dibenzylamine, α-phenylethylamine, β-phenylethylamine, ethylenediamine, diethylenetriamine, and the like aliphatic, cycloaliphatic, araliphatic amines containing up to and including about 18 carbon atoms, as well as heterocyclic amines, e.g., piperidine, morpholine, pyrrolidine, piperazine, and lower-alkyl derivatives thereo, e.g., 1-methylpiperidine, 4-ethylmorpholine, 1-isopropylpyrrolidine, 2-methylpyrrolidine, 1,4-dimethylpiperazine, 2-methylpiperidine, and the like, as well as amines containing water-solubilizing or hydrophilic groups, e.g., mono-, di-, and triethanolamine, ethyldiethanolamine, N-butylethanolamine, 2-amino-1-butanol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, tris(hydroxymethyl)aminomethane, N-phenylethanolamine, N-(p-tert-amylphenyl)-diethanolamine, galctamine, N-methylglycamine, N-methylglucosamine, ephedrine, phenylephrine, epinephrine, procaine, and the like. Further useful amine salts are the basic amino acid salts, e.g., lysine and arginine.
Examples of suitable pharmacologically acceptable quaternary ammonium cations are tetramethylammonium, tetraethylammonium, benzyltrimethylammonium, phenyltriethylammonium, and the like.
To obtain the optimum combination of biological response specificity, potency, and duration of activity, certain compounds within the scope of this invention are preferred.
It is preferred that in the 8α- side chain g be either one or 3, especially one, i.e., the natural chain length of the prostaglandins. Further when the other chain contains --(CH 2 ) m --CH 3 , it is preferred that m be 3. Further, it is preferred that h, be zero or one, most preferably one. For those compounds wherein R 7 is ##STR31## it is preferred that s be zero or one and T be chloro, fluoro, trifluoromethyl.
For those compounds wherein R 7 is ##STR32## it is preferred that R 3 and R 4 both be hydrogen.
Especially preferred are those compounds which satisfy two or more of the above preferences. Further, the above preferences are expressly intended to describe the preferred compounds within the scope of any generic formula of novel prostaglandin analogs disclosed herein.
The Charts herein describe methods whereby the novel prostaglandin analogs of this invention are prepared.
With respect to the Charts L 1 , L 2 , L 3 , R 1 , R 7 , Z 1 , Y 1 , g, m and X 1 are as defined above, except that R 1 (and X 1 when X 1 is --COOR 1 ) is an ester in preference to its acid or cationic embodiments.
Further, with respect to X, certain protected derivatives thereof are preferred to in place of the primary alcohol and amine embodiments or specifically indicated in the text accompanying the charts herein.
M 14 is ##STR33## wherein R 34 is a hydroxy-hydrogen replacing group;
M 9 is ##STR34##
M 17 is ##STR35## wherein R 10 is a blocking group.
R 5 is hydrogen or fluoro. R 36 is a non-reactive, organic radical, as hereinafter further specified, being, for example, alkyl-, aralkyl-, or arylsulfonyl. Conveniently R 36 represents the readily synthesized p-toluenesulfonyl or methylsulfonyl moiety. R 37 is N-phthalimido, e.g., ##STR36##
R 26 is hydrocarbyl, including alkyl, aralkyl, cycloalkyl, and the like. Examples of these hydrocarbyl groups include 2-methylbutyl, isopentyl, heptyl, octyl, nonyl, tridecyl, octadecyl, benzyl, phenethyl, p-methylphenethyl, 1-methyl-3-phenylpropyl, cycohexyl, phenyl, and p-methylphenyl.
G 1 is alkyl of one to 4 carbon atoms, cycloalkyl of 3 to 10 carbon atoms, inclusive, aralkyl of 7 to 12 carbon atoms, phenyl, or phenyl substituted with one or 2 fluoro, chloro, or alkyl of one to 4 carbon atoms, with the proviso that in a --Si(G 1 ) 3 moiety the various G 1 's are the same or different.
R 9 is an acyl group. Acyl groups according to R 9 , include:
(a) Benzoyl;
(b) Benzoyl substituted with one to 5, inclusive, alkyl of one to 4 carbon atoms, inclusive, phenylalkyl of 7 to 12 carbon atoms, inclusive, or nitro, with the proviso that not more than 2 substituents are other than alkyl, and that the total number of carbon atoms in the substituents does not exceed 10 carbon atoms, with the further proviso that the substituents are the same or different;
(c) Benzoyl substituted with alkoxycarbonyl of 2 to 5 carbon atoms, inclusive;
(d) Naphthoyl;
(e) Naphthoyl substituted with one to 9, inclusive, alkyl of one to 4 carbon atoms, inclusive, phenylalkyl of 7 to 10 carbon atoms, inclusive, or nitro, with the proviso that not more than 2 substituents on either of the fused aromatic rings are other than alkyl and that the total number of carbon atoms in the substituents on either of the fised aromatic rings does not exceed 10 carbon atoms, with the further proviso that the various substituents are the same or different;
(f) Alkanoyl of 2 to 12 carbon atoms, inclusive; or (g) formyl.
In introducing these acyl protecting groups into a hydroxy-containing compound herein, methods generally known in the art are employed. Thus, for example, an aromatic acid of the formula R 9 OH, wherein R 9 is as defined above (e.g., benzoic acid), is reacted with the hydroxy-containing compound in the presence of a dehydrating agent, e.g. sulfuric acid, zinc chloride, or phosphoryl chloride; or alternatively an anhydride of the aromatic acid of the formula (R 9 ) 2 O (e.g., benzoic anhydride) is used.
Preferably, however, the process described in the above paragraph proceeds by use of the appropriate acyl halide, e.g., R 9 Hal, wherein Hal is chloro, bromo, or iodo. For example, benzoyl chloride is reacted with the hydroxy-containing compound in the presence of a hydrogen chloride scavenger, e.g. an amine such as pyridine, triethylamine or the like. The reaction is carried out under a variety of conditions, using procedures generally known in the art. Generally mild conditions are employed: 20°-60° C., contacting the reactants in a liquid medium (e.g., excess pyridine or an inert solvent such as benzene, toluene, or chloroform). The acylating agent is used either in stoichiometric amount or in substantial stoichiometric excess.
As examples of R 9 , the following compounds are available as acids (R 9 OH), anhydrides (R 9 ) 2 O), or acyl chlorides (R 9 Cl): benzoyl; substituted benzoyl, e.g., 2-, 3-, or 4-)- methylbenzoyl, (2-, 3-, or 4-)-ethyl benzoyl, (2-, 3-, or 4-)-isopropylbenzoyl, (2-, 3-, or 4-)-tert-butylbenzoyl, 2,4-dimethylbenzoyl, 3,5-dimethylbenzoyl, 2-isopropyltoluyl, 2,4,6-trimethylbenzoyl, pentamethylbenzoyl, alphaphenyl(2-, 3-, 4-)-toluyl, (2-, 3-, or 4-)-phenethylbenzoyl, (2-, 3-, or 4-)nitrobenzoyl, (2,4-, 2,5-, or 2,3-)dinitrobenzoyl, 2,3-dimethyl-2-nitrobenzoyl, 4,5-dimethyl-2-nitrobenzoyl, 2-nitro-6-phenethylbenzoyl, 3-nitro-2-phenethylbenzoyl; 2-nitro-6-phenethylbenzoyl, 3-nitro-2-phenethylbenzoyl; mono esterified phthaloyl, isophthaloyl, or terephthaloyl; 1- or 2-naphthoyl; substituted naphthoyl, e.g., (2-, 3-, 4-, 5-, 6-, or 7-)-methyl-1-naphthoyl, (2- or 4-)ethyl-1-naphthoyl, 2-isopropyl-1-naphtholyl, 4,5-dimethyl-1-naphthoyl, (6-isopropyl-4-methyl-1-naphthoyl, 8-benzyl-1-naphthoyl, (3-, 4-, 5-, or 8-)-nitro-1-naphthoyl, 4,5-dinitro-1-naphthoyl, (3-, 4-, 6-, 7-, or 8-)methyl-1-naphthoyl, 4-ethyl-2-naphthoyl, and (5- or 8-)nitro-2-naphthoyl; and acetyl.
There may be employed, therefore, benzoyl chloride, 4-nitrobenzoyl chloride, 3,5-dinitrobenzoyl chloride, or the like, i.e. R 9 Cl compounds corresponding to the above R 9 groups. If the acyl chloride isnot available, it is prepared from the corresponding acid and phosphorus pentachloride as is known in the art. It is preferred that the R 9 OH, (R 9 ) 2 ), or R 9 Cl reactant does not have bulky hindering substituents, e.g. tert-butyl on both of the ring carbon atoms adjacent to the carbonyl attaching cite.
For the acyl groups with inversion of configuration at carbon, Chart D describes their introduction and use of such groups.
The acyl groups according to R 9 are removed by deacylation. Alkali metal carbonates are employed effectively at ambient temperature for this purpose. For example, potassium carbonate in methanol at about 25° C. is advantageously employed. R 10 is a blocking group. These blocking groups within the scope of R 10 are any group which replaces a hydroxy hydrogen and is neither attacked nor as reactive to the reagents used in the transformations used herein as an hydroxy is and which is subsequently replaceable with hydrogen in the preparation of the prostaglandin-type compounds. Several blocking groups are known in the art, e.g. tetrahydropyranyl. See for reference E. J. Corey, Proceedings of the Robert A. Welch Foundation Conferences on Chemical Research, 12, Organic Synthesis, pgs. 51-79 (1969). Those blocking groups which have been found useful include
(a) tetrahydropyranyl;
(b) tetrahydrofuranyl; and
(c) a group of the formula
--C(OR.sub.11)(R.sub.12)--CH(R.sub.13)(R.sub.14),
wherein R 11 is alkyl of one to 18 carbon atoms, inclusive, cycloalkyl of 3 to 10 carbon atoms, inclusive, aralkyl of 7 to 12 carbon atoms, inclusive, phenyl or phenyl substituted with one to 3 alkyl of one to 4 carbon atoms, inclusive, wherein R 12 and R 13 are alkyl of one to 4 carbon atoms, inclusive, phenyl, phenyl substituted with one, 2, or 3 alkyl of one to 4 carbon atoms, inclusive, or when R 12 and R 13 are taken together --(CH 2 ) a -- or --(CH 2 ) b --O--(CH 2 ) c , wherein a is 3, 4, or 5, or b is one, 2, or 3, and c is one, 2, or 3, with the proviso that b plus c is 2, 3, or 4, with the further proviso that R 12 and R 13 may be the same or different, and wherein R 14 is hydrogen or phenyl.
When the blocking group R 10 is tetrahydropyranyl, the tetrahydropyranyl ether derivative of any hydroxy moieties of the PG-type intermediates herein is obtained by reaction of the hydroxy-containing compound with 2,3-dihydropyran in an inert solvent, e.g. dichloromethane, in the presence of an acid condensing agent such as p-toluenesulfonic acid or pyridine hydrochloride. The dihydropyran is used in large stocihometric excess, preferably 4 to 10 times the stoichiometric amount. The reaction is normally complete in several hours at 20° to 50° C.
When the blocking group is tetrahydrofuranyl, 2,3-dihydrofuran is used, as described in the preceding paragraph, in place of the 2,3-dihydropyran.
When the blocking group is
--C(OR.sub.11)(R.sub.12)--CH(R.sub.13)(R.sub.14),
wherein R 11 , R 12 , R 13 , and R 14 are as defined above, the appropriate reagent is a vinyl ether, e.g. isobutyl vinyl ether or any vinyl ether of the formula
C(OR.sub.11)(R.sub.12)═C(R.sub.13)(R.sub.14),
wherein R 11 , R 12 , R 13 , and R 14 are as defined above; or an unsaturated cyclic or heterocyclic compound, e.g. 1-cyclohexen-1-yl methyl ether, or 5,6-dihydro-4-methoxy-2H-pyran. See C. B. Reese, et al., Journal of the Chemical Society 89, 3366 (1967). The reaction conditons for such vinyl ethers and unsaturated compounds are similar to those for dihydropyran above.
The blocking groups according to R 10 are removed by mild acidic hydrolysis. For example, by reaction with (1) hydrochloric acid in methanol; (2) a mixture of acetic acid, water, and tetrahydrofuran; or (3) aqueous citric acid or aqueous phosphoric acid in tetrahydrofuran, at temperatures below 55° C., hydrolysis of the blocking groups is achieved.
R 34 is a hydroxy-hydrogen replacing group which is defined herein to be acyl protecting group according to R 9 , a blocking group according to R 10 or a silyl group within the scope of --Si(G 1 ) 3 R 35 is either an R 10 blocking group or silyl group within the scope of --Si(G 1 ) 3 .
The symbol "n" is one or 2.
Z 2 is cis--CH═CH--CH 2 --(CH 2 ) g --C(R 5 ) 2 --, cis--CH 2 --CH═CH--(CH 2 ) g -CH 2 , --(CH 2 ) 3 --(CH 2 ) g --C(R 5 ) 2 --, or --CH 2 --O--CH 2 --(CH 2 ) g --CH 2 --, wherein R 5 and g are as defined above. Z 3 is oxa or methylene.
Y 2 is cis--CH═CH--, or trans--CH═CH--. Y 3 is cis--CH═CH--CH 2 --or trans--CH═CH--CH 2 --. Y 4 is cis--CH═CH--Ch 2 --, trans--CH═CH--CH 2 --, --(CH 2 ) 3 --, or trans--CH═C(Hal)--CH 2 --, wherein Hal is chloro, bromo, or iodo. Y 6 is Y 3 or --(CH 2 ) 3 -- or --C.tbd.C--CH 2 --. Y 7 is Y 3 or ##STR37## Y 8 is Y 3 or ##STR38## Charts A-G herein provide methods for preparing starting materials useful in the synthesis of the novel prostaglandin analogs herein. In particular, Charts A-C provide methods whereby novel 15-deoxy-11β-PGF.sub.β compounds are prepared. Charts D and E describe methods for diepimerization of PGF 2 α compounds to the corresponding 11β PGF 2 β compounds. Charts F and G provide methods whereby the C-1 carboxylic acids prepared in the preceeding Charts are transformed to corresponding C-1 alcohols and C-1 primary, secondary, or tertiary amines, respectively.
With respect to Chart A, a method is provided whereby the formula XXI bicyclic lactone aldehyde, known in the art in either optically active or racemic form, is transformed to the formula XLI 15-deoxy-11β-PGF 62 compounds.
The formula XXII compound is prepared from the formula XXI compound by a Wittig oxoalkylation. Reagents known in the art or prepared by methods known in the art are employed. The transenone lactone is obtained stereospecifically. See for reference D. H. Wadworth, et al., Journal of Organic Chemistry 30, 680 (1965).
In the preparation of the formula XXII compound, certain phosphonates are employed in the Wittig reaction. These phosphonates are of the general formula ##STR39## wherein L 1 and R 7 are as defined above and R 15 is alkyl of one to 8 carbon atoms, inclusive.
Phosphonates of the above general formula are prepared by methods known in the art. See Wadsworth, et al. as cited above.
Conveniently the appropriate aliphatic acid ester is condensed with the anion of dimethyl methylphosphonate as produced using n-butyllithium. For this purpose, acids of the general formula ##STR40## are employed in the form of their lower alkyl esters, preferably methyl or ethyl. The methyl esters for example are readily obtained by reaction of the corresponding acids with diazomethane.
For example, when R 7 is ##STR41## wherein T and s are as defined above, and R 3 and R 4 of the L 1 moiety are both hydrogen, the corresponding phenoxy or substituted phenoxy acetic acids are known in the art or readily available in the art. Those known in the art include those wherein the R 7 moiety is: phenoxy, (o-, m-, or p-)tolyloxy-, (o, m-, or p-)ethylphenoxy-, 4-ethyl-o-tolyoxy-, (o-, m-, or p-)propylphenoxy-, (o-, m-, or p-)-t-butylphenoxy-, (o-, m-, or p-)fluorophenoxy-, 4-fluoro-2,5-xylyloxy-, (o-, m-, or p-)chlorophenoxy-, (2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or 3,5-)dichlorophenoxy-, (o-, m-, or p-)trifluoromethylphenoxy-, or (o-, m-, or p-)methoxyphenoxy-.
Further, many 2-phenoxy- or substitued phenoxy propionic acids are readily available, and are accordingly useful for the preparation of the acids of the above formula wherein one and only one of R 3 and R 4 of the L 1 moiety is methyl and R 7 is phenoxy or substituted phenoxy. These 2-phenoxy or 2-substituted phenoxy propionic acids include those wherein the R 7 moiety is p-fluorophenoxy-, (o-, m-, or p-)chlorophenoxy-, (2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or 3,5-)dichorophenoxy-, (4- or 6-chloro-o-tolyloxy-, phenoxy-, (o-, m-, or p-)tolyloxy, 3,5-xylyloxy-, or m-trifluoromethylphenoxy-.
Finally there are available many 2-methyl- 2-phenoxy- or (2-substituted)phenoxypropionic acids, which are useful in the preparation of the above acids wherein R 3 and R 4 of the L 1 moiety are both methyl and R 7 is phenoxy or substituted phenoxy. These 2-methyl-2-phenoxy-, or (2-substituted)phenoxypropionic acids include those wherein R 7 is: phenoxy-, (o-, m-, or p-)chlorophenoxy-, (2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or 3,5-)dichlorophenoxy-.
Other phenoxy substituted acids are readily available by methods known in the art, for example, by Williamson synthesis of ethers using an α-halo aliphatic acid or ester with sodium phenoxide or a substituted sodium phenoxide. Thus, the (T) s -substituted sodium phenoxide is reacted with, for example, the α-chloro aliphatic acid, or the alkyl ester derivative thereof, with heating to yield the acid of the above general formula, which is recovered from the reaction mixture by conventional purification techniques.
There are further available phenyl substituted acids of the above formula wherein R 7 is phenyl, benzyl, phenylallyl or substituted phenyl, benzyl, or phenylallyl.
For example, when R 3 and R 4 of the L 1 moiety are both hydrogen and h is one there are available the following phenyl or substituted phenyl propionic acids: (o-, m-, or p-)chlorophenyl-, p-fluorophenyl-, m-trifluoromethylphenyl-, (o-, m-, or p-)methylphenyl-, (o-, m-, or p-)methoxyphenyl-, (2,4-, 2,5-, or 3,4-)dichlorophenyl-, (2,3-, 2,4-, 2,5-, 2,6-, or 3,4-)dimethylphenyl-, or (2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or 3,5-)dimethoxyphenyl-.
When one and only one of R 3 and R 4 of the L 1 moiety is methyl and h is one there are available, for example, the following 2-methyl-3-phenyl or substituted phenyl propionic acids: phenyl, o-chlorophenyl-, (o-, or p-)methylphenyl-, (o-, m-, or p-)methoxyphenyl-, (2,4- or 3,4-)-difluorophenyl-, 2,3-dimethylphenyl-, and (2,3-, 3,4-, or 4,5-)dimethoxyphenyl-.
When both R 3 and R 4 are methyl and h is one there are available, for example, the following 2,2-dimethyl-3-phenyl or substituted phenyl propionic acids: phenyl- and p-methylphenyl.
When one and only one of R 3 and R 4 is fluoro and h is one there is available, for example, 2-fluoro-3-phenyl propionic acid.
Phenyl substituted acids (as above wherein R 7 is benzyl) are available by methods known in the art, for example, by reacting a mixture of the appropriate methyl- or fluoro-substituted acetic acid, a secondary amine (e.g., diisopropylamine), n-butyllithium, and an organic diluent (e.g., tetrahydrofuran) with the appropriately substituted phenylallyl or benzyl chloride. Thus, the above acid is obtained by the following reaction (when h is not zero): ##STR42## The above reaction proceeds smoothly, ordinarily at 0° C. The product acid is recovered using conventional methods.
For the acids of the above formula wherein R 7 is n-alkyl, many such acids are readily available.
For example, when R 3 and R 4 of the L 1 moiety are both hydrogen there are available butyric, pentanoic, hexanoic, heptanoic, and octanoic acids.
For example, when one and only one of R 3 and R 4 of the L 1 moiety is methyl, there are available the following 2-methyl alkanoic acids: butyric, pentanoic, hexanoic, heptanoic, and octanoic.
For example, when one of the R 3 and R 4 of the L 1 moiety is fluoro there are available the following 2-fluoro alkanoic acids: butyric, pentanoic, hexanoic, heptanoic, and octanoic.
The acids of the above general formula wherein R 7 is alkyl and R 3 and R 4 of the L 1 moiety are fluoro are conveniently prepared from the corresponding 2-oxo-alkanoic acids, i.e. butyric, pentanoic, hexanoic, heptanoic, and octanoic. The transformation of these 2-oxo-alkanoic acids to the corresponding 2,2-difluoro alkanoic acids proceeds by methods known in the art, using known ketonic fluorinating reagents. For example, MoF 6 .BF 3 is advantageously employed in the fluorination. See Mathey, et al., Tetrahedron Lett. 27, 2965 (1971).
The formula XXIII compound in prepared from the formula XXII compound by optional photoisomerization when Y 2 is --CH═CH--, followed by separating the resulting trans-cis mixture of isomers. The photoisomerization proceeds by use of a conventional photon generating source which is capable of producing photons whose wavelength is between about 2800 to 4000 Angstroms. It is preferred to use a conventional photon generating source which is capable of producing photons whose wave length is about 3500 Angstroms. Irradiation continues until an equilibrium mixture of cis and trans isomers is obtained. The progress of the photoisomerization is conveniently monitored by conventional methods, e.g. silica gel thin layer chromatography (TLC). The resulting equilibrium mixture is then separated using conventional methods. For example, silica gel chromatography is advantageously employed.
The formula XXIV compound is prepared from the formula XXIII 3-oxo bicyclic lactone by transformation of the 3-oxo-moiety to the M 9 moiety.
The above 3-oxo bicyclic lactone is transformed to the corresponding 3α or 3β-hydroxy bicyclic lactone wherein M 9 is ##STR43## by reduction of the 3-oxo moiety, followed by separation of the 3α- and 3β-hydroxy epimers. For this reduction the known ketonic carbonyl reducing agents which do not reduce ester or acid groups or carbon-carbon double bonds (when such reduction is undesirale) are employed. Examples of these agents are the metal borohydrides, especially sodium, potassium, and zinc borohydrides, lithium(tri-tert-butoxy)-aluminum hydride, metal trialkyl borohydrides, e.g. sodium trimethoxy borohydride, lithium borohydride, and the like. In those cases in which carbon-carbon double bonds are not present, the boranes, e.g. disiamylborane (bis-3-methyl-2-butyl borane) are alternatively employed.
For the production of either C-15 epimerically pure product, the 15-epi compound is separated from the mixture by methods known in the art. For example, silica gel chromatography is advantageously employed.
The formula XXV compound is prepared from the formula XXIV compound by deacylation, as described above. The formula XXVI compound is then prepared from the formula XXV compound by replacing any free hydroxy moieties with blocking groups according to R 10 by the procedure described above. The formula XXVII compound is then prepared from the formula XXVI compound by reduction of the formula XXVI lactone to a lactol. Methods known in the art are employed. For example, diisobutylaluminum hydride is employed at -60 to -70° C.
The formula XXVII compound undergoes condensation to form the formula XXVIII enol ether. For this purpose a hydrocarbyloxy, and preferably an alkoxymethylenetriphenylphosphorane is useful. See for reference, Levine, Journal of the American Chemical Society 80, 6150 (1958). The reagent is conveniently prepared from a corresponding quaternary phosphonium halide in a base, e.g. butyllithum or phenyllithium, at low temperature, e.g. preferably below -10° C. The formula XXVII lactol is mixed with the above reagent and the condensation proceeds smoothly within the temperature range of -30° C. to +30° C. At higher temperatures the reagent is unstable, whereas at low temperatures the rate of condensation is undesirably slow. Examples of alkoxymethylenetriphenylphosphoranes preferred for the above purposes are methoxy-, ethoxy-, propoxy-, isopropoxy-, butoxy-, isobutoxy-, s-butoxy-, and t-butoxy- methylenetriphenylphosphorane. Various hydrocarbyloxymethylenetriphenylphosphoranes which are optionally substituted for the alkoxymethylenetriphenylphosphoranes and are accordingly useful for preparing the formula XXVII intermediates wherein R 26 is hydrocarbyl, include alkoxy-, aralkoxy-, cycloalkoxy-, and aryloxymethylenetriphenylphosphoranes. Examples of these hydrocarbyloxytriphenylphosphoranes are 2-methyl butyloxy-, isopentyloxy-, heptyloxy-, octyloxy-, nonyloxy-, tridecylethyloxy-, 1-methyl-3-phenylpropyloxy-, cyclohexyloxy-, phenoxy-, and p-methylphenoxy-, phenoxymethylenetriphenylphosphorane. See for reference, Organic Reactions, Vol. 14, pg. 346-348, John Wiley and Sons, New York, New York, (1965). The formula XXVIII enol intermediates are then hydrolyzed to the formula XXIX lactols. This hydrolysis is done under acidic conditions for example with perchloric acid or acetic acid. Tetrahydrofuran is a suitable diluent for this reaction mixture. Reaction temperatures of from 10° to 100° C. are employed. The length of time required for hydrolysis is determined in part by the hydrolysis temperature and using acetic acid-water-tetrahydrofuran at about 60° C. several hr. are sufficient to accomplish the hydrolysis.
The formula XXX compound is then prepared from the formula XXIX compound by oxidation of the formula XXIX lactol to a lactone. This transformation is carried out, using for example, silver oxide as an oxidizing reagent, and is followed by treatment with pyridine hydrochloride. Preparation of the formula XXXI compound proceeds from the formula XXX compound by transformation of any free hydroxy moieties to blocking groups according to R 10 , following the procedures herein described for such a transformation.
Thereafter the formula XXXII compound (wherein n is 2) is prepared from the formula XXXI compound by reduction of the formula XXXI lactone to a lactol. For example, diisobutylaluminum hydride is employed as is described above for the reduction of lactones to lactols. The formula XXXII lactol is alternately represented by the formula XXVII compound when n is one.
The formula XXXV compound is prepared from the formula XXXII compound by a Wittig carboxyalkylation, using the appropriate (ω-carboxyalkyl)triphenylphosphonium bromide with sodio dimethyl sulfinylcarbanide, at ambient temperature, and adding the formula XXXII lactol to this mixture. Thereafter the carboxy hydrogen of the compound so formed is transformed to an R 1 moiety by the methods and procedures hereinbelow described. Accordingly, there is prepared the formula XXXV cis-4,5-didehydro-PGF 1 α - or PGF 2 α -type compound.
The formula XXXVI compound is then prepared from the formula XXXV compound by catalytic hydrogenation of the formula XXXV compound. Methods known in the art for transformation of PG 2 -type compounds to PG 1 -type compounds are employed. Accordingly, metal catalysts (e.g. palladium) on a suitable support (e.g. carbon) at about 0° C. are employed under a hydrogen atmosphere. See for reference B. Samuelsson, Journal of Biological Chemistry, 239, 491 (1974).
The formula XXXII lactol is transformed into the corresponding formula XXXIV 5-oxa-PGF 1 α -type intermediate first by reduction of the formula XXXII lactol, for example, with aqueous methanolic or ethanolic sodium borohydride to the formula XXXIII compound. Alternatively, and preferably, the formula XXXIII compound is obtained by a one step reduction of the formula XXVI lactone, for example, with lithium aluminum hydride or diisobutyl aluminum hydride at a temperature ranging from 0° to 35° C.
For preparing the formula XXXIV compound, a Williamson synthesis is employed. For example, the formula XXXIII compound is condensed with a haloalkanoate within the scope of
Hal--(CH.sub.2).sub.g --CH.sub.2 --COOR.sub.1,
wherein Hal is chloro, bromo, or iodo and g is as defined above. Normally the reaction is done in the presence of a base such as n-butyllithium, phenyllithium, trimethyllithium, sodium hydride, or potassium t-butoxide.
Alternatively and preferably, an ortho-CH--CH is employed. Such reagents are available or are prepared by methods known in the art, for example, from the appropriate halonitrile by way of the corresponding imino ester hydrohalide as illustrated hereinafter.
The condensation is conveniently run in a solvent, such as tetrahydrofuran or dimethyl sulfoxide or especially if an organolithium compound is employed, preferably in dimethylformamide or hexamethylphosphoramide. The reaction proceeds smoothly at -20° to 50° C., but is preferably performed at ambient temperature. Following the condensation, the formula XXXIV compound is obtained by methods known in the art, for example, by hydrolysis in cold dilute mineral acid.
The formula XXXVII compound is then prepared from the formula XXXIV, XXXV, or XXXVI compound by first hydrolyzing any blocking groups according to R 10 and thereafter optionally separating any mixed C-15 epimers (i.e., when such separation has not heretofore been undertaken). Acidic conditions are employed in the hydrolysis as is described above.
The formula XXXVIII compound is then prepared from the formula XXXVII compound by a 9,11-diepimerization. Accordingly, by this transformation the 9α and 11α hydroxyls are converted to the 9β and 11β configuration as in the formula XXXVIII compound. Methods by which this 9,11-diepimerization are achieved are known in the art, and described in Charts D and E, hereinafter.
The formula XXXVIII tri-secondary hydroxyl compounds are then transformed to the corresponding formula XXXIX triacylate or tris-ethers by replacing each of the secondary hydroxyls of the formula XXXVIII compound with the hydroxy hydrogen replacing group according to R 34 . Methods for the introduction of these hydroxy hydrogen replacing groups according to R 34 are described above.
The formula XL compound is then prepared from the formula XXXIX compound by a reductive allylic deoxygenation. By this transformation the oxygen attached to the C-15 of formula XXXIX compound is replaced by hydrogen. Further, when the formula XXXIX compound is a 9,11-diacylate, the present transformation hydrolyzes these C-9 and C-11 acyl moieties, yielding a formula XLI 9,11-dihydroxy product.
The present transformation is accomplished employing the formula XXXIX free acid, or, if a C-1 alcohol corresponding to the formula XL carboxylic acid is desired, then a formula XXXIX C-1 lower alkyl ester (R 1 is lower alkyl) is employed. When the formula XXXIX compound is an ester, and the preparation of the corresponding acid is desired, then saponification methods hereinbelow described are employed.
The allylic deoxygenation proceeds by dissolving the 11β-PGF.sub.β compound in ammonia or a primary (lower alkyl)amine solvent with an ether-containing organic cosolvent such as tetrahydrofuran, diethyl ether, or dioxane. To the reaction mixture is added an alkali metal or an alkaline earth metal, being lithium, sodium, potassium, calcium, or magnesium (in order of their preference for accomplishing the present purpose). Finally, a proton source is provided, being selected from the lower alkanols, preferably ethanol, t-butanol, or neopenyl alcohol, or trace amounts of water.
The reaction then proceeds to completion at low temperature, preferably between -78° C. and 0° C.
Finally, the formula XLI compound is prepared from the formula XL compound by an optional hydrolysis of the blocking groups, employing methods described above.
Chart B provides a method whereby the formula XLII bicyclic lactone aldehyde is transformed to the corresponding formula XLVIII 15-deoxy-11β-PGF.sub.β compound.
The formula XLII compound is first transformed to the formula XLIII compound, employing a Wittig alkylation.
In this Wittig alkylation there are employed phosphonamides of the formula ##STR44## or thiophosphonates, as follows: ##STR45## wherein R 15 is as defined above. These phosphorus-containing compounds are employed in the Wittig alkylation by methods described in Chart A for the Wittig alkylation. However, there are employed higher temperatures in order to secure ease of elimination.
Further, these phosphorus containing compounds are known in the art or prepared by methods known in the art.
For example, N,N-dialkyl-methylphosphoramide is reacted with n-butyllithium and a primary alkyl or aralkyl halide of the formula ##STR46## wherein Y is chloro, bromo, or iodo, yielding the above N,N-dialkylphosphoramides. Further, the preparation of the above dialkyl thiophosphonates proceeds by reaction of a dialkyl methyl thiophosphonate with n-butyl lithium and the above alkyl or aralkyl halides. For a discussion of the synthetic routes, see Corey, et al., J.A.C.S. 88:5654-5657 (three publications).
The formula XLIII compound is obtained as a mixture of cis and trans unsaturated stereoisomers. This stereoisomeric mixture is readily separated by conventional (e.g. chromatographic) techniques.
The formula XLIII compound is then transformed to the formula XLIV compound by optional saturation or monohalogenation (i.e. at the latent C-14 position of the formula XLVIII product.)
When the saturated formula XLIV compound is to be prepared, catalytic hydrogenation techniques as described in the transformation of the formula XXXV compound to the formula XXXVI compound of Chart A, are employed.
The formula XLIV compound wherein Y 4 is trans-CH═C(Hal)--CH 2 -- is prepared from the formula XLIII compound by dihalogenation, followed by dehydrohalogenation. The halogenation proceeds by methods known in the art. The reaction proceeds slowly to completion, ordinarily within three to ten days when the molecular form of the halide (Hal) 2 in a diluent (e.g., carbon tetrachloride or a mixture of acetic acid and sodium acetate) is employed in this dihalogenation. Thereafter dehydrohalogenation proceeds by addition of an organic base, preferably amine base, to the halide. For example pyridine, or a diazobicycloalkene, is an especially useful amine base, although non-amine bases such as methanolic sodium acetate are likewise employed.
In any event, the chloro rather than bromo or iodo intermediates are preferred formula XLIV products, in that they lead to formula XLVI PG intermediates which are more easily dehydrohalogenated at C-13 and C-14, according to the procedures hereinafter described.
In each of the above described methods for the preparation of the formula XLIV compound wherein Y 4 is trans-CH═C(Hal)--CH 2 -- the desired formula XLIII product is often contaminated with its corresponding cis isomer and corresponding 13-halo isomers. In performing the below steps it is particularly desirable to obtain pure formula XLIV product in order to avoid creation of complicated mixtures of stereoisomers. Accordingly, the formula XLIV compound is subjected to conventional separation techniques (e.g. chromatography) to obtain pure product.
The formula XLV compound is then prepared from the formula XLIV compound, following the general procedure described in Chart A in preparation of the formula XXXII compound from the formula XXIV compound. Thereafter, this formula XLV compound is transformed to the corresponding formula XLVI compound, following the procedures of Chart A for the preparation of the formula XXXVII compound from the formula XXXII compound.
This formula XLVI compound is then optionally dehydrohalogenated, preparing the formula XLVII compound. The preferred method for this dehydrohalogenation proceeds using, as a reaction diluent, a mixture of dimethylsulfoxide (or a similar aprotic solvent) and methanol (between 5:1 and 10:1 by volume). Thereafter a strong organic base, for example, potassium, t-butoxide, or sodium methoxide is added and the reaction is allowed to proceed to completion at or below ambient temperature (0°-25° C.) The reaction is ordinarily complete within 24 hr.
The formula XLVII compound is then 9,11-diepimerized, yielding the formula XLVIII 15-deoxy-11β-PGF.sub.β compounds. This 9,11-diepimerization, as discussed in Chart A, proceeds by the methods hereinafter described (in Charts D and E).
Chart C provides a method whereby the formula LI 3,7-inter-m-phenylene- or 3,7-inter-m-phenylene-3-oxa-PGF.sub.α -type compound is transformed to corresponding formula LVII 15-deoxy-9β-PGF.sub.β compounds. The compounds according to formula LI which are employed as starting material for Chart C are known in the art or readily available by methods known in the art. For example, see U.S. Pat. 3,933,900, particularly Chart L therein which describes the preparation of 3,7-inter-m-phenylene-3-oxa-4,5,6-trinor-PGF 2 α -type compounds.
With respect to Chart C, the formula LII compound is prepared from the formula LI compound by cleavage of the 13,14-trans double bond, convenient by ozonolysis. Ozonolysis proceeds by bubbling dry oxygen, containing about 3 percent ozone, through a mixture of a formula LI compound in a suitable nonreactive diluent. For example, n-hexane is advantageously employed. The ozone may be generated using methods known in the art. See, for example, Fieser, et al., "Reagents for Organic Synthesis," John Wiley and Sons, Inc. (1967), pages 773-777. Reaction conditions are maintained until the reaction is shown to be complete, for example, by silica gel thin layer chromatography or when the reaction mixture no longer rapidly decolorizes a dilute solution of bromine in acetic acid.
The formula LIII compound is prepared from the formula LII compound by acylation, employing methods described above for introducing acyl protecting groups according to R 9 .
Thereafter the formula LIV and formula LV compounds are successively prepared from the formula LIII compound, employing the methods described above in Chart A and B. Thus, for example, the method described in Chart B for the transformation of the formula XLII compound to the formula XLIII and formula XLIV compounds, respectively are employed.
Thereafter the formula LV compound is transformed to the formula LVI compound by deacylation. Deacylation proceeds by the methods described above for the removal of acyl protecting groups according to R 9 .
The formula LVI compound is then transformed to the formula LVII compound by a 9,11-diepimerization. Methods described in Charts D and E hereinafter are employed in this transformation.
Finally, the formula LVIII compound is prepared from the formula LVII compound by optional 15-deoxygenation and optional dehydrohalogenation, as described above in Charts A and B, respectively.
As indicated above Chart D provides a method whereby each of the various PGF.sub.α or 15-deoxy-PGF.sub.α -type compounds herein (formula LXI) are transformed to corresponding formula LXV 11β-PGF.sub.β - or 15-deoxy-11β-PGF.sub.β -type compounds.
The formula LXI 15-hydroxy compound is transformed to the corresponding formula LXII compound by selective C-15 etherification with an R 10 blocking group. Selectivity of this reaction can be assured by first forming a cyclic boronate of the formula LXI 15-hydroxy compound with a slight stoichometric excess of the corresponding n-butyl-boronic acid. In a suitable organic diluent (e.g. methylene chloride) this transformation proceeds rapidly to completion. Thereupon, the 15-hydroxyl is etherified with R 10 blocking groups, following the procedures hereinabove described. Finally, the formula LXII compound is prepared by hydrolyzing the boronate, employing an alkaline metal hydroxide (e.g. sodium, lithium, or potassium hydroxide) in water and a water-miscible diluent capable of yielding a homogeneous reaction mixture (e.g. methanol THF, or ethanol) in the presence of dilute aqueous reaction peroxide.
The formula LXII compound is then 9,11-diepimerized to the formula LXIII compound. This diepimerization proceeds by the method described by J. E. Herz, et al., J. C. S. Perkin, I, 1438 (1974). Accordingly, the formula LXII compound is reacted with triphenylphosphine, a carboxylic acid (R 9 OH), in a di(loweralkyl)azo-dicarboxylate, in an organic diluent (e.g. tetrahydrofuran). The reaction proceeds to completion at ambient temperature, ordinarily within 24 hr. For the above purposes, the suitable carboxylic acids are those which yield acyl residues according to R 9 .
The formula LXIII 9,11-diacylate thusly produced is then deacylated by methods hereinabove described, yielding the formula LXIV compound. This formula LXIV compound wherein Y 8 represents an ether containing moiety, is then transformed to the formula LXV compound by hydrolysis of the R 10 blocking groups. Methods hereinabove described are employed.
Alternatively, the procedure of Chart D is modified by the elimination of the introduction and subsequent hydrolysis of the R 10 blocking groups. According to this modified procedure Chart D accomplishes the diepimerization by a two-step transformation (i.e. LXII to LXIII, and thereafter to LXIV).
Chart E provides a further method whereby the present 9,11-diepimerization is achieved.
By the method of this Chart the formula LXXI compound is 9,11-(alkyl or aryl)sulfonated, yielding the formula LXXII compound. This alkyl or aryl sulfonization proceeds by reaction of the corresponding alkyl or aryl sulfonyl chloride with the formula LXXI compound in amine solvents, especially pyridine.
Thus, p-toluenesulfonyl chloride and methylsulfonyl chloride yield, respectively, the formula LXXII bis-tosylates or bis-mesylates.
Thereafter the formula LXXII compound is diepimerized to the formula LXXIII compound by procedures described in R. Baker, et al., Journal of the Chemical Society (C), 1605 (1965) or E. J. Corey, et al., Chemical Communication 16:658 (1975).
By the first of these methods the formula LXII sulfonate is reacted with tetra-n-butyl ammonium acetate, followed by treatment with a deacylating agent (e.g. potassium methoxide in methanol).
Finally, the formula LXXIII compound is transformed to the formula LXXIV compound by hydrolysis of the optionally present R 10 blocking group.
Chart F provides a method whereby the formula XCI compound prepared according to Charts D and E is transformed to the formula XCII 2-decarboxy-2-hydroxymethyl compound. This transformation proceeds by methods known in the art for reducing prostaglandins to corresponding primary alcohols. Thus, for example, when the formula XCI compound is an acid or ester, the reduction proceeds with lithium aluminium hydride or diisobutyl aluminum hydride.
Useful reaction diluents include diethyl ether, tetrahydrofuran, dimethoxyethane, or like organic solvents. The reaction mixture is conveniently carried out temperatures of about -78 to 100° C., although preferably at about 0°-25° C.
When the formula XCI compound is an acid, reducing agents such as diborane are also employed, when double bond reduction is not a problem.
Chart G provides a method whereby the formula CI compound, prepared above, is transformed to the various 2-decarboxy-2-aminomethyl or 2-decarboxy-2-(substituted amino)methyl-15-deoxy-9β-PGF.sub.β -type compounds of formulas CIV, CVI, CVII, CVIII, CIX, or CX.
By the procedure of Chart G the formula CI compound is transformed to a formula CII mixed acid anhydride. These mixed anhydrides are conveniently prepared from the corresponding alkyl, aralkyl, phenyl, or substituted phenyl chloroformate in the presence of an organic base (e.g., triethylamine). Reaction diluents include water in combination with water miscible organic solvents (e.g., tetrahydrofuran). This mixed anhydride is then transformed to either the formula CIII PG-type amide or formula CV PG-type, azide.
For preparation of the 15-deoxy-11β-PGF.sub.β -type, amide (formula CIII) the formula CII mixed acid anhydride is reacted with liquid ammonia or ammonium hydroxide.
Alternatively, the formula CIII compound is prepared from the formula CI free acid by methods known in the art for transformation of carboxy acids to corresponding carboxyamides. For example, the free acid is transformed to a corresponding methyl ester (employing methods known in the art; e.g., excess ethereal diazomethane), and a methyl ester thus prepared is transformed to the formula CIII amide employing the methods described for the transformation of the formula CII mixed acid anhydride to the formula CIII amide.
Thereafter the formula CIV 2-decarboxy-2-aminomethyl-15-deoxy-11β-PGF.sub.β -type compound is prepared from the formula CIII compound by carbonyl reduction. Methods known in the art are employed in this transformation. For example, lithium aluminum hydride is conveniently employed.
The formula CII compound is alternatively used to prepare the formula CV azide. This reaction is conveniently carried out employing sodium azide by methods known in the art. See for example, Fieser and Fieser, Reagents for Organic Synthesis vol. 1, pgs. 1041-1043, wherein reagents and reaction conditions for the azide formation are discussed.
Finally, the formula CVI urethane is prepared from the formula CV azide by reaction with an alkanol, aralkanol, phenol, or substituted phenol. For example, when methanol is employed the formula CVI compound is prepared within R 1 is methyl. This formula CVI, PG-type product is then employed in the preparation of either the compound CVII or CVIII compound.
In the preparation of the formula CVII primary amine from the formula CVI urethane, methods known in the art are employed. Thus, for example, treatment of the formula CVII urethane with strong base at temperatures about 50° C. are employed. For example, sodium potassium or lithium hydroxide is employed.
Alternatively, the formula CVI compound is employed in the preparation of the formula CVII compound. Thus, when L 2 is alkyl the formula CVIII compound is prepared by reduction of the formula CVI urethane wherein R 1 is alkyl. For this purpose, lithium aluminum hydride is the conveniently employed reducing agent.
Thereafter, the formula CVIII product is used to prepare the corresponding CIX urethane by reaction of the formula CVIII secondary amine (wherein L 2 is alkyl) with an alkyl chloroformate. The reaction thus proceeds by methods known in the art for the preparation of carbamates from corresponding secondary amines. Finally, the formula CX product wherein L 2 and L 3 are both alkyl is prepared by reduction of the formula CIX carbamide. Accordingly, methods hereinabove described for the preparation of the formula CVIII compound from the formula CVI compound are used. Optionally, the various reaction steps herein are proceeded by the employment of blocking groups according to R 10 , thus necessitating their subsequent hydrolysis in preparing each of the various products above. Methods described hereinabove for the introduction and hydrolysis of blocking groups according to R 10 are employed.
Finally, the processes described above for converting the formula CII compound to the formula CVI compound and the various compounds thereafter, result in shortening the 8α-side chain of the formula CI compound by one carbon atom. Accordingly, the formula CI starting material should be selected so as to compensate for the methylene group which is consumed in the steps of the above synthesis. Thus, where a 2a-homo-product is desired a corresponding formula CI 2a,2b-dihomo starting material must be employed. Starting materials containing an additional methylene group in the formula CI compound between the Z 1 moiety and the carboxyl are prepared by methods known in the art or procedures described above. For example, Wittig reagents containing an additional methylene are known in the art or prepared by methods described above.
Chart H provides a method whereby the formula CXI compound is transformed to the formula CXIV or formula CXV prostaglandin analogs of the present invention.
The formula CXII compound is prepared from the formula CXI compound by selective transformation of the secondary hydroxyls of the formula CXI compound to alkyl or aryl sulfonyl derivatives. Methos of sulfonation hereinabove described (i.e. Chart E) are employed. Thus, for example, the corresponding alkyl or aryl sulfonyl chlloride and a tertiary amine condensing agent are reacted with the formula CXI compound to prepare the formula CXII product.
When the formula CXI compound of Chart H represents a 2-decarboxy-2-aminomethyl or 2-decarboxy-2-hydroxymethyl-PG-type compound, the selectively of the sulfonation of secondary hydroxyls (over the primary hydroxyl or the amine) is assured by first preparing a C-1 derivative of such a formula CXI compound. For example, such a formula CXI compound is first selectively silylated at C-1. (X 1 is --CH 2 OH) or t-butoxycarbonylated (X 1 is --CH 2 NH 2 ). Thereafter the sulfonation proceeds. Finally the silyl or t-butoxycarbonyl group is hydrolyzed under mild acidic conditions, e.g., acetic acid or dilute hydrochloric acid in acetic acid, respectively.
Silyl groups useful in the present process and methods for accomplishing the selective silylation are known in the art. See for example U.S. Pat. No. 3,822,303.
The formula CXIII compound is then prepared from the formula CXII compound by displacement with hydrazine in a solubilizing organic solvent. Thus, for example, suitable solvents include t-butanol in ethanol dimethylsulfoxide and hexamethylphosphoramide. Finally, this formula CXIII compound is transformed to the present title product by oxidation. This oxidation proceeds spontaneously by exposing the formula CXIII compound to air, or as catalyzed by the addition of copper (II) acetate, hydrogen peroxide (see Journal of Organic Chemistry 40, 456 (1975)) or mercuric oxide (see Journal of Organic Chemistry 17:1666 (1952)).
Optionally, the formula CXIII compound is transformed to the formula CXV dialkylate or diacylate or the formula CXVI or CXVII monoalkylates and acylates. In alkylating, the alkyl iodide corresponding to the desired product is employed. In the preparation of the acylated product, the acid anhydride or acid chloride is reacted with the formula CXIII hydrazine in the presence of a tertiary amine base. In the event undesired (e.g., C-1) esters are generated, the acylation is followed by saponification, for example, in methanolic sodium bicarbonate).
When the formula CXVI and formula CXVII monoacylates or alkylates are desired, a single equivalent of the corresponding alkylating or acylating agent is employed. Thereafter, the mixture of products is separated by conventional (e.g., chromatographic) means.
When the formula CXV dialkylate or bis(acylate) is desired, two equivalents of the appropriate alkylating or acylating agent are employed.
Optionally, the monoalkylates of formula CXVI and CXVII are prepared directly from the formula CXII compound by employing an alkylhydrazine in place of hydrazine in the transformation of the formula CXII to the formula CXIII product.
Chart J provides the method whereby the formula CXIV 9,11,15-trideoxy-11α,9α-epoxyimino-PGF-type compounds are prepared as well as their corresponding formula CXV acylates and alkylates.
With respect to Chart J, the formula CXXII compound is prepared from the formula CXXI compound by selective monosulfonation, preferably preparing the monotosylate (p-toluenesulfonate) or mesylate (methylsulfonate).
For this selective monosulfonation, the formula CXXI compound is reacted with somewhat less than two equivalents of the sulfonyl chloride corresponding to the sulfonate to be prepared. Further, the reaction is run at low temperature (e.g., at or below about 0° C.) When X 1 is --CH 2 OH or --CH 2 NL 2 L 3 , C-1 protection as described in Chart H is employed. However, such protected C-1 derivatives are hydrolyzed just prior to epoxyiminocyclization, described below.
The formula CXXIII compound is then prepared from the formula CXXII compound by reaction of the formula CXXII compound with N-hydroxyphthalimide in the presence of diethylazodicarboxylate and triphenylphosphine. A slight stoichiometric excess of both N-hydroxyphthalimide and diethylazodicarboxylate are employed. The reaction is run in organic solvents (e.g., tetrahydrofuran) and is ordinarily complete within several minutes. Formula CXXXIII product is then recovered by conventional (e.g., chromatographic) means.
the formula CXXIV analog is then prepared from the formula CXXIII compound by epoxyiminocyclization. Accordingly, the formula CXXIII compound is treated with an excess of hydrazine hydrate in, for example, a lower alkanol. The epoxyiminocyclization is ordinarily complete within several minutes, the reaction progress being conveniently monitored by silica gel TLC. Thereafter, the pure CXXIV product is obtained by conventional isolation and purification techniques.
Formula CXXV compound is then prepared from the formula CXXIV compound by alkylation or by acylation, for example as is described in Chart H for the preparation of a formula CXV - CXVII products.
Chart K provides a method whereby the formula CXXXI compound is transformed to the formula CXXXV 9,11,15-trideoxy-9α,11α-epoxyimino-PGF-type compounds and formula CXXXVI alkylates and acylates.
With respect to Chart K, the formula CXXXII compound is prepared from the formula CXXXI compound by a selective monosilylation (or disilylation when X 1 is not an ester or amide or amino) or by preparing a t-butoxycarbonyl derivative followed by selective monosilylation when X 1 is --CH 2 NL 2 L 3 .
The formula CXXXIII compound is then prepared from the formula CXXXII compound by sulfonation, likewise employing methods described above.
Thereafter the formula CXXXIV compounds is prepared from the formula CXXXIII compound by mild acetic hydrolysis of the silyl ether and t-butoxycarbonyl moiety when X 1 is --CH 2 NL 2 L 3 . Thereafter, the formula CXXXIV compound is transformed respectively to the formula CXXXV and CXXXVI compound by the method described in Chart J for the transformation of the formula CXXII compound to the formula CXXIV and CXXV compounds.
As discussed above, the processes herein described lead variously to carboxylic acids (X 1 is --COOR 1 and R 2 is hydrogen) ot to esters when preparing novel analogs wherein X 1 is --COOR 1 .
When the alkyl ester has been obtained and an acid is desired, saponification procedures, as known in the art for PGF-type compounds are employed.
For alkyl esters enzymatic processes for transformation of esters to their acid forms may be used by methods known in the art when saponification procedures would cause undesired molecular changes in the prostaglandin analog. See for reference E. G. Daniels, Process For Producing An Esterase, U.S. Pat. No. 3,761,356. When an acid has been prepared and an alkyl, cycloalkyl, or aralkyl ester is desired, esterification is advantgeously accomplished by interaction of the acid with the appropriate diazohydrocarbon. For example, when diazomethane is used, the methyl ester are produced. Similar use of diazoethane, diazobutane, and 1-diazo-2-ethylhexane, and diazodecane, for example, gives the ethyl, butyl, and 2-ethylhexyl and decyl esters, respectively. Similarly, diazocyclohexane and phenyldiazomethane yield cyclohexyl and benzyl esters, respectively.
Esterification with diazohydrocarbons is carried out by mixing a solution of the diazohydrocarbon in a suitable inert solvent, preferably diethyl ether, with the acid reactant, advantageouly in the same or a different inert diluent. After the esterification reaction is complete the solvent is removed by evaporation, and the ester purified if desired by conventional methods, preferably by chromatography. It is preferred that contact of the acid reactants with the diazohydrocarbon be no longer than necessary to effect the desired esterification, preferably about one to about ten minutes, to avoid undesired molecular changes. Diazohydrocarbons are known in the art or can be prepared by methods known in the art. See, for example, Organic Reactions, John Wiley and Sons, Inc., New York, N. Y., Vol. 8, pp. 389-394 (1954).
An alternative method for alkyl, cycloalkyl or aralkyl esterification of the carboxy moiety of the acid compounds comprises transformation of the free acid to the corresponding silver salt, followed by interaction of that salt with an alkyl iodide. Examples of suitable iodides are methyl iodide, ethyl iodide, butyl iodide, isobutyl iodide, tert-butyl iodide, cyclopropyl iodide, cyclopentyl iodide, benzyl iodide, phenethyl iodide, and the like. The silver salts are prepared by conventional methods, for example, by dissolving the acid in cold dilute aqueous ammonia, evaporating the excess ammonia at reduced pressure, and then adding the stoichiometric amount of silver nitrate.
Various methods are available for preparing phenyl or substituted phenyl esters within the scope of the invention from corresponding aromatic alcohols and the free acid PG-type compounds, differing as to yield and purity of product.
With regard to the preparation of the phenyl, particularly p-substituted phenyl esters disclosed herein (i.e., X 1 is --COOR 1 and R is p-substituted phenyl), such compounds are prepared by the method described in U.S. Pat. No. 3,890,372. Accordingly, by the preferred method described therein, the p-substituted phenyl ester is prepared first by forming a mixed anhydride, particularly following the procedures described below for preparing such anhydrides as the first step in the preparation of amido and cycloamido derivatives.
This PG-type anhydride is then reacted with a solution of the phenol corresponding to the p-substituted phenyl ester to be prepared. This reaction proceeds preferably in the presence of a tertiary amine such as pyridine. When the conversion is complete, the p-substituted phenyl ester has been recovered by conventional techniques.
having prepared the 9,11,15-trideoxy-PGF-type carboxylic acids, the corresponding carboxyamides are prepared by one of several amidation methods known in the prior art. See, for example, U.S. Pat. No. 3,981,868, issued Sept. 21, 1976 for a description of the preparation of the present amido and cycloamido derivatives of prostaglandin-type free acids and U.S. Pat. No. 3,954,741 describing the preparation of carbonylamido and sulfonylamido derivatives of prostaglandin-type free acids.
The preferred method by which the present amido and cycloamido derivatives of the 9-deoxy-9-methylene-PGF-type acids are prepared is, first, by transformation of such free acids to corresponding mixed acid anhydrides. By this procedure, the prostaglandin-type free acid is first neutralized with an quivalent of an amine base, and thereafter reacted a slight stoichiometric excess of a chloroformate corresponding to the mixed anhydride to be prepared.
The amine base preferred for neutralization is triethylamine, although other amines (e.g. pyridine, methyldiethylamine) are likewise employed. Further, a convenient, readily available chloroformate for use in the mixed anhydride production is isobutyl chloroformate.
The mixed anhydride formation proceeds by conventional methods and accordingly the 9,11,15-trideoxy-PGF-type free acid is mixed with both the tertiary amine base and the chloroformate in a suitable solvent (e.g. aqueous tetrahydrofuran), allowing the reaction to proceed at -10° to 20° C.
Thereafter, the mixed anhydride is converted to the corresponding amido or cycloamido derivative by reaction with the amine corresponding to the amide to be prepared. In the case where the simple amide (--NH 2 ) is to be prepared, the transformation proceeds by the addition of ammonia. Accordingly, the corresponding amine (or ammonia) is mixed with the mixed anhydride at or about -10 to +10° C., until the reaction is shown to be complete. For highly volatile amines, acid addition salts thereof (e.g., methylamine hydrochloride) are employed in place of the corresponding free base (e.g. methylamine).
Thereafter, the novel 9,11,15-trideoxy-PGF-type amido or cycloamido derivative is recovered from the reaction mixture by conventional techniques.
The carbonylamido and sulfonylamido derivative of the presently disclosed PG-type compounds are likewise prepared by known methods. See, for example, U.S. Pat. No. 3,954,741 for description of the methods by which such derivatives are prepared. By this known method, the prostaglandin-type free acid is reacted with a carboxyacyl of sulfonyl isocyanate, corresponding to the carbonylamido or sulfonylamido derivative to be prepared.
By another, more preferred method the sulfonylamido derivatives of the present compounds are prepared by first generating the PG-type mixed anhydride, employing the method described above for the preparation of the amido and cycloamido derivatives. Thereafter, the sodium salt of the corresponding sulfonamide is reacted with the mixed anhydride and hexamethylphosphoramide. The pure PG-type sulfonylamido derivative is then obtained from the resulting reaction mixture by conventional techniques.
The sodium salt of the sulfonamide corresponding to the sulfonylamido derivative to be prepared is generated by reacting the sulfonamide with alcoholic sodium methoxide. Thus, by a preferred method methanolic sodium methoxide is reacted with an equal molar amount of the sulfonamide. The sulfonamide is then reacted, as described above, with the mixed anhydride, using about four equivalents of the sodium salt per equivalent of anhydride. Reaction temperatures at or about 0° C. are employed.
The compounds of this invention prepared by the processes of this invention, in free acid form, are transformed to pharamcologically acceptable salts by neutralization with appropriate amounts of the corresponding inorganic or organic base, examples of which correspond to the cations and amines listed hereinabove. These transformations are carried out by a variety of procedures known in the art to be generally useful for the preparation of inorganic, i.e., metal or ammonium salts. The choice of procedure depends in part upon the solubility characteristics of the particular salt to be prepared. In the case of the inorganic salts, it is usually suitable to dissolve an acid of this invention in water containing the stoichiometric amount of a hydroxide, carbonate, or bicarbonate corresponding to the inorganic salt desired. For example, such use of sodium hydroxide, sodium carbonate, or sodium bicarbonate gives a solution of the sodium salt. Eavporation of the water or addition of a water-miscible solvent of moderate polarity, for example, a lower alkanol or a lower alkanone, gives the solid inorganic salt if that form is desired.
To produce an amine salt, an acid of this invention is dissolved in a suitable solvent of either moderate or low polarity. Examples of the former are ethanol, acetone, and ethyl acetate. Examples of the latter are diethyl ether and benzene. At least a stoichiometric amount of the amine corresponding to the desired cation is then added to that solution. If the resulting salt does not precipitate, it is usually obtained in solid form by addition of a miscible diluent of low polarity or by evaporation. If the amine is relatively volatile, any excess can easily be removed by evaporation. It is preferred to use stoichiometric amounts of the less volatile amines.
Salts wherein the cation is quaternary ammonium are produced by mixing an acid of this invention with the stoichiometric amount of the corresponding quaternary ammonium hydroxide in water solution, followed by evaporation of the water.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention can be more fully understood by the following examples and preparations.
All temperatures are in degrees centigrade.
IR (infrared) absorption spectra are recorded on a Perkin-Elmer Model 421 infrared spectrophotometer. Except when specified otherwise, undiluted (neat) samples are used.
UV (Ultraviolet) spectra are recorded on a Cary Model 15 spectrophotometer.
NMR (Nuclear Magnetic Resonance) spectra are recorded on a Varian A-60, A-60D, and T-60 spectrophotometer on deuterochloroform solutions with tetramethylsilane as an internal standard.
Mass spectra are recorded on an CEC model 21-110B Double Focusing High Resolution Mass Spectrometer or an LKB Model 9000 Gas-Chromatograph-Mass Spectrometer. Trimethylsilyl derivatives are used, except where otherwise indicated.
The Collection of chromatographic eluate fractions starts when the eluant front reaches the bottom of the column.
"Brine", herein, refers to an aqueous saturated sodium chloride solution.
The A-IX solvent system used in thin layer chromatography is made up from ethyl acetate-acetic acid-cyclohexane-water (90:20:50:100) as in M. Hamberg and B. Samuelsson, J. Biol, Chem. 241, 257 (1966).
Skellysolve-B (SSB) refers to mixed isomeric hexanes.
Silica gel chromatography, as used herein, is understood to include elution, collection of fractions, and combination of those fractions shown by TLC (thin layer chromatography) to contain the pure product (i.e., free of starting material and impurities).
Melting points (MP) are determined on a Fisher-Johns or Thomas-Hoover melting point apparatus.
Preparation 1 cis-4,5-Didehydro-cis-13-PGF 1 α, methyl ester (Formula XXXVII: R 1 is methyl, Z 2 is cis--CH 2 --CH═CH--(CH 2 ) 2 --, Y 2 is cis--CH═CH--, R 3 and R 4 of the L 1 moiety are hydrogen, and R 7 is n-butyl).
Refer to Chart A.
A. A solution of 34.3 g. of thallous ethoxide in 125 ml. of dry benzene is cooled inan ice bath, and thereafter a solution of 25 g. of dimethyl 2-oxo-heptyl-phosphonate in 75 ml. of benzene is added and thereafter rinsed with 50 ml. of benzene. The solution is stirred for 30 min. at 5° C. and thereafter 22.1 g. of crystalline 3α-benzoyloxy-5α-hydroxy-2β-carboxaldehyde-1α-cyclopentaneacetic acid, γ lactone is aded rapidly. This reaction mixture is then stirred for 13 hr. at ambient temperature yielding a brown solution of pH 9-10. Acetic acid (6 ml.) is added and the mixture is transferred to a beaker with 600 ml. of diethyl ether. Celite and 500 ml. of water is added, followed by the addition of 30 ml. (about 33 g.) of saturated potassium iodide. The mixture (containing a bright yellow precipitate of thallous iodide) is stirred for about 45 min., and thereafter filtered through a bed of Celite. The organic layer is then washed with water, aqueous potassium bicarbonate, and brine. Thereafter the resulting mixture is dried over magnesium sulfate and evaporated at reduced pressure, yielding 33.6 g. of an oil, which is then chromatographed on 600 g. of silica gel packed in 20 percent ethyl acetate in cyclohexane. Elution of 3α-benzoyloxy-5α-hydroxy-2β-(3-oxo-trans-1-octenyl)-1.alpha.-cyclopentaneacetic acid, γ lactone.
alternatively this product is prepared by adding 3α-benzoyloxy-2β-carboxaldehyde-5α-hydroxy-1α-cyclopentaneacetic acid γ lactone (3 g.) in 30 ml. of dichloromethane to a solution of dimethyl 2-oxo-heptylphosphonate (6.6 g.) and sodium hydride (1.35 g.) in 15 ml. of tetrahydrofuran. The resulting reaction mixture is then stirred for 2 hr. at about 25° C., acidified with acetic acid, and concentrated under reduced pressure. The residue is partitioned between dichloromethane and water, and the organic phase is concentrated. The residue is chromatographed on silica gel, eluting with ethyl acetate in Skellysolve B (1:1).
B. A solution of 16.3 g. of the reaction product of part A in one l. of acetone (agitated by bubbling nitrogen through the solution) is irradiated for 3 hr. in a Rayonet Photochemical Reactor (RPR-208, using 8 lamps) wherein the photo emission spectrum shows substantial intenstiy at a wave length at or around 3500 Angstroms. The solvent is then evaporated and the residue chromatographed on 1.5 kg. of silica gel packed in 10 percent ethyl acetate in cyclohexane. Elution yields crude 3α-benzoyloxy-5α-hydroxy2β-(3-oxo---cis-1-octenyl)-1.alpha.-cyclopentaneacetic acid γ-lactone. Further chromatographic purification yields the pure cis isomer.
C. Sodium borohydride (2.86 g.) is slowly added to a stirred suspension of 12.6 g. of anhydrous zinc chloride in 78 ml. of dimethyl ether in ethylene glycol dimethyl ether (glyme) with ice bath cooling. The mixture is stirred for 20 hr. at ambient temperature and thereafter cooled to -20° C. A solution of 8.0 g. of 3α-benzoyloxy-5α-hydroxy-2β-(3-oxo-cis-1-octenyl)-1.alpha.-cyclopentaneacetic acid γ lactone (part b) in 80 ml. of glyme is added over a period of 15 min. Stirring is continued for 24 hr. at -20° C. and thereafter 60 ml. of water is cautiously added. The reaction mixture is warmed to room temperature, diluted with ethyl acetate, and washed twice with brine. The aqueous layers are extracted with ethyl acetate. The combined organic extracts are dried over sodium sulfate and evaporated to yield an oil, which when chromatographed on 900 g. of silica gel packed in one percent acetone and methylene chloride, eluting with one to 15 percent acetone in methylene chloride yields the epimerically pure title product (2.17 g. of the 3S epimer and 5.1 g. of the 3R epimer).
The 3S epimer exhibits ultraviolet absorptions at λ max . equals 230 nm. (ε1300, 580). Infrared absorptions (cm. -1 ) are observed at 3530, 3460, 1755, 1715, 1705, 1600, 1585, 1495, 1315, 1280, 1235, 1170, 1125, 1075, 1035, 975, 910, and 710. NMR absorptions in CDCl 3 are observed at 4.2, 4.7, 4186-5.82, 7.18-7.63, and 7.8-8.15 δ.
The 3R epimer exhibits ultraviolet absorption at λ max . of 230nm. (ε12,560). NMR absorptions in CDCl 3 are observed 4.2-4.7, 4.86-5.82, 7.18-7.63, and 7.8-8.15.
D. A solution of 5 g. of the reaction product of part C in 150 ml. of methanol is purged with nitrogen. Thereafter, potassium carbonate (2.02 g.) is added and the resulting mixture is stirred at ambient temperature until thin layer chromatographic analysis shows the solvolysis to be complete (about 1.5 hr.). The methanol is then evaporated under reduced pressure. The residue is then shaken with ethyl acetate (250 ml.), brine (250 ml.), and 8 g. of potassium bisulfate. The aqueous layer is then extracted twice with 125 ml. of ethyl acetate and the organic extracts are dried over magnesium sulfate, and evaporated to yield an oil. This oil is then dissolved in chloroform and a few crystals of p-toluenesulfonic acid are added. When thin layer chromatography indicates the relactinization is complete (about 2 hr.), the reaction mixture is then ashed with aqeuous potassium bicarbonate, dried, and evaporated to yield an oil which is then chromatrographed using silica gel packed in one percent ethanol in methylene chloride for purification. Accordingly, 3 g. of the deacylated lactone are prepared.
E. A solution of 1.57 g. of the reaction product of part D above, in 35 ml. of methylene chloride (containing 2.5 ml. of dihydropyran and 100 mg. of pyridine hydrochloride) is allowed to stand for 23 hr. at ambient temperature. The reaction mixture is then washed with water, aqueous potassium bicarbonate, dried over magnesium sulfate, and evaporated, yielding an oil which is thereafter chromatographed on 200 g. of silica gel packed in one percent acetone in methylene chloride. Elution with from one to ten percent acetone in methylene chloride yields 1.7 g. of the bis-tetrahydropyranyl lactone corresponding to the lactone reaction product of part D above.
F. A solution of the reaction product of part E above in 20 ml. of toluene is cooled to -70° C. and thereafter 10 ml. of 10 percent diisobutylaluminum hydride in toluene is slowly added. The reaction mixture is then stirred at -70° C. until thin layer chromatographic analysis indicates that the reduction is complete (about 30 min.). Thereafter the cooling bath is removed and 9 ml. of a mixture of tetrahydrofuran and water (2:1) is added slowly. The reaction mixture is then stirred and allowed to warm to room temperature, and is then filtered through Celite. The filter cake is rinsed with benzene, combined organic extracts are then dried over magnesium sulfate and evaporated to yield 1.57 g. of 3α,5α-dihydroxy-2β -[(3S)-3-hydroxy-cis-1-octenyl]-1α-cyclopentaneacetaldehyde, γ-lactol, bis-tetrahydropyranyl ether.
G. A suspension of methoxymethyl-triphenylphosphonium chloride (32.4 g.) in 150 ml. of tetrahydrofuran is cooled to -15° C. To the suspension is added 69.4 ml. of n-butyllithium in hexane (1.6 molar) in 45 ml. of tetrahydrofuran. After 30 min. there is added a solution of 3α,5α-dihydroxy2β-[(3R)-3-hydroxy-cis-1-octenyl]-1α-cyclopentaneacetaldehyde γ-lactol bis-(tetrahydropyranylether), part F (10 g.), in 90 ml. of tetrahydroufuran. The mixture is stirred for 1.5 hr. while warming to 25° C. The resulting solution is thereafter concentrated under reduced pressure. The residue is partitioned between dichloromethane and water, the organic phase being dried and concentrated. This dry residue is then subjected to chromatography over silica gel eluting with cyclohexane and ethyl acetate (2:1). Those fractions as shown by thin layer chromatography to contain pure formula XXVIII compound are combined.
H. The reaction product of part G above in 20 ml. of tetrahydrofuran is hydrolyzed with 50 ml. of 66 percent aqueous acetic acid at about 57° C. for 2.5 hr. The resulting mixture is then concentrated under reduced pressure. Toluene is added to the residue and the solution is again concentrated. Finally the residue is subjected to chromatography on silica gel, eluting with chloroform and methanol (6:1). The formula XXIX compound is thereby obtained by combining and concentrating fractions as shown by thin layer chromatography to contain pure γ-lactol.
I 3-Carboxypropyltriphenylphosphonium bromide (prepared by heating 4-bromobutyric acid and triphenylphosphine in benzene at reflux for 18 hr., and thereafter purifying), 1.06 g., is added to sodiomethylsulfinylcarbanide prepared from sodium hydride (2.08 g., 57 percent) and 30 ml. of dimethylsulfoxide. The resulting Wittig reagent is combined with the formula XXIX lactol of part H above and 20 ml. of dimethylsulfoxide. The mixture is stirred overnight, diluted with about 200 ml. of benzene, and washed with potassium hydrogen sulfate solution. The two lower layers are washed with dichloromethane, the organic phases are combined, washed with brine, dried, and concentrated under reduced pressure. The residue is subjected to chromatography over acid washed silica gel, eluting with ethyl acetate and isomeric hexanes (3:1). Those fractions as shown to contain the desired compound by thin layer chromatography are combined to yield the free acid of pure title product.
J. The Reaction product of part I above is reacted with ethereal diazomethane preparing pure title methyl ester.
Preparation 2 cis-4,5-Didehydro-cis-13,11β-PGF 1 β, methyl ester (Formula XXXVIII: R 1 , Z 2 , Y 2 M 9 , L 1 , and R 7 are as defined in Preparation 1):
Refer to Charts A and D.
A. A solution of 8g. of the reaction product of Preparation 1 and 2.7 g. of n-butylboronic acid in 300 ml. of methylene chloride are heated to reflux. As 30 ml. aliquots of methylene chloride are evaporated, a like quantity is replaced until 150 ml. of methylene chloride are replaced. After to cooling to ambient temperature 0.6 g. of pyridine hydrochloride in 70 ml. of dihydropyran are added and the resulting mixture stirred at ambient temperature under nitrogen for 18 hr. Thereafter the mixture is concentrated to about 50 ml. and 100 ml. of methanol is added. After cooling is an ice-bath, a mixture of 30 ml. of 30 percent hydrogen peroxide and 150 ml. of aqueous sodium bicarbonate is added and the resulting solution stirred for one hr. Thereafter the mixture is poured into 300 ml. of ethyl acetate; the aqueous layer saturated with sodium chloride; and the resulting layer separated. The aqueous portion is extracted with ethyl acetate and the combined organic extracts are washed with brine, dried over sodium sulfate, and concentrated to an oil. This crude oil is then chromatographed on silica gel packed with 50 percent ethyl acetate in hexane and eluted with ethyl acetate and hexane, yielding the mono-tetrahydropyranyl ether as in formula LXII of Chart D.
B. A solution of 6.7 g. of the reaction product of part A, 15.5 g. of triphenylphosphine and 7.2 g. of benzoic acid in 200 ml. of dry tetrahydrofuran is cooled to 0° C. under a nitrogen atmosphere. Thereupon, 10.2 g. of diethyl azodicarboxylate in 10 ml. of tetrahydrofuran is added over one min. to the above solution (rapidly stirred). After about 10 min. the reaction is substantially complete, however, after an additional 45 min., the reaction being complete, the mixture is poured into 400 ml. of ethyl acetate and hexane (1:1). The mixture is then washed with 150 ml. of saturated sodium bicarbonate and brine, washed with brine, dried over sodium sulfate, and concentrated to a solid mass. This solid mass is then suspended in 15 percent ethyl acetate and hexane and 18 g. of triphenylphosphine oxide is precipitated and removed by filtration. The remaining oil is then chromatographed on 2 kg. of silica gel, packed with ethyl acetate and Skellysolve B, and eluted with various mixtures of ethyl acetate and Skellysolve B, yielding a dibenzoate, tetrahydropyranyl ether as in formula LXIII of Chart D.
C. A solution of 5.6 g. of the reaction product of part B in 15 ml. of dry methanol is stirred at ambient temperature under a nitrogen atmosphere, while 10 ml. of 25 percent sodium methoxide in methanol is added. After about 3 hr. the solution is poured into 300 ml. of ice-cold saturated ammonium chloride and 15 ml. of 2N sodium bisulfate. The resulting mixture is then extracted thoroughly with ethyl acetate and the combined organic extracts are washed with brine, dried over sodium sulfate, and concentrated to yield crude product. This crude product is then chromatographed on 300 g. of silica gel, packed with mixtures of ethyl acetate and hexane, then eluted with various mixtures of ethyl acetate and hexane, yielding a dihydroxy tetrahydropyranyl ether as in formula LXIV of Chart D.
D. A solution of 4.3 g. of the reaction product of part C in 100 ml. of a mixture of acetic acid, water, and tetrahydrofuran (3:1:1) is warmed to 40° C. for 2 hr. Thereupon the mixture is partitioned between 400 ml. of ethyl acetate in hexane (1:1) and 200 ml. of brine. The organic phase is then washed twice with brine, washed with saturated sodium bicarbonate (until basic), washed with brine, dried over sodium sulfate, and concentrated to an oil which is then chromatographically purified on silica gel, yielding the title product.
Preparation 3 15-Deoxy-cis-4,5-didehydro-13-cis-11β-PGF 1 β, methyl ester and 15-Deoxy-cis-4,5-didehydro-13,14-dihydrotrans-14,15-didehydro-11β-PGF 1 β, methyl ester (Formula XLI: R 1 , Z 2 , L 1 , and R 7 are as defined in Preparation 1 and Y 3 is cis--CH'CH--CH 2 -- or trans--CH 2 --CH═CH--, respectively).
Refer to Chart A.
A solution of 0.5 g. of cis-4,5-didehydro-cis-13-11β-PGF 1 β methyl ester, 0.83 g. of imidazole, and 0.92 g. of t-butyldimethylchlorosilane in 2 ml. of dry dimethylformamide is stirred at ambient temperature under a nitrogen atmosphere for 20 hr. The resulting solution is then cooled in an ice bath and 6.0 ml. of water is added. After 30 min. the mixture is poured into cold brine and extracted with hexane. The hexane extract is then washed with ice-cold 2N sodium bisulfate, ice-cold 2N sodium bisulfate, ice-cold saturated sodium bicarbonate, brine, and thereafter dried over sodium sulfate and concentrated to the formula XXXIX trimethylsilyl derivative of the starting material.
B. A solution of 1.0 g. of the reaction product of Part A in 22.0 ml. of methanol is treated with 15 ml. of 10 percent aqueous potassium hydroxide. After 48 hr. most of the methanol is evaporated under reduced pressure and the residue partitioned between hexane and an ice-cold 2N sodium bisulfate and brine. The aqueous portion is then extracted twice with hexane and the combined organic extracts are then washed twice with brine, dried over sodium sulfate, and concentrated to yield the free-acid of the reaction product of part A.
C. Methylamine (15 ml.) is condensed and maintained at -30 to -40° C. while 0.94 g. of the reaction product of part B in 2 ml. of a mixture of t-butanol and tetrahydrofuran (1:10) is added). Thereupon three small pieces of lithium metal (approximately one-third of a cm. long) are added at a rate of one per minute. After 10 min. a deep blue color persists. After 30 min. from the lithium addition, 10.0 g. of solid ammonium chloride are added and the solution becomes colorless. The methylamine is then allowed to evaporate at ambient temperature under a stream of nitrogen. Thereafter, ice-cold 2N aqueous sodium bisulfate is added and the resulting mixture extracted with 10 percent ethyl acetate in hexane. The combined organic extracts are then washed twice with brine, dried over sodium sulfate, and concentrated, yielding a mixture of the formula XL 15-deoxy compounds where Y is cis--CH═CH--CH 2 -- or trans--CH 2 --CH═CH--.
D. A solution of 0.77 g. of the reaction product of part C in 20 ml. of a mixture of 2N aqueous hydrochloric acid and tetrahydrofuran (1:4) is stirred at 25° C. for 18 hr. under a nitrogen atmosphere. The resulting mixture is then poured into brine and extracted three times with ethyl acetate. The combined organic extract is then washed twice with brine, dried over sodium sulfate, and concentrated to yield a mixture of the free acids of the title product.
E. The crude product of part D is then dissolved in 25 ml. of acetonitrile and treated with 2 ml. of diisopropylethylamine and 4 ml. of methyl iodide at ambient temperature under a nitrogen atmosphere. After 3 hr. the mixture is poured into brine and extracted 3 times with ethyl acetate. The combined organic extracts are then washed twice with brine, dried over sodium sulfate, and concentrated to an oil. The resulting product is then chromatographed on 75 g. of silica gel packed with 30 percent ethyl acetate in hexane. Elution with 40 to 50 percent ethyl acetate in hexane yields the respective title methyl esters.
Preparation 4 13,14-Didehydro-5-oxa-16-phenoxy-17,18,19,20-tetranor-15-deoxy-11β-PGF 1 β, methyl ester (formula XLVIII: R 1 is methyl, Z 2 is --CH 2 --O--(CH 2 ) 3 --, Y 6 is --C═CH 2 --, R 3 and R 4 of the L 1 moiety are both hydrogen, and R 7 is ##STR47##
Refer to Chart B.
A. Following the procedure of Preparation 1, but employing N,N-dimethyl-3-phenoxypropylphosphoamide in place of dimethyl-2-oxohexylphosphonate, there is prepared 3α-benzoyloxy-5α-hydroxy-2β-(4-phenoxy-trans-1-butenyl)-1α-cyclopentaneacetic acid γ-lactone and its corresponding cis-epimer.
B. A solution of the reaction product of part A (1.15 g.) in CC-4 (35 ml.) is treated with molecular chlorine (5.0 g.) and stirred. The resulting solution is then diluted with methylene chloride, washed with saline, and a sodium sulfate solution. This washed mixture is then dried and concentrated under reduced pressure. The residue thusly obtained is diluted with benzene and chromatographed on silica gel eluting with mixtures of hexane and ethyl acetate, yielding isomeric mixtures of 3α-benzoyloxy-5α-hydroxy-2β-(1,2-dichloro-4-phenoxybutyl)-1α-cyclopentaneacetic acid γ-lactone. These dichlorides are then diluted with pyridine (20 ml.) and heated at 100° C. for 4.5 hr. The resulting solution is then diluted with diethyl ether and washed with ice-cold dilute hydrochloric acid and brine. The resulting mixture is then dried and subject to silica gel chromatography eluting with mixtures of hexane and ethyl acetate, yielding 3α-benzoyloxy-5α-hydroxy-2β-(2-chloro-4-phenoxy-trans-1-butenyl)-1α-cyclopentaneacetic acid γ-lactone.
C. Following the procedure described in U.S. Pat. No. 3,931,279, at Preparation 12, parts E-G and Example 36, the reaction product of part B is transformed to 5-oxa-14-chloro-15-deoxy-16-phenoxy-17,18,19,20-tetranorPGF 1 α, methyl ester.
D. Following the procedure of Preparation 2, the reaction product of part C is transformed to 5-oxa-14-chloro-15-deoxy-16-phenoxy-17,18,19,20-tetranor-11β-PGF.sub.1 β, methyl ester.
E. A solution of potassium t-butoxide and t-butanol is treated with the reaction product of part D above. After several hours, the reaction mixture is diluted with diethyl ether and one percent aqueous potassium bisulfate is added. The aqueous phase is then extracted with diethyl ether and benzene and the combined organic extracts are washed with brine, dried and concentrated to yield crude title product. This crude product is then chromatographed on silica gel yielding 5-oxa-13,14-didehydro-15-deoxy-16-phenoxy-17,18,19,20-tetranor-11β-PGF 1 β, methyl ester.
Preparation 5 3,7-Inter-m-phenylene-3-oxa-13,14-dihydro-15-deoxy-17-phenyl-4,5,6,18,19,20-hexanor-11β-PGF 1 β, methyl ester (Formula LVII: R 1 is methyl, Z 3 is oxa, Y 1 is --(CH 2 ) 3 --, R 3 and R 4 of the L 1 moiety are both hydrogen, and R 7 is benzyl).
Refer to Chart C.
A. 3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-PGF 1 α, methyl ester (10 g.) in 200 ml. of methanol is cooled to 0° C. in an ice bath. A stream of ozone, is generated from a conventional ozone producing apparatus, is passed through the mixture until the starting material is completely consumed. Thereupon the resulting mixture is washed, concentrated under reduced pressure, and the residue chromatographed, yielding the corresponding formula LII compound.
B. Following the procedure of Preparation 4, part A, but employing N,N-dimethyl-4-phenylbutylphosphoramide in place of N,N-dimethyl-3-phenoxypropylphosphoramide, there is prepared 3,7-inter-m-phenylene-3-oxa-15-deoxy-17-phenyl-4,5,6,18,19,20-hexanor-PGF.sub.1α, methyl ester, from the reaction product of part A.
C. A solution of the reaction product of part B in acetone and benzene, containing a catalytic amount of tris-(triphenylphoshine)rhodium (I) chloride is shaken under a hydrogen atmosphere at ambient temperature under one to 3 atmospheres of pressure for 3.5 hr. The solvent is then concentrated under reduced pressure and the residue chromatographed, yielding 3,7-inter-m-phenylene-3-oxa-13,14-dihydro-15-deoxy-17-phenyl-4,5,6,18,19,20-hexanor-PGF 1 α, methyl ester.
D. Following the procedure of Preparation 2 (Parts B and C) the reaction product of part C above is transformed to 3,7-inter-m-phenylene-13,14-dihydro-15-deoxy-17-phenyl-4,5,6,18,19,20-hexanor-11β-PGF 1 β, methyl ester, the title product.
Preparation 6
2-Decarboxy-2-hydroxymethyl-15-deoxy-cis-13-cis-4,5-didehydro-11β-PGF.sub.1 β.
Refer to Chart F.
750 mg. of the reaction product of Preparation 3 dissolved in 50 ml. of diethyl ether are reacted with 500 mg. of lithium aluminum hydride at room temperature, with stirring. When the starting material is completely consumed (as indicated by thin layer chromatographic analysis) one ml. of water is cautiously added. Thereafter 0.8 ml. of 10 percent aqueous sodium hydroxide is added and the resulting mixture allowed to stir for 12 hr. Thereupon magnesium sulfate is added with stirring and the stirred mixture then filtered through magnesium sulfate and evaporated to a residue. Chromatographic purification yields pure title product.
Following the procedure of Preparation 6, but employing each of the various formula XCl 15-deoxy-11β-PGF β-type compounds there are prepared each of the various corresponding 2-decarboxy-2-hydroxymethyl-15-deoxy-11β-PGF 62 -type products of formula XCII.
Preparation 7
2-Decarboxy-2-aminomethyl-15-deoxy-cis-13-cis-4,5-didehydro-11β-PGF.sub.1 β.
Refer to Chart G.
A. The reaction product of Preparation 3 is dissolved in one ml. of 95 percent ethanol. The resulting mixture is then transferred to a steel Parr bomb rinsed with 2 one-half ml. aliquots of 95 percent ethanol and 200 mg. of ammonium chloride are added. Then the mixture is cooled in a dry ice acetone bath and ammonia is added until about 5 to 10 ml. has condensed. The bomb is then sealed and allowed to warm to room temperature. Thereafter the bomb is placed in an oven at 50° C. for 2 days cooled in a dry-ice acetone bath, and opened. Thereafter residual ammonia is evaporated with nitrogen and the product extracted with ethyl acetate, washed with water and saturated brine, dried over sodium sulfate, and evaporated to yield 15-deoxy-cis-13-cis-4,5-didehydro-11β-PGF 1 β, amide, formula CIII.
B. Lithium aluminum hydride (100 mg.) in 5 ml. of dry tetrahydrofuran under nitrogen is prepared. A solution of the reaction product of part A is then slowly added (being dissolved in a small amount of dry tetrahydrofuran). The resulting mixture is then stirred at room temperature for 48 hr. and thereafter one-tenth ml. of water is added while cooling the mixture in an ice bath. Thereafter 0.1 ml. of 15 percent sodium hydroxide and 0.3 ml. of water is added. The suspension is then filtered; dried over magnesium sulfate; washed with ethyl acetate; and evaporated to yield a residue of the title product.
Following the procedure of Preparation 7, but employing each of the various formula XCI 15-deoxy-11β-PGF 2 β-type compounds of formula CI there are prepared each of the various 2-decarboxy-2-aminomethyl-15-deoxy-11β-PGFβ-type compounds of Chart G.
Following the procedure of the above preparations, there are prepared each of the various formula CXI compounds of Chart H which are employed in the preparation of the novel formula CXIV compounds herein.
EXAMPLE 1
9,11,15-Trideoxy-9α,11α-azo-PGF 2 (Formula CIV: X 1 is --COOH, Z 1 is cis--CH═CH--(CH 2 ) 3 -, Y 1 is trans--CH═CH--CH 2 -, R 3 and R 4 of the L 1 moiety are hydrogen, and W 1 is ##STR48##
and R 7 is n-butyl).
A. Following the procedure of Preparation 3, 11β-PGF 2 β, methyl ester is transformed to a mixture of 15-deoxy-11β-PGF 2 β, methyl ester and 15-deoxy-13,14-dihydro-trans-14, 15-didehydro-11β-PGF 2 β, methyl ester.
A solution of 0.59 g. of 15-deoxy-11β-PGF 2 β, methyl ester (as prepared in part A) in 20 ml. of methylene chloride is cooled to -20° C. under a nitrogen atmosphere. Thereupon 0.57 g. of triethylamine is added, followed by addition of 0.30 ml. of methanesulfonyl chloride. After 10 min. the mixture is poured into a mixture of ice cold brine and 2N aqueous sodium bisulfate. The combined mixture is then extracted with ethyl acetate and the organic extracts washed with sodium bicarbonate and brine, dried over sodium sulfate, and concentrated to yield 0.80 g. of 15-deoxy-11β-PGF 2 β, methyl ester, 9,11-bis-(methanesulfonate). Silica gel TLC R f is 0.35 in ethyl acetate and hexane (1:1). Infrared absorptions are observed at 2980, 2890, 1750, 1460, 1440, 1350, 1240, 1180, 970, and 910 cm. -1 .
C. An oil suspension of 0.66 g. of the reaction product of part B in 75 ml. of methanol and water (2:1) is stirred in the presence of 0.28 g. of lithium hydroxide. After 5 hr. at ambient temperature the solution is poured into ice-cold 2N aqueous sodium bisulfate and brine and extracted with ethyl acetate. The combined organic extracts are then washed twice with brine, dried over sodium sulfate, and concentrated to yield 0.66 g. of an oil. This crude product is then chromatographed on 75 g. of silica gel (CC-4) packed with 30 percent ethyl acetate and hexane and eluted with 30 to 45 percent ethyl acetate in hexane, yielding 15-deoxy-11β-PGF 2 β, 9,11-bis-(methanesulfonate). Silica gel TLC R f is 0.28 in ethyl acetate, hexane, and acetic acid (50:50:1). Infrared absorptions are observed at 3300, 2970, 2890, 2700, 1715, 1460, 1410, 1350, 1175, 970, 910 cm. -1 . Characteristic NMR absorptions are observed at 5.50, 4.90, and 3.0 δ.
D. A solution of 0.24 g. of the reaction product of part C and 1.0 ml. of 95 percent hydrazine in 15 ml. of a mixture of t-butanol and ethanol (3:1) is warmed to reflux (in an oil bath, 95° C.) for 18 hr. After cooling, the mixture is concentrated to 0.59 g. of a crude product, 9,11,15-trideoxy-9α,11α-hydrazino-PGF 2 α. Silica gel TLC R f is 0.15 in a mixture of methanol, ethyl acetate, and ammonium hydroxide (50:50:2).
E. A solution of 0.50 g. of the reaction product of part D in 20 ml. of a mixture of methanol and diethyl ether (3:1) is treated with 5 mg. of cupric acetate. After 90 min., the mixture is then concentrated to an oil which is taken up with ethyl acetate and filtered from resulting insoluble material, yielding 0.37 g. of crude title product. This crude product is then chromatographed on silica gel, packed with ethyl acetate and cyclohexane (1:4). Eluting with 30 percent ethyl acetate and hexane yields 80 mg. of pure title product. Silica gel TLC R f is 0.18 in a mixture of ethyl acetate, cyclohexane, and acetic acid (30:70:1).
EXAMPLE 2
9α,11α-azo-9,11,15-trideoxy-PGF 2 , amide
A solution with 300 mg. of 9α,11α-azo-9,11,15-trideoxy PGF 2 in 8.0 ml. of dry acetonitrile is cooled to -10° C. under a nitrogen atmosphere. Thereafter 0.127 ml. of triethylamine is added followed by addition of 0.118 ml. of isobutylchloroformate. After 10 min. at -5° C., an ammonia saturated solution of 3 ml. of acetonitrile is added in one portion. After 5 min. at -5° C., and 10 min. at room temperature, the reaction mixture is diluted with ethyl acetate, and partitioned with a mixture of brine and KH 2 PO 4 (added to adjust pH to 4.5). The resulting layers are separated and the aqueous phase is extracted with ethyl acetate. The organic extract is then washed with brine, dried over sodium sulfate, and concentrated to yield 0.30 gms. of an oil. This oil is chromatographed on 50 gm. of silica gel packed and eluted with ethyl acetate, yielding 270 mg. of pure title product. TLC R f is 0.24 in a mixture of ethyl acetate and acetic acid (99:1). Infrared absorptions are observed at 3300, 3100, 2900, 2800, 1670, 1620, 1490, 1460, and 965 cm. -1 . NMR absorptions are observed at 6.0, 5.4, 5.10, 4.90, and 0.90δ. The high resolution mass spectrum for the monotrimethylsilyl derivative exhibits a molecular ion peak at 403.3036.
Example
9α,11α-azo-9,11,15-trideoxy-PGF 2 , p-carboxanilide (Formula IV: X 1 is COL 4 , L 4 is ##STR49##
and W 1 , Z 1 , Y 1 , L 1 , and R 7 are as defined in Example 1).
To a solution of 393 mg. of 9α,11α-azo-9,11,15-trideoxy-PGF 2 at -10° C. in 5 ml. of acetone is added 0.14 ml. of triethylamine, followed by addition of 0.13 ml. of isobutylchloroformate. The resulting mixture is then stirred at -10° C. for 10 min. and thereafter treated with a mixture of 250 mg. of p-aminobenzoic acid, 0.2 ml. of triethylamine, and 5 ml. of acetone. The resulting mixture is then warmed to 25° C. and stirred for 20 min. Thereafter the stirred mixture is poured into cold dilute aqueous sodium bisulfate and extracted with ethyl acetate. The organic extracts are then washed with brine, dried over magnesium sulfate and evaporated to yield crude product. This crude product is then chromatographed 75 g. of silica gel packed with 40% ethyl acetate in hexane. Eluting with 40 to 70% ethyl acetate in hexane yields pure title product.
EXAMPLE 4
9α,11α-azo-9,11,15-trideoxy-PGF 2 , methylsulphonylamide (Formula IV: X 1 is -COL 4 , L 4 is --NHSO 2 CH 3 , an Z1, W 1 , Y 1 , L 1 , and R 7 are as defined in Example 1).
To a stirred solution of 480 mg. of 9α,11α-azo-9,11,15-trideoxy-PGF 2 in 6.0 ml. of dimethylformamide 0.142 g. of triethylamine is added with stirring followed by addition of 0.19 g. of isobutyl chloroformate. This mixture is then stirred at 0° C. for 25 min. at which time 0.685 g. of methylsulfonamide sodium salt (prepared by adding 1.33 ml. of 4.4 N methanolic sodium methoxide to a solution of 0.604 g. of methanesulfonamide in 2.0 ml. of methanol, concentrating the mixture under reduced pressure, adding benzene to the residue, and again concentrating the mixture under reduced pressure). Thereafter 1.25 ml. of hexamethylphosphoramide is added and the mixture stirred at ambient temperature for 16 hrs. Acidification with cold dilute hydrochloric acid is followed by extraction with ethyl acetate. The organic extract is then washed with water, brine and dried over magnesium sulfate. Concentration at reduced pressure yields a residue which is chromatographed a 100 g. column of silica gel packed with 10% methanol in methylene chloride. Eluting with 7.5% methanol in methylene chloride yields pure title product.
EXAMPLE 5
9α,11α-azo-9,11,15-trideoxy-PGF 2 , p-hydroxybenzaldehyde semicarbazone ester (Formula IV: X 1 is --COOR 1 , and R 1 is ##STR50##
Z 1 , W 1 , Y 1 , L 1 , and R 7 are as defined in Example 1).
A solution of 1.0 g. of 9α,11α-azo-9,11,15-trideoxy-PGF 2 in 45 ml. of dry acetone is cooled to 0° C. and treated dropwise with 0.51 ml. of triethylamine. Thereafter 0.48 ml. of isobutylchloroformate is added. This mixture is stirred for 10 min. after which a triethylamine hydrochloride precipitate forms. A solution of 1.32 g. of p-hydroxybenzaldehyde semicarbazone in 13 ml. of pyridine is then added and the mixture allowed to warm to 25° C. This mixture is then stirred for 60 min. and thereafter concentrated under reduced pressure. The residue is then dissolved in ethyl acetate and filtered. The filter cake is then washed with ethyl acetate and the combined filtrate is evaporated and chromatographed on 200 g. of silica gel packed with 5% isopropanol and hexane. Eluting with isopropanol and hexane yields pure product which is then rechromatographed with tetrahydrofuran. Thereupon pure title produce is obtained.
Following the procedure of Example 1, but employing respectively the title products of Preparations 3-7 in place of the starting material therein, there ar prepared:
9,11,15-Trideoxy-9α,11α-azo-cis-13-cis-4,5-didehydro-PGF 1 ;
9,11,15-trideoxy-9α,11α-azo-3,7-inter-m-phenylene-3-oxa-13,14-dihydro-17-phenyl-4,5,6,18,19,20-hexanor-PGF 1 ;
9,11,15-trideoxy-9α,11α-azo-cis-13-cis-4,5-didehydro-2-decarboxy-2-hydroxymethyl-PGF 1 ; and
9,11,15-Trideoxy-9α,11α-azo-cis-13-cis-4,5-didehydro-2-decarboxy-2-aminomethyl-PGF 1 .
Further, following the procedure of the above Examples, there are prepared methyl esters of the above 9,11,15-trideoxy-9α,11α-azo-PGF-type free acids by esterification with ethereal diazomethane. Further following the procedure of Example 1 15-deoxy-11β-PGF 1 β is transformed to 9,11,15-trideoxy-9α,11α-azo-PGF 1 .
Following the procedure of Example 1, but employing corresponding starting material as described above, there are prepared 9,11,15-trideoxy-9α,11α-azo-PGF 2 - or PGF 1 -type compounds, in free acid, ester, or amide form, or as corresponding 2-decarboxy-2-aminomethyl or 2-hydroxy- methyl derivatives, which exhibit the following side chain variations:
16-Methyl-;
16,16-Dimethyl-;
16-Fluoro-;
16,16-Difluoro-;
17-Phenyl-18,19,20-trinor-;
17-(m-trifluoromethylphenyl)-18,19,20-trinor-;
17-(m-chlorophenyl)-18,19,20-trinor-;
17-(p-fluorophenyl)-18,19,20-trinor-;
16-Methyl-b 17-phenyl-18,19,20-trinor-;
16,16-Dimethyl-17-phenyl-18,19,20-trinor-;
16-Fluoro-17-phenyl-18,19,20-trinor-;
16,16-Difluoro-17-phenyl-18,19,20-trinor-;
16-Phenoxy-17,18,19,20-tetranor-;
16-(m-trifluoromethylphenoxy)-17,18,19,20-tetranor-;
16-(m-chlorophenoxy)- 17,18,19,20-tetranor-;
16-(p-fluorophenoxy)-17,18,19,20-tetranor-;
16-Phenoxy-18,19,20-trinor-;
16-Methyl-16-phenoxy-18,19,20-trinor-;
13,14-Didehydro-; 16-Methyl-13,14-didehydro-;
16,16-Dimethyl-13,14-didehydro-;
16-Fluoro-13,14-didehydro-
16,16-Difluoro-13,14-didehydro-;
17-Phenyl-18,19,20-trinor-13,14-didehydro-;
17-(m-trifluoromethylphenyl)-18,19,20-trinor-13,14-didehydro-;
17-(m-chlorophenyl)-18,19,20-trinor-13,14-didehydro-;
17-(p-fluorophenyl)-18,19,20-trinor-13,14-didehydro-;
16-Methyl-17-phenyl-18,19,20-trinor-13,14-didehydro-;
16,16-Dimethyl-17-phenyl-18,19,20-trinor-13,14-didehydro-;
16-Fluoro-17-phenyl-18,19,20-trinor-13,14-didehydro-;
16,16-Difluoro-17-phenyl-18,19,20-trinor-13,14-didehydro-;
16-Phenoxy-17,18,19,20-tetranor-13,14-didehydro-;
16-(m-trifluoromethylphenoxy)-17,18,19,20-tetranor:13,14-didehydro-;
16-(m-chlorophenoxy)-17,18,19,20-tetranor-13,14-didehydro-;
16-Phenoxy-18,19,20-trinor-13,14-didehydro-;
16-Methyl-16-phenoxy-18,19,20-trinor-13,14-didehydeo-;
13,14-Dihydro-;
16-Methyl-13,14-dihydro-;
16,16-Dimethyl-13,14-dihydro-;
16-Fluoro-13,14-dihydro-;
16,16-Difluoro-13,14-dihydro-;
17-Phenyl-18,19,20-trinor-13,14-dihydro-;
17-(m-trifluoromethylphenyl)-18,19,20-trinor-13,14-dihydro-;
17 -(m-chlorophenyl)-18,19,20-trinor-13,14-dihydro-;
17-(p-fluorophenyl)-18,19,20-trinor-13,14-dihydro-;
16-Methyl-17-phenyl-18,19,20-trinor-13,14-dihydro-;
16,16-Dimethyl-17-phenyl-18,19,20-trinor-13,14-dihydro-;
16-Fluoro-17-phenyl-18,19,20-trinor-13,14-dihydro-;
16,16-Difluoro-17-phenyl-18,19,20-trinor-13,14-dihydro-;
16-Phenoxy-17,18,19,20-tetranor-13,14-dihydro-;
16-(m-trifluoromethylphenoxy)-17,18,19,20-tetranor-13,14-dihydro-;
16-(m-chlorophenoxy)-17,18,19,20-tetranor-13,14-dihydro-;
16-(p-fluorophenoxy)-17,18,19,20-tetranor-13,14-dihydro-;
16-Phenoxy-18,19,20-trinor-13,14-dihydro-;
16-Methyl-16-phenoxy-18,19,20-trinor-13,14-dihydro-;
2,2-Difluoro-;
2,2-Difluoro-16-methyl-;
2,2-Difluoro-16,16-dimethyl-;
2,2-Difluoro-16-fluoro-;
2,2-Difluoro-16,16-difluoro-;
2,2-Difluoro-17-phenyl-18,19,20-trinor-;
2,2-Difluoro-17-(m-trifluoromethylphenyl)-18,19,20-trinor-;
2,2-Difluoro-17-(m-chlorophenyl)-18,19,20-trinor-;
2,2-Difluoro-17-(p-fluorophenyl)-18,19,20-trinor-;
2,2-Difluoro-16-methyl-17-phenyl-18,19,20-trinor-;
2,2-Difluoro-16,16-dimethyl-17-phenyl-18,19,20-trinor-;
2,2-Difluoro-16-fluoro-17-phenyl-18,19,20-trinor-;
2,2-Difluoro-16,16-difluoro-17-phenyl-18,19,20-trinor-;
2,2-Difluoro-16-phenoxy-17,18,19,20-tetranor-;
2,2-Difluoro-16-(m-trifluoromethylphenoxy)-17,18,19,20-tetranor-;
2,2-Difluoro-16-(m-chlorophenoxy)-17,18,19,20-tetranor-;
2,2-Difluoro-16-(p-fluorophenoxy)-17,18,19,20-tetranor-;
2,2-Difluoro-16-phenoxy-18,19,20-trinor-;
2,2-Difluoro-16-methyl-16-phenoxy-18,19,20-trinor-;
2,2-Difluoro-16-methyl-16-phenoxy-18,19,20-trinor-;
2,2-Difluoro-16-methyl-13,14-didehydro-;
2,2-Difluoro-16,16-dimethyl-13,14-didehydro-;
2,2-Difluoro-16-fluoro-13,14-didehydro-;
2,2-Difluoro-16,16-difluoro-13,14-didehydro-;
2,2-Difluoro-17-phenyl-18,19,20-trinor-13,14-didehydro-;
2,2-Difluoro-17-(m-trifluoromethylphenyl)-18,19,20-trinor-13,14-didehydro-;
2,2-Difluoro-17-(m-chlorophenyl)-18,19,20-trinor-13,14-didehydro-;
2,2-Difluoro-17-(p-fluorophenyl)-18,19,20-trinor-13,14-didehydro-;
2,2-Difluoro-16-methyl-17-phenyl-18,19,20-trinor-13,14-didehydro-;
2,2-Difluoro-16,16-dimethyl-17-phenyl-18,19,20-trinor-13,14-didehydro-;
2,2,16-Trifluoro-17-phenyl-18,19,20-trinor-13,14-didehydro-;
2,2,16,16-Tetrafluoro-17-phenyl-18,19,20-trinor-13,14-didehydro-;
2,2-Difluoro-16-phenoxy-17,18,19,20-tetranor-13,14-didehydro-;
2,2-Difluoro-16-(m-trifluoromethylphenoxy)-17,18,19,20-tetranor-13,14-didehydro-;
2,2-Difluoro-16-(m-chlorophenoxy)-17,18,19,20-tetranor-13,14-didehydro-;
2,2-Difluoro-16-phenoxy-18,19,20-trinor-13,14-didehydro-;
2,2-Difluoro-16-methyl-16-phenoxy-18,19,20-trinor-13,14-didehydro-;
2,2-Difluoro-13,14-dihydro-;
2,2-Difluoro-16-methyl-13,14-dihydro-;
2,2-Difluoro-16,16-dimethyl-13,14-dihydro-;
2,2,16-Trifluoro-13,14-dihydro-;
2,2,16,16-Tetrafluoro-13,14-dihydro-;
2,2-Difluoro-17-phenyl-18,19,20-trinor-13,14-dihydro-;
2,2-Difluoro-17-(m-trifluoromethylphenyl)-18,19,20-trinor-13,14-dihydro-;
2,2-Difluoro-17-(m-chlorophenyl)-18,19,20-trinor-13,14-dihydro-;
2,2-Difluoro-17-(p-fluorophenyl)-18,19,20-trinor-13,14-dihydro-;
2,2-Difluoro-16-methyl-17-phenyl-18,19,20-trinor-13,14-dihydro-;
2,2-Difluoro-16,16-dimethyl-17-phenyl-18,19,20-trinor-13,14-dihydro-;
2,2,16-Trifluoro-17-phenyl-18,19,20-dihydro-;
2,2,16,16-Tetrafluoro-17-phenyl-18,19,20-trinor-13,14-dihydro-;
2,2-Difluoro-16-phenoxy-17,18,19,20-tetranor-13,14-dihydro-;
2,2-Difluoro-16-(m-trifluoromethylphenoxy)-17,18,19,20-tetranor-13,14-dihydro-;
2,2-Difluoro-16-(m-chlorophenoxy)-17,18,19,20-tetranor-13,14-dihydro-;
2,2-Difluoro-16-(p-fluorophenoxy)-17,18,19,20-tetrnor-13,14-dihydro-;
2,2-Difluoro-16-phenoxy-18,19,20-trinor-13,14-dihydro-;
2,2-Difluoro-16-methyl-16-phenoxy-18,19,20-trinor-13,14-dihydro-;
16-Methyl-cis-13;
16,16-Dimethyl-cis-13-;
16-Fluoro-cis-13-;
16,16-Difluoro-cis-13-;
17-Phenyl-18,19,20-trinor-cis-13-;
17-(m-trifluoromethylphenyl)-18,19,20-trinor-cis-13-;
17-(m-chlorophenyl)-18,19,20-trinor-cis-13-;
17-(p-fluorophenyl)-18,19,20-trinor-cis-13-;
16-Methyl-17-phenyl-18,19,20-trinor-cis-13-;
16,16-Dimethyl-17-phenyl-18,19,20-trinor-cis-13-;
16-Fluoro-17-phenyl-18,19,20-trinor-cis-13-;
16,16-Difluoro-17-phenyl-18,19,20-trinor-cis-13-;
16-Phenoxy-17,18,19,20-tetranor-cis-13-;
16-(m-trifluoromethylphenoxy)-17,18,19,20-tetranor-cis-13-;
16-(m-chlorophenoxy)-17,18,19,20-tetranor-cis-13-;
16-(p-fluorophenoxy)-17,18,19,20-tetranor-cis-13-;
16-Phenoxy-18,19,20-trinor-cis-13-;
16-Methyl-16-phenoxy-18,19,20-trinor-cis-13-;
13,14-Dihydro-trans-14,15-didehydro-;
16-Methyl-13,14-dihydro-trans-14,15-didehydro-;
16,16-Dimethyl-13,14-dihydro-trans-14,15-didehydro-;
16-Fluoro-13,14-dihydro-trans-14,15-didehydro-;
16,16-Difluoro-13,14-dihydro-trans-14,15-didehydro-;
17-Phenyl-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
17-(m-trifluoromethylphenyl)-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
17-(m-chlorophenyl)-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
17-(p-fluorophenyl)-18,19,20trinor-13,14-dihydro-trans-14,15-didehydro-;
16-Methyl-17-phenyl-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
16,16-Dimethyl-17-phenyl-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
16-Fluoro-17-phenyl-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
16,16-Difluoro-17-phenyl-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
16-Phenoxy-17,18,19,20-tetranor-13,14-dihydro-trans-14,15-didehydro-;
16-(m-trifluoromethylphenoxy)-17,18,19,20-tetranor-13,14-dihydro-trans-14,15-didehydro-;
16-(m-chlorophenoxy)-17,18,19,20-tetranor-13,14-dihydro-trans-14,15-didehydro-;
16-(p-fluorophenoxy)-17,18,19,20-tetranor-13,14-dihydro-trans-14,15-didehydro-;
16-Phenoxy-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
16-Methyl-16-phenoxy-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
2,2-Difluoro-cis-13-;
2,2-Difluoro-16-methyl-cis-13-;
2,2-Difluoro-16,16-dimethyl-cis-13-;
2,2-Difluoro-16-fluoro-cis-13-;
2,2-Difluoro-16,16-difluoro-cis-13-;
2,2-Difluoro-17-phenyl-18,19,20-trinor-cis-13-;
2,2-Difluoro-17-(m-trifluoromethylphenyl)-18,19,20-trinor-cis-13-;
2,2-Difluoro-17-(m-chlorophenyl)-18,19,20-trinor-cis-13-;
2,2-Difluoro-17-(p-fluorophenyl)-18,19,20-trinor-cis-13-;
2,2-Difluoro-16-methyl-17-phenyl-18,19,20-trinor-cis-13-;
2,2-Difluoro-16,16-dimethyl-17-phenyl-18,19,20-trinor-cis-13-;
2,2-Difluoro-16-fluoro-17-phenyl-18,19,20-trinor-cis-13-;
2,2-Difluoro-16,16-difluoro-17-phenyl-18,19,20-trinor-cis-13-;
2,2-Difluoro-16-phenoxy-17,18,19,20-tetranor-cis-13-;
2,2-Difluoro-16-(m-trifluoromethylphenoxy)-17,18,19,20-tetranor-cis-13-;
2,2-Difluoro-16-(m-chlorophenoxy)-17,18,19,20-tetranor-cis-13-;
2,2-Difluoro-16-(p-fluorophenoxy)-17,18,19,20-tetranor-cis-13-;
2,2-Difluoro-16-phenoxy-18,19,20-trinor-cis-13-;
2,2-Difluoro-16-methyl-16-phenoxy-18,19,20-trinor-cis-13-;
2,2-Difluoro-16-methyl-16-phenoxy-18,19,20-trinor-cis-13-;
2,2-Difluoro-13,14-dihydro-trans-14,15-didehydro-;
2,2-Difluoro-16-methyl-13,14-dihydro-trans-14,15-didehydro-;
2,2-Difluoro-16,16-dimethyl-13,14-dihydro-trans-14,15-didehydro-;
2,2,16-Trifluoro-13,14-dihydro-trans-14,15-didehydro-;
2,2,16,16-Tetrafluoro-13,14-dihydro-trans-14,15-didehydro-;
2,2-Difluoro-17-phenyl-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-
2,2-Difluoro-17-(m-trifluoromethylphenyl)-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
2,2-difluoro-17-(m-chlorophenyl)-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
2,2-Difluoro-17-(p-fluorophenyl)-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
2,2-Difluoro-16-methyl-17-phenyl-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
2,2-Difluoro-16,16-dimethyl-17-phenyl-18,19,20-trinor- 13,14-dihydro-trans-14,15-didehydro-;
2,2,16-Trifluoro-17-phenyl-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
2,2,16,16-Tetrafluoro-17-phenyl-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
2,2-Difluoro-16-phenoxy-17,18,19,20-tetranor-13,14-dihydro-trans-14,15-didehydro-;
2,2-Difluoro-16-(m-trifluoromethylphenoxy)-17,18,19,20-tetranor-13,14-dihydro-trans-14,15-didehydro-;
2,2-Difluoro-16-(m-chlorophenoxy)-17,18,19,20-tetranor-13,14-dihydro-trans-14,15-didehydro-;
2,2-Difluoro-16-(p-fluorophenoxy)-17,18,19,20-tetranor-13,14-dihydro-trans-14,15-didehydro-;
2,2-Difluoro-16-phenoxy-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
2,2-Difluoro-16-methyl-16- phenoxy-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
Following the procedure of Example 1, but employing corresponding starting material as described above there are prepared 9,11,15-trideoxy-9α,11α-epoxymethano- or 11α,9α-epoxymethano-PGF 1 -type compounds, in free acid or methyl ester form or as 2-decarboxy-2-aminomethyl or 2-hydroxymethyl derivatives, which exhibit the following functional characteristics:
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-16-methyl-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-16,16-dimethyl-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-16-fluoro-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-16,16-difluoro-;
3,7-Inter-m-phenylene-3-oxa- 17-phenyl-4,5,6,18,19,20-hexanor-;
3,7-Inter-m-phenylene-3-oxa-17-(m-trifluoromethylphenyl)-4,5,18,19,20-hexanor;
3,7-Inter-m-phenylene-3-oxa-17-(m-chlorophenyl)-4,5,6,18,19,20-hexanor;
3,7-Inter-m-phenylene-3-oxa-17-(p-fluorophenyl)-4,5,6,18,19,20-hexanor-;
3,7-Inter-m-phenylene-3-oxa-16-methyl-17-phenyl-4,5,6,18,19,20-hexanor-;
3,7-Inter-m-phenylene-3-oxa-16,16-dimethyl-17-phenyl-4,5,6,18,19,20-hexanor;
3,7-Inter-m-phenylene-3-oxa-16-fluoro-17-phenyl4,5,6,18,19,20-hexanor;
3,7-Inter-m-phenylene-3-oxa-16,16-difluoro-17-phenyl-4,5,6,18,19,20-hexanor-;
3,7-Inter-m-phenylene-3-oxa-16-phenoxy-4,5,6,17,18,19,20-heptanor-;
3,7-Inter-m-phenylene-3-oxa-16-(m-trifluoromethylphenoxy)-4,5,6,17,18,19,20-heptanor-;
3,7-Inter-m-phenylene-3-oxa-16-(m-chlorophenoxy)-4,5,6,17,18,19,20-heptanor-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-16-(p-fluorophenoxy)-4,5,6,17,18,19,20-heptanor-;
3,7-Inter-m-phenylene-3-oxa-16-phenoxy-4,5,6,18,19,20-hexanor-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-16-methyl-16-phenoxy-4,5,6,18,19,20-hexanor-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-13,14-didehydro-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-16-methyl-13,14-didehydro-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-16,16-dimethyl-13,14-didehydro-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-16-fluoro-13,14-didehydro-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-16,16-difluoro-13,14-didehydro-;
3,7-Inter-m-phenylene-3-oxa-17-phenyl-4,5,6,18,19,20-hexanor-13,14-didehydro-;
3,7-Inter-m-phenylene-3-oxa-17-(m-trifluoromethylphenyl)-4,5,6,18,19,20-hexanor-13,14-didehydro-;
3,7-Inter-m-phenylene-3-oxa-17-(m-chlorophenyl)-4,5,6,18,19,20-hexanor-13,14-didehydro-;
3,7-Inter-m-phenylene-3-oxa-17-(p-fluorophenyl)4,5,6,18,19,20-hexanor-13,14-didehydro-;
3,7-Inter-m-phenylene-3-oxa-16-methyl-17-phenyl-4,5,6,18,19,20-hexanor-13,14-didehydro-;
3,7-Inter-m-phenylene-3-oxa-16,16-dimethyl-17-phenyl-4,5,6,18,19,20-hexanor-13,14-didehydro-;
3,7-Inter-m-phenylene-3-oxa-16-fluoro-17-phenyl-4,5,6,18,19,20-hexanor-13,14-didehydro-;
3,7-Inter-m-phenylene-3-oxa-16,16-difluoro-17-phenyl-4,5,6,18,19,20-hexanor-13,14-didehydro-;
3,7-Inter-m-phenylene-3-oxa-16-phenoxy-4,5,6,17,18,19,20-heptanor-13,14-didehydro-;
3,7-Inter-m-phenylene-3-oxa-16-(m-trifluoromethylphenoxy)-4,5,6,17,18,19,20-heptanor-13,14-didehydro-;
3,7-Inter-m-phenylene-3-oxa-16-(m-chlorophenoxy)-4,5,6,17,18,19,20-heptanor-13,14-didehydro-;
3,7-Inter-m-phenylene-3-oxa-16-phenoxy-4,5,6,18,19,20-hexanor-13,14-didehydro-;
3,7-Inter-m-phenylene-3-oxa-16-methyl-16-phenoxy-4,5,6,18,19,20-hexanor-13,14-didehydro-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-13,14-dihydro-;
3,7-Inter-m-phenylene-3-oxa- 4,5,6-trinor-16-16-methyl-13,14-dihydro-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-16,16-dimethyl-13,14-dihydro-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-16-fluoro-13,14-dihydro-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-16,16 -difluoro-13, 14-dihydro:;
3,7-Inter-m-phenylene-3-oxa-17-phenyl-4,5,6,18,19,20-trinor-13,14-dihydro:;
3,7-Inter-m-phenylene-3-oxa-17-(m-trifluoromethyl-phenyl)-4,5,6,18,19,20hexanor-13,14-dihydro-;
3,7-Inter-m-phenylene-3-oxa-17-(m-chlorophenyl)-4,5,6,18,19,20-hexanor-13,14-dihydro-;
3,7-Inter-m-phenylene-3-oxa-17-(p-fluorophenyl)-4,5,6,18,19,20-hexanor-13,14-dihydro-;
3,7-Inter-m-phenylene-3-oxa-16-methyl-17-phenyl-4,5,6,18,19,20-hexanor-13,14-dihydro-;
3,7-Inter-m-phenylene-3-oxa-16,16-dimethyl-17-phenyl-4,5,6,18,19,20-hexanor-13,14-dihydro-;
3,7-Inter-m-phenylene-3-oxa-16-fluoro-17-phenyl-4,5,6,18,19,20-hexanor-13,14-dihydro-;
3,7-Inter-m-phenylene-3-oxa-16,16-difluoro-17-phenyl-4,5,6,18,19,20-hexanor-13,14-dihydro-;
3,7-Inter-m-phenylene-3-oxo-16-phenoxy-4,5,6,17,18,19,20 -heptanor-13,14-dihydro-;
3,7-Inter-m-phenylene-3-oxa-16-(m-trifluoromethylphenoxy)-4,5,6,17,18,19,20-heptanor-13,14-dihydro-;
3,7-Inter-m-phenylene-3-oxa-16-(m-chlorophenoxy)-4,5,6,17,18.19.20-heptanor-13,14-dihydro-;
3,7-Inter-m-phenylene-3-oxa-16-(p-fluorophenoxy)-4,5,6,17,18,19,20-heptanor-13,14-dihydro-;
3,7-Inter-m-phenylene-3-oxa-16-16-phenoxy-4,5,6,18,19,20-hexanor-13,14-dihydro-;
3,7-Inter-m-phenylene-3-oxa-16-methyl-16-phenoxy-4,5,6,18,19,20-hexanor-13,14-dihydro-;
3,7-Inter-m-phenylene-4,5,6-trinor-;
3,7-Inter-m-phenylene-4,5,6-trinor-16-methyl-;
3,7-Inter-m-phenylene-4,5,6-trinor-16,16-dimethyl-;
3,7-Inter-m-phenylene-4,5,6-trinor-16-fluoro-;
3,7-Inter-m-phenylene-4,5,6-trinor-16,16-difluoro-;
3,7-Inter-m-phenylene-17-phenyl-4,5,6,18,19,20-hexanor-;
3,7-Inter-m-phenylene-17-(m-trifluoromethylphenyl)-4,5,6,18,19,20-hexanor-;
3,7-Inter-m-phenylene-17-(m-chlorophenyl)-4,5,6,18,19,20-hexanor:;
3,7-Inter-m-phenylene-17-(p-fluorophenyl)-4,5,6,18,19,20-hexanor-;
3,7-Inter-m-phenylene-16-methyl-17-phenyl-4,5,6,18,19,20-hexanor-;
3,7-Inter-m-phenylene-16,16-dimethyl-17-phenyl-4,5,6,18,19,20-hexanor-;
3,7-Inter-m-phenylene-16-fluoro-17-phenyl-4,5,6,18,19,20-hexanor-;
3,7-Inter-m-phenylene-16,16-difluoro-17-phenyl-4,5,6,18,19,20-hexanor-;
3,7-Inter-m-phenylene-16-phenoxy-17-phenyl-4,5,6,17,18,19,20-heptanor:;
3,7-Inter-m-phenylene-16-(m-trifluoromethylphenoxy)-4,5,6,17,18,19,20-heptanor:;
3,7-Inter-m-phenylene-16-(m-chlorophenoxy)-4,5,6,17,18,19,20-heptanor-;
3,7-Inter-m-phenylene-16-(p-fluorophenoxy)-4,5,6,17,18,19,20-heptanor:;
3,7-Inter-m-phenylene-16-phenoxy-4,5,6,18,19,20-hexanor:;
3,7-Inter-m-phenylene-16-methyl-16-phenoxy-4,5,6,18,19,20-hexanor-;
3,7-Inter-m-phenylene-4,5,6-trinor-13,14-didehydro-;
3,7-Inter-m-phenylene-4,5,6-trinor-16-methyl-13,14-didehydro-;
3,7-Inter-m-phenylene-4,5,6-trinor-16,16-dimethyl-13,14-didehydro-;
3,7-Inter-m-phenylene-4,5,6-trinor-16-fluoro-13,14-didehydro:;
3,7-Inter-m-phenylene-4,5,6-trinor-16,16-difluoro-13,14-didehydro-;
3,7-Inter-m-phenylene-17-phenyl-4,5,6,18,19,20-hexanor-14didehydro-;
3,7-Inter-m-phenylene-17-(m-trifluoromethylphenyl)-4,5,6,18,19,20-hexanor-13,14-didehydro-;
3,7-Inter-m-phenylene-17-(m-chlorophenyl)-4,5,6,18,19,20-hexanor-13,14-didehydro-;
3,7-Inter-m-phenylene-17-(p-fluorophenyl)-4,5,6,18,19,20-hexanor-13,14-didehydro-;
3,7-Inter-m-phenylene-16-methyl-17-phenyl-4,5,6,18,19,20-hexanor-13,14-didehydro-;
3,7-Inter-m-phenylene-16,16-dimethyl-17-phenyl-4,5,6,18,19,20-hexanor-13,14-didehydro-;
3,7-Inter-m-phenylene-16-fluoro-17-phenyl-4,5,6,18,19,20-hexanor-13,14-didehydro-;
3,7-Inter-m-phenylene-16,16-difluoro-17-phenyl-4,5,6,18,19,20-hexanor-13,14-didehydro-;
3,7-Inter-m-phenylene-16-phenoxy-4,5,6,17,18,19,20-heptanor-13,14-didehydro-;
3,7-Inter-m-phenylene-16-(m-trifluoromethylphenoxy)- 4,5,6,17,18,19,20-heptanor-13,14-didehydro-;
3,7-Inter-m-phenylene-16-(m-chlorophenoxy)-4,5,6,17,18,19,20-heptanor-13,14-didehydro-;
3,7-Inter-m-phenylene-16-phenoxy-4,5,6,18,19,20-hexanor-13,14-didehydro-;
3,7-Inter-m-phenylene-16-methyl-16-phenoxy-4,5,6,18,19,20-hexanor-13,14-didehydro-;
3,7-Inter-m-phenylene-4,5,6-trinor-13,14-didehydro-;
3,7-Inter-m-phenylene-4,5,6-trinor-16-methyl-13,14-dihydro-;
3,7-Inter-m-phenylene-4,5,6-trinor-16,16-dimethyl-13,14-dihydro-;
3,7-Inter-m-phenylene-4,5,6-trinor-16-fluoro-13,14-dihydro-;
3,7-Inter-m-phenylene-4,5,6-trinor-16,16-difluoro-13,14-dihydro-;
3,7-Inter-m-phenylene-17-phenyl-4,5,6,18,19,20-hexanor-13,14-dihydro-;
3,7-Inter-m-pheneylene-17-(m-trifluoromethylphenyl)-4,5,6,18,19,20-hexanor-13,14-dihydro-;
3,7-Inter-m-phenylene-17-(m-chlorophenyl)-4,5,6,18,19,20-hexanor-13,14-dihydro-;
3,7-Inter-m-phenylene-17-(p-fluorophenyl)- 4,5,6,18,19,20-hexanor-13,14-dihydro-;
3,7-Inter-m-phenylene-16-methyl-17-phenyl-4,5,6,18,19,20 -hexanor-13,14-dihydro-;
3,7-Inter-m-phenylene-16,16-dimethyl-17-phenyl-4,5,6,18,19,20-hexanor-13,14-dihydro-;
3,7-Inter-m-phenylene-16-fluoro-17-phenyl-4,5,6,18,19,20-hexanor-13,14-dihydro-;
3,7-Inter-m-phenylene-16,16-difluoro-17-phenyl-4,5,6,18,19,20-hexanor-13,14-dihydro-;
3,7-Inter-m-phenylene-16-phenoxy-4,5,6,17,18,19,20-heptanor-13,14-dihydro-;
3,7-Inter-m-phenylene-16-(m-trifluoromethylphenoxy)-4,5,6,17,18,19,20-heptanor-13,14-dihydro-;
3,7-Inter-m-phenylene-16-(m-chlorophenoxy)-4,5,6,17,18,19,20-heptanor-13,14-dihydro-;
3,7-Inter-m-phenylene-16-(p-fluorophenoxy)-4,5,6,17,18,19,20-heptanor-13,14-dihydro-;
3,7-Inter-m-phenylene-16-phenoxy-4,5,6,18,19,20-hexanor-13,14-dihydro-;
3,7-Inter-m-phenylene-16-methyl-16-phenoxy-4,5,6,18,19,20-hexanor-13,14-dihydro-;
5-Oxa-;
5-Oxa-16-methyl-;
5-Oxa-16,16-dimethyl-;
5-Oxa-16-fluoro-;
5-Oxa-16,16-difluoro-;
5-Oxa-17-phenyl-18,19,20-trinor-;
5-Oxa-17-(m-trifluoromethylphenyl)-18,19,20-trinor-;
5-Oxa-17-(m-chlorophenyl)-18,19,20-trinor-;
5-Oxa-17-(p-fluorophenyl)-18,19,20-trinor-;
5-Oxa-16-methyl-17-phenyl-18,19,20-trinor-;
5-Oxa-16,16-dimethyl-17-phenyl-18,19,20-trinor-;
5-Oxa-16-fluoro-17-phenyl-18,19,20-trinor-;
5-Oxa-16,16-difluoro-17-phenyl-18,19,20-trinor-;
5-Oxa-16-phenoxy-17,18,19,20-tetranor-;
5-Oxa-(m-trifluoromethylphenoxy)-17,18,19,20-tetranor-;
5-Oxa-16-(m-chlorophenoxy)-17,18,19,20-tetranor-;
5-Oxa-16-(p-fluorophenoxy)-17,18,19,20-tetranor-;
5-Oxa-16-phenoxy-18,19,20-trinor-;
5-Oxa-16-methyl-16-phenoxy-18,19,20-trinor-;
5-Oxa-13,14-didehydro-;
5-Oxa-16-methyl-13,14-didehydro-;
5-Oxa-16,16-dimethyl-13,14-didehydro-;
5-Oxa-16-fluoro-13,14-didehydro-;
5-Oxa-16,16-difluoro-13,14-didehydro-;
5-Oxa-17-phenyl-18,19,20-trinor-13,14-didehydro-;
5-Oxa-17-(m-trifluoromethylphenyl)-18,19,20-trinor-13,14-didehydro-;
5-Oxa-17-(m-chlorophenyl)-18,19,20-trinor-13,14-didehydro-;
5-Oxa-17-(p-fluorophenyl)-18,19,20-trinor-13,14-didehydro-;
5-Oxa-16-methyl-17-phenyl-18,19,20-trinor-13,14-didehydro-;
5-Oxa-16,16-dimethyl-17-phenyl-18,19,20-trinor-13,14-didehydro-;
5-Oxa-16-fluoro-17-phenyl-18,19,20-trinor-13,14-didehydro-;
5-Oxa-16,16-difluoro-17-phenyl-18,19,20-trinor-13,14-didehydro-;
5-Oxa-16-phenoxy-17,18,19,20-tetranor-13,14-didehydro-;
5-Oxa-16-(m-trifluoromethylphenoxy)-17,18,19,20-tetranor-13,14-didehydro-;
5-Oxa-16-(m-chlorophenoxy)-17,18,19,20-tetranor-13,14-didehydro-;
5-Oxa-16-phenoxy-18,19,20-trinor-13,14-didehydro-;
5-Oxa-16-methyl-16-phenoxy-18,19,20-trinor-13,14-didehydro-;
5-Oxa-13,14-dihydro-;
5-Oxa-16-methyl-13,14-dihydro-;
5-Oxa-16,16-dimethyl-13,14-dihydro-;
5-Oxa-16-fluoro-13,14-dihydro-;
5-Oxa-16,16-difluoro-13,14-dihydro-;
5-Oxa-17-phenyl-18,19,20-trinor-13,14-dihydro-;
5-Oxa-17-(m-trifluoromethylphenyl)-18,19,20-trinor-13,14-dihydro-;
5-Oxa-17-(m-chlorophenyl)-18,19,20-trinor-13,14-dihydro-;
5-Oxa-17-(p-fluorophenyl)-18,19,20-trinor-13,14-dihydro-;
5-Oxa-16-methyl-17-phenyl-18,19,20-trinor-13,14-dihydro-;
5-Oxa-16,16-Dimethyl-17-phenyl-18,19,20-trinor-13,14-dihydro-;
5-Oxa-16-fluoro-17-phenyl-18,19,20-trinor-13,14-dihydro-;
5-Oxa-16,16-difluoro-17-phenyl-18,19,20-trinor-13,14-dihydro-;
5-Oxa-16-phenoxy-17,18,19,20-tetranor-13,14-dihydro-;
5-Oxa-16-(m-trifluoromethylphenoxy)-17,18,19,20-tetranor-13,14-dihydro-;
5-Oxa-16-(m-chlorophenoxy)-17,18,19,20-tetranor-13,14-dihydro-;
5-Oxa-16-(p-fluorophenoxy)-17,18,19,20-tetranor-13,14-dihydro-;
5-Oxa-16-phenoxy-18,19,20-trinor-13,14-dihydro-;
5-Oxa-16-methyl-16-phenoxy-18,19,20-trinor-13,14-dihydro-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-cis-13-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-16-methyl-cis-13-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-16,16-dimethyl-cis-13-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-16-fluoro-cis-13-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-16,16-difluoro-cis-13-;
3,7-Inter-m-phenylene-3-oxa-17-phenyl-4,5,6,18,19,20-hexanor-cis-13-;
3,7-Inter-m-phenylene-3-oxa-17-(m-trifluoromethylphenyl)-4,5,6,18,19,20-hexanor-cis-13-;
3,7-Inter-m-phenylene-3-oxa-17-(m-chlorophenyl)-4,5,6,18,19,20-hexanor-cis-13-;
3,7-Inter-m-phenylene-3-oxa-17-(p-fluorophenyl)-4,5,6,18,19,20-hexanor-cis-13-;
3,7-Inter-m-phenylene-3-oxa-16-methyl-17-phenyl-4,5,6,18,19,20-hexanor-cis-13-;
3,7-Inter-m-phenylene-3-oxa-16,16-dimethyl-17-phenyl-4,5,6,18,19,20-hexanor-cis-13-;
3,7-Inter-m-phenylene-3-oxa-16-fluoro-17-phenyl-4,5,6,18,19,20-hexanor-cis-13-;
3,7-Inter-m-phenylene-3-oxa-16,16-difluoro-17-phenyl-4,5,6,18,19,20-hexanor-cis-13-;
3,7-Inter-m-phenylene-3-oxa-16-phenoxy- 4,5,6,17,18,19,20-heptanor-cis-13-;
3,7-Inter-m-phenylene-3-oxa-16-(m-trifluromethyl-phenoxy)-4,5,6,17,18,19,20-heptanor-cis-13-;
3,7-Inter-m-phenylene-3-oxa-16-(m-chlorophenoxy)-4,5,6,17,18,19,20-heptanor-cis-13-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-16-(p-fluorophenoxy)-4,5,6,17,18,19,20-heptanor-cis-13-;
3,7-Inter-m-phenylene-3-oxa-16-phenoxy-4,5,6,18,19,20-hexanor-cis-13-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-16-methyl-16-phenoxy-4,5,6,18,19,20-hexanor-cis-13-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-16-methyl-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-16,16-dimethyl-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-16-fluoro-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-3-oxa-4,5,6-trinor-16,16-difluoro-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-3-oxa-17-phenyl-4,5,6,18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-3-oxa-17-(m-trifluoromethylphenyl)-4,5,6,18,19,20-hexanor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-3-oxa-17-(m-chlorophenyl)-4,5,6,18,19,20-hexanor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-3-oxa-17-(p-fluorophenyl)-4,5,6,18,19,20-hexanor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-3-oxa-16-methyl-17-phenyl-4,5,6,18,19,20-hexanor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-3-oxa-16,16-dimethyl-17-phenyl-4,5,6,18,19,20-hexanor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-3-oxa-16-fluoro-17-phenyl-4,5,6,18,19,20-hexanor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-3-oxa-16,16-difluoro-17-phenyl-4,5,6,18,19,20-hexanor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-3-oxa-16-phenoxy-4,5,6,17,18,19,20-heptanor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-3-oxa-16-(m-trifluoromethylphenoxy)-4,5,6,17,18,19,20-heptanor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-3-oxa-16-(m-chlorophenoxy)-4,5,6,17,18,19,20-heptanor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-3-oxa-16-(p-fluorophenoxy)-4,5,6,17,18,19,20-heptanor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-3-oxa-16-phenoxy-4,5,6,18,19,20-hexanor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-3-oxa-16-methyl-16-phenoxy-4,5,6,18,19,20-hexanor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-4,5,6-trinor-cis-13-;
3,7-Inter-m-phenylene-4,5,6-trinor-16-methyl-cis-13-;
3,7-Inter-m-phenylene-4,5,6-trinor-16,16-dimethyl-cis-13-;
3,7-Inter-m-phenylene-4,5,6-trinor-16-fluoro-cis-13-;
3,7-Inter-m-phenylene-4,5,6-trinor-16,16-difluoro-cis-13-;
3,7-Inter-m-phenylene-17-phenyl-4,5,6,18,19,20-hexanor-cis-13-;
3,7-Inter-m-phenylene-17-(m-trifluoromethylphenyl)-4,5,6,18,19,20-hexanor-cis-13-;
3,7-Inter-m-phenylene-17-(m-chlorophenyl)-4,5,6,18,19,20-hexanor-cis-13-;
3,7-Inter-m-phenylene-17-(p-fluorophenyl)-4,5,6,18,19,20-hexanor-cis-13-;
3,7-Inter-m-phenylene-16-methyl-17-phenyl-4,5,6,18,19,20-hexanor-cis-13-;
3,7-Inter-m-phenylene-16,16-dimethyl-17-phenyl-4,5,6,18,19,20-hexanor-cis-13-;
3,7-Inter-m-phenylene-16-fluoro-17-phenyl-4,5,6,18,19,20-hexanor-cis-13-;
3,7-Inter-m-phenylene-16,16-difluoro-17-phenyl-4,5,6,18,19,20-hexanor-cis-13-;
3,7-Inter-m-phenylene-16-phenoxy-17-phenyl-4,5,6,18,19,20-heptanor-cis-13-;
3,7-Inter-m-phenylene-16-(m-trifluoromethylphenoxy)-4,5,6,17,18,19,20-heptanor-cis-13-;
3,7-Inter-m-phenylene-16-(m-chlorophenoxy)-4,5,6,17,18,19,20-heptanor-cis-13-;
3,7-Inter-m-phenylene-16-(p-fluorophenoxy)-4,5,6,17,18,19,20-heptanor-cis-13-;
3,7-Inter-m-phenylene-16-phenoxy-4,5,6,18,19,20-hexanor-cis-13-;
3,7-Inter-m-phenylene-16-methyl-16-phenoxy-4,5,6,18,19,20-hexanor-cis-13-;
3,7-Inter-m-phenylene-4,5,6-trinor-16-methyl-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-4,5,6-trinor-16,16-dimethyl-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-4,5,6-trinor-16-fluoro-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-4,5,6-trinor-16,16-difluoro-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-17-phenyl-4,5,6,18,19,20-hexanor-13,14-dihydro-trans-14,15-didehydro:;
3,7-Inter-m-phenylene-17-(m-trifluoromethylphenyl)-4,5,6,18,19,20-hexanor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-17-(m-chlorophenyl)-4,5,6,18,19,20-hexanor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-17-(p-fluorophenyl)-4,5,6,18,19,20-hexanor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-16-methyl-17-phenyl-4,5,6,18,19,20-hexanor-13,14-didehydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-16,16-dimethyl-17-phenyl-4,5,6,18,19,20-hexanor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-16-fluoro-17-phenyl-4,5,6,18,19,20-hexanor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-16,16-difluoro-17-phenyl-4,5,6,18,19,20-hexanor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-16-phenoxy-4,5,6,17,18,19,20-heptanor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-16-(m-trifluoromethylphenoxy)-4,5,6,17,18,19,20-heptanor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-16-(m-chlorophenoxy)-4,5,6,17,18,19,20-heptanor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-16-(p-fluorophenoxy)-4,5,6,17,18,19,20-heptanor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-16-phenoxy-4,5,6,18,19,20-hexanor-13,14-dihydro-trans-14,15-didehydro-;
3,7-Inter-m-phenylene-16-methyl-16-phenoxy-4,5,6,18,19,20-hexanor-13,14-dihydro-trans-14,15-didehydro;
5-Oxa-cis-13-;
5-Oxa-16-methyl-cis-13-;
5-Oxa-16,16-dimethyl-cis-13-;
5-Oxa-16-fluoro-cis-13-;
5-Oxa-16,16-difluoro-cis-13-;
5-Oxa-17-phenyl-18,19,20-trinor-cis-13-;
5-Oxa-17-(m-trifluoromethylphenyl)-18,19,20-trinor-cis-13-;
5-Oxa-17-(m-chlorophenyl)-18,19,20-trinor-cis-13-;
5-Oxa-17-(p-fluorophenyl)-18,19,20-trinor-cis-13-;
5-Oxa-16-methyl-17-phenyl-18,19,20-trinor-cis-13-;
5-Oxa-16,16-dimethyl-17-phenyl-18,19,20-trinor-cis-13-;
5-Oxa-16-fluoro-17-phenyl-18,19,20-trinor-cis-13-;
5-Oxa-16,16-difluoro-17-phenyl-18,19,20-trinor-cis-13-;
5-Oxa-16-phenoxy-17,18,19,20-tetranor-cis-13-;
5-Oxa-16-(m-trifluoromethylphenoxy)-17,18,19,20-tetranor-cis-13-;
5-Oxa-16-(m-chlorophenoxy)-17,18,19,20-tetranor-cis-13-;
5-Oxa-(p-fluorophenoxy)-17,18,19,20-tetranor-cis-13-;
5-Oxa-16-phenoxy-18,19,20-trinor-cis-13-;
5-Oxa-16-methyl-16-phenoxy-18,19,20-trinor-cis-13-;
5-Oxa-13,14-dihydro-trans-14,15-didehydro-;
5-Oxa-16-methyl-13,14-dihydro-trans-14,15-didehydro-;
5-Oxa-16,16-dimethyl-13,14-dihydro-trans-14,15-didehydro-;
5-Oxa-16-fluoro-13,14-dihydro-trans-14,15-didehydro;
5-Oxa-16,16-difluoro-13,14-dihydro-trans-14,15-didehydro-;
5-Oxa-17-phenyl-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
5-Oxa-17-(m-trifluoromethylphenyl)-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
5-Oxa-17-(m-chlorophenyl)-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
5-Oxa-17-(p-fluorophenyl)-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
5-Oxa-16-methyl-17-phenyl-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
5-Oxa-16,16-Dimethyl-17-phenyl-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro;
5-Oxa-16-fluoro-17-phenyl-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
5-Oxa-16,16-difluoro-17-phenyl-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
5-Oxa-16-phenoxy-17,18,19,20-tetranor-13,14-dihydro-trans-14,15-didehydro-;
5-Oxa-16-(m-trifluoromethylphenoxy)-17,18,19,20-tetranor-13,14-dihydro-trans-14,15-dihydro-;
5-Oxa-16-(m-chlorophenoxy)-17,18,19,20-tetranor-13,14-dihydro-trans-14,15-didehydro-;
5-Oxa-16-(p-fluorophenoxy)-17,18,19,20-tetranor-13,14-dihydro-trans-14,15-didehydro-;
5-Oxa-16-phenoxy-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-;
5-Oxa-16-methyl-16-phenoxy-18,19,20-trinor-13,14-dihydro-trans-14,15-didehydro-.
EXAMPLE 6
9α,11α-Methylhydrazine-9,11,15-trideoxy-PGE 2 , methyl ester (Formula IV: W 1 is ##STR51##
X 1 is --COOCH 3 , and Z 1 , Y 1 ' and R 7 are as defined above) and its 11α,9α-methylhydrazino isomer.
Refer to Chart H.
Following the procedure of Example 1, parts A, B, C, and D, but employing methylhydrazine in place of hydrazine in part D, there are obtained the mixture of title products. Chromatographing on silica gel yields isomerically pure title products.
Alternatively, the reaction product of part D of Example 1 is diluted in methanol and thereafter treated with a single stoichiometric equivalent of methyl iodide. The reaction mixture is then heated to reflux for about 6 hr. and when reaction is shown to be complete by silica gel TLC, diluted with ammonium hydroxide to pH 12. Title product is then obtained from the resulting reaction mixture by extraction with ethyl acetate, washing the extracts, and concentrating to yield pure isomerically mixed title products. Chromatographing on silica gel yields each pure isomeric title product.
Following the procedure described above but employing greater than 2 equivalents of methyl iodide, there is obtained N,N'-dimethyl-9α,11α-hydrazino-9,11,15-trideoxy-PGF 2 , methyl ester.
EXAMPLE 7
9α,11α-(Acetyl)hydrazino-9,11,15-trideoxy-PGF 2 , methyl ester (Formula IV: W 1 is ##STR52##
X 1 is --COOCH 3 , and Y 1 , L 1 , Z 1 , and R 7 are as defined in Example 1) and its 11α,9α-isomer.
Refer to Chart H.
9α,11α-hydrazine-9,11,15-trideoxy-PGF 2 , methyl ester (the methyl ester of Example 1, part D) in pyridine is treated with one equivalent of acetic anhydride at 10° C. for several days. When thin layer chromatographic analysis indicates monoacetylation to be complete, pure title product is covered by conventional separation and purification techniques as an epimeric mixture. Silica gel chromatography yields pure 9α,11α-(acetyl)hydrazino- and 11α,9α-(acetyl)hydrazino-isomers.
Further following the procedure of Example 7 but employing a substantial excess of acetic anhydride, there is prepared N,N'-bis(acetyl)-9α,11α-hydrazino-9,11,15-trideoxy-PGF 2 , methyl ester.
EXAMPLE 8
11α,9α-epoxyimino-9,11,15-trideoxy-PGF 2 , methyl ester (Formula IV: W 1 is ##STR53##
X 1 is --COOCH 3 , and Z 1 , Y 1 , L 1 , and R 7 are as defined in Example 1) and the corresponding free acid.
Refer to Chart J.
A. A solution of 1.0 g. of 15-deoxy-11β-PGF 2 β, methyl ester is 30 ml. of dry pyridine is cooled in an ice bath under a nitrogen atmosphere. Thereafter 0.8 g. of p-toluenesulfonyl chloride is added in one portion. After the solution become homogeneous, the resulting mixture is then allowed at 0° C. for several days. Thereafter the resulting solution is poured into 200 ml. of ice cold brine and 125 ml. of 2 N aqueous sodium bisulfate. The resulting mixture is then extracted twice with ethyl acetate in hexane (1:1) the combined organic extracts are then washed successively with brine, 2 N aqueous sodium bisulfate, and brine; dried over sodium sulfate; and concentrated to an oil. The resulting crude 15-deoxy-11β-PGF 2 β, 9-(p-toluenesulfonate), methyl ester, a CXXII compound, is chromatographed on silica gel, packed with ethyl acetate and hexane (1:4) and eluted with 20 to 30% ethyl acetate in hexane to yield 1.3 g. of pure title product. Silica gel TLC Rf is 0.38 in ethyl acetate and hexane (3:7). Infrared absorptions are observed at 3550, 2920, 2860, 1730, 1600, 1495, 1430, 1350, 1180, 1170, 1090, 1020, 970, 925, 860, 815, and 760 c -1 .
B. A solution of 0.70 g. of the reaction product of part A in 70 ml. of tetrahydrofuran under a nitrogen atmosphere at ambient temperature is treated with 0.43 g. of triphenylphosphine, 0.27 g. of N-hydroxyphthalimide, and 0.29 g. of diethylazodicarboxylate. After 15min. the resulting mixture is then concentrated to an oil and chromatographed on 300 g. of silica gel packed and eluted with diethyl ether in benzene (1:19), yielding 0.42 g. of pure 15-deoxy-PGF 2 β, methyl ester, 9-(p-toluenesulfonate), 11-phthalimide. Silica gel TLC Rf is 0.37 in diethyl ether and benzene (1:9). Infrared absorptions are observed at 2950, 2870, 1790, 1730, 1600, 1495, 1460, 1430, 1350, 1185, 1170, 1090, 1080, 970, 875, 815, 785, 755, 700 cm -1 . NMR absorptions are observed at 7.8, 7.35, 5.30, 4.70, 3.65, and 2.45 δ.
C. A solution of 0.40 g. of the reaction product of part B in 40 ml. of methanol is treated with a solution of 180 mg. of hydrazine hydrate and 2 ml. of methanol. After 1 hr. the resulting solution is then poured into ice cold brine and ethyl acetate and the aqueous and organic layer separated. The aqueous layer is then extracted again with ethyl acetate and the organic layers combined, washed with brine, dried over sodium sulfate, and concentrated to an oil. The crude oil is then chromatographed on 50 g. of silica gel packed with ethyl acetate and hexane (1:4) and eluted with ethyl acetate and hexane (1:3) yielding 161 mg. of pure 9α,11α-epoxyimino-9,11,15-trideoxy-PGF 2 , methyl ester. Silica gel TLC Rf is 0.24 in ethyl acetate and hexane (3:7). Infrared absorptions are observed at 3250, 2930, 2870, 1730, 1450, 1430, 1340, 1170, 1150, 1050, 965, and 915 cm -1 . NMR absorptions are observed at 5.35, 4.15, 3.65, and 3.40 δ. Mass spectrum exhibits a high resolution peak at 349.2585 and other peaks at 320, 318, 306, and 278.
D. The reaction product of part C in 25 ml. of methanol is cooled in an ice bath and 8 ml. of one N aqueous potassium hydroxide is added. The resulting solution is then stirred at ambient temperature for 4 hr., poured into 200 ml. of an ice cold buffer (pH 5), saturated with sodium chloride, and extracted twice with ethyl acetate. The combined ethyl acetate extracts are then washed with brine, dried over sodium sulfate, and concentrated to yield crude free acid. Title product is an oil. The crude free acid is then chromatographed on 20 g. of acid washed silica gel packed with ethyl acetate and hexane (3:7) and eluted with ethyl acetate and hexane (2:3), yielding 122 mg. of pure free acid. Crystallization from diethyl ether and hexane yielded a white crystalline solid melting point 53°-54° C. Silica gel TLC Rf is 0.22in ethyl acetate, hexane and acetic acid (50:50:1). Infrared absorptions are observed at 3250, 2940, 2870, 2550, 1710, 1440, 1340, 965, 910, and 730 cm -1 . NMR absorptions are observed at 10.2, 5.35, 4.20, 3.65, and 0.90 δ. The mass spectrum exhibits a high resolution peak at 407.2832 and other peaks at 392, 389, 378, 375, 364, and 336.
EXAMPLE 9
11α,9α-Epoxyimino-9,11,15-trideoxyPGF 2 , methyl ester (formula IV: W 1 is ##STR54##
X 1 is --COOCH 3 , and Y 1 , Z 1 , L 1 , and R 7 are as defined in Example 1).
Refer to Chart K.
A solution of 2.15 g. of 15-deoxy-11β-PGF 2 β, methyl ester is 6 ml. of dimethylformamide is cooled in an ice bath while a previously mixed solution of ice cold t-butyldimethylchlorosilane (0.97 g.) and imidazole (0.87 g.) in 6 ml. of dimethylformamide is added. After about 150 min., the resulting mixture is poured into 300 ml. of ice cold brine and extracted twice with ethyl acetate and hexane (1:1). The combined organic extracts are then washed with successively with cold 2 N aqueous sodium bisulfate, cold saturated aqueous sodium bicarbonate, in brine; dried over sodium sulfate; and concentrated to yield crude 15-deoxy-11β-PGF 2 β-9-(t-butyldimethylsilyl ether) methyl ester, as an oil. This crude product is then chromatographed on silica gel packed with ethyl acetate and hexane (1:19) and eluted with ethyl acetate and hexane (1:9), to yield 0.79 g. of pure title product. Silica gel TLC Rf is 0.31 in ethyl acetate and hexane (1:1). Infrared absorptions are observed at 3550, 2930, 2860, 1730, 1450, 1425, 1250, 1100, 970, 870, 835, and 775 cm -1 . NMR absorptions are observed at 5.40, 3.90, and 3.60 δ.
B. The reaction product of part A (0.72 g.) in 30 ml. of dichloromethane is cooled to -20° C. under a nitrogen atmosphere. Thereafter triethylamine (0.43 g.) is added followed by addition of methanesulfonyl chloride (0.24 ml.) After 15 min. the resulting mixture is then poured into ice cold brine and ethyl acetate, the layers separated, the aqueous phase extracted again with ethyl acetate. The combined organic extracts are then washed with brine, dried over sodium sulfate, and concentrted to yield 0.89 g. of pure formula CXXXIII 15-deoxy-11β-PGF 2 β, 9-(t-butyldimethylsilyl ether), 11-methanesulfonate, methyl ester. Silica gel TLC Rf is 0.17 in ethyl acetate and hexane (1:9). Infrared absorptions are observed at 2930, 2860, 1730, 1450, 1430 1170, 1105, 965, 910, 835, and 775 cm -1 .
C. A solution of 0.80 g. of the reaction product of part B in 15 ml. of a mixture of tetrahydrofuran and water in acetic acid (1:1:3) is stirred at ambient temperature under a nitrogen atmosphere for 30 hrs. The resulting mixture is then poured into 200 ml. of cold brine and 200 ml. of cold ethyl acetate and hexane (2:3). The layers are then separated and the aqueous phase extracted with 200 ml. of ethyl acetate and hexane (2:3). The combined organic extracts are then washed successively with brine, saturated aqueous sodium bicarbonate, in brine; dried over sodium sulfate; and concentrated to crude 15-deoxy-11β-PGF 2 β, 11-methyl sulfonate, methyl ester as an oil. This crude oil is then chromatographed on silica gel, packed with ethyl acetate and hexane (3:7) and eluted with ethyl acetate and hexane (1:1), yielding 0.54 g. of pure formula CXXXIV product. Silica gel TLC Rf is 0.18 in ethyl acetate and hexane (1:1). Infrared absorptions are observed at 3600, 2920, 2860, 1735, 1420, 1340, 1170, 1080, 970, 905, and 775 cm -1 . NMR absorptions are observed at 5.50, 4.90, 3.90, 3.65, and 2.95 δ.
D. A solution of the reaction product of part C (0.51 g.) in 10 ml. of dry tetrahydrofuran is treated at ambient temperature under nitrogen atmosphere with 0.47 g. of triphenylphosphine and 0.29 g. of N-hydroxyphthalimide and diethylazocarboxylate (0.31g.) in tetrahydrofuran (0.50 ml.). After 30 min. an additional quantity of the N-hydroxyphthalimide and diethylazocarboxylate (one-third of the original quantities of each) is added and the mixture thereafter concentrated to an oil, triturated with ethyl acetate and hexane (3:17), and filtered to remove the triphenylphosphine oxide. The crude 15-deoxy-11β-PGF 2 α, 9-phthalimide, methyl ester is then chromatographed on silica gel, packed with ethyl acetate and hexane (3:17) and eluted with 30- 40% ethyl acetate in hexane, yielding 0.49 g. of pure product, which readily crystallize after removal of solvent. Silica gel TLC Rf is 0.27 in ethyl acetate and hexane (3:7). Infrared absorptions are observed at 2940, 2860, 1790, 1730, 1630, 1460, 1430, 1350, 1190, 1170, 1120, 1080, 970, 905, 880, 755, and 700 cm -1 . Infrared absorptions are observed at 7.8, 5.50, 4.20, 4.90, 3.65, and 2.95 δ.
E. A solution of 0.47 g. of the reaction product of part D and 40 ml. of methanol under a nitrogen atmosphere is treated at 0° C. with 0.19 g. of hydrazine hydrate and 10 ml. of methanol. After 3 hr. at ambient temperature the resulting mixture is then poured into 100 ml. of ice cold brine and 150 ml. of ethyl acetate and hexane (1:1). The layers are then separated and the aqueous phase extracted again with ethyl acetate and hexane (1:1). The combined organic extracts are then washed with brine, dried over sodium sulfate, and concentrated to an oil, crude 9α,11α-epoxyimino-9,11,15-trideoxy-PGF 2 , methyl ester. This crude formula CXXXV product is then chromatographed on 75 g. of silica gel, packed with ethyl acetate and hexane (1:4), and eluted with 25- 30% ethyl acetate and hexane, yielding 210 mg. of pure title product. Silica gel TLC Rf is 0.403 in ethyl acetate and hexane, (1:1). Infrared absorptions are observed at 3250, 2950, 2870, 1740, 1450, 1430, 1360, 1240, 1170, 1150, 1050, 965, and 810 cm -1 . NMR absorptions are observed at 5.4, 5.25, 5.65, 3.45 δ. The mass spectrum exhibits a high resolution peak at 349.592.
F. A solution of 190 mg. of the reaction product of part E and 35 ml. of methanol is cooled in an ice bath while 11 ml. of 1 N aqueous potassium hydroxide is added. The resulting mixture is then allowed to warm to ambient temperature for 3 hr. Thereupon the mixture is poured into 150 ml. of buffer (pH 5), ice cold brine, and ethyl acetate. The layers are then separated and the aqueous layer extracted again with ethyl acetate. The comined organic extracts are then washed with brine, dried over sodium sulfate and concentrated to yield title free acid. This crude title free acid is then chromatographed on acid washed silica gel packed with ethyl acetate and hexane (3:7) and eluted with 30-40% ethyl acetate and hexane, yielding 82 mg. of pure title free acid. Silica gel TLC Rf is 0.23 in ethyl acetate hexane and acetic acid (50:50:1). Infrared absorptions are observed at 3300, 3150, 2900, 2840, 2500, 1740, 1440, 1240, 965, 910 cm -1 . NMR absorptions are observed at 8.25, 5.35, 4.30, and 3.335 δ.
EXAMPLE 10
N-Methyl-9α,11α-epoxyimino-9,11,15-trideoxy-PGF 2 , methyl ester (Formula IV: W 1 is ##STR55##
X 1 is --COCH 3 , Z 1 , Y 1 , L 1 , and R 7 are as defined in Example 1).
Following the procedure of Example 6 (alternate route), the methyl ester of Example 9 is transformed to the title product herein.
EXAMPLE 11
N-Acetyl-9α, 11α-epoxyimino-9,11,15-trideoxy-PGF 2 , methyl ester (Formula IV: W 1 is ##STR56##
X 1 is -COCH 3 , and Z 1 , Y 1 , and L 1 and R 7 are as defined in Example 1).
Following the procedure of Example 7, the title methyl ester of Example 9 is transformed to the title product herein.
Further following the procedure of Examples 10 and 11, but employing the title product of Example 8, there are prepared respectively N-methyl-11α,9α-epoxyimino-9,11,15-trideoxy-PGF 2 , methyl ester and N-acetyl-11α,9α-epoxyimino9,11,15-trideoxy-PGF 2 , methyl ester.
Further following the procedure of Examples 6-11, there are prepared prostaglandin analogs as free acids, esters, amides, primary amines (2-decarboxy-2-aminomethylPG compounds) or primary alcohols (2-decaroboxy-2-hydroxymethyl-PG), corresponding to each of the various 9α,11α-azo-9,11,15-trideoxy-PGF-type compounds described previously but in the form of:
11α,9α-epoxyimino-9,11,15-trideoxy-PGF-type compounds;
9α,11α-epoxyimino-9,11,15-trideoxy-PGF-type compounds;
N,n'- dimethyl-9α,11α-hydrazino-9,11,15-trideoxy-PGF-type compounds;
N,n'-bis(acetyl)-9α,11α-hydrazino-9,11,15-trideoxy-PGF-type compounds;
N-methyl-11α,9α-epoxyimino-9,11,15-trideoxy-PGF-type compounds;
N-acetyl-11α, 9α-epoxyimino-9,11,15-trideoxy-PGF-type compounds;
N-methyl-9α, 11α-epoxyimino-9,11,15-trideoxy-PGF-type compounds;
N-acetyl-]α,11α-epoxyimino-9,11,15-trideoxy-PGF-type compounds;
9α,11α-methylhydrazino-9,11,15-trideoxy-PGF-type compounds;
9α, 11α(acety)hydrazino-9,11,15-trideoxy-PGF-type compounds;
11α,9α-methylhydrazino-9,11,15-trideoxy-PGF-type compounds; and
11α,9α(acetyl)hydrazino-9,11,15-trideoxy-PGF-type compounds. | The present specification; provides bicyclic nitrogen-containing 9,11,15-trideoxy-prostaglandin F analogs which are useful anti-inflammatory agents, anti-asthma agents, and platelet aggregation inhibitors, and a process for their preparation. Included are compounds of the following structural formulas: ##STR1## Especially described in the present specification are 9,11-trideoxy-9α,11α-azo-PGF-type; 9,11,15-trideoxy-11α,9α-epoxyimino-PGF-type; 9,11,15-trideoxy-9α,11α-epoxyimino-PGF-type; N,N'-dialkyl-9,11,15-trideoxy-9α11α-hydrazino-PGF-type; N,N'-bis(alkylcarbonyl)-9,11,15-trideoxy-9α,11α-hydrazino-PGF-type; N-alkyl-9,11,15-trideoxy-11α,9α-epoxyimino-PGF-type; N-(alkylcarbonyl)-9,11,15-trideoxy-11α,9α-epoxyimino-PGF-type; N-alkyl-9,11,15-trideoxy-9α,11α-epoxyimino-PGF-type; N-(alkylcarbonyl)-9,11,15-trideoxy-9α,11α-epoxyimino-PGF-type; 9,11,15-trideoxy-9α,11α-alkylhydrazino-PGF-type; 9,11,15-trideoxy-9α,11-α-(alkylcarbonyl)hydrazino-PGF-type; 9,11,15-trideoxy-11α,9α-alkylhydrazino-PGF-type; and 9,11,15-trideoxy-11α,9α-(alkylcarbonyl)-hydrazino-PGF-type compounds. | 2 |
BACKGROUND
1. Field of the Invention
The present invention relates to motorized window shades.
2. Description of the Related Art
A roll-up window shade is well known. The shade can be moved manually up or down in front of a window to control the light level, room temperature, light flow, or to provide privacy. The known roll-up shade is relatively inexpensive and is easy to install. If the shade is damaged, a new shade can be replaced easily. These types of shades are sold in retail stores and do-it-yourself centers across the U.S. The shades are typically stocked in 3, 4, 5 and 6 foot widths. The shade can easily be cut to the proper width with a cutting device either at the point of sale or at installation time. The installer or homeowner can measure and install the shade on the same site visit.
The conventional roll-up shade has a first pin end and a second spring end with a rectangular barb extending outwardly. The pin end is inserted into a circular hole in a bracket. The spring end is mounted in a similar shaped bracket with a slot designed to keep the barb from rotating. The brackets are designed to be mounted inside a window frame i.e., inside the jamb, or along the outside of a window frame. The user pulls the roll-up shade down by a hem bar located along the bottom edge of the shade until the desired amount of shade material is showing. The user then eases up on the hem bar until the pawl mechanism in the spring end of the shade locks the shade into position. As the shade is being pulled down, the spring is being wound up.
When the user wants to put the shade up, the user pulls down on the hem bar slightly to disengage the pawl mechanism and then guides the hem bar upward as the spring pulls the fabric upward. If the user lets go of the shade as the shade is traveling upward the spring in the shade will cause the shade to travel upward out of control. The hem bar will continue to rotate around the roller until it stops. The setting of multiple shades at the same relative position can be a very time consuming process. The manually-operated shades are not capable of receiving inputs from time clocks, photo sensors, occupant sensors or infrared hand held transmitters.
It is known to replace the spring mechanism described above with a motor, typically a tubular motor, to allow the window shade to be rolled and unrolled (opened and closed) by remote control. Installation of these systems typically requires a skilled craftsman. The installer usually will need to make one visit to measure the window and another separate visit to install the system. In some systems, the hem bar located at the bottom of the shade travels in channels secured to the sides of the window opening, thus, decreasing the amount of light that can enter through the window when the shade is up. The motor is typically connected to a nearby power source with line voltage or low-voltage wiring.
A typical motorized roller shade is secured to the window opening with two mounting brackets. The single roller shade is custom made with a fabric of choice. The motor is installed inside the roller tube at the factory and line or low voltage wiring connects the motor to a nearby power source. If the unit fails, the unit must typically be returned to the manufacturer or a technician must visit the job site.
Multiple units can be grouped together by wiring the multiple units to each other or to a common control system. Installation of such wiring is beyond the capabilities of most homeowners, and thus, such units must be installed by a professional installer.
The prior art devices generally suffer from a number of disadvantages including the inability to communicate with other devices, lack of intelligent control, e.g. by a microprocessor, and thus, having inability to be programmed easily, bulky size causing difficulty in installation, an unattractive appearance and maintenance problems as well as inability to easily retrofit to existing manually actuated shades. These problems have severely limited the market for motorized rollup window shades.
SUMMARY
The system and method disclosed herein solves these and other problems by providing a remotely-controllable, self-powered, user-installable motorized window shade. In one embodiment, the motorized roll-up window shade includes a controller, a tubular motor provided to the controller. The tubular motor is configured to raise and lower the window shade. A first power source is provided to the controller and a two-way wireless communication system is provided to the controller. The controller is configured to control the motor in response to a wireless communication received from a group controller or central control system. The motorized shades can be used to produce a desired room temperature during the day and to provide privacy at night.
In one embodiment, the electronically-controlled motorized shade includes a light sensor. In one embodiment, the electronically-controlled motorized shade includes a temperature sensor. In one embodiment, the electronically-controlled motorized shade includes a second power source. In one embodiment, the electronically-controlled motorized shade includes a solar cell configured to charge the first power source. In one embodiment, the electronically-controlled motorized shade includes a shade position sensor. In one embodiment, the electronically-controlled motorized shade includes a turns counter to count turns of the tubular motor.
In one embodiment, the controller is configured to transmit sensor data according to a threshold test. In one embodiment, the threshold test includes a high threshold level, a low threshold level, and/or a threshold range.
In one embodiment, the controller is configured to receive an instruction to change a status reporting interval. In one embodiment, the controller is configured to receive an instruction to change a wakeup interval. In one embodiment, the controller is configured to monitor a status of one or more electronically-controlled motorized shades.
In one embodiment, the controller is configured to communicate with a central controller. In one embodiment, the central controller communicates with an HVAC system. In one embodiment, the central controller is provided to a home computer. In one embodiment, the central controller is provided to a zoned HVAC system. In one embodiment, the central controller cooperates with the zoned HVAC system to use the motorized shade to partially control a temperature of a desired zone.
In one embodiment, the controller is configured to use a predictive model to compute a control program. In one embodiment, the controller is configured to reduce power consumption by the tubular motor. In one embodiment, the controller is configured to reduce movement of the tubular motor.
In one embodiment, a group controller is configured to use a predictive model to compute a control program for the motorized shade. In one embodiment, the group controller is configured to reduce power consumption by the motorized shade. In one embodiment, the group controller is configured to reduce movement of the motorized shade.
In one embodiment, the shade material includes a plurality of conductors provided to the controller. In one embodiment, the shade material includes a connector for connecting a charger to the controller to provide power to recharge the power source. In one embodiment, the shade material includes a solar cell.
In one embodiment, the motorized shade system can easily be installed by a homeowner or general handyman. In one embodiment, the motorized shade system is used in connection with a zoned or non-zoned HVAC system to control room temperatures throughout a building. The motorized shade can also be used in connection with a conventional zoned HVAC system to provide additional control and additional zones not provided by the conventional zoned HVAC system. The motorized shade can be installed in place of a conventional manually-controlled window treatment.
In one embodiment, the motorized shade includes an optical sensor to measure the ambient light either inside or outside the building. In one embodiment, the motorized shade opens if the light exceeds a first specified value. In one embodiment, the motorized shade closes if the light exceeds a second specified value. In one embodiment, the motorized shade is configured to partially open or close in order to maintain a relatively constant light level in a portion of the building.
In one embodiment, the motorized shade is powered by an internal battery. A battery-low indicator on the motorized shade informs the homeowner when the battery needs replacement. In one embodiment, one or more solar cells are provided to recharge the batteries when light is available.
In one embodiment, one or more motorized shades in a zone communicate with a group controller. The group controller measures the temperature of the zone for all of the motorized shades that control the zone. In one embodiment, the motorized shades and the group controller communicate by wireless communication methods, such as, for example, infrared communication, radio-frequency communication, ultrasonic communication, etc. In one embodiment, the motorized shades and the group controller communicate by direct wire connections. In one embodiment, the motorized shades and the group controller communicate using powerline communication.
In one embodiment, one or more group controllers communicate through a central controller.
In one embodiment, the motorized shade and/or the group controller includes an occupant sensor, such as, for example, an infrared sensor, motion sensor, ultrasonic sensor, etc. The occupants can program the motorized shade or the group controller to bring the zone to different temperatures when the zone is occupied or to provide privacy (e.g., by closing the shade) when the zone is occupied. In one embodiment, the occupants can program the motorized shade or the group controller to bring the zone to different temperatures and/or light levels depending on the time of day, the time of year, the type of room (e.g., bedroom, kitchen, etc.), and/or whether the room is occupied or empty. In one embodiment, various motorized shades and/or group controllers through a composite zone (e.g., a group of zones such as an entire house, an entire floor, an entire wing, etc.) intercommunicate and change the temperature setpoints according to whether the composite zone is empty or occupied.
In one embodiment, the home occupants can provide a priority schedule for the zones based on whether the zones are occupied, the time of day, the time of year, etc. Thus, for example, if zone corresponds to a bedroom and zone corresponds to a living room, zone can be given a relatively lower priority during the day and a relatively higher priority during the night. As a second example, if zone corresponds to a first floor, and zone corresponds to a second floor, then zone can be given a higher priority in summer (since upper floors tend to be harder to cool) and a lower priority in winter (since lower floors tend to be harder to heat). In one embodiment, the occupants can specify a weighted priority between the various zones.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a typical home with windows and ductwork for a heating and cooling system.
FIG. 2 shows one example of a motorized shade mounted in a window.
FIG. 3 is a block diagram of a self-contained motorized shade.
FIG. 4A is a block diagram of a motorized shade with a fascia having a solar cell.
FIG. 4B is a block diagram of a motorized shade with a shade material having a solar cell.
FIG. 5 shows one embodiment of a motorized shade with fascia having a solar cell.
FIG. 6 is a block diagram of a system for controlling one or more motorized shades.
FIG. 7A is a block diagram of a centrally-controlled motorized shade system wherein the central control system communicates with one or more group controllers and one or more motorized shades independently of the HVAC system.
FIG. 7B is a block diagram of a centrally-controlled motorized shade system wherein the central control system communicates with one or more group controllers and the group controllers communicate with one or more motorized shades.
FIG. 8 is a block diagram of a centrally-controlled motorized shade system wherein a central control system communicates with one or more group controllers and one or more motorized shades and, optionally, controls the HVAC system.
FIG. 9 is a block diagram of an efficiency-monitoring centrally-controlled motorized shade system wherein a central control system communicates with one or more group controllers and one or more motorized shades and, optionally, controls and monitors the HVAC system.
FIG. 10 is a block diagram of a motorized shade configured to operate with a powered coil mounted on a window sill.
FIG. 11 is a block diagram of a basic group controller for use in connection with the systems shown in FIGS. 6-9 .
FIG. 12 is a block diagram of a group controller with remote control for use in connection with the systems shown in FIGS. 6-9 .
FIG. 13 shows one embodiment of a central monitoring system.
FIG. 14 is a flowchart showing one embodiment of an instruction loop for a motorized shade or group controller.
FIG. 15 is a flowchart showing one embodiment of an instruction and sensor data loop for a motorized shade or group controller.
FIG. 16 is a flowchart showing one embodiment of an instruction and sensor data reporting loop for a motorized shade or group controller.
FIG. 17 is a block diagram of a control algorithm for controlling the motorized shades.
FIG. 18 shows one embodiment of a motorized shade with internal batteries
FIG. 19 shows one embodiment of a motorized shade with internal batteries and a fascia.
DETAILED DESCRIPTION
FIG. 1 shows a home 100 with ducts for heating and cooling and windows on various sides of the house. For example, the home 100 includes north-facing windows 150 , 151 , an east-facing window 180 , south-facing windows 160 , 161 , and a west-facing window 170 . In the home 100 , an HVAC system provides heating and cooling light to the system of windows. In a conventional system, a thermostat monitors the air temperature and turns the HVAC system on or off. In a zoned system, sensors 101 - 105 monitor the temperature in various areas (zones) of the house. A zone can be a room, a floor, a group of rooms, etc. The sensors 101 - 105 detect where and when heating or cooling is needed. Information from the sensors 101 - 105 is used to control motors that adjust the flow of air to the various zones. The zoned system adapts to changing conditions in one area without affecting other areas. For example, many two-story houses are zoned by floor. Because heat rises, the second floor usually requires more cooling in the summer and less heating in the winter than the first floor. A non-zoned system cannot completely accommodate this seasonal variation. Zoning, however, can reduce the wide variations in temperature between floors by supplying heating or cooling only to the space that needs it.
FIG. 2 shows one example of a motorized shade 200 . The shade material 201 rolls on a tube 202 . A motor (not shown) rotates the tube 202 to raise and lower the shade material 201 to control the amount of light that passes through the window. The tube 202 is mounted to (or near) a window frame 250 .
FIG. 3 is a block diagram of a self-contained motorized shade as one embodiment of the motorized shade 200 . In the motorized shade shown in FIG. 3 , a mount 301 mounts the tube 202 to the window frame 250 (or near the window frame 250 ). The tube 202 includes a controller 301 . The controller 301 provides control for communications, power management, and other control functions. A motor 303 , such as, for example, a tubular motor with a gearbox, is provided to the controller 301 . In one embodiment, the motor 301 includes an internal turns counter and limit switches to limit the revolutions and set the stop points of the motor. In one embodiment, a turns counter 304 is provided to the controller 301 . A first power source 305 is provided to the controller 301 . In one embodiment, the first power source 305 includes a stack of batteries. In one embodiment, the batteries are rechargeable batteries. In one embodiment, the batteries are non-rechargeable batteries.
A radio-frequency transceiver 302 is provided to the controller. In one embodiment, an InfraRed (IR) and/or light sensor receiver is provided to the controller 301 . In one embodiment, a light-guiding apparatus 360 is provided to direct light to the IR receiver 308 . The light-guiding apparatus 360 can include, for example, a light-pipe, a mirror, a plastic light guide, etc. In one embodiment, at least a portion of the light-guiding apparatus 360 is provided to the mount 301 to reflect (or direct) IR light into the tube 202 and/or IR receiver 308 .
In one embodiment, an optional capacitor 306 is provided to the controller 301 . The controller 301 can extend the life of the first power source 305 by drawing power relatively slowly, and/or at relatively low voltage from the first power source 305 to charge the capacitor 306 . In one embodiment, the capacitor 306 is used, at least in part, to provide power for the controller 301 , the transceiver 302 , and/or the motor 303 .
In one embodiment, a solar cell 307 is provided to the controller 301 . In one embodiment, an RFID tag 309 is provided to the controller 301 .
In one embodiment, the IR receiver 308 is used to provide control inputs to the controller 301 . In one embodiment, IR control is used in lieu of RF control, and the RF transceiver 302 is omitted. In one embodiment, the IR receiver 308 is configured as a transceiver to allow two-way IR communications between the motorized shade and a controller. In one embodiment, IR control is used for programming the controller 301 (e.g., for inserting or reading an identification code) and RF control is used to raise and lower the blinds.
One or more attachments 350 are provided to attach the shade material 201 to the roller tube 202 . In one embodiment, the attachments 350 include a channel in the tube 202 and the upper end of the shade material 201 is configured to slide into the channel and be held in place by the channel. In one embodiment, the attachments 350 include one or more glue joints. In one embodiment, the attachments 350 include one or more capture devices that clamp onto the shade material.
In one embodiment, the shade material 201 includes one or more electrical conductors, such as, for example, (wires, wire meshes, metal foil, conductive polymers, etc.) In one embodiment, one or more of the attachments 350 are configured to make electrical contact with the one or more conductors in the shade material 201 . In one embodiment a power connector is provided to the one or more conductors in the shade material to allow a power source (e.g., a battery charger) to be connected to the powered shade to recharge the batteries 305 . In one embodiment, the power connector is provided to a lower portion of the shade material. In one embodiment, the one or more conductors in the shade material provide connections to power sources, such as, for example, solar cells (see e.g., FIG. 4 b ), pickup coils (see e.g., FIG. 10 ), etc.
In one embodiment, the tube 202 is made from aluminum or other conductive material, and a slot-type RF aperture is provided in the tube 202 to allow the RF transceiver 302 to communicate. In one embodiment, an RF antenna connection from the RF transceiver 302 is provided to the mount 301 to allow the mount and/or fascia to act as an antenna or portion of an antenna. In one embodiment, an RF antenna connection from the RF transceiver is provided to the tube 202 to allow the tube 202 to act as an antenna or portion of an antenna. In one embodiment, an RF antenna connection from the RF transceiver 302 is provided to one or more conductors in the shade material 301 to allow the one or more conductors to act as an antenna or portion of an antenna.
The controller 301 typically operates in a sleep-wakeup cycle to conserve power. The controller 301 wakes up at specified intervals and activates the transceiver 302 to listen for commands from a remote control or other control device or to send status information (e.g., fault, low battery, etc.).
FIG. 4A is a block diagram of an embodiment of a motorized shade as one embodiment of the motorized shade 200 that includes a solar cell 404 provided to the mount 301 . In one embodiment, the mount 301 includes a fascia as shown in FIG. 5 and the solar cell 404 is mounted to the outside of the fascia in order to receive sunlight. The motorized shade shown in FIG. 4A includes the other elements shown in FIG. 3 , including the tube 202 , the controller 301 , the motor 303 , the transceiver 302 , etc.
FIG. 4B is a block diagram of an embodiment of a motorized shade as one embodiment of the motorized shade 200 that includes a solar cell 504 provided to the shade material 201 . The solar cell 504 can be mounted to the shade material 201 and/or integrated into the shade material 201 . When the solar cell 504 is provided to the shade material 201 , then one or more of the attachments 350 are configured to provide electrical contact between the controller 301 and the solar cell 504 .
FIG. 5 shows one embodiment of a motorized shade with the solar cell 404 provided to a fascia 502 . As shown in FIG. 5 , the solar cells 404 and 504 are not mutually exclusive and can be used together if desired.
FIG. 6 is a block diagram of a system for controlling one or more motorized shades 200 . The system 600 allows the motorized shades 200 to be controlled in groups (where a group can be one motorized shade or a plurality of motorized shades). FIG. 6 shows five groups of motorized shades, labeled groups 650 - 654 . Groups 650 - 652 each have three or more motorized shades, group 653 has two shades, and group 654 has one motorized shade. One or more group controllers 607 , 608 can be used to control one or more groups of shades. The group controllers 607 , 608 can be hand-held remote-control type devices and/or wall-mounted controllers. A central control system 601 includes a processor 603 , a clock/calendar module 604 , and an RF transceiver 602 . In one embodiment, the central control system 601 is provided to an HVAC interface to a zoned or non-zoned HVAC system. In one embodiment, a sunlight sensor 610 is provided to the control system 601 . In one embodiment, the sunlight sensor 610 detects the amount of sunlight. In one embodiment the sunlight sensor 610 detects the amount and direction of the sunlight.
One or more group controllers 607 , 608 can be provided to various rooms in the house, such as for example, the bedrooms, kitchen, living room, etc. In one embodiment, the controllers 607 , 608 can be used to control any of the shades in the house. In one embodiment, a display on the group controller 607 , 608 allows the user to select which group of shades to control from a list of shade groups.
The central control system 601 is provided to a computer system (e.g., a personal computer system) by an interface 605 such as, for example, a USB interface, a firewire interface, a wired local area network (LAN) interface, a wireless local area network interface, a powerline networking interface, etc. The computer system 606 can be used to program and monitor the central control system 601 and to instruct the control system 601 as to the number of motorized shades, the identification codes for the shades, the location of the shades, the amount of privacy desired, how to interact with the HVAC system, etc. For example, if a window faces the street or other public areas, then the computer system 606 can be used to instruct the central control system 601 to provide a relatively high level of privacy for that window. By contrast, if a window faces a barrier of trees or bushes, then the computer system 606 can be used to instruct the central control system 601 to provide a relatively lower level of privacy for that window.
In one embodiment, a compass direction of each window (e.g., south facing, northwest facing, compass angle of the direction the window faces, etc.) corresponding to a motorized shade is provided to the central control system 601 . Thus, for example, the control system 601 will know that south-facing windows receive relatively more sunlight than north-facing windows. The central control system 601 can close the shades on south-facing windows in order to reduce cooling and reduce fading of carpets and furniture caused by sunlight. Alternatively, the central control system 601 can open the shades on south-facing windows in order to reduce heating loads during cold periods. In one embodiment, the central control system 601 can open the motorized shades during the day to let in sunlight, and close the motorized shades during the night to provide privacy. In one embodiment, the central controller 601 is configured to partially open or close the motorized shades to let in a desired amount of light. In one embodiment, the central controller 601 is configured to open and close shades in a particular group by the same amount for aesthetic purposes.
In one embodiment, the group controllers 607 , 608 can be used to control one or more groups of motorized shades. In one embodiment, the group controllers 607 , 608 send control signals directly to the motorized shades. In one embodiment, the group controllers 607 , 608 send control signals to the central controller 601 which then sends control signals to the motorized shades 200 .
The motorized shades 200 can be used to implement a motorized shade system. The motorized shades 200 can also be used as a remotely control motorized shade in places where the window is located so high on the wall that it cannot be easily reached. In one embodiment, the motorized shades 200 are self-powered and controlled by wireless communication. This greatly simplifies the task of retrofitting a home by replacing one or more manual window treatments with the motorized shades 200 .
The controller 301 controls the motor 303 . In one embodiment, the motor 303 provides position feedback to the controller 301 . In one embodiment, the controller 301 reports shade position to the central control system 601 and/or group controllers 607 , 608 . The motor 303 provides mechanical movements to control the light through the window. In one embodiment, the motor 303 includes a motor to control the amount of light that flows through the motorized shade 400 (e.g., the amount of light that flows from the window into the room). In one embodiment, the system 601 allows a user to set the desired room temperature and/or lighting. An optional sensor 404 is provided to the controller 301 .
In one embodiment, the motorized shade 200 includes a flashing indicator (e.g., a flashing LED or LCD) when the available power from the power source 305 drops below a threshold level.
The home occupants use the group controllers 607 , 608 or computer 606 to set a desired temperature, privacy, or lighting for the vicinity of the motorized shade 200 . If the room temperature is above the setpoint temperature, and the window light temperature is below the room temperature, then the controller 301 causes the motorized shade 200 to open the shade. If the room temperature is below the setpoint temperature, and the window light temperature is above the room temperature, then the controller 301 causes the motorized shade 200 to open the window. Otherwise, the controller 301 causes the motorized shade 200 to close the shade. In other words, if the room temperature is above or below the setpoint temperature and the temperature of the light in the window will tend to drive the room temperature towards the setpoint temperature, then the controller 301 opens the window to allow light into the room. By contrast, if the room temperature is above or below the setpoint temperature and the temperature of the light in the window will not tend to drive the room temperature towards the setpoint temperature, then the controller 301 closes the window.
In one embodiment, the controller 301 is configured to provide a few degrees of hysteresis (often referred to as a thermostat deadband) around the setpoint temperature in order to avoid wasting power by excessive opening and closing of the window.
The controller 301 conserves power by turning off elements of the motorized shade 400 that are not in use. The controller 301 monitors power available from the power sources 305 , 306 . When available power drops below a low-power threshold value, the motorized shade 200 informs the central controller 601 . When the controller senses that sufficient power has been restored (e.g., through recharging of one or more of the power sources, then the controller 301 resumes normal operation).
In one embodiment, the motorized shades 200 communicates with each other in order to improve the robustness of the communication in the system. Thus, for example, if a first motorized shade is unable to communicate with the group controller 601 but is able to communicate with a second motorized shade 200 , then the second motorized shade 200 can act as a repeater between the first motorized shade 200 and the group controller 601 .
The motorized shade system shown in FIG. 6 can be used in connection with a zoned or non-zoned HVAC system. For example, in winter, the system 600 can be used to open the shades of southerly windows on sunny days to provide some measure of solar heating. By contrast, in winter, the system 600 can be used to close the window shades windows in the evening in order to reduce heat loss and to provide privacy. For example, in winter, the system 600 can be used to close the shades of southerly windows on sunny days to reduce solar heating. By contrast, in summer, the system 600 can be used to open the window shades windows in the evening in order to radiate heat (reducing cooling loads).
Using the system 600 , the homeowner can select the relative priority of light, temperature, and privacy for each group of shades. The relative priorities can be adjusted based on day of the week, time of day, time of year, etc. In one embodiment, the system 600 is provided with an override switch (not shown) to change the relative priorities (e.g., temperature, privacy, light) based on whether the homeowner is at home or away from home. Thus, for example, while away from home, the homeowner can instruct the system 600 to minimize privacy and maximize HVAC efficiency; by contrast, when at home, the homeowner can instruct the system 600 to use different priorities that provide relatively more privacy.
In one embodiment, the user can use the computer system 606 to specify the relative desired privacy, temperature, and light levels, and the relative priorities of privacy, temperature, and light, for each group of shades in the house. In one embodiment, the settings can be specified as a matrix of settings according to the day of the week and/or the hour of the day and/or the time of year, etc.
In one embodiment, the user can create various “profiles” using the computer system. Thus, for example, the user can create a privacy profile, a summer profile, a morning profile, and evening profile, a default profile, a standard profile, a winter profile, etc. Thus, for example, the user can create a privacy profile wherein the various settings of the shade control system are adjusted to provide relatively more privacy. The user can create a summer profile wherein the various settings of the shade control system are adjusted to provide setting the user desires during summer (e.g., efficient use of cooling). The user can create a winter profile wherein the various settings of the shade control system are adjusted to provide settings the user desires during winter (e.g., efficient use of heating). In one embodiment, the system comes configured with a default profile that is configured to provide a balance of privacy, temperature, and light, summer cooling, winter heating, evening privacy, etc. In one embodiment, the default profile is computed by the shade control system according to the geographical location of the house.
In one embodiment, the control system 601 is an adaptive system (as shown, for example in FIG. 17 ) configured to learn and adapt. Thus, for example, the control system 601 , when provided with temperature data from a room corresponding to particular group of shades, can adapt to change in room temperature as that group of shades is raised and lowered.
In one embodiment, the user can create a standard profile that includes the user's standard desired settings for the system. The use of profiles allows the user to quickly and easily change the many operating parameters of the shade control system (e.g., using the controls 607 , 608 ) on a group-by-group, room-by-room basis, or on a whole-house basis.
Any number of independent groups can be controlled by the system 600 . FIG. 7A is a block diagram of a centrally-controlled zoned heating and cooling system wherein a central control system 710 communicates with one or more group controllers 707 708 and one or more motorized shades 702 - 705 . In the system 700 , the group controller 707 measures the temperature and/or light of a zone 711 , and the motorized shades 702 , 703 are used to regulate light to the zone 711 . The group controller 708 measures the temperature and/or light of a zone 712 , and the motorized shades 704 , 705 regulate light to the zone 712 . A central thermostat 720 controls the HVAC system 721 .
FIG. 7B is a block diagram of a centrally-controlled motorized shade system 750 that is similar to the system 700 shown in FIG. 7A . In FIG. 7B , the central system 710 communicates with the group controllers 707 , 708 , the group controller 707 communicates with the motorized shades 702 , 703 , the group controller 708 communicates with the motorized shades 704 , 705 , and the central system 710 communicates with the motorized shades 706 , 707 . In the system 750 , the motorized shades 702 - 705 are in zones that are associated with the respective group controller 707 , 708 that controls the respective motorized shades 702 - 705 . The motorized shades 706 , 707 are not associated with any particular group controller and are controlled directly by the central system 710 . One of ordinary skill in the art will recognize that the communication topology shown in FIG. 7B can also be used in connection with the system shown in FIGS. 8 and 9 .
The central system 710 an example of one embodiment of the central control system 601 . The central system 710 controls and coordinates the operation of the zones 711 and 712 , but the system 710 does not control the HVAC system 721 . In one embodiment, the central system 710 operates independently of the thermostat 720 . In one embodiment, the thermostat 720 is provided to the central system 710 so that the central system 710 knows when the thermostat is calling for heating, cooling, or fan.
The central system 710 coordinates and prioritizes the operation of the motorized shades 702 - 705 . In one embodiment, the home occupants and provide a priority schedule for the zones 711 , 712 based on whether the zones are occupied, the time of day, the time of year, etc. Thus, for example, if zone 711 corresponds to a bedroom and zone 712 corresponds to a living room, zone 711 can be given a relatively lower priority during the day and a relatively higher priority during the night. As a second example, if zone 711 corresponds to a first floor, and zone 712 corresponds to a second floor, then zone 712 can be given a higher priority in summer (since upper floors tend to be harder to cool and have different privacy requirements) and a lower priority in winter (since lower floors tend to be harder to heat and my require less privacy). In one embodiment, the occupants can specify a weighted priority between the various zones.
FIG. 8 is a block diagram of a centrally-controlled motorized shade system 800 . The system 800 is similar to the system 700 and includes the group controllers 707 , 708 to monitor the zones 711 , 712 , respectively, and the motorized shades 702 - 705 . The group controllers 707 , 708 and/or the motorized shades 702 - 705 communicate with a central controller 810 . In the system 800 , the thermostat 720 is provided to the central system 810 and the central system 810 controls the HVAC system 721 directly. The central system 810 an example of one embodiment of the central control system 601 .
Since the controller in FIG. 8 also controls the operation of the HVAC system 721 , the controller is better able to call for heating and cooling as needed to maintain the desired temperature of the zones 711 , 712 . If all, or substantially, all of the home is served by the group controllers and motorized shades, then the central thermostat 720 can be eliminated.
FIG. 9 is a block diagram of an efficiency-monitoring centrally-controlled motorized shade system 900 . The system 900 is similar to the system 800 . In the system 900 , a controller 910 includes an efficiency-monitoring system that is configured to receive sensor data (e.g., system operating temperatures, etc.) from the HVAC system 721 to monitor the efficiency of the HVAC system 721 . The central system 910 an example of one embodiment of the central control system 601 .
FIG. 10 is a block diagram of a motorized shade 1000 configured to operate with a powered coil mounted on a window sill. The motorized shade 1000 is one embodiment of the motorized shade 200 . The motorized shade 1000 includes the elements shown in FIG. 3 , and, in addition, the motorized shade 1000 includes a coil 1001 . The coil 1001 is provided to the controller 301 . In one embodiment, the coil 1001 is provided to the controller 301 through a conductive coupling 350 a and a conductive coupling 350 b . A powered coil 1002 is provided to a window sill such that when the shade 1000 is lowered to the window sill, the coil 1001 is in proximity to the coil 1002 . In one embodiment, alternating current power is provided to the coil 1002 from a power source 1003 . In one embodiment, the power source 1003 is provided to a wall outlet to receive standard household AC power. When the shade lowered, the coil 1001 electromagnetically couples to the coil 1002 to form a transformer such that power is provided from the coil 1002 to the coil 1001 . The power received by the coil 1001 is provided to the controller 301 and the controller 301 can store the received power in the optional capacitor 306 or in a rechargeable battery 305 . In one embodiment, one or both of the coils 1001 , 1002 include a core of magnetic material. In one embodiment, the magnetic field produced by the powered coil 1002 attracts the magnetic core of the coil 1001 to help hold the bottom of the shade material in place.
In one embodiment, the coil 1002 is continuously powered by the power source 1003 . In one embodiment, the controller 301 sends a pulse of power to the coil 1001 , which pulse is then coupled to the coil 1002 and provided by the coil 1002 to the power source 1003 . The power source 1003 , upon sensing the pulse from the controller 301 , then provides power to the coil 1002 in response to the power pulse from the controller 301 . In one embodiment, the controller 301 sends a second pulse to the coil 1001 to instruct the controller 1003 to de-power the coil 1002 .
In one embodiment, the power source 1003 senses the impedance of the coil 1002 (on a continuous or periodic basis) and provides power to the coil 1002 when the impedance of the coil 1002 indicates that the coil 1001 is in proximity to the coil 1002 .
Power provided to the coil 1002 will magnetically attract a magnetic core of the coil 1001 . In one embodiment, the motor 303 can provide sufficient torque to overcome such magnetic attraction and raise the shade. In one embodiment, the controller 301 sends a reverse current pulse to the coil 1001 to cause the magnetic field of the coil 1001 to substantially cancel the magnetic field of the coil 1002 in order to release the shade and allow the shade to then be raised by the motor 303 .
In one embodiment, the controller 301 automatically lowers the shade 1000 when available power from the battery pack 305 and/or capacitor 306 falls below a specified value. In one embodiment, the system controllers (e.g., the controllers 710 , 810 , 910 , etc.) instruct the controller 301 to lower the shade 1000 when the available power from the battery pack 305 and/or capacitor 306 falls below a specified value.
In one embodiment, a plurality of coils 1001 and/or 1002 are provided along the lower portion of the shade material 201 and the window sill respectively.
FIG. 11 is a block diagram of a basic group controller 1100 for use in connection with the systems shown in FIGS. 6-9 . In the group controller 1100 , an optional temperature sensor 1102 is provided to a controller 1101 . User input controls 1103 are also provided to the controller 1101 to allow the user to select a shade and specify a setpoint shade opening. A visual display 1110 is provided to the controller 1101 . The controller 1101 uses the visual display 1110 to show the current shade group, setpoint, power status, etc. The communication system 1181 is also provided to the controller 1101 . The power source 404 and, optionally, 405 are provided to provide power for the controller 1100 , the controls 1101 , the sensor 1103 , the communication system 1181 , and the visual display 1110 .
In systems where the central controller 1101 is used, the communication method used by the group controller 1100 to communicate with the motorized shade 1000 need not be the same method used by the group controller 1100 to communicate with the central controller 1101 . Thus, in one embodiment, the communication system 1181 is configured to provide one type of communication (e.g., infrared, radio, ultrasonic) with the central controller, and a different type of communication with the motorized shade 1000 .
In one embodiment, the group controller is battery powered. In one embodiment, the group controller is configured into a standard light switch and receives electrical power from the light switch circuit.
FIG. 12 is a block diagram of a group controller 1200 with remote control for use in connection with the systems shown in FIGS. 6-9 . The group controller 1200 is similar to the group controller 1100 and includes, the temperature sensor 1103 , the input controls 1102 , the visual display 1110 , the communication system 1181 , and the power sources 404 , 405 . In the group controller 1200 , the remote control interface 501 is provided to the controller 1101 .
In one embodiment, an occupant sensor 1201 is provided to the controller 1101 . The occupant sensor 1201 , such as, for example, an infrared sensor, motion sensor, ultrasonic sensor, etc., senses when the zone is occupied. The occupants can program the group controller 1101 to bring the zone to different temperatures and privacy levels when the zone is occupied and when the zone is empty. In one embodiment, the occupants can program the group controller 1101 to bring the zone to different temperatures or privacy levels depending on the time of day, the time of year, the type of room (e.g. bedroom, kitchen, etc.), and/or whether the room is occupied or empty. In one embodiment, a group of zones are combined into a composite zone (e.g., a group of zones such as an entire house, an entire floor, an entire wing, etc.) and the central system 601 , 810 , 910 changes the temperature setpoints of the various zones according to whether the composite zone is empty or occupied.
FIG. 13 shows one embodiment of a central monitoring station console 1300 for accessing the functions represented by the blocks 601 , 710 , 810 , 910 in FIGS. 6 , 7 , 8 , 9 , respectively. The station 1300 includes a display 1301 and a keypad 1302 . The occupants can specify light level settings, privacy levels, etc using the central system 1300 and/or the group controllers. In one embodiment, the console 1300 is implemented as a hardware device. In one embodiment, the console 1300 is implemented in software as a computer display, such as, for example, on a personal computer. In one embodiment, the zone control functions of the blocks 710 , 810 , 910 are provided by a computer program running on a control system processor, and the control system processor interfaces with personal computer to provide the console 1300 on the personal computer. In one embodiment, the zone control functions of the blocks 710 , 810 , 910 are provided by a computer program running on a control system processor provided to a hardware console 1300 . In one embodiment, the occupants can use the Internet, telephone, cellular telephone, pager, etc. to remotely access the central system to control the temperature, priority, etc. of one or more zones.
FIG. 14 is a flowchart showing one embodiment of an instruction loop process 1400 for a motorized shade or group controller. The process 1400 begins at a power-up block 1401 . After power up, the process proceeds to an initialization block 1402 . After initialization, the process advances to a “listen” block 1403 wherein the motorized shade or group controller listens for one or more instructions. If a decision block 1404 determines that an instruction has been received, then the process advances to a “perform instruction” block 1405 , otherwise the process returns to the listen block 1403 .
For a motorized shade, the instructions can include: open window, close window, open window to a specified partially-open position, report sensor data (e.g., light level, shade position, etc.), report status (e.g., battery status, window position, etc.), and the like. For a group controller, the instructions can include: report light sensor data, report status, etc. In systems where the central system communicates with the motorized shades through a group controller, the instructions can also include: report number of motorized shades, report motorized shade data (e.g., status, position, light, etc.), report motorized shade window position, change motorized shade window position, etc.
In one embodiment, the listen block 1403 consumes relatively little power, thereby, allowing the motorized shade or group controller to stay in the loop corresponding to the listen block 1403 and conditional branch 1404 for extended periods of time.
Although the listen block 1403 can be implemented to use relatively little power, a sleep block can be implemented to use even less power. FIG. 15 is a flowchart showing one embodiment of an instruction and sensor data loop process 1500 for a motorized shade or group controller. The process 1500 begins at a power-up block 1501 . After power up, the process proceeds to an initialization block 1502 . After initialization, the process advances to a “sleep” block 1503 wherein the motorized shade or group controller sleeps for a specified period of time. When the sleep period expires, the process advances to a wakeup block 1504 and then to a decision 1505 . In the decision block 1505 , if a fault is detected, then a transmit fault block 1506 is executed. The process then advances to a sensor block 1507 where sensor readings are taken. After taking sensor readings, the process advances to a listen-for-instructions block 1508 . If an instruction has been received, then the process advances to a “perform instruction” block 1510 ; otherwise, the process returns to the sleep block 1503 .
FIG. 16 is a flowchart showing one embodiment of an instruction and sensor data reporting loop process 1600 for a motorized shade or group controller. The process 1600 begins at a power-up block 1601 . After power up, the process proceeds to an initialization block 1602 . After initialization, the process advances to a check fault block 1603 . If a fault is detected then a decision block 1604 advances the process to a transmit fault block 1605 ; otherwise, the process advances to a sensor block 1606 where sensor readings are taken. The data values from one or more sensors are evaluated, and if the sensor data is outside a specified range, or if a timeout period has occurred, then the process advances to a transmit data block 1608 ; otherwise, the process advances to a sleep block 1609 . After transmitting in the transmit fault block 1605 or the transmit sensor data block 1608 , the process advances to a listen block 1610 where the motorized shade or group controller listens for instructions. If an instruction is received, then a decision block advances the process to a perform instruction block 1612 ; otherwise, the process advances to the sleep block 1609 . After executing the perform instruction block 1612 , the process transmits an “instruction complete message” and returns to the listen block 1610 .
The process flows shown in FIGS. 14-16 show different levels of interaction between devices and different levels of power conservation in the motorized shade and/or group controller. One of ordinary skill in the art will recognize that the motorized shade and group controller are configured to receive sensor data and user inputs, report the sensor data and user inputs to other devices in the zone control system, and respond to instructions from other devices in the zone control system. Thus, the process flows shown in FIGS. 14-16 are provided for illustrative purposes and not by way of limitation. Other data reporting and instruction processing loops will be apparent to those of ordinary skill in the art by using the disclosure herein.
In one embodiment, the motorized shade and/or group controller “sleep,” between sensor readings. In one embodiment, the central system 601 sends out a “wake up” signal. When a motorized shade or group controller receives a wake up signal, it takes one or more sensor readings, encodes it into a digital signal, and transmits the sensor data along with an identification code.
In one embodiment, the motorized shade is bi-directional and configured to receive instructions from the central system. Thus, for example, the central system can instruct the motorized shade to: perform additional measurements; go to a standby mode; wake up; report battery status; change wake-up interval; run self-diagnostics and report results; etc.
In one embodiment, the motorized shade provides two wake-up modes, a first wake-up mode for taking measurements (and reporting such measurements if deemed necessary), and a second wake-up mode for listening for commands from the central system. The two wake-up modes, or combinations thereof, can occur at different intervals.
In one embodiment, the motorized shades use spread-spectrum techniques to communicate with the group controllers and/or the central system. In one embodiment, the motorized shades use frequency-hopping spread-spectrum. In one embodiment, each motorized shade has an Identification code (ID) and the motorized shades attaches its ID to outgoing communication packets. In one embodiment, when receiving wireless data, each motorized shade ignores data that is addressed to other motorized shades.
In one embodiment, the motorized shade provides bi-directional communication and is configured to receive data and/or instructions from the central system. Thus, for example, the central system can instruct the motorized shade to perform additional measurements, to go to a standby mode, to wake up, to report battery status, to change wake-up interval, to run self-diagnostics and report results, etc. In one embodiment, the motorized shade reports its general health and status on a regular basis (e.g., results of self-diagnostics, battery health, etc.)
In one embodiment, the motorized shade use spread-spectrum techniques to communicate with the central system. In one embodiment, the motorized shade uses frequency-hopping spread-spectrum. In one embodiment, the motorized shade has an address or identification (ID) code that distinguishes the motorized shade from the other motorized shades. The motorized shade attaches its ID to outgoing communication packets so that transmissions from the motorized shade can be identified by the central system. The central system attaches the ID of the motorized shade to data and/or instructions that are transmitted to the motorized shade. In one embodiment, the motorized shade ignores data and/or instructions that are addressed to other motorized shades.
In one embodiment, the motorized shades, group controllers, central system, etc., communicate on a 900 MHz frequency band. This band provides relatively good transmission through walls and other obstacles normally found in and around a building structure. In one embodiment, the motorized shades and group controllers communicate with the central system on bands above and/or below the 900 MHz band. In one embodiment, the motorized shades and group controllers listen to a radio frequency channel before transmitting on that channel or before beginning transmission. If the channel is in use, (e.g., by another device such as another central system, a cordless telephone, etc.) then the motorized shades and/or group controllers change to a different channel. In one embodiment, the sensor, central system coordinates frequency hopping by listening to radio frequency channels for interference and using an algorithm to select a next channel for transmission that avoids the interference. In one embodiment, the motorized shade and/or group controller transmits data until it receives an acknowledgement from the central system that the message has been received.
Frequency-hopping wireless systems offer the advantage of avoiding other interfering signals and collisions. Moreover, there are regulatory advantages given to systems that do not transmit continuously at one frequency. Channel-hopping transmitters change frequencies after a period of continuous transmission, or when interference is encountered. These systems may have higher transmit power and relaxed limitations on in-band spurs.
In one embodiment, the controller 301 reads the sensors at regular periodic intervals. In one embodiment, the controller 301 reads the sensors at random intervals. In one embodiment, the controller 301 reads the sensors in response to a wake-up signal from the central system. In one embodiment, the controller 301 sleeps between sensor readings.
In one embodiment, the motorized shade transmits sensor data until a handshaking-type acknowledgement is received. Thus, rather than sleep if no instructions or acknowledgements are received after transmission (e.g., after the instruction block 1510 , 1405 , 1612 and/or the transmit blocks 1605 , 1608 ) the motorized shade retransmits its data and waits for an acknowledgement. The motorized shade continues to transmit data and wait for an acknowledgement until an acknowledgement is received. In one embodiment, the motorized shade accepts an acknowledgement from a zone thermometer and it then becomes the responsibility of the zone thermometer to make sure that the data is forwarded to the central system. The two-way communication ability of the motorized shade and zone thermometer provides the capability for the central system to control the operation of the motorized shade and/or zone thermometer and also provides the capability for robust handshaking-type communication between the motorized shade, the zone thermometer, and the central system.
In one embodiment of the system 600 shown in FIG. 6 , the motorized shades 602 , 603 send window temperature data to the group controller 601 . The group controller 601 compares the window temperature to the room temperature and the setpoint temperature and makes a determination as to whether the motorized shades 602 , 603 should be open or closed. The group controller 601 then sends commands to the motorized shades 602 , 603 to open or close the windows. In one embodiment, the group controller 601 displays the window position on the visual display 1110 .
In one embodiment of the system 600 shown in FIG. 6 , the group controller 601 sends setpoint information and current room temperature information to the motorized shades 602 , 603 . The motorized shades 602 , 603 compare the window temperature to the room temperature and the setpoint temperature and makes a determination as to whether to open or close the windows. In one embodiment, the motorized shades 602 , 603 send information to the group controller 601 regarding the relative position of the windows (e.g., open, closed, partially open, etc.).
In the systems 700 , 750 , 800 , 900 (the centralized systems) the group controllers 707 , 708 send room temperature and setpoint temperature information to the central system. In one embodiment, the group controllers 707 , 708 also send temperature slope (e.g., temperature rate of rise or fall) information to the central system. In the systems where the thermostat 720 is provided to the central system or where the central system controls the HVAC system, the central system knows whether the HVAC system is providing heating or cooling; otherwise, the central system uses window temperature information provide by the motorized shades 702 - 705 to determine whether the HVAC system is heating or cooling. In one embodiment, motorized shades send window temperature information to the central system. In one embodiment, the central system queries the motorized shades by sending instructions to one or more of the motorized shades 702 - 705 instructing the motorized shade to transmit its window temperature.
The central system determines how much to open or close motorized shades 702 - 705 according to the available heating and cooling capacity of the HVAC system and according to the priority of the zones and the difference between the desired temperature and actual temperature of each zone. In one embodiment, the occupants use the group controller 707 to set the setpoint and priority of the zone 711 , the group controller 708 to set the setpoint and priority of the zone 712 , etc. In one embodiment, the occupants use the central system console 1300 to set the setpoint and priority of each zone, and the group controllers to override (either on a permanent or temporary basis) the central settings. In one embodiment, the central console 1300 displays the current temperature, setpoint temperature, temperature slope, and priority of each zone.
In one embodiment, the central system allocates HVAC light to each zone according to the priority of the zone and the temperature of the zone relative to the setpoint temperature of the zone. Thus, for example, in one embodiment, the central system provides relatively more HVAC light to relatively higher priority zones that are not at their temperature setpoint than to lower priority zones or zones that are at or relatively near their setpoint temperature. In one embodiment, the central system avoids closing or partially closing too many windows in order to avoid reducing light in the window below a desired minimum value.
In one embodiment, the central system monitors a temperature rate of rise (or fall) in each zone and sends commands to adjust the amount each motorized shade 702 - 705 is open to bring higher priority zones to a desired temperature without allowing lower-priority zones to stray too far form their respective setpoint temperature.
In one embodiment, the central system uses predictive modeling to calculate an amount of window opening for each of the motorized shades 702 - 705 to reduce the number of times the windows are opened and closed and thereby reduce power usage by the motors 409 . In one embodiment, the central system uses a neural network to calculate a desired window opening for each of the motorized shades 702 - 705 . In one embodiment, various operating parameters such as the capacity of the central HVAC system, the volume of the house, etc., are programmed into the central system for use in calculating window openings and closings. In one embodiment, the central system is adaptive and is configured to learn operating characteristics of the HVAC system and the ability of the HVAC system to control the temperature of the various zones as the motorized shades 702 - 705 are opened and closed. In an adaptive learning system, as the central system controls the motorized shades to achieve the desired temperature over a period of time, the central system learns which motorized shades need to be opened, and by how much, to achieve a desired level of heating and cooling for each zone. The use of such an adaptive central system is convenient because the installer is not required to program HVAC operating parameters into the central system. In one embodiment, the central system provides warnings when the HVAC system appears to be operating abnormally, such as, for example, when the temperature of one or more zones does not change as expected (e.g., because the HVAC system is not operating properly, a window or door is open, etc.).
In one embodiment, the adaptation and learning capability of the central system uses different adaptation results (e.g., different coefficients) based on light levels, whether the HVAC system is heating or cooling, the outside temperature, a change in the setpoint temperature or priority of the zones, etc. Thus, in one embodiment, the central system uses a first set of adaptation coefficients when the HVAC system is cooling, and a second set of adaptation coefficients when the HVAC system is heating. In one embodiment, the adaptation is based on a predictive model. In one embodiment, the adaptation is based on a neural network.
FIG. 17 is a block diagram of a control algorithm 1700 for controlling the motorized shades. For purposes of explanation, and not by way of limitation, the algorithm 1700 is described herein as running on the central system. However, one of ordinary skill in the art will recognize that the algorithm 1700 can be run by the central system, by the group controller, by the motorized shade, or the algorithm 1700 can be distributed among the central system, the group controller, and the motorized shade. In the algorithm 1700 , in a block 1701 of the algorithm 1700 , the setpoint light levels from one or more group controllers are provided to a calculation block 1702 . The calculation block 1702 calculates the motorized shade settings (e.g., how much to open or close each motorized shade) according to the desired light level, privacy level, etc. In one embodiment, the block 1702 uses a predictive model as described above. In one embodiment, the block 1702 calculates the motorized shade settings for each group independently (e.g., without regard to interactions between group). In one embodiment, the block 1702 calculates the motorized shade settings for each zone in a coupled-zone manner that includes interactions between groups. In one embodiment, the calculation block 1702 calculates new window openings by taking into account the current window openings and in a manner configured to minimize the power consumed by opening and closing the motorized shades.
Window shade settings from the block 1702 are provided to each of the motorized shade motors in a block 1703 , wherein the motorized shades are moved to new opening positions as desired (and, optionally, one or more of the fans 402 are turned on to pull additional light from desired windows). After setting the new window openings in the block 1703 , the process advances to a block 1704 where new measurement values (e.g., temperature, light, privacy, etc.) are obtained from the group controllers (the new zone temperatures and light levels being responsive to the new motorized shade settings made in block 1703 ). The new zone temperatures are provided to an adaptation input of the block 1702 to be used in adapting a predictive model used by the block 1702 . The new zone temperatures also provided to a temperature input of the block 1702 to be used in calculating new motorized shade settings.
As described above, in one embodiment, the algorithm used in the calculation block 1702 is configured to predict the motorized shade opening needed to bring each group to the desired setting based on the current temperature, the available heating and cooling, the amount of light available through each motorized shade, etc. The calculating block uses the prediction model to attempt to calculate the motorized shade openings needed for relatively long periods of time in order to reduce the power consumed in unnecessarily by opening and closing the motorized shades. In one embodiment, the motorized shades are battery powered, and thus reducing the movement of the motorized shades extends the life of the batteries. In one embodiment, the block 1702 uses a predictive model that learns the characteristics of the system and the various zones and thus, the model prediction tends to improve over time.
In one embodiment, the group controllers report zone temperatures and/or light levels to the central system and/or the motorized shades at regular intervals. In one embodiment, the group controllers report zone temperatures to the central system and/or the motorized shades after the zone temperature has changed by a specified amount specified by a threshold value. In one embodiment, the group controllers report zone temperatures to the central system and/or the motorized shades in response to a request instruction from the central system or motorized shade.
In one embodiment, the group controllers report setpoint temperatures and/or light levels, zone priority values, etc. to the central system or motorized shades whenever the occupants change the setpoint temperatures or zone priority values using the user controls 1102 . In one embodiment, the group controllers report setpoint temperatures and zone priority values to the central system or motorized shades in response to a request instruction from the central system or motorized shades.
In one embodiment, the occupants can choose the thermostat deadband value (e.g., the hysteresis value) used by the calculation block 1702 . A relatively larger deadband value reduces the movement of the motorized shade at the expense of larger temperature variations in the zone.
In one embodiment, the occupant sensor 1201 is used to change the privacy priority from relatively lower to relatively higher priority. Thus, for example, the system can be configured to provide relatively more privacy when a room or area is occupied than when the area is unoccupied. In one embodiment, a hysteresis-like value is used in connection with the occupancy sensor such that the privacy setting of an area changes relatively slowly so that the motorized shades do not run up and down repeatedly if a person walks in and out the area detected by the occupant sensor 1201 . In one embodiment, the system 601 uses the data from the occupant sensor 1201 to learn when an area is likely to be occupied or unoccupied for a period of time and vary the privacy setting accordingly.
In one embodiment, the motorized shades report sensor data (e.g., window temperature, light, power status, position, etc.) to the central system and/or the group controllers at regular intervals. In one embodiment, the motorized shades report sensor data to the central system and/or the group controllers whenever the sensor data fails a threshold test (e.g., exceeds a threshold value, falls below a threshold value, falls inside a threshold range, or falls outside a threshold range, etc.). In one embodiment, the motorized shades report sensor data to the central system and/or the group controllers in response to a request instruction from the central system or group controller.
In one embodiment, the central system is shown in FIGS. 7-9 is implemented in a distributed fashion in the group controllers 1100 and/or in the motorized shades. In the distributed system, the central system does not necessarily exists as a distinct device, rather, the functions of the central system can be are distributed in the group controllers 1100 and/or the motorized shades. Thus, in a distributed system, FIGS. 7-9 represent a conceptual/computational model of the system. For example, in a distributed system, each group controller 100 knows its zone priority, and the group controllers 1100 in the distributed system negotiate to allocate the available light, privacy, heating/cooling, etc. among the zones. In one embodiment of a distributed system, one of the group controller assumes the role of a master thermostat that collects data from the other group controllers and implements the calculation block 1902 . In one embodiment of a distributed system, the group controllers operate in a peer-to-peer fashion, and the calculation block 1902 is implemented in a distributed manner across a plurality of group controllers and/or motorized shades.
In one embodiment, the motorized shade reports its power status to the central system or group controller. In one embodiment the central system or group controller takes such power status into account when determining new motorized shade openings. Thus, for example, if there are first and second motorized shades serving one zone and the central system knows that the first motorized shade is low on power, the central system will use the second motorized shade to modulate the light into the zone. If the first motorized shade is able to use the fan 402 or other light-based generator to generate electrical power, the central system will instruct the second motorized shade to a relatively closed position in and direct relatively more light through the first motorized shade when directing light into the zone.
In one embodiment, the central system or group controller instructs the shades to open in response to a fire or smoke alarm signal. In one embodiment, the central system or group controller instructs the shades to open or close in response to a signal from a burglar alarm system. In one embodiment, the central system or group controller instructs the shades to open or close in response to a window open, window close, door open, and/or door close signal from a burglar alarm-type system. In one embodiment, the group controller is provided to a network connection (e.g., an Internet connection, cellular telephone connection, telephone connection etc.) to allow the homeowner to remotely open or close the blinds or to remotely change priority parameters in the control system (e.g., desired relative priority of privacy, temperature, and light, desired temperature, desired privacy level, desired light level, etc.). In one embodiment, the user can remotely control the network-connected group controller via telephone or cellular telephone.
FIG. 18 shows one embodiment of a motorized shade, with a tubular motor 303 , internal batteries as the power source 350 , and an electronics module 1801 . The electronics module includes for example, the controller 301 , the optional capacitor 306 , the RF transceiver 302 , and the optional RFID tag 309 .
FIG. 19 shows one embodiment of a motorized shade with a tubular motor 303 , internal batteries as the power source 350 , the electronics module 1801 , and a fascia 1901 .
It will be evident to those skilled in the art that the motorized shade is not limited to the details of the foregoing illustrated embodiments and that the present motorized shade may be embodied in other specific forms without departing from the spirit or essential attributed thereof; furthermore, various omissions, substitutions and changes may be made without departing from the spirit of the invention. For example, although specific embodiments are described in terms of the 900 MHz frequency band, one of ordinary skill in the art will recognize that frequency bands above and below 900 MHz can be used as well. The wireless system can be configured to operate on one or more frequency bands, such as, for example, the HF band, the VHF band, the UHF band, the Microwave band, the Millimeter wave band, etc. One of ordinary skill in the art will further recognize that techniques other than spread spectrum can also be used and/or can be used instead spread spectrum. The modulation used is not limited to any particular modulation method, such that modulation scheme used can be, for example, frequency modulation, phase modulation, amplitude modulation, combinations thereof, etc. The one or more of the wireless communication systems described above can be replaced by wired communication. The one or more of the wireless communication systems described above can be replaced by powerline networking communication. The foregoing description of the embodiments is, therefore, to be considered in all respects as illustrative and not restrictive, with the scope of the invention being delineated by the appended claims and their equivalents. | An electronically-controlled roll-up window shade that can easily be installed by a homeowner or general handyman is disclosed. The motorized shade includes an internal power source, a motor, and a communication system to allow for remote control of the motorized shade. One or more motorized shades can be controlled singly or as a group. In one embodiment, the motorized shades are used in connection with a zoned or non-zoned HVAC system to reduce energy usage. In one embodiment, the motorized shade is configured to have a size and form-factor that conforms to a standard manually-controlled motorized shade. In one embodiment, a group controller is configured to provide thermostat information to the motorized shade. In one embodiment, the group controller communicates with a central monitoring system that coordinates operation of one or more motorized shades. In one embodiment, the internal power source of the motorized shade is recharged by a solar cell. | 4 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention is concerned with thermoplastic bag construction, and more particularly the construction of bags to be supplied in multiple bag packs wherein severable tabs interlock the bags and allow for a separable dispensing of the individual bags. Such bags normally incorporate integral handles and are mounted on a dispensing rack by the tabs which are severed as the individual bags are physically pulled from the rack.
The bags are frequently formed by utilization of flattened tube portions selectively severed from a length of tubing of appropriate material and subsequently heat sealed along the lower and upper edges thereof. An appropriate mouth-defining U-shaped cutout is normally made through the sealed upper edge, the cutout simultaneously defines opposed handles. The known bags have been formed both with and without side gussets.
2. Description of the Prior Art
Typical examples of the known prior art will be seen in the following patents:
U.S. Pat. No. 3,352,411, to Schwarzkopf
U.S. Pat. No. 4,062,170, to Orem
U.S. Pat. No. 4,165,832, to Kuklies et al.
U.S. Pat. No. 4,199,122, to Christie
Schwarzkopf illustrates a basic bag construction wherein a partially severed U-shaped flap defines a detachable tab which, upon separation from the bag, forms two handles. The partially severed flap constitutes the means by which the bag is mounted in a pack and on a dispensing rack.
The patent to Kuklies et al discusses the general nature of the known art, as exemplified by the Schwarzkopf patent, and proposes modifications in the handle configuration, the configuration of the bag mouth, and the location of the detachable tab. Basically, Kuklies et al provides a handle and mouth arrangement which includes an enlarged projecting detachable tab fixed centrally along the mouth by a perforated or tear area, the opposed ends of the mouth incorporating downwardly enlarged notches indicated as being for stress relief. Upon removal of the Kuklies bag from the mounting tab, the mouth of the bag retains, along each bag wall, an upwardly projecting flap with a perforation-defined edge and opposed enlarged end notches. The projecting flap and perforation edge, in the high stress area of the bag mouth, form areas of potential weakness.
Both Christie and Orem disclose racks for stacks of handle bags. The bags in Orem include detachable perforated tabs along the mouth-defining upper edges of the bag walls.
SUMMARY OF THE INVENTION
The bag construction in accordance with the present invention incorporates structural improvements which substantially enhance the appearance, strength, structural stability, and ease of use of the bag. The anticipated advantages are achieved through a unique formation and configuration of the bag at the handle and mouth area thereof.
More particularly, the present invention proposes formation of the bag with a continuous and uninterrupted upper or mouth edge which, at the opposite ends thereof, blends into the inner edges of the lateral handles through arcuate corners. The mouth of the proposed bag includes no unsightly flaps as may interfere with the introduction and removal of commodities. Similarly, the bag mouth has no roughened edge portions defined by the severing of a tab therefrom, as may tear when subjected to flexing or distortion during bag loading. Further, elimination of a tear-defined portion along the mouth edge avoids the necessity for enlarged stress-relieving notches which decrease the effective depth of the bag.
The present invention proposes provision of the pack-forming detachable tabs as minor integral extensions formed at a central or intermediate point along the inner edges of the bag handles of a bag remote from the mouth thereof. Positioned in this manner, a multiple-bag pack can be effectively mounted on a dispensing rack through an engagement of both sets of tabs. This in turn produces a stable orientation of the bags with a positive retention and positioning of both handles thereof for easy access to the handles and manipulation of the individual bags for removal from the pack.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a pack of bags formed in accord with the present invention;
FIG. 2 is a front elevational view of a single bag; and
FIG. 3 is a perspective view of a bag removed from the detachable mounting tabs and partially open.
DESCRIPTION OF PREFERRED EMBODIMENT
Referring now more specifically to the drawings, the bag 10, as illustrated, can conveniently be fabricated from a plastic tube gusseted, flattened and heat sealed at opposed upper and lower ends.
The formed bag includes planar opposed panels respectively designated as front panel 12 and rear panel 14 for purposes of illustration. The side edges of the overlying panels 12 and 14 are interconnected by full length inwardly folded integral gussets 16 which allow for an expansion of the bag in an obvious manner.
Both the upper and lower edges of the panels 12 and 14, as well as the corresponding end edges of the gusset 16, are heat sealed throughout the length thereof as at 18 and 20. The sealed structure is then cut away inwardly and centrally through the heat sealed upper edge 20 to define both a bag mouth 22 and a pair of laterally opposed handles 24. The defined handles 24 will generally taper along the height thereof from narrow lower portions adjacent the mouth 22 of the bag to relatively wider upper end portions at the defined seam 20. In forming the tapered configuration, the opposed inner edges of the handles 24, as will be best appreciated in FIG. 2, diverge downwardly and terminate in stress-relieving arcuate corner portions 26 which join the vertical handle edges with the straight or slightly arcuate bag mouth 22. As will be recognized, the bag mouth 22, inward of the opposed arcuate corners 26, is, in its entirety, at or below the arcuate corners 26. The handles are completed by the provision of integral inwardly directed mounting tabs 28, one provided at an intermediate point along the height of each handle 24 above the corresponding arcuate corners 26 and below the sealed upper edge 20, preferably at generally mid-height. Each detachable tab includes a mounting aperture 30 therethrough and a line of weakness 32, defined by a partial cut, perforations, or the like, slightly outward from the line of the handle edge to define a small residual flap 34 subsequent to detachment of the bag from the tabs 28.
Noting FIGS. 2 and 3 in particular, it will be appreciated that the generally U-shaped cut which defines the handles 24 and the bag mouth 22 extends through the inner folds of the opposed gussets 16, severing the central portions of the gussets above the bag mouth 22 and providing for a loop handle construction with each handle formed of both an inner gusset layer and an outer panel layer. The formed tabs 28 will comprise four layers and, until severed, provide for a positive retention of both the panels and inner gusset layers.
The upper portion cutout configures the front and rear panels 12 and 14 to define front and rear bag walls downward from the formed mouth 22, and upwardly extending handle-forming front and rear handle wall portions which terminate at the sealed upper edge 20 along each formed handle 24. These upwardly extending handle wall portions combine with the underlying separated gusset portions in forming what might be considered reinforced handles directly supportive of the four bag walls defined by the opposed panels and opposed gussets.
The described bag construction will normally be provided in a bag pack, as illustrated in FIG. 1. Such packs are formed preferably by a heat welding of the mounting tabs 28 to each other. This in turn can easily be effected simultaneously with the forming of the mounting apertures 30 through the aligned tabs 28 of a stack of bags 10 by utilizing a heated rod or the like. The rod, while forming the apertures through the thermoplastic material of the bag tabs, will also cause a melting and flowing of the material around the periphery of each aperture, fusing these peripheral areas together.
In use, the bag pack will normally mount over the rear portion of a rack with the bags individually forwardly drawn to detach from the tabs and engage the loop handles over opposed rack projections to maintain the individual bag upright and open. This general environment will be noted in the above referred to patents to Orem and Christie.
It is particularly to be appreciated that the provision of the tabs at an intermediate portion along the height of the inner edges of the opposed handles is significant in providing for mounting tabs at a location which stabilizes and both individually and directly supports the handle portions of the bags for easy and convenient access thereto. This in turn greatly facilitates the hand gripping of the handles and the forward drawing thereof to separate the handles from the mounting tabs and simultaneously open the handles for engagement over the rack projections.
It is also considered of particular significance that the tabs are formed remote from the bag mouth, thereby avoiding any disruption of the bag mouth through either the provision of a tear line therealong or a disruptive projection. As will be appreciated from a viewing of the basic rack constructions of the Orem and Christie patents, applicant, by providing the detachable mounting tabs at generally mid-height along the handle inner edges, insures that the slight remainder flaps which project upon severance from the tabs will be located laterally outward of the main body of the bag and the upwardly opening mouth through which the commodities are to be introduced. Similarly, the tab remainders in applicant's bag construction will have no effect on the structural integrity of the multiple ply handles which, in use, will be inwardly gathered toward each other with only minimal stress specifically along the inner edges of the gathered bag handles.
From the foregoing, it will be appreciated that a distinctive bag construction has been presented wherein specific provision is made to incorporate detachable mounting tabs on rack-mountable bags in a manner whereby the complete integrity of the mouth of the bag is retained, avoiding both mouth or edge weakening tear areas and edge disruptive flaps. Simultaneously, provision is made to locate the tabs in a manner whereby the individual laterally spaced handles are themselves directly supported and retained in a readily and easily accessible position for a direct physical grasping and movement thereof for disengagement from the tabs and a positioning of the individual bags in loading position.
The foregoing is considered illustrative of the principles of the invention. Suitable modifications and variations, as may occur to those skilled in the art, may be made without departing from the spirit or scope of the invention. | A thermoplastic bag having front and rear walls with smooth upper edges defining an open bag mouth. A pair of laterally spaced integral loop handles extend upward from the bag mouth and include detachable mounting tabs projecting laterally inward from the handles at an intermediate point along the height thereof. The tabs are remote from the bag mouth and, in a bag pack, form the securing area for the bags. | 1 |
FIELD OF TECHNOLOGY
The invention relates to a method and to devices for controlling the emission power in a communications system.
BACKGROUND
In communications systems, especially those operating in accordance with the GSM (Global System for Mobile communications) or UMTS (Universal Mobile Telecommunications System) standards, data or information is transmitted between a subscriber-side station and a network-side base station over radio interfaces. To set the required emission power in such cases what is known as the Shannon capacity is to be taken into account in each case. The Shannon capacity specifies the maximum volume of data or information that can be sent over a channel when the channel is affected by normal disturbance factors, including noise. The Shannon capacity thus specifies a relationship between emission power and signal-to-noise ratio which may not be exceeded if the receive quality is to be sufficient.
Noting the fact that the subscriber-side stations are mostly mobile stations with a portable energy source, research has long been directed towards minimizing the required signal-to-noise ratio for data transmission in wireless radio communications systems. In addition to the radio communications systems already mentioned, this typically also involves data networks, e.g. in accordance with the HiperLAN2 standard. To allow sending with the lowest possible emission power various methods of error correction have been developed, for example the method known as Forward Error Correction (FEC) referred to as Block FEC, Convolutional FEC, Turbo FEC or Coding FEC. Further error correction methods are what are known as ARQ (ARQ: Automatic Repeat Request) schemes, in which redundant data is transmitted, adaptive modulation methods and so on.
With these type of error correction methods there are especially methods in which a downlink channel is used from the receiver to the original sender, for example to retroactively request a retransmission of incorrect data symbols or, in the case of incremental redundancy, to request more redundancy to be transmitted, as with the ARQ method for example.
BRIEF SUMMARY
The object of the invention is to propose an alternative method for reducing the required emission power, in particular of a mobile station, as well as the corresponding devices for executing such a method.
This object is achieved by a method for controlling the send parameters for emitting data with the features of patent claim 1 or devices for executing such a method with the features of patent claims 12 and 13 .
The method for controlling the emission power of a sending station makes provision for the sending station to send a signal for transmitting data to a receiving station, for the receiving station to determine a measured value that is dependent on the data transmitted by the signal and transmit it to the sending station as control information for controlling its emission power.
In the case of amplitude modulation of the signal transmitted from the sending station the measured value can be analog power values of the receiving signal, also referred to below as reception power amplitude values. In the case of phase modulation of the signal to be transmitted the value can also be a phase angle for example which has been determined for an item of data received in the receiving station. For an analog measured value transferred to the sending station the value concerned is therefore one that, although it depends on data to be transmitted to the receiving station with the signal, will be determined before demodulation in the receiving station.
With phase modulation a number of items of data to be transmitted will often be combined into one modulation symbol which will then be used for modulation of the carrier. In this case the measured value in accordance with the invention relates to one of the symbols received with the signal. The individual data of the modulation symbol are only retrieved again after demodulation has taken place, which occurs after the measured value has been determined.
By sending back measured values (in the form of analog power values of received data for example) to a station originally sending this data, the originally sending station can check directly whether the data sent out was sufficiently correctly received. If it was not, an appropriate correction can be made to the emission power for subsequent send processes. Checking whether a sufficient receive quality is available is thus not undertaken on the receive side but on the send side.
Advantageous embodiments are the object of dependent claims.
Sending back of the measured values (in the form of the analog power values for example) can in such cases be performed in such a way that further disturbance effects are practically negligible during transmission of the measured values so that the measured values sent back will be correctly received in the sending station. To make this possible the signals are preferably sent back from the receiving station with significantly higher power than the emission power with which the data originally sent was emitted from the sending station. Coding and/or redundancy methods can also be usefully employed here to ensure that the measured values are sent in the downlink direction without errors. One thing that this procedure allows is very low send energy to be used at the sending station for which the energy consumption is to be reduced as much as possible and another is the sending back of the measured values to be undertaken independently of the required amount of energy to be used. This is of advantage if the sending station involved is a mobile subscriber station with limited battery power and the receiving station is a base station with no restriction as to power supply.
For the case of a fault established by the sending station and which cannot be tolerated during the original sending of data via the interface the sending station can send out correction data for the previously sent data to the receiving station communicating with it. This type of correction data can consist of a correction factor or an additive correction value. However it is also possible to also just have the original data sent again as correction data, typically with higher transmit energy.
Especially useful however (where the measured value is an analog power value) is repeated sending of the original data as correction data, in which case the correction data can then consist of the original data from which advantageously an appropriate difference value between the originally sent power value and the analog power value received on the receiver side is inserted or removed so that on the receiver side an addition of the received data from the same data origin can be undertaken. The adding of an original data value and this type of correction data value as well as division by two would lead on the receiver side to a corrected data value which, in the case where the correction data has been transmitted without any errors creates the originally sent data value.
Particularly useful here however is not only the fact that the data value is transmitted twice as a data value and as a correction data value, but the repeated transmission of this data value with a correction applied in each case. In this case after the data value first transmitted has been received in each case as well as the correction data value received later the received analog power values can be transmitted in the downlink direction to the sending station so that the latter can add or subtract any appropriate new correction value to the correction data of the repeated transmission sequence subsequently to be sent. The more of this type of transmitted data or correction data is stacked on the receiver side the smaller the effect is in the final analysis of noise on the radio interface.
Especially with a view to the last correction data value to be sent for which there is no return transmission of its measured value received on the receiver side (e.g. as an analog power value) a statistical evaluation can also be performed to enable a noise value which is not random to be generated or a non-random additive or multiplicative noise value to be established. This means that the correction data to be transmitted subsequently, especially the correction data value to be transmitted last, can be corrected in addition to the result of the last return transmission.
The sending station and receiving station in accordance with invention feature the components necessary to execute the method in accordance with the invention and are designed appropriately for their execution.
A camera for optically recording images and/or sequences of images and optional sound signals for electronic output of previously recorded images to a remote communication system device as receiving station via a radio interface is especially advantageous as a sending station with low transmit power. In this way pictures with higher resolution, that is pictures with a very high memory requirement can be recorded and stored without over filling the generally very limited availability of memory space with just a few individual pictures or with correspondingly higher resolution without even a single picture.
BRIEF DESCRIPTION OF THE DRAWINGS
Additional features and advantages of the present invention are described in, and will be apparent from, the following Brief Description of the Drawings and the Detailed Description.
FIG. 1 illustrates an exemplary arrangement with a communications interface and a station sending data over this interface as well as a station receiving this data with power values of data values sent consecutively mapped below the stations.
DETAILED DESCRIPTION
Whereas in typical communication systems, especially in radio communications systems, a plurality of different types of the devices are provided on the network side to communicate via individual base stations or access points AP with one or more subscriber-side stations MT, the method described below can already be used for communication between two individual stations AP, MT, as shown in FIG. 1 .
In the present exemplary embodiment data c 1 . . . c 4 is present in a first, e.g. subscriber-side station MT, which will referred to hereafter as the sending station MT, which is to be sent via a radio interface V to a station AP communicating with the sending station MT. In order to better identify it, this station receiving the data c 1 . . . c 4 will be identified as the receiving or returning station AP (AP: Access Point). At interface V, which is preferably designed as a radio interface, transmissions in the uplink direction UL will be transferred from the sending station MT to the receiving station AP, for example via an uplink connecting channel of a communications system. Furthermore data or information will be sent back from the receiving station AP to the sending or originally sending station MT via the interface V in the downlink direction DL, especially via a downlink connection channel of a communications system. As a rule the terms data, information and signaling are generally applicable. Without any intentional restriction they stand for traffic or communication between two stations.
The actual data source can be designed in different ways, for example with a microphone to record speech data, but can especially consist of an optical recording device for recording images or sequences of images. Especially in the case of an optical recording device it is possible to link the sending station MT with a camera CAM for recording images via an appropriate interface or to equip such a camera CAM directly with a corresponding communication device or station MT that can send in this way.
This makes it possible to send pictures or their data recorded by the camera CAM directly or after buffering to a correspondingly suitable device in the communications network. Such a device can for example be a monitor for monitoring purposes, but can also be a large-volume storage device in which a plurality of these types of pictures or pictures with extremely high resolution and correspondingly extremely high data rate can be stored. This means that the camera CAM is not restricted to recording images until its own memory is full. Particularly advantageous is an embodiment in which the image data which is recorded by the camera CAM is transmitted via the sending station MT, the radio interface V and a receiving station AP, with the receiving station AP on its side making it possible to access the internet for example in order to forward the data in a form in accordance with the internet protocol (IP), in which case, in a particularly advantageous embodiment, the final receiving device can be the personal computer (PC) of the person who is operating the camera CAM.
With the method described below it is assumed that the connection, especially a radio connection, is relatively good in the uplink direction or downlink direction from the original receiving station AP to the original sending station MT. A relatively good connection can be obtained by the sending station MT being located close to the receiving station AP, by the receiving station using a very high emission power Ic* for sending back and/or special coding or redundancy methods being used for sending back in the downlink direction from the receiving station AP to the original sending station MT.
The greatest proportion of energy consumption in transmission of data typically occurs in the high frequency part, that is in the power amplifier of the send device. Especially in the case of one-chip solutions, the required power for data processing in comparison to the required amplification power can normally be disregarded. While the network-side stations for communication systems normally have a sufficient power feed available from the fixed network connection so that the power consumption only represents a lower criterion, the power consumption of mobile stations which carry their own energy source is not negligible.
With the exemplary embodiment considered here the emission power Ic from the mobile, subscriber-side sending station MT to the receiving, especially network-side station AP should be minimized as much as possible, whereas in the reverse direction for sending back data and information there should be no power restriction, or in order to ensure an error-free transmission, even a particularly high level of energy should be used for sending the data.
It can be especially advantageous when the downlink channel from the original receiving station AP to the original sending station MT compared to the known error correction method, that is for example compared to a low data-rate ARQ channel, is expanded into a channel with a high or very high data rate. This makes it possible, in the downlink direction from the original receiving station AP to the original sending station MT, to transmit the analog power values of the received data or data symbols previously determined on the receiver side back to the original sender. Although the overall spectral effectiveness of the communications system is much reduced by this method of operation since the high proportion of data in the downlink channel DL blocks the transmission of useful data, the procedures described below can advantageously be employed to greatly lower the power consumption in the original sending station MT, which is very valuable for specific applications.
In accordance with the preferred exemplary embodiment, as is shown in the Figure, data c is sent out in a first step as data value c 1 with a specific emission power, e.g. Ic 1 =1. During the transmission via interface V in an uplink direction UL a noise signal n(t) affects the transmitted data c 1 . The noise signal involved n(t) can be both statistical noise, known as white noise, but also electromagnetic disturbance effects of other power sources with electromagnetic emissions.
Thus at the receiving station AP instead of the sent data value c 1 with an emission power Ic 1 =1, a data value c 1 * with a received receive signal power Ic 1 * is received, in which case this reception power Ic 1 * is generally not equal to 1 because of the effect of the noise signal n(t), i.e. Ic 1 *<>1. In the receiving station AP the corresponding analog power value Ic 1 * for the received data value c 1 * is determined and sent back via interface V in the downlink direction DL to the originally sending station MT. To do this the analog power value Ic 1 * is usefully converted into a digital value which is then sent back as a digital signal.
In the original sending station MT the received, returned analog power value Ic 1 * is compared with the emission power value Ic 1 and the power difference ΔIc 1 is determined.
In a second step for transmitting the original data value c 1 an emission power correction is performed, taking into account the power difference ΔIc 1 determined. Subsequently to do this for the preferred exemplary embodiment the original data value c 1 plus the defined difference power ΔIc 1 are combined into a correction data value c 2 , in which case the power difference ΔIc 1 in the case of a power Ic 1 * originally received too low on the receiver side is added in to form data correction value c 2 , whereas in the case of a power Ic 2 * received too high on the receiver side it is subtracted for creation of the data correction value c 2 . A data correction value c 2 created in this way is subsequently sent from the sending station MT to the receiving station AP in the uplink direction UL via interface V. Its emission power is, determined by the emission power on the previous emission plus/minus the received power difference, i.e. Ic 2 =Ic 1 +ΔIc 1 .
The receiving station handles the data correction value c 2 * now received just like the data value c 1 * received beforehand, which means that in its turn it determines an analog power value and sends back this value digitized in the downlink direction DL to the sending station MT. In this station the power difference ΔIc 2 is again determined between the received power value Ic 2 * and the sent power value Ic 2 =(Ic 1 *+ΔIc 1 ) in order to form a further data correction value c 3 on the sender side.
On the receiver side the received data c 1 * and data correction values c 2 *-c 4 * will be jointly processed to create the originally sent data value c 1 . Particularly useful here is adding the data c 1 * and the data correction values c 2 *-c 4 * and the subsequent division by the number of added values. This procedure, also generally known as stacking, produces a data value which is largely cleansed of the effects of noise signals n(t). The more data c 1 and data correction values c 2 -c 4 are transmitted from the sending station MT to the receiving station AP, the more accurately the originally sent data value c 1 can be reconstructed on the receiver side. Usefully the totally number of transmissions of data and data correction values to be undertaken can however be limited to a prespecified number which forms 1 symbol consisting in the exemplary embodiment shown of 4 data and data correction values or so-called chips 1 - 4 . Particular account should be taken of the fact that with an increasing number of transmissions, an increased rather than a reduced overall power consumption is to be observed.
Whereas with the exemplary embodiment shown, a correction for the last data correction value c 4 sent cannot be undertaken, for the case in which the noise signals n(t) do not merely correspond to a statistical noise but for example contain a linear trend or additive supplement, statistical evaluation is also possible in order, especially for the last data correction value c 4 to be transmitted, to predetermine a likely distortion by the noise signal n(t) and take it into account for generation of data correction value c 4 . These types of advance corrections can naturally also be applied to the other data correction values c 2 , c 3 . An application of previously determined non-statistical correction values is also especially possible for data values of other data or of other symbols to be sent later.
A large number of alternate embodiments is possible for the exemplary embodiment shown, of which only individual examples are described below.
Instead of sending a data value or data c 1 in each case and the associated data correction values c 2 -c 4 following on directly in the uplink direction UL, any type of scheme can also be introduced in which between the emission of the associated first data correction value c 2 or further data correction values c 3 , c 4 , data and data correction values of other original data are sent in each case. This means that the time required for the transmission, the receiver-side determination of the analog power and the return transmission as well as the send-side determination of a data correction value can be used by sending other data or data correction values.
Whereas with the exemplary embodiment described here the specified power difference was used to form a data correction value by addition of the original data value c 1 and the power difference value Dlc 1 , it is also possible to merely transfer the difference amount Dlc 1 as data correction value to the receiving station AP. In the latter no addition of the received values and subsequent division by the number of added values is then undertaken, but merely an addition of all associated data and data correction values of a shared data origin would be undertaken in order to reconstruct the original data value c 1 as regards its original power Ic 1 .
In a comparable way correction factors and such like can also be determined and applied.
There are various options for ensuring that transmission is as undisturbed as possible by noise signals n(t) during transmission of the analog power values Ic 1 *-Ic 3 *. One is to select a power for the downlink transmission DL that is so high that the influence of noise signals n(t) becomes negligible. Another is however to use various correction methods which are known per se which use repeated transmissions with redundant data or coded data.
The procedure for sending data c 1 and data correction values c 2 -c 4 from the sending station MT to the receiving station AP is roughly comparable with the situation of a CDMA (Code Division Multiple Access) procedure in which only one repetition code is used for all chips.
In particular combinations of the method described in this document are possible, with addition data transmission security procedures or error correction procedures so that transmission security is further enhanced. Where the send energy or emission power lc remains the same, if the correction methods described here are not adequate it is also possible to additionally increase the send energy lc generally used by sending station MT for new transmissions. This can be automated especially if the basic emission power is increased on determining the difference power values Al for the case where increased power differences ΔI are established. Conversely the basic emission power Ic can automatically be reduced if, when determining the power differences, it is established that only minimal or negligible power differences are to be identified between the sent data and the received data.
Use of the method described in this document is especially useful for existing radio communications systems: in which the connections in the upstream direction from a network-side station to a subscriber-side station are often designed for transmitting larger volumes of data than those in the opposite direction. This applies especially to the areas of the internet for which large volumes of data are retrieved from remote data sources by individual subscriber-side stations MT via the corresponding access points or network-side stations AP. With these types of system it is also especially not very disadvantageous for the conversion of the power values received on the subscriber side into analog data and its transmission as digitized data to generally require a higher volume of data for the downlink transfer than the volume required for uplink transfer.
In the downlink direction DL highly-developed and expensive modulation methods can also especially be used to transfer back with negligible disturbance the analog reception power values Ic 1 *-Ic 3 * determined for the receiving data values c 1 *-c 3 *. In the originally sending station MT securely received data can be processed in this way with a low additional power outlay which is negligible in comparison to the saved emission power since the demodulation of the data sent back is possible in the originally sending station MT with only slight additional power for processing the data.
For further clarification a description with the appropriate numerical values will now be provided for the exemplary embodiment described here. While the sent data value c 1 was transmitted with a standardized power value of Ic 1 =1-4, the effect of the additive noise or interference signal n(t) means that on the receiver side a data value c 1 * with a reception power value Ic 1 *=0.7 was received. This power value 0.7 will be fed back via the downlink channel DL to the sending station MT. This then sends, after determining the power difference ΔIc 1 =0.3 as a data correction value c 2 a data correction value with a correspondingly increased emission power Ic 2 =1.3 instead of the normal emission power I=1.0. This procedure with a plurality of values corrected accordingly corresponds to a repetition code, meaning the final symbol entry or evaluation only takes place when all individual chips or data and correction values or the complete code word have been received.
Although this reduces the possible data rate when sending from the sending station MT with an increasing number of chips c 1 -c 4 , in the case of a system such as HiperLAN2 with very high data rates of 54 Mbit/s for example, it is possible despite this to achieve transmission data rates of several Mbit/s, which also allows transmission of a picture from a digital camera to the access point or the receiving station AP in just a few seconds.
The number of chips used can usefully be adapted and selected individually so that it is made dependent on the desired emission power and the desired data rate. This is done by undertaking the appropriate signaling to the receiving station in a first step, so that this also obtains knowledge of the number and sequence of the received data for a shared data origin in each case. By changing the number of data chips per symbol the required emission power can thus be reduced or increased accordingly. When this is done it is useful to take account of the fact that as from a certain number of transmissions a certain level of send energy is in its turn required for these transmissions, so that a minimization function is to be used to determine the idea combination of number of data chips and individual emission powers in relationship to overall power in each case.
Usefully the modulations, data rates and emission powers for the downlink transmission from the receiver side to the sender side are also optimized to avoid disturbance of the transmissions in the uplink direction UL or of other stations in the environment by for example excessive emission powers in the downlink direction DL.
First simulations have shown that for the transmissions in the uplink direction UL emission powers below the Shannon capacity are actually possible. This is made possible by the information returned in the downlink direction, in which case an uplink connection channel can usefully be introduced for the downlink direction as a new superchannel which has a greater Shannon capacity than the uplink connection taken as such alone.
The proposed procedure can especially be used with OFDM (OFDM: orthogonal Frequency Division Multiplex) systems since OFDM extends the duration of each symbol. Thus the time for the round-trip delay for recording the received signal and its underlying signal processing and transmission in the downlink channel DL can be increased as much as is required. Each subcarrier of the OFDM symbol would be handled in parallel, which means that it would be given a separate channel in the downlink direction DL in each case. For greater round trip delays it is also possible to form a loop not with the next symbol in each case, but with a later symbol, meaning that symbol 1 is transmitted in upstream direction UL, with the downstream information being transmitted in a symbol 4 in the corresponding downlink channel DL. After symbol 1 symbol 2 would be transmitted in the uplink direction UL and the assigned downlink information in symbol 5 in the downlink direction etc.
The downlink channel DL transmits digitally coded analog values, which means that the quantization level is of interest. A method for reducing the quantization level is to store the quantization errors for each chip or data value and data correction value transmitted and to take account of this error value for the next value in the downlink channel DL so that the overall error is reduced.
Power value or reception power value here in particular mean the actual amplitudes of the received signal on the receiver side. Thus cases are also taken into account in which, instead of a positive reception power value, a reception power value with negative amplitude is received or entered. In particular positive and negative amplitudes when a signal is emitted can also be correctly recorded and processed by the method. In particular the amplitude values are transmitted with the appropriate leading sign in the downlink direction. | The invention relates to a method for controlling the emission power of an especially mobile emission station (MT). The aim of the invention is to keep the emission power to a minimum. To this end, a reception station (AP) which receives the emitted data (c 1 ) as reception data (c 1 *) determines the measuring values of the same, and sends them to the emission station (MT) via a secure connection (DL) which is not, or is only slightly, affected by disturbances. The measuring values (c 1 *) depend on the data (c 1 ) transferred by the signal. | 7 |
BACKGROUND OF THE INVENTION
According to DIN 55946 (German Industrial Standard 55946) bitumens are a dark colored, semisolid to brittle, meltable, high molecular weight hydrocarbon mixture which are obtained in the careful working up of petroleums and the portions soluble in carbon disulfide of the natural asphalts as well as mineral wax and montan wax (see Rompp Lexikon der Chemie, 7th edition, page 377).
These types of materials which are designated in the English speaking areas (especially the USA) as asphalt are employed in admixture with powdered limestone, pulverized granite, ground basalt, ground diabase, and ground gabbro in the building of streets.
In this connection the use of natural asphalt is of especial significance. Natural asphalt can be employed in admixture with bituminous binders according to DIN 1995 to produce montan rich covering layers (e.g. cast asphalt, asphalt concrete, sand asphalt and asphalt mastic. A natural asphalt of this type is e.g. Trinidad-Epure which has the following composition:
Soluble Bitumen 53 to 55 wt. %
Mineral portion 36 to 37 wt. %
Remaining components 9 to 10 wt. %
(See Handbuch fur Strassenwesen, Planung-Bau-Verkehr-Betrieb 1979, Otto Elsner Verlagsgesellschaft, Darmstadt.)
Trinidad-Epure as well as the other known asphalts have the disadvantage that they frequently form hard, compact masses which first must be broken into small pieces in order to be homogenously miscible with the materials used as additives.
It has already been proposed to prepare asphaltite in particulate condition and to improve the flowability of the granulate through special additives.
There is known from Austrian Pat. No. 280876 a process according to which particulate asphaltite is treated with a wetting liquid, e.g. black liquor, and the finished product then sealed in air tight containers.
There are known from European Pat. No. 24513 powdered bitumen concentrates which contain in addition to bitumen 10 to 80 wt. % of synthetic silica.
SUMMARY OF THE INVENTION
The object of the invention is a powdered, flowable and temperature stable bitumen concentrate.
The subject matter of the invention is a powdered bitumen concentrate containing a mixture consisting of (or consisting essentially of) synthetic silica and crystalline, powdered synthetic zeolite or a mixture of zeolites.
The bitumen portion based on the total mixture can be 30 to 70 wt. %, preferably 45 to 55 wt. %.
The portion of synthetic silica can be 8 to 50 wt. %, preferably 15 to 20 wt. % based on the total mixture.
The portion of zeolite or zeolite mixture can be 15 to 60 wt. %, preferably 30 to 40 wt. %, based on the total mixture.
As synthetic silica there can be used precipitated silica as well as pyrogenically produced silica.
The precipitated silica can have a BET surface area of 120 to 500 m 2 /g. Optionally they can be steam jet ground, spray dried or spray dried and ground.
The pyrogenically produced silica can have a BET surface area of 100 to 400 m 2 /g.
As precipitated silica there can be employed a silica having the following physicalchemical data.
______________________________________Appearance Loose, white powderX-ray structure amorphoussurface area 170 ± 25 m.sup.2 /g (according to BET)Average size of 18 NanometersThe primary particlesSpecific weight 2.05 g/mlDegree of purity SiO.sub.2 98% Na.sub.2 O 1% Al.sub.2 O.sub.3 0.2% SO.sub.3 0,8%Loss on drying.sup.(1) 6%Loss on calcining.sup.(2) (3) 5%pH-.sup.(4) 6.3Solubility practically insoluble in waterCharacteristics precipitated silicaBulk density.sup.(5) 200 g/LiterSieve residue according 0.2to Mocker (DIN 53 580)______________________________________ .sup.(1) DIN 53 198 preparation .sup.(2) based on the material dried for 2 hours at 105° C. (DIN 5 921)? .sup.(3) DIN 52 911 .sup.(4) DIN 53 200 .sup.(5) DIN 53 194
As precipitated silica there can be employed a silica which has the same physicalchemical data and differs merely in the height of the bulk density from that mentioned above. The bulk density can be 70 g/l for example.
As a precipated and spray dried silica there can be used a silica with the following physical-chemical data:
______________________________________Surface area according m.sup.2 g 190to BETAverage size of the Nanometer 18primary particleAverage size of the Micrometer 80secondary particlesBulk density (DIN 53 194) g/l 220Loss on drying (DIN 55 921) % 6(2 hours at 105° C.)Loss on calcining (DIN % 555 921 (2 hours at 1000° C.)pH (DIN 53 200) 6.3SiO.sub.2 (DIN 55 921).sup.(2) % 98Al.sub.2 O.sub.3 % 0.2Fe.sub.2 O.sub.3 % 0.03Na.sub.2 O % 1SO.sub.3 % 0.8Sieve residue according % 0.5to Mocker (DIN 53 580)Oil number (according g/100 g 230to DIN 53 199)______________________________________ .sup.(1) based on the material dried 2 hours at 105° C. .sup.(2) based on the material calcined at 2 hours 1000° C.
The same precipitated and spray dried silica can also be used in the ground condition with an average size of secondary particles of e.g. 5 micrometers.
The term zeolite corresponds to the description according to D. W. Breck, "Zeolite molecular sieves", Wiley Interscience 1974, pages 133 to 180. The zeolites employed can have a water content of up to 27%.
As powdered crystalline synthetic zeolites the bitumen concentrates of the invention contain a zeolite of Type A. The zeolite A has the following general formula:
1.0±0.2M.sub.2 O.Al.sub.2 O.sub.3.2.5±0.5SiO.sub.2.YH.sub.2 On
wherein M is a metal cation, such as e.g. sodium or potassium cation, n its valence and y has a value up to 5.
Preferably the bitumen concentrate can contain a zeolite of Type A which is produced according to the process of German AS No. 2333068, German AS No. 2447021, German AS No. 2517218 (and related Roebke U.S. Pat. No. 4,073,867), German OS No. 2651485 (and related Strack U.S. Pat. No. 4,303,629), German OS No. 2651446, German OS No. 2651436 (and related Strack U.S. Pat. No. 4,305,916), German OS No. 2651419 (and related Strack U.S. Pat. No. 4,303,628), German OS No. 2654120 (and related Strack U.S. Pat. No. 4,303,626) and/or German OS No. 2651437 (and related Strack U.S. Pat. No. 4,303,627). The entire disclosure of the Roebke and Strack U.S. patents are hereby incorporated by reference and relied upon.
The zeolite A employed also can be produced according to other known processes, e.g. according to German patent No. 1038017 or German AS No. 1667620.
Preferably there can be employed a zeolite A having the following physical-chemical properties:
______________________________________Loss on calcining <24%(according to DIN 55 921)Particle distribution (Coulter-Counter)Portion<15 micrometer 96-100 wt. %<10 micrometer 95-99 wt. %< 1 micrometer <5 wt. %______________________________________
Furthermore the bitumen concentrate of the invention can contain a zeolite of Type A having the general formula:
0.9±0.2M.sub.2 O.Al.sub.2 O.sub.3.XSio.sub.2.yH.sub.2 On
wherein M is a metal cation, such as e.g. sodium or potassium cation, n is its valency, X has a value greater than 3 and y has a value up to 9.
The zeolite Y can have the following physical-chemical properties:
______________________________________Loss on calcining <27%(according to DIN 55 921)Particle distribution (Coulter-Counter)Portion<15 micrometer 96-100 wt. %<10 micrometer 85-99 wt. %< 1 micrometer <20 wt. %______________________________________
These zeolite molecular sieve powders for example can be produced according to German AS No. 1098929, German AS, No. 12032329 or German AS No. 1263056.
Furthermore, the bitumen concentrate of the invention can contain as powdered zeolites a zeolite of type X having the following general formula:
0.9±0.2M.sub.2 O.Al.sub.2 O.sub.3.2.5±0.5SiO.sub.2.YH.sub.2 On
wherein M is a metal cation, e.g. sodium or potassium, n is its valence and y has a value up to 8.
The powdered zeolite can be produced according to German patent No. 1038016, German patent No. 1138383 or German OS No. 2028163.
The zeolite X employed can have the following physical-chemical properties:
______________________________________Loss on calcining <27 wt. %(DIN 55 921)Particle size distribution (Coulter-Counter)Portion<15 micrometer 96-100 wt. %<10 micrometer 85-99 wt. %< 1 micrometer 20 wt. %______________________________________
Furthermore, the bitumen concentrate can contain as powdery zeolites a zeolite of type P. The designated zeolite P is synonymous with the designation synthetic Philipsit and zeolite B. For example zeolite P can be produced according to the process of French patent 1213628 (Bayer AG).
The zeolite P employed can have the following physical-chemical properties:
______________________________________Loss on calcining <15 wt. %(DIN 55 921)Particle size distribution (Coulter-Counter)Portion<15 micrometer 99-100 wt. %<10 micrometer 97-99 wt. %< 1 micrometer 20 wt. %______________________________________
The bitumen concentrate of the invention furthermore can contain as powdered zeolites hydroxysodalite having the following general formula:
Na.sub.2 O.Al.sub.2 O.sub.3.2SiO.sub.2.2.5H.sub.2 O
Hydroxysodalite can be produced for example from zeolite A by means of boiling in aqueous soda lye (see D. W. Breck, Zeolite molecular sieves:, page 275 (1974) WileyInterscience Publication).
The hydroxysodalite employed can have the following physical-chemical properties:
______________________________________Loss on calcining <15 wt. %(DIn 55 921)Particle size distribution (Coulter-Counter)Portion<15 micrometer 99-100 wt. %<10 micrometer 90-99 wt. %< 1 micrometer 10 wt. %______________________________________
In a further illustrative form of the invention the bitumen concentrate of the invention can contain a mixture of the zeolites set forth. This mixture can be produced either by mixing the pure zeolites or through direct synthesis by means of a precipitation process. Mixtures which can be produced directly can be mixtures of zeolites A and P, zeolites A and X, zeolite A and hydroxysodalite, zeolites P and X or zeolites P and Y. In a preferred illustrative form the bitumen concentration can contain a mixture of zeolites X and zP in the ratio of 80 to 5:20 to 95.
A mixture of this type can be produced for example according to German OS No. 2028163, page 15, Table 3, Example 3 by means of a precipitation process.
For the production of the powdered bitumen concentrates of the invention in addition to already mentioned types of bitumen there are also suited the customary distillation bitumens as well as mixtures of distillation bitumens and products of the hard coal tar industry. According to DIN 52 00 of 1980 after the distillation of petroleum there remains as residue the distillation or street construction bitumen whose designation consists of the letter B and a number, which indicates the average penetration in 1/10 mm. The normal bitumens most used in the Federal Republic of Germany are B 25 (hard), B 45, B65, B80 and B200 (soft). Corresponding to the "Technische Lieferbedingungen fur Bindemittel auf Bitumen-und Teerbasis" (edition 1959) there can also be used further developed tar bitumens.
The bitumen concentrate of the invention can be produced by having the synthetic silica and the zeolite present in a mixer and mixing them thoroughly. The hot and liquid bitumen is allowed to flow in a thin jet while stirring the carrier components or is introduced through a nozzle or is sprayed on.
The bitumen concentrated of the invention has the following advantages:
1. simple storage in silos or sacks
2. unlimited durability
3. no susceptibility to influences of weather
4. simple dosing of bitumenous masses in the process of production since no melting is required
5. use of the complete capacity of the production plants (e.g. asphalt mixing plants)
6. assurance of the complete action of the individual components, synthetic silica and zeolite
7. no dangers to health (since it is free of carcinogenic dusts and fibers)
8. no danger to the environment
9. completely oder free in hot asphalt mixes
10. in spite of the high portion of bitumen it is powdered, temperature stable and flowable.
The bitumen concentrate of the invention can be used as additive material:
(a) for the production of asphalt mixtures for binding streets and bridges
(b) for the production of asphalt mixtures for above ground construction, e.g. floor pavements and industrial floor
(c) for improving or reconditioning old asphalt (recycling of waste asphalt coatings and
(d) for the production of bituminous building materials, such as e.g. roof paths, seam compositions, troweling compositions, roof coating compositions, insulation compositions, underground protection, corrosion protection, antisound composition.
In a special form of the invention the bitumen concentrate of the invention can be used to produce mastic asphalt.
Usable mastic asphalt mixes are described for example in European Pat. No. 48792, the entire disclosure of which is hereby incorporated by reference.
Furthermore, mastic asphalt is described in DIN 4109 Sheet 4, page 3, paragraph 5.3.5 (mastic asphalt marking) in DIN 18354 and in "Der Bundesanzeiger fur Verkehr, Technische Vorschriften und Richtlinine fur den Bau bituminoser Fahrbahndecken", part 6, page 7, edition of 1975.
Correspondingly mastic asphalt is a thick bituminous mass made of fine gravel, sand, filler and road making asphalt or road making asphalt together with natural asphalt, whose mineral mixture is low in hollow spaces. The binder content is so formulated to the hollow space of the mineral composition that these are completely filled up in the assembled condition and a slight excess of binder is present. This mixture is pourable and brushable in the hot condition and does not require any compression in asembling. The surface is post treated directly after the assembling by roughening or blunting.
There is required of mastic asphalt for street and floor pavements a high rigidity (resistance to deformation) and at the same time as good processability as possible. Since a hollow space free asphalt of this type undergoes no vibratory or roller compression there must be present a reasonable ability to be poured or smoothed. In road construction a large portion of the mastic asphalt is applied with finishers to obstructed surfaces so that even a stiff installed material can be subsequently processed. In other cases there are places where only hard construction can be carried out, such as e.g. on niches, on bridges, on ramps, with gutters, etc. Here only a pliable asphalt can be processed clearly.
There are special problems in laying mastic asphalt-industrial floors. The thickness of the coating varies between 20-40 mm, whereby unevenness of the underground must be considered. There is required a troublefree applying of the hot asphalt compositions as well as fissure free low-resistant smoothing. The goal always is large covering capacity of the transport since in the ultimate analysis the building work is very dependent on profit. With the industrial floors of improved coating capacity there is accepted a higher material cost if in the final analysis there is a price advantage.
The stiffness of mastic asphalt compositions can have their stiffness regulated by the mineral compositions referred to (e.g. "thick" filler) or reduction in bitumen up to the mineral limit. The increased rigidity obtained thereby in any case is a load on the coating capacity. It can be more significant to strive for a higher resistance to deformation or a lower depth of penetration and simultaneously a good pliability by effective additives.
The addition of precipitated silica alone to the mastic asphalt composition leads to a reduction of the depth of penetration, i.e. to an increase of the stability to deformation. Simultaneously the processing temperature must be increased around 20° C. which indicates a reduction of the ready processability of the mastic asphalt.
If crystalline synthetic zeolite is added to the asphalt mixture then there is reduced the depth of penetration and the processing temperature.
If there is added precipitated silica and crystalline, synthetic-zeolites to the mastic asphalt composition then the depth of penetration is clearly lowered, however, the processing temperature is only increased insignificantly. With a change of the ratio of precipitated silica and crystalline synthetic zeolite the temperature can be corrected. This means that zeolite in increased addition leads to more pliable mastic asphalt compositions, independently there is attained an increase of the form stability, the combination of precipitated silica however, brings about the clearest industrial construction advantage within the series of experiments.
The stiffening stability which is undesirable for the ready processability (plasticity, spreading) smoothness resulting from the addition of precipitated silica is removed through the dehydrating zeolites, whereby a brushable composition is maintained for a certain time span. The cooled paving, however, then after the end of all processing shows a smaller depth of penetration or an increased resistance to deformation whereto the zeolite itself contributes to the improvement. The combined use of precipitated silica and crystalline, synthetic zeolites leads to a mastic asphalt of improved stability and therewith to improved load carrying. This higher resistance to deformation is desired in building streets in special uses. Special coatings are used on bridges, highly used traffic crossings, ramps, etc. Industrial floors require high load carrying. Factory and storage sheds are expected to receive shelves palettes, machines, etc. The large loads are frequently transported on the floor only over small pressure areas (standing shelves). Undesired indentations are the result. Travelling takes place with fork-lift trucks and other powered vehicles which deliver strong loads to the floor and therewith leave tracks behind.
It is especially advantageous that the improvement of the stability of the mastic asphalt in using the combined additives silica/zeolite does not result in increasing the processability difficulties. Reduced m 2 -capacity of the portable columns are not desired since with the high portion of costs they negatively effect the final price of the laid floor.
The powdered bitumen concentrate of the invention is explained and described in more detail in the following examples.
The composition of the invention can comprise, consist essentially of, or consist of the stated materials.
BRIEF DESCRIPTION OF THE DRAWING
The single FIGURE of the drawing is a graph of the particle size distribution of a zeolite useful in the invention.
DETAILED DESCRIPTION
For the production of powdered bitumen concentrate in the laboratory there was carried out the following sequence of operations.
1. Heating the respective silica, zeolite, and bitumen to 140° C. in the drying cabinet.
2. The weighed out amounts of silica and zeolite are present in the mixing container. Portionwise addition of bitumen with stirring (by hand or with wing stirrer, depending on the amount), vigorous subsequent mixing up to visible homogenization.
3. Applying the still hot composition to a metal sheet, distribution until cooled to room temperature.
4. The cold, friable to granular composition is hammered and ground in a Braun-Cake mixer for about 30 seconds.
5. The powder is placed on a 0.75 mm sieve, sieved, homogenized in a glass container in a Turbula mixer.
As zeolite there was used a zeolite of type A (Wessalith® of Degussa AG) which was was produced according to German OS No. 2651436 (and related Strack U.S. Pat. No. 4,305,916) and has the particle spectrum of FIG. 1.
As synthetic silica there was employed the silica Sipernat 22® of Degussa AG.
Silica Sipernat 22® is a precipitated and spray dried silica having the following physical-chemical properties:
______________________________________Surface area according m.sup.2 /g 190to BETAverage size of the Nanometer 18primary particlesAverage size of the Micrometer 80secondary particlesBulk density (DIN g/l 22053 194)Loss on drying (DIN 55 291) % 6(2 hours at 105° C.)Loss on calcining (DIN 55 921) % 5(2 hours at 1000° C.)pH (DIN 53 200) 6.3SiO.sub.2 (DIN 55 921).sup.3 % 98Al.sub.2 O.sub.3 % 0.2Fe.sub.2 O.sub.3 % 0.03Na.sub.2 O % 1SO.sub.3 % 0.8Sieve residue according % 0.5to Mocker (DIN 53 580)Oil number (according g/100 g 230to DIN 53 199)______________________________________ .sup.1 based on the material dried for 2 hours at 105° C. .sup.2 in water: acetone or methanol 1:1 .sup.3 based on the material lacined for 2 hours at 1000° C. .sup.4 contains about 2% chemically bound carbonSIPERNAT 22 17 wt. %WESSALITH P 33 wt. %BITUMEN B 65 50 wt. % Product Description: dry, flowable and pourable, medium to black brown or grey powder
Bulk density 0,50-0.70 [kg/l]Particle distribution0-0.09 mm 2-4 wt. %0.09-0.2 mm 20-35 wt. %0.2-0.4 mm 10-25 wt. %0.4-0.8 mm 15-30 wt. %0.8-1.0 mm 4-12 wt. %1.0-2.0 mm 10-20 wt. %2.0 mm 2-8 wt. %______________________________________
The entire disclosure of German priority application P No. 3505051.9 is hereby incorporated by reference. | A powdered bitumen concentrate is prepared which contains a mixture of synthetic silica and crystalline, powdered synthetic zeolite or mixture of zeolites. | 2 |
TECHNICAL FIELD
The invention relates generally to a method of converting the configuration of a transmission pump into a later model year configuration transmission pump assembly. More specifically the invention relates to a method of converting a 1984-1994 General Motors 700 R4 transmission pump assembly into a 1995 or later configuration General Motors transmission pump assembly allowing a low cost replacement transmission pump.
BACKGROUND OF THE INVENTION
An automotive transmission multiplies engine torque or reduces engine rpm to match varying operating conditions in a manner optimizing engine power and torque. An automatic transmission generally comprises a torque converter, automatic transmission shafts, planetary gearsets providing different gear ratios, planetary holding members or clutches, transmission fluid pump, transmission shafts, hydraulic valves, shift linkage, converter housing, transmission case, transmission fluid pan, and an extension housing.
The automatic transmission is generally operated by a hydraulic fluid circuit. Pressure is developed by the transmission fluid pump, sometimes called an oil pump or front pump. The pump draws fluid from the transmission fluid pan and creates hydraulic pressure, which is then directed to other parts of the transmission to fill the torque converter, operate the holding member band and clutch assemblies, control shifting, lubricate the moving parts of the transmission, and circulate the fluid to and from an oil cooler for heat transfer. The pump is driven by the engine typically through driving lugs on the torque converter. When the engine is running, the pump produces power to operate the hydraulic system.
General Motors introduced a second generation transmission pump on its model 700 R4 transmission assembly in model year 1984 that remained basically unchanged through model year 1994. The 700 R4, (also designated 4L60E) utilizes a C-Vane type transmission oil pump comprising a pump body, a pump vane assembly, and a pump cover assembly. The 700 R4 transmission has been modified several times over the years. Some of these changes directly affected the compatibility of the transmission pumps between different model years.
When a transmission pump fails and needs to be replaced, the vehicle owner typically has a new or remanufactured transmission pump installed. New transmission pumps direct from the original equipment manufacturer (OEM) can be quite expensive. Significant cost savings can be obtained by using a remanufactured part. For example, a salvaged and remanufactured transmission pump from a 1984 model year 700-R4 transmission could be used for the same transmission for 1984-1994 model years. As these are older cars and cover over ten years of production, the number of salvageable transmission pumps are plentiful and comparatively low cost. However due to later model year changes in the transmission, the same pump could not be used for the same transmission of a 1995 model year. The limited number of salvaged transmission pumps from a transmission pump having a run of one or two years makes it virtually impossible to get a remanufactured part, thereby forcing the consumer to pay for a new OEM transmission pump.
Therefore, there remains a need in the art for a method of converting an older version of the transmission pump into a configuration compatible with later model year transmission pumps.
SUMMARY OF THE INVENTION
An object of the present invention is to provide an inexpensive and easily produced method for refurbishing transmission pump assemblies for later model year transmissions. These and other advantages are provided by a method of changing the configuration of a transmission pump assembly from a first configuration to a second configuration, the method comprising the following steps: a) providing a first configuration transmission pump assembly comprising a pump body and a pump cover, wherein the pump body and the pump cover each have a plurality of fluid passageways formed between worm tracks on at least one side thereof; b) removing a portion of the worm tracks from both the pump body and the pump cover; c) providing at least one insert; d) attaching the at least one insert into a predetermined position; and e) machining the pump cover and pump body to the second configuration.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention and developments thereof are described in more detail in the following by way of embodiments with reference to the drawings, in which:
FIG. 1 is an exploded perspective view of a typical automatic transmission showing the relative positions of the torque converter and fluid pump;
FIG. 2 is an exploded perspective view of a typical vane type fluid pump assembly;
FIG. 3 is a plan view of the worm track side of an unmodified pump body;
FIG. 4 is a perspective view of the front side of an unmodified pump body;
FIG. 5 is a plan view of the worm track side of a modified pump body;
FIG. 6 is a perspective view of the front side of a modified pump body;
FIG. 7 is a plan view of the worm track side of an unmodified pump cover;
FIG. 8 is a plan view of the worm track side of a modified pump cover;
FIG. 9 is a plan view of a portion of the worm track side of an unmodified pump body;
FIG. 10 is a plan view of the pump body shown in FIG. 9 having portions of the worm track removed;
FIG. 11 is a plan view of the pump body shown in FIG. 10 having grooves machined into the floor of the pump body;
FIG. 12 is a plan view of the pump body shown in FIG. 11 having inserts attached to change the worm tracks to the modified configuration;
FIG. 13 is a perspective view of the cast insert shown in FIG. 12;
FIG. 14 is a plan view of a riser ring casting;
FIG. 15 is a plan view of a riser ring.
FIG. 16 is a plan view of the pump cover shown in FIG. 7 having grooves machined into the floor of the pump body;
FIG. 17 is a perspective view of an insert;
FIG. 18 is a plan view of the pump cover shown in FIG. 16 having three inserts attached;
FIG. 19 is a plan view of the pump cover shown in FIG. 18 which is machined to its final configuration; and
FIG. 20 is a side elevational view of the pump cover.
FIG. 21 is a listing of the steps of the method of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 illustrates a partial exploded view of a typical automatic transmission assembly 110 . The torque converter 112 is housed in a converter housing 114 . Fluid pump assembly 116 is housed within a transmission case 118 . Extension housing 120 is attached to an end of the transmission case 118 opposite the converter housing 114 . Fluid pan 122 is attached to the bottom of transmission case 118 . The transmission assembly 110 also comprises a input shaft 124 which is driven by the engine (not shown).
Referring now to FIG. 2, a typical 1984 and on C-vane type fluid pump assembly 126 as used in a GM 700-R4 transmission is shown in an exploded perspective view. The major components of the fluid pump assembly 126 are the pump vane rotor assembly 128 , pump slide 130 , pump body 132 , pump stator, or cover 134 , and stator shaft 136 , shown herein attached to pump cover 134 . The pump body 132 and pump cover 134 each have corresponding fluid passageways 137 also referred to as worm grooves, separated from each other by passageway walls 160 , or worm tracks. Some of the passageways 137 have holes designed for fluid passage which allow fluid flow in a particular direction or that can open or close on demand. It is noted that the configuration shown is a 7-vane fluid pump. The number of vanes was increased to 10 staggered vanes in the 1986 model year, and then 13 vanes in 1997 model year.
Pump body 132 is shown in FIGS. 3 and 4, with FIG. 3 showing a plan view of the worm track side 138 of pump body 132 and FIG. 4 showing a perspective view of the front side 140 of the pump body 132 . A 10 vane rotor assembly 228 and associated pump slide 230 are shown mounted in the central recess of the worm track side 138 of pump body 132 . A seal drain passageway 152 is also partially shown as it is contiguous through the side of the pump body (not shown). A mounting register face 142 is shown machined into the radial outward portion of the front side 140 of the pump body 132 . Mounting bolt holes 144 are positioned about the mounting face 142 .
As previously mentioned, a series of changes were made to the fluid pump assembly 126 starting with the 1995 model year. These changes primarily involved changes to the configuration of the fluid passageways 137 to incorporate pulse width modulation. These changes were intended to help the transmission 110 run more smoothly and eliminate pressure spikes from the transmission pump assembly. Referring now to FIG. 5, a plan view of the worm track side 138 ′ of a 1995 and on model year configuration pump body 132 ′ is shown. The fluid passageways 137 that are modified are highlighted by being shown as darkened areas 146 . In addition, the seal drain passageway 152 was enlarged to improve fluid flow. Changes in the 1996 model year involved primarily the addition of risers on the torque converter side of the pump body. Referring now to FIG. 6, a perspective view of the front side 140 ′ of a 1996 and on model year configuration pump body 132 ″ is shown. Risers 148 are positioned about the circumference of register face 142 ′. The risers 148 were added to center the pump assembly 116 in the bell housing (not shown).
Referring now to FIG. 7, a plan view of the worm track side 150 of an unmodified pump cover 134 is shown. The fluid passageways 137 of the pump cover were also modified in the 1996 model year. A plan view of the worm track side 150 ′ of a modified pump cover 134 ′ is shown in FIG. 8 . The fluid passageways 137 that are modified are highlighted by being shown as darkened areas 146 .
The method 10 of converting the configuration of a transmission fluid pump assembly 116 in accordance with the present invention will now be described in detail and are listed for reference in FIG. 21 . The initial step is providing 12 a 1984-1994 model year transmission pump assembly 116 for a 700-R4 transmission assembly 110 . While a new OEM pump assembly 116 could be used, it is more economical to use a salvaged used pump assembly 116 .
The next step is to disassemble 14 the used, transmission pump core 116 into its three major components, the pump body 132 , pump cover 134 , and stator shaft 136 . The components are then degreased 16 . The modification of the pump body 132 is described next.
Transmission pumps are subjected to significant heat/cooling cycles during their operation and a used pump 126 may be slightly warped. Accordingly, the mounting register face 142 of the front side 140 of the pump body 132 is cut 18 on a lathe to remove any warpage due to service. The seal drain passage 152 is then machined 20 to enlarge the passageway 152 to the modified pump specifications. The pump body 132 is then bead-blasted 22 to clean up the surfaces for machining.
Referring now to FIGS. 9-13, the modification of the fluid passageways 137 is shown. FIG. 9 shows a partial plan view of a portion of an unmodified pump body 132 . The pump body is then placed on a CNC mill and portions 154 of the worm track wall 160 are cut away 24 as best shown in FIG. 10 . Special care is taken to the radius on the four sides created in the cavity. The next step is to cut 26 grooves 156 , 157 into the floor 158 of the pump body 132 which corresponds to the localized changes to the worm track wall 160 of the 1995 model of the pump body 132 ′. The grooves 156 , 157 are shown in dotted lines in FIG. 11 Referring now to FIGS. 12 and 13, insert 170 is created 28 to provide the new configuration of the worm track walls 160 and is generally shaped like the number “2”. The insert is made as an aluminum casting, however, it is not intended to be limited as such and may be machined or formed by any suitable means. The insert 170 is secured 30 within the corresponding groove 156 by an industrial adhesive 168 which is applied to the bottom and sides of the insert 170 . The industrial adhesive 168 may be any suitable adhesive which will permanently hold the insert 170 , even when post machining work is being done on the insert. An additional piece of aluminum 172 is secured 32 with industrial adhesive 168 within groove 157 to duplicate a second modification to the worm track walls 160 . The smaller insert 172 is typically oversize and then machined 34 (after the adhesive is dried) to its final dimensions to correspond with the specification of the modified pump body 132 ′ as shown in FIG. 12 .
After the adhesive is dried, the pump body 132 ′ is placed on a lathe. The register face 174 and the pump assembly recess face 176 are cut 36 to a tolerance of plus or minus two tenthousandths (0.0002) of an inch. The slide 230 , rotor vane assembly 228 , and other associated parts are installed 36 on the pump body. The pump body is now configured as 1995 model year modified pump body 132 ′ (see FIG. 5 ).
As previously discussed with relation to FIG. 6, the pump body 132 ′ was modified in the 1996 model year. For 1996 and on model years, the method of conversion 10 further comprises the addition of a riser ring 180 . The riser ring 180 is produced as follows. An aluminum ring 180 with risers 148 generally corresponding to the dimensions of the mounting register face 142 of the front side 140 of the pump body 132 , is cast 40 in a mold (a ring could also be machined but would be more costly if a significant number of pumps are being remanufactured). The as-cast ring 180 is placed on a lathe and the bottom 182 of the ring 180 is cut 42 flat. The outside diameter 184 and the inside diameter 186 are hand filed 44 to assure that it fits in a fixture (not shown). The fixture is a device used to hold 46 the ring 180 under the pump body 132 ′ in a manner that the bolt holes 144 in the pump body are used as guides to drill 48 the mounting holes 144 ′ in the ring 180 . Because these bolt holes 144 vary slightly from one pump to another, the pump body 132 ′ used to drill the holes 144 ′ is mated to the particular riser ring 180 . Industrial adhesive 168 is placed on the bottom face 182 of the ring 180 and the bottom face 182 is attached 50 to the register face 142 of the front side 140 of the pump body 132 such that the mounting holes 144 , 144 ′ are properly aligned.
After the adhesive has dried, the pump body 132 is placed in another special set of jaws on the lathe. The outside diameter of the riser ring is cut 52 to match the outside diameter of the pump body. The top face 183 of the ring is then cut 54 so that the thickness of the pump body 132 with the ring installed meets the dimension specification of the modified pump body 132 ′.
Referring again to FIGS. 7 and 8, the pump cover 134 must also be modified in a similar manner as the pump body 132 to convert it to the modified pump cover 134 ′ configuration. Referring now to FIGS. 16-20, the modification of the fluid passageways 137 on the pump cover 134 is shown. FIG. 16 shows a partial plan view of a portion of pump cover 134 . Hole 188 is plugged 56 with an aluminum rivet 192 . Grooves 194 , 196 , and 198 are cut 57 into the floor of the pump cover 134 to allow three inserts to be installed. Although not shown, portions of the worm groove walls may also be milled to allow additional room for installation of the inserts. Referring now to FIGS. 17 and 18, cast aluminum insert 190 is created 58 to provide portion of the new configuration of the worm track walls 160 and is generally shaped like the letter “L”. A second insert 200 is provided 60 and machined as a one inch square piece of aluminum, {fraction (3/16)}″ thick, with full radius on two sides. A third insert 202 is also provided 62 . The inserts 190 , 200 , 202 are attached 64 to the pump cover 134 with a suitable industrial adhesive. After the adhesive has dried sufficiently, the pump cover 134 is then milled 66 at locations 204 to the modified pump cover configuration 134 ′ as shown in FIG. 19 .
The pump cover 134 ′ is placed in the lathe and the back side, the side opposite the worm track side 138 , is cut 68 parallel to the worm track side 138 .
Referring now to FIG. 20, the three major holes 206 , 207 , 208 are centered, drilled, and reamed 70 to the larger hole specifications of the modified pump cover 134 ′ to a tolerance of plus or minus 0.0002″. The stator shaft 136 is then installed 72 through pump cover 134 ′ and it is placed back on the lathe. The worm track side 138 ′ of pump cover 134 ′ is faced 74 and it is now ready for assembly 76 with pump body 132 ′.
Although not specifically discussed several additional holes are enlarged and/or plugged to finalize the conversion. These operations are omitted as they are common machining procedures understood by those in the art.
The present invention provides a method of conversion of a transmission pump without requiring any welding. It is contemplated that the inserts could be replaced by direct welding in the locations to be modified and then machined to the proper configuration. However, the welds sections may have problems with porosity that even peening of the weld areas may not solve. In addition, the high temperatures involved in the welding process may warp the pump cover and the pump body.
The present invention shows a particular transmission pump assembly used in a General Motors application. It is contemplated that the method of the present invention could easily be adapted to be used to convert other transmission pump assemblies that have been changed by the manufacturer under similar conditions.
Although the present invention has been described above in detail, the same is by way of illustration and example only and is not to be taken as a limitation on the present invention. Accordingly, the scope and content of the present invention are to be defined only by the terms of the appended claims. | The present invention provides an inexpensive and easily produced method for refurbishing transmission pump assemblies. The method of converting a transmission pump assembly from a first configuration to a second configuration comprises the steps of: a) providing a first configuration transmission pump assembly comprising a pump body and a pump cover, wherein the pump body and the pump cover each have a plurality of fluid passageways formed between worm tracks on at least one side thereof; b) removing a portion of the worm tracks from both the pump body and the pump cover; c) providing at least one insert; d) attaching the at least one insert into a predetermined position; and e) machining the pump cover and pump body to the second configuration. | 8 |
This is a continuation-in-part of U.S. patent application Ser. No. 08/360,269, filed Dec. 21, 1994 now abandoned. The entire contents of that application are incorporated herein by reference.
FIELD OF INVENTION
This invention relates to improved porous ceramic based biomaterials, and methods for making such materials, and implants fashioned therefrom. In particular, this invention relates to methods of impregnating porous hydroxyapatite with polymeric materials such that when the resultant composite materials are used in prosthetic devices and implants, strength of the implant is enhanced and the interconnected macropores are retained.
BACKGROUND OF INVENTION
Porous Echinoderm and Scleractinian skeletal material has a unique carbonate structure. These materials are permeable with a uniform three dimensional, highly interconnected porosity. The microstructure of this material resembles cancellous bony tissue or bone. The similarity of these invertebrate skeletal materials in microstructure to bone makes them potentially highly useful as bone substitutes. Porites or Goniopera skeleton will resorb or degrade too rapidly to assure bone ingrowth. The natural carbonate skeletal materials, however, such as the calcite of Echinoid spine, or the aragonite skeletons are too brittle for many applications. This brittleness makes the natural carbonates particularly difficult to shape. They also lack the strength and durability required for some bone substitute applications.
A technique was developed to convert the aforementioned calcium carbonate materials into hydroxyapatite, while at the same time retaining the unique microstructure of the coral material. U.S. Pat. No. 3,929,971 (Roy) (incorporated herein by reference) discloses a hydrothermal exchange reaction for converting the porous carbonate coralline skeletal material into hydroxyapatite having the same microstructure as the carbonate skeletal starting material. These synthetic hydroxyapatite materials have been produced commercially for some time and are available from Interpore International, Irvine, Calif. under the trademark Interpore® Implant 200 (derived from coral of the genus Porites and having an average pore diameter of about 200 microns) and under the trademark ProOsteon® Implant 500 (derived from certain members of the family Goniopora and having an average pore diameter of about 500 microns).
Interpore® 200 and ProOsteon® Implant 500, also referred to as Replamineform hydroxyapatite and coralline hydroxyapatite, have been found to be useful as bone substitute materials in dental and surgical applications. These materials are essentially non-degradable, yet biocompatible, and resemble the microstructure of animal and human bone. The porosity of these coral derived materials has been characterized as polymodal by means of scanning electron microscope and mercury porosimetery. The macroporosity is characterized by macropores of 100-1000 μm. The microporosity is characterized by spaces between crystallites on the order of 0.1 μm and larger micropores on the order of 1 μm. More information concerning these materials can be found in the article by Drs. Eugene W. White and Edwin C. Shors entitled “Biomaterial Aspects of Interpore-200® Porous Hydroxyapatite,” which appeared in Dental Clinics of North America, Vol. 30, January 1986, pp. 49-67, incorporated herein by reference. While calcium phosphates such as Interpore®200, and ProOsteon® Implant 500 are desirable for many applications, and promote the ingrowth of bone and other tissue into and around the implant, they do not satisfy all of the needs of surgeons using them as bone replacements or implants. U.S. Pat. No. 4,976,736 (White and Shors) (incorporated by reference) also discloses biomaterials useful for orthopedic and dental applications in which two rates of degradation are sought. To accomplish this, the inventors disclose a biomaterial (and method for making such a biomaterial) which has a base portion of calcium carbonate and a surface layer of calcium phosphate or hydroxyapatite. The biomaterial may be machined into various shapes and sizes for orthopedic and dental applications. The biomaterial presents an interface of hydroxyapatite to tissue and body fluids at the site of the surgical defect. The unreacted carbonate behind the interface gradually gets replaced by new bone ingrowth, thereby more completely filling the implant site with the body's own bone material. In one embodiment mentioned in that patent, the macroporosity of the composite is filed with synthetic polymer such as polysulfone, polythylene, silicone rubber or polyurethane, either with positive injection pressure or by vacuum impregnation. After solification of the polymer, the carbonate may optionally be dissolved away with 10acetic acid, leaving behind the polymer that filled the pores.
Porous ceramics can also be manufactured using a variety of other methods. These ceramics, also made from calcium phosphates, can be used as bone graft substitutes. However, they also have mechanical limitations due to the porosity and to the brittle nature of ceramics. Some of these ceramics have microporosity in addition to macroporosity. Examples include U.S. Pat. Nos. 5,348,788; 5,455,100; and 5,487,933.
Tencer et al., in an article entitled, “Bone Ingrowth Into Polymer Coated Porous Synthetic Coralline Hydroxyapatite,” J. Orth. Res. pp. 275-82 (1987), discusses dip-coating the macroporosity or large pores of a coralline hydroxyapatite sample with a polylactic acid (DL-PLA) dilactic-polylactic acid polymer by dipping blocks for 5 seconds in a high (3:1), medium (10:1), or low (30:1) viscosity solution of DL-PLA in chloroform.
The authors state that they achieved a three-fold increase in compressive strength over untreated samples. This treatment, however, tends to fill the macroporosity and obscures or fills the surface openings of the macropores, which limits the rate and amount of bone ingrowth.
An effective means of increasing the strength of coralline hydroxyapatite, while maintaining an open macroporosity for bone ingrowth, has yet to be described. It is therefore an object of the invention to provide bone substitute or implant materials derived from coral or synthetic calcium phosphate ceramics for bone incorporation which preserves the unique porous macrostructure and surface properties thereof, while providing increased strength.
SUMMARY OF THE INVENTION
The disadvantages of the foregoing prior biomaterials are overcome and the foregoing and other objects are achieved by providing an improved method for manufacturing a ceramic based biomaterial with polymer infiltrated micorpores. The process includes infiltrating the porous ceramic biomaterial with a monomer mixture or solution, and perhaps a catalyst if necessary, and treating the resulting material under conditions which cause the monomer to polymerize in situ within the microporosity of the biomaterial, thus strengthening the material and giving it other useful properties.
The invention also provides as a biomaterial a calcium phosphate (hydroxyapatite) structure having a substantially uniform three dimensional macroporosity connected with an interior surface of the biomaterial. The porosity includes interconnected macropores having diameters in the range from about 100 microns to about 1000 microns. The micorporosity of the ceramic biomaterial is infiltrated by a monomer or prepolymer, a catalyst if necessary, and then polymerized such that the polymer fills (or mostly fills) the microporosity of the biomaterial, substantially without filling the macropores therein. For example, monomers of DL-lactide, L-lactide, or glycolide or co-monomers thereof, at or above their melting point can infiltrate the microporosity of coralline hydroxyapatite materials, and then in the presence of a suitable catalyst be thermally polymerized in situ to yield composite materials of increased strength and durability. This is possible due to the low viscosity of the molten monomers combined with adequate capillary action of the microporous spaces. Using this method, strength increases of more than three-fold over the untreated material have been realized, without disrupting the necessary avenues for bone ingrowth.
In another aspect, the invention provides a method for making an improved biomaterial comprising the steps of providing a coralline calcium carbonate material and converting this material to a porous calcium phosphate (or hydroxyapatite) structure by reacting the calcium carbonate structure under heat and pressure in the presence of a synthetic phosphate; and strengthening the porous hydroxyapatite structure by suffusing the interstices of the microporosity with a monomer solution so that the monomer only lightly coats (but does not fill) the interior walls of the macroporosity of the porous hydroxyapatite structure, and then polymerizing the monomer, preferably in the presence of a catalyst.
BRIEF DESCRIPTION OF THE DRAWINGS
Further features, objects, and advantages of the invention maybe understood by reference of the following detailed description of the preferred embodiments taken in conjunction with the drawings in which:
FIG. 1 is a photomicrograph (330×magnification) of a section of a porous hydroxyapatite sample infiltrated with a biopolymer in accordance with the present invention.
FIG. 2 is a photomicrograph (10,00×magnification) of a section of a porous hydroxyapatite sample infiltrated with a biopolymer in accordance with the present invention.
FIG. 3 is a scanning electron photomicrograph (5000×magnification) of the face of a non-impregnated specimen.
FIG. 4 is a scanning electron photomicrograph at a magnification of 5000×of the face of a non-impregnated specimen.
FIG. 5 is a schematic diagram showing the manner in which the coralline hydroxyapatite block was cut for mechanical testing.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The biocompatibility of hydroxyapatite is well established and it is available in dense and porous forms. Coralline hydroxyapatite is widely used as a bone substitute material in oral, periodontal and craniofacial surgery, and has recently been approved for various orthopedic applications, such as bone replacements due to trauma. Other applications are under consideration or investigation. Porous hydroxyapatite promotes bone ingrowth in and around the implant.
In accordance with the present invention, the calcium carbonate making up the microstructure of porous permeable animal skeletal material, e.g., the porous skeletal material of marine invertebrates, such as echinoid spine calcite, Porites skeletal aragonite and Goniopora skeletal aragonite (both calcite and aragonite being carbonates), is converted into whitlockite and hydroxyapatite by hydrothermal chemical exchange with a phosphate donor. The resulting synthetic phosphate (hydroxyapatite or whitlockite) converted skeletal material possesses substantially the same macroporosity (˜100-1000, μm pore diameter) of the original carbonate skeletal material from which it was derived, and preserves intact the interconnecting porosity which provides channels and interstices for bone and tissue ingrowth. These synthetic materials are useful for the manufacture of posthetic devices, such as body and bone implants, tooth fixation, massive hard tissue replacements and the like, since hydroxyapatite and whitlockite are biocompatible materials.
The synthetic phosphate materials prepared in accordance with this invention, as indicated hereinabove, are particularly useful as biomaterials for use in the manufacture of prosthetic devices or for use as implants in human hard tissue and the like. The surface of the materials of this invention, particularly those made from porous carbonate (aragonite) skeletal material of marine life, since they are comprised predominantly of hydroxyapatite Ca 10 (PO 4 ) 6 (OH) 2 with some carbonate present, approximate the carbonate composition of the inorganic component of hard human bone tissue. This hydroxyapatite surface has osteophilic and osteoconductive properties, and helps promote the growth of bone tissue into the porosity or voids in the biomaterial.
Materials of the present invention preferably have a microstructure which is macroporous, completely interconnected, approximating the same pore size as cancellous human bone which would allow permeation of body fluids and blood cells thereinto. Preferably the material includes at least some macropores communicating with the exterior surface of the implant, that is pores of sufficient size to allow infiltration of blood vessels and other tissues and nutrients necessary to form calcified bone tissue therein. The material also includes micropores, which are pores too small in diameter to permit ingrowth of calcified bone tissue. The present invention contemplates strengthening the material by infiltrating, and perhaps filling, the microporosity within the biomaterial while leaving macroporous passageways substantially unfilled and available for bone tissue ingrowth. Materials in accordance with this invention could be prepared which would be suitable for filling bony defects to stimulate bone formation. Applications are for bone reconstruction of the maxilla and mandible, where it would permit rapid ingrowth of hard tissue, as well as other bone repair functions such as segmental bone replacements for bone fractures, tumors, joint surgery and spinal fusion.
As indicated, various porous carbonate skeletal materials, particularly porous carbonate marine skeletal material, may be employed in the practice of this invention. Particularly useful, because of the vast quantities available, is the carbonate skeletal material of scleractinian coral Porites. This skeletal material is composed of the calcium carbonate (aragonite), and the average pore size is approximately 200 microns. Other corals of the genera Goniopora, Alveopora, Acropora and others may be suitably employed in the practice of this invention as the source of the calcium carbonate skeletal material for conversion by hydrothermal chemical exchange with a phosphate into hydroxyapatite. Goniopora has an average pore size of about 500 microns, and includes macropores ranging in size from 5 microns to about 1000 microns, making it suitable for orthopedic uses where larger amounts of bone and tissue ingrowth might be beneficial.
Where the carbonate skeletal material is made up of a calcite carbonate marine skeletal material, and where the calcite contains a substantial amount of magnesium associated therewith the hydrothermal chemical exchange produces whitlockite with a phosphate on the surface of the biomaterial. Both materials, however, hydroxyapatite and whitlockite, are useful materials, with the hydroxyapatite being preferred for the manufacture of human implants, such bone fillers and replacements and the like. Alternatively, the biomaterials of the present invention can be made in the form of porous hydroxyapatite (or whitlockite) granules. These granules can be dispensed into a cavity where bone repair is desired using a syringe adapted to deliver the particles into the cavity. The irregular surfaces of the particles create spaces between adjacent ones, permitting bone and other tissue to grow around the particles, and into their pores. The particles of the present invention are particularly useful for dental applications such as reconstruction of the alveolar ridge and for filling periodontal spaces. For periodontal use, granules having an average nominal diameter of about 425-600 microns and an average pore size of about 200 microns should be used; for reconstruction of the alveolar ridge, granules having an average nominal diameter of about 425 to 1000 microns and an average pore size of about 500 microns can be used. For orthopedic applications, larger granules having an average nominal diameter of 1-4 mm or 4-8 mm can be used, as can be blocks, right cylinders, or other appropriate geometric shapes and sizes. For some applications, it may be desirable to use as a starting material hydroxyapatite coated porous carbonate biomaterial such as one made in accordance with the method discussed in U.S. Pat. No. 4,976,736.
In the manufacture of the synthetic materials of this invention it would be desirable, before subjecting the naturally occurring porous carbonate skeletal material to hydrothermal chemical exchange with a phosphate, to first prepare the porous carbonate skeletal material by the removal of any organic material therefrom. A suitable technique for the removal of organic material from the porous skeletal material would be by immersion in a dilute (about 5%) aqueous solution of sodium hypochlorite. Usually an immersion time of about 30 hours removes substantially all of the organic matter. Following this the material is rinsed, preferably in deionized water, and dried, such as at a temperature of about 90° C. Any suitable technique for the removal of organic material, such as that described in SCIENCE, 119, 771 (1954), might be employed. If desired, the organic-free carbonate skeletal material after conversion by hydrothermal chemical exchange with a phosphate to hydroxyapatite, may be shaped into a desired form or structure, for example, cylinders, screws, nuts, bolts, pins, flat or curved plates and the like.
The conversion of porous carbonate skeletal materials into the improved phosphate biomaterials for the present invention preferably involves lower temperature and pressures than those disclosed in U.S. Pat. No. 3,929,971. The conversion may be carried out by placing blocks or granules of calcium carbonate in phosphate solution or by freeze drying the phosphate onto the carbonate base and then carrying out the hydroconversion in a steam filled autoclave. Preferred temperature range from about 200°-250° C., with about 225°-240° C. appearing optimum. Preferably, the pressure should be that developed in a sealed vessel or autoclave by the gaseous components contained therein, which is estimated to be about 500 to about 4000 p.s.i. If the conversion is carried out in a phosphate solution, such as ammonium phosphate, the temperature should preferably be about 235° C. and the pressure should be preferably about 2000 p.s.i., and the reaction should be carried out for about 10 to about 60 hours.
The chemical reaction involved in the conversion of calcium carbonate to hydroxyapatite is as follows:
10CaCO 3 +6(NH 4 )HPO 4 +2H 2 O→Ca 10 (PO4) 6 (OH) 2 +6(NH4) 2 CO 3 +4H 2 CO 3
Various substantially water-soluble phosphates may be employed as the phosphate contributing reactant in the hydrothermal chemical exchange reaction to produce the special materials of this invention. The preferred phosphates include ammonium phosphates or orthophosphates. Also useful would be the calcium orthophosphates and the acid phosphates, as well as orthophosphoric acid including its hydrates and derivatives and mixtures of a weak acid, such as acetic acid, with a phosphate.
Upon completion of the hydrothermal chemical exchange reaction, it has been shown by examination including optical microcopy and scanning electorn microscopy, that the resulting three-dimensional completely interpenetrating porous structure is the same as the original carbonate structure form which it was derived. The original calcium carbonate (aragonite) crystal structure of the resulting produced material is absent as determined by x-ray diffraction and by optical microscopy.
Materials exhibiting similar chemistry and morphology have been produced synthetically through various means including those described in U.S. Pat. Nos. 5,348,788, 5,455,100, and 5,487,933 (White) as well as through the use of reticulated foam ceramics.
One biopolymer useful in the present invention is gelatin, derived from high purity collagen by steam autoclaving collagen in aqueous solution at strength ranging from about 3% to about 30% by weight in water for injection or distilled water. Other biopolymers useful herein include those which can be made in solutions or gels of sufficient concentration to infiltrate and perhaps fill or mostly fill the microporosity in the porous hydroxyapatite structure. These biopolymers include collagen (naturally derived or genetically engineered), polyglycolic acid, polylactic acid and its copolymers such as L-lactide coglycolide or DL-lactide coglycolide.
Preferably, the solvent for the gelatin biopolymers is water. This affords several advantages including lack of toxicity. Also, solvent removal (drying) and crosslinking (discussed in more detail below) can be achieved by air-drying at room temperature. This decreases solvent and polymer migration, and avoids use of more problematic crosslinking methods such as radiation and glutaraldehyde.
In preparing coralline hydroxyapatite blocks strengthened with gelatin, two different methods were used to apply the gel solution to the hydroxyapatite. The first method was to pipette lines of solution along the top surface of IP500 blocks to precisely control the amount of gel solution added and to minimize the tendency for the solution to fill macropores and form macropore-bridging bubble films. However, the gelatin tended to stay localized in a trough shaped area near the application “line” and did not equilibrate evenly throughout the blocks even though the blocks appeared to have become uniformly moistened.
The second, and more preferred method, is to preheat the blocks to about 80° C. and then slowly dip the preheated blocks into the gel solution (also at about 80° C.) such that the solution has time to “wick” into the microporosity of the blocks thus preventing entrapment of air bubbles. As the solution wicks into the block, it is gradually lowered into solution while keeping the wetted zone at or above the liquid level. Following this dip submersion into the hot solution, each block is laid on a folded paper towel in an 80° oven to drain out most of the macropore-filling solution. Over a period of about five minutes, each block is moved to a dry area to resume drainage (2-3 times). This method does not retain a detrimental amount of excess solution when the block is removed from the oven for cool-down allowing the solution to gel followed by dry down in ambient air or with dry nitrogen. By allowing the block to cool to room temperature, the solution gels and prevents mass migration of the gelatin during drying.
Dried gelatin is resorbable in water or body fluids at body temperature. As it hydrates and dissolves, it will rapidly lose strength and eventually be completely resorbed. The rate at which the gelatin that is dried down in the microstructure will react with body fluids, for example, is not quantified, but for most indications the gelatin should be crosslinked to slow down and control its rate of resorption.
There are a number of ways to produce crosslinking. These include but are not limited to controlled heat treatment with or without vacuum, exposure to UV light or x-rays, and chemical “tanning” treatments such as with glutaraldehyde. Less preferred would be irradiation, with the effective dose in the range of 20-30 Mrad.
A more preferred crosslinking method, the dehydrothermal method, involves superdehydration by a combination of vacuum and heat as discussed in U.S. Pat. No. 4,280,954 (incorporated by reference herein). Gelatin normally retains some 100 bound moisture at ambient conditions. To effect the dehydrothermal crosslinking, the moisture content has to be lowered to about 0.1%.
To fabricate coralline hydroxyapatite strengthened with polylactic acid lightly coating the walls of the macroporosity and filling some or all of the microporosity, the blocks (or other suitable shapes) of coralline hydroxyapatite (such as Interpore 200 or Pro Osteon® 500) is prepared as desired and dried in a desiccator with vacuum, for example at 20° or 30° for 10-15 hr. or more over P 2 O 5 using blocks which have been predried at 160° C. at atmospheric pressure for at least 12 hours. A small wire frame such as a grid is used to support the porous hydroxyapatite samples to be infiltrated by the polylactic acid or other polymer. A catalyst such as tin (II) Octoate (Sn(II) (2-Ethylhexanoate)2) is loaded into a container on a wire grid by heating the catalyst in contact with the container grid or frame. The frame is placed in a container with a block of coralline hydroxyapatite thereon. The container also holds the lactic acid or other monomer such as ((3,5)-cis3, 6-Dimethyl-1,4 Dioxane-2,5-Dione (Aldrich), or other suitable monomer to make a biocompatible polymer. The block of coralline hydroxyapatite is held above the frame.
The container is sealed under dry nitrogen, heated and swirled to mix the catalyst and monomer and then positioned to allow the molten mixture to be absorbed by capillary action into the porosity of the coralline hydroxyapatite provided that heating is above the monomer melting point. The porous hydroxyapatite absorbs the monomer-catalyst mixture and is then heated at a temperature sufficient to ensure polymerization. Mechanical testing and examination of the polymer impregnated blocks under scanning electron microscopy demonstrated a significant increase in strength and that the macropores had their walls only lightly coated.
The following examples are illustrative of the practice of the invention, and are not intended to be limiting.
EXAMPLES
Example I
Experiments have been completed that establish a greater than four-fold compression strength increase, and a marked improvement in toughness and handling properties of ProOsteon® 500 and Interpore® 200. Screening experiments have been run using Kodak Bovine gelatin, bloom strength 260 (Kodak Catalog No. 137 6383). Aqueous solutions of gelatin have been prepared at 5%, 10%, 15%, 18%, 20% and 23% by dissolving gelatin in distilled water heated at 80° C. Solutions are prepared and used in a moisture-saturated oven. The saturated humidity is maintained by keeping a distilled water filled petri dish in the vacuum oven at atmospheric pressure. The vacuum oven is used because its tight closure, which facilitates humidity control. Unless the gel solution is in a humid environment, a thick “skin” rapidly forms, caused by water evaporation from the solution's surface. Such a skin changes the composition of the solution and interferes with the treatment of the HA.
Most of the preliminary tests were made with 10×10×45 mm ProOsteon® 500 blocks. Each individual block was given an identifying mark, weighed, and brought to treatment temperature by sealing it in a bottle and placing it in an 80° C. oven for at least one-half hour. This heat soak prevented the hot gel solution from gelling before it had time to penetrate the block. Sealing the parts in a bottle prevented premature uptake of moisture.
Table I summarizes averaged results for a recent round of tests of materials made in accordance with the invention (four blocks per test).
TABLE I
Result Summary for Gel Impregnation
of 10 × 10 × 45 mm IP500 by Dip/Drain Method
5% Gel
10% Gel
15% Gel
Solution
Solution
Solution
Weight Gain
2.2%
5.7%
9.5%
dry Gel
Strength Increase
1.8X
2.8X
4.2X
versus Control
Compression Strength
1138/7.8
1814/12.5
2680/18.5
psi/MPa
Example II
A test using a gel solution derived from the high purity collagen was also carried out as follows: 100 ml of a 10% solution by steam autoclaving the fibrous collagen. The gelatin had a white turbid appearance. At 80° C., the solution was extremely fluid but retained the white turbidity. Five ProOsteon® 500 blocks (10×10×45 mm) were treated by wetting and dipping them into the solution. The solution rapidly wicked into each block at a rate faster than has been observed for the equivalent concentration Kodak gel solutions. The average air dry gelatin weight gain was 7.9%. The blocks retained their whiteness unlike the commercial gel treated samples that took on characteristic amber cast. Although no compressive strength measurements have been made on these samples, the hand break strength appears comparable to earlier reinforced preparations.
Example III
To determine whether the gelatin imparted the strength enhancement by infiltrating the microporosity, thereby forming a true composite as hoped for, or by merely stiffening the material by acting as a surface coating on the walls of the macropores, a fluorescamine stain (Sigma), which would make the gelatin fluorescent under UV illumination, was used. Areas of the treated HA-containing gelatin fluoresce while regions that have not been penetrated by gelatin do not fluoresce. One polished block ProOsteon® 500 treated by pipette with 15% gel solution and having 2.1% dry gel weight gain was “stained” by dipping the polished surface in a 2% solution of Fluorescamine in DMSO. When examined under a fluorescence microscopy, the gel was clearly distributed throughout the regions that otherwise appeared to by hydroxyapatite. FIG. 1 shows a photomicrograph of a sample infiltrated with gelatin.
Example IV
Because there was the slight possibility that gelatin might have been smeared across the surface during the dry polishing in the above stain experiment, it was decided to crosscheck the fluorescent stain results as follows:
A 10×10×45 mm ProOsteon® 500 block that was impregnated with 15% Kodak gel solution and a 5×15×41 mm block of Interpore® 200 that was impregnated with 15% gel solution were soaked in a 1% glutaraldehyde solution for five days to chemically crosslink the gelatin and prevent it from smearing during polishing. These “tanned” blocks were rinsed in distilled water, dried and sliced on a diamond cutoff saw. The fresh cut surfaces were ground and polished to a 5 μm diamond polish.
The samples were stained with fluorescamine and examined under fluorescent light microscopy. Results clearly showed that the gelatin had penetrated the microscopy of both the ProOsteon® 500 and Interpore® 200 blocks. FIG. 2 is a photomicrograph of a sample infiltrated with gelatin and crosslinked with glutaraldehyde.
Example V
Approximately 12 mg. of stannous octoate (Sn(II) (2-Ethylhexanoate)2) was placed on the bottom of each of two 28×10−8 mm vials (Fisher) along with a small wire frame. The vials were dried at 150° C. for two hours. The hot vials were removed from the oven and covered loosely with rubber lined Bakelite caps. The still hot vials were then transferred to a desiccator at 23° C. and exposed to 10.0×10−3 mm Hg vacuum for four hours, at which point the desiccator was filled with dry nitrogen and the caps were quickly tightened upon the vials. The catalyst loaded wire frame equipped vials were tared and then transferred into a dry nitrogen filled glove bag. The dry nitrogen filled glove bag was equilibrated with P 2 O 5 . The catalyst loaded wire frame equipped vials were loaded with approximately 6.0 grams of monomer (2S)-cis-3,1-Dimethyl-1,4-Dioxane-2,5-Dione (Aldrich). The vials were placed inside of a desiccator over P 2 O 5 with the caps loosely in place, and exposed to 10.0×10−3 mm Hg vacuum for 18 hrs. to dry the monomer. Following this, the monomer and catalyst loaded wire frame equipped vials were equilibrated with dry nitrogen inside of the desiccator, and the caps were quickly secured as the vials were transferred into a dry nitrogen glove bag.
Four coralline hydroxyapatite blocks 10×10×45 mm (ProOsteon® Implant 500) were weighed (3.7 to 4.5 grams) and dried at 150° C. for 14 hrs. The still hot blocks were individually packaged in hot oven dried vials. The vials in turn were placed into a desiccator at 23° C. over P 2 O 5 for 14 hours at 10.0×10−3 mm Hg vacuum, with caps loosely in place. The desiccator was then equilibrated with dry nitrogen. The caps were quickly tightened on the vials as they were transferred from the desiccator to a dry nitrogen filled glove bag. The nitrogen inside the glove bag was exposed to P 2 O 5 for several hours to insure anhydrous conditions, and each of the catalyst loaded wire frame equipped vials received two dry coralline hydroxyapatite blocks. The weight of each block was then written upon the corresponding fully loaded vials after the cap was secured. The two vials were randomly labeled A and B. It is imperative that the wire frames are designed such that the blocks are supported above the monomer, and do not touch the monomer and catalyst in the bottom of the vial. The two fully loaded vials were then removed from the glove bag.
The two fully loaded sealed vials were placed upright into a 130° C. oven until the monomer had just melted (15 minutes) and then the vials were swirled for five minutes to mix the monomer with the catalyst. When the blocks were completely saturated, the vials were placed upright again to drain out any excess monomer from the blocks. The blocks were then curred to 96 hrs. at 145° C.
The two 10×10×45 mm coralline hydroxyapatite blocks, which were impregnated with Polylactic acid (PLA), were cut into three 1 cm cubes for mechanical testing. The remaining 1×1×1.5 cm block was kept for descriptive analysis. The three cubes from each block were marked with a pen on three orthogonal axes as shown in FIG. 5 . The three cubes from two of the blocks were soaked with distilled water for twenty-four hours before being compression tested on a Carver press equipped with a force gauge with full scale deflection of 500 lb. The blocks were oriented with the marked side facing up, and 1×15×15 mm balsa wood shims were placed on either side of the blocks during the compression test to insure even distribution of stress. The three cubes from the other two blocks were tested in a similar fashion, in a dry state. Two untreated coralline hydroxyapatite control blocks were tested in an identical fashion as the four PLA impregnated blocks, one dry and one wet. The results from these tests are contained in Table II. The wet HA-PLA cubes have a 5.15-fold increase in compressive strength over untreated wet controls. Literature values for the controls are 40-60 lb/cm2 (1.8-2.7 Mpa) (Tencer et al.).
TABLE II
HA-PLA
HA-PLA
HA-PLA
HA-PLA
control
control
dry
wet
dry
wet
CUBE
dry
wet
C-29-V-A
C-29-V-B
C-29-V-A
C-29-V-B
Lb/cm2
(1.00 lb/cm 2 = 0.044 MPa)
Strength
1
225
05
320
25
200
150
2
10
100
205
180
430
470
3
5
05
465
45
205
275
MEAN
80
37
330
83
278
298
Scanning electron micrographs (FIGS. 3 , 4 ) show that the polymer provides only a limited coating. The coating appears by scanning electron microscopy to be less then 5 μm in thickness. The white hydroxyapatite crystallites on the surface of the macropores can be seen protruding through the thin polymer coating. The control photographs (FIGS. 5 , 6 ) show the untreated hydroxyapatite by way of reference. Fluorescence microscopy using a fluorescein labeled polylactic acid stain indicate that the polymer is contained primarily within the micropores.
The manufacture of a composite employing the in situ polymerization of the monomer L-Lactide (3(S)-cis-3,6-Dimethyl-1,4-Dioxane-2,5-Dione), 0.2% of the catalyst Tin Octoate (Sn-II, (2-Ethyl Hexanoate)2), and 10×10×45 mm coralline hydroxyapatite blocks resulted in a material having superior compressive strength, without significant sacrifice of macropores (according to SEM), compared to the control. Compressive strengths of at least five-fold over the untreated blocks have been realized using the methods described herein as compared to the untreated material. The superiority of the method described herein is attributed to the filling of the microporosity with polymer.
Example VI
Additionally, a method was developed which utilizes glycolide monomer (1,4-dioxane-2,5-dione) to impregnate ProOsteon® blocks in a substantially similar fashion. The melting point of glycolide monomer is 83° C. The lower melting point (relative to lactide) coupled with the higher reactivity of glycolide with the catalyst (Sn-II octoate) allows the process to procede at lower temperatures. Similarly, co-polymers of lactide and glycolide may be used to achieve intermediate results.
Of course, other modifications, alterations and substitutions may be apparent to those skilled in the art in light of the foregoing disclosure. Therefore it is intended that the scope of the invention be governed by the following claims. | An improved porous ceramic biomaterial is disclosed in which a polymer such as polylactic acid is polymerized in situ to fill the micropores substantially without filling the macropores. The polymer reinforcement helps improve the strength of the implant while preserving its ability to support ingrowth of bone to help integrate the implant into its surgical environment. | 2 |
FIELD OF THE INVENTION
The invention relates to spacers for aerial cables for supporting one or more cables above the ground, and more particularly to an anti-dislodging cable retainer for aerial cable spacers.
BACKGROUND OF THE INVENTION
Overhead conductor cables are commonly suspended from a messenger cable typically made of high strength alloys. The messenger cable is supported on poles or towers with the conductor cable spacers arranged at spaced intervals along the messenger cable to suspend one or more conductor cables. Since many power circuits require three phase electric power, it is often convenient to suspend conductor cables in groups of three. A spacer supports all three conductor cables and simultaneously maintains the conductors in spaced relation.
If the advantages of suspending conductors in this manner are to be fully availed, it is essential that the spacer be easily attached to the messenger cable and to the conductor cables. To provide ease of attaching the spacer to the cables and to reduce the number of parts required, the means for retaining the cables in their respective seats of the spacer should accommodate cables of varying cross sectional diameters without requiring bushings, sleeves, grommets or the like.
The construction of the spacer should be such that all of its parts have both high mechanical and electrical strength and are durable in use. In addition, all parts of the spacer should be economical to manufacture and to assemble.
U.S. Pat. No. 4,020,277, issued Apr. 26,1977 to Hendrix Wire & Cable Corporation, the predecessor to the instant assignee, discloses a spacer for aerial cables. The spacer includes a body member having at least one generally arcuate cable retaining means adapted to engage a surface of the conductor cable and retain the cable in a concave seat of the spacer. One end of the cable retaining means is pivotally supported on the body member. Generally arcuate ratchet tooth means are provided adjacent the other end of the cable retaining means. Generally arcuate ratchet tooth means are also provided on the body member outwardly of the concave seat. The teeth of the retainer ratchet tooth means are engageable with the teeth of the body member ratchet tooth means when the retaining means is rotated about its pivotal support, thereby to firmly retain the conductor cable in the concave seat.
However, it has been found that the cable retainer may be dislodged by contact with branches or as the result of force imposed on the retainer due to a short circuit in one of the cables.
While unrelated to aerial cable spacers, there are patents which relate to the more general art of cable clamps. U.S. Pat. No 4,669,688 discloses a cable clamp which, when in a locked position, provides a protrusion with a tooth-like member which is held between a retaining member and an engaging member. U.S. Pat. Nos. 3,516,631, 4,128,918 and 4,609,171 disclose other similar cable clamps.
The structures shown in the above cable clamps are not adaptable to aerial cable spacers. For instance, one common difference from the aerial cable spacers such as shown in U.S. Pat. No. 4,020,277, is that the general cable clamps are limited to clamping cables of one or of a limited size in diameter. The aerial cable spacer of U.S. Pat. No. 4,020,277 is adapted to accommodate a greater range of cable sizes, with ease of replacing the cables and without reducing the effectiveness of the clamping ability of the cable retainer. In addition, the above general cable clamps have intricate components which are not durable for aerial cable spacer applications.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an aerial cable spacer which overcomes the above noted problems of the prior art.
It is a further object of the present invention to provide an aerial cable spacer having a cable retainer which resists being inadvertently dislodged.
It is still a further object of the present invention to provide an aerial cable spacer having a cable retainer which is not easily dislodged and which accommodates cables of a wide range of sizes.
It is yet a further object of the present invention to provide an aerial cable spacer having a cable retainer which is not easily dislodged and which can be used repeatedly without losing its effectiveness to retain the cable.
Yet a further object of the present invention is to provide an aerial cable spacer having a cable retainer which is not easily dislodged and which is cost effective to manufacture.
Still a further object of the present invention is to provide an aerial cable spacer having a cable retainer which is not easily dislodged and which is durable.
Still yet a further object of the invention is to provide a cable spacer made of the same material as the cable, thereby providing dielectric compatability.
The present invention therefore provides, a device for supporting and spacing aerial cables, the device comprising a main body portion, the main body portion having, a cable seat, a first side adjacent the cable seat, a second side adjacent the cable seat and opposite from the first side, an arcuate shaped protrusion extending along the first side, a plurality of teeth arranged in an arcuate shape along the first side; and a cable retaining arm having a first end pivotally coupled to the second side of the main body portion, a second end having a pawl which pivots about a first arcuate path, the first arcuate path substantially aligned with the plurality of teeth arranged in an arcuate shape, and an abutment surface which pivots about a second arcuate path, the second arcuate path substantially aligned with the arcuate shaped protrusion, the abutment surface slidably engageable with the arcuate shaped protrusion, whereby the cable retaining arm is adapted to engage a surface and arcuate shaped protrusion of a cable, the pawl is locked in a position along the plurality of teeth and the engaging abutment surface prevents the pawl from being inadvertently released from the plurality of teeth.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an elevational view of an aerial cable spacer, having a plurality of cable retainers, in accordance with the present invention;
FIG. 2 is an elevational view with phantom lines of a cable retainer of FIG. 1 in accordance with a first embodiment of the present invention;
FIG. 3 is a view of the cable retainer taken along line 3 — 3 of FIG. 2;
FIG. 4 is an elevational view of a cable seat of the body member shown in FIG. 2;
FIG. 5 is a view of the retainer taken along line 5 — 5 of FIG. 2;
FIG. 6 is a cross-sectional view of the retainer taken along line 6 — 6 of FIG. 2;
FIG. 7 is an elevational view with phantom lines of a cable retainer of FIG. 1 in accordance with a second embodiment of the present invention;
FIG. 8 is a view of the cable retainer taken along line 8 — 8 of FIG. 7;
FIG. 9 is a view of the retainer taken along line 9 — 9 of FIG. 7; and
FIG. 10 is a cross-sectional view of the retainer taken along line 10 — 10 of FIG. 9 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
In a first embodiment, the spacer shown in FIG. 1 includes the body member 10 and four generally arcuate retaining means 12 , 14 , 16 and 18 . The retaining means 12 , 14 and 16 are identical. The retaining means 18 is the same as the other retaining means except that it is narrower, shorter and has one fewer ratchet teeth.
Both the body member 10 and the retaining means 12 , 14 , 16 , 18 are made from a thermoplastic material, the preferred embodiment being a polymer which has a low dielectric constant and has both weather and track resistant qualities.
The body member 10 is provided with three generally concave conductor cable seats 20 , 22 and 24 and a generally concave messenger cable seat 26 . As can be seen from FIGS. 1 and 4, an arcuate shaped protrusion 28 , 30 , 32 and 34 is located at one side of each of the concave seats 20 , 22 , 24 and 26 . Each arcuate shaped protrusion 28 , 30 , 32 and 34 has a far side 36 , 38 , 40 and 42 facing away from the respective concave seat and a near side 44 , 46 , 48 and 50 facing towards the respective concave seat. FIG. 3 shows a view of the arcuate shaped protrusion 30 along line 3 — 3 of FIG. 2 .
The body member 10 is provided with four generally arcuate ratchet tooth means 52 , 54 , 56 and 58 located along the far side 36 , 38 , 40 and 42 of the respective arcuate shaped protrusion 28 , 30 , 32 and 34 . Each ratchet tooth means 52 , 54 , 56 and 58 includes a plurality of teeth as shown, for example, in FIG. 4 .
The body also comprises semi-cylindrical sockets 60 , 62 , 64 and 66 (FIG. 1 and 2 ). The sockets are located adjacent to the sides of the seats 20 , 22 , 24 and 26 respectively. The sockets are located opposite from the respective body ratchet tooth means 52 , 54 , 56 and 58 . The sockets are provided with slots 68 , 70 , 72 and 74 which are formed in part by the flanges 76 which form reinforcements for the sockets (see FIG. 4 ).
Each retaining means 12 , 14 , 16 , 18 comprises a pair of spaced generally arcuate arms 80 (FIGS. 5 and 6 ), connected together at one end by a generally cylindrical member 82 and at the other end by a transverse member 84 . The transverse member 84 is provided with a hole or “perforation 86 . The transverse member 84 of the retaining means are also provided with a pawl 88 (see FIGS. 5 and 6) as best seen” in FIG. 6 . Each of the arms 80 includes an abutment surface or notch 90 , as seen in FIG. 5 .
To assemble the parts of the spacer, it is only necessary to snap each of the generally cylindrical members 82 through the slots 68 , 70 , 72 and 74 and into the respective socket 58 , 60 , 62 and 64 .
To install the spacer, the retaining means are rotated to open positions in which they are temporarily retained because of the snug fit between the generally cylindrical members 82 and the respective socket 58 , 60 , 62 and 64 . The messenger cable seat 26 is then placed over the messenger cable 78 and the retaining means adjacent to it is partially closed to hold the messenger cable in its seat. Then the conductor cables 94 , 96 , and 98 are positioned in the seats 20 , 22 and 24 . The conductor cables 94 , 96 and 98 are provided with insulating sheaths 100 , 102 and 104 . The retaining means are each rotated to closed positions so that the pawl engages the respective body member ratchet tooth means, the abutment surfaces or notches engage the respective portions of the arcuate shaped protrusions (see FIGS. 2 and 3 ), and the curved central portions of the generally arcuate arms 80 firmly contact the conductor cables. Thus the conductor cables are firmly held in their respective seats. The retaining means for the messenger cable is rotated to a fully closed position so that the central portion of its generally arcuate arm 80 firmly contacts the messenger cable thereby to firmly hold it in its seat 26 .
The holes or perforations 86 may be used to close and open the retaining means by inserting a screwdriver or other elongate tool and, using the tool as a lever, either to tighten the retaining means with respect to the cable or to pry it open so that it may be rotated to an open position in the event is becomes necessary to repair or replace the cables.
As will be appreciated, the engaging abutment surface or notch 90 and arcuate shaped protrusion 28 , 30 , 32 , 34 prevents the cable retaining means 12 , 14 , 16 , 18 from being inadvertently dislodged.
FIGS. 7-10 disclose a cable retainer in accordance with a second embodiment of the present invention. The cable retainer of the second embodiment is identical to the cable retainer of the first embodiment with the following exceptions. As seen from FIGS. 9 and 10, the abutment surface is provided in the form of a pair of tangs 92 . The pair of tangs 92 engage the arcuate shaped protrusion 28 , 30 , 32 , 34 as seen in FIGS. 7 and 8.
It will be apparent to persons skilled in the art that a spacer embodying this invention is new, economical to manufacture and assemble and durable in use. It is also free from bushings, sleeves and grommets surrounding the messenger and conductor cables and the spacer can accommodate a wide range of cable sizes. Furthermore, it consists of only three parts, the body 10 , three identical retaining means 12 , 14 , and 16 and one slightly smaller retaining means 18 and all three of these parts are made of the same polymeric material at the same time using a single mold cut. The body and the retaining means are weather and track resistant. In addition, the novel cable retaining means resist forces tending to pull the cables out of their seats.
While a first and second embodiment of a spacer for aerial cables embodying the invention has been shown in the drawings, it is to be understood that this disclosure is for the purpose of illustration only, and that various changes in shape, proportion and arrangement of parts as well as the substitution of equivalent elements for those shown and described herein may be made without departing from the spirit and scope of the invention as set forth in the appended claims. | An aerial cable spacer is provided with an anti-dislodging cable retainer. The anti-dislodging cable retainer includes a cable seat. Adjacent the cable seat on one side are ratchet teeth and a guide. Adjacent the cable on the opposite side is a slot. The slot receives a retaining arm. At the end of the retaining arm is a ratchet tooth for engagement with the ratchet teeth. The end of the arm also includes either an abutment or groove to engage the guide and to maintain the engagement of the ratchet tooth with the ratchet teeth. | 7 |
BACKGROUND OF THE INVENTION
The present invention relates generally to plastic containers. More particularly, but not by way of limitation, this invention relates to an improved method and apparatus for making containers, such as bottles and cans, having improved gas transmission barrier characteristics.
In the food and beverage industry the trend is to move away from packaging perishable products in glass and metal containers and to substitute thermoplastic polymers for the container material. One of the most successful polymers for beverage containers to package beer, wine, and soft drinks has been polyethylene terephthalate (PET). One of the largest markets for PET containers has been in the two-liter carbonated drink field. Another area where PET is expected to be used extensively is in packaging beer and food. In either case, one of the most critical characteristics of the polyester package is the prevention of gas permeation through the wall of the container.
With carbonated soft drinks, the problem with gas permeation is the loss of carbonation (C0 2 gas) from the drink through the wall of the bottle or can. Compared to the small, densely-packed metal and glass molecules, polymer molecules are relatively large and form a permeable wall. Even the best polymer known at this time for gas barrier properties, ethylene vinyl alcohol (EVOH), has poor barrier ability when compared to the inorganics such as metals and glass.
On the other hand, beer and food containers preferably should present a good vapor barrier against the ingress of oxygen (O 2 ) into the container because of the accelerated spoilation of the food products caused by the presence of oxygen therein.
There have been several different methods developed in an attempt to increase the "shelf-life" of plastic containers. One of the most common methods involves creating a multi-layered container having a thin barrier layer of a material such as EVOH or polyvinylidene chloride (PVdC) buried between two or more layers of a container polymer such as PET, polypropylene, polystyrene, or PVC. This multi-layer container is difficult and expensive to manufacture since the barrier layers are either expensive (EVOH) or corrosive (PVdC). Also the process for forming a multi-layered material and making a container from it may be much more complex than single-layer processes.
Another method of creating a barriered polymer container is the process known as "dip-coating". In this process a polymer bottle made of a material such as PET, is first formed into its final shape and then the additional step of dipping the container into a coating solution is performed. This solution may be of a barrier material such as PVdC. This process, in addition to adding another expensive step to the container manufacture, also introduces a material to the container that prevents easy recycling. Because of the nature of PVdC, the coating must be removed by solvents before the polymer container can undergo normal recycling. In light of the trend toward compulsive container return laws in various states and a probable federal deposit/return law, all future container designs must be quickly and easily recyclable. Dip-coated bottles do not lend themselves to easy recycling.
U.S. Pat. No. 4,478,874 issued Oct. 23, 1984 to Granville J. Hahn describes an additional process for improving the gas barrier characteristics of thermoplastic containers. The process described in the patent involves ion-plating the container with a thin, flexible layer of an inorganic oxide.
The present invention overcomes the deficiencies of the barrier-layer containers and the dip-coated containers by providing a plastic container which provides excellent barrier characteristics, is cheaply and easily treated, and can be completely recycled by conventional recycling techniques without need for removal of dip-coated layers. This is achieved by impregnating the interior surface of a normal polymer container with an inorganic material such as a metallic oxide. The impregnation is done by gasless ion plating to provide an ultra-thin flexible coating of the inorganic material on the plastic substrate.
SUMMARY OF THE INVENTION
This invention provides improved apparatus for making open ended plastic containers having decreased gas permeability wherein the apparatus includes means for holding the containers, the improvement comprising an ionization and vaporization source located proximate the open end of the container.
In another aspect, this invention contemplates a method for making open ended plastic containers having decreased gas permeability that comprise the steps of: positioning said plastic container in ion coating apparatus with the open end unshielded; locating a vaporizing and ionizing source proximate said unshielded open end; and ionizing and vaporizing a material for deposition on the interior surface of the container.
BRIEF DESCRIPTION OF THE DRAWING
The foregoing and additional objects and advantages of the invention will become apparent as the following detailed description is read in conjunction with the accompanying drawing wherein like reference characters denote like parts in all views and wherein:
FIG. 1 is a schematic view of apparatus constructed in accordance with the invention for carrying out the process of the present invention.
FIG. 2 is a schematic view of a modified form of the apparatus of FIG. 1 that is also constructed in accordance with the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, which is a schematic illustration not drawn to scale, illustrates a vacuum chamber 8 including a vacuum pump 10 for reducing the pressure in the chamber 8 to a desired sub-atmospheric value and having a container holding fixture 12 removably located therein. The container of FIG. 1 is an open ended plastic preform 14 that is screwed into a rotatable base 16 of the fixture 12. The base 16 of the fixture 12 is rotatably supported on a bearing 18 and is caused to rotate by a motor 20. The base 16 has an opening 17 extending therethrough in general alignment with the open end of the preform 14 so that the interior of the preform is unshielded. The fixture 12 is electrically isolated from the remainder of the system.
An ionizable coating source or material 22 is held in a vaporizing filament 24. The filament 24 is electrically connected to and supported by a pair of terminals 26 forming a resistance heating element that is powered by an external AC power supply 28. The coating material 22, held in filament 24, is vaporized by heat energy.
Ionizing energy is provided by radio frequency generated by an RF source 30 and a biasing DC voltage from a DC source 32. The RF and DC are applied through appropriate circuits and the brush or commutator 33 to fixture 12. The fixture 12 acts as an antenna for radiating the RF during operation of the system.
The fixture 12 also includes a magnet support 34 that encompasses the preform 14. Also carried by the support 34 on the fixture 12 is an optional magnet 36, which may be a permanet magnet or an electro-magnet. The magnet 36 encircles the exterior of the preform 14 and sets up a magnetic field to increase the efficiency of the coating system. It is believed that the efficiency is increased by spiraling the thermionic electrons which prolongs the residency of the electrons, and thus increases the electron density in the interior of the container. This increased electron density increases the percentage of evaporant atoms that become ionized by collision with an electron.
In the event that only the interior of the preform 14 is to be plated, the support 34 can also act as a shield encompassing the exterior of the preform 14 as illustrated. If transparent materials are being plated, it may not be of great importance to prevent their plating out on the exterior. However, in the use of colored materials, it may sometimes be highly desirable to plate only the interior.
As a result of the vaporization of the coating material 22 and the ionizing and biasing field created by the DC/RF power supply and radiated by the fixture 12, a plasma of ionized aluminum (for example) forms between the filament 24 and the fixture 12. The bias aligns and stabilizes the flow of ions toward the preform 14. form 14.
The ions pass through the opening 17 and impinge on the inner surface of the preform 14 while traveling at very high velocities and apparently penetrate partially into the surface of the polymer. An even coating of the ionized material on the preform 14 can be obtained by rotating the preform 14 about one or more of its axes during the impingement cycle. The coating material 22 and the vaporizing filament 24 should be located proximate the open end of the preform 14 with a direct flow path for the vaporized material into the preform 14. Placing the filament as close as possible will provide the greatest density of ionized material in the interior and thus provide for the greatest efficiency.
The impingement cycle is maintained long enough to obtain a coating layer on the preform 14 that can adhere to and flow with the plastic because the preform 14 will eventually be expanded up to 8 times into a full sized bottle or container. The result is a clear flexible coating of aluminum oxide on the inner surface of the polyester preform 14, which penetrates partially into the polymer and plugs the interstices between the polymer chains, rendering the material substantially impermeable to gases. This plugging of the interstices is believed to be a main contributor to the improvement in gas barrier characteristics of the aluminum oxide coated container. While 500 Angstroms is considered a good coating thickness, other thicknesses ranging from less than 500 to as high as 5000 Angstroms or more might be used depending on the type of polymer, the container shape, and the size and thickness of the container.
In addition to the impingement coating of polyesters such as PET it is believed that most other polymers can also be coated successfully. It is also expected that other inorganic materials may be substituted for SiO, for example aluminum, aluminum oxide, titanium, titanium oxide, magnesium, magnesium oxide, tantalum and tantalum oxide. Most inorganic or metallic oxides should be adaptable to this process. It should also be noted that even though the metals of these plating compounds are generally opaque, their oxides are clear and thus they can be used on both clear and pigmented polymers without affecting the aesthetics of the containers.
Recyclability of the used coated containers is not affected detrimentally because of the extremely small amount of inorganic coating used. Because of its inert nature and presence in small amounts, the coating will not be noticeable in the recycled polymer. The amount of inorganic coating is less than 1% by weight of the polymer in the container. Some containers have inorganic pigments such as titanium dioxide mixed with their polymers in amounts as high as 25% by weight without affecting recyclability; therefore it can be seen how negligible the effect of the coating material is on recyclability using the present invention.
The Embodiment of FIG. 2
Referring to FIG. 2, shown therein is apparatus for carrying out the process of the invention. Where the components of the apparatus of FIG. 2 are identical to those of FIG. 1, they will be designated by the same reference characters used on those parts in the description of the embodiment of FIG. 1.
The apparatus of FIG. 2 includes a vacuum chamber 108 that is provided with a vacuum pump 10 to permit lowering of the pressure within the chamber 108 to the desired subatmospheric value.
As described in connection with FIG. 1, the filament 24 is supported between terminals 26 for the purpose of vaporizing the coating material 22. The terminals 26 are connected to a source of A/C power 28. A radio frequency source 30 and a DC voltage source 32 are connected by appropriate circuits and through brushes or communtators 33 to a plurality of rotatable bottle holders 110.
The holders 110 are arranged to be rotated by the motor 20 of FIG. 1 and are located in the chamber 108. Each of the rotatable bottle holders 110 has a bottle 112 mounted thereon for rotation therewith. Also mounted for rotation on each of the rotatable bottle holders 110 is a magnet support 114 which encompasses each of the bottles 112 and, encircling each support 114 is a magnet 116. The supports 114 and the magnets 116 provide the same functions previously described in connection with the support 34 and magnet 36 of the embodiment of FIG. 1.
The apparatus of FIG. 2 ionizes the material 22 which is then deposited on the interior of the bottles 112. The support 114, if configured as a shield, prevents the deposit on the exterior of the bottles 112. Rotation of the bottles 112 on the holders 110 aid in assuring that the layer of ionized material on each bottle 112 is are uniformly deposited on the interior surface of the bottles.
In the embodiment of FIG. 2, a substantially thinner layer of ionized material can be deposited on the interior surface of the bottles as compared to the deposition in the preform of FIG. 1. The difference in thickness results from the fact that the preform 14 of FIG. 1 is not a finished product. The preform 14 will be later heated and expanded to form completed bottles such as the bottles 112 of FIG. 2. In both cases, the ionized material is preferably deposited on the interior surface of the container. Relatively brittle materials, such as a silicon monoxide, can be deposited on the bottles 112 since no further expansion or stretching of the plastic occurs.
As compared to the deposition of ionized materials on the exterior of the bottles as taught in the prior art, the deposition of the ionized material on the interior of the bottle provides the advantage of not being subjected to inadvertent damage or partial destruction due to rough handling of the bottles. Stated in another way, the interior deposition of the material on the bottles provides a bottle having a greater integrity with respect to the possible permeation of gas either into or out of the bottle because it is less susceptible to damage. Thus, the bottles are more reliable from the standpoint of preventing either loss of gas from carbonated drinks or preventing spoilage of food due to the ingress of oxygen through the wall of the bottles.
Although specific embodiments of the present invention have been described in the detailed description above, the description is not intended to limit the invention to the particular forms or embodiments disclosed therein since they are to be recognized as illustrative rather than restrictive and it will be obvious to those skilled in the art that the invention is not so limited. For example it is contemplated that plating materials other than silicon monoxide, aluminum oxide, and titanium oxide can be used. One such material would be tantalum oxide. Also containers other than carbonated beverage bottles would benefit from the present invention, such as beer containers, food containers, and medicine containers. Thus the invention is declared to cover all changes and modifications of the specific examples of the invention herein disclosed for purposes of illustration, which do not constitute departures from the spirit and scope of the invention. | Apparatus for producing open ended plastic containers having decreased gas permeability that includes a vacuum chamber and a pump for regulating the pressure therein, an ionization source mounted in the chamber proximate the container's open end and a container holder located in the chamber. The container holder has a hole aligned with the open end and may include a shield that encompasses the exterior of the container and may include a magnet setting up a magnetic field on the exterior of the shield. In the method, a container is placed on the container holder in the chamber with the open end and hole aligned and with the shield and magnet located as described above. The coating material is vaporized and ionized so that the ionized material is deposited on the interior wall of the container. | 2 |
BACKGROUND OF THE INVENTION
The present invention is related to memory systems attached to computer central processing units, and in particular to memory systems attached to central processing units of microprocessors in a shared memory configuration.
Conventional microprocessors access random access memory through address and data buses and control signals. Some microprocessors use a common address/data bus which is time-multiplexed.
When the microprocessor CPU (central processing unit) reads data (which may include instructions) stored in the memory by performing a read operation, the microprocessor typically places an address on the microprocessor address bus (or common address/data bus) and requests a "read" operation via the control signals. Similarly, when the microprocessor writes data to the memory it typically first places an address on its address bus, and requests a "write" operation via its control signals. During subsequent steps of the write operation, the CPU places the data to be written on its data bus (or on the address/data bus in the case of a time-multiplexed address/data bus).
A cache is a small, fast memory logically located between the random access memory and the microprocessor CPU. A cache accelerates reads to the memory by holding the most recently accessed data.
The cache memory is not a random access memory, but rather an associative memory. When presented with an address and data as a result of a microprocessor write operation, the cache associates the address with the data and stores the data in its memory. When presented with an address as the result of a microprocessor read operation, the cache inspects the address to determine whether or not the cache has stored data associated with the address. If such an association exists, the cache "hits" and the data is presented to the microprocessor with no interaction on the part of the random access memory. Alternatively, if no such association exists, the cache "misses" and the random access memory must be read to fill the cache and to deliver the requested data to the microprocessor.
In the case of a cache miss, caches cause the microprocessor to stall the existing program flow and to perform a cache fill procedure to bring the requested data into the cache. This degrades the overall performance of the program.
For high performance applications, it is desirable to have as much data encached as possible. However, a problem exists when multiple microprocessors and other devices are allowed to read and write to the random access memory which is a shared memory (SM). It is possible that two or more devices use information stored in the same location in the shared memory. In such a case, it is important that all devices use this information consistently.
For example, it is possible that one microprocessor can encache a portion of the shared memory in its cache, and subsequently a second microprocessor or other device can overwrite the same location in the shared memory. The first microprocessor must be made aware that its encached copy of the shared memory data is no longer valid, since the data has been modified by another device. This is called the "cache consistency problem."
The shared memory is often used by two or more microprocessors or other processing engines to communicate with each other. An example of such a system is described in U.S. patent application Ser. No. 08/093,397, "Communication Apparatus and Methods," now U.S. Pat. No. 5,515,376, issued on May 7, 1996. In this system, multiple microprocessors and network controllers communicate through a shared memory for the purpose of forwarding packets of information between networks. A network controller writes the packet into a buffer in the shared memory, and writes control information associated with the packet into a descriptor in the shared memory. A microprocessor reads this information in order to process the packet. The network controller writes the information associated with a particular packet only once; therefore, once the writing has been completed, the microprocessor may read and encache this information. However, the network controller may use the same region of the shared memory later to store information for a new packet. At this point, the information stored in the microprocessor's cache is inconsistent with what has been written into the shared memory. The microprocessor must somehow be made to ignore what is stored in its cache and instead to read the new information from the shared memory.
One solution to the cache consistency problem is simply not to encache shared information in the first place. For example, the MIPS R3000 family microprocessor architecture[ref. MIPS RISC Architecture, by Gerry Kane, Prentice-Hall, 1988, hereby incorporated herein by reference] specifies certain portions of memory to be cacheable, and other portions to be uncacheable, as indicated by certain high-order bits in the microprocessor's internal, virtual address. In systems employing this microprocessor, shared information may be accessed via non-cacheable virtual addresses. However, this solution reduces performance for two reasons, discussed below.
First, a particular piece of shared information may be used multiple times by the program, for example, a packet header may be looked at several times by different steps in the packet-forwarding algorithm. Since this piece of information is not cached, it must be read from the shared memory once for each step, which is inefficient. This inefficiency may be partially overcome by explicitly reading the information only once and then storing it in a processor register or in non-shared, and therefore cacheable, memory. However, when written in a high-level-language program, these explicit operations may or may not be preserved by the high-level-language compiler. For example, the compiler may decide that these operations are redundant and remove them, leading to incorrect program operation.
Second, accesses to non-cacheable memory may not use the most efficient mode of microprocessor bus operation. For example, some MIPS R3000-family microprocessors, such as the R3052 and R3081 from Integrated Device Technology, Inc., use an efficient 4-word burst mode to read cacheable memory locations, but use a less efficient single-word mode to read non-cacheable locations.
Another solution to the cache inconsistency problem is to allow programs to encache shared information once, but then to explicitly flush (mark invalid) the cached information after it has been used. This guarantees that the cache will "miss" when the processor next attempts to read new information at a shared memory location that was previously encached. Disadvantages of this approach include program inefficiency (extra instructions are needed to flush the cache) and awkwardness (a high-level language may not be able to generate the low-level instructions needed to flush the cache).
Another solution to the cache inconsistency problem is called bus snooping. In the bus-snooping method, each microprocessor which shares the memory monitors all other microprocessors to detect memory write operations to locations which the microprocessor has encached. If any other microprocessor performs a write to an encached location, the first microprocessor invalidates its cache so that the next read reference to that location will cause a cache miss.
Bus snooping has the disadvantage of requiring additional bus-snooping and cache-monitoring logic to be present in each microprocessor, which can increase the cost and/or decrease the performance of the microprocessor. Also, bus snooping may not be supported at all by some classes of commercially available non-microprocessor devices, such as the network controllers mentioned previously.
SUMMARY
The present invention alleviates the above problems by allowing a given block of shared information to be read from the shared memory exactly once, by using efficient burst-mode transfers of this information to the microprocessor, and by automatically forcing a cache miss when new information is read. These results are obtained without the use of explicit copying from non-cacheable to cacheable memory, low-level cache-flushing operations, or bus-snooping hardware.
In many applications of shared memory with multiple microprocessors, cache inconsistency exists not because one microprocessor modifies the exact word that another microprocessor reads, but rather that the microprocessor caches entire blocks of memory, or cache lines, and a cache line contains both a word modified by one microprocessor and a different word read by another microprocessor. In other words, sometimes cache inconsistency exists because the microprocessor cache encaches at the cache line granularity, rather than at less than cache line granularity.
The present invention alleviates this problem by allowing only those portions of the shared memory that are actually utilized by each microprocessor to become encached in its corresponding active cache.
A memory access acceleration method commonly used in microprocessors is burst-mode block reads and writes. Burst mode allows blocks of information to be transferred to and from the microprocessor at the full rate of the memory system attached. A block is a physically contiguous, multiple word quantity of memory, located on a physical address boundary which is specific to the memory subsystem and the microprocessor. Burst-mode read or write is possible when the microprocessor is able to make a single, aligned, multiple-word request to the memory subsystem.
A microprocessor and a shared memory subsystem may use different clock frequencies for their operation, so that each may operate at a speed that is most advantageous according to design goals of cost, performance, individual component speeds, and so on. When different, asynchronous clocks are used for a microprocessor and memory, a performance penalty normally occurs as control signals and data are synchronized from one clock domain to the other. [For example, see Digital Design Principles and Practices, 2nd ed. (Prentice Hall, 1994), by John F. Wakerly, pp. 640-650 hereby incorporated herein by reference.] The present invention hides this penalty by bringing shared-memory data into the microprocessor's clock domain in advance, so that the microprocessor need not suffer a synchronization delay when reading shared-memory data.
Typical microprocessors often cannot perform burst operations to memory due to block misalignment reasons. The present invention allows unaligned blocks to be burst to the microprocessor.
In some embodiments, the present invention provides an "active" cache, that is, a cache that can encache data independently of the microprocessor, while the microprocessor executes other instructions. The active cache allows the microprocessor not to stall during the encache operation.
Sometimes a microprocessor cannot perform a burst read because a memory is too slow to be able to read data in burst mode at the speed required by the microprocessor. However, in some embodiments, the active cache of the invention is sufficiently fast to read data at the speed required by the microprocessor. Hence, even if the shared memory is not sufficiently fast to read data at the microprocessor burst mode speed, shared memory data can be encached and then read by the microprocessor from the cache in burst mode.
In computer networking applications, it is often desirable to compute a checksum on data that is read from a packet header by the microprocessor. The present invention allows such a checksum to be computed by the active cache as it is loaded into the active cache, thus relieving the microprocessor of this task.
The present invention provides in some embodiments shared memory caching without bus-snooping in an efficient manner.
The present invention provides in some embodiments cacheability of a random access memory at smaller granularity than the microprocessor cache line granularity.
The present invention provides in some embodiments an external cache which allows memory-mode bursts to a microprocessor on unaligned memory accesses.
The active cache of some embodiments of the present invention is connected to a microprocessor and to a shared memory as described in detail below. It should be understood that each microprocessor in the system utilizing the shared memory is connected to the memory and its own active cache in an identical manner. Each microprocessor may also have a private (non-shared) memory subsystem.
Although some embodiments include multiple microprocessors connected to a shared memory, in other embodiments the memory could be shared between a single microprocessor and, for instance, direct-memory access (DMA) devices, such as Local-Area-Network (LAN) controllers. For example, U.S. Pat. No. 5,237,670, "Method and Apparatus for Data Transfer Between Source and Destination Modules," hereby incorporated herein by reference, describes a shared memory that can be shared between multiple processors and LAN controllers, and previously referenced U.S. patent application Ser. No. 08/093,397, "Communication Apparatus and Methods," hereby incorporated herein by reference, now U.S. Pat. No. 5,515,376, issued on May 7, 1996, describes methods and data structures used by multiple processors and network controllers connected to such a shared memory.
In one embodiment, the typical memory operations of each microprocessor consist of reading a contiguous group of 1 to 16 words from a shared memory and operating on those words in the microprocessor. In this system, a word is a 32-bit quantity, a halfword is a 16-bit quantity, and a byte is an 8-bit quantity. The words read from the shared memory comprise a packet header describing a packet of information including a from-address, a to-address, a length, and other information.
The memory of the system is shared by multiple, identical microprocessor-and-active-cache combinations which access the memory in a round-robin or priority fashion as dictated by the needs of the application. Each microprocessor operates as follows.
The microprocessor determines the starting address of a packet header, HA, in the shared memory by reading a queue or descriptor ring of packet headers as described in previously referenced U.S. patent application Ser. No. 08/093,397, "Communication Apparatus and Methods." The microprocessor dequeues the packet for its use and marks the packet in-use. The microprocessor then accesses the appropriate packet header in the shared memory utilizing the present invention.
The microprocessor contains an internal data cache. The internal cache has the characteristic that it is physically (as opposed to virtually) tagged. That is, physical addresses are used to access the internal cache. However, programs executing in the microprocessor utilize virtual memory addresses to access data. These virtual memory addresses are automatically translated by the microprocessor into physical addresses and then applied to the internal cache to determine the presence or absence of the data in the internal cache. Virtual addresses in the microprocessor additionally have the property that the data at their corresponding physical addresses may be indicated as internally cacheable or non-cacheable, according to certain high-order bits of the virtual address. When a reference is made to an internally non-cacheable virtual memory address, the referenced physical memory is never internally cached.
The external active cache of some embodiments of the present invention uses a conventional memory-address decoding technique to map the active cache into the address space of the physical memory. The active cache is memory-mapped into a single distinct block of the physical address space of the microprocessor. This block space has no realization in the physical memory, so memory-mapped active-cache requests have no conflict with actual physical memory addresses.
The active cache decodes each microprocessor address using its request-reception circuit. For each microprocessor address, there are three possibilities:
(1) The memory access is not directed to the active cache or to the shared memory. In this case, the request-reception circuit ignores the request, allowing it to be handled elsewhere in the microprocessor's (private, non-shared) memory subsystem.
(2) The memory access is a direct request to the shared memory. In this case, the request-reception circuit passes the request to the shared memory. The access may utilize part of the active-cache circuit, but it does not change the state of the active cache memory.
(3) The memory access is an active-cache request. In this case, the active cache decodes the request and processes it as discussed next.
The two distinct virtual memory blocks into which the active cache is mapped are used to determine the basic operation of an active-cache request. Each of the virtual address blocks is mapped to the same physical address block, namely, the physical address block onto which the active cache is memory-mapped.
The first virtual block is dedicated to updating the active cache by requesting it to encache-data. This is accomplished by a single "write" operation by the microprocessor.
The second virtual block is dedicated to data-accessing requests to obtain data from the active cache. This is accomplished by one or more "read" operations by the microprocessor.
Two different virtual blocks are used so that the block corresponding to the encache-data request can be indicated as internally non-cacheable while the other block, dedicated to data accessing requests, can be indicated as internally encacheable. Using an internally non-cacheable block for the encache-data request has two benefits. First, internal cache space is not consumed as the result of an encache-data request. Second, the internal microprocessor cache in some embodiments may use a "write-back" discipline in which write data may initially be written only to the internal cache and not to the external bus. Using an internally non-cacheable block for the encache-data request in such an embodiment guarantees that the encache-data request will appear as soon as possible on the external bus.
Updating the active cache by requesting it to encache-data is described below. Addresses in active cache's physical-address block are decoded by the request-reception circuit in the active cache. A microprocessor write operation in this physical-address block indicates an encache-data request to the active cache. The details of the request are contained in the "write address" and the "write data" of the microprocessor write operation. The "write address" is selected within the virtual block dedicated to updating the cache in a way that ensures correct operation of the microprocessor's internal cache, as described later. The "write data" contains a word count and a physical base address for the shared-memory data to be encached.
The format of the write address and write data vary depending on the embodiment. For example, in some embodiments, two words are sometimes written to provide enough bits to specify the base address, the word count, and other details for an encache-data request.
In some embodiments, the encache-data request write address contains 32 bits (8 hexadecimal digits), formatted as shown below:
A9ppsssy 16
where:
A9--indicates the non-cacheable, memory-mapped virtual address block
pp--process id
sss--miss optimization (don't care)
y--indicates binary xx00 where xx is don't care
In the microprocessor, hexadecimal virtual memory addresses of A9xxxxxx (where x is "don't care") are interpreted as being internally non-cacheable. Since these addresses are non-cacheable, the microprocessor places the physical address of the virtual block on its address bus, and the "write" command on its control bus. (In some embodiments, the microprocessor contains a "write buffer", and hence the request may be delayed). The physical address placed on the address bus by the microprocessor is not a memory address, but rather parameters used by the present invention as shown in the format of the address. The ppsss bits of the address are unused by the active cache and are only manipulated by the microprocessor software to ensure that previous active-cache updates which may be internally encached in the microprocessor will not be returned erroneously.
The write data contains 32 bits (8 hexadecimal digits), formatted as shown below:
vwmmmmmm 16
where:
v--indicates binary xxxb where x is don't-care and b is the most-significant bit of the word count of the data to be read
w--four least-significant bits of the word count of the data to be read
mmmmmm--the 24-bit physical byte address of the memory data to be encached
The above encache-data request is used in the present invention to cause the requested shared-memory data to be stored in the active cache memory. The memory address mmmmmm of the requested data may be unaligned with respect to 4-word boundaries, or any other boundaries, in the shared memory.
While the active cache is being updated in accordance with an encache-data request, a checksum is calculated by the active cache on the data read from the shared memory. The checksum is preserved in the active cache and may be read when a specific read-data request is performed.
In order to retrieve the data encached in the active cache, a protocol similar to the encache-request is employed, as described below.
An active-cache read request consists of a microprocessor memory read operation to the second specific virtual-memory block that is mapped into the physical address space of the active cache. The request-reception circuit of the active cache interprets microprocessor read operations to the active cache's physical-address block as requests to the active cache to deliver encached data.
The format of the read request address depends on the embodiment.
In some embodiments, the read request address contains 32 bits (8 hexadecimal digits), formatted as shown below:
89msssww 16
where:
89--indicates the cacheable, memory-mapped virtual address block
m--determines whether the request is a data read (1xxx 2 ) or a checksum read (0xxx 2 )
sss--miss optimization (don't care)
ww--indicates the byte address of the data to be read. The two low-order bits of ww are always 0, yielding a word address; and the two high-order bits of ww are ignored, leaving four bits that specify any one of 16 words
In the microprocessor, the blocks whose hexadecimal virtual memory addresses are 89xxxxxx (where x is don't care) are marked as being internally cacheable. More particularly, the "8" means internally cacheable, and the following "9" indicates an active cache request. The first read operation (and first read after write) by the microprocessor to the physical address block corresponding to the 89xxxxxx virtual address block will cause the microprocessor to place the physical address of the virtual block on its address bus, and the "read" command on its control bus. In some embodiments, the physical address corresponding to the virtual address 8xxxxxxx is 0xxxxxxx. Thus, the address 09msssww will appear on the microprocessor address bus. In some embodiments, this read will cause any outstanding write operations in the write buffer to be forced to completion, or "flushed," as well.
The request-reception circuit of the active cache decodes read operations to the active cache's physical address block 09msssww as active-cache read requests. The active cache delivers to the microprocessor the data it previously encached, with no further shared-memory interaction.
Since the microprocessor's virtual address block corresponding to active-cache read requests is marked as internally cacheable, the microprocessor's internal cache may encache data that it reads from the active cache. Therefore, multiple microprocessor reads to the physical addresses of the data encached by the active cache of the present invention, subsequent to the first read after write, will "hit" in the internal microprocessor cache, reducing the access time for such subsequent read operations. The ppsss bits of the address are unused by the active cache and are only manipulated by the microprocessor software to ensure that data fetched by previous active-cache encache-data requests which may be internally encached in the microprocessor will not be returned erroneously. See the MICROPROCESSOR SOFTWARE OPERATIONS section below.
The active cache has the ability to return a checksum of the encached data, which it calculated in response to an encache-data request. When the m field in the address of the read-data request has its high order bit cleared and the ww field has a particular value (xx101100 2 in one embodiment), the active cache returns the checksum it has stored rather than the encached data. When the high order bit of the m field is set, the ww field determines the address of the encached data to be returned.
Each of the above virtual memory addresses is mapped by the microprocessor to the physical memory addresses 09xxxxxx 16 , where xxxxxx are the appropriate bits from the read or write request virtual addresses. The active cache monitors the microprocessor addresses for these physical addresses.
Other features and advantages of the invention are described below. The invention is defined by the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 depicts an active cache of the present invention attached to a shared memory and a microprocessor.
FIG. 2 illustrates the block structure of the active cache of FIG. 1.
FIG. 3 illustrates timing diagrams of the system of FIG. 1.
FIG. 4 is a block diagram of a circuit used in the system of FIG. 1.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1, microprocessor 101 is in some embodiments a microprocessor of type IDT79R3052 available from Integrated Device Technology, 2975 Stender Way, P.O. Box 58015, Santa Clara, Calif. 95052-8015. Microprocessor 101 is connected via address/data bus 102 and control lines 103 to cache 200.
The address/data bus 102 has two portions. The first portion is a multiplexed address/data bus 102m having 32 bits, [31..0], which carry address information or data during different steps of a bus transaction. The second portion is a non-multiplexed address bus 102a having two bits, [3..2], which carry address bits 3 and 2 throughout a bus transaction. During the address portion of a transaction, bits [31..4] of bus 102m and bits [3..2] of bus 102a carry the 30-bit word address. Bus 102a provides the least significant bits of the word address. Each word consists of 4 bytes. Bits [3..0] of bus 102m carry byte enable information which includes the byte address within the word.
During the data portion of the transactions bits [31..0] of bus 102m carry data. See "IDT79R3051 Family Hardware User's Manual", Integrated Device Technology, Inc., 1990, pp. 6-1 through 8-10, hereby incorporated herein by reference.
Cache 200 is connected to shared memory (SM) 104 via SM address bus 105, SM data bus 106, and SM control lines 107. The shared memory is used to store packet descriptor rings and packet buffers as well as packet statistics and other information that is shared by multiple microprocessors in some embodiments. See previously referenced U.S. Pat. No. 5,237,670, "Method and Apparatus for Data Transfer Between Source and Destination Modules," for an example of shared memory 104.
The microprocessor 101 and the shared memory 104 typically use clock signals to control their operation, as understood by those skilled in the art. In particular, the microprocessor 101 and the shared memory 104 may be controlled by different, asynchronous clocks, MCLK 108 and SMCLK 109. In this case, the active cache references microprocessor address/data bus 102 and control lines 103 to MCLK 108, while referencing SM address bus 105, SM data bus 106, and SM control lines 107 to SMCLK 109. In the discussion that follows, reference to the appropriate clock signal is implied.
In some embodiments, the system of FIG. 1 includes one or more other microprocessors and a separate active cache for each microprocessor. Each active cache is connected to a separate port of shared memory 104. Each port has lines similar to lines 105, 106, 107. In some embodiments, each microprocessor, or a group of microprocessors, is controlled by a separate clock.
The microprocessor reads or writes memory in two steps. In the first step, the memory address is placed on the address/data bus 102 and the address latch enable (ALE) control line 103a is asserted. In the second step, the read (RD) line 103r or the write (WR) line 103w is asserted, according to the type of access, and the address/data bus 102 is used to transfer data between the microprocessor and the memory.
Two of the address bits, [3..2], are handled specially and are driven on non-multiplexed address bus 102a throughout both steps. The burst (BURST) line 103b may be asserted during a transaction to indicate that multiple data words are to be transferred, a block of 4 words in the case of the aforementioned IDT79R3052 microprocessor. Such a burst always begins on a 4-word boundary (address bits [3..2] are initially 0), and the microprocessor increments address bits [3..2] on non-multiplexed address bus 102a as each word is transferred.
The read clock enable (RDCEN) line 103c functions as a ready signal to indicate to the microprocessor when the memory has completed (or is about to complete) transferring each word of a transaction. Different microprocessors may define control signals to accomplish similar functions in a variety of ways, as understood by those skilled in the art.
To request access to the shared memory, the control circuit 209 asserts the request (SMREQ) line 107q. Control circuit 209 also indicates the type of access by asserting the read (SMRD) line 107r or the write (SMWR) line 107w. The shared memory 104 responds by asserting the grant (SMGNT) line 107g when the memory 104 is ready to transfer one word of data.
The control circuit 209 can request a burst transfer from the shared memory by asserting the burst (SMBRST) line 107b whenever cache 200 needs to transfer additional words beyond the one currently being requested. If during some period n of the clock SMCLK, SMREQ 107q is asserted and SMBRST 107b is not asserted, the shared memory 104 assumes a non-block transfer and ignores SMREQ 107q during the next period n+1 of clock SMCLK. The shared memory however does asserts SMGNT 107g to grant the request made during the clock period n. If during a period n SMREQ 107q is asserted and SMBRST 107b is also asserted, the shared memory 104 will not ignore SMBRST 107b during clock period n+1. In either case, shared memory 104 asserts SMGNT 107g once for each 1-word access of cache 200 to the shared memory.
Some embodiments do not have SMBRST 107b.
FIG. 2 shows the active cache 200. Data is encached into and read from a cache memory 201, of conventional design in some embodiments. Memory 201 has a single read port and a single write port. Data is written by specifying an address using the Write Addr input, applying data to the Data In input, and asserting an appropriate write-enable input (not shown). Data is read by specifying an address using the Read Addr input; the specified data word appears at the Data Out output. In some embodiments, the cache memory 201 contains 16 32-bit words. In other embodiments, other sizes of memory are used with an appropriate adjustment in the sizes of addresses and data.
Control of the active cache 200 is provided by address latch 203b, address decode logic 202, SM word counter 208, cache-write address counter 215, burst counter 216, and a control circuit 209. In some embodiments, latch 203b, logic 202, counters 208 and 216, and circuit 209 are implemented using programmable logic devices (PLDs). In some embodiments, the data-path logic 222 which includes counter 215 is implemented in an application-specific integrated circuit (ASIC).
The control circuit 209 includes a state machine. Circuit 209 includes also an enabling circuit for enabling registers to be loaded and enabling counters to be reset, loaded, incremented, or decremented. Circuit 209 also includes a detection circuit to detect various conditions in the data path 222 and counters. The state machine moves from state to state in response to its current state and the inputs provided by the microprocessor 101, the shared memory 104, and the detection circuit. The enabling circuit controls the registers, counters, and other data-path elements as a function of the state machine's current state and inputs.
As understood by practitioners of the art, the active cache's circuit elements can be partitioned among PLDs, ASICs, and other digital logic components in a variety of other ways, as dictated by design flexibility, component availability and density, and cost, without changing the basic operation of the active cache described below.
Shared memory requests and active-cache requests are received by the active cache via the address/data bus 102 and control lines 103. The address is latched into address latches 203a and 203b when the microprocessor asserts its address latch enable ALE signal 103a. The two address latches 203a and 203b operate in tandem and each one latches all or a subset of the address bits on address/data bus 102 as required. Two latches are provided, with some address bits being duplicated, merely for convenience of grouping the circuit elements.
In some embodiments, address latch 203a latches all 32 address bits provided by the microprocessor 101 on multiplexed address/data bus 102m, and is packaged in an application-specific integrated circuit (ASIC) as part of the data-path logic 222, while address latch 203b is implemented in one or more external PLDs and captures only a few high-order address bits which are used by the address decode logic 202.
The active cache 200 monitors read and write requests from the microprocessor 101 using the address-decode logic 202 to decode addresses captured in the address latch 203b. A CPU write data register 205 captures the data from the microprocessor multiplexed address/data bus 102m during the second step of a data write operation. Together, elements 102, 103, 202, 203a, 203b, and 209 comprise the request-reception circuit.
Once a microprocessor request has been made, address decode logic 202 of the request-reception circuit decodes the 8 high-order bits of the address present in address latch 203b. Depending on the address, one of three outcomes is possible:
(1) The address does not select the active cache or the shared memory. In this case, the request-reception circuit ignores the request, allowing it to be handled elsewhere. Other devices, such as memory devices or memory-mapped I/O devices not shown in the drawings, may be selected by address-decode logic 202 and activated by conventional means, in which case the active cache and the shared memory are not involved. This case will not be discussed further.
(2) The address selects shared memory 104. In this case, the request-reception circuit passes the request to the shared memory, as discussed shortly.
(3) The address selects an active-cache request. In this case, the active cache employs the read and write lines 103r and 103w to further decode the request into one of two requests--an encache-data request or a read-data request--and processes the request as discussed later.
Shared-Memory Request Passthrough
The active cache is effectively bypassed for both read and write operations to the shared memory, as described below.
When the microprocessor address selects shared memory 104, the request is passed, with clock synchronization as required, through the active cache to the shared memory. The address of the shared-memory request is passed from the address latch 203a on to the shared-memory address bus 105 via a three-state multiplexer 204 controlled by control circuit 209. The output of multiplexer 204 is disabled at all times except during shared-memory request passthrough and active-cache encache-data requests, discussed later. Thus, other devices may access the shared memory when the three-state multiplexer 204 is disabled.
If the operation is a shared-memory write request, as determined by control circuit 209 via microprocessor control lines RD 103r and WR 103w, the data from the microprocessor is passed on to the shared memory via the CPU write data register 205, three-state bus driver 206, and shared-memory data bus 106. Note that the three-state bus-driver 206 has its output disabled at all times except during these shared-memory writes.
When the write operation is completed, the SM grant (ready) signal 107g from shared memory 104 is passed, after appropriate synchronization, to the microprocessor ready signal RDCEN 103c.
As will be understood by those skilled in the art, it is also possible to perform a "posted" write operation, in which RDCEN 103c is asserted and the microprocessor 101 is allowed to continue operation before the shared memory has written the data in CPU write data register 205 to the address specified in address latch 203a. In this case, additional elements are added to the system of FIG. 2 to ensure that the microprocessor does not overwrite the "posted" address and data before the write operation has actually completed.
If the operation is a shared-memory read request, then the three-state bus driver 206 is disabled, and the shared memory provides data and places it on shared-memory data bus 106. The control circuit 209 enables the CPU read data register 210 and three-state multiplexer 212 which controls the flow of the data onto the multiplexed address/data bus 102m. The grant (ready) signal 107g from shared memory 104 is passed, after appropriate synchronization, to the microprocessor ready signal RDCEN 103c.
Active-Cache Requests
In the cases where the microprocessor request is an active-cache request, as determined by address-decode logic 202 in the request-reception circuit, the active cache is used as described below. The active cache is designed in such a way that an encache-data request should precede any set of read-data requests. However this is not checked by the active cache, which may return stale or invalid data otherwise.
The active cache determines whether the microprocessor's request is an encache-data request or a read-data request by inspecting the microprocessor control lines 103.
Encache-Data Request
If an active-cache request is decoded by the address-decode logic 202 (bits [27..24] of the address on bus 102m are 9), and if the microprocessor control lines 103 indicate a write, as determined by WR 103w being asserted, the request is an encache-data request. In this case, the control circuit 209 enables encache-data request parameters, provided in the "data" portion (vwmmmmmm 16 , where v=xxxb 2 ) of the microprocessor write operation, to be captured.
Specifically, the control circuit 209 enables the SM address counter 207 to be loaded with the low-order 24 bits [23..0] (mmmmmm 16 ) of the "data" provided on the multiplexed address/data bus 102m. This "data" is actually the starting address in SM of the data to be encached by the encache-data request. Note that although this memory address is a "byte" address, it should be aligned on a full-word boundary (i.e., the two low-order bits should be 0, since each word contains four bytes).
The address specified in data bits [23..0] of encache-data request may be unaligned with respect to 4-word boundaries in the shared memory 104. As understood by those skilled in the art, with the addition of byte-alignment circuits (not shown), the address could also be unaligned with respect to 1-word boundaries.
The control circuit 209 also enables the SM word counter 208 to be loaded with bits [28..24] (b 2 w 16 ) of the "data" on multiplexed address/data bus 102m, which is the word count of the request. Note that this value counts full words, not bytes.
In some embodiments, the control circuit 209 also captures one or more of bits [31..29] of the "data" on multiplexed address/data bus 102m, to control other aspects of the encache-data operation. For example, one or more of bits [31..29] select a checksum pattern in some embodiments as discussed later.
At this time, the memory-control circuit 209 does not enable the three-state output of multiplexer 204 or bus driver 206, since the address from the microprocessor write operation is not used by the shared memory 104 and since the data is not used until later.
At this point, the physical memory address and the word count of the encache-data request have been captured in SM address counter 207 and SM word counter 208. The control circuit 209 signals the microprocessor 101 that the "write" operation is complete, thereby freeing the microprocessor to continue its program flow. Simultaneously, control circuit 209 resets the checksum register 214 to clear any residual data checksum, resets the cache-write address counter 215 to 0, and resets the burst counter 216 to 0. Finally, control circuit 209 changes a state bit or bits in its state machine to indicate that it is "BUSY" processing an encache-data request. The control circuit 209 is now responsible for completing the operation specified by the encache-data request, as follows.
In some embodiments, logic in the control circuit 209 determines at this time whether the low-order two bits of SM address counter 207 are 0 (the address is aligned on a full-word boundary). If they are not 0, the control circuit 209 aborts the encache-data operation and signals an error to the microprocessor 101.
The control circuit examines the output of SM word counter 208 to determine whether the word count is 4 words or greater. If true, the control circuit performs a 4-word burst read from the shared memory 104 independently of the microprocessor. To accomplish that, circuit 209 selects the SM address counter 207 as the source to multiplexer 204, enables the three-state output of multiplexer 204, and asserts the SMREQ 107q, SMBRST 107b, and SMRD 107r control lines to the shared memory. This indicates to the shared memory that the active cache would like to begin a burst read operation.
At the same time, the control circuit 209 sets up to receive burst data from the shared memory 104 and write the data into the cache memory 201. The shared-memory grant signal SMGNT 107g is asserted once for each word to be received from the shared memory. For each word, the control circuit 209 enables the cache read data register 211 to capture the word from the shared memory data bus 106 and write the word into the cache memory 201. The cache memory word at address specified by WADDR[5..2] is written, where WADDR[5..2] is the current value of the cache-write address counter 215.
At the same time that each word in the cache read data register 211 is written into the cache memory 201, the ones'-complement adder 213 may add all or part of this same data to the checksum register 214 to produce a running checksum, as explained later. For each word, the control circuit 209 also increments SM address counter 207 by 4 (to the next word address), decrements SM word counter 208 by 1 (one word), and increments the cache-write address counter 215 by 1 (one word). Thus, received words from the shared memory 104 are written into sequential locations in the cache memory 201.
In some embodiments, the shared memory has a structure similar to that disclosed in aforementioned U.S. Pat. No. 5,237,670, and one word is transferred from the shared memory 104 to the cache memory 201 each time that grant signal SMGNT 107g is asserted. The counters 207 and 208 are adjusted as described above at the end of the clock SMCLK period in which the grant signal 07g is asserted, while each data transfer occurs and the counter 215 is incremented during the following clock SMCLK period. Other embodiments increment or decrement one or more of the counters at different times relative to the actual data transfer, depending on the type and degree of pipelining employed. Also, other embodiments use a different form of the ready signal SMGNT, including but not limited to an SMGNT signal that is asserted once to indicate that all four words will be transferred in a single burst with no interruption.
In some embodiments in which SMGNT 107g is asserted once per 1 word transfer, after three assertions of the grant signal SMGNT 107g, the burst from shared memory is almost complete. At this time, the control circuit 209 negates the SMBRST signal 107b, indicating that the current request is for the last word of the burst.
After each assertion of the grant signal SMGNT 107g, indicating that one word from shared memory will be transferred, the control circuit 209 increments burst counter 216 to keep track of the number of words that have been written into the cache memory 201.
Upon completing a burst as described above, the control circuit 209 once again checks the SM word counter 208. If the word count is greater than or equal to 4, the control circuit 209 repeats the process just explained. If the word count is 0, then the encache-data request is complete. When the encache-data request is complete, the control circuit 209 changes the "BUSY" state bit(s) to indicate that the request is now complete.
When the control circuit 209 determines that the word count in SM word counter 208 is greater than 0 but less than 4 words, either as a result of an encache-data request of less than 4 words or the residual request from a non-multiple-of-4-words encache-data request, the active cache performs a word by word read from shared memory 104. This read is similar to the burst read from the shared memory described above, except that it may terminate early, as explained below.
If the value of the SM word counter 208 is 1, then a single-word read of shared memory is performed. This is accomplished in the same way as the 4-word burst explained previously, except that the SMBRST control line 107b to the shared memory is negated rather than asserted. The data read from the shared memory is stored in the cache memory 201 and possibly added to the checksum register 214 as before. The SM address counter 207 is incremented by 4, the cache-write address counter 215 is incremented by 1, and the SM word counter 208 is decremented by 1 and reaches its final count of 0. The encache-data request is therefore complete.
If the value of the SM word counter 208 is 2 or 3, in some embodiments a 4-word burst read of shared memory is performed. However, when the SM word counter 208 reaches 0, the control circuit 209 immediately changes the "BUSY" state bit(s) to indicate that the encache-data request is now complete. The remaining 1 or 2 words of the 4-word burst from shared memory are not stored in the cache memory 201, nor are they added to the checksum register 214.
A 4-word burst is performed above, even though only 2 or 3 words are needed, as a matter of convenience in the design of the shared-memory control circuit. Another embodiment performs a 2- or 3-word burst by negating the SMBRST control line 107b after receiving the first or second grant signal on SMGNT 107g. In yet another embodiment, the 2 or 3 reads are accomplished as 2 or 3 individual single-word reads in which the SMBRST control line 107b is not asserted for any of the reads. One of these alternative embodiments may be selected based on a trade-off between a possible increase in the complexity of the control circuit and a possible increase or decrease in the speed or efficiency with which a non-multiple-of-4-words transfer is accomplished.
Checksum Operations
As previously indicated, the checksum register 214 may accumulate a running checksum of all or some of the data that is written into the cache memory 201 as the result of an encache-data request. In some embodiments, the encached data is a packet header, and the checksum is the ones'-complement sum of selected halfwords of the packet header. These halfwords comprise the "IP header" field of the packet header, where "IP" (the Internet Protocol) is a well-known packet protocol that uses a ones'-complement checksum to detect errors in the packet header.
Depending on the packet's source, for example, an Ethernet network or an FDDI network, the IP header may appear in a different location relative to the beginning of the packet header. As a result the IP header may appear in a different position in the block of words that are written into the cache memory 201 as the result of an encache-data request. Also, since the IP header is defined as a certain number of halfwords, only half of a given word that is written into cache memory 201 may belong to the IP header.
The data selector 218 in FIG. 2 provides the active cache with the ability to selectively include or not include data words in the checksum accumulated by the checksum register 214. The data selector has two halves, one half for each of the two halfwords that make up the output of the cache read data register 211. For each halfword, there is a CKSME control input from control circuit 209, namely, CKSMEH for the high order halfword of the word and CKSMEL for the low order halfword. When a CKSME input is asserted, the data selector passes the corresponding halfword from the output of the cache read data register 211 to the input of the ones'-complement adder 213. When a CKSME input is negated, the data selector forces the corresponding halfword input of the ones'-complement adder 213 to zero, thus effectively eliminating that halfword from the checksum computation.
In other embodiments, the checksum pattern is established on a byte-by-byte basis, with the data selector 218 having four CKSME inputs, or on a full word basis, with the data selector 218 having only one CKSME input.
The selection of which halfwords are to be included in a checksum calculation is made by the control circuit 209. As each word is written into the cache memory 201, the control circuit 209 decodes the current value of the cache-write address counter 215, and asserts or negates CKSMEH and CKSMEL according to whether the corresponding halfword should be included in the checksum.
For example, in an IP packet received from an Ethernet network, the first seven halfwords of the packet header contain "MAC-layer" information, and the next ten halfwords contain the IP header. Table 1 shows the required values of CKSMEH and CKSMEL as a function of the cache-memory address. (In the table, "0" means negated and "1" means asserted. )
TABLE 1______________________________________Values of CKSMEH and CKSMEL for Ethernet IPheaders.Cache-MemoryAddress CKSMEH CKSMEL______________________________________0 0 01 0 02 0 03 0 14 1 15 1 16 1 17 1 18 1 09-15 0 0______________________________________
On the other hand, in an IP packet received from an FDDI network, the first ten halfwords of the packet header contain "MAC-layer" information, and the next ten halfwords contain the IP header. Table 2 shows the required values of CKSMEH and CKSMEL.
TABLE 2______________________________________Values of CKSMEH and CKSMEL for FDDI IPheaders.Cache-MemoryAddress CKSMEH CKSMEL______________________________________0 0 01 0 02 0 03 0 04 0 05 1 16 1 17 1 18 1 19 1 010-15 0 0______________________________________
When satisfying an encache-data request, the control circuit 209 in some embodiments selects the checksum pattern in Table 1 or the checksum pattern in Table 2 according to one of the encache-data-request parameter bits (bit 31 in some embodiments, that is, the most significant bit of v) that was provided in the data portion of the encache-data request, described previously. The program running on the microprocessor 101 sets or clears this bit according to the source, Ethernet or FDDI, of the packet whose header is being encached. In some embodiments, the control circuit 209 uses a single predetermined pattern that is not a function of the encache-data-request parameter bits.
In some embodiments using other checksum patterns, the control circuit 209 provides other patterns selected by additional encache-data-request parameter bits.
In some embodiments, the checksum pattern to be used may not be known at the time that the encache-data request is made. For example, the checksum pattern may be a function of information contained in the beginning portion of the packet header. In some embodiments, the control circuit 209 decodes information in one or more words in the beginning portion of the packet header as it is encached, and selects a checksum pattern based on such dynamically decoded information.
Other embodiments provide additional copies of the checksum circuit comprising elements 213, 214, and 218 in FIG. 2, a corresponding number of additional decoded sets of CKSME outputs from the control circuit 209, and a corresponding number of additional inputs on three-state multiplexer 212, so that additional, alternative checksums may be computed and any or all of these may be read by the microprocessor 101.
Some network protocols may use checksum operations other than ones'-complement addition, for example, two's-complement addition or a cyclic redundancy check (CRC) calculation. In such a case, the ones'-complement adder 213 is changed to an appropriate adder or other functional unit, and the control circuit 209 selects the appropriate adder or other functional unit according to the required checksum pattern.
Read-Data Request
An active-cache read-data request begins, like other memory operations, with the microprocessor 101 placing a memory address on address/data bus 102 and asserting the ALE signal, which causes the address to be captured by address latches 203a and 203b. If an active-cache request is decoded by the address-decode logic 202 and the microprocessor control lines 103 indicate a read, as determined by RD 103r being asserted, the request is a read-data request. In this case, the active cache is employed to deliver previously encached data. Again, it is assumed by the active cache that an encache-data request has preceded a read-data request, but this condition is not checked.
At this time, the control circuit does not enable the three-state output of multiplexer 204, since the address from the microprocessor read operation is not used by the shared memory 104. The bus driver 206 is not enabled, since data is not driven toward the shared memory by a read operation.
A logic circuit (not shown) attached to address latch 203b examines the high order bit 23. If this bit is 0 and the word address in the cache memory of the request is 1011 2 , the request is for the checksum in register 214. Otherwise, the request is for data in the cache memory 201.
The memory read address 09msssww 16 captured in address latch 203a contains the word address in the cache memory 201 of the request in bits 5..2. The length of the read-data request is determined by examining the BURST control line 103b from the microprocessor, and may be either 1 word or 4 words. If the BURST control line 103b is asserted, the read-data request is for 4 words of data. If the BURST control line 103b is negated, then the read-data request is for 1 word of data. The control circuit 209 determines the length of the request.
A data-read request of either length is satisfied as follows. Address bits [5..4] from the address latch 203b and address bits [3..2] received from the microprocessor on non-multiplexed address bus 102a are combined by the data path logic 222 to form a 4-bit address RADDR[5..2]. This 4-bit address is applied to the read-address input of the cache memory 201 to select an encached word to be read. In response to the read-data request, the control circuit 209 selects the cache memory as the source for three-state multiplexer 212 and enables the three-state multiplexer 212 to drive the microprocessor address/data bus 102m. When the control circuit 209 determines (using a technique described later) that valid data has been encached into the selected location in the cache memory 201, control circuit 209 also asserts the RDCEN line 103c which serves as a ready line for the microprocessor 101. At this point, the microprocessor captures the data word on the address/data bus 102m. If a 4-word burst has been requested, the microprocessor 101 increments address bits [3..2] on non-multiplexed address bus 102a to select the next word of the burst. If a 4-word burst has been requested, then the control circuit 209 repeats this process until each word of the 4-word burst has been read.
As noted previously, the address/data and control lines of the microprocessor 101 are referenced to a clock signal MCLK 108, while the SM address, data, and control lines are referenced to a clock signal SMCLK 109. If MCLK and SMCLK are the same clock, that is, if they have identical frequency and phase, then the control circuit 209 can control the RDCEN line 103c as follows. For each active-cache read operation, circuit 209 compares the 4-bit cache read address RADDR[5..2] on bus 102 with WADDR[5..2], the current value in the cache-write address counter 215. If RADDR[5..2] is less than WADDR[5..2], or if the "BUSY" state bit(s) indicate that the previous encache-data request is complete, then the RDCEN line 103c is asserted. Otherwise, the RDCEN line 103c is held negated until the write address WADDR[5..2] becomes larger than the requested read address RADDR[5..2] or the encache-data request is complete. Note that there is no checking to determine whether the read address is beyond the range requested by a given encache-data request. In some embodiments, the control circuit 209 signals an error to the microprocessor by conventional means, such as a bus error, in this case.
If MCLK and SMCLK are synchronized but have different frequency and/or phase (for example, SMCLK is derived from MCLK by a divide-by-2 circuit), then the control circuit 209 can control the RDCEN line 103c in a way similar to that described above. In particular, the decision to assert or negate RDCEN can be made one word at a time, but additional logic may be needed to adjust the timing of the comparison and control operations with respect to the two clocks.
In some embodiments, MCLK and SMCLK are completely asynchronous. In some such embodiments, MCLK has a higher frequency than SMCLK. Communication of "ready" information between the two clock domains is accomplished by a 1-bit control signal "RDYTOGGLE" diagrammed in FIG. 3. The control circuit 209 clears this signal at system reset, and toggles it (complements its value) once for each time that a word is transferred from the shared memory 104 to the cache memory 201. Toggling occurs on the rising edge of SMCLK, since the transfers are synchronized to the rising edge of SMCLK.
The control circuit 209 also contains a flip-flop 410 (FIG. 4) which samples RDYTOGGLE using MCLK, that is, an edge-triggered flip-flop whose D input receives RDYTOGGLE and whose clock input receives MCLK and whose Q output is called RDYTOGGLE1. Since the MCLK's clock period is shorter than that of SMCLK, and changes on RDYTOGGLE must be separated by an integral number of SMCLK periods, all changes on RDYTOGGLE are guaranteed to be seen on RDYTOGGLE1. Although the RDYTOGGLE1 output may become metastable because of the asynchronous input change, it will with high probability be stable by the end of one MCLK period. For a metastability discussion, see, for example, Digital Design Principles and Practices, 2nd ed. (Prentice Hall, 1994), by John F. Wakerly, pp. 642-650 hereby incorporated herein by reference. The control circuit 209 contains a second edge-triggered flip-flop 420 whose D input receives RDYTOGGLE1 and whose clock input receives MCLK and whose Q output is called RDYTOGGLE2. RDYTOGGLE1 and RDYTOGGLE2 are XORed by XOR gate 430. If RDYTOGGLE1 and RDYTOGGLE2 have different values, as indicated by a "1" on the output of gate 430, then a change has been received on RDYTOGGLE, indicating that one word has been transferred from the shared memory 104 to the cache memory 201. This fact can be reliably observed on RDYTOGGLE1 and RDYTOGGLE2 in the MCLK clock domain, even though the transfer occurred in the SMCLK domain.
The burst counter 216 is used in conjunction with the above-described mechanism in some embodiments to keep track of how many words have been transferred from the shared memory 104 to the cache memory 201. The burst counter 216 is clocked by MCLK and, as mentioned previously, is reset to 0 by an encache-data request. At the end of each subsequent MCLK period in which RDYTOGGLE1 and RDYTOGGLE2 have different values, the burst counter 216 is incremented. In effect, the burst counter 216 "shadows" the value of the cache write-address counter 215, but in the MCLK rather than the SMCLK clock domain. Thus, RDCEN can be generated in a way similar to that previously described for the case of synchronous clocks, except that the cache read address RADDR[5..2] is now compared with the state of the burst counter 216 instead of the cache write-address counter 215.
When the microprocessor 101 has issued an active-cache read request, and the address latch 203b has captured bit 23 of bus 102m, if this bit is cleared and RADDR[5..2] has the value 1011 2 , the microprocessor is requesting a read of the checksum register 214. This is accomplished by selecting the checksum register 214 on multiplexer 212 when this condition is true.
In some embodiments, the address latches 203a, 203b, the SM word counter 208, the burst counter 216, the CPU write data register 205, a portion of the control circuit 209, and the read address changes of memory 201 are referenced with respect to the clock MCLK. The remaining clocked portions of the cache 200, including the write address changes of memory 201, are referenced with respect to the clock SMCLK.
The Appendix attached hereto illustrates PLD equations, written in Abel, of PLD module smctl1 clocked by the clock MCLK and of PLD module smctl2 clocked by the clock SMCLK. The two modules incorporate the counters 216, 208 and a portion of the control circuit 209.
MICROPROCESSOR SOFTWARE OPERATIONS
Certain address and/or data bits in the requests are set up in a way that eliminates cache inconsistency and minimizes cache misses, as will now be described.
The microprocessor determines, by conventional means, the starting address, HA, in shared memory of a block of data such as a packet header. This block of data has a certain number of data words, WC. WC is in the range 1 through 16. The maximum of 16 corresponds to the size of the cache memory 201 in some embodiments. However, 1-word blocks are not normally encached because they can be read more efficiently without being encached.
In order to encache the desired block, the microprocessor performs a write operation to the hexadecimal virtual address A9ppsss0 16 . The program controlling the microprocessor is written in some embodiments in the C programming language which allows specifying virtual addresses explicitly. As described earlier, pp is used as a process identifier. The most significant bit of pp is used to select the checksum register during a read-data request, and the seven remaining bits are unused by the active cache. So, 128 process identifiers can be obtained using these seven bits. Each different software process uses a pair of these identifiers, 00 and 01 for the first process, 02 and 03 for the second, and so on, for 64 possible processes.
Note that if a process is going to set the most significant bit of pp to select the checksum register during a read-data request immediately following an encache-data request, then it will also set that bit during the encache-data request. This will allow the read-data request to use the same physical address on bus 102 as the encache-data request and thus will force the microprocessor to flush its write buffer before the read. This bit is ignored in the rest of this discussion.
Each process alternates which of its process identifiers to use on each successive encache-data request. For example, the first process uses pp=00 on its first request, pp=01 on its second request, pp=00 on its third request, and so on. This discipline ensures that successive encache-data requests, even when made by the same process, will be made to different hexadecimal addresses. As will be seen, this, in turn, guarantees that a read-data request made after a new encache-data request will cause a miss in the microprocessor's internal data cache, forcing the microprocessor to fetch newly-encached data from the active cache.
Also as described earlier, the bits sss in the address portion of the encache-data request are not used by the active cache. However, they may be chosen in a way that minimize misses in the microprocessor's internal data cache. In particular, these bits determine the line or lines of the microprocessor's internal data cache into which data from a read-data request will be encached. The line or lines may be chosen in a way to minimize internal misses. For example, the software may allocate a "dummy" 16-word data structure, aligned on a cache line, at or near the top of its run-time stack, and choose the sss bits so that a read-data request uses the same cache line(s) as the dummy data structure. In this way, a read-data request is guaranteed not to cause any useful run-time-stack data to be overwritten in the microprocessor's internal cache, as long as the internal cache is big enough to hold the top of the entire run-time stack. Likewise, program read and write operations near the top of the run-time stack (which are likely) will not overwrite internally encached results of a read-data request. The number of sss bits is such that an optimal value of the sss bits can be selected for a microprocessor internal data cache as large as 64K (2 16 ) bytes.
As described earlier, the data value for the encache-data request is vwmmmmmm 16 where mmmmmm is the shared memory address of the first word to be encached and the five low-order bits of vw contain the word count WC, with a valid range of 1-16.
Since the 3052 microprocessor used in some embodiments contains a "write buffer", the write operation may be delayed, since the microprocessor's internal bus controller gives read operations priority over write operations. In normal operation there is no assurance that a given write operation will be completed before a subsequent read operation is performed on the bus. It is therefore important to ensure that an encache-data request (a write operation) has been received by the active cache before a subsequent, corresponding read-data request is received. The conventional means of forcing a write to occur before a read is through a separate "write-buffer-flush" operation. In the present invention, the same effect is obtained automatically as a side effect of the read-data request, as will now be explained.
The first read-data request after an encache-data request is made to the hexadecimal virtual address 89ppsss0 16 , using the same value of ppsss that was used in the corresponding encache-data request. In the 3052 microprocessor of some embodiments, both virtual addresses A9ppsss0 16 and 89ppsss0 16 map into the same physical address, 09ppsss0 16 . The write buffer recognizes this equivalence. If a read operation is requested at the same physical address as a pending write, the write buffer defers the read operation until the pending write has been completed. Therefore, no explicit write-buffer-flush operation is required. Successive read-data requests can be made to any address in the active cache's address space. The active cache's control circuit 209 will throttle such read operations (using RDCEN) as described previously if the requested data has not been encached.
In the typical use of the active cache, the two low-order bits of sss will be 0, so that the dummy data structure mentioned previously will be aligned on a 64-byte (16-word) boundary, corresponding to the size of the cache memory 201, and the first read-data request will be for the first word in the cache memory 201.
In practice, the software for the microprocessor 101 is written so that the starting address HA of a block of data to be encached is determined as early as possible and the encache-data request is made as soon as possible. The software is further written so that as many other computations as possible are performed by the microprocessor before a corresponding read-data request is made. This is done to maximize the probability that the encache-data request has been received by the active cache and that the first group of 4 words from the shared memory has been encached before the read-data request is made.
Three features of the invention enhance the ability of the microprocessor to continue performing computations while data is being encached by the active cache. First, the encache-data request is made by a write operation, which does not stall the microprocessor 101's internal pipeline unless the write buffer is full. Second, the microprocessor's address/data bus 102 is freed for other operations such as reading or writing private memory as soon as the encache-data request has been received by the active cache 200. Third, in some embodiments, the microprocessor is allowed to perform ordinary, direct read and write operations to the shared memory 104 even while an encache-data request is being satisfied. The control means 209 gives higher priority to such operations than to shared-memory read operations that encache data into the cache memory 201.
While the invention has been illustrated with respect to the embodiments described above, the invention is not limited thereto. The invention is not limited by a particular type of microprocessor, memory, or cache components. In some embodiments, different-type microprocessors with identical or different active cache systems share a memory. Other embodiments and variations are within the scope of the invention, as defined by the appended claims. ##SPC1## | An active cache memory for use with microprocessors is disclosed. The cache is external to the microprocessor and forms a second level cache which is novel in that it is capable of performing transfers from external random access memory independently of the microprocessor. The cache also provides the ability to encache misaligned references and to transfer data to the microprocessor in bursts. | 6 |
FIELD
[0001] The present application relates to a process for manufacturing a paperboard from a high consistency pulp slurry of cellulosic fibers containing high levels of intrafiber crosslinked celluosic fibers.
SUMMARY
[0002] This application is directed to a process for manufacturing a paperboard from a high consistency pulp slurry containing high levels of crosslinked cellulosic fibers by dispersing the fibers in a screen with a rotor in the screen and then passing the fibers through the screen basket with a hole diameter of at least 2 mm and forming the cellulosic fibers on a foraminous support. Another slurry of regular cellulosic fibers is deposited on at least one side of the first slurry during the formation process.
BRIEF DESCRIPTION OF THE DRAWINGS
[0003] The foregoing aspects and many of the attendant advantages of this disclosure will become more readily appreciated as the same become better understood by reference to the following detailed description, when taken in conjunction the accompanying drawings, wherein:
[0004] FIG. 1 is a schematic representation of the equipment components utilized in the present application.
[0005] FIG. 2 is a lobed rotor.
[0006] FIG. 3 is a foil rotor.
[0007] FIG. 4 is a bump rotor.
[0008] FIG. 5 is a schematic cross-sectional view of a two ply paperboard.
[0009] FIG. 6 shows a wall section of a hot cup container.
DETAILED DESCRIPTION
[0010] High consistency slurries containing high levels of crosslinked cellulosic fibers cannot be used in paperboard machines due to plugging of the screen by the high levels of crosslinked cellulosic fibers in the slurry. A process for using the high consistency slurry containing high levels of crosslinked cellulosic fibers has been discovered which overcomes this problem.
[0011] Referring to FIG. 1 , a high consistency slurry of cellulosic fibers is formed in a dispersion medium, such as water, in a slurry tank, 10 . The resulting slurry is then pumped to a consistency regulator, 12 , where dilution water is added to maintain a fixed consistency. Subsequently the slurry is pumped to the machine chest, 14 , and then into a screen basket, 16 , which may be vertically or horizontally mounted. Various types of rotors may be mounted in the screen basket such as a lobed, foil or bump rotor manufactured by GL&V, Watertown, N.Y. The rotors serve to disperse the fibers in the screen and force acceptable fibers through the screen basket and then to a headbox 18 . Fibers that are rejected pass to a flat screen, 16 a, where they are further separated into rejects which are discarded and acceptable fibers which are returned to the machine chest, 14 . The headbox may be a single ply headbox, a multiply headbox or two or more single ply headboxes arranged to form two or more layers formed by combining one layer from each single ply headbox. From the headbox, the pulp is formed on the wire, 20 , dewatered and dried.
[0012] In one embodiment of the method, at least one high consistency slurry of cellulosic fibers is formed in an aqueous dispersion medium. The cellulosic fibers which are both crosslinked cellulosic fibers and regular cellulosic fibers, are dispersed in a screen by means of a rotor in the screen and then passed through the screen which has a hole diameter of at least 1.5 mm. The cellulosic fibers are formed on a foraminous support. Rotors can be of various types such as lobed, foil, bump, and S; the listing is not meant to limit the types suitable for this application and known by the skilled artisan. In another embodiment the fibers are passed through a screen which has a hole diameter of at least 2 mm. Screen hole sizes up to 6 mm can be used. As used herein, the term “consistency” means the percent solids content of a liquid and solid mixture, for example, a consistency of 2 percent cellulosic fibers means there are two grams of cellulosic fibers in one hundred grams of fiber and liquid. In another embodiment the slurry consistency is at least 2.5 percent and in yet another embodiment the slurry consistency is at least 3 percent. A high consistency slurry means a solid content of 3 to 4 percent, a medium consistency slurry means a solid content of 1 to 2 percent and a low consistency slurry means a solid content of less than 1 percent solids.
[0013] Crosslinked cellulosic fibers can be present in the high consistency slurry at levels of at least 35 percent by weight of the total fibers in the high consistency slurry. In one embodiment they are present at a level of at least 40 percent by weight of the total fiber content in the high consistency slurry. In another embodiment they are present at a level of at least 50 percent by weight of the total fiber content in the high consistency slurry and in yet another embodiment they are present at a level of at least 60 percent by weight of the total fiber in the high consistency slurry.
[0014] The preferred crosslinked cellulosic fibers for use in the application are crosslinked cellulosic fibers. Any one of a number of crosslinking agents and crosslinking catalysts, if necessary, can be used to provide the crosslinked fibers to be included in the layer. The following is a representative list of useful crosslinking agents and catalysts. Each of the patents noted below is expressly incorporated herein by reference in its entirety.
[0015] Suitable urea-based crosslinking agents include substituted ureas, such as methylolated ureas, methylolated cyclic ureas, methylolated lower alkyl cyclic ureas, methylolated dihydroxy cyclic ureas, dihydroxy cyclic ureas, and lower alkyl substituted cyclic ureas. Specific urea-based crosslinking agents include dimethyldihydroxy urea (DMDHU, 1,3-dimethyl-4,5-dihydroxy-2-imidazolidinone), dimethyloldihydroxy-ethylene urea (DMDHEU, 1,3-dihydroxymethyl-4,5-dihydroxy-2-imidazolidinone), dimethylol urea (DMU, bis[N-hydroxymethyl]urea), dihydroxyethylene urea (DHEU, 4,5-dihydroxy-2-imidazolidinone), dimethylolethylene urea (DMEU, 1,3-dihydroxymethyl-2-imidazolidinone), and dimethyldihydroxyethylene urea (DMeDHEU or DDI, 4,5-dihydroxy-1,3-dimethyl-2-imidazolidinone).
[0016] Suitable crosslinking agents include dialdehydes such as C 2 -C 8 dialdehydes (e.g., glyoxal), C 2 -C 8 dialdehyde acid analogs having at least one aldehyde group, and oligomers of these aldehyde and dialdehyde acid analogs, as described in U.S. Pat. Nos. 4,822,453; 4,888,093; 4,889,595; 4,889,596; 4,889,597; and 4,898,642. Other suitable dialdehyde crosslinking agents include those described in U.S. Pat. Nos. 4,853,086; 4,900,324; and 5,843,061. Other suitable crosslinking agents include aldehyde and urea-based formaldehyde addition products. See, for example, U.S. Pat. Nos. 3,224,926; 3,241,533; 3,932,209; 4,035,147; 3,756,913; 4,689,118; 4,822,453; 3,440,135; 4,935,022; 3,819,470; and 3,658,613. Suitable crosslinking agents may also include glyoxal adducts of ureas, for example, U.S. Pat. No. 4,968,774, and glyoxal/cyclic urea adducts as described in U.S. Pat. Nos. 4,285,690; 4,332,586; 4,396,391; 4,455,416; and 4,505,712.
[0017] Other suitable crosslinking agents include carboxylic acid crosslinking agents such as polycarboxylic acids. Polycarboxylic acid crosslinking agents (e.g., citric acid, propane tricarboxylic acid, and butane tetracarboxylic acid) and catalysts are described in U.S. Pat. Nos. 3,526,048; 4,820,307; 4,936,865; 4,975,209; and 5,221,285. The use of C 2 -C 9 polycarboxylic acids that contain at least three carboxyl groups (e.g., citric acid and oxydisuccinic acid) as crosslinking agents is described in U.S. Pat. Nos. 5,137,537; 5,183,707; 5,190,563; 5,562,740; and 5,873,979.
[0018] Polymeric polycarboxylic acids are also suitable crosslinking agents. Suitable polymeric polycarboxylic acid crosslinking agents are described in U.S. Pat. Nos. 4,391,878; 4,420,368; 4,431,481; 5,049,235; 5,160,789; 5,442,899; 5,698,074; 5,496,476; 5,496,477; 5,728,771; 5,705,475; and 5,981,739. Polyacrylic acid and related copolymers as crosslinking agents are described U.S. Pat. Nos. 5,549,791 and 5,998,511. Polymaleic acid crosslinking agents are described in U.S. Pat. No. 5,998,511 and U.S. application Ser. No. 09/886,821.
[0019] Specific suitable polycarboxylic acid crosslinking agents include citric acid, tartaric acid, malic acid, succinic acid, glutaric acid, citraconic acid, itaconic acid, tartrate monosuccinic acid, maleic acid, polyacrylic acid, polymethacrylic acid, polymaleic acid, polymethylvinylether-co-maleate copolymer, polymethylvinylether-co-itaconate copolymer, copolymers of acrylic acid, and copolymers of maleic acid. Other suitable crosslinking agents are described in U.S. Pat. Nos. 5,225,047; 5,366,591; 5,556,976; and 5,536,369.
[0020] Suitable crosslinking catalysts can include acidic salts, such as ammonium chloride, ammonium sulfate, aluminum chloride, magnesium chloride, magnesium nitrate, and alkali metal salts of phosphorous-containing acids. In one embodiment, the crosslinking catalyst is sodium hypophosphite.
[0021] The crosslinking agent is applied to the cellulosic fibers as they are being produced in an amount sufficient to effect intrafiber crosslinking. The amount applied to the cellulosic fibers may be from about 1% to about 25% by weight based on the total weight of fibers. In one embodiment, crosslinking agent in an amount from about 4% to about 6% by weight based on the total weight of fibers. Mixtures or blends of crosslinking agents may be used.
[0022] Although available from other sources, noncrosslinked cellulosic fibers usable in the present application are derived primarily from wood pulp. Suitable wood pulp fibers for use with the application can be obtained from well-known chemical processes such as the kraft and sulfite processes, with or without subsequent bleaching. Pulp fibers can also be processed by thermomechanical, chemithermomechanical methods, or combinations thereof. The preferred pulp fiber is produced by chemical methods. Groundwood fibers, recycled or secondary wood pulp fibers, and bleached and unbleached wood pulp fibers can be used. Softwoods and hardwoods can be used. Details of the selection of wood pulp fibers are well known to those skilled in the art. These fibers are commercially available from a number of companies, including Weyerhaeuser Company, the assignee of the present invention. For example, suitable cellulose fibers produced from southern pine that are usable with the present application are available from Weyerhaeuser Company under the designations CF416, CF405, NF405, PL416, FR416, FR516, and NB416. Dissolving pulps from northern softwoods include MAC11 Sulfite, M919, WEYCELL and TR978 all of which have an alpha content of 95% and PH which has an alpha content of 91%. High purity mercerized pulps such as HPZ, HPZ111, HPZ4, and HPZ-XS available from Buckeye and Porosonier-J available from Rayonier are also suitable.
[0023] Screen hole diameter can vary. In one embodiment the hole diameter is at least 2 mm, in another embodiment the hole diameter is at least 3 mm. Rotors in the screen used to disperse the fibers and force the fibers through the screen can be lobed, bump or foil rotors. Foil rotors can have from four to ten foils.
[0024] Hot foods, particularly hot liquids, are commonly served and consumed in disposable containers. These containers are made from a variety of materials including paperboard and foamed polymeric sheet material. One of the least expensive sources of paperboard material is cellulose fibers. Cellulose fibers are employed to produce excellent paperboards for the production of hot cups, paper plates, and other food and beverage containers. Conventional paperboard produced from cellulosic fibers, however, is relatively dense, and therefore, transmits heat more readily than, for example, foamed polymeric sheet material. Thus, hot liquids are typically served in double cups or in cups containing multiple plies of conventional paperboard.
[0025] It is desirable to manufacture a paperboard produced from cellulosic material that has good insulating characteristics, that will allow the user to sense that food in the container is warm or hot and at the same time will allow the consumer of the food beverage in the container to hold the container for a lengthy period of time without the sensation of excessive temperature. It is further desirable to provide a paperboard that can be tailored to provide a variety of insulating characteristics.
[0026] Referring to FIG. 5 , the substrate 50 for the insulating paperboard 52 of the present application is produced in a conventional manner from readily available fibers such as cellulosic fibers. At least one ply, 54 , of the paperboard contains crosslinked fibers. The paperboard of the present application can be made in a single-ply, a two-ply construction, or a multi-ply construction, as desired. While the paperboard of the present application may employ synthetic fibers as set forth above, it is most preferred that paperboard comprise all or substantially all of the cellulosic fibers.
[0027] The distinguishing characteristic of the present application is that at least one ply of the paperboard, whether a single-ply or a multiple-ply structure, contains crosslinked cellulosic fibers. The crosslinked cellulosic fibers increase the bulk density of the paperboard and thus the insulating characteristics. As used herein, crosslinked cellulosic fibers are kinked, twisted, curly, cellulosic fibers. It is preferred, however, that the fibers be produced by intrafiber crosslinking of the cellulosic fibers as described earlier.
[0028] Paperboard of the present application may have a broad set of characteristics. For example, its basis weight can range from 200 gsm to 500 gsm, more preferably, from 250 gsm to 400 gsm. Most preferably, the basis weight of the paperboard is equal to or greater than 250 gsm. To achieve the insulating characteristics of the present invention, it is preferred that the paperboard has a density of less than 0.5 g/cc, more preferably, from 0.3 g/cc to 0.45 g/cc, and most preferably, from 0.35 g/cc to 0.40 g/cc.
[0029] When at least one ply of the paperboard contains crosslinked cellulosic fibers in accordance with the present invention, advantageous temperature drop characteristics can be achieved. These temperature drop characteristics can be achieved by altering the amount of crosslinked cellulosic fiber introduced into the paperboard, by adjusting the basis weight of the paperboard, by adjusting the caliper of the paperboard after it has been produced by running it, for example, through nip rolls, and of course, by varying the number and thickness of additional plies incorporated in the paperboard structure. It is preferred that this paperboard have a caliper greater than or equal to 0.5 mm, a basis weight equal to or greater than 250 gsm, and a density less than 0.5 g/cc defined below.
[0030] The paperboard of the present application can be a single-ply product. When a single-ply product is employed, the low density characteristics of the paperboard allow the manufacture of a thicker paperboard at a reasonable basis weight. To achieve the same insulating characteristics with a normal paperboard, the normal paperboard thickness would have to be doubled relative to that of the present invention. Using the crosslinked cellulosic fibers of the present invention, an insulating paperboard having the same basis weight as a normal paperboard can be made. This effectively allows the manufacture of insulating paperboard on existing paperboard machines with minor modifications and minor losses in productivity. Moreover, a one-ply paperboard has the advantage that the whole structure is at a low density.
[0031] Alternatively, the paperboard of the application can be multi-ply product, and include two, three, or more plies. Paperboard that includes more than a single-ply can be made by combining the plies either before or after drying. It is preferred, however, that a multi-ply paperboard be made by using multiple headboxes arranged sequentially in a wet-forming process, or by a baffled headbox having the capacity of receiving and then laying multiple pulp furnishes. The individual plies of a multi-ply product can be the same or different.
[0032] The paperboard of the present application can be formed using conventional papermaking machines including, for example, Rotoformer, Fourdrinier, cylinder, inclined wire Delta former, and twin-wire forming machines.
[0033] When a single-ply paperboard is used in accordance with the present invention, it is preferably homogeneous in composition. The single ply, however, may be stratified with respect to composition and have one stratum enriched with crosslinked cellulosic fibers and another stratum enriched with non-crosslinked cellulosic fibers. For example, one surface of the paperboard may be enriched with crosslinked cellulosic fibers to enhance that surface's bulk and the other surface enriched with non-crosslinked fibers to provide a smooth, denser, less porous surface.
[0034] The most economical paperboard to produce is homogeneous in composition. The crosslinked cellulosic fibers are uniformly intermixed with the regular cellulosic fibers. For example, in the headbox furnish it is preferred that the crosslinked cellulosic fibers present in high consistency slurry be present in an amount from about 25% to about 100%, and more preferably from about 30% to about 70%. In one embodiment the crosslinked cellulosic fibers are present at a level of at least 35 percent by weight of the total fiber content. In another embodiment the crosslinked fibers are present at a level of alt least 50 percent by weight of total fiber content. In yet another embodiment the crosslinked fibers are present at a level of at least 60 percent by weight of the total fiber content. In a two-ply structure, for example, the first ply may contain 100% non-crosslinked cellulosic fibers while the second ply may contain from 25% to 100% crosslinked cellulosic fibers or from 30% to 70% crosslinked cellulosic fibers. In a three-ply layer, for example, the bottom and top layers may comprise 100% of non-crosslinked cellulosic fibers while the middle layer contains from about 25% to about 100% and preferably from about 30% to about 70% of crosslinked cellulosic fibers.
[0035] When crosslinked cellulosic fibers are used in paperboard in accordance with the present invention, it has been found that the paperboard exiting the papermaking machine can be compressed to varying degrees to adjust the temperature drop characteristics across the paperboard. The paperboard once leaving the papermaking machine may be compressed or reduced in caliper by up to 50%, and more preferably, from 15% to 25%. This same result can be achieved by lowering the basis weight of the paperboard.
[0036] The paperboard of the present application can be utilized to make a variety of structures, particularly containers, in which it is desired to have insulating characteristics. One of the most common of these containers is the ubiquitous hot cup utilized for hot beverages such as coffee, tea, and the like. Other insulating containers such as the ordinary paper plate can also incorporate the paperboard of the present invention. Also, carry-out containers conventionally produced of paperboard or of foam material can also employ the paperboard of the present invention. FIG. 6 shows a wall section of a hot cup type container produced which may comprise one or more plies 62 and 64 , one of which, in this instance, 64 , contains crosslinked cellulosic fibers. In this embodiment the crosslinked cellulosic fibers are in the interior ply 64 . A liquid impervious backing is preferably extruded or poly coated to the interior ply coated to the. The backing may comprise, for example, a variety of thermoplastic materials, such as polyethylene. It is preferred that the paperboard used in the bottom of the cup contain no bulky fibers.
EXAMPLES 1-9
[0037] High consistency slurries were prepared at a 3.2 percent consistency containing 50 to 65 percent by weight citric acid crosslinked cellulosic fibers. The crosslinked fiber was deflaked with a standard Beloit Jones refiner with a zero load. Douglas Fir cellulosic fibers were used as the other component in the high consistency slurry. In some cases the Douglas Fir was refined to 650 CSF. A screen hole size of 2 mm was used in all cases. A rotor with six foils, a bump rotor and a lobed rotor, all well known in the art and manufactured by GL&V, Watertown, N.Y., were used in the screen for different trials. Trials were conducted on a pilot screen machine at GL&V, Watertown, N.Y., that allowed stock to be recirculated through the unit back to the screen tank pump. Flow rates ranged from approximately 3785 l/m (1000 gpm) to 5678 l/m (1500 gpm). Fiber reject rates were run at 10 to 13 percent.
TABLE 1 Screen Trials Basket Deflaked Hole size, Condition HBA Consistency Doug Fir mm Rotor 2 53% 1% non refined 2 6 foils 1 53% 3.2% non refined 2 6 foils 3 60% 3.2% non refined 2 bump 4 60% 3.2% non refined 2 lobed 5 60% 3.2% non refined 2 lobed 6 60% 3.2% non refined 2 lobed 7 60% 3.2% non refined 2 lobed 8 65% 3.2% 650 CSF 2 lobed 9 65% 3.2% 650 CSF 2 lobed
[0038] Condition 2 ran well at 10 percent reject rates and feed rates of 3255 l/m (860 gpm) to 5300 l/m (1400 gpm). Condition 1 ran at a reject rate of 17% but when the reject rate was reduced, the reject line plugged into the center of the screen basket with thick stock.
[0039] Condition 3 was run with GL&V's barracuda rotor, a bump rotor, in a random pattern. The run was started with a full reject line but as soon as the accepts line was opened, the flow started to fall off due to stock thickening. The rotor is noted for tendency to fractionate fiber.
[0040] All the remaining runs ran well as follows:
[0041] Condition 4, the run was made with an 11% reject rate, 0.14 kPa (3 lb) differential pressure to the screen and a rotor speed of 900 RPM. Increasing the rotor speed to 1000 RPM had no impact.
[0042] Condition 5, the rotor speed was dropped to 800 RPM, at this point the reject flow started to drop off and the rotor speed was returned to 900.
[0043] Condition 6 was the same as condition 4.
[0044] Condition 7, the inlet pressure was increased 0.48 kPa (10 lb), feed flow increased from 900 GPM to 4164 l/m (1100 GPM) and the differential pressure increased to 0.17 (3.5 lb). This condition ran well.
[0045] Condition 8 was run at a reject rate of 15% with a 3123 I/m (825 GPM) feed flow rate.
[0046] Condition 9 was run at a at 13% reject rate with a 3785 l/m (1000 GPM) feed flow rate.
[0047] Theses results indicate that screening at 3.2% consistency and 50% to 65% HBA was successful with a lobed style rotor design.
[0048] Fiber samples were obtained from the feed stock, the accepts line and the reject line and microscopically analyzed for fiber content. The results, shown in Table 2, indicate that, using various rotor and the 2 mm screen hole size, there was no selective fractionation of the crosslinked fiber.
TABLE 2 Microstructure - Screen Slush Samples Bleached Softwood Crosslinked Rotor Type Condition Kraft % fiber, % Lobed, F 9 40 60 Lobed, A 9 35 65 Lobed, R 9 38 62 6 Foils, F 1 46 54 6 Foils, A 1 44 56 6 Foils, R 1 45 55 6 Foils, F 2 41 59 6 Foils, A 2 41 59 6 Foils, R 2 46 54 Bump, F 3 39 61 Bump, A 3 39 61 Bump, R 3 38 62 F, feed stock; A, Accepts; R, Rejects
EXAMPLE 10
[0049] A 3 to 3.2 percent high consistency slurry was prepared containing 40 percent by weight crosslinked cellulosic fibers; Douglas Fir wet lap was used as the regular fiber. A screen with a 4 mm hole diameter and a six foil rotor was used prior to the mid ply headbox. A separate slurry containing only Douglas Fir or Pine fibers was refined to 500 CSF and diluted to 0.5 percent consistency prior to pumping the slurry to the outer headboxes. A paperboard was formed on a 500 cm paperboard machine.
EXAMPLE 11
[0050] A 3 to 3.2 percent high consistency slurry is prepared containing 40 percent by weight crosslinked cellulosic fibers; Douglas Fir wet lap is used as the regular fiber. A screen with a 2 mm hole diameter equipped with a lobed rotor is used prior to the mid-ply headbox. A separate slurry containing only Douglas Fir or Pine fibers is refined to 500 CSF and diluted to 0.5 percent consistency prior to pumping the slurry to the outer headboxes. A paperboard is formed on a 500 cm paperboard machine.
EXAMPLE 12
[0051] A 3 to 3.2 percent high consistency slurry is prepared containing 50 percent by weight crosslinked cellulosic fibers; Douglas Fir wet lap is used as the regular fiber. A screen with a 2 mm hole diameter equipped with a lobed rotor is used prior to the mid-ply headbox. A separate slurry containing only Douglas Fir or Pine fibers is refined to 500 CSF and diluted to 0.5 percent consistency prior to pumping the slurry to the outer headboxes. A paperboard is formed on a 500 cm paperboard machine.
EXAMPLE 13
[0052] A 3 to 3.2 percent high consistency slurry is prepared containing 55 percent by weight crosslinked cellulosic fibers; Douglas Fir wet lap is used as the regular fiber. A screen with a 2 mm hole diameter equipped with a lobed rotor is used prior to the mid-ply headbox. A separate slurry containing only Douglas Fir or Pine fibers is refined to 500 CSF and diluted to 0.5 percent consistency prior to pumping the slurry to the outer headboxes. A paperboard is formed on a 500 cm paperboard machine. | A process is described for manufacturing a paperboard from a high consistency slurry containing high levels of crosslinked cellulosic fibers by dispersing the fibers in a screen with a rotor in the screen and then passing the fibers through the screen basket with a hole diameter of at least 2 mm and forming the cellulosic fibers on a foraminous support. Another slurry of regular cellulosic fibers is deposited on at least one side of the first slurry during the formation process. The formed web is dewatered and dried. | 3 |
BACKGROUND OF THE INVENTION
[0001] This invention relates generally to axial flow fans and, more particularly, to a method and apparatus for reducing their clearance flow losses.
[0002] Axial flow fans are used in a wide variety of applications, including HVAC, refrigeration, automotive, power systems and aerospace. In each of these applications, efficiency and space limitations are especially important considerations.
[0003] Significant efficiency loss occurs in axial flow fans due to backflow in the clearance region between the fan rotor and the casing. The rotor may utilize conventional blades that extend outward with blade tips approaching the casing, or it may utilize blades that include a rotating shroud attached to the blade tips. In either case backflow is driven from the high pressure side of the rotor to the suction side across the clearance gap, leading to reduced performance, increased noise level and reduced stability and stall-margin.
[0004] Various designs have been proposed for increasing fan efficiency by reducing or controlling clearance flows. The designs generally involve an interruption or decrease in the size of the gap. One approach is the use of a tip seal structure wherein a circumferentially extending groove in the casing circumscribes the tips of the blades as shown and described in U.S. Pat. No. 4,238,170. In another approach, an axial fan is provided with a casing having a bellmouth, and the shroud is so formed as to create a separation bubble between the bellmouth and the shroud in order to limit the circulation flow as shown in U.S. Pat. No. 7,086,825 assigned to the assignee of the present invention.
[0005] Fan stability is affected by rotating flows within the clearance gap. These flows tend to develop into organized rotating cells which can lead to strong through-flow oscillations and excessive noise.
[0006] Various designs have been proposed to improve fan stability by controlling these rotating flows. These designs are generally classified as casing treatment.
SUMMARY OF THE INVENTION
[0007] Briefly, in accordance with one aspect of the invention, a sharp, forward facing step is provided in the fan casing which, when combined with an overlapping rearward facing step in the fan blade tips, tends to disrupt the backflow so as to thereby restrict clearance flow loss.
[0008] In accordance with another aspect of the invention, each of the blades has an attached vane on its suction side, with the vanes having a rearward facing step that overlaps the casing forward facing step.
[0009] In the drawings as hereinafter described, a preferred embodiment is depicted; however, various other modifications and alternate constructions can be made thereto without departing from the spirit and scope of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 is a perspective view of an axial fan assembly in accordance with the present invention.
[0011] FIG. 2 is an enlarged view of a portion thereof.
[0012] FIGS. 3A and 3B are respective front and end views of a normal blade tip.
[0013] FIG. 3C is an axial cross sectional view thereof in relationship to the casing.
[0014] FIGS. 4A and 4B are respective front and end views of a blade tip with a step in accordance with the present invention.
[0015] FIGS. 5A and 5B are respective front and end views of a blade tip with a vane in accordance with the present invention.
[0016] FIG. 6 is a suction side view of a blade tip and vane in accordance with the present invention.
[0017] FIG. 7 is a pressure side view of a blade tip and vane in accordance with the present invention.
[0018] FIG. 8 is a radially inward view of a blade tip and vane in accordance with the present invention.
[0019] FIG. 9 is an axial cross sectional view of the FIGS. 4A and 4B embodiment of the blade tip in relationship to the casing.
[0020] FIG. 10 is an axial cross sectional view as seen along lines 10 - 10 of FIG. 2 .
[0021] FIG. 11 is an axial cross sectional view as seen along lines 11 - 11 of FIG. 2 .
[0022] FIG. 12 is a partial view thereof showing the flow of air therein.
[0023] FIG. 13 is an axial cross sectional view of the apparatus as shown in FIG. 11 but with an added inlet bellmouth insert.
[0024] FIG. 14 is a perspective view of an axial fan in accordance with an alternative embodiment of the invention.
[0025] FIG. 15 is an enlarged view of a portion thereof.
[0026] FIG. 16 is an axial end view thereof.
[0027] FIGS. 17A and 17B are other perspective views thereof.
[0028] FIG. 18 is an axial end view of another alternative embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0029] Referring to FIGS. 1 and 2 , the invention is shown generally at 10 as applied to an axial fan assembly 11 that includes in serial airflow relationship an axial fan 12 and a stator 13 . The axial fan 12 includes a rotatable hub 14 and a plurality of fan blades 16 . The stator 13 includes a stationary hub and a plurality of radially extending stationary vanes 17 having their radially outer ends integrally connected to a cylindrical outer housing 18 . In operation, the fan 12 is rotated at relatively high speeds to induce the flow of air through the casing 18 , and in the process it creates a swirl in the direction of the fan rotation. The stator vanes 17 are so disposed and shaped as to substantially remove the swirl from the main airflow stream such that the flow at the downstream end is substantially axial in direction.
[0030] As is well known in the art, the dimensions of the axial fan 12 are such that the radial clearance between the ends of the fan blades 16 and the inner diameter of the casing 18 are as small as possible but without engagement between the two elements. Because of this necessary radial clearance, there is a tendency for the air within the casing 18 to flow back through the radial gap to the forward side of the fan 12 . This results directly in reduced pressure rise and efficiency. The present invention is intended to significantly reduce the backflow.
[0031] Referring now to FIGS. 3A and 3B , a normal blade is shown at 16 A, with a generally planar tip being shown in FIG. 3B . That is, the blade tip is slightly curved to accommodate the curved inner diameter of the casing 18 A, but is of a substantially constant radius throughout the length of the blade tip. The blade tip of blade 16 A in combination with a standard casing 18 A is shown in FIG. 3C .
[0032] In FIGS. 4A and 4B , the blade 16 B is shown to have a blade tip with a rearwardly facing (i.e. toward the downstream or pressure side of the blade 16 B) step as shown at 19 . That is, that portion 21 of the blade tip nearest the leading edge is of one fixed radius and that portion 22 thereof nearest the trailing edge is of a constant reduced radius. The face of the step 19 is generally planar in form and is aligned tangentially (i.e. normal to the fan axis).
[0033] Referring now to FIG. 9 , where the blade 16 B is shown with its blade tip profile that includes the rearwardly extending step 19 and the leading edge portion 21 and trailing edge portion 22 . Here it will be seen that the casing 18 B includes a matching forward facing step 23 which interconnects a larger radius portion 24 and a smaller radius portion 26 of the casing 18 . The forward facing step 23 is a generally planar surface and is aligned tangentially such that the rearwardly facing step 19 is generally parallel with and in close proximity to the forwardly facing step 23 . Similarly, the blade tip leading edge portion 21 is closely radially spaced from the larger radius portion 24 , and the trailing edge portion 22 of the blade tip is closely radially spaced from the smaller radius portion 26 of the casing 18 . This combination is provided for the purpose of reducing the backflow and its associated swirl that would otherwise result in a normal blade tip and casing relationship as shown in FIGS. 3A and 3B .
[0034] Referring now to FIGS. 5A and 5B , a blade 16 C is shown with a rearwardly facing step 19 , leading edge portion 21 and trailing edge portion 22 as shown in FIGS. 4A and 4B . However, the blade 16 C is further modified to include a vane 27 which is attached to the suction side of the blade as shown in FIG. 2 and which forms part of the blade tip as shown in FIGS. 5A and 5B .
[0035] The vane 27 can best be seen in FIGS. 6 , 7 and 8 where it is shown as being attached to the blade 16 C. FIG. 6 shows the blade 16 from the suction side, FIG. 7 shows it from the pressure side and FIG. 8 shows it from the radially inward direction as shown in FIG. 8 . As will be seen, the vane 27 forms a part of the blade tip and is placed approximately in the middle of the suction side of the blade 16 C and extends approximately one-third of the way across. The size and shape of the vane 27 can be selectively varied to meet the particular axial fan assembly and operating requirements.
[0036] An important feature of the vane 27 is that it too includes a rearwardly extending step 28 as will be seen in FIG. 7 . This step 28 also interfaces with the forward facing step 23 of the casing 18 B in a manner similar to the rearwardly facing step 19 of the blade tip as discussed hereinabove to provide a further reduction of backflow that would otherwise occur around the blade tips. This can be seen in FIG. 11 wherein the rearwardly facing step 28 of the vane 27 is closely aligned with the forward facing step 23 of the casing 18 B. In order to understand the structure of the blade tip of blade 16 C, FIGS. 10 and 11 should be referred to in combination. FIG. 10 is a sectional view through the stepped tip at a point forward of the vane 27 , whereas FIG. 11 is a sectional view thereof at a point that includes both the stepped tip and the vane 27 .
[0037] The design of both the casing and the fan rotor are such that they can be produced using straight-pull tooling (e.g. injection molding or die casting).
[0038] In operation, as will be seen in FIG. 12 , the relationship of the stepped blade tip and casing produces a convoluted path for the tip clearance leakage flow, which is highly restrictive. The effect is essentially similar to a labyrinth seal where the backflow and recirculation is forced to turn abruptly multiple times. Each flow turning produces a pressure drop which then enables the flow system to withstand a higher differential pressure and a lower leakage loss.
[0039] The embodiment of FIG. 11 can be used as shown without the use of inlet bellmouth insert. It will operate similarly but will benefit from the further use of an inlet bellmouth insert 29 as shown in FIG. 13 .
[0040] An alternative embodiment of the present invention is shown in FIGS. 14-17 wherein the fan blades 16 D have a blade tip vane 31 which extends almost the full tangential span of the blade tip. That is, ends 32 and 33 extend to just short of the edges of the fan blade 16 D as shown. In such a case, the step feature is entirely within the tip vane and not in the blade tip, as shown in FIG. 17A and 17B wherein the tip vane 31 is located axially forward of the entire blade tip.
[0041] In FIG. 18 , there is shown an embodiment wherein the size of the tip vane 34 is lengthened along the tangential direction such that it extends at it two ends just beyond the edges of the blade 16 E. As discussed hereinabove, this variation is in keeping with the practice of selectively varying the size and shape of the vane to meet the particular axial fan assembly and operating requirements.
[0042] It should be understood that the present invention can be used by itself for the reduction of backflow, or it may be used in combination with the wedges that are shown and described in the patent application being filed concurrently herewith and assigned to the assignee of the present invention.
[0043] Although preferred and alternative embodiments of the invention have been disclosed and described, one of ordinary skill in the art would recognize that certain modifications would come within the scope of this invention. For that reason, the following claims should be studied to determine the true scope and content of the invention. | An axial fan assembly including a casing wall with a forward facing step formed therein and a fan rotor with blade tips, each having an aft facing step which radially overlaps the casing step so as to reduce the clearance backflow loss in the assembly. A vane is attached to the suction side of each of the blade tips with the vane having an aft facing step which radially overlaps the casing forward facing step to promote further reduction of clearance backflow. Variations on the invention include the option of an additional inlet bellmouth piece that further restricts the clearance flow and wedges integral to the casing step to improved flow stability. | 5 |
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] Not Applicable
FEDERALLY SPONSORED RESEARCH
[0002] Not Applicable
SEQUENCE LISTING OR PROGRAM
[0003] Not Applicable
37 C.F.R. 1.71 AUTHORIZATION
[0004] A portion of the disclosure of this patent document contains material that is subject to copyright protection. The copyright owner has no objection to the facsimile reproduction by anyone of the patent document or the patent disclosure, as it appears in the Patent and Trademark Office records, but otherwise reserves all copyright rights whatsoever.
BACKGROUND
[0005] 1. Field of Invention
[0006] The present invention relates to a system and method of uniquely identified payment devices to universally categorize payments and exchange transaction data between payment devices and financial institutions through ATM networks.
[0007] 2. Description of Prior Art
[0008] For purposes of this description, “chip” is any integrated circuit microchip that can store and process data affecting a payment initiator. A “card” includes any portable, embossed device free of any physically attached connector that contains in its substrate a means, including a chip, to electronically store and process information. An ATM is an automated teller machine or automated transaction machine that is designed to accept and read an electronic chip or card and operates by design without any human intervention other than by the carrier.
[0009] Prior art to the present invention covers two principal areas, the automatic teller machine (ATM), and a card with an embedded integrated circuit chip, known as the smart card or the chip card. ATMs are nearly ubiquitous in many countries. Cards throughout the world are reaching monumental proportions.
[0010] ATM Usage and Functions
[0011] In the U.S., approximately 324,000 ATMs now bring banking closer to the customer. With interbank access among ATMs, holders of an access card can bank and transact from almost anywhere. Annually, there are about 1.3 billion ATM transactions. Research shows that most customers use an ATM anywhere from two to four times per month. Online bankers use the ATM roughly 11 times each month, partly because online bankers from home cannot make deposits and withdrawals for paper-based items.
[0012] Traditional functions of ATMs are cash withdrawals, deposits, fund transfers and balance queries. Those remain as powerful reasons to bypass teller lines during business hours or to transact 24×7 whenever convenient for the customer. Still, the principal convenience of an ATM to a customer remains as the easy, secure access to currency. Witness the recent conversion of Western European currencies into the euro. On Jan. 1, 2002, these market economies converted to the euro, and ATMs reached an all-time high in single day usage as economic units rushed to obtain the new euro bills.
[0013] ATMs have expanded their functionality to create greater profitability for ATM owners, which include both retail and banking firms. In the push for more versatility, banks have Web-enabled ATMs to promote goods and offer services, such as postage stamps and downloaded music. Self-service machines run in cost anywhere from $5,000 for a cash-only ATM all the way to $50,000 for a state-of-the-art ATM. Although these newer ATMs resemble PCs in functionality, banks realize that extended waiting time in the ATM line burdens their customer. This would otherwise defeat the mantra of the ATM's goal of speed to transact and withdraw money.
[0014] To date, ATMs have a myriad of patents that address multifunctionality. U.S. Pat. No. 6,308,887 issued to Korman, et al., in 2001 anticipates the use of nearly unlimited “standard” and proprietary protocols and certain sensors so that the transaction machine network can process all kinds of transactions. The claims do not cover the use of smart card sensors for any purpose in an interface with the ATM. U.S. patent application Ser. No. 20010014881 of Drummond et al. published on Aug. 16, 2001 contains two claims relevant to prior art. One covers a method to use an ATM with a card interface to change the stored value on a smart card and a second is an ATM that reads an account number from a card. However, these claims do not extend to uploading to the institution operating the ATM or to downloading onto the card itself generalized transaction histories of the cardholder. U.S. patent application Ser. No. 20010013551 of Ramachandran published on Aug. 16, 2001 claims a portable device to transfer and import cardholder information onto a single card. This includes a device to operate an ATM and transfer stored values on smart cards. The claimed apparatus related to smart cards is dedicated to adjusting stored values only.
[0015] Many banking functions are now available through personal ATMs. VeriFone Personal ATM™ is one such device. With a serial port connecting a reader with a consumer device or appliance, the owner uses a chip card (smart card) to initiate a wide variety of transactions. Multiple applications include electronic cash withdrawals, bill payment, stored value (electronic purses), retail purchases, fund transfers, electronic commerce, portfolio management and other user-authenticated transactions. As long as there is connectivity, the consumer can freely transact at home, at the office, in a public location, at a kiosk, or at a merchant's place of business.
[0016] The merchant point-of-sale (POS) terminal can perform bank-like ATM functions. U.S. Pat. No. 5 , 992 , 570 issued to Walter, et al. in 1999 is a self-service POS ATM unit. The claimed apparatus allows a user purchasing items at a merchant to independently scan and pay for items without store assistance. The POS unit also performs a variety of bank-like ATM functions, including cash withdrawals, cash deposits, interaccount transfers and balance queries. Although the preferred embodiment includes use of a chip card for payment, the novelty does not extend to upload of payment categorization data to the bank or download of the same onto the chip card.
[0017] Thus, nearly all prior art on ATM design and usage focuses on one-way transmission of traditional banking information. When money is tendered, the ATM dispenses a desired good or service as the customer executes an authenticated instruction (e.g., password protection). In fact, the universal upload of card information from the read-only memory (ROM) is typically limited to the card identity, holder identity and some means of authentication. Beyond this information, the card may upload a remaining balance for stored value balances, otherwise known as an electronic purse. Normally, financial institutions do not use their ATM networks to capture card transaction histories, except for cash withdrawals and debits. One-way channel delivery strategy forces the Internet banking customer to download critical banking information into their own stationary or portable computer device or system. The chip card can change all that.
[0018] Chip Card Usage and Components
[0019] Smart or chip cards throughout the world offer features affecting nearly every facet of commerce. Cards are used for secured access, identification, mass transit, and payment transactions within a closed or semi-closed environment. Accordingly, prior art on chip cards is enormous. Chip cards boast tremendous storage and processing power in view of their cost and compact size. The embedded microchip allows cards to operate in a variety of networking environments. In theory, this technical capability allows a card processing infrastructure to sharply curtail the number of cards an economic unit needs to carry.
[0020] Countries, such as France and Venezuela, have made the chip card nearly universal for their citizenry. The total number of chip cards manufactured for use within the United States and Canada rose from approximately 20 million in 1999 to about 28 million in 2000—a 37% growth. The fastest growing market segment was circulation in the financial market sector, with a 244% growth rate. Still, this amounts only to chip cards with chips in circulation, as opposed to actual demand for and usage of data on that embedded chip. As the case is in the U.S., reduction of fraud and other benefits related to payments are achieved only when a sufficient mass of networked readers can accept and read the chip card.
[0021] Chip cards appear in two versions for technical functionality. The basic version contains a microcontroller semiconductor device that performs computations, secured data storage, encryption and decision making. A microcontroller acts much like a PC's central processing unit, with a microprocessor, memory, and other functional hardware elements. A very smart card has a battery that charges and retains power when connected with a terminal device.
[0022] The weakness in prior art for electronically driven payments is demonstrated by tracing the emergence of technology in the payments process. The primary dual functions of payments are authentication and transmission of value. Only one payment form dispenses with both functions instantaneously—the delivery of currency (absent counterfeiting needs no authentication of the holder and the transmission of value is simply the currency's face value. The magnetically-encoded stripe card then arrived. This card authenticates the holder, but verification is limited to efforts at POS. Verification includes signatures, Personal Identification Numbers (PINs), and biometric methods. Magnetic strip cards already are vulnerable to extensive fraud. Now, with online commerce, authentication creates a new fraud exposure
[0023] Chip cards can enhance safety for their authorized holders and merchant-payees. No matter what type of card is presented, there must be an electronic reader. Chip card readers are now not only prevalent among merchants at POS, but are installed within ATMs owned by banks and stationed either on-site or off-site. To enable consumers and businesses to transact independent of personal merchant participation, chip cards can now be read by holder-managed devices, including PC-connected readers, mobile phones, phones, and other consumer appliances.
[0024] The opportunity among prior art for chip cards and chip card readers is not readily discerned. Chip cards are only one of many choices for payment authentication, but they do offer greater security and privacy. Even the use of a card for authentication in payments is now in question, at least in online transactions. Single use “credit card” numbers are now available for authentication, with the initial log-in done with the chip card. The singular advantage of the chip card is dynamic exchange and storage of data, which occurs as soon as the card is accepted by the reader. As the cost of chip cards continues to fall, multiple applications become more promising. However, this cost is directly dependent on the amount of storage capacity required by the chip card manufacturer to perform the desired functions and applications.
[0025] The Problem of Multiple Cards for Holders
[0026] In today's payment environment, a frequent card payer is challenged to sensibly manage card-generated payment transaction data from numerous cards. The holder has multiple cards—credit cards, debit and ATM cards, phone cards, transit cards, gift cards, loyalty cards, and merchant cards. Transactions at POS sometimes print a statement, sometimes they do not. The holder can attempt to maintain tedious records, but she must comb through monthly mailed or electronically transmitted statements to her PC with the mass of slips accumulated at POS. If she is an active Internet shopper, printers typically generate letter-sized paper and not the typical register receipt or charge slip. Each month, proper data capture must emerge from paper receipts from a multitude of readers, printers, appliances, and devices, in addition to electronically processed, paperless transactions.
[0027] The proliferation of multiple cards with multiple functions is an ongoing burden to the economic unit. In the magnetic stripe market, prior art attempts to consolidate the replication of cards. In the invention described in U.S. Pat. No. 6,189,787 issued to Dorf in 2001, the prior art is the creation of multifunctional cards. This invention, however, is limited to the magnetically-encoded striped card and does not contemplate chip cards. Further, it does not give any issuer or merchant an incentive to surrender loyalty benefits of a dedicated card and separate branding.
[0028] Prior art on smart cards emphasize the combination of multiple applications, including payment, onto one card. Without government mandate, merchants and card issuers as well as vendors on competing platforms find few advantages in collapsing the branding and purchasing power on the same card. The proliferation of smart card readers has no clear benefit to the economic unit unless it can either use multiple applications and/or capture transaction data in a standardized format for financial management. Transaction, loyalty, payment, credit and debit, and ATM cards all compete for space in the wallet. These cards fall in cost of production for the issuer as long as the data storage capacity is as low as possible. Issuers find few advantages in allowing other merchant data to occupy the card. This leaves the economic unit without a universal merchant-issuer card that is interoperable for transaction data capture.
[0029] Chip Card Data Capture
[0030] Prior art allows smart cards to capture and present transactional data to the holder, but no universal system of indexing and categorization exists to benefit the holder. Three patents are relevant on recording transactional data onto smart cards. None remove the laborious task of initially categorizing such data. U.S. Pat. No. 5,649,118 issued to Carlisle et al. in 1997 provides for consolidating transactional capability with multiple merchants onto a single card carrying suitable firewall security on the same chip. This does not provide for movement of all transactional data to a single merchant or bank for further processing or analysis for the benefit of the holder. U.S. Pat. No. 6,129,274 issued to Suzuki in 2000 presents a novel means to have the chip card capture transactional data at POS. This data is downloaded to the holder's PC but not uploaded to an institution.
[0031] U.S. Pat. No. 5,859,419 issued to Wynn in 1999 intends to consolidate multiple account transaction activity with a single chip card. This prior art recommends the use of categories for the convenience of the cardholder. However, assignment of a category to a transaction or payment is purely discretionary and left to the holder to use their PC or other device. This task is not delegated up to their financial institution, card issuer, or merchant.
[0032] U.S. Pat. No. 5,559,313 issued to Claus, et al. in 1996 comes the closest in concept to the present invention. The chip card tracks individual purchased items and categorizes them with a series of translation tables. There is no card reader-centric categorization code that assists in the translation. The holder's PC extracts transaction data in tabular format for further use and presentation to the holder. However, there is no upload of that data to the holder's bank or card issuer for processing and subsequent return of a report to the holder.
[0033] Even if the chip card captures spending data at point-of-payment, the holder still must download that data and use personal financial management (PFM) software. If the holder decides to shift that burden to the financial institution, that channel requires active use of a PC or other Internet device requiring either time-consuming connection step or the more expensive, always-on connection. A more efficient, electronically seamless channel must exist, and a financial institution could assume that task for the economic unit/cardholder. This would unify the capture and presentation of payment data, particularly if the financial institution is a trusted source and prepared to leverage the opportunity.
[0034] Expenditure Tracking by Cards
[0035] Expenditure tracking for households and businesses is achieved through a variety of patented and non-patented PFM tools. PFM tools include Pocket Quicken® that runs on a Palm Pilot. The stylus is faster to enter transactional data than the manual method. However, this solution does not electronically connect the POS terminal with the handheld PDA. A proper solution would remove any manual movement or involvement by the customer other than presenting the chip card for payment processing.
[0036] Online access devices such as credit cards and debit cards authorize payment with an embossed account number on one side and a magnetic stripe containing account information in machine-readable form on the other side. Debit cards deduct funds directly from the end user's bank account using an ATM or POS terminal. With either type of card, the merchant handling the transaction has a relationship with the bank and card association. Credit card associations have traditionally offered expenditure classification for cardholders. The production of such card data relies solely on the merchant's identity, i.e., its standard industry classification (SIC) code.
[0037] Credit card associations and providers, such as Visa, MasterCard, and American Express all provide periodic classification of charges on a periodic basis for individual and corporate cardholders. However, those summaries are incomplete in two key aspects. First categorization is forced upon the cardholder based on the identity of the merchant, which may sell multiple types of goods and services. The more critical problem is that the only categorized transactions are those processed by the network. Average Americans carry at least five, sometimes even 10 charge cards. Therefore, only manual or keyed-in consolidation of categorized expenditure is available. Categories are not universal among various card products. Nor are card payments automatically consolidated.
[0038] Another patent, U.S. Pat. No. 5,748,908 issued to Yu in 1998, tracks expenditures made with credit cards and debit cards and sends the data through the network, but does not contemplate a card carrying multiple merchant data capture capability to store categorized data on a single card.
[0039] Individual economic units cannot accurately track their spending without PC use or extraordinary manual effort to sort and aggregate transactions with cash, checks, credit cards, debit cards, smart cards and electronic devices. Even if individualized payment management through PFM software is reliable, no efficient channel exists to collect data that resides on home PCs and laptop computers.
[0040] The prior art carries no effective and uniform means to uniquely identify cards. U.S. Pat. No. 6,189,787, issued to Dorf in 2001, proposes various types of cards, each with a unique identification number approved for use by the American Banking Association. The restrictions on utility are obvious. The numbering system may not provide a unique, universal address recognized globally. Further, the address might not be readily convertible or usable within an Internet environment where communication must be rapid and targeted.
[0041] Overall, the prior art does not give economic units paying by card a standardized, user-friendly categorization tool resting within a single, uniquely addressed card that can efficiently and conveniently send that data for management by the holder's financial institution or to the holder's own managed database.
SUMMARY OF THE INVENTION
[0042] It is an object of the present invention to establish a pervasive global network addressing system for all essential components of the card payment network beginning with the payment device carried by its holder to the networked electronic junctions to the terminal destination where transaction data resides within an institution.
[0043] It is a further object of the present invention to logically assign within a card network to each and every ATM/POS reader a universal expenditure (UEX) code within a numerical range of the UEX code assignments. The logical mapping for each and every such ATM/POS reader is achieved via a telecommunications network programming the internal operating system of each ATM/POS reader.
[0044] It is still another object to enable merchant-managed chip card readers and cardholder-managed chip card readers with assigned UEX codes to automatically categorize card payment transactions during the time of interface between the merchant and the cardholder. Another object of the invention is to utilize a multi-application chip card to record and store card payment transaction data when payments are made at merchant POS terminals or user-managed computer device-connected card terminals.
[0045] An additional object of the invention is to allow a holder to carry a single chip card independent of all other cards to record and store payment transaction data that is categorized according to UEX codes.
[0046] A further object of the invention is to upload card payment transaction data through ATMs to the cardholder's financial institution.
[0047] A further object is to allow ATMs to download categorized payment transaction data maintained by a financial institution onto a cardholder's chip card, which can then download such data onto one's own computer device for further processing and reporting.
[0048] In addition, the present invention uses ATMs to print out a summary of categorized payment transactions initiated by the cardholder.
DRAWINGS
[0049] In the drawings, closely related figures have the same number but different alphabetic suffixes.
[0050] [0050]FIG. 1 displays the card payment network layout to assign and maintain global network addresses for various components of the network.
[0051] [0051]FIG. 2 is a dynamic presentation of how data components of a card change when a transaction is processed by a card reader to assign a UEX code.
[0052] [0052]FIGS. 3A and 3B illustrate the upload and download of categorized transaction data through a chip card when inserted into a cash-dispensing ATM connected to the card holder's financial institution.
[0053] [0053]FIG. 4 is a diagram of prior art, U.S. Pat. No. 5,559,313, where a cardholder downloads categorized payment transaction data from a chip card to a holder-managed computer device.
[0054] [0054]FIG. 5 shows how global network addresses are assigned to various components of a card payment network, beginning with the card, cardholder, POS terminal, ATM, and user-managed card reader.
DETAILED DESCRIPTION OF THE INVENTION
[0055] The Figures depict preferred embodiments of the present invention for purposes of illustration only. One skilled in the art will readily recognize from the following discussion that alternative embodiments of the structures and methods illustrated herein may be employed without departing from the principles of the invention described herein.
[0056] [0056]FIG. 1 shows one embodiment of the network to assign and maintain unique global network addresses to components of the network. Card readers 102 , 104 and 106 are able to accept cards for reading, writing and payment processing. Card reader 102 may be a merchant's POS terminal that processes credit card transactions. Card reader 104 is a PC-connected device at cardholder's home. Card reader 106 is located inside a kiosk on a college campus. Through network 120 , and wired/wireless connection 130 , terminal database server 140 is able to monitor the location of card readers 102 , 104 , and 106 within the entire network. Through connection 150 , terminal ID table 160 maintains a specific unique global network address for each of card readers 102 , 104 and 106 . Table 160 also contains a UEX code assignment program 210 a from FIG. 2 for each card reader in the entire network. Through connection 170 , terminal database server 140 accesses Internet protocol version 6 (IPv6) table 180 . Next, terminal database server 140 assigns a UEX code for card readers 102 , 104 , and 106 . Table 180 assigns unique global IPv6 addresses to each of the card readers and other essential components of network 120 . For IPv6 address assignment in FIG. 1, database server 160 assigns and uniquely identifies card readers 102 , 104 , and 106 . Card reader 102 might have an IPv6 network address of AA01:9090:1111:1212:0192:0168:0123:0101. Card reader 104 might be assigned an IPv6 network address of AA01:9090:1111:1212:0192:0168:0123:0203. Similarly, card reader 106 might be assigned a network address of AA01:9090:1111:1212:0192:0168:0123:0222. Each physical card reader requires only one unique address.
[0057] Terminal ID table 160 and IPv6 table 180 are components of a relational database. The logical key of this database is the logical terminal address. Since network 120 is made up of routers, switches and computers, the table lookup is done with a structured query language command known as a table join. For performance reasons and physical memory constraints, it is advisable to split a database into smaller manageable tables. In IPv6 table 180 there are two columns. One column is the primary key of the table that is the terminal ID address. The other column are the values of the IPv6 addresses. Within the 128-bit address, there is ample room for logically identifying latitude, longitude coordinates, store ID, country code, province, and department code. The nomenclature of the IPv6 address is 8 groups of 4 hexadecimal numbers. The eight groups are separated by seven colons altogether. The colons mean nothing to a computer or router, except to serve as a visual aid. As a shorthand notation, because of the expansiveness of the address one colon may substitute for one or more groups of 4 hexadecimal zeroes. For example, card reader 102 can have an IPv6 address of FFAE::090F. Card reader 104 can have address of BBBB::000C. Both of these addresses would appear as an entry in IPv6 table 180 . Double colons are used between groups when there are one or more groups of consecutive sets of hexadecimal zeros. Further, double colons only appear once in an IPv6 address.
[0058] IPv6 is the most recent international data network addressing scheme being promulgated and logically augmented by the Internet Engineering Task Force (IETF). The IETF is composed principally of high technology firms such as Sun Microsystems and Cisco Systems. Other key members include Nokia, ATT and NTT of Japan. The IETF is responsible for laying down the networking Internet protocols (IP) such as FTP, POP, and SMNP so that computer systems around the work can communicate over the Internet. Without such fundamental standards in place, the World Wide Web is impossible. IP is the bedrock networking foundation based on an open set of standards that any computer vendor can choose to follow. In the late 1900's, proprietary networking protocols such as IBM's Systems Network Architecture (SNA) and Digital Equipment's DECNET made it possible for monolithic computer networks to be from one vendor only. As personal computers and LANs exploded in complexity and in network topologies and companies were consolidated and sold off, IT managers had to merge disparate networks and computer systems. This phenomenon, with the growth of Websites, led to the gradual exhaustion of IPv4 addresses, which in turn led to the birth of IPv6 addressing.
[0059] From the network perspective, if there is no common protocol between two different and geographically distinct data centers, there can be no efficient means of transferring accurately and swiftly other than bulk data transfer from magnetic tapes. For transaction-intensive computer systems, this is clearly unfeasible. IP allows overnight transfers of hundreds of thousands of transaction records into a corporate database. However, the proliferation and rapid ascendancy of the open IP standard known as IPv4 has caused a serious and potentially worldwide problem for government and corporate network planners. The IPv4 protocol is predicated on the well-known 32-bit addressing scheme. Based upon the binary arithmetic, 2 to the 32 nd power is exactly 4,294,967,294 unique host addresses. However, population growth and worldwide acceptance of mobile devices is quickly exhausting unique addresses. There are now an estimated one billion mobile phones in use. Since these and other electronic devices have no native intelligence, network architects demand that the next generation of Internet addresses accommodate the global requirement of uniqueness. Thus, the IETF has proposed a new set of Internet addresses known as the IPv6 . Technically, IPv4 despite its incumbency is the current Internet networking standard. Numerically, the IPv4 is a 48 -bit addressing scheme. IPv6 addressing encompasses 6 bytes as opposed to the 4-byte IPv4 scheme. To give a relative magnitude of IPv4 addresses versus the proposed IPv6 addresses, the Ipv4 addressing scheme can barely handle the present day worldwide Internet addresses today. IPv6 can handle over 4 billion present day Internet IPv4 addressing schemes. Another more poignant mathematical analogy is that for each square meter of planet Earth, IPv6 can accommodate 1500 unique and distinct IPv6 addresses. Thus it is obvious that the present invention allows for generous IPv6 addressing of readers and cards to no matter what future growth may affect global payments environments.
[0060] Prior art network addressing schemes such as those based upon satellite radio frequency are inferior because they are analog by design. Technically, the radio transmission frequencies must be unique and the integrated circuits must translate a series of sinusoidal waves subject to unpredictable atmospheric conditions into a logically coherent binary stream. Witness the present day problems with cellular networks and the frequency of dropped calls for no apparent reason. Similarly, computer companies such as Microsoft have come up with a proprietary nomenclature of tagging computers. This may be fine within a computer network built exclusively around Microsoft operating systems, but this naming convention is ill-equipped for tagging computer devices, portable devices, and cards all connected via the Internet. The present invention avoids ambiguity and incompatibility of network address schemes and answers the crucial threshold of interoperability across borders.
[0061] [0061]FIG. 2 is a visual layout of the architecture of card reader 102 . Its card slot 240 is where the cardholder inserts card 200 a prior to the specific transaction. The internal components of card reader 102 include uniform expenditure (UEX) assigned code 210 a , merchant ID 210 b , network operating system 210 c , IPv6 address 210 d , and UEX assignment program 210 e . Network OS 210 c reads card 200 a during the authorization process to read the cardholder's account and approve the transaction. For card reader 102 , its UEX assignment program 210 e accepts a single uniform expenditure classification for all transactions processed by card reader 102 , unless and until it is re-programmed with a different UEX code. Terminal ID table 160 from FIG. 1 uses network 120 and network links 130 and 112 to pre-program card reader 102 with a single category selected from a set of UEX categories. One universal set is used for economic units that are households. Another universal set is used for business entities.
[0062] In the preferred embodiment, card 200 a is a plastic, paper, polymer, or other non-metallic wallet-sized card that contains a read-write electronic component. Magnetically encoded stripe 202 on card 200 a processes legacy transactions. Since magnetically-encoded stripes lack read-write programmability, a common choice is a card with an inserted programmable integrated circuit chip 218 , also known as a microcontroller. Microcontroller chip 218 includes microprocessor 220 , random access memory (RAM) 222 , read-only memory (ROM) 224 , non-volatile memory 226 , and a card reader interface 228 . Other elements of microcontroller 218 may include a clock, a random number generator, interrupt control, control logic, a charge pump, and power connections. Card reader interface 228 allows the card to communicate with various electronic devices. Microprocessor 220 is the CPU of card 200 a . RAM 222 stores calculated results as stack memory. ROM 224 has the card's operating system, fixed data, standard routines, and look up tables. Non-volatile memory 226 (such as EPROM or EEPROM) retains information that is not lost when the card is not receiving current through card reader 102 . Such information typically is changeable based on the card or other events, such as a card identification number, a personal identification number, authorization levels, cash balances, credit limits, etc. Card reader interface 228 includes the software and hardware necessary for communication with the outside world.
[0063] The preferred embodiment reaches into ROM 224 to add transaction field software logic 224 a , UEX table 224 b , and a permanent, unique and specific IPv6 global network address in IPv6 224 c . With prior art, holder of cards carries many types of credit cards, loyalty cards, and membership cards in her wallet. Without promoting or discouraging the evolution of multifunctional smart cards, cardholder may use card 200 a to record transactional and payments data, even if the card is not used for actual payment. In this sense, card 200 a may act as an electronic register of all transactions conducted with any type of card, as long as card reader 102 can read and write onto card 200 a . Nonvolatile memory 226 records and stores all such transactions. Later, in FIG. 3, such data is either uploaded or downloaded, which depends on cardholder's needs, and her financial institution's capabilities.
[0064] The present invention also acknowledges the practicality of wireless communications used between card 200 a and card reader 102 . Contact communications require that the cardholder or merchant slide card 200 a into the physical slot 240 found in reader 102 . This type of contact technology is found prevalent in PCMCIA type 2 and type 3 card slots in millions of laptops. Manufacturing tolerances allow for a snug and secure fit for transferring electrical signals between the card and the remaining circuit board. The short range, low power antenna 250 provides a contactless and wireless solution between card 200 a and card reader 102 . By using available surface mount technology and CMOS (complementary metallic semiconductor technology as a part of the physical makeup of chip 218 , wireless communications can be performed without exorbitant signal loss. Sophisticated error correction algorithms can be borne by the card reader 102 , as opposed to chip 218 , to provide an asymmetric, yet reliable communications between the card 102 and the wireless antenna 250 . Industry initiatives such as the Bluetooth 4 meter transmission range and the most robust WIFI 802.11 standards for wireless Ethernet demonstrate that wireless communications augment mobility, flexibility and timely convenience for the end user, merchant, and customer. Further advances of the contactless communications can be extrapolated to watches, calculators, PDAs, cell phones and practically any device that is lightweight, portable and requires relatively small amounts of electrical power to perform the necessary communications and calculations on behalf of the user or customer.
[0065] As technology advances, an alternative embodiment for microcontroller chip 218 in card 200 a dispenses with the use of an integrated circuit chip. Instead, storage would lie in the card 200 a 's substrate as a structural logical arrangement of molecular and atomic structures. This would provide even smaller and cheaper means for processing and storing data.
[0066] In an alternative embodiment, chips containing the suitable memory and processing power for payment transactions do not even need to reside on a card. As long as the chip is retained and managed by the payment initiator, it can reside on or within any other non-metallic medium under the possession and control of the initiator. It could lie in a key ring attachment, token, or piece of jewelry. As discussed above, card reader 102 need not have a physical slot as long as an optical beam can read the contents of the chip. Typically card payments initiated at POS allow convenience to the initiator when she surrenders card 200 a briefly to the merchant for authorization through reader 102 . Still, if the merchant carries a wireless chip reader, the alternative embodiment can reduce fraud because the payment initiator authenticate with the scan and immediately view the merchant's screen details of the actual authorized payment. In prior art, card swiping by the merchant outside of the presence of the payment initiator allows the merchant to save the carbon slip or record the card number for a future, unauthorized payment transaction.
[0067] The embodiment of card 200 a can be an additional feature of a multiapplication chip card, particularly if issuance of the card becomes universal among a large population. Or, even if multiple cards do not, independent of this invention, consolidate into a single-card solution, card 200 a may be totally independent and separately manufactured and circulated. This type of recording card 200 a may be inserted immediately after the primary payment device has been used or presented by the payment initiator, whether by cash, check, payment card, etc. This embodiment can serve the dedicated use of an electronic payment register for the holder as an economic unit. Card 200 a becomes a universal tool for payment data capture with a single requirement. The point-of-payment allows card 200 b to record a UEX code, regardless if the payment channel was cash, check, wireless or other tool or medium for payment.
[0068] With a universal card network platform, special attributes can be attached to all transactions that are processed with the card and even those processed by the issuing bank on behalf of the holder in other bank payment channels used by the same holder. Returning to FIG. 2, after card 200 a is inserted into card slot 240 and accepted by card reader 102 , UEX code assignment 210 a sends a signal to card transaction journal 226 a for the particular uniform expenditure code for the specific transaction. Card 200 b now contains in its non-volatile memory 266 b the card transaction data that includes the expenditure code for the transaction.
[0069] With respect to each outstanding card 200 a , non-volatile memory 226 stores and maintains card transaction journal 226 a . If circulation of card 200 a is limited to a single card for identification and payment purposes by its holder, card 200 a may also serve as a unique and personal identification device for individuals worldwide.
[0070] In FIG. 3A, card 200 b contains card transactions data residing in transaction journal 266 a accumulated over a period of time. Holder of card 200 b has a demand deposit account with financial institution 302 , which has issued to holder card 200 b . This card has ATM capability and houses chip 218 with a configuration according to FIG. 2. Non-volatile memory 266 in card 200 b has a series of payment transactions, categorized according to UEX table 224 b.
[0071] Holder of card 200 b now has three choices to release categorized payment transaction data to a secure site for further processing. First, she may present card 200 b to merchant 310 that has a POS terminal with smart card reader. Prior art includes merchant managed processing or self-service processing of the card transaction. Through telecommunications link 312 , card 200 b may be able to transmit the contents of transaction journal 266 a . However, this embodiment may not be preferable, particular where merchant 310 does not perceive the need to assist holder's financial institution. Where holder chooses to undertake the work with a self-service checkout device under prior art (U.S. Pat. No. 5,992,570), the device does not contemplate uploading multiple transactions data to the bank. The communication is limited to authorization to access credit or payment for a single transaction in question, not for prior transactions.
[0072] The second choice also contemplates prior art. Card 200 b is inserted inside a portable or customer-managed chip card reader 400 that can read smart cards. FIG. 4 contains a partial layout of U.S. Pat. No. 5,559,313 issued to Claus et al. in 1996. Stored expenditure classifications associated with specific items purchased are available as data is passed into holder's PC, laptop, PDA or other consumer appliance. Holder uses personal financial management software to process and analyze such data and generate reports.
[0073] The third and final choice demonstrates the novelty and utility of the present invention. Financial institution 302 owns and maintains a multiapplication ATM that can read smart cards and more particularly, card 200 b . Holder of card 200 b seeks, more often than not, currency from ATM 320 . ATM 320 can perform basic banking functions for holder of card 200 b , who selects key 320 a for deposits, 320 b for withdrawals, and 320 c for account balance inquiries. The key for 320 d allows holder to conduct a variety of retail functions, such as purchasing stamps, entertainment tickets, and transportation cards.
[0074] By frequenting one of financial institution's ATMs for cash at least monthly, if not weekly, holder of card 200 b is assured that with each trip to the ATM, the batched payment transactions data in payment transaction journal 226 c are uploaded to her financial institution through upload process 324 . If multi-purpose ATM 320 opens its data channel, this circumvents the time-consuming and tedious task of using holder's home PC to make an Internet connection to upload transaction data to the institution. Of course, the customer still retains the option of uploading through a device at home than can read transaction data off card 200 b.
[0075] Similarly, card 200 a with read-write capability will, when inserted into ATM 320 , accept bank transaction data during download process 334 , similar in purpose to process 324 . Now holder of card 320 as an updated transaction file with which she may transfer it to card reader 400 attached to her PC or other holder-managed device.
[0076] [0076]FIG. 3B shows why uploading transaction data through the financial institution's ATM network is perhaps superior to using one's own Internet connection. An ATM data upload relies on the financial institution's own high-speed connection 335 (T-1 or higher) to transmit data. Upload process 324 in FIG. 3A is instantaneous and concurrent during a standard ATM transaction. In FIG. 3B, server 330 of financial institution directs data flow. Server 330 posts all card-uploaded transactions through link 345 into Demand Deposit Account Payment/Debit transaction database 340 . If financial institution 302 is also the customer's card issuer, credit card transaction data inside the institution in database 360 can be returned to holder of card 200 a during download process 334 while she conducts a transaction through ATM 320 .
[0077] All the typical steps of transferring data into one's PC for these transactions are common prior art. Bank customer database 350 provides the logical link between the demand deposit account transaction database 340 and credit card transaction database 360 . Upload process 324 and download process 334 in FIG. 3A are immediately commenced upon insertion of card 200 a into card reader 310 , as server 330 's software interrogates customer account database 350 in order to retrieve the timely DDA transaction database 340 and debit/credit card database 360 . This enables proper execution of download process 334 and upload process 324 , which is for all intents and purposes simultaneous for the customer while she is engaged at the ATM.
[0078] Financial institution 302 may also use upload process 324 to capture all transaction data stored on card 200 b , even for transactions not actually processed by the institution. The card 200 a and ATM 320 interface allows the transfer of such data onto universal customer payment database 370 through link 375 . This database sweeps in all payment transactions of customer, whether or not processed by institution 302 , as long as a UEX code 266 a has been assigned by server 330 . Under prior art in U.S. patent application Ser. No. 09965100 filed by Yu, et al. in 2001, server 330 can apply a post-processing filter for payment transactions under universal expenditure categories for household and for business purposes. As transaction data is properly channeled inside financial institution 302 can use server 330 can assemble targeting marketing profiles to enhance their services to customers.
[0079] [0079]FIG. 4 is the prior art where card 200 b is a smart card with tables on its chip for categorized payment transactions. Holder of card 200 b inserts the card is process 380 into PC-attached card reader 400 . Cable 405 connects the reader to customer's PC 410 . U.S. Pat. No. 5,559,313 issued to Claus et al. in 1999 captures smart card classified payments and transfers the data into PC 410 for processing and analysis with PFM software, such as Money® or Quicken®. Personal printer 420 , which is connected by printer cable 415 to PC 410 can generate printed summaries of categorized payments.
[0080] [0080]FIG. 5 shows the hardware and software components of the IPv6 addressing scheme as applied to the network of cards and devices within the present invention. Server 180 is the IPv6 address allocator and master repository of all IPv6 addresses used in the payment system. There will be a pool of available addresses to assign to each set of newly minted card 200 a . For example, an arbitrary Ipv6 address might be CC00:0002:1111:5555:0222:0001:767A:2222. Once this address is assigned, server 180 will keep a separate database table for assigned IPv6 addresses for smart cards. IDE (Integrated Development Environment) 730 is readily available from Gemplus, Hypercom and VeriFone. The newly manufactured card 200 a before a card customer uses it, will have burned into the non-volatile memory 226 a the unique IPv6 address of BB.09.09.11.22.01. Similarly, IDE 140 may be from Hypercom, Ingenico (Fr) and VeriFone. The IDE 730 will download IPv6 address CC00:0002:1111:5555:0222:0001:767A:2222 onto non-volatile memory 224 c on card 200 a . This is done before the card from the cardholder's financial institution is sent for personal or business use. Globe 1000 contains the universe of assigned unique IPv6 network addresses. Conceivably, there can be several IPv6 addresses for each person, business establishment, legal entity, and economic unit, with an immutable IPv6 address for device and card they own and carry.
[0081] Wherever there is a human being as an economic unit, a single, uniquely addressed chip card may be assigned by a bank or government entity or ministry within each jurisdiction. Under the embodiment of the present invention, the security advantages to government and business of unique addresses for every person will need to be balanced against the legitimate privacy concerns of the individual.
[0082] This invention embodies using the uniqueness and extensibility of the IPv6 address as also a bona fide database key into a banking payment system. As described above, the Ipv6 address provides ample logical space to identify individual physical smart cards 200 a and use the same key as a logical view port of the UEX tables for payment classification.
[0083] While the card system described herein is the preferred embodiment of the present invention, the claimed invention is not limited to the precise description in any way, and that changes may be made to the embodiment without limiting the scope of the invention as described in the claims that follow. | Uniquely identified chips on portable payment devices can categorize customer transactions under universal sets of expenditure categories for household and business use based on certain characteristics of card readers that process payments. The expansive storage on the payment cards allows holders to upload batched transaction data derived from prior payment transactions by interfacing the cards into on-site and off-site ATMs that are linked to their card issuer or financial institution. Similarly, those same cards can use the properly linked ATM to download from the institution categorized payments data onto the storage medium inside the cards. This data would then be transferred through a card reader into the holder's own maintained transaction databases residing in a PC, laptop or other enabling appliance in her possession. To facilitate unique global addressing of card, card readers, and holders themselves, each component of the extended payment network all the way to the payer is identified with a unique global network addresses. This enhances overall security within the economy as well as efficient flow and assignment of categorization labels to payment transactions. | 6 |
CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit under 35 U.S.C. §371 of published PCT patent application number PCT/EP 2011/063301, filed Aug. 2, 2011, claiming priority to French patent application number FR1056578 filed on Aug. 12, 2010, and published as WO2012/019944 on Feb. 16, 2012, the entire contents of which is hereby incorporated by reference herein.
TECHNICAL FIELD OF INVENTION
The present invention relates to a control panel, in particular for a motor vehicle, having resistive keys.
BACKGROUND OF INVENTION
The present invention relates more particularly to a control panel intended to be arranged in the passenger space of a motor vehicle, in particular on the dashboard, and which includes at least one control button in the form of a resistive key designed to control a determined function, for example to control starting or stopping of the air-conditioning function.
The control panel includes a cover which is mounted on a support and which is provided with at least one detection zone designed to form a control button. A force sensor is arranged between the cover and the support, behind the detection zone, so as to produce an electrical control signal when a user applies a sufficient pressure force to the detection zone.
To compensate for the mechanical plays between the force sensor and the detection zone, it is known to arrange a spacing plate made of elastomeric material between the force sensor and the cover that must allow a direct transmission of the tactile pressure force to the force sensor via the spacing plate to be ensured under all circumstances. To this end, the spacing plate is mounted axially compressed between the force sensor and the cover.
To allow the detection of the tactile pressure, it is necessary for the thickness of the cover in the detection zone to be relatively small so as to allow a slight elastic deformation of the cover towards the sensor on tactile pressure. Now, the mounting of the spacing plate in compression between the sensor and the cover tends to cause a permanent outward deformation of the cover at the level of the spacing plate that degrades the external appearance of the cover. Moreover, the distribution of the pressure over the spacing plate is not even, the pressure generally being mainly on the outer peripheral edge of the spacing plate.
These disadvantages are particularly prejudicial in applications subject to large temperature variations, as in a motor vehicle, which can result in a loss of pressure on the spacing plate.
SUMMARY OF THE INVENTION
The present invention is intended to remedy the disadvantages mentioned above by proposing a simple, effective and economic solution.
To this end, the invention proposes a control panel, in particular for a motor vehicle, including a cover which is mounted on a support and which is provided with at least one zone for detection of a tactile pressure forming a control button, in which a force sensor having a zone sensitive to pressure is arranged between the cover and the support, behind the detection zone, so as to detect the actuation of the control button to produce an electrical control signal when a user applies a determined tactile pressure force to the detection zone, the tactile pressure force being transmitted axially to the sensitive zone via a spacing plate made of elastically compressible material which is inserted between the sensor and the cover, characterised by the fact that the inside surface of the cover includes a series of relief elements which are distributed over the inside surface of the cover opposite the sensitive zone so as to form a plurality of localised zones of increased pressure on the spacing plate, the said localised zones of increased pressure being uniformly distributed so that the spacing plate applies a substantially even pre-stressing force over the sensitive zone.
The invention is particularly advantageous as it allows mounting to be effected in which the residual axial pressure applied to the force sensor at rest, i.e. in the absence of tactile pressure, is lesser. Thus, the force sensor is mounted without excessive compression between its support and the cover with the spacing plate, which reduces the risks of distortion of the materials forming the assembly.
In the case of a force sensor operating with a prestress, the prestress produced by the pressure of the spacing plate on the sensitive zone of the sensor can be appropriately adjusted over the whole surface of the spacing plate by means of the relief elements, without having to apply a high pressure to guarantee that the prestress is sufficient.
In accordance with other advantageous characteristics of the invention: at least one of the relief elements has an axial thickness which varies in a transversal direction so as to compensate for the variations in intensity of the pressure force at rest of the cover on the spacing plate along the said transversal direction; the cover has a curved profile in the detection zone, and the axial thickness of the relief elements varies proportionally to the curvature of the cover relative to the support; the relief elements are separated from each other by interstitial spaces so as to allow sufficient flexion of the detection zone of the cover when a tactile pressure force is applied; the relief elements are formed of ribs; the relief elements are arranged in at least one line which is substantially parallel with the external outline of the sensitive zone; the relief elements are formed in one piece with the cover; the force sensor is of the type with detection of a variation in electrical resistance between conductive tracks; it includes a plurality of detection zones forming a plurality of control buttons associated with a plurality of force sensors, each force sensor including a spacing plate and a series of associated relief elements; the axial thickness of the relief elements is generally increasing in the transversal direction, from the periphery of the portion including the detection zones to a central part of the said portion; a small plate made of more rigid material than the material forming the spacing plate is inserted between the spacing plate and the sensitive zone of the sensor in order to contribute to even distribution of the prestressing force and the tactile pressure source over the sensitive zone of the sensor.
BRIEF DESCRIPTION OF DRAWINGS
Other characteristics, aims and advantages of the invention will become apparent on reading the following detailed description and taking into account the attached drawings, given as a non-limiting example and in which:
FIGS. 1 and 2 are exploded perspective views which show diagrammatically a control panel fitted with resistive keys provided with force sensors and with spacing plates in accordance with a first embodiment of the invention;
FIG. 3 is a partial view in axial section which shows diagrammatically the structure of a force sensor with which the control panel of FIGS. 1 and 2 is fitted;
FIG. 4 is a view from above which shows diagrammatically a film carrying a plurality of force sensors designed to be fitted to the control panel of FIGS. 1 and 2 ;
FIG. 5 is an exploded perspective view which shows diagrammatically a second embodiment of a control panel in accordance with the teachings of the invention;
FIG. 6 is a view in axial section through the plane 6 - 6 of FIG. 5 which shows diagrammatically the cover of the control panel of FIG. 5 and the relief elements with which it is fitted;
FIG. 7 is a diagram showing the distribution of the pressure applied by the cover to the spacing plate of a force sensor within the framework of a control panel of the prior art;
FIG. 8 is a diagram similar to that of FIG. 7 showing the distribution of the pressure applied by the cover to the spacing plate of a force sensor within the framework of a control panel in accordance with the second embodiment of the invention shown in FIG. 5 ;
FIG. 9 is a perspective view from below of the cover of a control panel in accordance with a third embodiment in which the axial thickness of the relief elements varies;
FIG. 10 is a view in axial section through the plane 10 - 10 of FIG. 9 which shows diagrammatically the cover of the control panel of FIG. 9 ;
FIGS. 11 and 12 are perspective views from below of the cover of a control panel in accordance with modified embodiments in which the arrangement of the relief elements is different.
DETAILED DESCRIPTION
In the remainder of the description, identical or similar elements can be designated by identical references.
FIGS. 1 and 2 show a control panel 10 for a motor vehicle dashboard formed in accordance with a first embodiment in accordance with the teachings of the invention. It here includes a cover 12 which is mounted on a support 14 , the outside surface 16 of the cover 12 including a plurality of detection zones Z 1 , Z 2 , Z 3 , Z 4 , Z 5 of a tactile pressure forming a plurality of control buttons B 1 , B 2 , B 3 , B 4 , B 5 , or resistive keys.
In the remainder of the description, an axial orientation will be used in non-limiting manner along an axis X 1 substantially at right-angles to the general plane of the cover 12 , orientated from the bottom towards the top, i.e. from the support 14 towards the outside surface 16 of the cover 12 , which generally corresponds to an orientation from the bottom towards the top considering FIGS. 1 and 2 .
Each control button B 1 , B 2 , B 3 , B 4 , B 5 here includes a force sensor 18 that is arranged between the cover 12 and the support 14 , behind and axially opposite the associated detection zone Z 1 , Z 2 , Z 3 , Z 4 , Z 5 . Each force sensor 18 is designed to detect the actuation of the associated control button B 1 , B 2 , B 3 , B 4 , B 5 to produce an electrical control signal when a user applies a tactile pressure force of sufficient intensity to the associated detection zone Z 1 , Z 2 , Z 3 , Z 4 , Z 5 .
In accordance with an advantageous characteristic of the invention, each force sensor 18 is of the type with resistance variable as a function of the force, for example of the FSR (force sensing resistor) type as described and illustrated in the documents US2006/0007172A1 and WO2009/070503A1 which are incorporated here by reference.
Preferably, a force sensor 18 mounted under mechanical prestress is used here, as has been shown in FIGS. 3 and 4 . The force sensor 18 here includes a first 20 and a second 22 substrate at least one of which is flexible when a tactile pressure force is applied to the associated detection zone Z 1 , Z 2 , Z 3 , Z 4 , Z 5 . Electrical conductive tracks 24 , 26 are arranged, for example in the form of interdigitated combs, on a face of the first substrate 20 opposite a resistive coating 28 arranged on the opposite face of the second substrate 22 , so as to define a zone sensitive to pressure 30 which is generally superimposed on the associated detection zone Z 1 , Z 2 , Z 3 , Z 4 , Z 5 . In the rest state of the force sensor 18 , in the absence of tactile pressure force, the resistive coating 28 is in electrical contact with portions of conductive tracks 24 , 26 .
Advantageously, the five control buttons B 1 , B 2 , B 3 , B 4 , B 5 being positioned in substantially adjacent manner on the cover 12 , it is possible to arrange the five associated force sensors 18 on the same substrate 20 , 22 . Thus, as shown in FIGS. 1 , 2 , and 4 , the force sensors 18 are in the form of a film 32 including an electrical connection ribbon 33 designed to allow the connection of the five sensors 18 to an electronic control unit (not shown).
In accordance with the embodiment shown, a spacing plate 34 made of elastically compressible material is mounted between each sensor 18 and the cover 12 , opposite the detection zone Z 1 , Z 2 , Z 3 , Z 4 , Z 5 so as to take up the mechanical plays between the sensor 18 and the cover 12 . Preferably, the five spacing plates 34 provided for the five sensors 18 are all formed by molding in a same plate 36 made of silicone or of elastomeric material.
It will be noted that, due to the rigidity of the cover 12 in the detection zone Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , the operating plays, i.e. the axial displacements of the cover 12 in the detection zone, can be less than the mechanical plays. The spacing plate 44 therefore allows the mechanical plays to be taken up to allow the detection of the axial displacements X 1 of the cover 12 due to tactile pressures.
In accordance with the embodiment shown, an intermediate plate 38 is arranged between the support 14 of the cover 12 and the film 32 carrying the force sensors 18 . The intermediate plate 38 , which is fixed on the support 14 , forms a support for the force sensors 18 . It is preferably made from a sufficiently rigid material, for example polycarbonate (PC) or methyl polymethacrylate (PMMA) to allow the mounting of the force sensors 18 in prestress, i.e. to allow the force sensors 18 to be axially compressed between the intermediate plate 38 and the cover 12 with interposition of the small plate 36 between the force sensors 18 and the cover 12 .
In accordance with the teachings of the invention, the inside surface 40 of the cover 12 includes a series S 1 , S 2 , S 3 , S 4 , S 5 of relief elements 42 which are distributed over the inside surface of the cover 12 , opposite the sensitive zone 30 , so as to form a plurality of localized zones of increased pressure 44 on the spacing plate 34 , as will be explained in more detail in relation to FIGS. 7 and 8 and with the second embodiment shown in FIG. 5 .
FIGS. 5 and 6 show diagrammatically a second embodiment of the control panel 10 in accordance with the invention in which the mounting of the force sensors 18 is simplified because the film 32 provided with the force sensors 18 rests directly on the upper face of the support 14 . Moreover, the general shape of the control panel 10 is here generally parallelepipedal which allows the characteristics of the invention to be revealed. Of course, the control panel 18 could adopt any shape suited to its arrangement in the passenger space of a vehicle.
In the example embodiment shown, the control panel 10 includes six detection zones Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 and therefore six series S 1 , S 2 , S 3 , S 4 , S 5 , S 6 of associated relief elements 42 . The detection zones are here all identical and of rectangular shape. Of course, the control panel 10 could include detection zones of distinct shapes, these shapes having in particular to be suited to the ergonomic requirements of the controls.
FIG. 7 shows the distribution of the pressure applied by a conventional cover 12 , having no relief elements, on a spacing plate 34 and FIG. 8 shows the distribution of the pressure applied by the cover 12 fitted with relief elements 42 in accordance with the invention on the spacing plate 34 . As can be seen, in the case of the prior art, the pressure is mainly applied to the periphery of the spacing plate 34 and at four localized points in the proximity of the center of the spacing plate 34 . Contrarily, in the case of the invention, the distribution of the pressure on the spacing plate 34 is better distributed due to the multiplicity of the relief elements 42 the positioning and distribution of which are so selected as to optimize the distribution of the pressure and thus allow the spacing plate 34 to apply a substantially even pressure over the sensitive zone 30 of the pressure sensor 18 . Thus, in the example shown, the relief elements 42 are made in the form of ribs spaced apart from each other and arranged in a rectangular line substantially parallel with the rectangular outline of the spacing plate 34 and of the sensitive zone 30 . Here there are eight ribs that produce eight localized zones of increased pressure 44 .
Due to the distribution of the relief elements 42 and therefore the optimized distribution of the localized zones of increased pressure 44 , the prestressing force applied by the spacing plate 34 to the sensitive zone 30 of the force sensor 18 is more even. The elasticity and the flexibility of the material forming the spacing plate 34 contribute to transmission and substantially even distribution of the prestressing force from the cover 12 and its relief elements 42 to the sensitive zone 30 .
Advantageously, the interstitial spaces 46 between the relief elements 42 are designed to allow sufficient flexion of the detection zone Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 of the cover 12 when a tactile pressure force is applied, preventing the relief elements 42 from making the cover 12 excessively rigid in the detection zone Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 .
The number and the dimensions of the relief elements 42 and of the interstitial spaces 46 can be adjusted depending on the pressure distribution and flexibility requirements of the detection zone Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 .
As can be seen in FIG. 6 , the cover 12 includes a thin portion 48 , here defining a rectangular zone in which the adjacent detection zones Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 are arranged. This thin portion 48 offers a greater flexibility than the other zones of the cover 12 to allow the detection of the tactile pressures by the force sensors 18 .
Due to the location of the fixing points of the cover 12 on the support 14 on the periphery of the thin portion 48 and due to the flexibility of this thin portion 48 which deforms, the pressure applied by the cover 12 to the spacing plates 34 tends to be higher at the periphery of the thin portion 48 relative to the center of the thin portion 48 .
Also, to further improve the evenness of the prestressing force on the force sensors 18 , the invention proposes in a third embodiment shown in FIGS. 9 and 10 , adjustment of the axial thickness of the relief elements 42 depending on their position relative to the periphery of the thin portion 48 . Thus, considering the view in axial section of FIG. 10 , it is found that in each series S 1 , S 3 , S 5 , the axial thickness of the ribs 42 is increasing in a transversal direction X 2 from the periphery of the thin portion 48 to its center. This arrangement in accordance with the invention allows compensation for the pressure differences applied by the cover 12 to the spacing plates 34 .
In accordance with a modified embodiment (not shown), the thickness of the relief elements 42 can also be adjusted so as to compensate for the effects of a curvature of the cover 12 in the case of a cover 12 having a particular non-rectilinear transversal profile.
Preferably, the relief elements 42 are made in one piece with the cover 12 , for example by molding.
In accordance with modified embodiments, shown in particular in FIGS. 11 and 12 , the relief elements 42 can have different forms, for example the form of ribs arranged in a circle, as in FIG. 11 , or ribs arranged in a cross, as in FIG. 12 .
The relief elements 42 could adopt forms other than ribs. However, the choice of ribs has the advantage of allowing easy manufacture, including by molding, while permitting a certain precision and great freedom in the positioning of the localized zones of increased pressure 44 . Moreover, the ribs allow these effects to be obtained without causing detrimental stiffening of the cover 12 in the detection zones Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 .
Advantageously, to obtain a yet more uniform distribution of the pressure over the sensitive zone 30 , each spacing plate 34 can be provided on its lower surface with a small plate made of material more rigid than the elastomeric material forming the spacing plate 34 . The small plate is for example made of relatively rigid thermoplastic material, compared to the elastomeric material forming the spacing plate 34 . The small plate can be made by over molding with the said spacing plate 34 . Each small plate extends generally over the whole area of the associated sensitive zone 30 to distribute the pressure over the whole of the sensitive zone 30 .
The control panel 10 has been described here with a plurality of control buttons B 1 , B 2 , B 3 , B 4 , B 5 . Of course, the invention applies to the modified embodiments that would include a single control button or a different number of control buttons.
While this invention has been described in terms of the preferred embodiments thereof, it is not intended to be so limited, but rather only to the extent set forth in the claims that follow. | A control panel comprising a cover that is equipped with at least one zone for detecting tactile contact forming a control button, in which a force sensor comprising a pressure-sensitive zone is arranged between the cover and the support so as to detect actuation of the control button, the force of the tactile contact being transmitted axially to the sensitive zone via a spacer plate made of an elastically compressible material that is inserted between the sensor and the cap, characterized in that the internal surface of the cap comprises a series of protruding elements that are distributed over the internal surface of the cap opposite the sensitive zone so as to form a number of regularly distributed zones of localized overpressure. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates generally to knitting machines and, more particularly, to knitting machines that can electromagnetically select the needles in the machine.
2. Description of the Prior Art
There are presently known knitting machines of the type in which sliding selection devices can occupy two different positions, that is, can be either in the active position or the inactive position. U.S. Pat. No. 4,481,793 describes such a knitting machine in which each needle may be selected electromagnetically according to the so-called "three-track" technique, in order to execute different designs or shapes. In that three-track system, the needles may be controlled individually to place them into a working position, a tucking position, or an out-of-action position. To accomplish this, the sliding devices are each movable into two different positions by electromagnetic selection stations and are juxtaposed in pairs, one pair per needle, by means of a so-called two-arm lever.
There is also known from Swiss Pat. No. 641,852 a knitting machine in which the sliding devices are arranged to cooperate with each needle by a two-arm lever, but in that case the two-arm levers may occupy three different positions.
In both of these cases, the two-arm levers are arranged in such a way as to occupy three different positions corresponding to the desired three different needle positions.
One drawback in this known "3-track" solution is that it does not allow for the addition of any supplementary "track".
Swiss Pat. No. 448,358 describes a mechanical device applied to rectilinear knitting machines that have stitch cams with two working faces in tiers, or arranged in a staggered fashion, in which the needle butts of the jacks activate the needles which may be placed in contact, at will, by a known selector mechanism. The needle butts that are engaged with one of the two tier faces are used to make regular or standard stitches, and the butts engaged with the other face are used to make lengthened stitches.
OBJECT AND SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide an electromechanical needle selection apparatus that can eliminate the above-noted drawbacks inherent in the prior art.
In effect, the purpose of this invention is to supply a supplementary possible selection by appropriate devices to have, for instance, a machine permitting knitting of lengthened stitches as desired so that the supplemented length thus obtained may make it possible to transfer stitches from one needle bed to another, particularly at the edges and at cables.
The arrangement of a supplementary selection possibility, according to the invention, may also be used to obtain a machine which permits incorporation within the known "3-track" positions of a supplementary position in the form of a "stitch transfer" position.
In accordance with an aspect of the present invention, a knitting machine is provided with electromagnetic selection of needles and with a stitch transfer capability, the machine being of the kind including needle beds arranged in pairs having grooves in which are located the needles and the needle selectors. The needles are capable of being positioned either at the level of the needle bed or above it and the selectors are provided with needle butts that can be positioned at different levels in relation to the needle bed, as well as in different positions along the grooves. Electromagnetic selector stations are provided to operate sliding devices to occupy two different positions, with a pair of sliding devices provided for each needle. Fixed vertical cams are formed on the knitting carriage and cooperate with specifically arranged two-arm levers that accomplish the needle selection. The two-arm levers are so constructed and arranged such that they can be oriented in four different positions by action of the sliding devices, which include two lower selectors. These two lower selector elements are activated in such a way as to produce the four positions of the two-arm levers.
The above and other objects, features, and advantages of the present invention will become apparent from the following detailed description of illustrative embodiments thereof to be read in conjunction with the accompanying drawings, in which like reference numerals represent the same or similar elements.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an elevation in partial cross section of a needle bed, illustrating a "tuck" selection;
FIG. 2 is a schematic representation of a knitting cam box with two knitting systems, including vertical cams, stitch cams in tiers, and selection stations in conjunction with a knitting carriage;
FIG. 3 is a portion of FIG. 2 on a larger scale, illustrating different needle selections;
FIG. 4 is an elevation in partial cross section similar to FIG. 1, illustrating an "off" selection;
FIG. 5 is a plan view along arrow C in FIG. 4;
FIG. 6 is an elevation in partial cross section similar to FIG. 1, illustrating a selection for "knitting lengthened stitches";
FIG. 7 is a plan view along arrow D in FIG. 6;
FIG. 8 is an elevation in partial cross section similar to FIG. 1, illustrating a selection for "normal stitch knitting;"
FIG. 9 is a plan view along arrow E in FIG. 8;
FIG. 10 is a simplified view of a needle butt engaged with a recessed tier of a stitch cam for "knitting normal stitches;"
FIG. 11 is a simplified view corresponding to FIG. 10, wherein the needle butt is engaged with the forward tier of the stitch cam for "lengthened stitch knitting."
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The needle bed 1 of FIG. 1 is of the kind found in a rectilinear knitting machine, which generally has two needle beds arranged in pairs in an inverted V shape, and which has several parallel grooves 2. In each groove 2 is arranged a needle 3 connected to a jack 4, a two-arm lever 5, and a tuck selector 6. Jack 4 is composed of a flexible arm 7, which has a butt 8 generally at the middle of jack 4 and a sliding foot 9 at the distal end of needle 3. Groove 2 is deepened toward the back of the needle bed, which is toward the right in FIG. 1, and thereby forms two slide faces 11 and 12 on which needle 3 and gliding foot 9 slide, respectively. Needle 3 includes a needle hook 13 with a latch 14 in the known manner, and jack 4 has a retaining lug 15. The needle can be placed permanently in the out-of-action position manually by driving needle butt 8 of jack 4 in groove 2 so that a retaining lug 15 located behind butt 8 passes under a wire 16, which keeps jack 4 in this position and the needle inactive as long as no manual displacement is made.
The two-arm lever 5 pivots on pin 18, which is rigidly connected to needle bed 1, and has an upper arm 19 and a lower arm 20, which together form a fork in which tuck selector 6 is guided. Lower arm 20 makes contact with flexible arm 7 of jack 4 between retaining lug 15 and gliding foot 9 of jack 4. Two-arm lever 5 also is provided with a feeler 21, diametrically opposite the fork with respect to pivoting pin 18. A limiting wire 22, which is rigidly attached to needle bed 1, limits a farthest rotary position of said two-arm lever 5 in the clockwise direction. Tuck selector 6 can slide lengthwise over a distance limited by lug 23 acting on nose 24 of tuck selector 6, that is, it abuts the flank of butt 25 of tuck selector 6. This butt 25 may or may not work with cam track 26, as will be described in detail below.
An auxiliary needle bed 27 is mounted on needle bed 1, in the rearmost extensions of grooves 2, and it has several grooves 28 that are double in number to the number of grooves 2 of needle bed 1. In grooves 28 are arranged slide devices in the form of a first lower selector 29a and a second lower selector 29b, alternating in juxtaposition and retained vertically by wires 30 and 31, which are rigidly attached with auxiliary needle bed 27. An upper selector 32 is also part of the sliding devices is arranged on each lower selector 29a or 29b, respectively.
For each needle bed there is a cam box 33, as shown in FIG. 2, composed of a first knitting system 34 and a second knitting system 35. Each cam box 33 has fixed cams 36, 39, and 41, and stitch cams 37 that are movable in a plane parallel to the cam box. Stitch cams 37 are arranged in tiers permitting the needle butts to traverse in regular or special operation. Lifting cams 40 are provided and are movable only in a plane perpendicular to the cam box. Lifting cams 40 may be placed into a remote or closer position with respect to their needle bed, at the operator's option, and these positions are changed only for the operation of transferring stitches. Fixed vertical cams 42, as shown FIG. 1, are provided for each knitting system, and these comprise fixed cams 42a and 42b for knitting system 34 and cams 42b and 42c for knitting system 35 of FIG. 2. It will be appreciated that fixed vertical cam 42b works with both knitting systems.
In FIG. 2, a cam track 26a, 26b is shown provided for each knitting system, and these tracks are formed by upper cams 43a and 43b and lower cams 44a and 44b, respectively. Each cam track 26a and 26b has, respectively, at its inlet and at its outlet funnel-shaped entries 45, an ascending portion 46a and a descending portion 46b, in the direction of movement of the cam boxes.
Furthermore, a fixed vertical cam 47, as shown, is provided for each knitting system and comprises a vertical cam 47a pertaining to knitting system 34 and a vertical cam 47b pertaining to knitting system 35, as shown in FIG. 2. Each knitting system is directly preceded, as seen from the direction of movement of the cam boxes, by a selector station, as shown in FIG. 2. When the cam boxes are displaced in the direction indicated by arrow A, selector station 48 precedes knitting system 34 and selector station 49 precedes knitting system 35. During movement in reverse, selector station 50 precedes knitting system 35 and selector station 49 precedes knitting system 34. Thus, selector station 49 is provided to work with both knitting systems 34 or 35, depending on the direction of movement of the cam boxes.
Each selector station 48, 49, and 50, as shown in FIG. 3, has a base plate 51 on which are mounted two identical selection half-stations 52 and 53 to form the selector channel in which the upper selectors 32 of FIG. 1 move. This arrangement is intended to accommodate travel in either direction. In this example, the upper selectors 32 move with respect to the knitting system in the direction shown by arrow A. The selector channel has an entry which narrows down and is bordered by flanks 55 and 56 and by a selection point that is defined as the narrowest point of the channel between poles 57 and 58 of the selector electromagnets (not shown). The selector channel also has an outlet which widens and is bordered by the selector point and by flanks 61 and 62.
To select any needle freely without restriction, either in the out-of-action position, the tuck position, the regular stitch in-action position, or in the lengthened stitch in-action position, the operator makes his selection of the two different positions available for upper selectors 32, two of which are provided for each needle 3. The two different positions are attained if either one of the selector electromagnets is excited and the upper selector 32 is at the narrowest portion of the channel against its pole 57 or 58. Then, the selector follows side 61 or 62 and is drawn by magnetic attraction outside the longitudinal symmetric plane of the selector station.
Upper selector 32 is mounted on lower selector 29a or 29b (FIGS. 4, 6, and 8). The latter must therefore follow the movements of the former and, thus, occupies one of the two different positions described above. The left or inner end of the lower selector 29a has a contact face 64a located at an upper level relative the bottom of groove 28, connected by a flexible arm 68 to central portion 70, as seen in FIGS. 1, 4, 6, and 8.
Lower selector 29b is juxtaposed to lower selector 29a and separated by a non-magnetic track wall 72, as shown in FIGS. 5, 7, and 9. Its left or inner end has a contact face 64b located at a lower level relative to the bottom of groove 28. Also, a broadened end 69 is added to the same end of lower selector 29b, in the direction of the lower selector 29a, and enables the operator to adjust the level of contact face 64a of lower selector 29a, as shown in FIG. 5.
The two lower selectors 29a and 29b each act on the same two-arm lever 5 through a broadened end 73 of a notch 67 formed in the end of two-arm lever 5 opposite arms 19 and 20. This broadened end 73 is shown in FIGS. 5, 7, and 9 is located opposite the left ends of lower selectors 29a and 29b.
In order to aid understanding of the present invention, the principle of needle selection in "four tracks" will be described with reference to the drawings. Considering FIGS. 1 and 3, assume that the cam boxes are moved in the direction of arrow A, and that selectors 32 are in a "working" position being so placed by selector station 48 during the previous passage of the cam boxes in the opposite direction. Fixed vertical cam 42a presses on all the lower butts 66 of the tuck selectors 6, against a spring effect of spring 65 and of the flexible arm 7 of jack 4. For this reason, every two-arm lever 5 revolves around its axis 18 and notch 67 of the two-arm lever 5 is above the left end of lower selector 29a or 29b.
Selector station 48 displaces upper selectors 32 in the two different positions, and once the selection has been made, fixed vertical cam 42a is bypassed under the action of spring 65 and flexible arm 7 of jack 4, and the two-arm levers 5 tend to revert to their positions according to FIG. 1.
Lower selectors 29a and 29b, the upper selectors 32 of which are selected at 32a, have their left ends advanced so that notches 67 abut contact faces 64a of lower selectors 29a which in turn come into contact with the broadened end 69 of the lower selectors 29b, thus preventing two-arm levers 5 from returning, as represented in FIG. 4. Needle butts 66 of the corresponding pins will remain pushed inside needle bed 1 and thus be in position 8a of FIG. 3. The corresponding needles 3 will be out of action.
Lower selectors 29a, for which the upper selectors 32 are selected at 32a, will have their left ends pushed back and lower selectors 29b, for which the upper selectors 32 are selected at 32b, will have their left ends advanced, so that notches 67 abut contact faces 64b, as shown in FIG. 6. Their two-arm levers 5 thus return to a medium position where they do not press any more on flexible arms 7 of jack 4, so that the corresponding needle butts 8 completely come out of needle bed 1 and will be engaged by the cams of the knitting system 34, but above all by the stitch cams that are arranged in tiers. See position 8c of FIG. 3. Thus, the corresponding needles 3 will form lengthened stitches.
Lower selectors 29a, the upper selectors 32 of which are selected at 32b, will have their left ends advanced, and lower selectors 29b, the upper selectors 32 of which are selected at 32a, will have their left ends pushed back, so that notches 67 will abut contact faces 64a, as shown in FIGS. 8 and 9, in a lowered position because of the flexible arm 68 of the lower selectors 29a. Thus, two-arm levers 5 will return to a second medium position where they press again partially on flexible arms 7 of jacks 4, so that the respective needle butts 8 partially come out of needle bed 1 and will be engaged by the cams of knitting system 34. See position 8b of FIG. 3. Thus, the corresponding needles 3 will form regular or standard stitches.
Lower selectors 29a and 29b, the upper selectors of which are selected at 32b, will have their left ends pushed back so that they are beyond the reach of notches 67, as shown in FIG. 1. Thus, their two-arm levers 5 will return to the position shown in FIG. 1, under the pressure of spring 65. These two-arm levers 5 no longer press on their jacks 4 which are therefore engaged by the cams of the knitting system. Butts 25 of the corresponding tuck selectors 6 follow the path of cams 26a, shown in FIG. 3, and they ascend into the ascending portion 46a, so that their lower butts 66 are pushed into the operational area of fixed vertical cam 47a and according to the same principle as vertical cam 42a, it presses on lower butts 66 of the respective tuck selector 6. Needle butt 8 of the corresponding jack 4 is momentarily pushed down and assumes position 8d of FIG. 3. Once released by vertical cam 47a, the descending portion 46b replaces tuck selector 6 into its position shown in FIG. 1 and needle butt 8 of jack 4 returns into the operational area of the cams and is pushed down by stitch cam 37. The needles so selected will tuck the yarn. The same process takes place for the second knitting system, in this case knitting system 35, by means of fixed vertical cam 42b of selector station 49 and of vertical fixed cam 47b.
FIG. 10 represents the relationship between butt 8 on needle jack 4 and a stitch cam 37. More specifically, butt 8 is engaged with the recessed tier of stitch cam 37 and this position corresponds to the operation for "knitting normal stitches."
Similarly, FIG. 11 represents a different engagement between butt 8 and stitch cam 37 in which the needle butt 8 is engaged with the forward tier of the stitch cam. In this position the "lengthened stitch knitting" operation is provided.
By a judicious combination of the individual position of the paired selectors acting on the same needle, four different positions are obtained for each two-arm lever and, thus, four selected positions of the needle for a single passage of the knitting system. In principle, it is unimportant of the idea of the invention that instead of and in place of the individual selection of needles making lengthened stitches, it is possible also to choose another application of individual selection thus created, for instance by combining in one cam box and one run of the needles the four positions: knitting, tucking, out-of action, and transfer of stitches, without any restriction.
The above description is given on the preferred embodiments of the invention, but it will be apparent that many modifications and variations could be effected by one skilled in the art without departing from the spirit or scope of the novel concepts of the invention, so that the scope of the invention should be determined by the appended claims only. | In a knitting machine, electromagnetically controlled selector stations cooperate with sliding devices to enable them to assume two different positions. The sliding devices act in pairs on each needle of the knitting machine, and fixed vertical cams act on so-called two-arm levers to release them after selection, with the two-arm levers being retained or not by the sliding devices. Provision is made so that the two-arm levers can be oriented in four different positions. Each pair of sliding devices is composed of a first lower selector and a juxtaposed second lower selector, each of which can be moved into two different positions so as to produce the different four positions of the two-arm levers, in this way the needles may be controlled individually into tucking, out-of-action, standard knitting, and lengthened stitch knitting positions. | 3 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present invention claims priority of Korean Patent Application No. 10-2008-0131661, filed on Dec. 22, 2008, which is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates generally to an educational system and method using virtual reality; more particularly, to an educational system and method, which implement a virtual space in which students located in a classroom and a lecturer located at a remote place appear, thus supporting learning which allows the students to interact with virtual reality content while the students feel as if they were immersed in learning content.
BACKGROUND OF THE INVENTION
[0003] Recently, the importance of an education having a basis in reality has been emphasized for the learning of foreign languages and the like. Accordingly, some public institutions provide a learning space by establishing English villages for experience-based English learning or the like. However, a lot of people cannot access the English village due to the spatial restrictions thereof. Accordingly, efforts to overcome this problem using electronic learning (e-learning) services recently introduced with the development of information communication technology, that is, remote video education and a virtual classroom enabling learning in an Internet-based virtual learning space, have been made.
[0004] However, remote video education is disadvantageous because it provides a method for learning that has only a simple format. Further, a virtual classroom has a problem in that learning is mainly conducted using an avatar rather than the student him or herself, so that it is difficult for the student to have a sense of reality or immersion as if he or she were really appearing in the virtual space. Such a conventional technology is configured such that an image of a lecturer at a remote place or an image of a student is simply projected to a preset location on a screen and such that a background is simply changed, thus making it difficult to efficiently provide virtual reality-based education having a reality.
[0005] Therefore, an educational system and method capable of providing experience-based education while overcoming spatial restrictions using computer technology are currently required.
SUMMARY OF THE INVENTION
[0006] In view of the above, the present invention to provide an experience-based educational system and method, which implement virtual reality and provide an interface for recognizing the gestures of a user and interacting with the user, thus increasing the sense of reality of the education.
[0007] Further, the present invention provides an experience-based educational system and method, which allow a user located at a remote place and a user located in a classroom to share a single virtual world with each other without simply changing the background of a screen, thereby increasing a sense of immersion of a student in learning.
[0008] In accordance with a first aspect of the present invention, there is provided an educational system using virtual reality, including: an image computer for extracting an image of a student from an entire image acquired by capturing the student; a remote lecturer computer for extracting an image of a lecturer at a remote place from an entire image acquired by capturing the remote lecturer; a classroom lecturer computer for executing learning content in which a virtual space is implemented, and performing real-time communication with the remote lecturer computer; and a virtual reality computer for combining the image of the student and the image of the remote lecturer with the virtual space of the learning content.
[0009] In accordance with a second aspect of the present invention, there is provided an educational method using virtual reality, including: extracting an image of a student from an entire image acquired by capturing the student; extracting an image of a lecturer at a remote place from an entire image acquired by capturing the remote lecturer; executing learning content in which a virtual space is implemented, and performing real-time communication with the remote lecturer; and combining the image of the student and the image of the remote lecturer with the virtual space of the learning content.
[0010] In accordance with the present invention, it is possible to provide the educational system and method capable of providing experience-based education while overcoming spatial restrictions using virtual reality. Further, the classroom and the remote lecturer appear in the same virtual space, gestures of the student are recognized and the content is conducted, thereby increasing the sense of immersion of the student in the class.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The objects and features of the present invention will become apparent from the following description of embodiments given in conjunction with the accompanying drawings, in which:
[0012] FIG. 1 is a block diagram showing the construction of an educational system using virtual reality in accordance with an embodiment of the present invention;
[0013] FIG. 2 is a diagram showing an example of the educational system using virtual reality of FIG. 1 ;
[0014] FIG. 3 is a diagram showing the classroom of FIG. 1 in which learning content is being executed;
[0015] FIG. 4 is a diagram showing the classroom of FIG. 1 in which a student and a remote lecturer appear in the learning content of FIG. 3 and the learning is being conducted; and
[0016] FIG. 5 is a flow chart showing an educational method using virtual reality in accordance with the embodiment of the present invention.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0017] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings which form a part hereof.
[0018] FIG. 1 is a block diagram showing the construction of an educational system using virtual reality in accordance with the embodiment of the present invention.
[0019] The educational system in accordance with the embodiment of the present invention may be operated in physically separated spaces, i.e., a classroom 100 and a remote place 105 . For example, in case of foreign language education, students and a lecturer located in the classroom 100 in Korea can conduct a class with the support of a remote lecturer located at the remote place 105 by connecting the classroom 100 with the remote place 105 while conducting the class in the classroom 100 .
[0020] A first student camera 110 captures an image from each student. A first image computer 120 extracts only an image of the student from the entire image captured by the first student camera. In an embodiment, a blue carpet 115 may be used to facilitate a procedure for extracting the image of the student. When the first student camera 110 captures an image from the student standing on the blue carpet 115 , an advantage of facilitating the procedure for extracting only the image of the student from a background is obtained. When the student does not need to move or when it is possible to use only a two-dimensional image of the student, a blue screen instead of the blue carpet 115 may be used to allow the student to stand or sit in front of the blue screen, and thus to acquire the image of the student.
[0021] In an embodiment, the virtual reality of the present invention may be implemented using three-dimensional images. In this case, to implement a three-dimensional image of the student, two or more cameras and image computers, including a second student camera 112 and a second image computer 122 , are used. The first and second cameras 110 and 112 may be implemented as a single stereo camera. The first and second student cameras 110 and 112 implemented as the stereo camera may be respectively located at the front and the back of the inside of the classroom. In this case, as learning content, three-dimensional image-based learning content may be used.
[0022] Meanwhile, a remote lecturer camera 180 captures an image of a lecturer at the remote place. A remote lecturer computer 190 extracts an image of the remote lecturer from the entire image captured by the remote lecturer camera 180 . In an embodiment, a blue screen 185 may be used to facilitate a procedure for extracting the image of the remote lecturer. When the remote lecturer camera 180 captures an image from the remote lecturer standing in front of the blue screen 185 , an advantage of facilitating the procedure for extracting the image of the remote lecturer from a background is obtained. When the remote lecturer needs to move or when a three-dimensional image of the remote lecturer is used, a blue carpet instead of the blue screen 185 is used to allow the remote lecturer to stand or move on the blue carpet, and thus to capture a three-dimensional image of the remote lecturer using the remote lecturer camera 180 implemented as a stereo camera or the like.
[0023] A virtual reality computer 150 implements a virtual space in which the student and the remote lecturer appear by combining images contained in the learning content, the image of the student, and the image of the remote lecturer with each other.
[0024] The learning content is created in advance, and a procedure for creating the content is divided into a raw content production operation such as three-dimensional modeling, voice recording, the production of animation, and the production of images, and a content packaging operation of positioning the raw content and defining rules reacting on various types of interaction with the student and the lecturer. The creation of learning content that can be used by the virtual reality computer 150 is completed only after the two operations have been completed.
[0025] In order to combine the images of the student and the lecturer with the images of the learning content, spatial information awareness technology is used. The virtual reality computer 150 calculates the relative locations of the first and second student cameras 110 and 112 and the bottom of the classroom to align the bottom of the real world with the bottom of the virtual world using the spatial information awareness technology, which allows the motion of the student in the real world to be naturally implemented even in the virtual world. As long as the cameras are not moved after the educational system in accordance with an embodiment of the present invention has been installed, there is no need to align the bottoms again, and thus the aligning is also performed in advance.
[0026] The operations to be performed by the virtual reality computer 150 for each frame of the camera are as follows. First, the first and second cameras 110 and 112 capture each student. The first and second image computers 120 and 122 extract images of the student and calculate the location of the world coordinates of the student using the location of the feet of the student. Further, the remote lecturer camera 180 captures the remote lecturer, and the remote lecturer computer 190 extracts an image of the remote lecturer. A three-dimensional virtual space is constructed using the extracted images of the student and the remote lecturer and other virtual objects contained in the learning content. The student and the remote lecturer share the same virtual space with each other, thus increasing the sense of reality and immersion of the student in the class.
[0027] In an embodiment, the first and second image computers 120 and 122 may be implemented to recognize the gestures of the student. A method of estimating the locations of the hands, feet or head of an object using information such as the color or motion of the image of the object may be used as a gesture recognition method. In this case, learning interaction based on the locations of the hands, feet or head of the student can be performed, and a scenario used in the learning content may be performed based on the action of the student using the results of the successive estimation of the locations of the hands, feet or head. The performance of the scenario used in the learning content is basically implemented on the basis of rules predefined by the manipulation of the classroom lecturer computer 140 of the lecturer in the classroom.
[0028] A projector 170 outputs results implemented in a three-dimensional virtual space. The projector 170 generally outputs the results on a large screen such as a classroom screen 175 depending on the characteristics of the educational system using virtual reality.
[0029] Meanwhile, a monitoring camera 145 captures a learning scene in the classroom and allows both the lecturer in the classroom and the lecturer at the remote place to monitor the progress of learning in the classroom.
[0030] In order to implement the educational system and method using virtual reality, an audio system is also required. A student microphone 130 receives the voice of the student, and a remote lecturer microphone 196 receives the voice of the remote lecturer. The classroom lecturer computer 140 processes the voice of the student, and the remote lecturer computer 190 processes the voice of the remote lecturer, respectively.
[0031] Further, learning content executed by the classroom lecturer computer 14 also contains unique voices. A sound mixer 160 mixes the voices of the learning content, the voice of the student, and the voice of the remote lecturer with each other. A classroom speaker 165 outputs the mixed voice. A remote lecturer speaker 198 outputs the voice to the remote lecturer. Here, the speaker may be implemented by one of similar sound output devices such as an earphone or a headphone.
[0032] FIG. 2 is a diagram showing an example of the educational system using virtual reality of FIG. 1 .
[0033] The educational system in accordance with an embodiment of the present invention includes two parts, i.e., a classroom 100 and a remote place 105 . The classroom 100 is a space in which learning is conducted, and the remote place 105 is a space in which a remote lecturer supports a class.
[0034] Both a projector 170 and a large classroom screen 175 are installed at the front of the inside of the classroom 100 . A virtual world is implemented on the large classroom screen 175 . The virtual world includes the image of each student, the image of the native lecturer, and other virtual objects of learning content executed by a classroom lecturer computer 140 . Since the virtual world is mapped to the real world, the motion of the student in the classroom 100 is mapped to the motion of the student in the virtual world without change. In an embodiment, the locations of the hands, feet or head of the student are tracked so that the gestures of the student are recognized by the system, and thus an event may be generated. For the other virtual objects constituting the virtual world, objects having animation inserted thereinto, as well as static objects, may be used, and as a result, the reality may be increased. The native lecturer at the remote place 105 can monitor a situation in the classroom using the images transmitted from a monitoring camera 145 . When the native lecturer performs a certain conversion and performs a certain action in front of a blue screen 185 , images corresponding to the conversation and action are captured by a remote lecturer camera 180 , and are then transmitted to the student in the classroom through the classroom screen 175 .
[0035] FIG. 3 is a diagram showing the classroom of FIG. 1 in which learning content is being executed.
[0036] When a lecturer in the classroom turns on the educational system in accordance with the embodiment of the present invention, the virtual space is implemented on a classroom screen 175 depending on the substance of learning content. The virtual space corresponds to the result prior to being combined with the images of a student and a remote lecturer.
[0037] Various virtual spaces may be created depending on the substance of the learning content. For example, the gate, ticket office, passersby, internal structure, and trains of the Boston subway are modeled without change, and may be implemented in the virtual world. When the student is situated in the virtual space, the student views him or herself appearing on the screen and may have an experience as if he or she were visiting the inside of the Boston subway while moving in the subway. When the remote lecturer is suitably situated in the virtual space as a ticket office worker, a police, a passerby or the like, the student can further improve his or her feeling of experience through actual conversation with the remote lecturer. The virtual space can be continuously changed by the manipulation of the classroom lecturer, and thereby the student can continuously conduct learning activities having new content while the virtual space is changing.
[0038] FIG. 4 is a diagram showing the classroom of FIG. 1 in which a student and a remote lecturer appear inside the learning content and a class is being conducted.
[0039] When a student 410 stands on a blue carpet 115 , an image of the student 420 appears on a classroom screen 175 , and avatars 440 , which are virtual objects, appear on the screen by the manipulation of a classroom lecturer. The student 410 can perform a conversation with the avatars. In this case, the avatars 440 may be manipulated by the classroom lecturer. During the learning, the student 410 can proceed with his or her learning using gestures while freely moving on the blue carpet 115 .
[0040] As the classroom lecturer replaces learning content, the background may change and a new scenario may be implemented. A few of the avatars 440 in the virtual space can be replaced with a native lecturer 430 , and the student 410 can more freely perform a conversation with the native lecturer 430 . The classroom lecturer and the remote lecturer observe the course of the class using the images transmitted from a monitoring camera 145 and can evaluate the student.
[0041] FIG. 5 is a flow chart showing an educational method using virtual reality in accordance with an embodiment of the present invention.
[0042] First, each student in a classroom is captured and an image of the student is extracted at step S 510 . A remote lecturer is captured and an image of the remote lecturer is extracted in step S 520 . Next, learning content in which a virtual space is implemented is executed in step S 530 , the images of the student and the remote lecturer are combined with the virtual space of the learning content in step S 540 , and an image of the combined virtual reality is output at step S 550 .
[0043] The embodiment including an audio system may be configured to receive the voices of the student and the remote lecturer, mix voices contained in the learning content with the voices of the student and the remote lecturer, and output the mixed voice. Here, the embodiment is implemented such that a remote lecturer computer processes the voice of the remote lecturer and the classroom lecturer computer processes the voice of the student.
[0044] Further, modules, function blocks or means according to the present embodiment may be implemented using various well-known devices such as electronic circuits, integrated circuits (ICs), or Application Specific Integrated Circuits (ASICs), and may be implemented as individual components. Further, as an alternative, two or more components may be integrated into a single component.
[0045] While the invention has been shown and described with respect to the embodiments, it will be understood by those skilled in the art that various changes and modification may be made without departing from the scope of the invention as defined in the following claims. | An educational system using virtual reality includes an image computer for extracting an image of a student from an entire image acquired by capturing the student; a remote lecturer computer for extracting an image of a lecturer at a remote place from an entire image acquired by capturing the remote lecturer. Further, the educational system using the virtual reality includes a classroom lecturer computer for executing learning content in which a virtual space is implemented, and performing real-time communication with the remote lecturer computer; and a virtual reality computer for combining the image of the student and the image of the remote lecturer with the virtual space of the learning content. | 7 |
[0001] The present applications claims priority to German patent application no: DE 20 2009 007 156.1, filed May 18, 2009.
FIELD OF THE INVENTION
[0002] This invention relates to a profile rail system for covering at least one covering edge.
DESCRIPTION OF THE PRIOR ART
[0003] An arrangement with magnetic fastening device for covering of a joint or an edge is known from EP 1 837 454 A2. This arrangement comprises a base rail and a cover rail that can be adjusted relative to one another. The base rail is attached to a base while the cover rail extends over edges of covering. Permanent magnets with opposite polarity are provided in the base and cover rails to hold the cover rail on the base rail. In this way, the cover rail is preloaded when it is pulled onto adjacent coverings. In addition, no fastening means can be seen from the visible side of the covering. This arrangement has proven its value in practice and is the starting point for the present invention.
[0004] It is the problem of this invention to provide a profile rail system of the type mentioned above that is characterized by improved functionality.
[0005] This problem is solved according to the invention by the following characteristics.
BRIEF SUMMARY OF THE INVENTION
[0006] The profile rail system according to the invention is used to cover at least one covering edge. The covering may consist of any material such as laminate, wood, parquetry, a polymer, natural or artificial stone. This list is not exhaustive but just exemplary. If the profile rail system covers only one covering edge, it is used as trimming or ramp. Alternatively, the profile rail system can cover multiple covering edges so that it is provided between two coverings, especially in an expansion joint or a transition from one covering to another. The profile rail system can be used on floor, wall, and ceiling coverings as well as a baseboard or stair edge profile. This, too, should be considered exemplary and not exhaustive. The profile rail system comprises a base rail that can preferably be attached to a base. The preferred means for fastening are screws, dowels, or glued joints. However it is not required that the rail be fastened to a base. The base rail may for example have a leg that slides under the adjacent covering to achieve attachment of the base rail. Furthermore, the profile rail system comprises a cover rail that can be adjusted relative to the base rail. The cover rail is preferably movable relative to the base rail for height adjustment of the cover rail to match the thickness of the respective adjacent covering. To ensure proper sealing of the covering by the cover rail, at least one permanent magnet is provided that pulls the cover rail against the base rail. Specifically, this permanent magnet is to apply a tensile force to the cover rail to pull it against the adjacent covering. However, it has proven disadvantageous to use two magnets with opposite polarity for applying this tensile force. If two magnets are used, very different field strengths may result depending on the geometry of the profile rail system and the relative positioning of base rail and cover rail that may in some cases even cause the magnets to repel each other. This issue has resulted in the fact that magnetic profile rail systems for covering edges of coverings have not yet caught on. This issue can be solved by refraining from using magnets with opposite polarity and instead making both the base rail and the cover rail or at least a section thereof magnetizable. The result is that the permanent magnet is neither functionally associated with the base rail nor with the cover rail but represents a fastening means that forms a non-positive joint of the two rails. In this way, the base rail or cover rail is magnetized always and regardless of the respective rail geometry with a polarity opposite to that of the permanent magnet, which facilitates a constant strong tensile force of the cover rail against the base rail across the entire adjustment path of the cover rail. This makes the magnetic holding system of the cover rail fit for practical application and brings out its advantages particularly well. In particular, the holding system, unlike a screwed joint, is not visible from outside. Since the cover rail is only held in a non-positive joint and not in positive engagement like a snap-in connection, the cover rail can easily be removed from the base rail by overcoming the holding force. In this way, the space underneath the cover rail can easily be made accessible. This is particularly important for revisions. The space under the cover rail can also easily be used as a cable duct, and a cable can be installed or replaced even after the profile rail system has been completed. The magnetic attachment of the cover rail also eliminates fatigue of the holding mechanism of the cover rail as is known, for example, from snap-in plug-and-socket-type connections. Ferromagnetic materials have particularly proven their value as magnetizable materials for the base or cover rail since these can achieve considerably higher coercive field strengths than paramagnetic materials. Preferred materials are iron, cobalt and/or nickel and alloys made thereof. Many ferromagnetic materials are very hard and thus difficult to machine. Many ferromagnetic materials are also subject to corrosion.
[0007] Due to poor machinability it is typically not beneficial to manufacture the entire base rail or cover rail from a magnetizable material although this is generally possible. Instead, it is advantageous if the base rail or the cover rail, respectively, is at least made of two pieces. This rail comprises at least one non-ferromagnetic profile rail to which at least one ferromagnetic metal sheet is attached. In this way, the magnetizable material does not have to be incorporated in the typically complex shape of the profile rail. It is sufficient to produce a more or less narrow strip of sheet metal from the ferromagnetic material. The profile rail can be made of an easily moldable, castable, or extrudable material so that even complex shapes can be produced cost-effectively. Such manufacturing methods are not feasible with justifiable effort for ferromagnetic materials. But a simple sheet metal strip of a ferromagnetic material can be manufactured easily and at low cost.
[0008] It is preferred for easily achieving a positive, form-fitting connection of the ferromagnetic sheet and the profile rail that the profile rail comprises at least one undercut holder into which the ferromagnetic sheet can be slid.
[0009] This holder can for example be formed by two vertical ribs that are undercut on the sides that face each other. These ribs and a base leg form a pocket that holds the ferromagnetic sheet. The undercut of the holder ensures that the ferromagnetic sheet can withstand tensile forces applied by permanent magnets.
[0010] It is a major problem of permanent-magnet holding systems that the Lorentz force depends on the spacing between the magnet and the ferromagnetic material. This force declines with the third power of the spacing so that sufficient holding force is feasible at a very narrow height adjustment range only if the permanent magnet is fixed.
[0011] It is useful for solving this problem if the permanent magnet is in abutment with the base rail and the cover rail at various positions of the cover rail. This can easiest be achieved by making the permanent magnet freely adjustable between the base rail and the cover rail. Alternatively, the permanent magnet could also be pivoted, however this is typically not required. This measure ensures that the relative spacing between the permanent magnet on the one hand and the cover or base rail on the other always zero, allowing the permanent magnet to exert its maximum force effect in every relative position of the cover and base rails. This ensures a large height adjustment range of the profile rail system so that it can handle all types of covering used in practice.
[0012] Abutment of the permanent magnet is simply achieved by arranging the permanent magnet at an acute angle to the base or cover rail. In this way, the permanent magnet can constantly remain in contact with the base rail or cover rail and apply the desired tensile force by changing its set angle to the base or cover rail.
[0013] It is advantageous for another improvement of the force effect between the permanent magnet and the base or cover rail that the permanent magnet is rounded at the contact surfaces with the base or cover rail. This rounding increases the effective area of the permanent magnet. This effective area would be relatively small for a knife-type edge of the permanent magnet since it would only ensure contact of the permanent magnet along a line and that contact would decline rapidly at a very small distance from the contact line between the permanent magnet and the base or cover rail, respectively. The mutual increase in spacing is reduced many times over by the rounded shape of the permanent magnet so that a considerably larger area contributes to the magnetic flux. This increases the Lorentz force that is proportional to the cross-sectional area of the magnetic flux.
[0014] If the cover rail is to be height-adjustable and pivotable, it is beneficial that the rounding is convex. This increases the cross-sectional area of the magnetic flux in two dimensions so that the permanent magnet can be rotated about two axes. Thus both the height and the angular position of the cover rail can be adjusted about a longitudinal axis of the cover rail without reducing the force effect of the permanent magnet.
[0015] Despite the described measures aimed at increasing the cross-sectional area of the magnetic flux, it is relatively small in relation to a flatly positioned magnet because only a small portion of the available magnetic area can be utilized. Therefore, either a larger number of magnets or magnets with a higher coercive field strength such as samarium cobalt magnets are preferred. If however such magnets rest evenly on a ferromagnetic material, they can virtually not be separated from the ferromagnet without using destructive forces. This is why care should be taken to avoid level contact of the permanent magnet with the ferromagnetic material when the profile rail is installed. To ensure this in all circumstances, it is advantageous to cover the base or cover rail partially by a non-ferromagnetic material. Such non-ferromagnetic materials can include a plastic, aluminum, copper or the like, this list to be considered exemplary, not exhaustive. The cover prevents level contact of the permanent magnet with the ferromagnetic material so that the holding force between the cover rail and the base rail remains within acceptable limits during installation of the profile rail system as well. Alternatively or in addition, the contact surface of the ferromagnetic material and the permanent magnet can also have a non-level shape. For example, the contact surface could be domed or tilted.
[0016] It is finally advantageous for a simple design of the profile rail system if the permanent magnet has opposite magnetic poles at its contact sites with the base or cover rail. In this way, the full length of the permanent magnet can be utilized for adjusting the cover rail relative to the base rail.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF DRAWINGS
[0017] Other advantages and characteristics of this invention will be explained in the detailed description below with reference to the associated figures that contain several embodiments of this invention. It should however be understood that the figure is just used to illustrate the invention and does not limit the scope of protection of the invention.
Wherein:
[0018] FIG. 1 is a three-dimensional representation of a profile rail system;
[0019] FIG. 2 is a cross-sectional view of the profile rail system according to FIG. 1 along the cutting line II-II;
[0020] FIG. 3 is the cross-sectional view according to FIG. 2 with the height of the cover rail changed; and
[0021] FIG. 4 is a view of the profile rail system 1 from direction IV with the cover rail tilted.
DETAILED DESCRIPTION OF THE INVENTION
[0022] FIG. 1 shows a profile rail system 1 for covering two edges 2 of coverings 3 . The profile rail system 1 comprises a base rail 4 and a cover rail 5 .
[0023] The base rail 4 comprises a base leg 6 that can be attached to a base 7 . The base leg 6 has several holes 8 for this purpose into which screws that are not shown here can be inserted. The base leg 6 can either be directly screwed onto the base 7 , or glued to it or attached to it indirectly using dowels.
[0024] The base rail 4 also comprises two vertical guide ribs 9 that limit the lateral movability of the cover rail 5 and thus facilitate the installation of the profile rail system. As an alternative to the embodiment shown, a variant can be conceived that makes do without guide ribs 9 .
[0025] Two holding ribs 10 are provided on the base leg 6 of the base rail 4 that comprise undercuts 11 that face each other. These holding legs 10 form a holder 12 for a ferromagnetic sheet metal piece 13 that can be slid into the holder 12 . Alternatively, the narrowest distance between the holding ribs 10 can be made slightly smaller than the width of the ferromagnetic sheet metal piece 13 so that the ferromagnetic sheet metal piece 13 can be snapped into the holder 12 from the top. It is preferred in this case that the undercut 11 of the holding ribs 10 is dimensioned particularly small.
[0026] The base leg 6 forms a profile rail 14 together with the guide ribs 9 and the holder 12 that is shown as a one-piece component made by extrusion molding. This profile rail 14 and a ferromagnetic sheet metal piece 13 form the base rail 4 .
[0027] The cover rail 5 comprises two cover wings 15 that cover the two covering edges 2 . In addition, the cover rail 5 comprises two guide ribs 16 that interact with the guide ribs 9 of the base rail 4 and implement the guide effect.
[0028] A holder 17 for another ferromagnetic sheet metal piece 18 is provided on the guide ribs 16 . This holder 17 has an undercut 19 like the holder 12 of the base rail 4 . The undercut 19 can be formed in the same way as the undercut 11 of the base leg 6 . In particular, it is conceived that the ferromagnetic sheet metal piece 18 can be slid or snapped into the holder 17 .
[0029] It is important for achieving secure covering of the covering edges 2 that the cover wings 15 are pulled towards the coverings 3 . The tensile force is applied by several permanent magnets 20 that are arranged at an acute angle 21 to the base rail 4 . These permanent magnets 20 are placed along the length of the profile rail system 1 , and FIG. 1 only shows one of the permanent magnets 20 .
[0030] The permanent magnet 20 is rounded at the contact areas with the ferromagnetic sheet metal pieces 13 , 18 to increase the cross-sectional area of the magnetic flux and thus the force effect of the permanent magnet 20 . A cylindrical rounding 22 is formed in the contact area with the base rail 4 . It is not important whether this rounding is of circular, elliptical, parabolic or another cylindrical design.
[0031] The permanent magnet 20 comprises a convex rounding 23 in the contact area with the ferromagnetic sheet metal piece 18 on the cover rail. Unlike the cylindrical rounding, this convex rounding 23 allows pivoting of the cover rail 5 about a longitudinal axis of the profile rail system 1 without reducing the cross-sectional area of the magnetic flux to a single point. As an alternative to the embodiment shown in FIG. 1 , both contact areas of the permanent magnet 20 can be cylindrical or convex in design. The exact shape of a convex rounding 23 of the permanent magnet 20 does not matter. The permanent magnet 20 can have a convex rounding 23 in the shape of a ball, an ellipsoid, a paraboloid or another shape.
[0032] To prevent the permanent magnet 20 from abutting level with the ferromagnetic sheet metal piece 13 , 18 , the ferromagnetic sheet metal piece 13 , 18 is partially covered by a non-ferromagnetic material 24 . Thus the set angle 21 of the permanent magnet 20 can no longer be reduced to zero so that the permanent magnet 20 has a generally line or point-shaped contact with the ferromagnetic sheet metal piece 13 , in any position it can take. If the surface of the ferromagnetic sheet metal piece 13 is not even, level abutment of the permanent magnet 20 is ruled out by its shape so that the non-ferromagnetic material 24 is expendable.
[0033] The function of the profile rail system 1 will be explained with reference to the cross-sectional views shown in FIG. 2 or 3 below; the same reference symbols denote the same components. The cross-sectional view shows in particular that the permanent magnet 20 has a line-shaped contact site 25 with the ferromagnetic sheet metal piece 13 . The contact site 26 with the ferromagnetic sheet metal piece 18 however is point-shaped due to the convex design of the permanent magnet 20 .
[0034] It can clearly be seen in FIGS. 2 and 3 that relatively large areas around the contact sites 25 , 26 have a very small spacing between the permanent magnet 20 on the one hand and the ferromagnetic sheet metal piece 13 , 18 on the other. A relatively high magnetic flux occurs in these areas, resulting in an increased force effect. This force effect is aimed at tipping the permanent magnet 20 so that the angle 21 is reduced. This produces a tensile force towards the base rail 4 that acts on the cover rail 5 , and this force presses the cover rail 5 against the floor coverings 3 . The ferromagnetic sheet metal pieces 13 , 18 can be moved relative to each other.
[0035] A comparison of FIGS. 2 and 3 shows that the area of the contact sites 25 , 26 is generally dependent on the angle 21 and thus on the spacing between the cover rail 5 and the base rail 4 . This results in an about equal force effect of the permanent magnet 20 in both cases so that the cover rail 5 is pulled towards the floor coverings 3 with an approximately constant force regardless of the thickness of the coverings 3 .
[0036] FIG. 4 is a view of the profile rail system 1 from direction IV. Unlike the representation in FIGS. 1 to 3 , the cover rail 5 is tilted about a longitudinal axis 27 here. This tilt provides compensation for differences in thickness of the coverings 3 on both sides of the profile rail system 1 . The tilting of the cover rail 5 has no effect on the area of the contact site 25 due to the convex rounding 23 of the permanent magnet 20 . This ensures that the force effect of the permanent magnet 20 is generally independent of the tilt of the cover rail 5 .
[0037] In deviation from the embodiment shown, the cover ail may only comprise one cover wing 15 . In this case, the profile rail system 1 is used as a border for a covering 3 . It is also conceivable to provide cover wings 15 of different lengths to compensate for greater height differences between adjacent coverings than could be compensated by tilting the cover rail 15 .
[0038] Finally, it is conceivable to arrange the cover wings 15 at an angle to each other to produce a stair edge profile for remodeling staircases.
[0039] Since some of the embodiments of this invention are not shown or described, it should be understood that a great number of changes and modifications of these embodiments is conceivable without departing from the rationale and scope of protection of the invention as defined by the claims.
LIST OF REFERENCE SYMBOLS
[0000]
1 Profile rail system
2 Covering edge
3 Covering
4 Base rail
5 Cover rail
6 Base leg
7 Base
8 Hole
9 Guide rib
10 Holding rib
11 Undercut
12 Holder
13 Ferromagnetic sheet metal piece
14 Profile rail
15 Cover wing
16 Guide rib
17 Holder
18 Ferromagnetic sheet metal piece
19 Undercut
20 Permanent magnet
21 Acute angle
22 Cylindrical rounding
23 Convex rounding
24 Non-ferromagnetic material
25 Contact site
26 Contact site
27 Longitudinal axis | A profile rail system ( 1 ) is used to cover a covering edge ( 2 ). The profile rail system ( 1 ) consists of at least one base rail ( 4 ) and at least one cover rail ( 5 ) that can be adjusted relative to the base rail. The base rail ( 4 ) and cover rail ( 5 ) are held together by at least one permanent magnet ( 20 ) in such a way that the cover rail ( 5 ) is pulled towards the base rail ( 4 ). At least a section of the base rail ( 4 ) and cover rail ( 5 ) can be magnetized to achieve a polarity-independent force effect of the permanent magnet ( 20 ). | 4 |
BACKGROUND OF THE INVENTION
[0001] This invention relates to novel isothiazole derivatives that are useful in the treatment of hyperproliferative diseases, such as cancers, in mammals. This invention also relates to a method of using such compounds in the treatment of hyperproliferative diseases in mammals, especially humans, and to pharmaceutical compositions containing such compounds.
[0002] It is known that a cell may become cancerous by virtue of the transformation of a portion of its DNA into an oncogene (i.e. a gene that upon activation leads to the formation of malignant tumor cells). Many oncogenes encode proteins which are aberrant tyrosine kinases capable of causing cell transformation. Alternatively, the overexpression of a normal proto-oncogenic tyrosine kinase may also result in proliferative disorders, sometimes resulting in a malignant phenotype. It has been shown that certain tyrosine kinases may be mutated or overexpressed in many human cancers such as brain, lung, squamous cell, bladder, gastric, breast, head and neck, oesophageal, gynecological and thyroid cancers. Furthermore, the overexpression of a ligand for a tyrosine kinase receptor may result in an increase in the activation state of the receptor, resulting in proliferation of the tumor cells or endothelial cells. Thus, it is believed that inhibitors of receptor tyrosine kinases, such as the compounds of the present invention, are useful as selective inhibitors of the growth of mammalian cancer cells.
[0003] It is known that polypeptide growth factors, such as vascular endothelial growth factor (VEGF) having a high affinity to the human kinase insert-domain-containing receptor (KDR) or the murine fetal liver kinase 1 (FLK-1) receptor, have been associated with the proliferation of endothelial cells and more particularly vasculogenesis and angiogenesis. See PCT international application publication number WO 95/21613 (published Aug. 17, 1995). Agents, such as the compounds of the present invention, that are capable of binding to or modulating the KDR/FLK-1 receptor may be used to treat disorders related to vasculogenesis or angiogenesis such as diabetes, diabetic retinopathy, hemangioma, glioma, melanoma, Kaposi's sarcoma and ovarian, breast, lung, pancreatic, prostate, colon and epidermoid cancer.
[0004] Isothiazole derivatives useful as herbicides are referred to in U.S. Pat. Nos. 4,059,433 and 4,057,416, both assigned to FMC Corporation.
SUMMARY OF THE INVENTION
[0005] The present invention relates to compounds of the formula 1
[0006] and to pharmaceutically acceptable salts, prodrugs and solvates thereof, wherein:
[0007] wherein X 1 is O or S;
[0008] R 1 is H, C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, —C(O)(C 1 -C 10 alkyl), —(CH 2 ) t (C 6 -C 10 aryl), —(CH 2 ) t (4-10 membered heterocyclic), —C(O)(CH 2 ) t (C 6 -C 10 aryl), or —C(O)(CH 2 ) t (5-10 membered heterocyclic), wherein t is an integer from 0 to 5; said alkyl group optionally includes 1 or 2 hetero moieties selected from O, S and —N(R 6 )— with the proviso that two O atoms, two S atoms, or an O and S atom are not attached directly to each other; said aryl and heterocyclic R 1 groups are optionally fused to a C 6 -C 10 aryl group, a C 5 -C 8 saturated cyclic group, or a 5-10 membered heterocyclic group; 1 or 2 carbon atoms in the foregoing heterocyclic moieties are optionally substituted by an oxo (═O) moiety; the —(CH 2 ) t — moieties of the foregoing R 1 groups optionally include a carbon-carbon double or triple bond where t is an integer from 2 to 5; and the foregoing R 1 groups, except H, are optionally substituted by 1 to 3 R 4 groups;
[0009] R 2 is selected from the list of substituents provided in the definition of R 1 , —SO 2 (CH 2 ) t (C 6 -C 10 aryl), —SO 2 (CH 2 ) t (5-10 membered heterocyclic), and —OR 5 , t is an integer ranging from 0 to 5, the —(CH 2 ) t — moieties of the foregoing R 2 groups optionally include a carbon-carbon double or triple bond where t is an integer from 2 to 5, and the foregoing R 2 groups are optionally substituted by 1 to 3 R 4 groups;
[0010] or R 1 and R 2 may be taken together with the nitrogen to which each is attached to form a 4-10 membered saturated monocyclic or polycyclic ring or a 5-10 membered heteroaryl ring, wherein said saturated and heteroaryl rings optionally include 1 or 2 heteroatoms selected from O, S and —N(R 6 )— in addition to the nitrogen to which R 1 and R 2 are attached, said —N(R 6 )— is optionally ═N— or —N═ where R 1 and R 2 are taken together as said heteroaryl group, said saturated ring optionally may be partially unsaturated by including 1 or 2 carbon-carbon double bonds, and said saturated and heteroaryl rings, including the R 6 group of said —N(R 6 )—, are optionally substituted by 1 to 3 R 4 groups;
[0011] R 3 is H, C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, —(CH 2 ) t (C 6 -C 10 aryl), or —(CH 2 ) t (5-10 membered heterocyclic), wherein t is an integer from 0 to 5; said alkyl group optionally includes 1 or 2 hetero moieties selected from O, S and —N(R 6 )— with the proviso that two O atoms, two S atoms, or an O and S atom are not attached directly to each other; said aryl and heterocyclic R 3 groups are optionally fused to a C 6 -C 10 aryl group, a C 5 -C 8 saturated cyclic group, or a 5-10 membered heterocyclic group; 1 or 2 carbon atoms in the foregoing heterocyclic moieties are optionally substituted by an oxo (═O) moiety; the —(CH 2 ) t — moieties of the foregoing R 3 groups optionally include a carbon-carbon double or triple bond where t is an integer from 2 to 5, and the foregoing R 3 groups are optionally substituted by 1 to 5 R 4 groups;
[0012] each R 4 is independently selected from C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, halo, cyano, nitro, trifluoromethyl, trifluoromethoxy, azido, —OR 5 , —C(O)R 5 , —C(O)OR 5 , —NR 6 C(O)OR 5 , —OC(O)R 5 , —NR 6 SO 2 R 5 , —SO 2 NR 5 R 6 , —NR 6 C(O)R 5 , —C(O)NR 5 R 6 , —NR 5 R 6 , —S(O) j R 7 wherein j is an integer ranging from 0 to 2, —SO 3 H, —NR 5 (CR 6 R 7 ) t OR 6 , —(CH 2 ) t (C 6 -C 10 aryl), —SO 2 (CH 2 ) t (C 6 -C 10 aryl), —S(CH 2 ) t (C 6 -C 10 aryl), —O(CH 2 ) t (C 6 -C 10 aryl), —(CH 2 ) t (5-10 membered heterocyclic), and —(CR 6 R 7 ) m OR 6 , wherein m is an integer from 1 to 5 and t is an integer from 0 to 5; said alkyl group optionally contains 1 or 2 hetero moieties selected from O, S and —N(R 6 )— with the proviso that two O atoms, two S atoms, or an O and S atom are not attached directly to each other; said aryl and heterocyclic R 4 groups are optionally fused to a C 6 -C 10 aryl group, a C 5 -C 8 saturated cyclic group, or a 5-10 membered heterocyclic group; 1 or 2 carbon atoms in the foregoing heterocyclic moieties are optionally substituted by an oxo (═O) moiety; and the alkyl, aryl and heterocyclic moieties of the foregoing R 4 groups are optionally substituted by 1 to 3 substituents independently selected from halo, cyano, nitro, trifluoromethyl, trifluoromethoxy, azido, —NR 6 SO 2 R 5 , —SO 2 NR 5 R 6 , —C(O)R 5 , —C(O)OR 5 , —OC(O)R 5 , —NR 6 C(O)R 5 , —C(O)NR 5 R 6 , —NR 5 R 6 , —(CR 6 R 7 ) m OR 6 wherein m is an integer from 1 to 5, —OR 5 and the substituents listed in the definition of R 5 ;
[0013] each R 5 is independently selected from H, C 1 -C 10 alkyl, —(CH 2 ) t (C 6 -C 10 aryl), and —(CH 2 ) t (5-10 membered heterocyclic), wherein t is an integer from 0 to 5; said alkyl group optionally includes 1 or 2 hetero moieties selected from O, S and —N(R 6 )— with the proviso that two O atoms, two S atoms, or an O and S atom are not attached directly to each other; said aryl and heterocyclic R 5 groups are optionally fused to a C 6 -C 10 aryl group, a C 5 -C 8 saturated cyclic group, or a 5-10 membered heterocyclic group; and the foregoing R 5 subsituents, except H, are optionally substituted by 1 to 3 substituents independently selected from halo, cyano, nitro, trifluoromethyl, trifluoromethoxy, azido, —C(O)R 6 , —C(O)OR 6 , —CO(O)R 6 , —NR 6 C(O)R 7 , —C(O)NR 6 R 7 , —NR 6 R 7 , hydroxy, C 1 -C 6 alkyl, and C 1 -C 6 alkoxy; and,
[0014] each R 6 and R 7 is independently H or C 1 -C 6 alkyl;
[0015] with the proviso that said compound of formula 1 is not 1-methyl-3-(4-carbamoyl-3-ethoxy-5-isothiazolyl)urea, 1,1-dimethyl-3-(4-carbamoyl-3-ethoxy-5-isothiazolyl)urea, 1-methyl-3-(4-carbamoyl-3-propoxy-5-isothiazolyl)urea, 1-methyl-3-(4-carbamoyl-3-(methylthio)-5-isothiazolyl)urea, 1-methyl-3-(4-carbamoyl-3-(ethylthio)-5-isothiazolyl)urea, 1,1-dimethyl-3-(4-carbamoyl-3-(ethylthio)-5-isothiazolyl)urea, 1-methyl-3-(4-carbamoyl-3-(propylthio)-5-isothiazolyl)urea, 1,1-dimethyl-3-(4-carbamoyl-3-(propylthio)-5-isothiazolyl)urea, or 1-methyl-3-(4-carbamoyl-3-(isopropylthio)-5-isothiazolyl)urea.
[0016] Preferred compounds include those of formula 1 wherein R 2 is H and R 1 is C 1 -C 10 alkyl optionally substituted by 1 or 2 substituents independently selected from —NR 5 R 6 , —NR 5 (CR 6 R 7 ) t OR 6 and —(CH 2 ) t (5-10 membered heterocyclic) wherein t is an integer from 0 to 5. Specific preferred R 1 groups include propyl, butyl, pentyl and hexyl optionally substituted by dimethylamino, hydroxy, pyrrolidinyl, morpholino, and ethyl-(2-hydroxy-ethyl)-amino.
[0017] Other preferred compounds include those of formula 1 wherein R 2 is H and R 1 is —(CH 2 ) t (5-10 membered heterocyclic), wherein t is an integer from 0 to 5; said heterocyclic group is optionally fused to a C 6 -C 10 aryl group, a C 5 -C 8 saturated cyclic group, or a 5-10 membered heterocyclic group; and said R 1 group, including the optionally fused portions of said R 1 group, is optionally substituted by 1 or 2 substituents independently selected from C 1 -C 4 alkyl, hydroxy and hydroxymethyl. Specific preferred heterocyclic groups of said R 1 group are morpholino, pyrrolidinyl, imidazolyl, piperazinyl, piperidinyl, and 2,5-diaza-bicyclo[2.2.1]hept-2-yl, the t variable of said R 1 group ranges from 2 to 5, and said heterocyclic groups are optionally substituted by hydroxy, hydroxymethyl and methyl.
[0018] Other preferred compounds include those of formula 1 wherein R 3 is —(CH 2 ) t (C 6 -C 10 aryl) wherein t is an integer from 1 to 3 and said R 3 group is optionally substituted by 1 to 4 R 4 groups. Specific preferred R 3 groups include benzyl optionally substituted by 1 to 4 substituents independently selected from halo and C 1 -C 4 alkyl. More specific preferred R 3 groups include benzyl substituted by 1 to 4 substituents independently selected from methyl, fluoro, chloro and bromo.
[0019] Specific embodiments of the present invention include the following compounds:
[0020] 5-{3-[3-(4-Methyl-piperazin-1-yl)-propyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0021] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-(3-{4-[ethyl-(2-hydroxy-ethyl)-amino]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0022] 3-(2-Fluoro-4-methyl-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0023] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-(3-4-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0024] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(6-dimethylamino-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0025] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0026] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0027] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0028] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[-(1-methyl-pyrrolidin-2-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0029] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0030] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-{4-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0031] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(3-hydroxy-5-pyrrolidin-1-yl)-pentyl)-ureido}-isothiazole-4-carboxylic acid amide;
[0032] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(3,4-dihydroxy-pyrrolidin-1-yl]-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0033] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[4-(3,4-dihydroxy-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0034] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(2-hydroxymethyl-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0035] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[4-(2-hydroxymethyl-pyrrolidin-1-yl)-butyl-]-ureido}-isothiazole-4-carboxylic acid amide;
[0036] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(3-hydroxy-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0037] 3-(4-Bromo-2,6-difluoro-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido}-isothiazole-4-carboxylic acid amide;
[0038] mesylate salt of 3-(4-Bromo-2,6-difluoro-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido}-isothiazole-4-carboxylic acid amide;
[0039] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(4-hydroxy-5-piperidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0040] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(3-hydroxy-5-piperidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0041] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[4-(2-hydroxymethyl-piperidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0042] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-(3-{4-[ethyl-(2-hydroxy-ethyl)-amino]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0043] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(5-hydroxy-6-piperidin-1-yl)-hexyl)-ureido}-isothiazole-4-carboxylic acid amide;
[0044] 3-(4-Bromo-2,3,6-trifluoro-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0045] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0046] hydrochloride salt of 3-(4-Bromo-2,6-difluoro-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido}-isothiazole-4-carboxylic acid amide;
[0047] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(3-hydroxy-5-pyrrolidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0048] 5-[3-(4-Pyrrolidin-1-yl-butyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0049] 5-[3-(3-Hydroxy-5-pyrrolidin-1-yl-pentyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0050] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[3-(5-methyl-2,5-diazabicyclo[2.2.1]hept-2-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0051] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-{3-[3-(5-methyl-2,5-diaza-bicyclo[2.2.1]hept-2-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0052] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-{3-[2-(1-methyl-pyrrolidin-2-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0053] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0054] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-{3-[4-(2-hydroxymethyl-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0055] 5-{3-[2-(1-Methyl-pyrrolidin-2-yl)-ethyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0056] 5-[3-(4-Dimethylamino-butyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0057] 5-[3-(3-Dimethylamino-propyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0058] 5-[3-(3-Hydroxy-5-isopropropylamino-pentyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0059] 5-[3-(3-Isopropylamino-propyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0060] 5-{3-[4-(4-Methyl-piperazin-1-yl)-butyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0061] 5-(3-{4-[4-(2-Hydroxy-ethyl)-piperazin-1-yl]-butyl}-ureido)-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0062] 5-[3-(3-Pyrrolidin-1-yl-propyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0063] 5-[3-(4-Hydroxy-5-piperidin-1-yl-pentyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0064] 3-(4Chloro-2,6-difluoro-benzyloxy)-5-[3-(4-imidazol-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0065] 5-(3-{4-[Ethyl-(2-hydroxy-ethyl)-amino]-butyl-ureido)-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0066] 3-(4-Chloro-(2,3,6-trifluoro-benzyloxy)-5-{3-[4-(2-hydroxmethyl-piperidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0067] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-[3-(3-hydroxy-5-pyrrolidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0068] 3-(4-Bromo-2,6-difluoro-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0069] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-{3-[2-(1-methyl-pyrrolidin-2-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0070] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(4-dimethylamino-butyl)-ureido}-isothiazole-4-carboxylic acid amide;
[0071] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(3-dimethylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0072] 3-(4-Bromo-2,3,6-trifluoro-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0073] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-[3-(4-imidazol-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0074] 3-(4-Chloro-2,3,6-difluoro-benzyloxy)-5-(3-{3-[ethyl-(2-hydroxy-ethyl)-amino]-propyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0075] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-(3-{3-[ethyl-(2-hydroxy-ethyl)-amino]-propyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0076] 5-[3-(3-Methylamino-propyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0077] 5-[3-(3-Amino-propyl)-3-methyl-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0078] 5-[3-(4-Diethylamino-butyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0079] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0080] 3-(3-Chloro-2,6-difluoro-4-methyl-benzyloxy)-5-[3-(4-dimethylamino-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0081] 5-(3-{4-[Bis-(2-hydroxy-ethyl)-amino]-butyl}-ureido)-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0082] and the pharmaceutically acceptable salts and hydrates of the foregoing compounds.
[0083] The invention also relates to a pharmaceutical composition for the treatment of a hyperproliferative disorder in a mammal which comprises a therapeutically effective amount of a compound of formula 1, or a pharmaceutically acceptable salt or hydrate thereof, and a pharmaceutically acceptable carrier. In one embodiment, said pharmaceutical composition is for the treatment of cancer such as brain, lung, squamous cell, bladder, gastric, pancreatic, breast, head, neck, renal, prostate, colorectal, oesophageal, gynecological (such as ovarian) or thyroid cancer. In another embodiment, said pharmaceutical composition is for the treatment of a non-cancerous hyperproliferative disorder such as benign hyperplasia of the skin (e.g., psoriasis) or prostate (e.g., benign prostatic hypertropy (BPH)).
[0084] The invention also relates to a pharmaceutical composition for the treatment of pancreatitis or kidney disease (including proliferative glomerulonephritis and diabetes-induced renal disease) in a mammal which comprises a therapeutically effective amount of a compound of formula 1, or a pharmaceutically acceptable salt or hydrate thereof, and a pharmaceutically acceptable carrier.
[0085] The invention also relates to a pharmaceutical composition for the prevention of blastocyte implantation in a mammal which comprises a therapeutically effective amount of a compound of formula 1, or a pharmaceutically acceptable salt or hydrate thereof, and a pharmaceutically acceptable carrier.
[0086] The invention also relates to a pharmaceutical composition for treating a disease related to vasculogenesis or angiogenesis in a mammal which comprises a therapeutically effective amount of a compound of formula 1, or a pharmaceutically acceptable salt or hydrate thereof, and a pharmaceutically acceptable carrier. In one embodiment, said pharmaceutical composition is for treating a disease selected from the group consisting of tumor angiogenesis, chronic inflammatory disease such as rheumatoid arthritis, atherosclerosis, skin diseases such as psoriasis, excema, and scleroderma, diabetes, diabetic retinopathy, retinopathy of prematurity, age-related macular degeneration, hemangioma, glioma, melanoma, Kaposi's sarcoma and ovarian, breast, lung, pancreatic, prostate, colon and epidermoid cancer.
[0087] The invention also relates to a method of treating a hyperproliferative disorder in a mammal which comprises administering to said mammal a therapeutically effective amount of the compound of formula 1, or a pharmaceutically acceptable salt or hydrate thereof. In one embodiment, said method relates to the treatment of cancer such as brain, squamous cell, bladder, gastric, pancreatic, breast, head, neck, oesophageal, prostate, colorectal, lung, renal, gynecological (such as ovarian) or thyroid cancer. In another embodiment, said method relates to the treatment of a non-cancerous hyperproliferative disorder such as benign hyperplasia of the skin (e.g., psoriasis) or prostate (e.g., benign prostatic hypertropy (BPH)).
[0088] The invention also relates to a method for the treatment of a hyperproliferative disorder in a mammal which comprises administering to said mammal a therapeutically effective amount of a compound of formula 1, or a pharmaceutically acceptable salt or hydrate thereof, in combination with an anti-tumor agent selected from the group consisting of mitotic inhibitors, alkylating agents, anti-metabolites, intercalating antibiotics, growth factor inhibitors, cell cycle inhibitors, enzymes, topoisomerase inhibitors, biological response modifiers, anti-hormones, and anti-androgens.
[0089] The invention also relates to a method of treating pancreatitis or kidney disease in a mammal which comprises administering to said mammal a therapeutically effective amount of a compound of formula 1, or a pharmaceutically acceptable salt or hydrate thereof.
[0090] The invention also relates to a method of preventing blastocyte implantation in a mammal which comprises administering to said mammal a therapeutically effective amount of a compound of formula 1, or a pharmaceutically acceptable salt or hydrate thereof.
[0091] The invention also relates to a method of treating diseases related to vasculogenesis or angiogenesis in a mammal which comprises administering to said mammal an effective amount of a compound of formula 1, or a pharmaceutically acceptable salt or hydrate thereof. In one embodiment, said method is for treating a disease selected from the group consisting of tumor angiogenesis, chronic inflammatory disease such as rheumatoid arthritis, atherosclerosis, skin diseases such as psoriasis, excema, and scleroderma, diabetes, diabetic retinopathy, retinopathy of prematurity, macular degeneration, hemangioma, glioma, melanoma, Kaposi's sarcoma and ovarian, breast, lung, pancreatic, prostate, colon and epidermoid cancer.
[0092] Further the compounds of the present invention may be used as contraceptives in mammals.
[0093] Patients that can be treated with the compounds of formulas 1, and the pharmaceutically acceptable salts and hydrates of said compounds, according to the methods of this invention include, for example, patients that have been diagnosed as having psoriasis, BPH, lung cancer, bone cancer, pancreatic cancer, skin cancer, cancer of the head and neck, cutaneous or intraocular melanoma, uterine cancer, ovarian cancer, rectal cancer or cancer of the anal region, stomach cancer, colon cancer, breast cancer, gynecologic tumors (e.g., uterine sarcomas, carcinoma of the fallopian tubes, carcinoma of the endometrium, carcinoma of the cervix, carcinoma of the vagina or carcinoma of the vulva), Hodgkin's disease, cancer of the esophagus, cancer of the small intestine, cancer of the endocrine system (e.g., cancer of the thyroid, parathyroid or adrenal glands), sarcomas of soft tissues, cancer of the urethra, cancer of the penis, prostate cancer, chronic or acute leukemia, solid tumors of childhood, lymphocytic lymphonas, cancer of the bladder, cancer of the kidney or ureter (e.g., renal cell carcinoma, carcinoma of the renal pelvis), or neoplasms of the central nervous system (e.g., primary CNS lymphoma, spinal axis tumors, brain stem gliomas or pituitary adenomas).
[0094] The present invention also relates to intermediates selected from the group consisting of (2,6-difluoro-4-methyl-phenyl)-methanol, (2,3,6-trifluoro-4-methyl-phenyl)-methanol, (4-bromo-2,6-difluoro-phenyl)-methanol, (4-bromo-2,3,6-trifluoro-phenyl)-methanol, (4-chloro-2,6-difluoro-phenyl)-methanol, (3-chloro-2,6-difluoro-phenyl)-methanol, and (4-chloro-2,3,6-trifluoro-phenyl)-methanol.
[0095] The present invention also relates to an intermediate selected from the group consisting of:
[0096] The present invention also relates to an intermediate selected from the group consisting of:
[0097] wherein R 3 is as defined above.
[0098] The present invention also relates to a method of preparing a compound of formula 1 which comprises either
[0099] (a) treating a compound of formula 18
[0100] with a compound of the formula R 3 —X wherein X is a halo group and R 3 is as defined above, and treating the resulting compound with a compound of the formula R 1 R 2 NH wherein R 1 and R 2 are as defined above; or,
[0101] (b) treating a compound of the formula 25
[0102] wherein R 3 is as defined above, with a compound of the formula R 1 R 2 NH wherein R 1 and R 2 are as defined above.
[0103] The term “halo”, as used herein, unless otherwise indicated, includes fluoro, chloro, bromo or iodo. Preferred halo groups are fluoro, chloro and bromo.
[0104] The term “alkyl”, as used herein, unless otherwise indicated, includes saturated monovalent hydrocarbon radicals having straight, cyclic or branched moieties. It is understood that for cyclic moieties at least three carbon atoms are required in said alkyl group.
[0105] The term “alkenyl”, as used herein, unless otherwise indicated, includes monovalent hydrocarbon radicals having at least one carbon-carbon double bond and also having straight, cyclic or branched moieties as provided above in the definition of “alkyl”.
[0106] The term “alkynyl”, as used herein, unless otherwise indicated, includes monovalent hydrocarbon radicals having at least one carbon-carbon triple bond and also having straight, cyclic or branched moieties as provided above in the definition of “alkyl”.
[0107] The term “alkyoxy”, as used herein, unless otherwise indicated, includes O-alkyl groups wherein “alkyl” is as defined above.
[0108] The term “aryl”, as used herein, unless otherwise indicated, includes an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, such as phenyl or naphthyl.
[0109] The term “4-10 membered heterocyclic”, as used herein, unless otherwise indicated, includes aromatic and non-aromatic heterocyclic groups containing one or more heteroatoms each selected from O, S and N, wherein each heterocyclic group has from 4-10 atoms in its ring system. Non-aromatic heterocyclic groups include groups having only 4 atoms in their ring system, but aromatic heterocyclic groups must have at least 5 atoms in their ring system. An example of a 4 membered heterocyclic group is azetidinyl (derived from azetidine). An example of a 5 membered heterocyclic group is thiazolyl and an example of a 10 membered heterocyclic group is quinolinyl. Examples of non-aromatic heterocyclic groups are pyrrolidinyl, tetrahydrofuranyl, tetrahydrothienyl, tetrahydropyranyl, tetrahydrothiopyranyl, piperidino, morpholino, thiomorpholino, thioxanyl, piperazinyl, azetidinyl, oxetanyl, thietanyl, homopiperidinyl, oxepanyl, thiepanyl, oxazepinyl, diazepinyl, thiazepinyl, 1,2,3,6-tetrahydropyridinyl, 2-pyrrolinyl, 3-pyrrolinyl, indolinyl, 2H-pyranyl, 4H-pyranyl, dioxanyl, 1,3-dioxolanyl, pyrazolinyl, dithianyl, dithiolanyl, dihydropyranyl, dihydrothienyl, dihydrofuranyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, 3-azabicyclo[3.1.0]hexanyl, 3-azabicyclo[4.1.0]heptanyl, 3H-indolyl and quinolizinyl. Examples of aromatic heterocyclic groups are pyridinyl, imidazolyl, pyrimidinyl, pyrazolyl, triazolyl, pyrazinyl, tetrazolyl, furyl, thienyl, isoxazolyl, thiazolyl, oxazolyl, isothiazolyl, pyrrolyl, quinolinyl, isoquinolinyl, indolyl, benzimidazolyl, benzofuranyl, cinnolinyl, indazolyl, indolizinyl, phthalazinyl, pyridazinyl, triazinyl, isoindolyl, pteridinyl, purinyl, oxadiazolyl, thiadiazolyl, furazanyl, benzofurazanyl, benzothiophenyl, benzothiazolyl, benzoxazolyl, quinazolinyl, quinoxalinyl, naphthyridinyl, and furopyridinyl. The foregoing groups, as derived from the compounds listed above, may be C-attached or N-attached where such is possible. For instance, a group derived from pyrrole may be pyrrol-1-yl (N-attached) or pyrrol-3-yl (C-attached).
[0110] The phrase “pharmaceutically acceptable salt(s)”, as used herein, unless otherwise indicated, includes salts of acidic or basic groups which may be present in the compounds of formula 1. The compounds of formula 1 that are basic in nature are capable of forming a wide variety of salts with various inoroanic and organic acids. The acids that may be used to prepare pharmaceutically acceptable acid addition salts of such basic compounds of formula 1 are those that form non-toxic acid addition salts, i.e., salts containing pharmacologically acceptable anions, such as the hydrochloride, hydrobromide, hydroiodide, nitrate, sulfate, bisulfate, phosphate, acid phosphate, isonicotinate, acetate, lactate, salicylate, citrate, acid citrate, tartrate, pantothenate, bitartrate, ascorbate, succinate, maleate, gentisinate, fumarate, gluconate, glucaronate, saccharate, formate, benzoate, glutamate, methanesulfonate, ethanesulfonate, benzenesulfonate, p-toluenesulfonate and pamoate [i.e., 1,1′-methylene-bis-(2-hydroxy-3-naphthoate)] salts.
[0111] Those compounds of the formula 1 that are acidic in nature, are capable of forming base salts with various pharmacologically acceptable cations. Examples of such salts include the alkali metal or alkaline earth metal salts and particularly, the sodium and potassium salts.
[0112] Certain compounds of formula 1 may have asymmetric centers and therefore exist in different enantiomeric forms. This invention relates to the use of all optical isomers and stereoisomers of the compounds of formula 1 and mixtures thereof. The compounds of formula 1 may also exist as tautomers. This invention relates to the use of all such tautomers and mixtures thereof.
[0113] The subject invention also includes isotopically-labelled compounds, and the pharmaceutically acceptable salts thereof, which are identical to those recited in formula 1, but for the fact that one or more atoms are replaced by an atom having an atomic mass or mass number different from the atomic mass or mass number usually found in nature. Examples of isotopes that can be incorporated into compounds of the invention include isotopes of hydrogen, carbon, nitrogen, oxygen, phosphorous, fluorine and chlorine, such as 2 H, 3 H, 13 C, 14 C, 15 N, 18 O, 17 O, 35 S, 18 F, and 36 Cl, respectively. Compounds of the present invention, prodrugs thereof, and pharmaceutically acceptable salts of said compounds or of said prodrugs which contain the aforementioned isotopes and/or other isotopes of other atoms are within the scope of this invention. Certain isotopically-labelled compounds of the present invention, for example those into which radioactive isotopes such as 3 H and 14 C are incorporated, are useful in drug and/or substrate tissue distribution assays. Tritiated, i.e., 3 H, and carbon-14, i.e., 14 C, isotopes are particularly preferred for their ease of preparation and detectability. Further, substitution with heavier isotopes such as deuterium, i.e., 2 H, can afford certain therapeutic advantages resulting from greater metabolic stability, for example increased in vivo half-life or reduced dosage requirements and, hence, may be preferred in some circumstances. Isotopically labelled compounds of formula 1 of this invention and prodrugs thereof can generally be prepared by carrying out the procedures disclosed in the Schemes and/or in the Examples and Preparations below, by substituting a readily available isotopically labelled reagent for a non-isotopically labelled reagent.
[0114] This invention also encompasses pharmaceutical compositions containing and methods of treating bacterial infections through administering prodrugs of compounds of the formula 1. Compounds of formula 1 having free amino, amido, hydroxy or carboxylic groups can be converted into prodrugs. Prodrugs include compounds wherein an amino acid residue, or a polypeptide chain of two or more (e.g., two, three or four) amino acid residues is covalently joined through an amide or ester bond to a free amino, hydroxy or carboxylic acid group of compounds of formula 1. The amino acid residues include but are not limited to the 20 naturally occurring amino acids commonly designated by three letter symbols and also includes 4-hydroxyproline, hydroxylysine, demosine, isodemosine, 3-methylhistidine, norvalin, beta-alanine, gamma-aminobutyric acid, citrulline homocysteine, homoserine, ornithine and methionine sulfone.
[0115] Additional types of prodrugs are also encompassed. For instance, free carboxyl groups can be derivatized as amides or alkyl esters. The amide and ester moieties may incorporate groups including but not limited to ether, amine and carboxylic acid functionalities. Free hydroxy groups may be derivatized using groups including but not limited to hemisuccinates, phosphate esters, dimethylaminoacetates, and phosphoryloxymethyloxy carbonyls, as outlined in D. Fleisher, R. Bong, B. H. Stewart, Advanced Drug Delivery Reviews (1996) 19, 115. Carbamate prodrugs of hydroxy and amino groups are also included, as are carbonate prodrugs and sulfate esters of hydroxy groups. Derivatization of hydroxy groups as (acyloxy)methyl and (acyloxy)ethyl ethers wherein the acyl group may be an alkyl ester, optionally substituted with groups including but not limited to ether, amine and carboxylic acid functionalities, or where the acyl group is an amino acid ester as described above, are also encompassed. Prodrugs of this type are described in R. P. Robinson et al., J. Medicinal Chemistry (1996) 39, 10.
DETAILED DESCRIPTION OF THE INVENTION
[0116] Compounds of the formula 1 and their pharmaceutically acceptable salts and solvates may be prepared as described below. Unless otherwise indicated, R 1 , R 2 and R 3 are as defined above.
[0117] The compounds of the present invention are readily prepared by following the procedures outlined in the schemes illustrated above and typical synthetic procedures familiar to those skilled in the art. Scheme 1 illustrates the condensation of malononitrile with an isocyanate, oxidation with sulfur, alkylation with an R 3 containing compound, and hydration of the nitrile to provide the final compound. In step 1 of Scheme 1, the compound of formula 4 may be prepared by treating the compound of formula 3 and the compound of formula 2 (R 1 and R 2 are not H but otherwise are as defined above) with a suitably strong base, such as an alkoxide base, preferably sodium ethoxide, in a protic solvent, such as an alcohol, preferably ethanol, at a temperature ranging from −20° C. to 50° C., preferably 0° C. to 25° C., over a period of about 12 to 24 hours. In step 2 of Scheme 1, the compound of formula 5 may be prepared by treating the compound of formula 4 with sulfur (about 1 equivalent to excess) in a polar solvent, such as an alcoholic solvent, preferably methanol, at a temperature ranging from 25° C. to 80° C., preferably about 65° C., for a period of about 12 to 48 hours, preferably about 24 hours. In step 3 of Scheme 1, the compound of formula 6 may be prepared by treating the compound of formula 5 with an R 3 -containing electrophile, such as a halide, preferably a chloride, bromide or iodide of such compound, in a polar solvent, preferably tetrahydrofuran (THF) or N,N-dimethylformamide (DMF), using about 1 to 5 equivalent, preferably a bit over 1 equivalent, and a base, such as a tertiary amine base, preferably diisopropylethylamine, for a period of about 12 to 48 hours, preferably about 24 hours, at a temperature ranging from 0° C. to 80° C., preferably about 25° C. In step 4 of Scheme 1, the compound of formula 1 (wherein X 1 is S) may be prepared by treating the compound of formula 6 under strongly acidic conditions, such as concentrated sulfuric acid, for a period of about 1 to 12 hours, preferably about 1.5 hours, at a temperature ranging from 25° C. to 100° C., preferably about 25° C., or under basic conditions, such as with aqueous sodium hydroxide (10%), for a period ranging from 6 to 24 hours at a temperature ranging from 25° C. to 120° C., preferably about 100° C.
[0118] Scheme 2 illustrates another method of preparing the compounds of formula 1 wherein X 1 is S. In step 1 of Scheme 2, the compound of formula 7 may be prepared by condensation of the compound of formula 3 with an alkoxycarbonyl isothiocyanate, such as ethoxy carbonyl isothiocyanate, in the presence of a strong base, such as an alkoxide base, preferably sodium ethoxide, in a polar solvent, such as an alcoholic solvent, preferably ethanol, for a period ranging from 12 to 24 hours at a temperature ranging from about 0° C. to 30° C. In step 2 of Scheme 2, the compound of formula 8 may be prepared by oxidative cyclization of the compound of formula 7 by treating the compound of formula 7 with about 1 equivalent of sulfur in an alcoholic solvent, such as methanol, at a temperature ranging from about 50° C. to 80° C., preferably about 65° C., for a period ranging from 24 to 48 hours. In step 3 of Scheme 2, the compound of formula 9 may be prepared by treating the compound of formula 8 with an R 3 -containing electrophile, such as a halide, preferably the chloride, bromide or iodide of such compound, in a polar solvent, such as THF, at a temperature ranging from 25° C. to 40° C. for a period ranging from 12 to 24 hours. In step 4 of Scheme 2, the compound of formula 10 may be prepared by hydrolysing the compound of formula 9 with a suitably strong acid, such as concentrated sulfuric acid, at a temperature ranging from 80° C. to 120° C. for a period of about 6 to 18 hours. In step 5 of Scheme 2, the compound of formula 11 (wherein Ph is phenyl) may be prepared by treating the compound of formula 10 with an aryl or alkyl chloroformate, such as phenyl chloroformate, and a suitably strong base, such as pyridine, in a polar aprotic solvent, preferably THF or CH 2 Cl 2 , at a temperature ranging from 25° C. to 40° C. for a period ranging from 12 to 24 hours. In step 6 of Scheme 2, the compound of formula 1 (wherein X 1 is S) may be prepared by treating the compound of formula 11 with an excess (about 1.1 to 6 equivalents) of a primary or secondary amine of the formula R 1 R 2 NH in a polar aprotic solvent, such as THF or a THF/DMF mixture, at a temperature ranging from 23° C. to 60° C. for a period ranging from 6 to 24 hours.
[0119] Scheme 3 illustrates a method of preparing the compounds of formula 1 wherein X 1 is O. The starting compound of formula 4 may be prepared as described above with reference to Scheme 1. In step 1 of Scheme 3, a solution of the salt of formula 4 in an inert solvent containing water or, preferably, in water alone, is treated with an oxidizing reagent, preferably dihydrogen peroxide. The mixture is held at a temperature and time sufficient to effect dissolution and cyclization, preferably at reflux for about 15 minutes, and then cooled to provide the compound of formula 12. In step 2 of Scheme 3, the compound of formula 12 is added to an acid solution, preferably concentrated sulfuric acid, followed by water sufficient to effect hydration, preferably about 10 equivalents, and is stirred at a temperature ranging from −20° C. and 100° C., preferably ambient temperature, for a period to effect hydration, preferably overnight. The mixture is then treated with water or, preferably, ice to provide the compound of formula 13. In step 3 of Scheme 3, the compound of formula 13 is treated with a base, preferably potassium tert-butoxide, in an inert solvent, preferably DMF, at a temperature ranging from −78° C. to 100° C., preferably ambient temperature. To this mixture is added an R 3 containing electrophile, such as an R 3 containing alkyl halide or sulfonate, preferably an iodide or bromide of such compound. The mixture is stirred until the reaction is complete as judged by TLC analysis to provide the compound of formula 1 (wherein X 1 is O).
[0120] Scheme 4 illustrates another method of preparing the compounds of formula 1 wherein X 1 is S. In step 1 of Scheme 4, the procedure follows the synthetic procedure outlined in M. Yokoyama and K. Sato, Synthesis, 813 (1988). Following this, the compound of formula 3 is treated with an alkyl thiol, such as 4-methoxy benzyl mercaptan, and a suitably strong base, such as sodium hydroxide, in a polar solvent, such as an alcohol/water mixture, preferably 1:1 ethanol/water, at a temperature ranging from −10° C. to 30° C., preferably about 0° C., for a period ranging from 2 to 6 hours, preferably about 3 hours, to provide the compound of formula 14. In step 2 of Scheme 4, the compound of formula 15 (Ph is phenyl) may be prepared by treating the compound of formula 14 with an alkoxy carbonyl isothiocyanate, such as phenoxy carbonyl isothiocyanate, in an aprotic solvent, such as ethyl acetate, at about 0° C. for about 12 to 36 hours. In step 3 of Scheme 4, the compound of formula 16 may be prepared by treating the compound of formula 15 with an oxidizing agent, such as bromine or iodine, preferably iodine, and a mild base, such as pyridine, in a polar solvent, such as acetonitrile, for about 1 hour at about 0° C. In step 4 of Scheme 4, the compound of formula 17 may be prepared by deprotection of the 4-methoxy benzyl group by treating the compound of formula 16 with mercuric acetate, about 1 equivalent, in the presence of an acid, preferably trifluoroacetic acid (TFA), with an excess of anisole, preferably 10 equivalents, at a temperature ranging from 0° C. to ambient temperature for a period ranging from 10 to 24 hours. In step 5 of Scheme 4, the compound of formula 18 may be prepared by hydration of the compound of formula 17 with a suitably strong acid, such as concentrated sulfuric acid, at a temperature ranging from 15° C. to 80° C., preferably ambient temperature, for a period ranging from 12 to 24 hours, preferably 18 hours. In step 6 of Scheme 4, the compound of formula 1 may be prepared by treating the compound of formula 18 with an R 3 -containing electrophile, such as a halide, preferably the chloride, bromide or iodide of such compound, and a suitably strong base, such as diisopropyl ethyl amine, in a polar solvent, preferably DMF, at a temperature ranging from 0° C. to 50° C., preferably 25° C., for a period ranging from 12 to 24 hours. The resulting compound is then treated with a primary or secondary amine of the formula R 1 R 2 NH (about 1.1 to 6 equivalents) in a THF/DMF mixture at a temperature ranging from 25° C. to 65° C. for a period ranging from 18 to 36 hours.
[0121] Scheme 5 illustrates another method of preparing a compound of formula 1 wherein X 1 is O. In step 1 of Scheme 5, a mixture of a thiocyanate salt, preferably potassium thiocyanate, in an inert solvent, preferably ethyl acetate, is stirred, preferably vigorously, under an inert atmosphere, overnight to powder the salt. This mixture is then treated with an aryl chloroformate of the formula 19 (Ph is phenyl) and the resulting mixture is stirred at a temperature ranging from −40° C. to ambient temperature, preferably about 5° C., for a period sufficient to effect reaction, preferably about 8 hours. The solid byproduct is filtered off and the product is kept cool, preferably not above ambient temperature. The product is redissolved in a suitable inert solvent, preferably ether, and additional insoluble byproduct is removed. After concentration, the product is again redissolved in a suitable inert solvent, preferably hexane, and additional insoluble byproducts removed. The compound of formula 20 is then isolated. In step 2 of Scheme 5, an acidic solution, preferably ethereal HCl, is treated with the compound of formula 3. Upon dissolution, the solution is cooled, preferably to 10° C., and is treated with an alcohol, preferably benzyl alcohol. After additional stirring, the mixture is held at a given temperature, preferably about 5° C., for a period sufficient to allow complete reaction, typically about 4 days, to provide the compound of formula 21. In step 3 of Scheme 5, a solution of the compound of formula 21 in a suitable inert solvent, preferably acetonitrile, at a temperature ranging from −40° C. to ambient temperature, preferably 0° C., is treated with a solution of the compound of formula 20 in a suitable inert solvent, preferably acetonitrile. The reaction is kept at a temperature ranging from 0° C. to ambient temperature, preferably ambient temperature, to effect reaction. The mixture is then kept at a temperature appropriate to increase solidification of the product, preferably about 5° C., for period sufficient to maximize yield, preferably about 2 days. The compound of formula 22 (Bn is benzyl) is then isolated. In step 4 of Scheme 5, the compound of formula 22 is taken up in a suitable inert solvent, preferably acetonitrile, at a temperature ranging from −40° C. and 40° C., preferably 0° C., and treated with a base, preferably pyridine, and an oxidant, preferably a solution of bromine or iodine in a suitable inert solvent, preferably acetonitrile. The mixture is then stirred at a temperature sufficient to effect reaction, preferably at 0° C. for about 1 hour followed by another hour at ambient temperature. The mixture is then allowed to stand at a temperature sufficient to increase solidification, preferably at 5° C., for a sufficient period, preferably overnight. The compound of formula 23 is then isolated. In step 5 of Scheme 5, the hydration and deprotection of the compound of formula 23 is effected by treatment with an acid, preferably concentrated sulfuric acid. If the compound of formula 23 is sufficiently wet with water from the previous step, no additional water is added. If the compound of formula 23 is dry, then additional water is added, preferably about 10 equivalents. The reaction is carried out at a temperature ranging from −20° C. to 100° C., preferably ambient temperature, for a period sufficient to effect complete reaction, typically marked by complete dissolution and preferably about 3 hours. After the reaction is completed, additional sulfuric acid is added to achieve complete conversion. The mixture is then treated with water or, preferably, ice. The compound of formula 24 is then isolated. In step 6 of Scheme 5, the compound of formula 24 is combined with a trivalent phosphine, preferably triphenyl phosphine, and an R 3 containing alcohol, and is treated with an azodicarboxylate derivative, preferably diisopropyl azodicarboxylate, and stirring is continued for a period of at least 1 minute. The compound of formula 25 is then isolated. In step 7 of Scheme 5, a mixture of the compound of formula 25 in a suitable inert solvent, preferably THF, is treated with a desired amine of the formula R 1 R 2 NH and kept at a temperature sufficient to effect reaction, typically 0° C. to 100° C., preferably 50° C. to 70° C., for a period ranging from 1 hour to 48 hours, preferably overnight. The compound of formula 1 (wherein X 1 is O) is then isolated.
[0122] The compounds of the present invention may have asymmetric carbon atoms. Such diasteromeric mixtures can be separated into their individual diastereomers on the basis of their physical chemical differences by methods known to those skilled in the art, for example, by chromatography or fractional crystallization. Enantiomers can be separated by converting the enantiomeric mixtures into a diastereomeric mixture by reaction with an appropriate optically active compound (e.g., alcohol), separating the diastereomers and converting (e.g., hydrolyzing) the individual diastereomers to the corresponding pure enantiomers. All such isomers, including diastereomer mixtures and pure enantiomers are considered as part of the invention.
[0123] The compounds of formula 1 that are basic in nature are capable of forming a wide variety of different salts with various inorganic and organic acids. Although such salts must be pharmaceutically acceptable for administration to animals, it is often desirable in practice to initially isolate the compound of formula 1 from the reaction mixture as a pharmaceutically unacceptable salt and then simply convert the latter back to the free base compound by treatment with an alkaline reagent and subsequently convert the latter free base to a pharmaceutically acceptable acid addition salt. The acid addition salts of the base compounds of this invention are readily prepared by treating the base compound with a substantially equivalent amount of the chosen mineral or organic acid in an aqueous solvent medium or in a suitable organic solvent, such as methanol or ethanol. Upon careful evaporation of the solvent, the desired solid salt is readily obtained. The desired acid salt can also be precipitated from a solution of the free base in an organic solvent by adding to the solution an appropriate mineral or organic acid.
[0124] Those compounds of formula 1 that are acidic in nature, are capable of forming base salts with various pharmacologically acceptable cations. Examples of such salts include the alkali metal or alkaline-earth metal salts and particularly, the sodium and potassium salts. These salts are all prepared by conventional techniques. The chemical bases which are used as reagents to prepare the pharmaceutically acceptable base salts of this invention are those which form non-toxic base salts with the acidic compounds of formulas 1. Such non-toxic base salts include those derived from such pharmacologically acceptable cations as sodium, potassium, calcium and magnesium, etc. These salts can easily be prepared by treating the corresponding acidic compounds with an aqueous solution containing the desired pharmacologically acceptable cations, and then evaporating the resulting solution to dryness, preferably under reduced pressure. Alternatively, they may also be prepared by mixing lower alkanolic solutions of the acidic compounds and the desired alkali metal alkoxide together, and then evaporating the resulting solution to dryness in the same manner as before. In either case, stoichiometric quantities of reagents are preferably employed in order to ensure completeness of reaction and maximum yields of the desired final product.
[0125] Included in the present invention are compounds identical to the compounds of formula 1 but for the fact that one or more hydrogen or carbon atoms are replaced by isotopes thereof. Such compounds are useful as research and diagnostic tools in metabolism pharmokinetic studies and in binding assays. Specific applications in research include radioligand binding assays, autoradiography studies and in vivo binding studies. Included among the radiolabelled forms of the compounds of formula 1 are the tritium and C 14 isotopes thereof.
[0126] The in vitro activity of the compounds of formula 1 in inhibiting the KDR/VEGF receptor may be determined by the following procedure.
[0127] The ability of the compounds of the present invention to inhibit tyrosine kinase activity may be measured using a recombinant enzyme in an assay that measures the ability of compounds to inhibit the phosphorylation of the exogenous substrate, polyGluTyr (PGT, Sigma™, 4:1). The kinase domain of the human KDR/VEGF receptor (amino acids 805-1350) is expressed in Sf9 insect cells as a glutathione S-transferase (GST)-fusion protein using the baculovirus expression system. The protein is purified from the lysates of these cells using glutathione agarose affinity columns. The enzyme assay is performed in 96-well plates that are coated with the PGT substrate (0.625 μg PGT per well). Test compounds are diluted in dimethylsulfoxide (DMSO), and then added to the PGT plates so that the final concentration of DMSO in the assay is 1.6% (v/v). The recombinant enzyme is diluted in phosphorylation buffer (50 mM Hepes, pH 7.3, 125 mM NaCl, 24 mM MgCl 2 ). The reaction is initiated by the addition of ATP to a final concentration of 10 μM. After a 30 minute incubation at room temperature with shaking, the reaction is aspirated, and the plates are washed with wash buffer (PBS-containing 0.1% Tween-20). The amount of phosphorylated PGT is quantitated by incubation with a HRP-conjugated (HRP is horseradish peroxidase) PY-54 antibody (Transduction Labs), developed with TMB peroxidase (TMB is 3,3′,5,5′-tetramethylbenzidine), and the reaction is quantitated on a BioRad™ Microplate reader at 450 nM. Inhibition of the kinase enzymatic activity by the test compound is detected as a reduced absorbance, and the concentration of the compound that is required to inhibit the signal by 50% is reported as the IC 50 value for the test compound.
[0128] To measure the ability of the compounds to inhibit KDR tyrosine kinase activity for the full length protein that exists in a cellular context, the porcine aortic endothelial (PAE) cells transfected with the human KDR (Waltenberger et al., J. Biol. Chem. 269:26988, 1994) may be used. Cells are plated and allowed to attach to 96-well dishes in the same media (Ham's F12) with 10% FBS (fetal bovine serum). The cells are then washed, re-fed with serum depleted media that contains 0.1% (v/v) bovine serum albumin (BSA), and allowed to incubate for 24 hours. Immediately prior to dosing with compound, the cells are re-fed with the serum depleted media (without BSA). Test compounds, dissolved in DMSO, are diluted into the media (final DMSO concentration 0.5% (v/v)). At the end of a 2 hour incubation, VEGF 165 (50 ng/ml final) is added to the media for an 8 minute incubation. The cells are washed and lysed in HNTG buffer (20 mM Hepes, pH 7.5, 150 mM NaCl, 0.2% Triton™ X-100, 10% glycerol, 0.2 mM PMSF (phenymethylsulfonyl fluoride), 1 μg/ml pepstatin, 1 μg/ml leupeptin, 1 μg/ml aprotonin, 2 mM sodium pyrophosphate, 2 mM sodium orthovanadate). The extent of phosphorylation of KDR is measured using an ELISA assay. The 96-well plates are coated with 1 μg per well of goat anti-rabbit antibody. Unbound antibody is washed off the plate and remaining sites are blocked with Superblock buffer (Pierce) prior to addition of the anti-flk-1 C-20 antibody (0.5 μg per plate, Santa Cruz). Any unbound antibody is washed off the plates prior to addition of the cell lysate. After a 2 hour incubation of the lysates with the flk-1 antibody, the KDR associated phosphotyrosine is quantitated by development with the HRP-conjugated PY-54 antibody and TMB, as described above. The ability of the compounds to inhibit the VEGF-stimulated autophosphorylation reaction by 50%, relative to VEGF-stimulated controls is reported as the IC 50 value for the test compound.
[0129] The ability of the compounds to inhibit mitogenesis in human endothelial cells is measured by their ability to inhibit 3 H-thymidine incorporation into HUVE cells (human umbilical vein endothelial cells, Clonetics™). This assay has been well described in the literature (Waltenberger J et al. J. Biol. Chem. 269: 26988, 1994; Cao Y et al. J. Biol. Chem. 271: 3154, 1996). Briefly, 10 4 cells are plated in collagen-coated 24-well plates and allowed to attach. Cells are re-fed in serum-free media, and 24 hours later are treated with various concentrations of compound (prepared in DMSO, final concentration of DMSO in the assay is 0.2% v/v), and 2-30 ng/ml VEGF 165 . During the last 3 hours of the 24 hour compound treatment, the cells are pulsed with 3 H thymidine (NEN, 1 μCi per well). The media are then removed, and the cells washed extensively with ice-cold Hank's balanced salt solution, and then 2 times with ice cold trichloroacetic acid (10% v/v). The cells are lysed by the addition of 0.2 ml of 0.1 N NaOH, and the lysates transferred into scintillation vials. The wells are then washed with 0.2 ml of 0.1 N HCl, and this wash is then transferred to the vials. The extent of 3 H thymidine incorporation is measured by scintillation counting. The ability of the compounds to inhibit incorporation by 50%, relative to control (VEGF treatment with DMSO vehicle only) is reported as the IC 50 value for the test compound.
[0130] The activity of the compounds of formula 1, in vivo, can be determined by the amount of inhibition of tumor growth by a test compound relative to a control. The tumor growth inhibitory effects of various compounds are measured according to the methods of Corbett T. H., et al. “Tumor Induction Relationships in Development of Transplantable Cancers of the Colon in Mice for Chemotherapy Assays, with a Note on Carcinogen Structure”, Cancer Res., 35, 2434-2439 (1975) and Corbett, T. H., et al., “A Mouse Colon-tumor Model for Experimental Therapy”, Cancer Chemother. Rep. ( Part 2)”, 5, 169-186 (1975), with slight modifications. Tumors are induced in the flank by s.c. injection of 1×10 6 log phase cultured tumor cells suspended in 0.1-0.2 ml PBS. After sufficient time has elapsed for the tumors to become palpable (5-6 mm in diameter), the test animals (athymic mice) are treated with active compound (formulated by dissolution in appropriate diluent, for example water or 5% Gelucire™ 44/14 m PBS by the intraperitoneal (ip) or oral (po) routes of administration once or twice daily for 5-10 consecutive days. In order to determine an anti-tumor effect, the tumor is measured in millimeters with Vernier calipers across two diameters and the tumor volume (mm 3 ) is calculated using the formula: Tumor weight=(length×[width] 2 )/2, according to the methods of Geran, R. I., et al. “Protocols for Screening Chemical Agents and Natural Products Against Animal Tumors and Other Biological Systems”, Third Edition, Cancer Chemother. Rep., 3, 1-104 (1972). The flank site of tumor implantation provides reproducible dose/response effects for a variety of chemotherapeutic agents, and the method of measurement (tumor diameter) is a reliable method for assessing tumor growth rates.
[0131] Administration of the compounds of the present invention (hereinafter the “active compound(s)”) can be effected by any method that enables delivery of the compounds to the site of action. These methods include oral routes, intraduodenal routes, parenteral injection (including intravenous, subcutaneous, intramuscular, intravascular or infusion), topical, and rectal administration.
[0132] The amount of the active compound administered will be dependent on the subject being treated, the severity of the disorder or condition, the rate of administration and the judgement of the prescribing physician. However, an effective dosage is in the range of about 0.001 to about 100 mg per kg body weight per day, preferably about 1 to about 35 mg/kg/day, in single or divided doses. For a 70 kg human, this would amount to about 0.05 to about 7 g/day, preferably about 0.2 to about 2.5 g/day. In some instances, dosage levels below the lower limit of the aforesaid range may be more than adequate, while in other cases still larger doses may be employed without causing any harmful side effect, provided that such larger doses are first divided into several small doses for administration throughout the day.
[0133] The active compound may be applied as a sole therapy or may involve one or more other anti-tumour substances, for example those selected from, for example, mitotic inhibitors, for example vinblastine; alkylating agents, for example cis-platin, carboplatin and cyclophosphamide; anti-metabolites, for example 5-fluorouracil, cytosine arabinoside and hydroxyurea, or, for example, one of the preferred anti-metabolites disclosed in European Patent Application No. 239362 such as N-(5-[N-(3,4-dihydro-2-methyl-4-oxoquinazolin-6-ylmethyl)-N-methylamino]-2-thenoyl)-L-glutamic acid; growth factor inhibitors; cell cycle inhibitors; intercalating antibiotics, for example adriamycin and bleomycin; enzymes, for example interferon; and anti-hormones, for example anti-estrogens such as Nolvadex™ (tamoxifen) or, for example anti-androgens such as Casodex™ (4′-cyano-3-(4-fluorophenylsulphonyl)-2-hydroxy-2-methyl-3′-(trifluoromethyl)propionanilide). Such conjoint treatment may be achieved by way of the simultaneous, sequential or separate dosing of the individual components of the treatment.
[0134] The pharmaceutical composition may, for example, be in a form suitable for oral administration as a tablet, capsule, pill, powder, sustained release formulations, solution, suspension, for parenteral injection as a sterile solution, suspension or emulsion, for topical administration as an ointment or cream or for rectal administration as a suppository. The pharmaceutical composition may be in unit dosage forms suitable for single administration of precise dosages. The pharmaceutical composition will include a conventional pharmaceutical carrier or excipient and a compound according to the invention as an active ingredient. In addition, it may include other medicinal or pharmaceutical agents, carriers, adjuvants, etc.
[0135] Exemplary parenteral administration forms include solutions or suspensions of active compounds in sterile aqueous solutions, for example, aqueous propylene glycol or dextrose solutions. Such dosage forms can be suitably buffered, if desired.
[0136] Suitable pharmaceutical carriers include inert diluents or fillers, water and various organic solvents. The pharmaceutical compositions may, if desired, contain additional ingredients such as flavorings, binders, excipients and the like. Thus for oral administration, tablets containing various excipients, such as citric acid may be employed together with various disintegrants such as starch, alginic acid and certain complex silicates and with binding agents such as sucrose, gelatin and acacia. Additionally, lubricating agents such as magnesium stearate, sodium lauryl sulfate and talc are often useful for tableting purposes. Solid compositions of a similar type may also be employed in soft and hard filled gelatin capsules. Preferred materials, therefore, include lactose or milk sugar and high molecular weight polyethylene glycols. When aqueous suspensions or elixirs are desired for oral administration the active compound therein may be combined with various sweetening or flavoring agents, coloring matters or dyes and, if desired, emulsifying agents or suspending agents, together with diluents such as water, ethanol, propylene glycol, glycerin, or combinations thereof.
[0137] Methods of preparing various pharmaceutical compositions with a specific amount of active compound are known, or will be apparent, to those skilled in this art. For examples, see Remington's Pharmaceutical Sciences, Mack Publishing Company, Easter, Pa., 15th Edition (1975).
[0138] The examples and preparations provided below further illustrate and exemplify the compounds of the present invention and methods of preparing such compounds. It is to be understood that the scope of the present invention is not limited in any way by the scope of the following examples and preparations.
PREPARATION 1
Dimethylcarbamoylisothiocyanate
[0139] A three liter, three-neck flask fitted with a mechanical stirrer was charged with dimethylcarbamyl chloride (250 mL, 2.70 mol) in anhydrous acetonitrile (1.5 L) and heated to reflux. Next was added potassium thiocyanate (270 g, 2.8 mol, pre-dried at 160° C. under high vacuum for 3 hours) portionwise over 1 hour with caution as the reaction bubbled violently at the start of each addition. After the final addition, the mixture was heated at reflux for an additional 1 hour. The heating mantle was removed and the mixture stirred at ambient temperature for an additional 2.5 hours and was then stored in the refrigerator overnight. The mixture was filtered to remove unwanted solid material and the filtrate concentrated. To the resulting oil was added ether (1 L) and the solid and thick material discarded. The filtrate was again concentrated affording the desired material a dull orange oil (204 g, 1.57 mol, 58%). 1 H NMR (400 MHz, CDCl 3 ) δ2.90 (s, 3H), 2.98 (s, 3H) ppm.
Sodium, 2,2-dicyano-1-(3,3-dimethyl-ureido)-ethenethiolate
[0140] To a 1 M solution of sodium ethoxide in ethanol (prepared by treating 110 mL of anhydrous ethanol with 2.5 g (0.11 mole) of sodium) was added malononitrile (7.2 g, 0.11 mole) at 0° C. Dimethylcarbamoylisothiocyanate (14.3 g, 0.110 mole) was added, and the resulting mixture was allowed to warm to ambient temperature overnight. The mixture was concentrated in vacuo. The residue was treated with hexanes and was concentrated in vacuo to a solid. The residue was triturated with hexanes, collected by filtration and dried in vacuo affording 20 g (83%) of sodium; 2,2-dicyano-1-(3,3-dimethyl-ureido)-ethenethiolate as a colorless solid: 1 H NMR (400 MHz, DMSO-d 6 ) δ8.40 (s, 1H), 2.78 (s, 6H) ppm; 13 C NMR (100 MHz, DMSO-d 6 ): δ189.9, 154.3, 121.4, 118.7, 57.9, 36.5 ppm.
3-(4-Cyano-3-mercapto-isothiazol-5-yl)-1,1-dimethyl-urea
[0141] A mixture of sodium, 2,2-dicyano-1-(3,3-dimethyl-ureido)-ethenethiolate (5.0 g, 23 mmol), sulfur (0.734 g, 23 mmol) and 46 mL of methanol was stirred at reflux for 24 hours. The mixture was filtered, and the filtrate was concentrated in vacuo. The residue was diluted with water and the resulting mixture was extracted twice with ethyl acetate. The aqueous layer was acidified with 1 M HCl (aq) and was extracted into ethyl acetate. The organic layer was dried over Na 2 SO 4 , filtered and concentrated. The solid residue was collected and dried in vacuo yielding 2.0 g (40%) of 3-(4-cyano-3-mercapto-isothiazol-5-yl)-1,1-dimethyl-urea as a yellow solid: 1 H NMR (400 MHz, DMSO-d 6 ) δ2.97 (s, 6H) ppm; MS (APCl, m/z): 227 [M−H] −
General Procedure for the Alkylation of 3-(4-Cyano-3-mercapto-isothiazol-5-yl)-1,1-dimethyl-urea
[0142] To a mixture of 3-(4-cyano-3-mercapto-isothiazol-5-yl)-1,1-dimethyl-urea (0.20 g, 0.88 mmol), the appropriate alkyl chloride, alkyl bromide or alkyl iodide (0.90 mmol) and THF or DMF was added diisopropylethylamine (0.116 g, 0.90 mmol). The resulting mixture was stirred for 24 hours at ambient temperature. The mixture was parititioned between 1M aqueous HCl and ethyl acetate. The organic layer was removed, and the aqueous layer was extracted three times with ethyl acetate. The combined organic layers were dried over Na 2 SO 4 , filtered and concentrated in vacuo. The residue was filtered through a small pad of silica gel eluting with ethyl acetate-hexanes (1:1), affording the alkylated product.
3 -(4-Cyano-3-hexylsulfanyl-isothiazol-5-yl)-1,1-dimethyl-urea
[0143] Following the above general procedure using iodohexane (0.19 g, 0.90 mmol) as the alkyl iodide afforded 0.14 g (51%) of 3-(4-cyano-3-hexylsulfanyl-isothiazol-5-yl)-1,1-dimethyl-urea as a colorless solid: 1 H NMR (400 MHz, acetone-d 6 ) δ9.82 (bs, 1H), 3.20 (t, 2H, J=7.2 Hz), 3.11 (s, 6H), 1.71 (p, 2H, J=7.2 Hz), 1.43 (m, 2H), 1.31 (m, 4H), 0.88 (t, 3H, J=6.0 Hz) ppm; MS (APCl, m/z): 313 [M+H] + .
EXAMPLE 1
5-(3,3-Dimethyl-ureido)-3-hexylsulfanyl-isothiazole-4-carboxylic Acid Amide
[0144] A mixture of 3-(4-cyano-3-hexylsulfanyl-isothiazol-5-yl)-1,1-dimethyl-urea (0.09 g, 0.29 mmol) and concentrated sulfuric acid (0.18 mL) was stirred at ambient temperature for 1.5 hours. The mixture was diluted with ice water, extracted three times into ethyl acetate. The combined organic layers were dried over Na 2 SO 4 , filtered and concentrated in vacuo affording 0.076 g (78%) of 5-(3,3-dimethyl-ureido)-3-hexylsulfanyl-isothiazole-4-carboxylic acid amide as a colorless solid: 1 H NMR (300 MHz, acetone-d 6 ) δ7.08 (bs, 2H), 3.20 (t, 2H, J=7.2 Hz), 3.02 (s, 6H), 1.63 (p, 2H, J=7.2 Hz), 1.35 (m, 2H), 1.23 (m, 4H) 0.78 (t, 3H, J=6.9 Hz) ppm; MS (APCl, m/z): 331 [M+H] + .
PREPARATION 2
Sodium; 2,2-dicyano-1-ethoxycarbonylamino-ethenethiolate
[0145] Sodium metal (1.01 g, 44 mmol) was dissolved in 40 mL of ethanol at ambient temperature. The resulting solution was cooled in an ice bath, and malononitrile (2.91 g, 44 mmol) was added. The ice bath was removed, and the mixture was stirred at ambient temperture for 30 minutes. After cooling to 0° C., ethoxycarbonylisothiocyanate (5.77 g, 44 mmol) was added, and the mixture was allowed to warm to ambient temperature overnight. The mixture was concentrated in vacuo, and the residue solidified upon repeated dilution with hexane and concentration in vacuo. The resulting yellow solids were collected and dried in vacuo, affording 10.74 g (100%) of sodium, 2,2-dicyano-1-ethoxycarbonylamino-ethenethiolate as a light yellow solid that containd 0.5 molar equiv. of ethanol as indicated by 1 H NMR spectroscopy. 1 H NMR (300 MHz, DMSO-d 6 ) δ4.36 (t, 0.5 H, J=5.0 Hz (EtOH)), 4.03 (q, 2H, J=7.1 Hz), 3.43 (dq, 1H J=5.0, 6.7 Hz (EtOH)), 1.26 (t, 3H, J=7.3 Hz), 1.06 (t, 1.5H, J=7.0 Hz (EtOH)) ppm; MS (APCl, m/z): 197 [M−Na] − .
Sodium, 4-cyano-5-ethoxycarbonylamino-isothiazole-3-thiolate
[0146] A mixture of sodium, 2,2-dicyano-1-ethoxycarbonylamino-ethenethiolate (3.3 g, 15 mmol), sulfur (0.48 g, 15 mmol) and methanol (30 mL) was heated at reflux for 24 hours. The mixture was filtered and concentrated in vacuo, and the gummy residue was triturated twice with 10:1 ether-ethyl acetate to afford 2.6 g (69%) of sodium, 4-cyano-5-ethoxycarbonylamino-isothiazole-3-thiolate as a yellow solid. 1 H NMR (400 MHz, DMSO-d 6 ) δ3.99 (q, 2 H, J=6.8 Hz), 1.16 (t, 3H, J=7.2 Hz) ppm; MS (APCl, m/z): 228 [M−Na] − .
(4-Cyano-3-pentylsulfanyl-isothiazol-5-yl)-carbamic Acid Ethyl Ester
[0147] A mixture of sodium, 4-cyano-5-ethoxycarbonylamino-isothiazole-3-thiolate (5.0 g, 20 mmol), 1-iodopentane (4.0 g, 20 mmol) and tetrahydrofuran (20 mL) was stirred at ambient temperature for 16 hours. After concentration in vacuo, the residue was partitioned between ethyl acetate and brine. The aqueous layer was extracted three times with ethyl acetate, and the combined organic layers were dried over Na 2 SO 4 , filtered and concentrated in vacuo. The residue was filtered through a pad of silica gel using 1:1 ethyl acetate-hexane as eluent. The filtrated was concentrated and the residue was recrystallized from cold aqueous methanol, affording 2.5 g (42%) (4-cyano-3-pentylsulfanyl-isothiazol-5-yl)-carbamic acid ethyl ester as a colorless solid. An additional 0.5 g (8.4%) was obtained by concentration of the mother liquor and purification by radial chromatography (4 mm plate, 4:1 hexane-ethyl acetate). 1 H NMR (400 MHz, acetone-d 6 ) δ11.1 (bs, 1 H), 4.32 (q, 2H, J=7.2 Hz), 3.21 (t, 2H, J=7.2 Hz), 1.73 (p, 2H, J=6.8 Hz), 1.44-1.28 (m, 7H), 0.90 (t, 3H, J=7.6 Hz) ppm; MS (APCl, m/z): 312 [M+Na] 30 .
5-Amino-3-pentylsulfanyl-isothiazole-4-carboxylic Acid Amide
[0148] A mixture of (4-Cyano-3-pentylsulfanyl-isothiazol-5-yl)-carbamic acid ethyl ester (2.7 g, 9.0 mmol) and concentrated sulfuric acid (5 mL) was heated to 100° C. for 6 hours. After cooling to ambient temperature, the mixture was diluted with ice water, extracted three times with ethyl acetate, and the combined organic layers were dried over Na 2 SO 4 , filtered and concentrated in vacuo, affording 2.2 g (100%) of 5-amino-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide as a yellow oil. 1 H NMR (400 MHz, CDCl 3 ) δ3.26 (t, 2 H, J=7.2 Hz), 1.71 (m, 2H), 1.43-1.19 (m, 4H), 0.88 (t, 3H, J=6.8 Hz) ppm.
(4-Carbamoyl-3-pentylsulfanyl-isothiazol-5-yl)-carbamic Acid Phenyl Ester
[0149] To a solution of 5-amino-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide (2.2 g, 9.0 mmol) in 36 mL of tetrahydrofuran was added pyridine (0.90 g, 11 mmol) and phenyl chloroformate (1.7 g, 11 mmol). After stirring for 3 hours, additional pyridine (0.15 g, 1.9 mmol) and phenyl chloroformate (0.29 g, 1.9 mmol) was added, and the mixture was stirred at room temperature overnight. The mixture was concentrated in vacuo, diluted with water and extracted 2× with CH 2 Cl 2 , 1× with ethyl acetate. The combined organic layers were washed with brine, dried over MgSO 4 , filtered and concentrated in vacuo. The residue was triturated for 12 hours with ether-hexane, and the resulting solids were collected and dried in vacuo, affording 2.6 g (79%) of (4-carbamoyl-3-pentylsulfanyl-isothiazol-5-yl)-carbamic acid phenyl ester as a colorless solid. 1 H NMR (300 MHz, CDCl 3 ) δ7.41 (t, 2 H, J=7.3 Hz), 7.29-7.20 (m, 3H), 3.31 (t, 2H, J=7.3 Hz), 1.72 (m, 2H), 1.50-1.30 (m, 4H), 0.90 (t, 3H, J=7.1 Hz) ppm; MS (APCl, m/z): 366 [M+H] + .
EXAMPLE 2
3-Pentylsulfanyl-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic Acid Amide
[0150] To a mixture of (4-carbamoyl-3-pentylsulfanyl-isothiazol-5-yl)-carbamic acid phenyl ester (0.10 g, 0.27 mmol) and 1 mL of tetrahydrofuran was added N-3-aminopropylpyrollidine (0.175 g, 1.4 mmol). After stirring for 72 hours at ambient temperature, the mixture was poured into 1M NaOH, extracted twice with ethyl acetate, and the combined organic layers were dried over Na 2 SO 4 , filtered and concentrated. Purification of the residue by radial chromatography (2 mm plate, 3% ethanol-CH 2 Cl 2 −30% ethanol-CH 2 Cl 2 containing 0.5% NH 4 OH), followed by concentration and trituration of the residue with ether-hexane afforded 0.076 g (78%) of 3-pentylsulfanyl-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide as a colorless solid 1 H NMR (400 MHz, CDCl 3 ) δ7.57 (bs, 1H), 7.06 (bs, 2H), 3.35 (m, 2H), 3.26(m, 2H), 2.53 (t, 2H, J=6.8 Hz), 2.47(m, 4H), 1.73 (m, 8H), 1.4-1.2 (m, 4H), 0.88 (t, 3H, J=7.2 Hz) ppm; MS (APCl, m/z): 400 [M+H] + .
PREPARATION 3
3-(4-Cyano-3-hydroxy-isothiazol-5-yl)-1,1-dimethyl-urea (Sodium Salt)
[0151] A solution of 3-(2,2-Dicyano-1-mercapto-vinyl)-1,1-dimethyl-urea (sodium salt) (30 g, 137 mmol) in water (300 mL) was treated at ambient temperature with hydrogen peroxide (14 mL of a 10 M solution). The reaction warmed and thickened with solid formation and so was treated with additional water (100 mL). The mixture was heated to reflux for 15 minutes, effecting complete dissolution and then cooled to ambient temperature. After 1 hour at ambient temperature, the mixture was concentrated to a constant weight (35 g, >100% due to water content) and was used immediately in the next step.
5-(3,3-Dimethyl-ureido)-3-hydroxy-isothiazole-4-carboxylic Acid Amide
[0152] The solid obtained in the previous step (35 g) was added to concentrated sulfuric acid (150 mL) followed by water (5 mL) and stirred at ambient temperature overnight. The mixture was treated with ice (500 g) and stirred 2 hours. The mixture was filtered and air pulled through the cake overnight. The solid was crushed with mortar and pestle and kept under high vacuum until constant weight (21.7 g, 94.2 mmol, 69% over two steps).
EXAMPLE 3
5-(3,3-Dimethyl-ureido)-3-heptyloxy-isothiazole-4-carboxylic Acid Amide
[0153] A suspension of 5-(3,3-Dimethyl-ureido)-3-hydroxy-isothiazole-4-carboxylic acid amide (200 mg, 0.87 mmol) in DMF (5 mL) was treated with KOtBu (107 mg, 0.96 mmol) at ambient temperature causing complete dissolution. Next was added 1-iodoheptane (1 mL) and the reaction stirred at ambient temperature until complete dissappearance of starting materials as measured by TLC using hexane/ethyl acetate/methanol/acetic acid (48/48/2/2) as eluent. The reaction mixture was then concentrated by rotary evaporation under high vacuum, the residue dissolved in ethyl acetate and methanol, and was then purified via radial chromatography (2 mm plate) using the same eluent as for TLC affording two components. The more polar material was identified as the N-alkyated adduct (102 mg, 0.311 mmol, 36%). 1 H NMR (400 MHz, CDCl 3 ) δ0.86 (t, J=6.7 Hz, 3H), 1.25-1.31 (m, 8H), 1.64-1.70 (m, 2H), 3.07 (s, 6H), 3.68 (t, J=7.2 Hz, 2H), 5.40 (s, 1H), 8.86 (s, 1H), 12.1 (s, 1H), ppm; 13 C NMR (101 MHz, CDCl 3 ) δ13.94, 22.45, 26.48, 28.74, 29.52, 31.52, 36.11, 42.54, 166.99 ppm; MS (APCl, m/z): 329 [M+H] + . The less polar material was the O-alkyated adduct (134 mg, 0.408 mmol, 48%). 1 H NMR (400 MHz, CDCl 3 ) δ0.88 (t, J=6.8 Hz, 3H), 1.24-1.50 (m, 8H), 1.75-1.88 (m, 2H), 3.07 (s, 6H), 4.43 (t, J=6.7 Hz, 2H), 5.42 (s, 1H), 7.25 (s, 1H appears to be superimposed on CDCl 3 peak), 11.6 (s, 1H) ppm; 13 C NMR (101 MHz, CDCl 3 ) δ13.94, 22.45, 25.86, 28.83, 31.60, 36.11, 68.69, 97.69, 154.15, 162.27, 166.20, 169.45 ppm; MS (APCl, m/z): 329 [M+H] + .
PREPARATION 4
2-Cyano-thioacetimidic Acid 4-methoxy-benzyl Ester
[0154] To a solution of sodium hydroxide (13 g, 0.32 mol) in 750 mL of 1:1 ethanol-water at 0° C. was added 4-methoxybenzylmercaptan (50 g, 0.324 mol) and malononitrile (21 g, 0.324 mol). After stirring for 3 hours at 0° C., the mixture was diluted with 500 mL of saturated aqueous NH 4 Cl, diluted with 4 l of water and filtered. The solids were washed with ether, and the filtrated was diluted with an equal volume of hexane and filtered. The combined solids were dried in vacuo, affording 43 g (60%) of 2-cyano-thioacetimidic acid 4-methoxy-benzyl ester as a colorless solid. 1 H NMR (400 MHz, CDCl 3 ) δ7.22 (d, 2H, J=7.6 Hz), 6.84 (d, 2H, J=8.8 Hz), 4.74 (bs, 1H), 3.98 (s, 2H), 3.78 (s, 3H) ppm; MS (APCl, m/z): 221 [M+H] + .
2-Cyano-3-mercapto-3-phenoxycarbonylamino-thioacrylimidic acid 4-methoxy-benzyl Ester
[0155] To a solution of of 2-cyano-thioacetimidic acid 4-methoxy-benzyl ester (42 g, 0.19 mol) in 191 mL of ethyl acetate at 0° C. was added phenoxycarbonylisothiocyanate (34 g, 0.19 mol), and the mixture was stirred at 0° C. for 24 hours. The mixture was diluted with ether and filtered. The solids were washed with ether, collected and dried in vacuo, affording 56 g (73%) of 2-cyano-3-mercapto-3-phenoxycarbonylamino-thioacrylimidic acid 4-methoxy-benzyl ester as a yellow solid. 1 H NMR (400 MHz, CDCl 3 ) δ12.81(s, 1H), 9.01 (s, 1H), 8.68 (s, 1H) 7.28-6.99 (m, 7H), 6.69 (d, 2H, J=8.8 Hz), 4.17 (s, 2H), 3.64 (s, 3H) ppm; MS (APCl, m/z): 400 [M+H] + .
[4-Cyano-3-(4-methoxy-benzylsulfanyl)-isothiazol-5-yl]-carbamic Acid Phenyl Ester
[0156] To a mixture of 2-Cyano-3-mercapto-3-phenoxycarbonylamino-thioacrylimidic acid 4-methoxy-benzyl ester (11 g, 28 mmol) and ethyl acetate (250 mL) was added, at 0° C., pyridine (4.4 g, 55 mmol). A solution of iodine (7.0 g, 28 mmol) in 350 mL of ethyl acetate was added dropwise over 1 hour. The resulting suspension was stirred for 1 hour, treated with 200 mL of 1 M HCl and filtered, affording 7.0 g (64%) of [4-cyano-3-(4-methoxy-benzylsulfanyl)-isothiazol-5-yl]-carbamic acid phenyl ester as a colorless solid. The filtrate was extracted with 1 l of ethyl acetate, and the organic phase was washed with aqueous NaHCO 3 , dried over Na 2 SO 4 , filtered and concentrated, yielding an additional 2.8 g (26%) of [4-cyano-3-(4-methoxy-benzylsulfanyl)-isothiazol-5-yl]-carbamic acid phenyl ester. 1 H NMR (400 MHz, CDCl 3 ) δ11.95 (s, 1H), 7.35 (t, 2H, J=8.4 Hz), 7.20 (m, 3H), 7.13 (d, 2H, J=8.0 Hz), 6.78 (t, 2H, J=8.6 Hz), 4.34 (s, 2H), 3.73 (s, 3H) ppm; MS (APCl, m/z): 398 [M+H] + .
(4-Cyano-3-mercapto-isothiazol-5-yl)-carbamic Acid Phenyl Ester
[0157] To a mixture of [4-cyano-3-(4-methoxy-benzylsulfanyl)-isothiazol-5-yl]-carbamic acid was added mercuric acetate (0.80 g, 2.5 mmol). The mixture was allowed to warm to room temperature overnight. After concentration in vacuo, the mixture was diluted with 100 mL of water and 100 mL of ethyl acetate. Hydrogen sulfide was bubbled in slowly until precipitation of the mercury salts was complete. The mixture was diluted with brine, extracted 3× with 200 mL of ethyl acetate, and the combined organic layers were filtered through celite, dried over Na 2 SO 4 , filtered and concentrated in vacuo, affording 0.70 g (100%) of (4-cyano-3-mercapto-isothiazol-5-yl)-carbamic acid phenyl ester as a colorless solid. 1 H NMR (400 MHz, acetone-d 6 ) δ7.47 (t, 2H, J=7.6 Hz), 7.35-7.30 (m, 3H) ppm; MS (APCl, m/z): 276 [M−H] − .
(4-Carbamoyl-3-mercapto-isothiazol-5-yl)-carbamic Acid Phenyl Ester
[0158] A mixture of (4-cyano-3-mercapto-isothiazol-5-yl)-carbamic acid phenyl ester (0.70 g, 2.5 mmol), 2,6-di-tert-butyl-4-methylphenol (BHT) (one crystal) and concentrated sulfuric acid (3 mL) was stirred for 18 hours at room temperature. The mixture was diluted with ice water, extracted 3× with ethyl acetate, and the combined organic layers were dried over Na 2 SO 4 , filtered and concentrated in vacuo. The residue was dissolved in 10 mL of ethanol at 0° C. and was treated with 0.096 g (2.5 mmol) of NaBH 4 . After stirring for 30 minutes, the mixture was acidified with 1 M HCl, extracted into ethyl acetate, dried over Na 2 SO 4 , filtered and concentrated in vacuo, affording 0.60 g (81%) of (4-carbamoyl-3-mercapto-isothiazol-5-yl)-carbamic acid phenyl ester as a yellow solid. 1 H NMR (400 MHz, acetone-d 6 ) δ13.0 (s, 1H), 11.0-10.9 (bs, 1H), 10.3 (s, 1H), 7.47 (t, 2H, J=6.8 Hz), 7.37-7.30 (m, 4H) ppm; MS (APCl, m/z): 296 [M+H] + .
EXAMPLE 4
5-[3-(3-Chloro-4-fluoro-benzyl)-ureido]-3-(4-methyl-benzylsulfanyl)-isothiazole-4-carboxylic Acid Amide
[0159] To a mixture of (4-carbamoyl-3-mercapto-isothiazol-5-yl)-carbamic acid phenyl ester (0.075 g, 0.25 mmol) in 0.5 mL of DMF was added 4-methylbenzylchloride (0.036 g, 0.25 mmol), followed by N,N-diisopropylethylamine (0.033 g, 0.25 mmol). After stirring for 18 hours at ambient temperature, tetrahydrofuran (1 mL) was added, followed by 3-chloro-4-fluorobenzylamine (0.081 g, 0.51 mmol). After stirring for 24 hours at 45° C., the mixture was diluted with 1M HCl, extracted 3× with ethyl acetate, and the combined organic layers were dried over Na 2 SO 4 , filtered and concentrated in vacuo. The residue was purified by radial chromatography on silica gel eluting with ethyl acetate-hexane, affording 26 mg of 5-[3-(3-chloro-4-fluoro-benzyl)-ureido]-3-(4-methyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide as a colorless solid. HPLC ret. time: 4.9 minutes. 1 H NMR (400 MHz, acetone-d 6 ) δ7.95 (bs, 1H), 7.54 (dd, 1H, J=2, 7.2 Hz), 7.39 (m, 1H), 7.31-7.25 (m, 3H), 7.11 (d, 2H, J=8.0 Hz), 7.01 (bs, 2H), 4.48 (m, 4H), 2.28 (s, 3H) ppm; MS (APCl, m/z): 465 [M+H] + .
PREPARATION 5
2-Cyano-acetimidic Acid Benzyl Ester
[0160] To a solution of ethereal HCl (4.00 L, 1M, 4.00 mol) was added warmed (liquified) malononitrile (252 mL, 4.00 mol). Upon dissolution, the solution was cooled to 10° C. Next was added benzyl alcohol (414 mL, 4.00 mol) and the mixture stirred at 10° C. for 0.5 hour. The reaction flask was placed in the refrigerator and allowed to stand at 5° C. for 4 days. The solid obtained was filtered cold, washed with cold ether (1.5 L) and dried under vacuum (40 mm Hg) for 1 hour affording 545 g (2.59 mol, 65%) of the Pinner adduct as a white solid. The neutralization of this HCl salt was carried out as follows. A solution of potassium carbonate (359 g, 2.59 mol) in water (700 mL) was prepared and cooled to 5° C. The solution was added to a separatory funnel along with ether (2 L) and THF (500 mL). The entire separatory funnel was placed in an ice bath until the temperature of the extractant solution was 5° C. The Pinner adduct (545 g, 2.59 mol) was then added to the separatory funnel and the funnel was shaken vigorously for 5 minutes. The aqueous layer was discarded and the organic layer collected following filtration of suspended particles. The organic layer was placed again into the separatory funnel, shaken with brine and allowed to settle completely to allow virtual complete removal of brine layer. The organic layer was concentrated on a rotary evaporator and the unstable product (327 g, 1.88 mmol, 73%) used immediately in the next step.
Phenoxycarbonylisothiocyanate
[0161] A suspension of KSCN (80 g, 823 mmol, from a fresh, previously unopened bottle) in ethyl acetate (2 L, dry) was stirred vigorously overnight under an atmosphere of nitrogen in order to powder the KSCN. The fine suspension was then treated dropwise with phenyl chloroformate (100 mL, 800 mmol) over 1 hour. The reaction was stirred overnight at ambient temperature and then stirred at 5° C. for 8 hours. The KCl produced was filtered off and the solvent removed by rotary evaporation taking care not to warm the product above ambient temperature. The product was redissolved in ether (2 L), the additional precipitate removed by filtration and discarded, and the ethereal solution of product again concentrated under reduced pressure taking care not to warm the product above ambient temperature. The product was redissolved in hexane (2 L), the additional precipitate removed by filtration and discarded, and the hexane solution of product again concentrated under reduced pressure taking care not to warm the product above ambient temperature. The product so obtained (101 g, 564 mmol, 68%) was highly pure and could be stored at −5° C. for a matter of several days, or at room temperature for a few hours, but was typically used quickly, as in the current example. 1 H NMR (400 MHz, CDCl 3 ) δ7.10-7.21 (m, 2H), 7.21-7.31 (m, 1H), 7.31-7.45 (m, 2H) ppm; 13 C NMR (101 MHz, CDCl 3 ) δ120.75, 126.77, 129.65, 150.46 ppm; IR (neat) 1190, 1232, 1491, 1590, 1751, 1960 cm−1.
2-Cyano-3-mercapto-3-phenoxycarbonylamino-acrylimidic Acid Benzyl Ester
[0162] To a stirred 0° C. solution of 2-cyano-acetimidic acid benzyl ester (327 g, 1.88 mol) in acetonitrile (1 L) was added a 0° C. solution of phenoxycarbonylisothiocyanate (353 g, 1.97 mol) in acetonitrile (1 L). The reaction was allowed to warm to ambient temperature and was stirred overnight. The mixture was then placed in the refrigerator and kept still at 5° C. for 48 hours. The solid product was filtered, compressed, and washed with 20° C. acetonitrile (3×200 mL). Air was then drawn though the relatively stable solid followed by further drying under high vacuum to yield a yellow solid (282 g, 798 mmol, 42%). 1 H NMR (400 MHz, DMSO) δ5.39 (s, 2H), 7.11-7.19 (m, 2H), 7.20-7.24 (m, 1H), 7.36-7.46 (m, 7H), 10.23 (broad s, 1H), 10.67 (s, 1H), 12.19 (broad s, 1H) ppm; MS (APCl, m/z): 354 [M+H] + .
(3-Benzyloxy-4-cyano-isiothiazol-5-yl)-carbamic Acid Phenyl Ester
[0163] To a 0° C. suspension of the adduct, 2-cyano-3-mercapto-3-phenoxycarbonylaminoacrylimidic acid benzyl ester (282 g, 798 mmol) in acetonitrile (2 L) was added pyridine (129 mL, 1.60 mol). Next was added a solution of bromine (41.1 mL, 798 mmol) in acetonitrile (200 mL) over 15 minutes. The reaction was stirred at 0° C. for an additional 1 hour and then at ambient temperature for 2 hour. The mixture was placed in the refigerator and held at 5° C overnight. The solid product was filtered and washed with 0° C. ether (1 L), dried in the same funnel by drawing air through the solid for 4 hours. The solid was added to water (1 L), stirred vigorously for 1 hour, filtered and dried in the same funnel by drawing air through the solid overnight to afford a white solid (320 g pure though still containing some water) that was used, as is, in the next step. 1 H NMR (400 MHz, DMSO) δ5.35 (s, 2H), 7.25-7.45 (m, 10H), 13.20 (broad s, 1H) ppm; MS (APCl, m/z): 350 [M−H] − .
(4-Carbamoyl-3-hydroxy-isothiazol-5-yl)-carbamic Acid Phenyl Ester
[0164] The wet solid, (3-Benzyloxy-4-cyano-isothiazol-5-yl)-carbamic acid phenyl ester, (320 g) was added slowly to concentrated sulfuric acid (650 mL) over 1.5 hours. Additional concentrated sulfuric acid (100 mL) was added and the mixture stirred a further 3 hours. The viscous solution was diluted by slow addition of ice (2000 g) followed by vigorous stirring for an additional 2 hours. The acid was partially removed by dividing the suspension into eight containers that were placed in a centrifuge, spun at 3000 rpm for 45 minutes at 21° C. The aqueous layer was discarded, additional pure water was added, the pellet resuspended, and the process repeated. After seven dilution/centrifugation/redilution cycles, the pH of the aqueous layer had increased to ˜4 and the solid was collected and dried by drawing air through a cake in a funnel for 2 days. The less-wet solid was crushed, placed again in the filter, and air was again drawn through the solid for another day. This process was repeated until the solid was dry to afford a tan solid (234 g, 105% over two steps, minor impurities present—did not interfere appreciably with the subsequent steps). 1 H NMR (400 MHz, DMSO) δ7.00 (broad s, 1H), 7.27-7.31 (m, 3H), 7.40-7.45 (m, 2H), 7.89 (s, 1H), 8.08 (s, 1H), 11.92 (s, 1H); MS (APCl, m/z): 184 [M−(H and PhOH)] − .
[4-Carbamoyl-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic Acid Phenyl Ester
[0165] To a suspension of (4-carbamoyl-3-hydroxy-isothiazol-5-yl)carbamic acid phenyl ester (1.77 g, 6.23 mmol), triphenylphosphine (1.99 g, 7.59 mmol), o,o′-difluoro-p-methylbenzyl alcohol (1.00 g, 6.32 mmol) in THF (21 mL) was added diisopropyl azodicarboxylate (DIAD, 1.49 mL, 7.59 mmol) slightly faster than dropwise. The reaction mixture warmed and became clear. After stirring for 15 minutes, the majority of THF was removed by rotary evaporation and the crude mixture purified on silica gel using chloroform/acetone/acetic acid (98.5/0.75/0.75) as eluent to afford a white solid (802 mg, 1.91 mmol, 30%).
EXAMPLE 5
3-(2,6-Difluoro-4-methyl-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic Acid Amide
[0166] To a suspension of [4-Carbamoyl-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester (125 mg, 0.298 mmol) in THF (1 mL) was added 1-(3-aminopropyl)-4-methylpiperazine (70 mg, 0.45 mmol). The mixture was shaken at 50° C. overnight, cooled to ambient temperature, and loaded directly onto a radial chromatograph followed by elution with chloroform/methanol/concentrated ammonium hydroxide (50/5/1) to afford a white solid (121 mg, 0.251 mmol, 84%). 1 H NMR (400 MHz, CDCl 3 ) δ1.72 (t, J=5.81 Hz, 2H), 2.20-2.85 (m, 10H), 2.28 (s, 3H superimposed on multiplet from 2.20-2.85), 2.35 (s, 3H superimposed on multiplet from 2.20-2.85), 3.39 (t, J=5.4 Hz, 2H), 5.51 (s, 2H), 5.74 (broad s, 1H), 6.74 (d, J=8.3 Hz, 2H), 7.05 (s, 1H), 7.58 (broad s, 1H), 11.01 (broad s, 1H) ppm; MS (APCl, m/z): 483 [M+H] + .
Synthesis of Representative Fluorotoluene Derivatives
[0167] [0167]
1,3-Difluoro-5-methyl-benzene (G=H)
[0168] A mixture of 1-bromomethyl-3,5-difluoro-benzene (75 g, 0.362 mol), Pd/C (5%, 5 g), and sodium acetate (208 g, 2.54 mol) in ether (300 mL) was treated with hydrogen gas (50 psi) in a Parr shaker for 2 days. The mixture was filtered through Celite and the organic solution washed three times with saturated aqueous sodium bicarbonate solution. The aqueous layers were washed with ether and the combined organic layers dried (MgSO 4 ), filtered, and partially concentrated by evaporation using a cold water bath. The volatile product was obtained as a mixture with ether and the ratio (˜3:2, ether:product, g:g) calculated based on 1 H NMR integration to determine actual yield (45.5 g, 0.355 mol, 98%) of product for scaling reagents in the ensuing reaction. 1 H NMR (400 MHz, CDCl 3 ) δ2.25 (s, 3H), 6.51-6.56 (m, 1H), 6.58-6.60 (m, 2H) ppm.
1,2,5-Trifluoro-3-methyl-benzene (G=F)
[0169] The title compound was prepared from 1-bromomethyl-2,3,5-trifluoro-benzene by a procedure analogous to that for 3,5-difluorotoluene, above. 1 H NMR (400 MHz, CDCl 3 ) δppm; MS (APCl, m/z): [M+H] + .
Synthesis of Representative Benzyl Alcohols for Conversion to R 3
[0170] [0170]
(2,6-Difluoro-4-methyl-phenyl)-methanol (G=H, G′=Me, G″=F)
[0171] A solution of 1,3-difluoro-5-methyl-benzene (45.5 g, 0.355 mol, mixed with a small volume of ether) in dry THF (1.77 L) was cooled to −78° C. under nitrogen and treated dropwise with n-BuLi (142 mL of a 2.5 M solution in hexanes, 0.355 mol). The solution was stirred an additional 25 minutes and was then treated with DMF (27.5 mL, 0.355 mol). After stirring an additional 45 minutes, the solution was treated with acetic acid (40.6 mL, 0.71 mol) and the flask removed from the −78° C. bath. The mixture was stirred at ambient temperature for 2 hours and was then treated successively with water (300 mL) and MeOH (300 mL). Next was added, portionwise, NaBH 4 (26.8 g, 0.71 mol) followed by stirring for 1 hour. The flask was cooled in an ice bath and the mixture treated with 6 N HCl until pH ˜5. The mixture was concentrated via rotary evaporation to remove THF and MeOH and the product extracted with ether and washed several times with small volumes of water and once with brine. The ether layer was dried (MgSO 4 ), filtered, and concentrated to afford an oil (45 g, 0.285 mol, 80%) that solidified upon refrigeration. 1 H NMR (400 MHz, CDCl 3 ) δ1.75 (t, J=6.5 Hz, 1H), 2.32 (s, 3H), 4.72 (d, J=6.4 Hz, 2H), 6.69 (d, J=7.9 Hz, 2H) ppm.
(2,3,6-Trifluoro-4-methyl-phenyl)-methanol (G=F, G′=Me, G″=F)
[0172] The title compound was prepared from 1,2,5-trifluoro-3-methyl-benzene by a procedure analogous to that for (2,6-difluoro-4-methyl-phenyl)-methanol, above. 1 H NMR (400 MHz, CDCl 3 ) δ1.87 (broad s, 1H), 2.28 (d, J=1.9 Hz, 3H), 4.74 (s, 2H), 6.68-6.72 (m, 1H) ppm.
(4-Bromo-2,6-difluoro-phenyl)-methanol (G=H, G′=Br, G″=F)
[0173] The title compound was prepared from 1-bromo-3,5-difluoro-benzene by a procedure analogous to that for (2,6-difluoro-4-methyl-phenyl)-methanol, above with the following exception: lithium diisopropylamide (LDA) was used in place of n-BuLi and deprotonation time was extended to 45 minutes. 1 H NMR (400 MHz, CDCl 3 ) δ1.91 (t, J=6.5 Hz, 1H), 4.71 (d, J=6.4 Hz, 2H), 7.06-7.12 (m, 2H) ppm.
(4-Bromo-2,3,6-trifluoro-phenyl)-methanol (G=F, G′=Br, G″=F)
[0174] The title compound was prepared from 1-bromo-2,3,5-trifluoro-benzene by a procedure analogous to that for (2,6-difluoro-4-methyl-phenyl)-methanol, above with the following exception: lithium diisopropylamide (LDA) was used in place of n-BuLi and deprotonation time was extended to 45 minutes. 1 H NMR (400 MHz, CDCl 3 ) δ1.89 (t, J=6.5 Hz, 1H), 4.75 (d, J=6.4 Hz, 2H), 7.11-7.15 (m, 1H) ppm.
(3-Chloro-2,6-difluoro-phenyl)-methanol (G=Cl, G′=H, G″=F)
[0175] The title compound was prepared from 1-chloro-2,4-difluoro-benzene by a procedure analogous to that for (2,6-difluoro-4-methyl-phenyl)-methanol, above. 1 H NMR (400 MHz, CDCl 3 ) δ1.90 (t, J=6.4 Hz, 1H), 4.78 (d, J=6.4 Hz, 2H), 6.87 (app. dt, J=1.8, 8.9 Hz, 1H), 7.32 (app. dt, J=5.8, 2.8 Hz, 1H) ppm.
(2-Fluoro-4,6-dimethyl-phenyl)-methanol (G=H, G′=Me, G″=Me)
[0176] A solution of N,N,N′,N′-tetramethylethylenediamine (13.4 mL, 88.6 mmol) in THF (115 mL) was cooled to −78° C. and treated with sec-BuLi (68.2 mL of of 1.3 M solution in cyclohexane, 88.6 mmol). The resulting yellow solution was stirred for 20 minutes at −78° C. and was then treated with a solution of 1-fluoro-3,5-dimethyl-benzene (10.0 g, 80.5 mmol) in THF (56 mL). The mixture was stirred for 1 hour at −78° C. and was then treated with a solution of DMF (6.86 mL, 88.6 mmol) in THF (26 mL). The reddish-brown mixture was stirred an additional 1 hour, and was then treated with HOAc (10 mL) and water (200 mL). The mixture was warmed to ambient temperature, extracted with ether (500 mL) and the aqueous layer extracted with additional ether (2×300 mL). The combined organic extracts were combined and washed successively with 0.2 M HCl (2×200 mL), water (500 mL) and brine (300 mL). The organic layer was dried (MgSO 4 ) and concentrated to afford the aldehyde as a clear oil (11.9 g, 78.2 mmol, 97%). The aldehyde was then dissolved in THF (100 mL), MeOH (100 mL), and water (100 mL) and treated portionwise with NaBH 4 (2.96 g, 78.2 mmol). The mixture was stirred at ambient temperature for 1 hour and was then concentrated under reduced pressure to remove the THF and MeOH. The remaining aqueous layer was extracted twice with ether (600 mL and 200 mL) and the combined organic layers washed successively with 0.1 M HCl (300 mL), water (300 mL), and brine (300 mL). The organic layer was dried (MgSO 4 ) and concentrated to afford an oil (10.8 g, 70.4 mmol, 90%). 1 H NMR (400 MHz, CDCl 3 ) δ2.28 (s, 3H), 2.38 (s, 3H), 4.70 (s, 2H), 6.71 (d, J=10.6 Hz, 1H), 6.79 (s, 1H) ppm.
(2-Fluoro-4-methyl-phenyl)-methanol (G=H, G′=Me, G″=H)
[0177] A solution of 4-bromo-3-fluorotoluene (12.2 g, 64.7 mmol) in THF (170 mL) was cooled to −78° C. and treated dropwise with n-BuLi (25.9 mL of a 2.5 M solution in hexanes, 65 mmol). After stirring for 1 hour, the solution was treated with N,N-dimethylformamide (DMF) (5.5 mL, 71 mmol) and stirred an additional 30 minutes followed by addition of acetic acid (12 mL). The flask was removed from the cold-bath and allowed to warm to ambient temperature. Next was added water and the product extracted with ether. The organic layer was washed successively with dilute HCl and brine and was then dried (MgSO 4 ) and concentrated. The procedure was repeated (using 11.8 g 4-bromo-3-fluorotoluene) and the combined material subjected to the following reduction: The aldehyde (17.6 g, 127 mmol) was dissolved in THF (165 mL), MeOH (165 mL), and water (165 mL). Next was added NaBH 4 (5.3 g, 140 mmol) portionwise over several minutes (bubbling, exothermic) and stirring was continued for 2 hours. The reaction was diluted with a large volume of ether and was treated with dilute HCl to quench. The layers were separated and the organic layer was dried (MgSO 4 ) and concentrated to afford the product as an oil (17.0 g, 121 mmol, 95%). 1 H NMR (400 MHz, CDCl 3 ) δ2.33 (s, 3H), 4.69 (s, 2H), 6.86 (d, J=11.2 Hz, 1H), 6.93 (d, J=7.24-7.28 (m, 1H) ppm.
(4-Chloro-2,5-difluoro-phenyl)-methanol
[0178] To a mixture of 4-chloro-2,5-difluoro-benzoic acid (15 g, 78 mmol) tetrahydrofuran (THF) (75 mL) and trimethylborate (26 mL, 230 mmol) was added borane-methylsulfide complex (86 mL, 86 mmol, 10 M solution in DMS), and the mixture was stirred for 18 hours at ambient temperature. Additional borane-methylsulfide complex (2.47 mL, 24.7 mmol) was added to drive the reaction to completion. The mixture was poured into 1M aqueous NaOH, extracted 3× with ether, and the combined organic layers were dried over anhydrous MgSO 4 , filtered and concentrated in vacuo. Trituration of the solid residue with ether-hexane afforded 14 g of (4-chloro-2,5-difluoro-phenyl)-methanol as a colorless solid. 1 H NMR (400 MHz, CDCl 3 ) 67 7.26 (dd, 1H, J=6, 8.8 Hz), 7.11 (dd, 1H, J=6, 9.2 Hz), 4.71 (d, 2H, J=6.0 Hz), 1.80 (t, 1H, J=6.0 Hz) ppm.
tert-Butyl-(2,3-difluoro-benzyloxy)-dimethyl-silane
[0179] To a solution of (2,3-difluoro-phenyl)-methanol (5.0 g, 35 mmol), imidazole (4.9 g, 72 mmol) and DMF (40 mL) was added tert-butyldimethylchlorosilane (5.4 g, 36 mmol). After stirring at ambient temperature for 24 hours, the mixture was partitioned between 400 mL of ether and 100 mL of water. The organic layer was washed twice with water, dried over MgSO 4 , filtered and concentrated in vacuo, affording 6.8 g of tert-butyl-(2,3-difluoro-benzyloxy)-dimethyl-silane as a colorless oil. 1 H NMR (400 MHz, CDCl 3 ) δ7.22 (m, 1H), 7.04 (m, 2H), 4.79 (s, 2H), 0.91 (s, 9H), 0.12 (s, 6H) ppm.
tert-Butyl-(2,3-difluoro-4-methyl-benzyloxy)-dimethyl-silane
[0180] To a solution of TMEDA (3.9 mL, 3.0 g, 26 mmol) in THF (33 mL) at −78° C. was added sec butyllithium (20 mL, 1.3 M in hexane, 26 mmol). After stirring for 20 minutes, a solution of tert-butyl-(2,3-difluoro-benzyloxy)-dimethyl-silane (6.0 g, 23 mmol) in 17 mL of THF was added dropwise. After stirring for 1 hour, the solution was added dropwise to a solution of methyl iodide (8 mL) in THF (40 mL) at −20° C. After stirring for 18 hours, the mixture was quenched with saturated aqueous NH 4 Cl, extracted 3× into ether, and the combined organic layers were dried over MgSO 4 , filtered and concentrated in vacuo, giving 6.6 g of tert-butyl-(2,3-difluoro-4-methyl-benzyloxy)-dimethyl-silane as a light yellow oil. 1 H NMR (400 MHz, CDCl 3 ) δ7.07 (app. t, 1H, J=7.2 Hz), 6.89 (app. t, 1H, J=7.3 Hz), 4.74 (s, 2H), 2.26 (d, 3H, J=1.9 Hz), 0.87 (s, 9H), 0.07 (s, 6H) ppm.
(2,3-Difluoro-4-methyl-phenyl)-methanol
[0181] To a solution of tert-butyl-(2,3-difluoro-4-methyl-benzyloxy)-dimethyl-silane (6.5 g, 24 mmol) in THF (24 mL) was added tetrabutylammonium fluoride (24 mL of a 1M solution in THF, 24 mmol). After stirring at ambient temperature for 1 hour, the mixture was poured into water, acidified with 1M aqueous HCl, extracted 3× with ethyl acetate, and the combined organic layers were dried over Na 2 SO 4 , filtered and concentrated in vacuo. The residue was purified by silica gel chromatography (10:1 to 2:1 hexane-ethyl acetate), affording (2,3-Difluoro-4-methyl-phenyl)-methanol as a light yellow oil.
1-Bromo-2,5-difluoro-4-methyl-benzene
[0182] A mixture of 2,5-difluorotoluene (25 g, 0.20 mol) and iron powder (11 g, 0.2 mol) was cooled to −5° C. Bromine was added dropwise such that the internal temperature of the reaction did not rise above 0° C. After stirring for 3 hours, the mixture was diluted with ether, filtered and washed with aqueous sodium thiosulfate solution. The aqueous layer was extracted with ether, and the combined organic layers were dried over MgSO 4 , filtered and concentrated in vacuo. Distillation at atmospheric pressure gave 34 g of 1-bromo-2,5-difluoro-4-methyl-benzene as a colorless oil (b.p. 180 oC). 1 H NMR (300 MHz, CDCl 3 ) δ7.20 (dd, 1H, J=6.0, 8.5 Hz), 6.93 (m, 1H), 2.23 (s, 3H) ppm.
(2,5-Difluoro-4-methyl-phenyl)-methanol
[0183] A mixture of 1-bromo-2,5-difluoro-4-methyl-benzene (3.3 g, 16 mmol) and ether (75 mL) was cooled to −78° C., and a solution of n-butyllithium in hexane (5.4 mL, 2.5 M, 13.5 mmol) was added dropwise. After stirring for 1 hour, dimethylformamide (1.1 mL, 14 mmol) was added, and the mixture was stirred for 1 hour. The mixture was treated with 1M HCl and water, warmed to ambient temperature and was extracted 3× with ether. The combined organic layers were dried over MgSO 4 , filtered and concentrated in vacuo. The residue was diluted with tetrahydrofuran (50 mL), and the mixture was treated with sodium borohydride (0.50 g, 13.5 mmol) and ethanol (2 mL). After stirring for 30 minutes, the mixture was diluted cautiously with 0.5M aqueous HCl, extracted 3× with ethyl acetate, and the combined organic layers were dried over Na 2 SO 4 , filtered and concentrated in vacuo. Recrystallization of the residue from hexane afforded 1.24 g (54%) of (2,5-difluoro-4-methyl-phenyl)-methanol as a colorless solid. 1 H NMR (400 MHz, CDCl 3 ) δ7.05 (dd, 1H, J=6.0, 9.2 Hz), 6.84 (dd, 1H, J=6.4, 10 Hz), 4.68 (d, 2H, J=6.0 Hz), 2.23 (s, 3H), 1.76 (t, 1H, J=6.0 Hz) ppm.
(5-Chloro-2-fluoro-4-methyl-phenyl)-methanol
[0184] (5-Chloro-2-fluoro-4-methyl-phenyl)-methanol was prepared in analogous fashion to (2,5-difluoro-4-methyl-phenyl)-methanol using 2-chloro-5-fluorotoluene as starting material. 1 H NMR (400 MHz, CDCl 3 ) δ7.38 (d, 1H, J=6.8 Hz), 6.92 (d, 1H, J=10 Hz), 4.69 (s, 2H), 2.34 (s, 3H) ppm.
4-Chloro-2,6-difluoro-benzaldehyde
[0185] To a solution of 3,5-difluoro-1-chlorobenzene (5.0 g, 34 mmol) in tetrahydrofuran (70 mL) at −78° C. was added a solution of n-butyllithium in hexane (12.1 mL, 2.5 M, 30 mmol). After stirring for 1 hour, dimethylformamide (5.2 mL, 67 mmol) was added, and the mixture was stirred for 1.5 hours. The mixture was warmed to ambient temperature, diluted with ether and poured into 150 mL of 0.5 M aqueous HCl. The aqueous phase was extracted 3× into ether, and the combined organic layers were dried over MgSO 4 , filtered and concentrated in vacuo, affording 5.72 g (96%) of 4-chloro-2,6-difluoro-benzaldehyde as a colorless solid. 1 H NMR (400 MHz, CDCl 3 ) δ10.27 (s, 1H), 7.04 (d, 2H, J=7.9 Hz) ppm.
(4-Chloro-2,6-difluoro-phenyl)-methanol
[0186] To a mixture of 4-chloro-2,6-difluoro-benzaldehyde (5.7 g, 32 mmol), tetrahydrofuran (150 mL) and ethanol (20 mL) was added sodium borohydride (1.2 g, 32 mmol) at 0° C. The mixture was stirred for 30 minutes, warmed to ambient temperature, and additional sodium borohydride (0.40 g, 11 mmol) was added to drive the reaction to completion (TLC). The mixture was concentrated in vacuo, diluted with ether and treated cautiously with 1M aqueous HCl. The aqueous phase was extracted 3× with ether, and the combined organic layers were dried over MgSO 4 , filtered and concentrated. Trituration of the residue with pentane afforded 4.8 g (83%) of (4-chloro-2,6-difluoro-phenyl)-methanol as a colorless solid. 1 H NMR (300 MHz, CDCl 3 ) δ7.04 (d, 2H, J=7.1 Hz), 4.73 (s, 2H) ppm.
General Procedure for the Preparation of Isothiazole Phenyl Carbamates: [4-Carbamoyl-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic Acid Phenyl Ester
[0187] To a mixture of (4-carbamoyl-3-hydroxy-isothiazol-5-yl)-carbamic acid phenyl ester (2.1 g, 7.6 mmol), (2,5-difluoro-4-methyl-phenyl)-methanol (1.2 g, 7.6 mmol), triphenylphosphine (2.1 g, 8.0 mmol) and tetrahydrofuran (19 mL) was added diethylazodicarboxylate (1.3 mL, 8.0 mmol). After stirring for 16 hours at ambient temperature, additional (2,5-difluoro-4-methyl-phenyl)-methanol (0.24 g, 1.5 mmol), triphenylphosphine (0.42 g, 1.6 mmol) and diethylazodicarboxylate (0.30 mL, 1.8 mmol) were added, and the mixture was stirred for 1 hour. After concentrating in vacuo, the mixture was purified by silica gel chromatography eluting with acetone-acetic acid-methylene chloride (0.5%,0.5%,99%), affording, after trituration from ether-hexane, 1.1 g (35%) of [4-carbamoyl-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester as a colorless solid. HPLC ret. time: 4.8 min. 1 H NMR (400 MHz, CD 3 OD) δ7.40 (t, 2H, J=8.0 Hz), 7.27 (t, 1H, J=7.2 Hz), 7.20 (d, 2H, J=8.4 Hz), 7.17 (dd, 1H, J=6.0,9.2 Hz), 7.00 (dd, 1H, J=6.4, 10 Hz), 5.49 (s, 2H), 2.24 (s, 3H) ppm.
[4-Carbamoyl-3-(2,3-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic Acid Phenyl Ester
[0188] Preparation of the title compound as described for example 3 using (2,3-difluoro-4-methyl-phenyl)-methanol afforded 1.7 g (57%) of [4-carbamoyl-3-(2,3-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester as a colorless solid. HPLC ret. time: 4.8 minutes. 1 H NMR (400 MHz, CDCl 3 ) δ11.38 (s, 1H), 7.40 (t, 2H, J=8.0 Hz), 7.26 (t, 1H, J=7.2 Hz), 7.20 (d, 1H, J=8.4 Hz), 7.14 (b, 1H), 7.11 (t, 1H, J=7.6 Hz), 6.94 (t, 1H, J=7.2 Hz), 5.6 (b, 1H), 5.52 (s, 2H), 2.31 (d,3H, J=1.7 Hz) ppm.
[4-Carbamoyl-3-(2,5-difluoro-4-chloro-benzyloxy)-isothiazol-5-yl]-carbamic Acid Phenyl Ester
[0189] Preparation of the title compound as described for example 3 using (2,5-difluoro-4-chloro-phenyl)-methanol afforded 0.86 g (26%) of [4-carbamoyl-3-(2,5-difluoro-4-chloro-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester as a colorless solid. HPLC ret. time: 4.8 minutes. 1 H NMR (400 MHz, DMSO-d 6 ) δ11.73 (s, 1H), 8.04 (s, 1H), 7.77 (m, 2H), 7.51 (m, 2H), 7.36 (m, 3H), 7.23 (s, 1H), 5.51 (s, 2H) ppm.
[4-Carbamoyl-3-(2,6-difluoro-4-chloro-benzyloxy)-isothiazol-5-yl]-carbamic Acid Phenyl Ester
[0190] Preparation of the title compound as described for example 3 using (2,6-difluoro-4-chloro-phenyl)-methanol afforded 0.86 g (26%) of [4-carbamoyl-3-(2,6-difluoro-4-chloro-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester as a colorless solid. HPLC ret. time: 4.5 minutes. 1 H NMR (400 MHz, CDCl 3 , CD 3 OD) δ7.31 (t, 2H, J=8.0 Hz), 7.18 (t, 1H, J=7.6 Hz), 7.10 (d, 2H, J=7.6 Hz), 6.92 (d, 2H, J=7.2 Hz), 5.45 (s, 2H) ppm.
General Procedure for the Preparation of Isothiazole Ureas
EXAMPLE 6
3-(2,5-difluoro-4-methyl-benzyloxy)-5-[3-(4-pyrrolidin-1-yl butyl)-ureido]-isothiazole-4-carboxylic Acid Amide
[0191] A mixture of [4-carbamoyl-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester (0.34 g, 0.81 mmol), 4-pyrrolidinobutylamine (0.12 g, 0.81 mmol) and tetrahydrofuran (2.8 mL) was shaken at 45-50° C. for 24 hours. The mixture was concentrated and purified by radial chromatography (4 mm plate, CH 3 OH—CHCl 3 —NH 4 OH (10:89:1) to (15:84:1)), affording 0.31 g of the title compound as a colorless solid. The material was dissolved in ca. 10 mL of 4:1 methanol-chloroform at −10° C. and was treated with a solution of methanesulfonic acid (0.043 mL in 0.5 mL of CH 3 OH). After stirring for 5 minutes, the mixture was concentrated in vacuo, and the residue was triturated with methanol-ether, affording 0.35 g of the title compound (82%) as a colorless solid. HPLC ret. time: 3.3 minutes. 1 H NMR (400 MHz, D 2 O) δ6.74 (dd, 1H, J=6.0, 9.6 Hz), 6.63 (dd, 1H, J=6.4, 10.4 Hz), 4.61 (s, 2H), 3.44 (m, 2H), 3.05-2.98 (m, 4H), 2.98-2.81 (m, 2H), 2.62 (s, 3H), 1.95-1.93 (m, 4H), 1.83-1.80 (m, 2H), 1.6-1.5 (m, 2H), 1.4-1.3 (m, 2H) ppm; MS (APCl, m/z): 468 [M+H] + .
EXAMPLE 7
3-(2,5-difluoro-4-methyl-benzyloxy)-5-[3-(4-hydroxy-5-piperidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic Acid Amide
[0192] The title compound was prepared from [4-carbamoyl-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 5-amino-1-piperidin-1-yl-pentan-2-ol by the procedure analogous to Example 6. HPLC ret. time: 3.3 minutes. 1 H NMR (400 MHz, CD 3 OD) δ7.18 (dd, 1H, J=6.0, 9.2 Hz), 7.05 (dd, 1H, J=6.0, 10 Hz), 5.47 (s, 2H), 3.80 (m, 1H), 3.23 (t, 2H, J=6.4 Hz), 2.7-2.4 (m, 7H), 2.25 (s, 3H), 1.8-1.4 (m, nH) ppm; MS (APCl, m/z): 512 [M+H] + .
EXAMPLE 8
(R)-3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(3-hydroxy-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic Acid Amide
[0193] The title compound was prepared from [4-carbamoyl-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and (R)-1-(4-amino-butyl)-pyrrolidin-3-ol by the procedure analogous to Example 6. HPLC ret. time: 3.2 minutes. 1 H NMR (400 MHz, CD 3 OD) δ7.19 (dd, 1H, J=6.0, 9.2 Hz), 7.04 (dd, 1H, J=6.0, 10 Hz), 5.45 (s, 2H), 4.34 (m, 1H), 3.23 (m, 2H), 2.86 (dd, 1H, J=6.0, 10.4 Hz), 2.78 (m, 1H), 2.65-2.54 (m, 4H), 2.25 (s, 3H), 2.14 (m, 1H), 1.73 (m, 1H), 1.56 (m, 4H) ppm; MS (APCl, m/z): 484 [M+H] + .
EXAMPLE 9
3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(6-dimethylamino-hexyl)-ureido]-isothiazole-4-carboxylic Acid Amide
[0194] The title compound was prepared from [4-carbamoyl-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and N1,N1-Dimethyl-hexane-1,6-diamine by the procedure analogous to Example 6. HPLC ret. time: 3.4 minutes. 1 H NMR (400 MHz, CD 3 OD) δ7.18 (dd, 1H, J=6.0, 9.2 Hz), 7.03 (dd, 1H, J=6.4, 10 Hz), 5.45 (s, 2H), 3.19 (t, 2H, J=7.2 Hz), 2.28 (m, 2H), 2.24 (s, 3H), 2.22 (s, 6H), 1.55-1.45 (m, 4H), 1.35-1.33 (m, 4H) ppm; MS (APCl, m/z): 470 [M+H] + .
EXAMPLE 10
3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(2-hydroxymethyl-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic Acid Amide
[0195] The title compound was prepared from [4-carbamoyl-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and (S)-[1-(4-amino-butyl)-pyrrolidin-2-yl]-methanol by the procedure analogous to Example 6. HPLC ret. time: 3.2 minutes. 1 H NMR (400 MHz, CD 3 OD) δ7.18 (dd, 1H, J=6.0, 9.2 Hz), 7.04 (dd, 1H, J=6.4, 10 Hz), 5.45 (s, 2H), 3.62-3.56 (m, 2H), 3.29-3.23 (m, 2H), 3.02 (m, 1H), 2.78 (m, 1H), 2.83 (m, 1H), 2.51 (m, 2H), 2.24 (d, 3H, J=1.6 Hz), 2.02 (m, 1H), 1.88-1.56 (m, 7H) ppm; MS (APCl, m/z): 498 [M+H] + .
EXAMPLE 11
3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(3-hydroxy-piperidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic Acid Amide
[0196] The title compound was prepared from [4-carbamoyl-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 1-(4-amino-butyl)-piperidin-3-ol by the procedure analogous to Example 6. HPLC ret. time: 3.3 minutes. 1 H NMR (400 MHz, CD 3 OD) δ7.18 (dd, 1H, J=6.8, 9.6 Hz), 7.04 (dd, 1H, J=5.6, 10 Hz), 5.45 (s, 2H), 3.64 (m, 1H), 3.24-3.22 (m, 2H), 2.90 (m, 1H), 2.73 (m, 1H), 2.37 (m, 2H), 2.25 (d, 3H, J=1.6 Hz), 1.99-1.87 (m, 3H), 1.74 (m, 1H), 1.74-1.53 (m, 6H) ppm; MS (APCl, m/z): 498 [M+H] + .
EXAMPLE 12
3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic Acid Amide
[0197] The title compound was prepared from [4-carbamoyl-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and N1-Isopropyl-pentane-1,5-diamine by the procedure analogous to Example 6. HPLC ret. time: 3.4 minutes. 1 H NMR (300 MHz, CD 3 OD) δ7.20 (dd, 1H, J=5.7, 9.0 Hz), 7.06 (dd, 1H, J=6.3, 10 Hz), 5.47 (s, 2H), 3.23 (t, 2H, J=6.6 Hz), 2.93 (s, 1H, J=6.3 Hz), 2.70 (m, 2H), 2.27 (d, 3H, J=1.8 Hz), 1.7-1.5 (m, 4H), 1.5-1.3 (m, 2H), 1.11 (d, 6H, J=6.6 Hz) ppm; MS (APCl, m/z): 470 [M+H] + .
EXAMPLE 13
3-(2,3-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(3,4-dihydroxy-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic Acid Amide
[0198] The title compound was prepared from [4-carbamoyl-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 1-(4-amino-butyl)-pyrrolidine-3,4-diol by the procedure analogous to Example 6. HPLC ret. time: 3.1 minutes. 1 H NMR (400 MHz, CD 3 OD) δ7.17 (t, 1H, J=7.6 Hz), 7.03 (t, 1H, J=7.3 Hz), 5.49 (s, 2H), 4.01 (s, 2H), 3.21 (s, 2H), 2.93 (m, 2H), 2.48 (m, 4H), 2.29 (s, 3H), 1.54 (bs, 4H) ppm; MS (APCl, m/z): 500 [M+H] + .
EXAMPLE 14
3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(3-hydroxy-5-pyrrolidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic Acid Amide—Methanesulfonate Salt
[0199] The title compound was prepared from [4-carbamoyl-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 1-amino-5-pyrrolidin-1-yl-pentan-3-ol by the procedure analogous to Example 6. HPLC ret. time: 3.1 minutes. 1 H NMR (400 Mhz, D 2 O) δ6.81 (d, 2H, J=7.2 Hz), 5.17 (s, 2H), 3.61 (bm, 1H), 3.47 (bm, 2H), 3.2-3.0 (m, 4H), 2.89 (m, 2H), 2.62 (s, 3H), 1.94 (m, 2H), 1.85-1.2 (m, 6H) ppm; MS (APCl, m/z): 518 [M+H] + .
EXAMPLE 15
3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(3-hydroxy-5-pyrrolidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic Acid Amide—Methanesulfonate Salt
[0200] The title compound was prepared from [4-carbamoyl-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 1-amino-5-pyrrolidin-1-yl-pentan-3-ol by the procedure analogous to Example 6. HPLC ret. time: 3.3 minutes. 1 H NMR (400 MHz, CD 3 OD) δ7.17 (d, 2H, J=6.4 Hz), 5.51 (s, 2H), 3.64 (bm, 1H), 3.24 (t, 2H, J=6.0 Hz), 2.92 (m, 1H), 2.72 (m, 1H), 2.39 (m, 2H), 1.98 (m, 1H), 1.87 (m, 2H), 1.75 (m, 1H), 1.54 (m, 4H), 1.22 (m, 2H) ppm; MS (APCl, m/z): 517 [M+H] + .
EXAMPLE 16
3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(3-hydroxy-5-pyrrolidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic Acid Amine—Methanesulfonate Salt
[0201] The title compound was prepared from [4-carbamoyl-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 1-amino-5-pyrrolidin-1-yl-pentan-3-ol by the procedure analogous to Example 6. HPLC ret. time: 3.3 minutes. 1 H NMR (400 MHz, CD 3 OD) δ7.17 (d, 2H, J=6.4 Hz), 5.51 (s, 2H), 3.64 (bm, 1H), 3.24 (t, 2H, J=6.0 Hz), 2.92 (m, 1H), 2.72 (m, 1H), 2.39 (m, 2H), 1.98 (m, 1H), 1.87 (m, 2H), 1.75 (m, 1H), 1.54 (m, 4H), 1.22 (m, 2H) ppm; MS (APCl, m/z): 517 [M+H] + .
EXAMPLE 17
5-(3-{4-[Bis-(2-hydroxy-ethyl)-amino]-butyl}-ureido)-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic Acid Amide
[0202] The title compound was prepared from [4-carbamoyl-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 2-[(4-amino-butyl)-(2-hydroxy-ethyl)-amino]-ethanol by the procedure analogous to Example 6. HPLC ret. time: 3.1 minutes. 1 H NMR (400 MHz, CD 3 OD) δ7.20 (dd, 1H, J=6.0, 9.2 Hz), 7.04 (dd, 1H, J=6.8, 9.6 Hz), 5.45 (s, 2H), 3.63 (t, 4H, J=5.6 Hz), 3.28 (m), 2.74 (m, 4H), 2.68 (m, 2H), 2.25 (d, 3H, J=2.0 Hz), 1.56 (m, 4H) ppm; MS (APCl, m/z): 502 [M+H] + .
EXAMPLE 18
3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(3,4-dihydroxy-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic Acid Amide
[0203] The title compound was prepared from [4-carbamoyl-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 1-(4-amino-butyl)-pyrrolidine-3,4-diol by the procedure analogous to Example 8. HPLC ret. time: minutes. 1 H NMR (400 MHz, CD 3 OD) δ7.20 (dd, 1H, J=6.0, 9.2 Hz), 7.04 (dd, 1H, J=6.8, 9.6 Hz), 5.45 (s, 2H), 3.63 (t, 4H, J=5.6 Hz), 3.28 (m), 2.74 (m, 4H), 2.68 (m, 2H), 2.25 (d, 3H, J=2.0 Hz), 1.56 (m, 4H) ppm.
EXAMPLE 19
5-[3-(4-tert-Butylamino-3-hydroxy-butyl)-ureido]-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic Acid Amide
[0204] The title compound was prepared from [4-carbamoyl-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 4-amino-1-tert-butylamino-butan-2-ol by the procedure analogous to Example 6. HPLC ret. time: 3.3 minutes. 1 H NMR (400 MHz, CD 3 OD) δ7.18 (dd, 1H, J=6.8, 9.6 Hz), 7.04 (dd, 1H, J=6.4, 10 Hz), 5.45 (s, 2H), 3.66 (m, 1H), 3.34 (t, 2H, J=7.6 Hz), 2.58 (m, 2H), 2.25 (s, 3H), 1.69-1.60 (m, 2H), 1.12 (s, 9H) ppm; MS (APCl, m/z): 486 [M+H] + .
EXAMPLE 20
3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic Acid Amide—Hydrochloride Salt
[0205] The title compound was prepared from [4-carbamoyl-3-(2,6-difluoro-4-chloro-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 3-(4-methyl-piperazin-1-yl)-propylamine by the procedure analogous to Example 6. 1 H NMR (400 MHz, D 2 O) δ6.86 (bm, 2H), 5.20 (s, 2H), 3.4-2.6 (bm, 8H), 3.10 (b, 2H), 2.63 (b, 5H), 1.67 (m, 2H) ppm; MS (APCl, m/z): 503 [M+H] + .
EXAMPLE 21
3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(3-hydroxy-5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic Acid Amide
[0206] The title compound was prepared from [4-carbamoyl-3-(2,6-difluoro-4-chloro-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 1-amino-5-isopropylamino-pentan-3-ol by the procedure analogous to Example 6. HPLC ret. time: 3.2 minutes. 1 H NMR (400 MHz, CD 3 OD) δ7.17 (d, 1H, J=7.6 Hz), 5.52 (s, 2H), 3.69 (m, 1H), 3.34 (t, 2H, J=6.4 Hz), 2.80 (s, 1H, J=6.0 Hz), 2.73 (m, 2H), 1.68-1.58 (m, 4H), 1.06 (d, 6H, J=6.0 Hz) ppm; MS (APCl, m/z): 506 [M+H] + .
EXAMPLE 22
3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(3-hydroxy-5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic Acid Amide
[0207] The title compound was prepared from [4-carbamoyl-3-(2,6-difluoro-4-chloro-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 1-amino-5-isopropylamino-pentan-3-ol by the procedure analogous to Example 6. HPLC ret. time: 3.2 minutes. 1 H NMR (400 MHz, CD 3 OD) δ7.17 (d, 1H, J=7.6 Hz), 5.52 (s, 2H), 3.69 (m, 1H), 3.34 (t, 2H, J=6.4 Hz), 2.80 (s, 1H, J=6.0 Hz), 2.73 (m, 2H), 1.68-1.58 (m, 4H), 1.06 (d, 6H, J=6.0 Hz) ppm; MS (APCl, m/z): 506 [M+H] + .
EXAMPLE 23
3-(2,5-Difluoro-4-methyl-benzyloxy)-5-(3-{6-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-hexyl}-ureido)-isothiazole-4-carboxylic Acid Amide
[0208] The title compound was prepared from [4-carbamoyl-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 2-[4-(6-amino-hexyl)-piperazin-1-yl]-ethanol by the procedure analogous to Example 6. HPLC ret. time: 3.0 minutes. 1 H NMR (400 MHz, CD 3 OD) δ7.17 (d, 1H, J=6.4, 9.6 Hz), 7.01 (m, 1H), 5.44 (s, 2H), 3.64 (t, 2H, J=5.6 Hz), 3.18 (t, 2H, J=6.8 Hz), 2.7-2.4 (bm, 8H), 2.50 (t, 2H, J=6.0 Hz), 2.23 (m, 2H), 2.23 (s, 3H), 1.50 (m, 4H), 1.35 (m, 4H) ppm; MS (APCl, m/z): 555 [M+H] + .
EXAMPLE 24
3-(4-Chloro-2,5-difluoro-benzyloxy)-5-[3-(6-dimethylamino-hexyl)-ureido]-isothiazole-4-carboxylic Acid Amide
[0209] The title compound was prepared from [4-carbamoyl-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 2-[4-(6-amino-hexyl)-piperazin-1-yl]-ethanol by the procedure analogous to Example 6. HPLC ret. time: 3.0 minutes. 1 H NMR (400 MHz, CD 3 OD) δ7.17 (d, 1H, J=6.4, 9.6 Hz), 7.01 (m, 1H), 5.44 (s, 2H), 3.64 (t, 2H, J=5.6 Hz), 3.18 (t, 2H, J=6.8 Hz), 2.7-2.4 (bm, 8H), 2.50 (t, 2H, J=6.0 Hz) 2.33 (m, 2H), 2.23 (s, 3H), 1.50 (m, 4H), 1.35 (m, 4H) ppm; MS (APCl, m/z): 555 [M+H] + .
EXAMPLE 25
5-{3-[3-(4-Methyl-piperazin-1-yl)-propyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic Acid Amide
[0210] The title compound was prepared from [4-carbamoyl-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 3-(4-methyl-piperazin-1-yl)-propylamine by the procedure analogous to Example 1. MS (APCl, m/z): 501 [M+H] + .
EXAMPLE 26
3-(2-Fluoro-4-methyl-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic Acid Amide
[0211] The title compound was prepared from [4-carbamoyl-3-(2-fluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 3-(4-methyl-piperazin-1-yl)-propylamine by the procedure analogous to Example 1. MS (APCl, m/z): 465 [M+H] + .
EXAMPLE 27
3-(2-Fluoro-4-methyl-benzyloxy)-5-[amino-pentyl)-ureido]-isothiazole-4-carboxylic Acid Amide
[0212] The title compound was prepared from [4-carbamoyl-3-(2-fluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and N-isopropyl-pentane-1,5-diamine by the procedure analogous to Example 1. MS (APCl, m/z): 452 [M+H] + .
EXAMPLE 28
3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic Acid Amide
[0213] The title compound was prepared from [4-carbamoyl-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 4-pyrrolidin-1-yl-butylamine by the procedure analogous to Example 1. 1 H NMR (400 MHz, CDCl 3 ) δ1.63 (br. s, 4H), 1.83 (br. s, 4H), 2.34 (s, 3H), 2.46-2.52 (m, 6H), 3.28 (s, 2H), 5.40 (s, 1H), 5.50 (s, 2H), 6.74 (d, J=8.3 Hz, 2H), 6.98 (s, 1H), 7.94 (br. s, 1H), 10.83 (br. s, 1H) ppm; MS (APCl, m/z): 468 [M+H] + .
EXAMPLE 29
3-(2,6-Difluoro-4-methyl-benzyloxy)-5-(3-{4-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-butyl}-ureido)-isothiazole-4-carboxylic Acid Amide
[0214] The title compound was prepared from [4-carbamoyl-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 2-[4-(4-amino-butyl)-piperazin-1-yl]-ethanol by the procedure analogous to Example 1. MS (APCl, m/z): 527 [M+H] + .
EXAMPLE 30
3-(4-Bromo-2,6-difluoro-benzyloxy)-5-[3-(4-pyrrolidin-1yl-butyl)-ureido]-isothiazole-4-carboxylic Acid Amide
[0215] The title compound was prepared from [3-(4-bromo-2,6-difluoro-benzyloxy)-4-carbamoyl-isothiazol-5-yl]-carbamic acid phenyl ester and 4-pyrrolidin-1-yl-butylamine by the procedure analogous to Example 1. MS (APCl, m/z): 532 and 534 [M+H] + .
EXAMPLE 31
3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(4-hydroxy-5-piperidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic Acid Amide
[0216] The title compound was prepared from [4-carbamoyl-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 5-amino-1-piperidin-1-yl-pentan-2-ol by the procedure analogous to Example 1. MS (APCl, m/z): 512 [M+H] + .
EXAMPLE 32
3-(4-Bromo-2,3,6-trifluoro-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic Acid Amide
[0217] The title compound was prepared from [3-(4-bromo-2,3,6-trifluoro-benzyloxy)-4-carbamoyl-isothiazol-5-yl]-carbamic acid phenyl ester and 3-(4-methyl-piperazin-1-yl)-propylamine by the procedure analogous to Example 1. MS (APCl, m/z): 565 and 567 [M+H] + .
EXAMPLE 33
3-(2,6-Difluoro-4-methyl-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic Acid Amide
[0218] The title compound was prepared from [4-Carbamoyl-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and and 3-(4-methyl-piperazin-1-yl)-propylamine by the procedure analogous to Example 1. MS (APCl, m/z): 483 [M+H] + .
EXAMPLE 34
3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(3-hydroxy-5-pyrrolidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic Acid Amide
[0219] The title compound was prepared from [4-carbamoyl-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 1-amino-5-pyrrolidin-1-yl-pentan-3-ol by the procedure analogous to Example 1. MS (APCl, m/z): 498 [M+H] + .
EXAMPLE 35
5-[3-(4-Pyrrolidin-1-yl-butyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic Acid Amide
[0220] The title compound was prepared from [4-carbamoyl-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 4-pyrrolidin-1-yl-butylamine by the procedure analogous to Example 1. MS (APCl, m/z): 486 [M+H] + .
EXAMPLE 36
5-[3-(3-Hydroxy-5-pyrrolidin-1-yl-pentyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide
[0221] The title compound was prepared from [4-carbamoyl-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 1-amino-5-pyrrolidin-1-yl-pentan-3-ol by the procedure analogous to Example 1. MS (APCl, m/z): 516 [M+H] + .
EXAMPLE 37
5-{3-[2-(1-Methyl-pyrrolidin-2-yl)-ethyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxisothiazole-4-carboxylic Acid Amide
[0222] The title compound was prepared from [4-carbamoyl-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 2-(1-methyl-pyrrolidin-2-yl)-ethylamine by the procedure analogous to Example 1. MS (APCl, m/z): 472 [M+H] + .
EXAMPLE 38
5-[3-(4-Dimethylamino-butyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic Acid Amide
[0223] The title compound was prepared from [4-carbamoyl-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and N,N-dimethyl-butane-1,4-diamine by the procedure analogous to Example 1. MS (APCl, m/z): 460 [M+H] + .
EXAMPLE 39
5-[3-(3-Dimethylamino-propyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy-isothiazole-4-carboxylic Acid Amide
[0224] The title compound was prepared from [4-carbamoyl-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and N,N-dimethyl-propane-1,3-diamine by the procedure analogous to Example 1. MS (APCl, m/z): 446 [M+H] + .
EXAMPLE 40
5-[3-(3-Hydroxy-5-isopropylamino-pentyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic Acid Amide
[0225] The title compound was prepared from [4-carbamoyl-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 1-amino-5-isopropylamino-pentan-3-ol by the procedure analogous to Example 1. MS (APCl, m/z): 504 [M+H] + .
EXAMPLE 41
5-[3-(3-Isopropylamino-propyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic Acid Amide
[0226] The title compound was prepared from [4-carbamoyl-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and N-isopropyl-propane-1,3-diamine by the procedure analogous to Example 1. MS (APCl, m/z): 460 [M+H] + .
EXAMPLE 42
5-{3-[4-(4-Methyl-piperazin-1-yl)-butyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic Acid Amide
[0227] The title compound was prepared from [4-carbamoyl-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 4-(4-methyl-piperazin-1-yl)-butylamine by the procedure analogous to Example 1. MS (APCl, m/z): 515 [M+H] + .
EXAMPLE 43
5-(3-{4-[4-(2-Hydroxy-ethyl)-piperazin-1-yl]-butyl}-ureido)-3-(2,3,6-trifluoro-4-benzyloxy)-isothiazole-4-carboxylic Acid Amide
[0228] The title compound was prepared from [4-carbamoyl-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 2-[4-(4-amino-butyl)-piperazin-1-yl]-ethanol by the procedure analogous to Example 1. MS (APCl, m/z): 545 [M+H] + .
EXAMPLE 44
5-[3-(3-Pyrrolidin-1-yl-propyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic Acid Amide
[0229] The title compound was prepared from [4-carbamoyl-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 3-pyrrolidin-1-yl-propylamine by the procedure analogous to Example 1. MS (APCl, m/z): 472 [M+H] + .
EXAMPLE 45
5-[3-(4-Hydroxy-5-piperidin-1-yl-pentyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic Acid Amide
[0230] The title compound was prepared from [4-carbamoyl-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 5-amino-1-piperidin-1-yl-pentan-2-ol by the procedure analogous to Example 1. MS (APCl, m/z): 530 [M+H] + .
EXAMPLE 46
5-(3-{4-[Ethyl-(2-hydroxy-ethyl)-amino]-butyl}-ureido)-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic Acid Amide
[0231] The title compound was prepared from [4-carbamoyl-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 2-[(4-amino-butyl)-ethyl-amino]-ethanol by the procedure analogous to Example 1. MS (APCl, m/z): 504 [M+H] + .
EXAMPLE 47
3-(4-Bromo-2,6-difluoro-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic Acid Amide
[0232] The title compound was prepared from [3-(4-bromo-2,6-difluoro-benzyloxy)-4-carbamoyl-isothiazol-5-yl]-carbamic acid phenyl ester and 3-(4-methyl-piperazin-1-yl)-propylamine by the procedure analogous to Example 1. MS (APCl, m/z): 547 and 549 [M+H] + .
EXAMPLE 48
3-(2,6-Difluoro-4-methyl-benzyloxy)-5-{3-[2-(1-methyl-pyrrolidin-2-yl)-ethyl]-ureido}-isothiazole-4-carboxylic Acid Amide
[0233] The title compound was prepared from [4-carbamoyl-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 2-(1-methyl-pyrrolidin-2-yl)-ethylamine by the procedure analogous to Example 1. MS (APCl, m/z): 454 [M+H] + .
EXAMPLE 49
3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(4-dimethylamino-butyl)-ureido]-isothiazole-4-carboxylic Acid Amide
[0234] The title compound was prepared from [4-carbamoyl-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and N,N-dimethyl-butane-1,4-diamine by the procedure analogous to Example 1. MS (APCl, m/z): 442 [M+H] + .
EXAMPLE 50
3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(3-dimethylamino-propyl)-ureido]-isothiazole-4-carboxylic Acid Amide
[0235] The title compound was prepared from [4-carbamoyl-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and N,N-dimethyl-propane-1,3-diamine by the procedure analogous to Example 1. MS (APCl, m/z): 428 [M+H] + .
EXAMPLE 51
3-(4-Bromo-2,3,6-trifluoro-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic Acid Amide
[0236] The title compound was prepared from [3-(4-bromo-2,3,6-trifluoro-benzyloxy)-4-carbamoyl-isothiazol-5-yl]-carbamic acid phenyl ester and 4-pyrrolidin-1-yl-butylamine by the procedure analogous to Example 1. MS (APCl, m/z): 550 and 552 [M+H] + .
EXAMPLE 52
5-[3-(3-Methylamino-propyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic Acid Amide
[0237] The title compound was prepared from [4-carbamoyl-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and N-methyl-propane-1,3-diamine by the procedure analogous to Example 1. MS (APCl, m/z): 432 [M+H] + .
EXAMPLE 53
5-[3-(3-Amino-propyl)-3-methyl-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic Acid Amide
[0238] The title compound was prepared from [4-carbamoyl-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and N-methyl-propane-1,3-diamine by the procedure analogous to Example 1. MS (APCl, m/z): 432 [M+H] + .
EXAMPLE 54
5-[3-(4-Diethylamino-butyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic Acid Amide
[0239] The title compound was prepared from [4-carbamoyl-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and N,N-diethyl-butane-1,4-diamine by the procedure analogous to Example 1. MS (APCl, m/z): 488 [M+H] + .
EXAMPLE 55
3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic Acid Amide
[0240] The title compound was prepared from [4-carbamoyl-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 3-pyrrolidin-1-yl-propylamine by the procedure analogous to Example 1. MS (APCl, m/z): 454 [M+H] + .
EXAMPLE 56
3-(3-Chloro-2,6-difluoro-4-methyl-benzyloxy)-5-[3-(4-dimethylamino-butyl)-ureido]-isothiazole-4-carboxylic Acid Amide
[0241] The title compound was prepared [4-carbamoyl-3-(3-chloro-2,6-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and N,N-diethyl-butane-1,4-diamine by the procedure analogous to Example 1. MS (APCl, m/z): 476 [M+H] + .
EXAMPLE 57
5-(3-{4-[Bis-(2-hydroxy-ethyl)-amino]-butyl}-ureido)-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic Acid Amide
[0242] The title compound was prepared from [4-carbamoyl-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-carbamic acid phenyl ester and 2-[(4-amino-butyl)-(2-hydroxy-ethyl)-amino]-ethanol by the procedure analogous to Example 1. MS (APCl, m/z): 502 [M+H] + .
[0243] The following specific compounds were prepared using the general synthetic procedures described above with reference to Schemes 1-5 and the specific synthetic procedures described in the above preparations and examples.
[0244] (3-tert-Butyl-isothiazol-5-yl)-(6,7-dimethoxy-quinolin-4-yl)-amine;
[0245] 3-Ethylsulfanyl-5-(3-hexyl-ureido)-isothiazole-4-carboxylic acid amide;
[0246] 5-(3-Benzyl-ureido)-3-ethylsulfanyl-isothiazole-4-carboxylic acid amide;
[0247] 3-Ethylsulfanyl-5-(3-ethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0248] 3-Ethylsulfanyl-5-[(pyrrolidine-1-carbonyl)-amino]-isothiazole-4-carboxylic acid amide;
[0249] 5-(3-Butyl-ureido)-3-ethylsulfanyl-isothiazole-4-carboxylic acid amide;
[0250] 5-(3,3-Dimethyl-ureido)-3-propylsulfanyl-isothiazole-4-carboxylic acid amide;
[0251] 5-(3-Methyl-ureido)-3-propylsulfanyl-isothiazole-4-carboxylic acid amide;
[0252] 5-(3-Butyl-ureido)-3-propylsulfanyl-isothiazole-4-carboxylic acid amide;
[0253] 5-(3-Methyl-ureido)-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0254] 5-(3,3-Dimethyl-ureido)-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0255] 5-(3,3-Dimethyl-ureido)-3-isopropylsulfanyl-isothiazole-4-carboxylic acid amide;
[0256] 3-Pentylsulfanyl-5-ureido-isothiazole-4-carboxylic acid amide;
[0257] 3-Benzylsulfanyl-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0258] 5-(3,3-Dimethyl-ureido)-3-propoxy-isothiazole-4-carboxylic acid amide;
[0259] 3-Butoxy-4-carbamoyl-isothiazol-5-yl)-carbamic acid ethyl ester;
[0260] 5-(3,3-Dimethyl-ureido)-3-phenethylsulfanyl-isothiazole-4-carboxylic acid amide;
[0261] 5-(3,3-Dimethyl-ureido)-3-hexylsulfanyl-isothiazole-4-carboxylic acid amide;
[0262] 3-(4-Chloro-butylsulfanyl)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0263] 3-Butoxy-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0264] 3-Butylsulfanyl-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0265] 3-Cyclohexylsulfanyl-5-(3-methyl-ureido)-isothiazole-4-carboxylic acid amide;
[0266] 5-(3,3-Dimethyl-ureido)-3-(3-methyl-butylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0267] 5-(3,3-Dimethyl-ureido)-3-pentyloxy-isothiazole-4-carboxylic acid amide;
[0268] 5-(3,3-Dimethyl-ureido)-3-prop-2-ynylsulfanyl-isothiazole-4-carboxylic acid amide;
[0269] 5-(3,3-Dimethyl-ureido)-3-heptylsulfanyl-isothiazole-4-carboxylic acid amide;
[0270] 5-(3,3-Dimethyl-ureido)-3-isobutylsulfanyl-isothiazole-4-carboxylic acid amide;
[0271] 5-(3-Methyl-ureido)-3-phenylsulfanyl-isothiazole-4-carboxylic acid amide;
[0272] 5-(3,3-Dimethyl-ureido)-3-(3-hydroxy-butylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0273] 5-Amino-3-propoxy-isothiazole-4-carboxylic acid amide;
[0274] 3-Propoxy-5-(3-propyl-ureido)-isothiazole-4-carboxylic acid amide;
[0275] 5-(3-Butyl-ureido)-3-propoxy-isothiazole-4-carboxylic acid amide;
[0276] 5-(3-Ethyl-ureido)-3-propoxy-isothiazole-4-carboxylic acid amide;
[0277] 5-(3-Pentyl-ureido)-3-propoxy-isothiazole-4-carboxylic acid amide;
[0278] 5-(3-Hexyl-ureido)-3-propoxy-isothiazole-4-carboxylic acid amide;
[0279] 5-[(Azetidine-1-carbonyl)-amino]-3-propoxy-isothiazole-4-carboxylic acid amide;
[0280] Piperidine-1-carboxylic acid (4-carbamoyl-3-propoxy-isothiazol-5-yl)-amide;
[0281] 5-(3-Phenethyl-ureido)-3-propoxy-isothiazole-4-carboxylic acid amide;
[0282] 3-Propoxy-5-[(pyrrolidine-1-carbonyl)-amino]-isothiazole-4-carboxylic acid amide;
[0283] 5-(3,3-Dimethyl-ureido)-3-methylsulfanyl-isothiazole-4-carboxylic acid amide;
[0284] 3-Cyclopentylsulfanyl-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0285] 5-(3-Benzyl-ureido)-3-propoxy-isothiazole-4-carboxylic acid amide;
[0286] 5-(3,3-Dimethyl-ureido)-3-(naphthalen-1-ylmethylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0287] 3-[4-Carbamoyl-5-(3,3-dimethyl-ureido)-isothiazol-3-ylsulfany]-propionic acid;
[0288] 3-Propoxy-5-ureido-isothiazole-4-carboxylic acid amide;
[0289] 3-Propoxy-5-(3-pyridin-3-yl-ureido)-isothiazole-4-carboxylic acid amide;
[0290] 5-(3,3-Dimethyl-ureido)-3-(4-methyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0291] 5-(3,3-Dimethyl-ureido)-3-(4-methoxy-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0292] 5-(3,3-Dimethyl-ureido)-3-(4-methyl-pentylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0293] 5-(3-Butyl-ureido)-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0294] 5-Acetylamino-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0295] 5-Benzoylamino-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0296] 3-Decyloxy-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0297] Morpholine-4-carboxylic acid (4-carbamoyl-3-pentylsulfanyl-isothiazol-5-yl)-amide;
[0298] 5-[3-(2-Hydroxy-ethyl)-ureido]-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0299] 5-[(3-Hydroxy-azetidine-1-carbonyl)-amino]-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0300] 5-[3-(3-Hydroxy-propyl)-ureido]-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0301] 3-Pentylsulfanyl-5-(3-propyl-ureido)-isothiazole-4-carboxylic acid amide;
[0302] 5-(3,3-Dimethyl-ureido)-3-hexyloxy-isothiazole-4-carboxylic acid amide;
[0303] 5-(3,3-Dimethyl-ureido)-3-heptyloxy-isothiazole-4-carboxylic acid amide;
[0304] 5-(3-Isobutyl-ureido)-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0305] 5-(3-Furan-2-ylmethyl-ureido)-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0306] 5-(3,3-Dimethyl-ureido)-3-octyloxy-isothiazole-4-carboxylic acid amide;
[0307] 5-(3,3-Dimethyl-ureido)-3-(3-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0308] 3-Allyloxy-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0309] 5-(3,3-Dimethyl-ureido)-3-nonyloxy-isothiazole-4-carboxylic acid amide;
[0310] 5-(3,3-Dimethyl-ureido)-3-(naphthalen-2-ylmethylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0311] 5-(3,3-Dimethyl-ureido)-3-(3-methyl-but-2-enyloxy)-isothiazole-4-carboxylic acid amide;
[0312] 5-(3,3-Dimethyl-ureido)-3-(3-phenyl-allyloxy)-isothiazole-4-carboxylic acid amide;
[0313] 5-(3,3-Dimethyl-ureido)-3-pent-2-enyloxy-isothiazole-4-carboxylic acid amide;
[0314] 5-(3,3-Dimethyl-ureido)-3-(2-methyl-allyloxy)-isothiazole-4-carboxylic acid amide;
[0315] 3-Benzyloxy-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0316] 5-(3,3-Dimethyl-ureido)-3-phenethyloxy-isothiazole-4-carboxylic acid amide;
[0317] 3-(2-Cyclohexyl-ethoxy)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0318] 5-(3-Ethyl-ureido)-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0319] 5-[3-(3-Dimethylamino-propyl)-ureido]-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0320] 5-(3,3-Dimethyl-ureido)-3-(2-fluoro-3-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0321] 5-(3,3-Dimethyl-ureido)-3-(3-methoxy-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0322] 3-Pentylsulfanyl-5-(3-thiophen-2-ylmethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0323] 5-[3-(3-Methyl-butyl)-ureido]-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0324] 5-[3-(4-Hydroxy-butyl)-ureido]-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0325] 5-[3-(3-Methoxy-propyl)-ureido]-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0326] 4-Hydroxy-piperidine-1-carboxylic acid (4-carbamoyl-3-pentylsulfanyl-isothiazol-5-yl)-amide;
[0327] 5-(3,3-Dimethyl-ureido)-3-(3-trifluoromethyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0328] 5-(3,3-Dimethyl-ureido)-3-(4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0329] 5-(3,3-Dimethyl-ureido)-3-(naphthalen-2-ylmethoxy)-isothiazole-4-carboxylic acid amide;
[0330] 3-Heptyloxy-5-(3-methyl-urcido)-isothiazole-4-carboxylic acid amide;
[0331] 3-(3,5-Dimethyl-benzyloxy)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0332] 5-(3,3-Dimethyl-ureido)-3-(2-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0333] [3-(4-Carbamoyl-3-pentylsulfanyl-isothiazol-5-yl)-ureido]-acetic acid methyl ester;
[0334] 5-[3-(5-Methyl-furan-2-ylmethyl)-ureido]-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0335] 5-[3-(2-Hydroxy-propyl)-ureido]-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0336] 5-[(2,5-Dihydro-pyrrole-1-carbonyl)-amino]-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0337] 5-{3-[2-(1H-midazol-4-yl)-ethyl]-ureido}-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0338] 3-Pentylsulfanyl-5-[3-(tetrahydro-furan-2-ylmethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0339] 5-[3-(2-Cyano-ethyl)-ureido]-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0340] 5-(3-Cyclopropylmethyl-ureido)-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0341] 5-(3-Allyl-ureido)-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0342] 5-[3-(2-Dimethylamino-ethyl)-ureido]-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0343] 3-Hexylsulfanyl-5-(3-isobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[0344] 3-Hexylsulfanyl-5-(3-propyl-ureido)-isothiazole-4-carboxylic acid amide;
[0345] 5-(3,3-Dimethyl-ureido)-3-(3-fluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0346] 3-(3,5-Difluoro-benzyloxy)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0347] 5-(3-Butyl-ureido)-3-heptyloxy-isothiazole-4-carboxylic acid amide;
[0348] 3-(3-Chloro-benzyloxy)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0349] 5-(3,3-Dimethyl-ureido)-3-(3-iodo-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0350] 5-(3,3-Dimethyl-ureido)-3-(3-phenoxy-propoxy)-isothiazole-4-carboxylic acid amide;
[0351] 5-(3,3-Dimethyl-ureido)-3-(4-phenoxy-butoxy)-isothiazole-4-carboxylic acid amide;
[0352] 5-(3,3-Dimethyl-ureido)-3-(3-m-tolyl-propoxy)-isothiazole-4-carboxylic acid amide;
[0353] 3-(5-Cyano-pentyloxy)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0354] 5-(3,3-Dimethyl-ureido)-3-methoxy-isothiazole-4-carboxylic acid amide;
[0355] 3-(5-Chloro-pentyloxy)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0356] 3-(4-Cyano-butoxy)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0357] 5-(3-Furan-2-ylmethyl-ureido)-3-hexylsulfanyl-isothiazole-4-carboxylic acid amide;
[0358] 5-(3-Butyl-ureido)-3-hexylsulfanyl-isothiazole-4-carboxylic acid amide;
[0359] 3-Hexylsulfanyl-5-[3-(3-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0360] 3-Pentylsulfanyl-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0361] 3-Hexylsulfanyl-5-[3-(2-hydroxy-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0362] 3-Benzylsulfanyl-5-(3-methyl-ureido)-isothiazole-4-carboxylic acid amide;
[0363] 5-{3-[2-(1-Methyl-1H-pyrrol-2-yl)-ethyl]-ureido}-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0364] 3-Benzylsulfanyl-5-(3-butyl-ureido)-isothiazole-4-carboxylic acid amide;
[0365] Benzoic acid 2-[4-carbamoyl-5-(3,3-dimethyl-ureido)-isothiazol-3-yloxy]-ethyl ester;
[0366] 5-(3,3-Dimethyl-ureido)-3-(2-phenoxy-ethoxy)-isothiazole-4-carboxylic acid amide;
[0367] 3-(3-Benzyloxy-propoxy)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0368] 5-(3,3-Dimethyl-ureido)-3-(3,3-diphenyl-propoxy)-isothiazole-4-carboxylic acid amide;
[0369] 3-(6-Chloro-hexyloxy)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0370] 5-(3,3-Dimethyl-ureido)-3-(2-ethoxy-ethoxy)-isothiazole-4-carboxylic acid amide;
[0371] 5-(3,3-Dimethyl-ureido)-3-(4-vinyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0372] 3-Cyclohexylmethoxy-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0373] 5-(3,3-Dimethyl-ureido)-3-(4-phenyl-butoxy)-isothiazole-4-carboxylic acid amide;
[0374] 5-(3,3-Dimethyl-ureido)-3-[3-(3-methoxy-phenyl)-propoxy]-isothiazole-4-carboxylic acid amide;
[0375] 3-(2,5-Dimethyl-benzyloxy)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0376] 3-Hexylsulfanyl-5-{3-[2-(1H-imidazol-4-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0377] 3-Hexylsulfanyl-5-[3-(4-hydroxy-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0378] 3-Hexylsulfanyl-5-[3-(2-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0379] 3-Benzylsulfanyl-5-[3-(2-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0380] 3-Benzylsulfanyl-5-(3-benzyl-ureido)-isothiazole-4-carboxylic acid amide;
[0381] 3-Benzylsulfanyl-5-(3-furan-2-ylmethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0382] 3-Benzylsulfanyl-5-(3-isobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[0383] 3-Hexylsulfanyl-5-(3-pentyl-ureido)-isothiazole-4-carboxylic acid amide;
[0384] 3-Hexylsulfanyl-5-(3-methyl-ureido)-isothiazole-4-carboxylic acid amide;
[0385] 3-Hexylsulfanyl-5-[3-(3-methyl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0386] 5-(3-Ethyl-ureido)-3-hexylsulfanyl-isothiazole-4-carboxylic acid amide;
[0387] 5-[3-(2-Morpholin-4-yl-ethyl)-ureido]-3-pentylsulfanyl-isothiazole-4-carboxylic acid amide;
[0388] 5-[3-(2,3-Dihydroxy-propyl)-ureido]-3-heptyloxy-isothiazole-4-carboxylic acid amide;
[0389] 3-Heptyloxy-5-[3-(2-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0390] 5 3-Heptyloxy-5-[3-(2-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0391] 3-Heptyloxy-5-[3-(5-hydroxy-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0392] 3-Heptyloxy-5-[3-(3-hydroxy-2,2-dimethyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0393] 3-Heptyloxy-5-[3-(2-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0394] 3-Heptyloxy-5-[3-(3-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0395] 3-Heptyloxy-5-[3-(2-hydroxy-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0396] 3-Heptyloxy-5-[3-(4-hydroxy-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0397] 5-(3,3-Dimethyl-ureido)-3-(5-methyl-hexyloxy)-isothiazole-4-carboxylic acid amide;
[0398] 5-(3,3-Dimethyl-ureido)-3-(naphthalen-1-ylmethoxy)-isothiazole-4-carboxylic acid amide;
[0399] 5-(3,3-Dimethyl-ureido)-3-(3-phenyl-propoxy)-isothiazole-4-carboxylic acid amide;
[0400] 5-(3,3-Dimethyl-ureido)-3-(4-methyl-pentyloxy)-isothiazole-4-carboxylic acid amide;
[0401] 3-(3-Bromo-benzyloxy)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0402] 3-(3,4-Dimethyl-benzyloxy)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0403] 3-(2,4-Dimethyl-benzyloxy)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0404] 3-(3,5-Bis-trifluoromethyl-benzyloxy)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0405] 3-(4-Chloro-benzylsulfanyl)-5-[3-(3-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0406] 3-Benzylsulfanyl-5-[3-(3-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0407] 3-(4-Chloro-benzylsulfanyl)-5-(3-furan-2-ylmethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0408] 3-(4-Chloro-benzylsulfanyl)-5-[3-(2-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0409] 3-Hexylsulfanyl-5-[3-(2-morpholin-4-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0410] 3-(4-Chloro-benzylsulfanyl)-5-(3-isobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[0411] 5-(3-Benzyl-ureido)-3-(4-chloro-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0412] 3-(4-Chloro-benzylsulfanyl)-5-(3-methyl-ureido)-isothiazole-4-carboxylic acid amide;
[0413] 5-(3-Butyl-ureido)-3-(4-chloro-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0414] 5-[3-(2-Dimethylamino-ethyl)-ureido]-3-hexylsulfanyl-isothiazole-4-carboxylic acid amide;
[0415] 3-Hexylsulfanyl-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0416] 5-[3-(3-Dimethylamino-propyl)-ureido]-3-hexylsulfanyl-isothiazole-4-carboxylic acid amide;
[0417] 3-Hexylsulfanyl-5-{3-[3-(2-oxo-pyrrolidin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0418] 3-(4-Chloro-benzylsulfanyl)-5-[3-(2,3-dihydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0419] 3-(4-Chloro-benzylsulfanyl)-5-[3-(5-hydroxy-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0420] 3-(4-Chloro-benzylsulfanyl)-5-[3-(4-hydroxy-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0421] 3-(4-Chloro-benzylsulfanyl)-5-[3-(2-hydroxy-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0422] 5-[3-(2,3-Dihydroxy-propyl)-ureido]-3-hexylsulfanyl-isothiazole-4-carboxylic acid amide;
[0423] 3-Hexylsulfanyl-5-[3-(2-hydroxy-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0424] 3-Benzylsulfanyl-5-[3-(2,3-dihydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0425] 3-Hexylsulfanyl-5-[3-(5-hydroxy-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0426] 3-Benzylsulfanyl-5-[3-(2-hydroxy-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0427] 3-(4-Chloro-benzylsulfanyl)-5-[3-(2-hydroxy-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0428] 3-(4-Chloro-benzylsulfanyl)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0429] 3-Benzylsulfanyl-5-[3-(5-hydroxy-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0430] 1-(4-Cyano-3-pentylsulfanyl-isothiazol-5-yl)-3-methyl-urea;
[0431] 5-(3,3-Dimethyl-ureido)-3-(2,4,6-trimethyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0432] 5-(3,3-Dimethyl-ureido)-3-(2-trifluoromethyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0433] 5-(3,3-Dimethyl-ureido)-3-(4-trifluoromethyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0434] 3-(2,4-Dimethyl-benzylsulfanyl)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0435] 5-(3,3-Dimethyl-ureido)-3-(2-fluoro-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0436] 5-(3,3-Dimethyl-ureido)-3-(3-methyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0437] 5-(3,3-Dimethyl-ureido)-3-(2-fluoro-3-methyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0438] 3-(4-Chloro-benzyloxy)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0439] 3-(2-Chloro-benzylsulfanyl)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0440] 1-Methyl-3-[3-pentylsulfanyl-4-(1H-tetrazol-5-yl)-isothiazol-5-yl]-urea;
[0441] 5-(3,3-Dimethyl-ureido)-3-(4-fluoro-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0442] 3-(3-Chloro-benzylsulfanyl)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0443] 3-(2,5-Dimethyl-benzylsulfanyl)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0444] 3-(1-Bromo-naphthalen-2-ylmethylsulfanyl)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0445] 3-(3,4-Dimethyl-benzylsulfanyl)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0446] 3-(Biphenyl-4-ylmethoxy)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0447] 5-(3,3-Dimethyl-ureido)-3-(2-fluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0448] 3-(2-Chloro-benzyloxy)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0449] 5-(3,3-Dimethyl-ureido)-3-(4-isopropyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0450] 5-(3,3-Dimethyl-ureido)-3-(2,3,4,5,6-pentamethyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0451] 3-(4-Chloro-benzylsulfanyl)-5-[3-(2-dimethylamino-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0452] 3-(4-Chloro-benzylsulfanyl)-5-[3-(3-dimethylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0453] 3-(4-Chloro-benzylsulfanyl)-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0454] 3-(4-Chloro-benzylsulfanyl)-5-{3-[2-(1H-imidazol-4-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0455] 3-(4-Chloro-benzylsulfanyl)-5-{3-[2-(1-methyl-1H-pyrrol-2-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0456] 3-(4-Chloro-benzylsulfanyl)-5-[3-(2-morpholin-4-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0457] 3-(4-Chloro-benzylsulfanyl)-5-{3-[3-(2-oxo-pyrrolidin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0458] 3-But-2-enyloxy-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0459] 5-(3,3-Dimethyl-ureido)-3-(4-methoxy-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0460] 3-(2,4-Difluoro-benzyloxy)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0461] 5-(3-sec-Butyl-ureido)-3-(4-chloro-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0462] 3-(4-Chloro-benzylsulfanyl)-5-[3-(2,2-dimethyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0463] 3-(4-Chloro-benzylsulfanyl)-5-[3-(1-ethyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0464] 3-(4-Chloro-benzylsulfanyl)-5-(3-cyclopropylmethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0465] 3-(4-Chloro-benzylsulfanyl)-5-[3-(1-methyl-1-phenyl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0466] 3-(4-Chloro-benzylsulfanyl)-5-[3-(3,4-difluoro-benzyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0467] 3-(4-Bromo-2-fluoro-benzyloxy)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0468] 3-(4-tert-Butyl-benzyloxy)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0469] 5-(3-isobutyl-ureido)-3-(4-methyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0470] 5-(3-Butyl-ureido)-3-(4-methyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0471] 5-[3-(3-Hydroxy-propyl)-ureido]-3-(4-methyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0472] (4-Carbamoyl-3-mercapto-isothiazol-5-yl)-carbamic acid phenyl ester;
[0473] 5-(3-Butyl-ureido)-3-(3,4-dichloro-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0474] 3-(3,4-Dichloro-benzylsulfanyl)-5-(3-isobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[0475] 3-(3,4-Dichloro-benzylsulfanyl)-5-[3-(3-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0476] 4-[4-Carbamoyl-5-(3-isobutyl-ureido)-isothiazol-3-ylsulfanylmethyl]-benzoic acid methyl ester;
[0477] 4-[5-(3-Butyl-ureido)-4-carbamoyl-isothiazol-3-ylsulfanylmethyl]-benzoic acid methyl ester;
[0478] 4-{4-Carbamoyl-5-[3-(3-hydroxy-propyl)-ureido]-isothiazol-3-ylsulfanylmethyl}-benzoic acid methyl ester;
[0479] 3-(3,3-Diphenyl-propylsulfanyl)-5-[3-(3-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0480] 3-(3,3-Diphenyl-propylsulfanyl)-5-(3-isobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[0481] 5-(3-Butyl-ureido)-3-(3,3-diphenyl-propylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0482] 5-[3-(2-Dimethylamino-ethyl)-ureido]-3-(3,3-diphenyl-propylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0483] 3-Hexylsulfanyl-5-[3-(2-methoxy-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0484] 3-Hexylsulfanyl-5-[3-(2-pyridin-2-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0485] 3-Hexylsulfanyl-5-[3-(2-pyrrolidin-1-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0486] 5-(3,3-Dimethyl-ureido)-3-(2-methoxy-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0487] 3-(2,3-Dichloro-benzyloxy)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0488] 3-Benzylsulfanyl-5-[3-(2-dimethylamino-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0489] 5-[3-(2-Dimethylamino-ethyl)-ureido]-3-(4-methyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0490] 5-[3-(2-Dimethylamino-ethyl)-ureido]-3-(4-methoxy-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0491] 5-[3-(2-Dimethylamino-ethyl)-ureido]-3-(3-methoxy-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0492] 5-[3-(2-Dimethylamino-ethyl)-ureido]-3-(2-methyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0493] 5-[3-(2-Dimethylamino-ethyl)-ureido]-3-(2-methoxy-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0494] 3-{4-Carbamoyl-5-[3-(2-dimethylamino-ethyl)-ureido]-isothiazol-3-ylsulfanylmethyl}-benzoic acid methyl ester;
[0495] 3-Benzylsulfanyl-5-[3-(3-pyrrolid in-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0496] 3-(4-Methyl-benzylsulfanyl)-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0497] 3-(4-Methoxy-benzylsulfanyl)-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0498] 3-(3-Methoxy-benzylsulfanyl)-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0499] 3-(3-Methoxy-benzylsulfanyl)-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0500] 4-{4-Carbamoyl-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazol-3-ylsulfanylmethyl}-benzoic acid methyl ester;
[0501] 3-(2-Chloro-benzylsulfanyl)-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0502] 3-(2-Fluoro-benzylsulfanyl)-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0503] 5-(3-Isobutyl-ureido)-3-(2-methyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0504] 5-(3-Isobutyl-ureido)-3-(3-methoxy-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0505] 5-(3-Isobutyl-ureido)-3-(4-methoxy-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0506] 5-(3-Isobutyl-ureido)-3-(3-methyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0507] 3-(2-Fluoro-benzylsulfanyl)-5-(3-isobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[0508] 3-(4-Fluoro-benzylsulfanyl)-5-(3-isobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[0509] 3-(2-Fluoro-3-methyl-benzylsulfanyl)-5-(3-isobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[0510] 3-(2,4-Difluoro-benzylsulfanyl)-5-(3-isobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[0511] 3-(5-Chloro-thiophen-2-ylmethylsulfanyl)-5-(3-isobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[0512] 3-(Benzo[1,3]dioxol-5-ylmethylsulfanyl)-5-(3-isobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[0513] 5-(3-Cyclopropylmethyl-ureido)-3-(3,4-dimethyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0514] 3-(3,4-Dimethyl-benzylsulfanyl)-5-(3-isobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[0515] 3-(4-Bromo-2-fluoro-benzylsulfanyl)-5-(3-isobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[0516] 3-(2,4-Dimethyl-benzylsulfanyl)-5-(3-isobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[0517] 3-(3,4-Dimethyl-benzylsulfanyl)-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0518] 3-(4-Bromo-2-fluoro-benzylsulfanyl)-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0519] 5-(3-Cyclopropylmethyl-ureido)-3-(4-methyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0520] 3-(3,4-Dimethyl-benzylsulfanyl)-5-[3-(2-morpholin-4-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0521] 5-[3-(2,2-Dimethyl-propyl)-ureido]-3-(4-methyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0522] 5-(3-Cyclopropylmethyl-ureido)-3-(3,4-dichloro-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0523] 5-(3-Cyclopropylmethyl-ureido)-3-(3-methoxy-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0524] 3-(4-Bromo-2-fluoro-benzylsulfanyl)-5-[3-(3,4-difluoro-benzyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0525] 5-[3-(3,4-Difluoro-benzyl)-ureido]-3-(3,3-diphenyl-propylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0526] 5-[3-(3,4-Difluoro-benzyl)-ureido]-3-(4-methoxy-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0527] 5-[3-(3,4-Difluoro-benzyl)-ureido]-3-(3,4-dimethyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0528] 3-(3-Methyl-benzylsulfanyl)-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0529] 5-[3-(2-Dimethylamino-ethyl)-ureido]-3-(3-methyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0530] 5-[3-(2-Dimethylamino-ethyl)-ureido]-3-(3,4-dimethyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0531] 3-(4-Bromo-2-fluoro-benzylsulfanyl)-5-[3-(3-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0532] 3-{4-Carbamoyl-5-[3-(3,4-difluoro-benzyl)-ureido]-isothiazol-3-ylsulfanylmethyl}-benzoic acid methyl ester;
[0533] 3-{4-Carbamoyl-5-[3-(3-hydroxy-propyl)-ureido]-isothiazol-3-ylsulfanylmethyl}-benzoic acid methyl ester;
[0534] 5-[3-(3,4-Difluoro-benzyl)-ureido]-3-phenethylsufanyl-isothiazole-4-carboxylic acid amide;
[0535] 5-[3-(3,4-Difluoro-benzyl)-ureido]-3-(4-methyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0536] 5-[3-(3,4-Difluoro-benzyl)-ureido]-3-(2,4-dimethyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0537] 3-(4-tert-Butyl-benzylsulfanyl)-5-(3,3-dimethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0538] 3-(4-Methyl-benzylsulfanyl)-5-[3-(2-phenyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0539] 5-[3-(1,2-Dimethyl-propyl)-ureido]-3-(4-methyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0540] 5-[3-(3,5-Difluoro-benzyl)-ureido]-3-(4-methyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0541] 5-{3-[1-(4-Fluoro-phenyl)-ethyl]-ureido)-3-(4-methyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0542] 5-[3-(3-Fluoro-benzyl)-ureido]-3-(4-methyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0543] 5-[3-(4-Fluoro-2-trifluoromethyl-benzyl)-ureido]-3-(4-methyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0544] 5-[3-(3-Chloro-4-fluoro-benzyl)-ureido]-3-(4-methyl-benzylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0545] 3-(4-Bromo-2-fluoro-benzyloxy)-5-(3-isobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[0546] 3-(4-Bromo-2-fluoro-benzyloxy)-5-(3-butyl-ureido)-isothiazole-4-carboxylic acid amide;
[0547] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(2,2-dimethyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0548] 3-(4-Bromo-2-fluoro-benzyloxy)-5-(3-furan-2-ylmethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0549] 5-(3-Allyl-ureido)-3-(4-bromo-2-fluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0550] 3-(4-Bromo-2-fluoro-benzyloxy)-5-(3-cyclobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[0551] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(3,3-dimethyl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0552] 3-(4-Bromo-2-fluoro-benzyloxy)-5-(3-cyclopropylmethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0553] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(3-phenyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0554] 5-[3-(2-Isopropylamino-ethyl)-ureido]-3-(4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0555] 5-(3-Cyclohexylmethyl-ureido)-3-(4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0556] 5-(3-Isobutyl-ureido)-3-(4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0557] 5-[3-(3-Dimethylamino-propyl)-ureido]-3-(4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0558] 3-(5-Chloro-thiophen-2-ylmethylsulfanyl)-5-[3-(3,4-difluoro-benzyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0559] 3-(5-Chloro-thiophen-2-ylmethylsulfanyl)-5-(3-cyclopropylmethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0560] 3-(5-Chloro-thiophen-2-ylmethylsulfanyl)-5-[3-(2-morpholin-4-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0561] 3-(5-Chloro-thiophen-2-ylmethylsulfanyl)-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0562] 5-[3-(3,4-Difluoro-benzyl)-ureido]-3-(5-methyl-thiophen-2-ylmethylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0563] 3-(5-Chloro-thiophen-2-ylmethoxy)-5-(3-cyclopropylmethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0564] 5-(3-Isobutyl-ureido)-3-(5-methyl-thiophen-2-ylmethylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0565] 3-(5-Chloro-thiophen-2-ylmethoxy)-5-[3-(3,4-difluoro-benzyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0566] 5-(3-Cyclopropylmethyl-ureido)-3-(5-methyl-thiophen-2-ylmethylsulfanyl)-isothiazole-4-carboxylic acid amide;
[0567] 3-(5-Methyl-thiophen-2-ylmethylsulfanyl)-5-[3-(2-morpholin-4-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0568] 3-(5-Methyl-thiophen-2-ylmethylsulfanyl)-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0569] 3-(4-Chloro-benzyloxy)-5-[3-(3-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide
[0570] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(3,4-difluoro-benzyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0571] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(2-dimethylamino-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0572] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(3-dimethylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0573] 3-(4-Chloro-2-fluoro-benzyloxy)-5-(3-furan-2-ylmethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0574] 3-(4-Chloro-2-fluoro-benzyloxy)-5-[3-(2-morpholin-4-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0575] 3-(2,3-Dichloro-benzyloxy)-5-[3-(2-morpholin-4-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0576] 3-(2,3-Dichloro-benzyloxy)-5-[3-(3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0577] 3-(2,3-Dichloro-benzyloxy)-5-[3-(3-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0578] 3-(2,3-Dichloro-benzyloxy)-5-[3-(2-pyrrolidin-1-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0579] 3-(2,3-Dichloro-benzyloxy)-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0580] 3-(2,3-Dichloro-benzyloxy)-5-{3-[2-(1H-imidazol-4-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0581] 3-(2,3-Dichloro-benzyloxy)-5-[3-(1-ethyl-pyrrolidin-2-ylmethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0582] 3-(2,3-Dichloro-benzyloxy)-5-[3-(2-isopropylamino-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0583] 3-(2,3-Dichloro-benzyloxy)-5-[3-(3-diethylamino-2-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0584] 3-(4-Chloro-2-fluoro-benzyloxy)-5-[3-(3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0585] 3-(4-Chloro-2-fluoro-benzyloxy)-5-[3-(2-pyrrolidin-1-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0586] 3-(4-Chloro-2-fluoro-benzyloxy)-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0587] 3-(4-Chloro-2-fluoro-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0588] 3-(4-Chloro-2-fluoro-benzyloxy)-5-[3-(3-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0589] 3-(4-Chloro-2-fluoro-benzyloxy)-5-[3-(3,4-difluoro-benzyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0590] 3-(4-Chloro-2-fluoro-benzyloxy)-5-[3-(2-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0591] 5-(3-Cyclopropylmethyl-ureido)-3-(2,3-dichloro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0592] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(3-isopropylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0593] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(2-sec-butylamino-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0594] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(2-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0595] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(2-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0596] 3-(2,3-Difluoro-benzyloxy)-5-[3-(2-morpholin-4-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0597] 3-(2,3-Difluoro-benzyloxy)-5-[3-(3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0598] 3-(2,3-Difluoro-benzyloxy)-5-(3-isobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[0599] 3-(2,3-Difluoro-benzyloxy)-5-[3-(2-pyrrolidin-1-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0600] 3-(2,3-Difluoro-benzyloxy)-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0601] 3-(2-Fluoro-3-methyl-benzyloxy)-5-[3-(2-morpholin-4-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0602] 3-(2-Fluoro-3-methyl-benzyloxy)-5-(3-isobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[0603] 3-(2-Fluoro-benzyloxy)-5-[3-(2-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0604] 3-(2-Fluoro-benzyloxy)-5-[3-(2-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0605] 5-[3-(2-Dimethylamino-propyl)-ureido]-3-(2-fluoro-3-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0606] 3-(2-Fluoro-3-methyl-benzyloxy)-5-[3-(2-pyrrolidin-1-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0607] 3-(2-Fluoro-3-methyl-benzyloxy)-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0608] 3-(2,3-Difluoro-benzyloxy)-5-[3-(2-dimethylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0609] 3-(2-Fluoro-3-methyl-benzyloxy)-5-[3-(3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0610] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(5-methyl-furan-2-ylmethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0611] 3-(3-Fluoro-2,4-dimethyl-benzyloxy)-5-(3-isobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[0612] 3-(4-Chloro-2-fluoro-benzyloxy)-5-[3-(3-hydroxy-2-methyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0613] 3-(4-Chloro-2-fluoro-benzyloxy)-5-[3-(2-methyl-3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0614] 3-(2,3-Dichloro-benzyloxy)-5-[3-(3-hydroxy-2-methyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0615] 3-(2,3-Dichloro-benzyloxy)-5-[3-(2-methyl-3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0616] 3-(3-Fluoro-4-methyl-benzyloxy)-5-[3-(3-hydroxy-2-methyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0617] 3-(3-Fluoro-4-methyl-benzyloxy)-5-[3-(2-methyl-3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0618] 3-(3,4-Dichloro-benzyloxy)-5-[3-(3-hydroxy-2-methyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0619] 3-(3,4-Dichloro-benzyloxy)-5-[3-(2-methyl-3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0620] 3-(2,3-Dichloro-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0621] 3-(2,3-Difluoro-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0622] 3-(3-Fluoro-4-methyl-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0623] 3-(4-Chloro-benzyloxy)-5-[3-(2-morpholin-4-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0624] 3-(4-Chloro-benzyloxy)-5-[3-(3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0625] 3-(4-Chloro-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0626] 3-(2,5-Difluoro-benzyloxy)-5-[3-(3-hydroxy-2-methyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0627] 3-(2,5-Difluoro-benzyloxy)-5-[3-(2-morpholin-4-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0628] 3-(2,5-Difluoro-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0629] 3-(2,5-Difluoro-benzyloxy)-5-[3-(2-methyl-3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0630] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(2-isopropylamino-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0631] 3-(3-Fluoro-2,4-dimethyl-benzyloxy)-5-[3-(2-isopropylamino-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0632] 3-(3-Fluoro-2,4-dimethyl-benzyloxy)-5-[3-(3-isopropylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0633] 5-[3-(2-sec-Butylamino-ethyl)-ureido]-3-(3-fluoro-2,4-dimethyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0634] 3-(3-Fluoro-2,4-dimethyl-benzyloxy)-5-[3-(2-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0635] 3-(3-Fluoro-2,4-dimethyl-benzyloxy)-5-[3-(2-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0636] 5-[3-(2-sec-Butylamino-ethyl)-ureido]-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0637] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(3-isopropylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0638] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(2-isopropylamino-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0639] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(2-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0640] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0641] 3-(2,4-Dimethyl-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0642] 5-[3-(3-Imidazol-1-yl-propyl)-ureido]-3-(4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0643] 3-(2-Fluoro-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0644] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(2-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0645] 5-[3-(3,3-Dimethyl-butyl)-ureido]-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0646] 5-(3-Cyclopropylmethyl-ureido)-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0647] 5-[3-(2,2-Dimethyl-propyl)-ureido]-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0648] 3-(3-Fluoro-2,4-dimethyl-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0649] 3-(2-Fluoro-4,6-dimethyl-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0650] 3-(4-Chloro-2-fluoro-benzyloxy)-5-{3-[2-(1H-imidazol-4-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0651] 3-(2,3-Dichloro-benzyloxy)-5-[3-(3-imidazol-1-yl-2-methyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0652] 3-(2,3-Dichloro-benzyloxy)-5-[3-(2-methyl-3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0653] 3-(4-Chloro-2-fluoro-benzyloxy)-5-[3-(2-hydroxy-3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0654] 3-(4-Chloro-2-fluoro-benzyloxy)-5-[3-(3-imidazol-1-yl-2-methyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0655] 3-(2,3-Dichloro-benzyloxy)-5-[3-(2-methyl-3-piperidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0656] 3-(2,3-Dichloro-benzyloxy)-5-[3-(2-hydroxy-3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0657] 3-(5-Chloro-thiophen-2-ylmethoxy)-5-[3-(3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0658] 3-(5-Chloro-thiophen-2-ylmethoxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0659] 3-(5-Chloro-thiophen-2-ylmethoxy)-5-(3-furan-2-ylmethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0660] 3-(5-Chloro-thiophen-2-ylmethoxy)-5-[3-(3-hydroxy-2-methyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0661] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0662] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0663] 3-(2,4-Dimethyl-benzyloxy)-5-[3-(3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0664] 3-(4-Methyl-benzyloxy)-5-[3-(3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0665] 3-(2-Fluoro-benzyloxy)-5-[3-(3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0666] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0667] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-[3-(3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0668] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-[3-(2-hydroxy-3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0669] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-[3-(3-imidazol-1-yl-2-methyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0670] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-[3-(2-methyl-3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0671] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-[3-(3-hydroxy-2-methyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0672] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-[3-(2-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0673] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-(3-furan-2-ylmethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0674] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-{3-[3-(2,6-dimethyl-morpholin-4-yl)-2-methyl-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0675] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-{3-[2-(3H-imidazol-4-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0676] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-[3-(3-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0677] 3-(4-Chloro-2-fluoro-benzyloxy)-5-[3-(3-isopropylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0678] 3-(2,3-Dichloro-benzyloxy)-5-[3-(2-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0679] 3-(5-Chloro-thiophen-2-ylmethoxy)-5-[3-(2-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0680] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(3-phenyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0681] 5-(3-Cyclobutyl-ureido)-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0682] 5-[3-(2,3-Difluoro-benzyl)-ureido]-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0683] 3-(2-Fluoro-4-methyl-benzyloxy)-5-(3-isobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[0684] 5-(3-Allyl-ureido)-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0685] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0686] 3-(3-Fluoro-2,4-dimethyl-benzyloxy)-5-[3-(3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0687] 3-(2-Fluoro-4,6-dimethyl-benzyloxy)-5-[3-(3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0688] 3-(2-Fluoro-4,6-dimethyl-benzyloxy)-5-[3-(2-methyl-3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0689] 5-{3-[3-(2,6-Dimethyl-morpholin-4-yl)-2-methyl-propyl]-ureido}-3-(2-fluoro-4,6-dimethyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0690] 3-(2-Fluoro-4,6-dimethyl-benzyloxy)-5-[3-(2-hydroxy-3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0691] 3-(2-Fluoro-4,6-dimethyl-benzyloxy)-5-[3-(3-imidazol-1-yl-2-methyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0692] 3-(2-Fluoro-4,6-dimethyl-benzyloxy)-5-{3-[2-(1H-imidazol-4-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0693] 3-(2-Fluoro-4,6-dimethyl-benzyloxy)-5-[3-(3-isopropylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0694] 3-(2-Fluoro-4,6-dimethyl-benzyloxy)-5-[3-(3-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0695] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(4-morpholin-4-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0696] 3-(4-Chloro-2-fluoro-benzyloxy)-5-[3-(4-morpholin-4-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0697] 3-(4-Chloro-2-fluoro-benzyloxy)-5-(3-morpholin-2-ylmethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0698] 3-(2,3-Dichloro-benzyloxy)-5-(3-morpholin-2-ylmethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0699] 2-Aminomethyl-morpholine-4-carboxylic acid [4-carbamoyl-3-(2,3-dichloro-benzyloxy)-isothiazol-5-yl]-amide;
[0700] 3-(2-Fluoro-4-methyl-benzyloxy)-5-13-(2-morpholin-4-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0701] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(2-methyl-3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0702] 5-{3-[3-(2,6-Dimethyl-morpholin-4-yl)-2-methyl-propyl]-ureido}-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0703] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(2-hydroxy-3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0704] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(4-morpholin-4-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0705] 3-(2,4-Dimethyl-benzyloxy)-5-[3-(2-hydroxy-3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0706] 3-(2,4-Dimethyl-benzyloxy)-5-[3-(2-methyl-3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0707] 3-(2,4-Dimethyl-benzyloxy)-5-[3-(2-morpholin-4-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0708] 3-(2,4-Dimethyl-benzyloxy)-5-[3-(4-morpholin-4-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0709] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(2-methyl-allyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0710] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(3-cyclohexylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0711] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(4-dimethylamino-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0712] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(3-dimethylamino-2,2-dimethyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0713] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0714] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0715] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(2-hydroxy-3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0716] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(3-imidazol-1-yl-2-methyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0717] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(3-hydroxy-2-methyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0718] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(2-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0719] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-(3-furan-2-ylmethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0720] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[2-(1H-imidazol-4-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0721] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(3-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0722] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(3-isopropylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0723] 5-(3-{3-[Bis-(2-hydroxy-ethyl)-amino]-propyl)-ureido)-3-(4-bromo-2-fluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0724] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(3-diethylamino-2-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0725] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(3-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0726] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(2-hydroxy-3,3-dimethyl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0727] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(2,3-dihydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0728] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(3-hydroxy-2-methyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0729] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-[3-(4-morpholin-4-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0730] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-3-[2-(-methyl-pyrrolidin-2-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0731] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-{3-[3-(2-oxo-pyrrolidin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0732] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-[3-(2-hydroxy-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0733] 5-(3-Cyclopropylmethyl-ureido)-3-(2,3-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0734] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-(3-[3-(4-methyl-piperazin-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0735] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(2-methyl-3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0736] 3-(2,4-Dimethyl-benzyloxy)-5-{3-[3-(2,6-dimethyl-morpholin-4-yl)-2-methyl-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0737] 5-[3-(3-Cyclohexylamino-propyl)-ureido]-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0738] 3-(2-Fluoro-4-methyl-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0739] 3-(2-Fluoro-4-methyl-benzyloxy)-5-{3-[2-(1H-imidazol-4-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0740] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(2-methyl-allyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0741] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(3-imidazol-1-yl-2-methyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0742] 3-(4-Bromo-2-fluoro-benzyloxy)-5-{3-[3-(2,6-dimethyl-morpholin-4-yl)-2-methyl-propyl]-ureido}-isothiazole-4-carboxylic acid amide
[0743] 5-(3-Allyl-ureido)-3-(2-fluoro-4,6-dimethyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0744] 3-(4-Bromo-2-fluoro-benzyloxy)-5-{3-[3-(2-methyl-piperidin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0745] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(2-methyl-3-piperidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0746] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(2-methyl-3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0747] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0748] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0749] 3-(4-Bromo-2-fluoro-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0750] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(4-morpholin-4-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0751] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-[3-(2-morpholin-4-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0752] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-{3-[2-(1-methyl-1H-pyrrol-2-yl)-ethyl]-isothiazole-4-carboxylic acid amide;
[0753] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-[3-(2,3-dihydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0754] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-(3-isobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[0755] 5-(3-Allyl-ureido)-3-(2,3-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0756] 5-(3-Cyclohexylmethyl-ureido)-3-(2,3-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0757] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-[3-(2-piperidin-1-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0758] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-[3-(2-methyl-3-piperidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0759] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-13-[3-(2,6-dimethyl-morpholin-4-yl)-2-methyl-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0760] 3-(5-Chloro-thiophen-2-ylmethoxy)-5-[3-(3-isopropylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0761] 3-(2-Fluoro-4-methyl-benzyloxy)-5-{3-[2-(3-methyl-3H-imidazol-4-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0762] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(2-pyrrolidin-1-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0763] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(2-methyl-3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0764] 5-[3-(1-Benzyl-pyrrolidin-3-yl)-ureido]-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0765] 5-[3-(1-Ethyl-pyrrolidin-2-ylmethyl)-ureido]-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0766] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(3-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0767] 5-[3-(3-Dimethylamino-2,2-dimethyl-propyl)-ureido]-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0768] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(2-methyl-3-piperidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0769] 3-(2-Fluoro-4-methyl-benzyloxy)-5-{3-[2-(1-methyl-pyrrolidin-2-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0770] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0771] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0772] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(3-methyl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0773] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-(3-morpholin-2-ylmethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0774] 2-Aminomethyl-morpholine-4-carboxylic acid [4-carbamoyl-3-(2,3-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-amide;
[0775] 3-(2,3-Dichloro-benzyloxy)-5-[3-(3-isopropylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0776] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-[3-(3-isopropylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0777] 5-[3-(3-Cyclohexylamino-propyl)-ureido]-3-(2,3-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0778] 3-(2,3-Difluoro-4-iodo-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0779] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(3-imidazol-1-yl-2-methyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0780] 3-(2-Fluoro-4-methyl-benzyloxy)-5-(3-furan-2-ylmethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0781] 5-(3-{3-[Bis-(2-hydroxy-ethyl)-amino]-propyl}-ureido)-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0782] 5-[3-(3-Diethylamino-2-hydroxy-propyl)-ureido]-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0783] 3-(4-Bromo-2-fluoro-benzyloxy)-5-{3-[3-(2-oxo-pyrrolidin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0784] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(2-hydroxy-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0785] 3-(4-Bromo-2-fluoro-benzyloxy)-5-(3-methyl-ureido)-isothiazole-4-carboxylic acid amide;
[0786] 5-[3-(2-Dimethylamino-ethyl)-ureido]-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0787] 5-[3-(3-Dimethylamino-propyl)-ureido]-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0788] 3-(4-Bromo-2-fluoro-benzyloxy)-5-(3-ethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0789] 3-(2-Fluoro-4-methyl-benzyloxy)-5-(3-methyl-ureido)-isothiazole-4-carboxylic acid amide;
[0790] 3-(4-Bromo-2-fluoro-benzyloxy)-5-(3-propyl-ureido)-isothiazole-4-carboxylic acid amide;
[0791] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(3-hydroxy-2-methyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0792] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(2-hydroxy-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0793] 3-(2-Fluoro-4-methyl-benzyloxy)-5-{3-[2-(1-methyl-1H-pyrrol-2-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0794] 3-(4-Ethyl-2,3-difluoro-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0795] 3-(4-Ethyl-2,3-difluoro-benzyloxy)-5-[3-(3-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0796] 3-(4-Ethyl-2,3-difluoro-benzyloxy)-5-[3-(3-hydroxy-2-methyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0797] 3-(4-Ethyl-2,3-difluoro-benzyloxy)-5-[3-(3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0798] 3-(4-Ethyl-2,3-difluoro-benzyloxy)-5-[3-(4-morpholin-4-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0799] 3-(4-Ethyl-2,3-difluoro-benzyloxy)-5-[3-(3-imidazol-1-yl-2-methyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0800] 3-(4-Ethyl-2,3-difluoro-benzyloxy)-5-{3-[2-(1H-imidazol-4-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0801] 3-(4-Ethyl-2,3-difluoro-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0802] 3-(4-Ethyl-2,3-difluoro-benzyloxy)-5-(3-furan-2-ylmethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0803] 3-(4-Ethyl-2,3-difluoro-benzyloxy)-5-[3-(3-isopropylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0804] 5-{3-[3-(2,6-Dimethyl-morpholin-4-yl)-2-methyl-propyl]-ureido}-3-(4-ethyl-2,3-difluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0805] 3-(4-Ethyl-2,3-difluoro-benzyloxy)-5-[3-(2-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0806] 5-[3-(4-Dimethylamino-butyl)-ureido]-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0807] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(3-dibutylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0808] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(3-diethylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0809] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(6-dimethylamino-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0810] 3-(2-Fluoro-4-methyl-benzyloxy)-5-{3-[3-(2-methyl-piperidin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0811] 5-[3-(3-Dibutylamino-propyl)-ureido]-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0812] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-(3-isobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[0813] 5-(3-Cyclopropylmethyl-ureido)-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0814] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[2-(1-methyl-1H-pyrrol-2-yl)-ethyl]-isothiazole-4-carboxylic acid amide;
[0815] 5-[3-(3-Cyclohexylamino-propyl)-ureido]-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0816] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0817] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[2-(1-methyl-pyrrolidin-2-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0818] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(2,3-dihydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0819] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-(3-morpholin-2-ylmethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0820] 2-Aminomethyl-morpholine-4-carboxylic acid [4-carbamoyl-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-amide;
[0821] 5-(3-Allyl-ureido)-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0822] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(tetrahydro-furan-2-ylmethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0823] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-(3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0824] 5-[3-(3-Cyclohexylamino-propyl)-ureido]-3-(4-ethyl-2,3-difluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0825] 3-(4-Ethyl-2,3-difluoro-benzyloxy)-5-(3-isobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[0826] 5-(3-Cyclopropylmethyl-ureido)-3-(4-ethyl-2,3-difluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0827] 3-(4-Ethyl-2,3-difluoro-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0828] 5-(3-Allyl-ureido)-3-(4-ethyl-2,3-difluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0829] 5-[3-(3-Diethylamino-propyl)-ureido]-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0830] 5-[3-(6-Dimethylamino-hexyl)-ureido]-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0831] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0832] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(2-morpholin-4-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0833] 3-(2-Fluoro-4-methoxy-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0834] 3-(2-Fluoro-4-methoxy-benzyloxy)-5-[3-(2-morpholin-4-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0835] 3-(2-Fluoro-4-methoxy-benzyloxy)-5-[3-(3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0836] 3-(2-Fluoro-4-methoxy-benzyloxy)-5-[3-(4-morpholin-4-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0837] 5-(3-{3-[Bis-(2-hydroxy-ethyl)-amino]-propyl}-ureido)-3-(2-fluoro-4-methoxy-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0838] 3-(2-Fluoro-4-methoxy-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0839] 5-[3-(3-Dimethylamino-propyl)-ureido]-3-(2-fluoro-4-methoxy-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0840] 5-[3-(4-Dimethylamino-butyl)-ureido]-3-(2-fluoro-4-methoxy-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0841] 3-(2-Fluoro-4-methoxy-benzyloxy)-5-[3-(3-isopropylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0842] 5-[3-(3-Cyclohexylamino-propyl)-ureido]-3-(2-fluoro-4-methoxy-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0843] 3-(4-Ethyl-2,5-difluoro-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4carboxylic acid amide;
[0844] 3-(2-Fluoro-4-methoxy-benzyloxy)-5-[3-(3-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0845] 3-(4-Ethyl-2,5-difluoro-benzyloxy)-5-[3-(4-morpholin-4-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0846] 3-(4-Ethyl-2,5-difluoro-benzyloxy)-5-[3-(3-imidazol-1-yl-2-methyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0847] 3-(4-Ethyl-2,5-difluoro-benzyloxy)-5-[3-(3-hydroxy-2-methyl-pr opyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0848] 3-(4-Ethyl-2,5-difluoro-benzyloxy)-5-[3-(3-morpholin-4-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0849] 3-(4-Ethyl-2,5-difluoro-benzyloxy)-5-[3-(2-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0850] 3-(4-Ethyl-2,5-difluoro-benzyloxy)-5-(3-furan-2-ylmethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0851] 3-(4-Ethyl-2,5-difluoro-benzyloxy)-5-{3-[2-(3H-imidazol-4-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0852] 3-(4-Ethyl-2,5-difluoro-benzyloxy)-5-[3-(3-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0853] 3-(4-Ethyl-2,5-difluoro-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0854] 3-(4-Ethyl-2,5-difluoro-benzyloxy)-5-(3-isobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[0855] 5-[3-(2,3-Dihydroxy-propyl)-ureido]-3-(4-ethyl-2,3-difluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0856] 3-(2-Fluoro-4-methyl-benzyloxy)-5-(3-morpholin-2-ylmethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0857] 2-Aminomethyl-morpholine-4-carboxylic acid [4-carbamoyl-3-(2-fluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-amide;
[0858] 3-(2-Fluoro-4-methyl-benzyloxy)-5-(3-{3-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-propyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0859] 3-(2-Fluoro-4-methyl-benzyloxy)-5-{3-[3-(2-oxo-pyrrolidin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0860] 5-[3-(3-Diethylamino-2-hydroxy-propyl)-ureido]-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0861] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(2-morpholin-4-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0862] 5-(3-{3-[Bis-(2-hydroxy-ethyl)-amino]-propyl}-ureido)-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0863] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0864] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0865] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-[3-(2-morpholin-4-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0866] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-[3-(4-morpholin-4-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0867] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0868] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-(3-cyclopropylmethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0869] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-[3-(3-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0870] 5-[3-(6-Dimethylamino-hexyl)-ureido]-3-(2-fluoro-4,6-dimethyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0871] 5-[3-(4-Dimethylamino-butyl)-ureido]-3-(2-fluoro-4,6-dimethyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0872] 3-(2-Fluoro-4,6-dimethyl-benzyloxy)-5-(3-{3-[4-(2-hydroxy-ethyl)-piperazin-1-yl-propyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0873] 5-[3-(3-tert-Butylamino-propyl)-ureido]-3-(2-fluoro-4,6-dimethyl-benzyloxy) -isothiazole-4-carboxylic acid amide;
[0874] 5-[3-(6-Dimethylamino-hexyl)-ureido]-3-(2,4,6-trifluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0875] 3-(4-Ethyl-2,5-difluoro-benzyloxy)-5-[3-(3-isopropylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0876] 5-[3-(3-Cyclohexylamino-propyl)-ureido]-3-(4-ethyl-2,5-difluoro-benzyloxy) -isothiazole-4-carboxylic acid amide;
[0877] 3-(2-Chloro-4-methyl-benzyloxy)-5-[3-(4-morpholin-4-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0878] 3-(2-Chloro-4-methyl-benzyloxy)-5-[3-(6-dimethylamino-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0879] 3-(2-Chloro-4-methyl-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0880] 3-(2-Chloro-4-methyl-benzyloxy)-5-[3-(2-morpholin-4-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0881] 3-(2-Chloro-4-methyl-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0882] 5-[3-(3-Imidazol-1-yl-propyl)-ureido]-3-(2,4,6-trifluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0883] 5-[3-(4-Dimethylamino-butyl)-ureido]-3-(2,4,6-trifluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0884] 5-[3-(4-tert-Butylamino-3-hydroxy-butyl)-ureido]-3-(2-fluoro-4,6-dimethyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0885] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-(3-{4-[4-(;
[0886] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(4-methyl-piperazin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0887] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-(3-{4-[4-(3-hydroxy-propyl)-piperazin-1-yl]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0888] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-(3-{3-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-propyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0889] 5-[3-(3-tert-Butylamino-propyl)-ureido]-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0890] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(6-dimethylamino-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0891] 3-(2,4-Difluoro-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0892] 3-(2,4-Difluoro-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0893] 3-(2,4-Difluoro-benzyloxy)-5-[3-(3-isopropylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0894] 3-(2,4-Difluoro-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0895] 3-(2-Fluoro-4-trifluoromethyl-benzyloxy)-5-[3-(2-morpholin-4-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0896] 3-(2,4-Difluoro-benzyloxy)-5-[3-(6-dimethylamino-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0897] 3-(2,4-Difluoro-benzyloxy)-5-[3-(3-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0898] 3-(2,5-Dichloro-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0899] 3-(2,5-Dichloro-benzyloxy)-5-[3-(3-isopropylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0900] 3-(2,5-Dichloro-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0901] 3-(2,5-Dichloro-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0902] 3-(2,5-Dichloro-benzyloxy)-5-[3-(6-dimethylamino-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0903] 3-(2,5-Dichloro-benzyloxy)-5-[3-(3-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0904] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0905] 5-(3-{3-[Bis-(2-hydroxy-ethyl)-amino]-propyl}-ureido)-3-(4-chloro-2,5-difluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0906] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-{3-[4-(4-methyl-piperazin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0907] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-(3-{3-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-propyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0908] 5-{3-[4-(4-Benzyl-piperazin-1-yl)-butyl]-ureido}-3-(4-chloro-2,5-difluoro-benzyloxy-isothiazole-4-carboxylic acid amide;
[0909] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-[3-(6-dimethylamino-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0910] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-[3-(3-isopropylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0911] 5-[3-(2-Azepan-1-yl-ethyl)-ureido]-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0912] 5-[3-(1-Aza-bicyclo[2.2.2]oct-4-ylmethyl)-ureido]-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0913] 5-[3-(4-tert-Butylamino-3-hydroxy-butyl)-ureido]-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0914] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(4-hydroxy-1-methyl-pyrrolidin-2-ylmethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0915] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-[3-(3-diethylamino-2-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0916] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-[3-(5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0917] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-(3-{4-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0918] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-[3-(3-hydroxy-2-methyl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0919] 2-Aminomethyl-morpholine-4-carboxylic acid [4-carbamoyl-3-(4-chloro-2,5-difluoro-benzyloxy)-isothiazol-5-yl]-amide;
[0920] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-(3-morpholin-2-ylmethyl-ureido)-isothiazole-4-carboxylic acid amide;
[0921] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-{3-[2-(1-methyl-pyrrolidin-2-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0922] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-(3-{4-[4-(3-hydroxy-propyl)-piperazin-1-yl]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0923] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0924] 3-(3-Fluoro-2,4-dimethyl-benzyloxy)-5-[3-(2-morpholin-4-y-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0925] 5-(3-{4-[Bis-(2-hydroxy-ethyl)-amino]-butyl}-ureido)-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0926] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(5-morpholin-4-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0927] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[5-(4-methyl-piperazin-1-yl)-pentyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0928] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-(3-{5-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-pentyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0929] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[7-(4-methyl-piperazin-1-yl)-heptyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0930] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[6-(4-methyl-piperazin-1-yl)-hexyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0931] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-(3-{6-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-]-hexyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0932] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-(3-{7-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-heptyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0933] 3-(2,5-Dichloro-4-methyl-benzyloxy)-5-{3-[4-(4-methyl-piperazin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0934] 3-(2,5-Dichloro-4-methyl-benzyloxy)-5-[3-(6-dimethylamino-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0935] 3-(2,5-Dichloro-4-methyl-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0936] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(5-methyl-2,5-diaza-bicyclo[2.2.1]hept-2-yl)-butyl]-ureido)-isothiazole-4-carboxylic acid amide;
[0937] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(octahydro-pyrido[1,2-a]pyrazin-7-ylmethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0938] 3-(2-Fluoro-4-methyl-benzyloxy)-5-{3-[7-(4-methyl-piperazin-1-yl)-heptyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0939] 3-(2-Fluoro-4-methyl-benzyloxy)-5-{3-[6-(4-methyl-piperazin-1-yl)-hexyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0940] 3-(2-Fluoro-4-methyl-benzyloxy)-5-(3-{7-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-heptyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0941] 3-(2-Fluoro-4-methyl-benzyloxy)-5-(3-{6-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-hexyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0942] 3-(2-Fluoro-4-methyl-benzyloxy)-5-(3-{5-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-pentyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0943] 3-(2-Fluoro-4-methyl-benzyloxy)-5-{3-[5-(4-methyl-piperazin-1-yl)-pentyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0944] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-{3-[5-(4-methyl-piperazin-1-yl)-pentyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0945] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-(3-{5-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-pentyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0946] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-{3-[7-(4-methyl-piperazin-1-yl)-heptyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0947] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-(3-{7-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-heptyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0948] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-{3-[6-(4-methyl-piperazin-1-yl)-hexyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0949] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-{3-[6-(4-propyl-piperazin-1-yl)-hexyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0950] 5-(3-{5-[4-(2-Hydroxy-ethyl)-piperazin-1-yl]-pentyl}-ureido)-3-(4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0951] 5-(3-{6-[4-(2-Hydroxy-ethyl)-piperazin-1-yl]-hexyl}-ureido)-3-(4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0952] 3-(2,4-Dimethyl-benzyloxy)-5-{3-[5-(4-methyl-piperazin-1-yl)-pentyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0953] 3-(2,4-Dimethyl-benzyloxy)-5-{3-[7-(4-methyl-piperazin-1-yl)-heptyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0954] 3-(2,4-Dimethyl-benzyloxy)-5-{3-[6-(4-methyl-piperazin-1-yl)-hexyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0955] 3-(2,4-Dimethyl-benzyloxy)-5-(3-{7-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-heptyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0956] 5-(3-{4-[Bis-(2-hydroxy-ethyl)-amino]-butyl}-ureido)-3-(4-chloro-2,5-difluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0957] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-[3-(5-morpholin-4-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0958] 7-{3-[4-Carbamoyl-3-(4-chloro-2,5-difluoro-benzyloxy)-isothiazol-5-yl]-ureidomethyl}-octahydro-pyrido[1,2-a]pyrazine-2-carboxylic acid tert-butyl ester;
[0959] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-{3-[4-(5-methyl-2,5-diaza-bicyclo[2.2.1]hept-2-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0960] 5-[3-(4-tert-Butylamino-3-hydroxy-butyl)-ureido]-3-(4-chloro-2,5-difluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0961] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-[3-(octahydro-pyrido [1,2-a]pyrazin-7-ylmethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0962] 5-[3-(5-Isopropylamino-pentyl)-ureido]-3-(2,4,5-trifluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0963] 5-[3-(6-Dimethylamino-hexyl)-ureido]-3-(2,4,5-trifluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0964] 5-[3-(4-Pyrrolidin-1-yl-butyl)-ureido]-3-(2,4,5-trifluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0965] 5-(3-{6-[4-(2-Hydroxy-ethyl)-piperazin-1-yl]-hexyl}-ureido)-3-(2,4,5-trifluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0966] 5-(3-{7-[4-(2-Hydroxy-ethyl)-piperazin-1-yl]-heptyl}-ureido)-3-(2,4,5-trifluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0967] 5-[3-(2-Morpholin-4-yl-ethyl)-ureido]-3-(2,4,5-trifluoro-benzyloxy)-isothiazole-4-carboxylic acid amide
[0968] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0969] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0970] 5-(3-{3-[Bis-(2-hydroxy-ethyl)-amino]-propyl}-ureido)-3-(4-chloro-2,6-difluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0971] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[2-(1-methyl-pyrrolidin-2-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0972] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-(3-{4-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0973] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(6-dimethylamino-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0974] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-(3-{4-[4-(3-hydroxy-propyl)-piperazin-1-yl]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0975] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-(3-{5-[4-(2-hydroxy-ethyl)-piperazin-1-yl ]-pentyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0976] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-(3-{6-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-hexyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0977] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0978] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[4-(4-methyl-piperazin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0979] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[5-(4-methyl-piperazin-1-yl)-pentyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0980] 5-[3-(4-tert-Butylamino-3-hydroxy-butyl)-ureido]-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0981] 3-(2-Fluoro-4-methyl-benzyloxy)-5-{3-[4-(5-methyl-2,5-diaza-bicyclo[2.2.1]hept-2-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[0982] 3-(2-Fluoro-4-methyl-benzyloxy)-5-(3-{4-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0983] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(3-isopropylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0984] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0985] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-(3-{4-[4-(3-hydroxy-propyl)-piperazin-1-yl]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0986] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(3-isopropylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0987] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(6-dimethylamino-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0988] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(6-dimethylamino-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0989] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0990] 5-(3-{3-[Bis-(2-hydroxy-ethyl)-amino]-propyl}-ureido)-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0991] 5-[3-(4-tert-Butylamino-3-hydroxy-butyl)-ureido]-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0992] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0993] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-(3-{4-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0994] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-(3-{5-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-pentyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0995] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-(3-{6-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-hexyl}-ureido)-isothiazole-4-carboxylic acid amide;
[0996] 4-{3-[4-Carbamoyl-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazol-5-yl]-ureido}-butyric acid
[0997] 5-(3-{3-[Bis-(2-hydroxy-ethyl)-amino]-propyl}-ureido)-3-(2-chloro-5-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[0998] 3-(2-Chloro-5-fluoro-4-methyl-benzyloxy)-5-[3-(5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[0999] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(6-dimethylamino-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1000] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1001] 5-(3-{3-[Bis-(2-hydroxy-ethyl)-amino]-propyl}-ureido)-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1002] 5-[3-(4-tert-Butylamino-3-hydroxy-butyl)-ureido]-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1003] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1004] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-(3-{4-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1005] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-(3-{5-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-pentyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1006] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-(3-{6-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-hexyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1007] 5-[3-(3-tert-Butylamino-propyl)-ureido]-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1008] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[3-hydroxy-5-(4-methyl-piperazin-1-yl)-pentyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1009] 3-(2-Chloro-5-fluoro-4-methyl-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1010] 3-(2-Chloro-5-fluoro-4-methyl-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1011] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-{3-[3-hydroxy-5-(4-methyl-piperazin-1-yl-pentyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1012] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(3-hydroxy-5-pyrrolidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1013] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-[3-(3-hydroxy-5-pyrrolidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1014] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(3-hydroxy-5-pyrrolidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1015] 3-(2-Chloro-5-fluoro-4-methyl-benzyloxy)-5-[3-(6-dimethylamino-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1016] 3-(2-Chloro-5-fluoro-4-methyl-benzyloxy)-5-(3-{4-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1017] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[3-hydroxy-5-(4-methyl-piperazin-1-yl)-pentyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1018] 3-(5-Chloro-2-fluoro-4-methyl-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1019] 3-(5-Chloro-2-fluoro-4-methyl-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1020] 5-(3-{3-[Bis-(2-hydroxy-ethyl)-amino]-propyl}-ureido)-3-(5-chloro-2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1021] 5-[3-(4-tert-Butylamino-3-hydroxy-butyl)-ureido]-3-(2-fluoro-4,6-dimethyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1022] 3-(5-Chloro-2-fluoro-4-methyl-benzyloxy)-5-[3-(6-dimethylamino-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1023] 3-(5-Chloro-2-fluoro-4-methyl-benzyloxy)-5-[3-(5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1024] 5-[3-(6-Dimethylamino-hexyl)-ureido]-3-(2,4,6-trifluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1025] 3-(5-Chloro-2-fluoro-4-methyl-benzyloxy)-5-(3-{4-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1026] 3-(5-Chloro-2-fluoro-4-methyl-benzyloxy)-5-{3-[4-(4-methyl-piperazin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1027] 3-(5-Chloro-2-fluoro-4-methyl-benzyloxy)-5-(3-{4-[4-(3-hydroxy-propyl)-piperazin-1-yl]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1028] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(2-morpholin-4-yl-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1029] 5-[3-(4-tert-Butylamino-3-hydroxy-butyl)-ureido]-3-(4-chloro-2,6-difluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1030] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[4-(5-methyl-2,5-diaza-bicyclo[2.2.1]hept-2-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1031] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(3-hydroxy-5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1032] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-[3-(3-hydroxy-5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1033] 3-(5-Chloro-2-fluoro-4-methyl-benzyloxy)-5-(3-{5-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-pentyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1034] 3-(5-Chloro-2-fluoro-4-methyl-benzyloxy)-5-(3-{6-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-hexyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1035] 7-{3-[4-Carbamoyl-3-(4-chloro-2,6-difluoro-benzyloxy)-isothiazol-5-yl]-ureidomethyl)}-octahydro-pyrido[1,2-a]pyrazine-2-carboxylic acid tert-butyl ester;
[1036] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-[3-(3-hydroxy-5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1037] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(octahydro-pyrido[1,2-a]pyrazin-7-ylmethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1038] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-(3-{3-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-propyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1039] 5-(3-{4-[Bis-(2-hydroxy-ethyl)-amino]-butyl}-ureido)-3-(4-chloro-2,6-difluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1040] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-(3-{3-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-propyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1041] 5-(3-{3-[Bis-(2-hydroxy-ethyl)-amino]-propyl}-ureido)-3-(2,3-dichloro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1042] 3-(2,3-Dichloro-4-methyl-benzyloxy)-5-[3-(6-dimethylamino-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1043] 3-(2,3-Dichloro-4-methyl-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1044] 3-(2,3-Dichloro-4-methyl-benzyloxy)-5-(3-{4-[4-(3-hydroxy-propyl)-piperazin-1-yl]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1045] 5-(3-{4-[Bis-(2-hydroxy-ethyl)-amino]-butyl}-ureido)-3-(2,3-dichloro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1046] 3-(2,3-Dichloro-4-methyl-benzyloxy)-5-(3-{5-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-pentyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1047] 3-(2,3-Dichloro-4-methyl-benzyloxy)-5-(3-{6-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-hexyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1048] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-(3-{5-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-pentyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1049] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-(3-{6-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-hexyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1050] 5-(3-{4-[Bis-(2-hydroxy-ethyl)-amino]-butyl}-ureido)-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1051] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-{3-[4-(5-methyl-2,5-diaza-bicyclo[2.2.1]hept-2-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1052] 3-(2,4-Dimethyl-benzyloxy)-5-[3-(5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1053] 3-(4-Ethyl-benzyloxy)-5-(3-{5-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-pentyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1054] 3-(4-Ethyl-benzyloxy)-5-(3-{6-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-hexyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1055] 5-[3-(6-Dimethylamino-hexyl)-ureido]-3-(4-ethyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1056] 3-(4-Ethyl-benzyloxy)-5-[3-(5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1057] 3-(2-Fluoro-4-methyl-benzyloxy)-5-(3-{5-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-pentyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1058] 3-(2-Fluoro-4-methyl-benzyloxy)-5-(3-{6-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-hexyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1059] 5-[3-(6-Dimethylamino-hexyl)-ureido]-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1060] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1061] 3-Heptyloxy-5-(3-{5-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-pentyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1062] 3-Heptyloxy-5-(3-{6-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-hexyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1063] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(3,4-dihydroxy-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1064] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[4-(3,4-dihydroxy-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1065] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1066] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide
[1067] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1068] 5-[3-(5-Isopropylamino-pentyl)-ureido]-3-(2,4,6-trifluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1069] 5-(3-{3-[Bis-(2-hydroxy-ethyl)-amino]-propyl}-ureido)-3-(2,4,6-trifluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1070] 5-[3-(4-tert-Butylamino-3-hydroxy-butyl)-ureido]-3-(2,4,6-trifluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1071] 5-[3-(4-Pyrrolidin-1-yl-butyl)-ureido]-3-(2,4,6-trifluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1072] 5-(3-{4-[4-(2-Hydroxy-ethyl)-piperazin-1-yl]-butyl}-ureido)-3-(2,4,6-trifluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1073] 5-(3-{5-[4-(2-Hydroxy-ethyl)-piperazin-1-yl]-pentyl}-ureido)-3-(2,4,6-trifluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1074] 5-(3-{6-[4-(2-Hydroxy-ethyl)-piperazin-1-yl]-hexyl}-ureido)-3-(2,4,6-trifluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1075] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1076] 3-(4-Bromo-2-fluoro-benzyloxy)-5-[3-(4-tert-butylamino-3-hydroxy-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1077] 3-(4-Bromo-2-fluoro-benzyloxy)-5-(3-{4-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1078] 3-(4-Bromo-2-fluoro-benzyloxy)-5-(3-{5-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-pentyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1079] 3-(2-Fluoro-4,6-dimethyl-benzyloxy)-5-[3-(5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1080] 5-(3-{3-[Bis-(2-hydroxy-ethyl)-amino]-propyl}-ureido)-3-(2-fluoro-4,6-dimethyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1081] 3-(2-Fluoro-4,6-dimethyl-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1082] 3-(2-Fluoro-4,6-dimethyl-benzyloxy)-5-(3-{4-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1083] 3-(2-Fluoro-4,6-dimethyl-benzyloxy)-5-(3-{5-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-pentyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1084] 3-(2-Fluoro-4,6-dimethyl-benzyloxy)-5-(3-{6-[4-(2-hydroxy-ethyl)-piperazin-1-yl ]-hexyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1085] 3-[1-(4-Chloro-2,6-difluoro-phenyl)-ethoxy]-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1086] 3-[1-(4-Chloro-2,6-difluoro-phenyl)-ethoxy]-5-(3-{5-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-pentyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1087] 5-[3-(6-Dimethylamino-hexyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1088] 5-[3-(5-Isopropylamino-pentyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1089] 5-(3-{6-[4-(2-Hydroxy-ethyl)-piperazin-1-yl]-hexyl}-ureido)-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1090] 5-[3-(4-tert-Butylamino-3-hydroxy-butyl)-ureido]-3-[1-(4-chloro-2,6-difluoro-phenyl)-ethoxy]-isothiazole-4-carboxylic acid amide;
[1091] 5-(3-{5-[4-(2-Hydroxy-ethyl)-piperazin-1-yl]-pentyl}-ureido)-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1092] 3-[1-(4-Chloro-2,6-difluoro-phenyl)-ethoxy]-5-[3-(5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1093] 5-[3-(4-tert-Butylamino-3-hydroxy-butyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(3-hydroxy-5-pyrrolidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1094] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(2-hydroxymethyl-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1095] 5-(3-{5-[4-(2-Hydroxy-ethyl)-piperazin-1-yl]-pentyl}-ureido)-3-(4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1096] 5-(3-{6-[4-(2-Hydroxy-ethyl)-piperazin-1-yl]-hexyl}-ureido)-3-(4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1097] 5-[3-(6-Dimethylamino-hexyl)-ureido]-3-(4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1098] 5-[3-(6-Dimethylamino-hexyl)-ureido]-3-heptyloxy-isothiazole-4-carboxylic acid amide;
[1099] 3-Heptyloxy-5-[3-(5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1100] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[4-(2-hydroxymethy)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1101] 3-(5-Chloro-2-fluoro-4-methyl-benzyloxy)-5-{3-[4-(2-hydroxymethyl-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1102] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(3-hydroxy-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1103] 5-[3-(6-Dimethylamino-hexyl)-ureido]-3-(2,3,5,6-tetrafluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1104] 5-(3-{6-[4-(2-Hydroxy-ethyl)-piperazin-1-yl]-hexyl}-ureido)-3-(2,3,5,6-tetrafluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1105] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-{3-[4-(2-hydroxymethyl-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1106] 5-[3-(4-Pyrrolidin-1-yl-butyl)-ureido]-3-(2,3,5,6-tetrafluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1107] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-{3-[4-(3-hydroxy-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1108] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-{3-[4-(3,4-dihydroxy-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1109] 5-[3-(4-tert-Butylamino-3-hydroxy-butyl)-ureido]-3-(2,3,5,6-tetrafluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1110] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[4-(3-hydroxy-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1111] 5-[3-(5-Isopropylamino-pentyl)-ureido]-3-(2,3,5,6-tetrafluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1112] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-{3-[2-(octahydro-pyrido[1,2-a]pyrazin-7-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1113] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[6-(4-methyl-piperazin-1-yl)-hexyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1114] 3-(2-Fluoro-4-methyl-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1115] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(4-piperidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1116] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(4-piperidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1117] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-[3-(4-piperidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1118] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-[3-(4-piperidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1119] 3-(4-Bromo-2,6-difluoro-benzyloxy)-5-[3-(6-dimethylamino-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1120] 3-(4-Bromo-2,6-difluoro-benzyloxy)-5-[3-(5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1121] 3-(4-Bromo-2,6-difluoro-benzyloxy)-5-(3-{6-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-hexyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1122] 3-(4-Bromo-2,6-difluoro-benzyloxy)-5-(3-{5-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-pentyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1123] 3-(4-Bromo-2,6-difluoro-benzyloxy)-5-[3-(4-tert-butylamino-3-hydroxy-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1124] 3-(4-Bromo-2,6-difluoro-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1125] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-(3-{4-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1126] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(4-hydroxy-5-piperidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide
[1127] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(4-hydroxy-5-piperidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1128] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(4-hydroxy-5-isobutylamino-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1129] 5-[3-(4-tert-Butylamino-3-hydroxy-butyl)-ureido]-3-(2-fluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1130] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(3,4-dihydroxy-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1131] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[4-(3,4-dihydroxy-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1132] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-{3-[4-(3,4-dihydroxy-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1133] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(3,4-dihydroxy-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1134] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1135] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(4-hydroxy-5-morpholin-4-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1136] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(5-hydroxy-6-morpholin-4-yl-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1137] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(5-hydroxy-6-morpholin-4-yl-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1138] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(4-hydroxy-5-piperidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide
[1139] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(4-hydroxy-5-piperidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1140] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-[3-(4-hydroxy-5-piperidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1141] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(3-hydroxy-piperidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1142] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[4-(3-hydroxy-piperidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1143] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-(3-[4-(3-hydroxy-piperidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1144] 3-(2,6-Difluoro-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1145] 3-(2,6-Difluoro-benzyloxy)-5-[3-(6-dimethylamino-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1146] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(5-hydroxy-6-morpholin-4-yl-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1147] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(4-hydroxy-5-morpholin-4-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1148] 3-(2-Fluoro-4-methyl-benzyloxy)-5-[3-(5-hydroxy-6-morpholin-4-yl-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1149] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(5-hydroxy-6-isobutylamino-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1150] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(5-hydroxy-6-piperidin-1-yl-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1151] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(6-hydroxy-7-morpholin-4-yl-heptyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1152] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(4-hydroxy-5-morpholin-4-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1153] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(7-dimethylamino-6-hydroxy-heptyl)-ureido]-isothiazole-4-carboxylic acid amide
[1154] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(6-hydroxy-7-piperidin-1-yl-heptyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1155] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[4-(2-methoxymethyl-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1156] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[4-(2-hydroxymethyl-piperidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1157] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-(3-{4-[ethyl-(2-hydroxy-ethyl)-amino]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1158] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-(3-{4-[ethyl-(2-hydroxy-ethyl)-amino]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1159] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-(3-{4-[ethyl-(2-hydroxy-ethyl)-amino]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1160] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(2-methoxymethyl-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1161] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(2-hydroxymethyl-piperidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1162] 5-[3-(6-Dimethylamino-hexyl)-ureido]-3-(2,3,6-trifluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1163] 5-{3-[3-(4-Methyl-piperazin-1-yl)-propyl]-ureido}-3-(2,3,6-trifluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1164] 3-(2,3-Difluoro-4-methyl-benzyloxy)-5-[3-(5-hydroxy-6-piperidin-1-yl-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1165] 3-(4-Chloro-2-fluoro-benzyloxy)-5-[3-(5-hydroxy-6-piperidin-1-yl-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1166] 3-(4-Ethyl-2,3-difluoro-benzyloxy)-5-[3-(5-hydroxy-6-piperidin-1-yl-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1167] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(5-hydroxy-6-piperidin-1-yl-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1168] 3-(4-Chloro-2-fluoro-benzyloxy)-5-[3-(5-hydroxy-6-morpholin-4-yl-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1169] 3-(4-Chloro-2-fluoro-benzyloxy)-5-[3-(6-hydroxy-7-morpholin-4-ylheptyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1170] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(6-hydroxy-7-morpholin-4-yl-heptyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1171] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(6-hydroxy-7-morpholin-4-yl-heptyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1172] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(5-hydroxy-6-piperidin-1-yl-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1173] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(6-hydroxy-7-piperidin-1-yl-heptyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1174] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(7-dimethylamino-6-hydroxy-heptyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1175] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(6-hydroxy-7-piperidin-1-yl-heptyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1176] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(7-dimethylamino-6-hydroxy-heptyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1177] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(5-hydroxy-6-isobutylamino-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1178] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(5-hydroxy-6-isobutylamino-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1179] 3-(4-Bromo-2,3,6-trifluoro-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1180] 3-(4-Bromo-2,3,6-trifluoro-benzyloxy)-5-[3-(6-dimethylamino-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1181] 3-(2-Fluoro-4-methyl-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1182] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(2-hydroxymethyl-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1183] 3-(3-Chloro-2,6-difluoro-benzyloxy)-5-[3-(6-dimethylamino-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1184] 3-(3-Chloro-2,6-difluoro-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1185] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1186] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1187] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(3-hydroxy-5-pyrrolidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1188] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(4-hydroxy-5-piperidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1189] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(4-piperidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1190] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(3-hydroxy-5-pyrrolidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1191] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(3-hydroxy-pyrrolidin-1-yl)-butyl]-ureido{-isothiazole-4-carboxylic acid amide;
[1192] 5-[3-(4-Pyrrolidin-1-yl-butyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1193] 5-{3-[3-(4-Methyl-piperazin-1-yl)-propyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1194] 5-[3-(3-Hydroxy-5-pyrrolidin-1-yl-pentyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1195] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1196] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-{3-[4-(2-hydroxymethyl-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1197] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-(3-{4-[ethyl-(2-hydroxy-ethyl)-amino]-butyl}-ureido)-isothiazole-4-carboxylic acid amide
[1198] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-[3-(4-hydroxy-5-piperidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1199] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-{3-[4-(3-hydroxy-piperidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1200] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1201] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[2-(1-methyl-pyrrolidin-2-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1202] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[4-(2-hydroxymethyl-piperidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1203] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[3-(5-methyl-2,5-diaza-bicyclo[2.2.1]hept-2-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1204] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[3-(5-methyl-2,5-diaza-bicyclo[2.2.1]hept-2-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1205] 3-(4-Chloro-2,5-difluoro-benzyloxy)-5-{3-[4-(2-hydroxymethyl-piperidin-1-y)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1206] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-ethyl-3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1207] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-ethyl-3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1208] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-{3-[3-(5-methyl-2,5-diaza-bicyclo[2.2.1]hept-2-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1209] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-{3-[2-(1-methyl-pyrrolidin-2-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1210] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1211] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-{3-[4-(2-hydroxymethyl-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1212] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido)-isothiazole-4-carboxylic acid amide;
[1213] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-(3-{4-[ethyl-(2-hydroxy-ethyl)-amino]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1214] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-ethyl-3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1215] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-ethyl-3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1216] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-ethyl-3-(4-piperidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1217] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-ethyl-3-(4-piperidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1218] 5-(3-Methyl-ureido)-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1219] 5-(3-Ethyl-ureido)-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1220] 5-(3-Cyclopropylmethyl-ureido)-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1221] 5-(3-Cyclobutyl-ureido)-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1222] 5-(3-Allyl-ureido)-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1223] 5-(3-isobutyl-ureido)-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1224] 5-[3-(3-Hydroxy-propyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1225] 5-{3-[2-(1-Methyl-pyrrolidin-2-yl)-ethyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1226] 5-[3-(2-Dimethylamino-ethyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1227] 5-[3-(4-Dimethylamino-butyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1228] 5-[3-(7-Dimethylamino-6-hydroxy-heptyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1229] 5-{3-[4-(5-Methyl-2,5-diaza-bicyclo[2.2.1]hept-2-yl)-butyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1230] 5-[3-(3-Dimethylamino-propyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1231] 5-[3-(3-Hydroxy-5-isopropylamino-pentyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1232] 5-[3-(3-Isopropylamino-propyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1233] 5-{3-[3-(4-Methyl-piperazin-1-yl)-propyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1234] 5-{3-[4-(4-Methyl-piperazin-1-yl)-butyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1235] 5-{3-[5-(4-Methyl-piperazin-1-yl)-pentyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1236] 5-{3-[6-(4-Methyl-piperazin-1-yl)-hexyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1237] 5-{3-[3-Hydroxy-5-(4-methyl-piperazin-1-yl)-pentyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1238] 5-(3-{4-[4-(2-Hydroxy-ethyl)-piperazin-1-yl]-butyl}-ureido)-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1239] 5-(3-{4-[4-(3-Hydroxy-propyl)-piperazin-1-yl]-butyl}-ureido)-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1240] 5-[3-(3-Pyrrolidin-1-yl-propyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1241] 5-[3-(3-Hydroxy-5-pyrrolidin-1-yl-pentyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1242] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-methyl-3-(4-piperidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1243] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-methyl-3-(4-piperidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1244] 5-[3-(4-Pyrrolidin-1-yl-butyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1245] 5-[3-(4-Hydroxy-5-piperidin-1-yl-pentyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy-isothiazole-4-carboxylic acid amide;
[1246] 5-[3-(5-Hydroxy-6-piperidin-1-yl-hexyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1247] 5-[3-(5-Hydroxy-7-piperidin-1-yl-heptyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1248] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1249] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1250] 5-[3-(4-Hydroxy-5-morpholin-4-yl-pentyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1251] 5-[3-(5-Hydroxy-6-morpholin-4-yl-hexyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1252] 5-[3-(5-Hydroxy-7-morpholin-4-yl-heptyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1253] 5-[3-(2-Morpholin-4-yl-ethyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1254] 5-[3-(4-Morpholin-4-yl-butyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1255] 5-(3-{3-[Bis-(2-hydroxy-ethyl)-amino)-propyl}-ureido)-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1256] 5-(3-{4-[Bis -(2-hydroxy-ethyl)-amino]-butyl}-ureido)-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1257] 5-(3-{4-[Ethyl-(2-hydroxy-ethyl)-amino]-butyl}-ureido)-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1258] 5-[3-(3-tert-Butylamino-propyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1259] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(4-imidazol-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1260] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-{3-[4-(3-hydroxy-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1261] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-[3-(4-imidazol-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1262] 5-{3-[4-(2-Methoxymethyl-pyrrolidin-1-yl)-butyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1263] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-methyl-3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1264] 5-{3-[4-(3-Hydroxy-pyrrolidin-1-yl)-butyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1265] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-methyl-3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido)-isothiazole-4-carboxylic acid amide;
[1266] 5-{3-[4-(3,4-Dihydroxy-pyrrolidin-1-yl)-butyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1267] 5-{3-[4-(2-Hydroxymethyl-pyrrolidin-1-yl)-butyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1268] 5-{3-[4-(3-Hydroxy-piperidin-1-yl)-butyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1269] 5-{3-[4-(2-Hydroxymethyl-piperidin-1-yl)-butyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1270] 5-[3-(3-Cyclohexylamino-propyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1271] 5-(3-{4-[Bis-(2-hydroxy-propyl)-amino]-butyl}-ureido)-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1272] 5-{3-[3-(5-Methyl-2,5-diaza-bicyclo[2.2.1]hept-2-yl)-propyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1273] 5-[3-(3-Imidazol-1-yl-propyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1274] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-{3-[4-(2-hydroxymethyl-piperidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1275] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-[3-(3-hydroxy-5-pyrrolidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1276] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-{3-[4-(3-hydroxy-piperidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1277] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-[3-(4-hydroxy-5-piperidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1278] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-(3-methyl-ureido)-isothiazole-4-carboxylic acid amide;
[1279] 5-(3-Cyclopropylmethyl-ureido)-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1280] 5-(3-Cyclobutyl-ureido)-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1281] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(3-hydroxy-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1282] 5-(3-Allyl-ureido)-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1283] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-(3-isobutyl-ureido)-isothiazole-4-carboxylic acid amide;
[1284] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-{3-[2-(1-methyl-pyrrolidin-2-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide
[1285] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(2-dimethylamino-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1286] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(4-dimethylamino-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1287] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(7-dimethylamino-6-hydroxy-heptyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1288] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(5-methyl-2,5-diaza-bicyclo[2.2.1]hept-2-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1289] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(3-dimethylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1290] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(3-hydroxy-5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1291] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(3-isopropylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1292] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(4-methyl-piperazin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1293] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-{3-[5-(4-methyl-piperazin-1-yl)-pentyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1294] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-{3-[6-(4-methyl-piperazin-1-yl)-hexyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1295] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-{3-[3-hydroxy-5-(4-methyl-piperazin-1-yl)-pentyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1296] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-(3-{4-[4-(3-hydroxy-propyl)-piperazin-1-yl]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1297] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(3-pyrrolidin-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1298] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-{3-[4-(3,4-dihydroxy-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1299] 5-{3-[4-(4-Acetyl-piperazin-1-yl)-butyl]-ureido}-3-(4-chloro-2,6-difluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1300] 5-{3-[4-(4-Acetyl-piperazin-1-yl)-butyl]-ureido}-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1301] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(3-hydroxy-piperidin-1-yl)-butyl]=3-methyl-ureido}-isothiazole-4-carboxylic acid amide;
[1302] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-(3-{4-[ethyl-(2-hydroxy-ethyl)-amino]-butyl}-3-methyl-ureido)-isothiazole-4-carboxylic acid amide;
[1303] 3-(2,3,6-Trifluoro-4-methyl-benzyloxy)-5-ureido-isothiazole-4-carboxylic acid amide;
[1304] 3-(4-Bromo-2,6-difluoro-benzyloxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1305] 3-(4-Bromo-2,3,6-trifluoro-benzyloxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1306] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-(3-{4-[ethyl-(2-hydroxy-ethyl)-amino]-butyl}-3-methyl-ureido)-isothiazole-4-carboxylic acid amide;
[1307] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(3-hydroxy-5-pyrrolidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1308] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(4-hydroxy-5-piperidin-1-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1309] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(5-hydroxy-6-piperidin-1-yl-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1310] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(6-hydroxy-7-piperidin-1-yl-heptyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1311] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(4-hydroxy-5-morpholin-4-yl-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1312] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(5-hydroxy-6-morpholin-4-yl-hexyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1313] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(6-hydroxy-7-morpholin-4-yl-heptyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1314] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(4-morpholin-4-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1315] 5-(3-{4-[Bis-(2-hydroxy-ethyl)-am ino]-butyl}-ureido)-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1316] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-(3-{4-[ethyl-(2-hydroxy-ethyl)-amino]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1317] 5-[3-(3-tert-Butylamino-propyl)-ureido]-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1318] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(2-methoxymethyl-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1319] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(3-hydroxy-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1320] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(3,4-dihydroxy-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1321] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(2-hydroxymethyl-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1322] 5-[3-(4-Imidazol-1-yl-butyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1323] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-{3-[4-(3,4-dihydroxy-pyrrolidin-1-yl)-butyl-ureido}-isothiazole-4-carboxylic acid amide;
[1324] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-[3-(4-imidazol-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1325] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-{3-[5-(4-methyl-piperazin-1-yl)-pentyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1326] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-{3-[3-hydroxy-5-(4-methyl-piperazin-1-yl)-pentyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1327] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-(3-{4-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-butyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1328] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-{3-[4-(5-methyl-2,5-diaza-bicyclo[2.2.1]hept-2-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1329] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(3-hydroxy-piperidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1330] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(2-hydroxymethyl-piperidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1331] 5-[3-(3-Cyclohexylamino-propyl)-ureido]-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1332] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-{3-[3-(5-methyl-2,5-diaza-bicyclo[2.2.1]hept-2-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1333] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-ureido-isothiazole-4-carboxylic acid amide;
[1334] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-(3-ethyl-ureido)-isothiazole-4-carboxylic acid amide;
[1335] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(3-cyclopropylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1336] 5-[3-(3-Cyclopropylamino-propyl)-ureido]-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1337] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-(3-{3-[ethyl-(2-hydroxy-ethyl)-amino]-propyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1338] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-(3-{3-[ethyl-(2-hydroxy-ethyl)-amino]-propyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1339] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-(3-{3-[4-(2-hydroxy-ethyl)-piperazin-1-yl]-propyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1340] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-[3-(3-hydroxy-5-isopropylamino-pentyl)-ureido)-isothiazole-4-carboxylic acid amide;
[1341] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1342] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-(3-{3-[ethyl-(2-hydroxy-ethyl)-amino]-propyl}-ureido)-isothiazole-4-carboxylic acid amide;
[1343] 5-{3-[2-(1-Methyl-pyrrolidin-2-yl)-ethyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy-isothiazole)-4-carboxylic acid amide;
[1344] 5-[3-(4-Dimethylamino-butyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1345] 5-[3-(3-Dimethylamino-propyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1346] 5-[3-(3-Hydroxy-5-isopropylamino-pentyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1347] 5-[3-(3-Isopropylamino-propyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1348] 5-{3-[4-(4-Methyl-piperazin-1-yl)-butyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1349] 5-(3-{4-[4-(2-Hydroxy-ethyl)-piperazin-1-yl]-butyl}-ureido)-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1350] 5-(3-{4-[4-(3-Hydroxy-propyl)-piperazin-1-yl]-butyl}-ureido)-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1351] 5-[3-(3-Pyrrolidin-1-yl-propyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1352] 5-[3-(4-Hydroxy-5-piperidin-1-yl-pentyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1353] 5-(3-Ethyl-ureido)-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1354] 5-(3-Methyl-ureido)-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1355] 5-(3-{4-[Bis-(2-hydroxy-propyl)-amino]-butyl}-ureido)-3-(2,6-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1356] 5-{3-[3-(4-Acetyl-piperazin-1-yl)-propyl]-ureido}-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1357] 5-{3-[3-(4-Acetyl-piperazin-1-yl)-propyl]-ureido}-3-(4-chloro-2,3,6-trifluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1358] 3-(1,3-Difluoro-naphthalen-2-ylmethoxy)-5-(3-{4-[ethyl-(2-hydroxy-ethyl)-amino]-butyl}-ureido)-isothiazole-4-carboxylic acid amide'
[1359] 5-{3-[3-(4-Acetyl-piperazin-1-yl)-propyl]-ureido}-3-(4-chloro-2,6-difluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1360] 5-{3-[4-(4-Acetyl-piperazin-1-yl)-butyl]-ureido}-3-(4-chloro-2,3,6-trifluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1361] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-[3-(3-imidazol-1-yl-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1362] 5-[3-(2-Amino-ethyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1363] 5-[3-(4-Amino-butyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1364] 5-[3-(5-Amino-pentyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1365] 5-[3-(6-Amino-hexyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1366] 5-[3-(7-Amino-heptyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1367] 3-(1,3-Difluoro-naphthalen-2-ylmethoxy)-5-{3-[2-(1-methyl-pyrrolidin-2-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1368] 3-(1,3-Difluoro-naphthalen-2-ylmethoxy)-5-{3-[4-(2-hydroxymethyl-pyrrolidin-1-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1369] 3-(1,3-Difluoro-naphthalen-2-ylmethoxy)-5-{3-[3-(5-methyl-2,5-diaza-bicyclo[2.2.1]hept-2-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1370] 3-(1,3-Difluoro-naphthalen-2-ylmethoxy)-5-[3-(4-pyrrolidin-1-yl-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1371] 3-(1,3-Difluoro-naphthalen-2-ylmethoxy)-5-{3-[3-(4-methyl-piperazin-1-yl)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1372] 5-(3-{4-[Ethyl-(2-hydroxy-ethyl)-amino]-butyl}-ureido)-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1373] 5-{3-[4-(3-Hydroxy-piperidin-1-yl)-butyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1374] 5-[3-(3-tert-Butylamino-propyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1375] 5-{3-[4-(3-Hydroxy-pyrrolidin-1-yl)-butyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1376] 5-{3-[4-(3,4-Dihydroxy-pyrrolidin-1-yl)-butyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1377] 5-{3-[4-(2-Hydroxymethyl-pyrrolidin-1-yl)-butyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1378] 5-{3-[4-(2-Hydroxymethyl-piperidin-1-yl)-butyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1379] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-(3-methyl-ureido)-isothiazole-4-carboxylic acid amide;
[1380] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-{3-[2-(1-methyl-pyrrolidin-2-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1381] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(2-dimethylamino-ethyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1382] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(4-dimethylamino-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1383] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(5-methyl-2,5-diaza-bicyclo[2.2.1]hept-2-yl)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1384] 5-(3-{4-[Bis-(2-hydroxy-ethyl)-amino]-butyl}-ureido)-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1385] 5-{3-[3-(5-Methyl-2,5-diaza-bicyclo[2.2.1]hept-2-yl)-propyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1386] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(3-dimethylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1387] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(3-hydroxy-5-isopropylamino-pentyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1388] 5-[3-(3-Cyclohexylamino-propyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1389] 3-(2,6-Difluoro-4-methyl-benzyloxy)-5-[3-(3-isopropylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1390] 5-[3-(3-Amino-propyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1391] 5-{3-[2-(2-Amino-ethoxy)-ethyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1392] 5-[3-(4-Pyrrolidin-1-yl-butyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1393] 5-{3-[3-(4-Methyl-piperazin-1-yl)-propyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1394] 5-[3-(4-Amino-butyl)-ureido]-3-(4-chloro-2,6-difluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;5-[3-(7-Amino-heptyl)-ureido]-3-(4-chloro-2,6-difluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1395] 5-[3-(5-Amino-pentyl)-ureido]-3-(4-chloro-2,6-difluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;5-[3-(4-Amino-butyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1396] 5-[3-(3-Azepan-1-yl-propyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1397] 5-[3-(3-Diethylamino-propyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1398] 5-[3-(3-Methylamino-propyl)-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1399] 5-{3-[3-(2-Methyl-piperidin-1-yl)-propyl]-ureido}-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1400] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(pyridin-2-ylamino)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1401] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[3-(pyridin-2-ylamino)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1402] 5-[3-(6-Amino-hexyl)-ureido]-3-(4-chloro-2,6-difluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1403] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[4-(pyridin-2-ylamino)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1404] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-{3-[4-(pyridin-2-ylamino)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1405] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-{3-[3-(pyridin-2-ylamino)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1406] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[3-(pyridin-2-ylamino)-propyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1407] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-[3-(4-cyclopropylamino-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1408] 5-[3-(3-Amino-propyl)-3-methyl-ureido]-3-(2,3,6-trifluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1409] 3-(3-Chloro-2,6-difluoro-4-methyl-benzyloxy)-5-{3-[2-(1-methyl-pyrrolidin-2-yl)-ethyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1410] 3-(3-Chloro-2,6-difluoro-4-methyl-benzyloxy)-5-[3-(3-dimethylamino-propyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1411] 3-(3-Chloro-2,6-difluoro-4-methyl-benzyloxy)-5-[3-(4-dimethylamino-butyl)-ureido]-isothiazole-4-carboxylic acid amide;
[1412] 5-[3-(2-Amino-ethyl)-ureido]-3-(4-chloro-2,6-difluoro-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1413] 5-[3-(2-Amino-ethyl)-ureido]-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1414] 5-[3-(7-Amino-heptyl)-ureido]-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1415] 5-[3-(3-Amino-propyl)-ureido]-3-(2,5-difluoro-4-methyl-benzyloxy)-isothiazole-4-carboxylic acid amide;
[1416] 3-(2,5-Difluoro-4-methyl-benzyloxy)-5-{3-[4-(pyridin-4-ylamino)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1417] 3-(4-Chloro-2,6-difluoro-benzyloxy)-5-{3-[4-(pyridin-4-ylamino)-butyl]-ureido}-isothiazole-4-carboxylic acid amide;
[1418] 3-(4-Chloro-2,3,6-trifluoro-benzyloxy)-5-{3-[4-(pyridin-4-ylamino)-butyl]-ureido}-isothiazole-4-carboxylic acid amide. | The present invention relates to compounds of the formula 1
and to pharmaceutically acceptable salts, prodrugs and solvates thereof, wherein X 1 , R 1 , R 2 and R 3 are as defined herein. The invention also relates to pharmaceutical compositions containing the above compounds and to methods treating hyperproliferative disorders in mammals by administering the above compounds. | 2 |
This application is a division of Ser. No. 103,305, filed 10/1/87, now U.S. Pat. No. 4,795,831, which is a division of Ser. No. 834,945, filed 2/28/86, now U.S. Pat. No. 4,716,241.
BACKGROUND OF THE INVENTION
The present invention relates to an intermediate for the preparation of N-(L-aspartyl)-N'-(2,2,5,5-tetramethylcyclopentanecarbonyl)-R-1,1-diaminoethane (hereinafter referred to as "gem-sweetener") represented by the formula: ##STR3##
The gem-sweetener is a known compound which is disclosed in European patent application No. 128654A. The compound possesses a high degree of sweetness, without undesirable flavor notes and also possesses a high degree of stability in all types of aqueous systems and even upon cooking.
It is known that the compound is prepared by the steps shown in the following scheme. ##STR4##
This method involves dangerous reactions, that is, Grignard reaction and hydroboration, and boron hydride which is used in the step of hydroboration is very expensive. Further, the total yield is only about 8% which is very low.
As the result of studies on an industrially advantageous process for the preparation of gem-sweetener, it has been found that 2,2,5,5-tetramethylcyclopentane carboxylic acid which is an intermediate for the preparation of gem-sweetener can be prepared without the above-described disadvantages of the known methods.
SUMMARY OF THE INVENTION
In accordance with the present invention, there is provided a novel compound which is useful as an intermediate for the preparation of gem-sweetener and which is represented by the formula (I): ##STR5## wherein R 1 is hydrogen and R 2 is cyano, formyl, carbamoyl, alkanesulfonyloxy, or ##STR6## wherein R 3 and R 4 are the same or different and are alkyl, substituted alkyl or R 1 and R 2 are combined to be methylsulfinylmethylene, acetoxymethylthiomethylene, halomethylthiomethylene, methylthiomethylene, alkoxymethylene, or --CH 2 --O--.
DESCRIPTION OF THE INVENTION
In the definitions of the individual groups in formula (I), the alkyl or alkyl moiety of alkanesulfonyloxy and alkoxymethylene includes straight or branched alkyl having 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, etc.
The substituents of substituted alkyl include alkoxy, hydroxy and halogen. The definition of alkyl moiety of alkoxy is the same as that described above.
The halo group of halomethylthiomethylene and halogen include chloro, bromo, etc. The following is a general scheme for the production of the desired intermediates of the present invention:
In the scheme, each symbol has the following meaning. ##STR7##
PROCESS 1
Compound 1, i.e. 2,2,5,5-tetramethylcyclopentanone is reduced in an inert solvent in the presence of a catalyst such as Raney nickel or a reducing agent such as sodium borohydride to provide Compound 2, i.e. 2,2,5,5-tetramethylcyclopentanol. The reduction is carried out at a temperature ranging from the room temperature to 180° C. for 3 to 30 hours. As the solvent, water, methanol, ethanol, dioxane, tetrahydrofuran, etc. may be used alone or in combination.
Compound 1 is a known compound which can be readily prepared from cyclopentanone, as shown in Reference Example 1.
PROCESS 2
Compound 2 is allowed to react with an alkanesulfonyl chloride in the presence of a base in an inert solvent to provide Compound 3, that is, 1-alkanesulfonyloxy-2,2,5,5-tetramethylcyclopentane. As the inert solvent, halogenated lower alkanes, for example, methylene chloride etc. are used. As the base, pyridine, triethylamine, etc. are used. The reaction is carried out at 0° to 100° C. for 1 to 40 hours.
PROCESS 3
Compound 3 is allowed to react with sodium cyanide in the presence of dimethylsulfoxide in a sealed tube at 150° to 300° C. for 5 to 30 hours to obtain Compound 4, that is, 1-cyano-2,2,5,5-tetramethylcyclopentane.
PROCESS 4
Compound 4 is subjected to hydrolysis in an aqueous solution of alkali hydroxides, for example, sodium hydroxide and potassium hydroxide to obtain Compound 5, that is, (2,2,5,5-tetramethylpentane-1-yl) carboxamide. The reaction is carried out at 0° to 110° C. for 1 to 30 hours.
PROCESS 5
Compound 1 is dissolved in an inert solvent, for example, dioxane, tetrahydrofuran, etc., and sodium hydride is added to the solution. After the solution is heated to 70° to 100° C., dimethylsulfoxide is added to the solution and the mixture is subjected to reaction with heating under reflux usually for 2 to 5 hours to provide Compound 6, i.e. 2,2,5,5-tetramethylcyclopentylidenemethyl methyl sulfoxide.
PROCESS 6
Compound 6 is allowed to react with acetic anhydride in the presence of a base in an inert solvent to provide Compound 7, i.e. 2,2,5,5-tetramethylcyclopentylidenemethyl acetoxymethyl sulfide. As the inert solvent, ethylene dichloride, chloroform, etc. are used and as the base, pyridine, etc. are used.
Pyridine can be used to serve as the solvent as well. The reaction is carried out at a temperature ranging from room temperature to 120° C. for 3 to 20 hours.
PROCESS 7
Compound 6 is allowed to react with acetyl halide, if necessary, in an inert solvent to provide Compound 8, i.e. 2,2,5,5-tetramethylcyclopentylidenemethyl halomethyl sulfide. As the inert solvent, methylene chloride, chloroform, tetrahydrofuran, etc. are used. As the acetyl halide, acetyl chloride, etc. are used in an amount more than the equivalent amount of Compound 6. The reaction is carried out at 0° to 120° C. for 1 to 30 hours.
PROCESS 8
Compound 6 is reduced in the presence of a reducing agent such as lithium aluminum hydride, if necessary, in an inert solvent to provide Compound 9, i.e. 2,2,5,5-tetramethylcyclopentylidenemethyl methylsulfide. As the inert solvent, tetrahydrofuran, dioxane, etc. are used. The reaction is carried out at around the room temperature for about 10 hours.
PROCESS 9
Compound 7, 8 or 9 is subjected to reaction with a lower alkanol in the presence of bromine under cooling to provide Compound 10, i.e. 1-formyl-2,2,5,5-tetramethylcyclopentane. The reaction is carried out at a temperature of from -30° to 80° C., preferably from -20° to 30° C. for 0.5 to 10 hours. The lower alkanol includes methanol, ethanol, etc.
PROCESS 10
Compound 7 which can be obtained according to Process 6 is subjected to reaction with an alkanol or a substituted alkanol in the presence of a halogenating agent in an inert solvent to provide Compound 10. The alkanol includes alkanols having 1 to 10 carbon atoms such as methanol, ethanol, propanol, etc. The substituent of the substituted alkanol includes lower alkoxy, hydroxy and halogen.
The halogenating agent includes chlorine, bromine, iodine, N-bromosuccinimide, etc, but bromine is preferable. The inert solvent includes halogenated lower alkanes such as chloroform, methylene chloride, etc., and ethers such as tetrahydrofuran, diethylether, etc.
A large excess (usually 50 to 500 equivalent weight) of alkanols is used on the basis of Compound 7 so as to serve also as a solvent. Usually 1 to 5 equivalent weight, preferably 3 to 3.5 equivalent weight, of the halogenating agent is used on the basis of Compound 7. The reaction is carried out at a temperature of -78° to 50° C. and is completed usually within 20 to 100 hours.
PROCESS 11
Compound 10 is subjected to incubation under basic conditions, for example, in the presence of 0.1 to 20 equivalent weight of a base such as sodium hydroxide and potassium hydroxide, in an inert solvent to provide Compound 11. The incubation of Compound 10 may be carried out using the reaction mixture obtained in Process 10 without isolating Compound 10. The inert solvent includes water, methanol, ethanol, dioxane, tetrahydrofuran and their mixture. The reaction is carried out usually at a temperature ranging from room temperature to 100° C. for 1 to 30 hours.
PROCESS 12
Compound 10 or Compound 11 is subjected to acid hydrolysis to provide Compound 12, i.e., 1-formyl-2,2,5,5-tetramethylcyclopentane.
The reaction is carried out in an inert solvent such as tetrahydrofuran in the presence of acid such as hydrochloride at room temperature for 1 to 10 hours.
PROCESS 13
Compound 13, i.e. 1-methylene-2,2,5,5-tetramethylcyclopentane, is oxidized by a peroxidizing agent such as m-chloroperbenzoic acid (MCPBA), if necessary, in an inert solvent to provide Compound 14, i.e. 1-methylene-2,2,5,5-tetramethylcyclopentane oxide. As the inert solvent, acetonitrile, tetrahydrofuran, methanol, etc. are used. The reaction temperature depends on the oxidizing agent. It may be around the room temperature when m-chloroperbenzoic acid is used, where the reaction completes in 1 to 10 hours. Compound 13 is a known compound which can be prepared according to the procedure shown in Reference Example 3.
PROCESS 14
Compound 14 is treated with a solution of a Lewis acid in an appropriate solvent, for example, ether to provide Compound 12. The Lewis acid includes boron trifluoride (BF 3 ), magnesium bromide, etc. An appropriate amount of the Lewis acid to be used is usually 1 to 10% (W/W) on the basis of the substrate. The reaction is carried out at 0° to 100° C. for 0.5 to 10 hours.
Processes P-15 to P-18 mentioned in the above scheme are known processes and are described later in Reference Examples.
In the Processes described above, the purification and isolation of the desired compounds are carried out according to the known methods. When the desired compound is in the form of an oily substance at room temperature, the compound is purified by rectification. When the compound is in a solid form at room temperature, the compound is purified by concentration, extraction, crystallization, etc.
Certain specific embodiments of the invention are illustrated by the following representative examples.
EXAMPLE 1
P-1 and P-2
(1) 54.9 g of 2,2,5,5-tetramethylcyclopentanone was dissolved in a solvent mixture of 95 ml of methanol and 95 ml of water, and 24.0 g of sodium borohydride was added thereto. The mixture was stirred at 70° C. for 15 hours. The reaction solution was concentrated under reduced pressure, and 100 ml of water was added thereto. The mixture was twice extracted with 100 ml of chloroform, and the organic layers were combined and washed with 100 ml of an aqueous saturated sodium chloride solution. Then, the solution was concentrated under reduced pressure. The liquid residue was distilled under reduced pressure, whereby 43.25 g of 2,2,5,5-tetramethylcyclopentanol was obtained as a colorless oily substance (b.p. 40° C./3 mmHg).
______________________________________IR ν.sub.OH 3450 cm.sup.-1.sup.1 H--NMR (90 MHz in CDCl.sub.3); δ0.93(s, 6H), 1.04(s, 6H), 1.25(m, 4H), 3.24(s, 1H)Elemental analysis as C.sub.9 H.sub.18 OCalculated: C 75.99% H 12.76%Found: C 75.88% H 12.67%______________________________________
(2) 2.84 g of 2,2,5,5-tetramethylcyclopentanol and 3.2 ml of pyridine were dissolved in 20 ml of methylene chloride, and 4.5 g of methanesulfonyl chloride was added thereto. The mixture was stirred at room temperature for 12 hours, and then 50 ml of aqueous saturated sodium hydrogen carbonate solution was added thereto. The mixture was extracted with 50 ml of ethyl acetate, and the organic layer was washed with aqueous 10% copper sulfate solution, and concentrated under reduced pressure. The resulting residue was recrystallized from n-hexane, whereby 1.26 g of 1-methanesulfonyloxy-2,2,5,5-tetramethylcyclopentane was obtained (m.p. 46° C.).
______________________________________.sup.1 H--NMR (90 MHz in CDCl.sub.3); δ1.03(s, 6H), 1.13(s, 6H), 1.56(m, 4H), 3.03(s,3H), 4.26(s, 1H)IR (KBr) 1170, 1350 cm.sup.-1Elemental analysis as C.sub.10 H.sub.20 O.sub.3 SCalculated: C 54.51% H 9.15%Found: C 54.28% H 9.11%______________________________________
EXAMPLE 2
P-3
20 ml of dimethylsulfoxide was added to 1.10 g of 1-methanesulfonyloxy-2,2,5,5-tetramethylcyclopentane and 980 mg of sodium cyanide, and the mixture was stirred with heating at 200° C. for 20 hours in a sealed tube.
After cooling, 200 ml of water was added thereto, and the mixture was extracted with 300 ml of ethyl acetate. The organic layer was washed with 200 ml of water, and concentrated under reduced pressure. The thus obtained oily substance was subjected to silica gel column chromatography using ethyl acetate-n-hexane as an eluent, whereby 340 mg of 1-cyano-2,2,5,5-tetramethylcyclopentane was obtained (b.p. 106° C./35 mmHg).
______________________________________.sup.1 H--NMR (90 MHz in CDCl.sub.3); δ1.19(s, 6H), 1.25(s, 6H), 1.67(m, 4H), 2.34(s,1H)IR (neat) 2200 cm.sup.-1Elemental analysis as C.sub.10 H.sub.17 NCalculated: C 79.41% H 11.33%Found: C 79.40% H 11.35%______________________________________
EXAMPLE 3
P-4
760 mg of 1-cyano-2,2,5,5-tetramethylcyclopentane was dissolved in 5 ml of aqueous 3N sodium hydroxide solution and 10 ml of MeOH, and the solution was stirred at room temperature for 10 hours. Then, 10 ml of water was added thereto, and the mixture was twice extracted with 30 ml of chloroform. The organic layers were combined, washed with 50 ml of water and concentrated under reduced pressure. The thus obtained residue was recrystallized from n-hexane, whereby 640 mg of (2,2,5,5-tetramethylcyclopentane-1-yl) carboxamide was obtained (m.p. 97.7° C.).
______________________________________.sup.1 H--NMR (90 MHz in CDCl.sub.3); δ1.11(s, 6H), 1.14(s, 6H), 1.55(m, 4H), 1.92(s,1H), 5.40(s, 1H), 5.76(s, 1H)Elemental analysis as C.sub.10 H.sub.19 ONCalculated: C 70.96%, H 11.32%, N 8.28%Found: C 70.79%, H 11.32%, N 8.29%______________________________________
EXAMPLE 4
P-5
28.0 g of 2,2,5,5-tetramethylcyclopentanone was dissolved in 50 ml of tetrahydrofuran, and 9.8 g of 50% sodium hydride was added thereto. The mixture was heated under reflux.
A mixed solution of 40 ml of dimethylsulfoxide and 50 ml of tetrahydrofuran was slowly added dropwise at the same temperature. The mixture was further heated at the same temperature for 3 hours, and cooled. Then, 200 ml of water was added thereto, and the mixture was twice extracted with 200 ml of ethyl acetate. The organic layers were washed with an aqueous saturated sodium chloride solution, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the residue was crystallized from 70 ml of n-hexane, whereby 29.2 g of 2,2,5,5-tetramethylcyclopentylidenemethyl methyl sulfoxide was obtained (m.p. 74.7° C.).
______________________________________.sup.1 H--NMR (90 MHz in CDCl.sub.3); δ1.09(s, 3H), 1.15(s, 3H), 1.23(s, 3H), 1.43(s,3H), 1.62(s, 4H), 2.57(s, 3H), 5.90(s, 1H)IR ν.sub.S═O 1050 cm.sup.-1Elemental analysis as C.sub.11 H.sub.20 OSCalculated: C 65.95% H 10.06%Found: C 65.76% H 10.00%______________________________________
EXAMPLE 5
P-6
5.0 g of 2,2,5,5-tetramethylcyclopentylidenemethyl methyl sulfoxide, 5.2 g of acetic anhydride, 3.5 g of pyridine and 5 ml of 1,2-dichloroethane were mixed, and heated under reflux for 7.5 hours. After cooling, 50 ml of aqueous saturated sodium hydrogen carbonate solution was added thereto, and the mixture was extracted with 200 ml of ethyl acetate. The organic layer was washed with 80 ml of aqueous 10% copper sulfate solution and again with 80 ml of water.
The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The liquid residue was subjected to silica gel column chromatography using ethyl acetate-n-hexane as an eluent and then distilled under reduced pressure, whereby 5.2 g of 2,2,5,5-tetramethylcyclopentylidenemethyl acetoxymethyl sulfide was obtained as a colorless oily substance (b.p. 81° C./2 mmHg).
______________________________________IR ν.sub.C═O 1750 cm.sup.-1.sup.1 H--NMR (90 MHz in CDCl.sub.3); δ1.07(s, 6H), 1.24(s, 6H), 1.56(s, 4H), 2.08(s,3H), 5.17(s, 2H), 5.75(s, 1H)Elemental analysis as C.sub.13 H.sub.20 O.sub.2 SCalculated: C 64.96% H 8.39%Found: C 64.83% H 8.27%______________________________________
EXAMPLE 6
P-7
1.0 g of 2,2,5,5-tetramethylcyclopentylidenemethyl methyl sulfoxide was dissolved in 10 ml of methylene chloride, and 470 mg of acetyl chloride was added dropwise. The mixture was subjected to reaction at room temperature for 12 hours, and then 50 ml of 5% sodium hydrogen carbonate was added thereto. The mixture was extracted twice with 50 ml of chloroform, and the organic layers were dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, whereby 960 mg of 2,2,5,5-tetramethylcyclopentylidenemethyl chloromethyl sulfide was obtained.
______________________________________.sup.1 H--NMR (90 MHz in CDCl.sub.3); δ1.09(s, 6H), 1.24(s, 6H), 1.57(s, 4H), 4.73(s,2H), 5.71(s, lH)Elemental analysis as C.sub.11 H.sub.19 SClCalculated: C 60.39% H 8.75%Found: C 60.43% H 8.81%______________________________________
EXAMPLE 7
P-8
20 g of 2,2,5,5-tetramethylcyclopentylidenemethyl methyl sulfoxide was dissolved in 200 ml of tetrahydrofuran, and 4.0 g of lithium aluminum hydride was added thereto in small portions. The mixture was stirred at room temperature for 10 hours, and then 100 ml of ethyl acetate was added dropwise thereto. After the mixture was subjected to filtration, the filtrate was concentrated under reduced pressure. The oily substance was subjected to silica gel column chromatography using ethyl acetate-n-hexane as an eluent, whereby 13.8 g of 2,2,5,5-tetramethylcyclopentylidenemethyl methyl sulfide was obtained as an oily substance.
______________________________________.sup.1 H--NMR (90 MHz in CDC1.sub.3); δ1.04(s, 6H), 1.24(s, 6H), 1.55(s, 4H), 2.22(s,3H), 5.48(s, 1H)Elemental analysis as C.sub.11 H.sub.20 SCalculated: C 71.67% H 10.94%Found: C 71.51% H 10.72%______________________________________
EXAMPLE 8
P-9
4.5 mg of 2,2,5,5-tetramethylcyclopentylidenemethyl acetoxymethyl sulfide was dissolved in 90 ml of methanol, and the solution was cooled to -50° C. 8.63 g of bromine was added thereto at the same temperature, and the mixture was warmed gradually up to room temperature.
After stirring at room temperature for 8 hours, 300 ml of water was added thereto, and the mixture was extracted twice with 200 ml of chloroform. The organic layers were combined, washed with 300 ml of aqueous saturated sodium hydrogen carbonate solution and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure. The liquid residue was distilled under reduced pressure, whereby 2.47 g of 1-formyl-2,2,5,5-tetramethylcyclopentane was obtained as a colorless oily substance (b.p. 102° C./45 mmHg).
______________________________________.sup.1 H--NMR (90 MHz in CDCl.sub.3); δ1.10(s, 6H), 1.19(s, 6H), 1.62(s, 4H), 1.91(d,J = 5.4 Hz, 1H), 9.77(d, J = 5.4 Hz, 1H)IR ν.sub.C=O 1710 cm.sup.-1 (neat)Elemental analysis as C.sub.10 H.sub.18 OCalculated: C 77.86% H 11.76%Found: C 77.83% H 11.77%______________________________________
EXAMPLE 9
P-10
96.8 g of 2,2,5,5-tetramethylcyclopentylidenemethyl acetoxymethyl sulfide was dissolved in 1.6 l of methanol, and the solution was cooled to -50° C. Then, a solution of 204.8 g of bromine in 400 ml of chloroform was added dropwise thereto at the same temperature, and the mixture was stirred for one hour. After further stirring at room temperature for 24 hours, the reaction mixture was added dropwise to 1.6 l of aqueous 2N sodium hydroxide solution with ice cooling. The mixture was extracted twice with 500 ml of chloroform, and the organic layers were combined and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure.
The residue was distilled under reduced pressure, whereby 57.6 g of 1-formyl-2,2,5,5-tetramethylcyclopentanedimethyl acetal was obtained as an oily substance.
______________________________________Yield: 72%, (b.p. 49-52° C./0.4 mmHg).sup.1 H--NMR (90 MHz in CDCl.sub.3); δ0.96(s, 6H), 1.04(s, 6H), 1.43(s, 4H), 1.45(d,J = 9 Hz, 1H), 3.27(s, 2H), 4.37(d, J = 9 Hz, 1H)Elemental analysis as C.sub.12 H.sub.24 O.sub.2Calculated: C 71.95% H 12.08%Found: C 72.22% H 12.30%______________________________________
EXAMPLE 10
P-11
10.0 g of 1-formyl-2,2,5,5-tetramethylcyclopentanedimethyl acetal was dissolved in 20 ml of methanol and 10 ml of aqueous 1N sodium hydroxide solution, and the solution was heated under reflux for 2 hours. After the reaction, the reaction mixture was cooled, and extracted twice with 100 ml of chloroform. The organic layers were combined, and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure. The residue was distilled under reduced pressure, whereby 4.45 g of 2,2,5,5-tetramethylcyclopentylidenemethyl methyl ether was obtained as an oily substance. Yield: 53%. (b.p. 40°-42° C./0.1 mmHg).
______________________________________.sup.1 H--NMR (90 MHz in CDCl.sub.3); δ1.02(s, 6H), 1.17(s, 6H), 1.49(s, 4H), 3.45(s,3H), 5.63(s, 1H)Elemental analysis as C.sub.11 H.sub.20 OCalculated: C 78.51% H 11.98%Found: C 78.79% H 12.19%______________________________________
EXAMPLE 11
P-12
20.0 g of 1-formyl-2,2,5,5-tetramethylcyclopentane dimethylacetal was dissolved in 200 ml of tetrahydrofuran, and 100 ml of 1N hydrochloric acid was added thereto. The mixture was vigorously stirred at room temperature for 3 hours, and 400 ml of water was added thereto. The mixture was extracted twice with 400 ml of ethyl acetate. The organic layers were combined, washed with 1 l of water and then with 1 l of aqueous saturated sodium chloride solution, and dried over anhydrous sodium sulfate.
After filtration, the solvent was evaporated under reduced pressure, and the residue was distilled under reduced pressure, whereby 13.6 g of 1-formyl-2,2,5,5-tetramethylcyclopentane was obtained as a colorless oily substance. Yield 88%. (b.p. 102° C./45 mmHg).
______________________________________.sup.1 H--NMR (90 MHz in CDCl.sub.3); δ1.10(s, 6H), 1.19(s, 6H), 1.62(s, 4H), 1.91(d,J = 5.4 Hz, 1H), 9.77(d, J = 5.4 Hz, 1H)IR ν.sub.C═O.sup.neat 1710 cm.sup.-1Elemental analysis as C.sub.10 H.sub.18 OCalculated: C 77.86% H 11.76%Found: C 77.83% H 11.77%______________________________________
EXAMPLE 12
P-12
10 g of 2,2,5,5-tetramethylcyclopentylidenemethyl methyl ether was dissolved in 100 ml of tetrahydrofuran, and 50 ml of 6N-hydrochloric acid was added thereto. The mixture was vigorously stirred at room temperature for 3 hours, and then treated in the same manner as in Example 11 to obtain 8.60 g of 1-formyl-2,2,5,5-tetramethylcyclopentane. Yield 94%.
EXAMPLE 13
P-13
43.44 g of 1-methylene-2,2,5,5-tetramethylcyclopentane was dissolved in 600 ml of acetonitrile, and 147.9 g of m-chloroperbenzoic acid was added thereto in small portions with ice cooling. After stirring at room temperature for 7 hours, 480 ml of aqueous 10% sodium thiosulfate solution and 500 ml of aqueous saturated sodium hydrogen carbonate solution were added thereto, and the precipitate was removed by filtration. The filtrate was extracted twice with 500 ml of ethyl acetate, and the organic layers were combined. The solvent was evaporated under reduced pressure. The residue was distilled under reduced pressure, whereby 42.04 g of 1-methylene-2,2,5,5-tetramethylcyclopentane oxide was obtained as an oily substance (b.p. 54° C./15 mmHg).
______________________________________.sup.1 H--NMR (90 MHz in CDCl.sub.3); δ0.87(s, 6H), 1.01(s, 6H), 1.65(s, 4H), 2.63(s,2H)Elemental analysis as C.sub.10 H.sub.18 OCalculated: C 77.86% H 11.76%Found: C 77.65% H 11.78%______________________________________
EXAMPLE 14
P-14
3.08 g of 1-methylene-2,2,5,5-tetramethylcyclopentane oxide was dissolved in 40 ml of ethyl acetate, and the solution was cooled to -50° C. Then, 0.14 g of boron tetrafluoride-ether complex was added thereto, and the mixture was stirred at room temperature for one hour. Then, 50 ml of aqueous saturated sodium hydrogen carbonate solution was added thereto, and the resulting two layers were separated. The organic layer was concentrated under reduced pressure, and distilled under reduced pressure, whereby 2.68 g of 1-formyl-2,2,5,5-tetramethylcyclopentane was obtained as an oily substance (b.p. 102° C./45 mmHg).
______________________________________IR ν.sub.C═O 1710 cm.sup.-1 (neat).sup.1 H--NMR (90 MHz in CDCl.sub.3); δ1.10(s, 6H), 1.19(s, 6H), 1.62(s, 4H), 1.91(d,J = 5.4 Hz, 1H), 9.77(d, J = 5.4 Hz, 1H)Elemental analysis as C.sub.10 H.sub.18 OCalculated: C 77.86% H 11.76%Found: C 77.83% H 11.77%______________________________________
REFERENCE EXAMPLE 1
Preparation of 2,2,5,5-tetramethylcyclopentanone
1.5 l of tetrahydrofuran was added to 144 g of 50% sodium hydride and a solution of 53.6 g of cyclopentanone in 350 ml of terahydrofuran was added dropwise thereto with ice cooling in a nitrogen gas stream. Then, a solution of 285 ml of dimethy sulfate and 120 ml of tetrahydrofuran was slowly added dropwise thereto with ice cooling, and the mixture was heated under reflux for 2 hours.
After cooling, 100 ml of t-butanol was slowly added dropwise thereto to decompose excess sodium hydride, and then 1.0 l of water was added thereto. The reaction mixture was further heated for 2 hours under reflux to decompose excess dimethyl sulfate. After cooling, the resulting two layers were separated and the organic layer was washed with aqueous saturated sodium chloride solution, and dried over anhydrous sodium sulfate. The solvent was distilled away under reduced pressure, and the residue was distilled under reduced pressure, whereby 59 g of 2,2,5,5-tetramethylcyclopentanone was obtained (b.p. 55° C./20 mmHg).
______________________________________ .sup.1 H--NMR (90 MHz in CDCl.sub.3); δ 1.04(s, 12H), 1.77(s, 4H) IR ν.sub.C═O 1734 cm.sup.-1 (neat)______________________________________
REFERENCE EXAMPLE 2
Preparation of 1,2,2,5,5-pentamethylcyclopentanol
100 ml of a 3M methylmagnesium bromide/ether solution was added to a solution of 30 g of 2,2,5,5-tetramethylcyclopentanone in 50 ml of ether under a nitrogen gas atmosphere, and the mixture was stirred at room temperature overnight. Then, 65 ml of aqueous saturated ammonium chloride solution was added dropwise thereto and the mixture was stirred for 10 minutes. The ether layer was subjected to decantation and the residue was extracted with ether. The ether layers were dried over anhydrous sodium sulfate, and concentrated under reduced pressure, whereby 30 g of 1,2,2,5,5-pentamethylcyclopentanol was obtained.
1 H-NMR (90 MHz in CDCl 3 ); δ; 1.00(s, 12H), 1.03(s, 3H), 1.55(m, 4H).
IR ν O-H 3480 cm -1 (neat).
REFERENCE EXAMPLE 3
Preparation of 1-methylene-2,2,5,5-tetramethylcyclopentane
30 g of 1,2,2,5,5-pentamethylcyclopentanol was dissolved in 150 ml of pyridine, and 20 ml of thionyl chloride was added dropwise thereto with ice cooling. The reaction mixture was stirred overnight and subjected to filtration. Ether and water were added to the filtrate, and the resulting layers were separated. The organic layer was washed twice with 200 ml of water, and then dried over anhydrous sodium sulfate. The solvent was distilled away under reduced pressure, whereby 10.8 g of 1-methylene-2,2,5,5-tetramethylcyclopentane was obtained (b.p. 137°-140° C./760 mmHg).
1 H-NMR (90 MHz in CDCl 3 ); δ;
1.10(s, 12H), 1.76(s, 4H), 4.76(s, 2H).
REFERENCE EXAMPLE 4
Preparation of 2,2,5,5-tetramethylcyclopentanecarboxylic acid
3.38 g of (2,2,5,5-tetramethylcyclopentane-1-yl) carboxamide was dissolved in 30 ml of methanol, and 15 ml of an aqueous 3N sodium hydroxide solution was added thereto. Then, the mixture was heated at 80° C. for 5 hours. After cooling, 40 ml of 2N hydrochloric acid was added thereto, and the mixture was extracted with 100 ml and 50 ml of ethyl acetate. The organic layers were combined, washed with 100 ml of water and 50 ml of aqueous saturated sodium chloride solution, and then dried over anhydrous magnesium sulfate. After removal of magnesium sulfate by filtration, the filtrate was concentrated under reduced pressure, whereby 3.20 g of 2,2,5,5-tetramethylcyclopentanecarboxylic acid was obtained. Yield 94%. (m.p. 113.6° C.).
______________________________________ IR ν.sub.max.sup.KBr cm.sup.-1 2930, 1693 .sup.1 H--NMR (90 MHz in CDCl.sub.3); δ 1.11(s, 12H), 1.53(s, 4H), 2.19(s, 1H)______________________________________
REFERENCE EXAMPLE 5
Preparation of 2,2,5,5-tetramethylcyclopentanecarboxylic acid
2.47 g of 1-formyl-2,2,5,5-tetramethylcyclopentane was dissolved in 26 ml of acetone, and 5.2 ml of Jones' reagent was added thereto with ice cooling. After stirring at room temperature for 4 hours, 26 ml of water, 26 ml of ethyl acetate and 2.6 ml of isopropyl alcohol were added thereto, and the mixture was stirred at room temperature for 30 minutes, and the resulting layers were separated. The organic layer was washed with water and aqueous saturated sodium chloride solution, dried over anhydrous magnesium sulfate, and subjected to filtration. The filtrate was concentrated under reduced pressure, whereby 2.51 g of 2,2,5,5-tetramethylcyclopentanecarboxylic acid was obtained. Yield 92%.
REFERENCE EXAMPLE 6
Preparation of ultimate sweetening compound
2.51 g of 2,2,5,5-tetramethylcyclopentanecarboxylic acid was dissolved in 10 ml of toluene, and 2.5 ml of thionyl chloride was added thereto. The mixture was stirred at 80° C. for 3 hours. The reaction solution was concentrated and then distilled under reduced pressure, whereby 2.0 g of 2,2,5,5-tetramethylcyclopentanecarbonyl chloride was obtained. Yield 69%. (b.p. 110°-120° C./60 mmHg).
REFERENCE EXAMPLE 7
(1) 50 g of L-alanine methyl ester hydrochloride was dissolved in a solvent mixture of 357 ml of N,N-dimethylformamide and 357 ml of tetrahydrofuran, and the mixture was cooled to -50° C. Then, a solution of 72.3 g of triethylamine in 179 ml of tetrahydrofuran was added thereto at the same temperature, and a solution of 67.4 g of 2,2,5,5-tetramethylcyclopentanecarbonyl chloride in 179 ml of tetrahydrofuran was further added thereto at the same temperature.
The mixture was warmed to room temperature with stirring and the reaction was further carried out at room temperature for 90 minutes. After the reaction, 1.8 l of water was added thereto, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and aqueous saturated sodium chloride solution, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, whereby 89.6 g of (-)-N-(2,2,5,5-tetramethylcyclopentanecarbonyl) alanine methyl ester was obtained as crystals. Yield 98.3%. (m.p. 86.7° C.).
______________________________________[α].sub.D.sup.20 -58.0° (c = 0.2, MeOH).sup.1 H--NMR (90 MHz in CDCl.sub.3); δ1.10(s, 12H), 1.39(d, J = 8 Hz, 3H), 1.55(m, 4H),1.86(s, 1H), 3.74(s, 3H), 4,69(quint. J = 8 Hz, 1H),5.87(br.s, 1H)IRν.sub.max.sup.KBr cm.sup.-1 3300, 2920, 1760, 1650,______________________________________1540
(2) 87.6 g of (-)-N-(2,2,5,5-tetramethylcyclopentanecarbonyl) alanine methyl ester was dissolved in 700 ml of methanol, and an ammonia gas was blown therein till saturation with cooling. The reaction solution was kept in a closed vessel at room temperature for 20 hours.
Then, the mixture was concentrated under reduced pressure, whereby 82.8 g of (-)-N-(2,2,5,5-tetramethylcyclopentanecarbonyl) alanine amide was obtained as crystals. Yield 100%. (m.p. 155.4° C.).
______________________________________[α].sub.D.sup.20 -41.2° (c = 0.2, MeOH).sup.1 H--NMR (90 MHz in CDCl.sub.3); δ1.05(s, 12H), 1.34(d, J = 8 Hz, 3H), 1.50(m, 4H),1.88(s, 1H), 4.63(quint, J = 8 Hz, 1H)IR ν.sub.max.sup.KBr cm.sup.-1 3370, 3190, 2920, 1680, 1650, 1620,______________________________________1500
(3) 6.00 g of (-)-N-(2,2,5,5-tetramethylcyclopentanecarbonyl) alanine amide was suspended in 20 ml of benzyl alcohol, and 9.16 g of iodobenzene diacetate was added thereto with ice cooling. The mixture was stirred at the same temperature for 3 hours, and further at room temperature for 3 hours. Then, 100 ml of aqueous saturated sodium hydrogen carbonate solution and 300 ml of chloroform were added thereto, and the resulting layers were separated. The organic layer was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, and the residue was crystallized from 20 ml of toluene, whereby 6.70 g of (-)-N-(2,2,5,5-tetramethylcyclopentanecarbonyl)-N'-benzyloxycarbonyl-1,1-diaminoethane was obtained. Yield 77%. (m.p. 146.5° C.).
______________________________________[α].sub.D.sup.20 -22° (c = 0.2, MeOH).sup.1 H--NMR (90 MHz in CDCl.sub.3); δ1.03(s, 9H), 1.06(s, 3H), 1.50(m, 7H), 1.74(s,1H), 5.05(s, 2H), 5.18(q, J = 8 Hz, 1H), 7.30(s, 5H)IR ν.sub.max.sup.KBr cm.sup.-1 3280, 2920, 1690, 1660, 1640, 1560,1515______________________________________
(4) 3.46 g of (-)-N-(2,2,5,5-tetramethylcyclopentanecarbonyl)-N'-benzyloxycarbonyl-1,1-diaminoethane was dissolved in 30 ml of tetrahydrofuran, and 1.20 g of acetic acid and 350 mg of 10% palladium-carbon catalyst were added thereto. The mixture was stirred at room temperature under the atmospheric pressure for 5 hours while blowing hydrogen therein. After the reaction, 1.01 g of triethylamine was added thereto, and the catalyst was removed by filtration. The filtrate was concentrated to about 10 ml under reduced pressure (solution A).
Separately, 3.57 g of N.sup.α -benzyloxycarbonyl-β-benzyl-L-aspartic acid was dissolved in a solvent mixture of 10 ml of tetrahydrofuran and 10 ml of N,N-dimethylformamide, and the solution was cooled to -78° C. Then, a solution of 1.01 g of triethylamine in 3 ml of tetrahydrofuran and a solution of 1.37 g of isobutyl chloroformate in 3 ml of tetrahydrofuran were added thereto, and the mixture was stirred for one hour (solution B).
The solution A was added to the solution B at -78° C., and the mixture was stirred at the same temperature for 30 minutes, and further at room temperature for one hour.
Then, 200 ml of water was added thereto, and the mixture was extracted with 350 ml of ethyl acetate. The organic layer was washed successively with 100 ml of aqueous 10% citric acid solution, 150 ml of aqueous saturated sodium hydrogen carbonate solution, and aqueous saturated sodium chloride solution, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and purified by column chromatography on silica gel using chloroform as an eluent, whereby 3.30 g of N-(N.sup.α -benzyloxycarbonyl-β-benzyl-L-aspartyl)-N'-(2,2,5,5-tetramethylcyclopentanecarbonyl)-R-1,1-diaminoethane was obtained as crystals. Yield 79%. (m.p. 115.7° C.).
______________________________________[α].sub.D.sup.20 -28.5° (c = 0.2, MeOH).sup.1 H--NMR (90 MHz in CDCl.sub.3); δ1.04(s, 9H), 1.08(s, 1H), 1.44(d, J = 8 Hz, 3H),2.84(ABdq. J.sub.AB = 18 Hz, J.sub.AX = J.sub.BX = 6 Hz, 2H), 4.48(m,1H), 5.06(s, 4H), 5.28(q, J = 8 Hz, 1H), 7.30(s,10H)IR ν.sub.max.sup.KBr cm.sup.-1 3350, 3290, 3240, 2920, 1740, 1710,1650, 1540, 1510______________________________________
(5) 5.52 g of N-(N.sup.α -benzyloxycarbonyl-β-benzyl-L-aspartyl)-N'-(2,2,5,5-tetramethylcyclopentanecarbonyl)-R-1,1-diaminoethane was dissolved in a solvent mixture of 50 ml of methanol and 20 ml of water, and 1.1 g of 10% palladium-carbon catalyst was added thereto. Then, the mixture was subjected to catalytic reduction at the ordinary temperature under a hydrogen pressure of 15 kg/cm 2 for 5 hours. After the reaction, the catalyst was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was crystallized from 20 ml of water, whereby 2.26 g of N-L-aspartyl-N'-(2,2,5,5-tetramethylcyclopentanecarbonyl)-R-1,1-diaminoethane was obtained. Yield 69%.
______________________________________[α].sub.D.sup.20 19.7° (c = 1, H.sub.2 O).sup.1 H--NMR (90 MHz in DMSO--d.sub.6); δ1.04(s, 12H), 1.24(d, J = 8 Hz, 3H), 1.48(m, 4H),1.96(s, 1H), 3.70(m, 1H)IR ν.sub.max.sup.KBr cm.sup.-1 3300, 1670, 1555, 1505 | Novel cyclopentane derivatives which are useful as an intermediate for the preparation of N-(L-aspartyl)-N'-(2,2,5,5-tetramethylcyclopentanecarbonyl)-R-1,1-diaminoethane are represented by the formula (I) ##STR1## wherein R 1 is hydrogen and R 2 is cyano, formyl, carbamoyl, alkanesulfonyloxy, or ##STR2## wherein R 3 and R 4 are the same or different and represent alkyl, substituted alkyl or R 1 and R 2 are combined to be methylsulfinylmethylene, acetoxymethylthiomethylene, halomethylthiomethylene, methylthiomethylene, alkoxymethylene, or --CH 2 --O--. | 2 |
TECHNICAL FIELD
The present invention relates generally to containers and particularly to packages which are folded from a single package blank and to package blanks as such. Conveniently, the packages can be used for storing, shipping, shop presentation and by the end user, especially in connection with loose foodstuff.
BACKGROUND ART
Numerous packages which are foldable from a single package blank are known in the art. For example, DE 44 07 877 A1 discloses a cube-shaped container with a bottom wall, side walls, and a hinged lid. The lid is provided with a triangular tongue and one of the side walls comprises two layers. In the closed disposition of the container, the tongue is inserted between these two layers.
SUMMARY OF THE INVENTION
Under consideration of the known packages, it is an underlying technical problem of the present invention to provide a package which is inexpensive to manufacture, sufficiently stable to protect the contents of the package and repeatedly and consistently openable and closeable. Further, it is an underlying technical problem of the present invention to provide a package blank for producing such a package.
According to one aspect of the present invention, this problem is solved by a package, folded from a single package blank and comprising front wall, back wall and side wall segments. The front and the back wall segments extend into congruent closure segments defining an end of the package. At least two of the closure segments overlay one another in a substantially coplanar manner to form a pocket with one open side, and at least a further one of the closure segments is inserted into the pocket from the open side thereof in such a manner as to permit repeatable opening and closing of the package end. The package further comprises tabs and flaps on margins of the segments to permit, by folding and attaching, formation of the package from the blank.
In another aspect according to the invention, there is provided a foldable package blank, comprising front wall, back wall and side wall segments. The front and the back wall segments extend into congruent closure segments. At least two of the closure segments are arranged to be foldable on top of one another to form a pocket with one open side, and at least a further one of the closure segments is arranged to be insertable into the pocket from the open side thereof in such a manner as to permit repeatable opening and closing of an end of the package. The blank further comprises tabs and flaps on margins of the segments to permit, by folding and attaching, formation of the package from the blank.
The package according to the invention provides significant advantages over previously known packages. It is designed such that closure segments which are substantially congruent, overlie one another in a substantially coplanar manner to form a pocket with one open side. A further one of the package closure segments is, in the closed disposition of an end of the package, inserted into this pocket from the open side thereof. The pocket of congruent closure segments consequently surrounds the further closure segment substantially entirely. A locking effect of the further closure segment in the pocket is thus achieved. As this locking effect is achieved without making use of any latching or notching action, consistent and reliable functioning of the closure mechanism in accordance with the present invention is obtained without wear of the constituting elements of the closure. To this end, the plane defined by the substantially coplanar closure segments can preferably be angled relative to the front wall and the back wall segments from which the closure segments extend, typically in an obtuse angle. In a further preferred embodiment, the pocket is dimensioned such that friction between the pocket and the further closure segment enhances the locking effect. The inventive solution advantageously permits a manufacturer to design the shape of the closure to resemble the shape of the packaged goods.
A preferred embodiment of the invention suggests a shape of the congruent closure segments, which is substantially triangular. Accordingly, the closure of the package resembles a peak. Alternatively, the congruent closure segments can be of substantially semi-circular shape.
A further preferred feature of the inventive solution contributes to the repeatable and consistent opening and closing of the package end. Accordingly, each side wall segment is provided with crease lines to permit relative movement between the front wall and the back wall segments when the further closure segment is moved between the open and closed dispositions of the package end. In particular, the crease lines permit to move the front and the back wall segments towards and away from one another by enabling mainly the respective side wall segments to deform. Accordingly, the front and the back wall segments can be moved substantially without deformation thereof.
It has been found that crease lines substantially in the shape of an inverted Y represent a particularly beneficial compromise between simple and less costly manufacturing and consistent deformation of the side wall segments. Additionally, storage space within the inventive package is maximized.
Generally, the package can be of any desired cross-sectional shape. However, for most space efficient storage of several packages, it is preferred that the packages are of substantially rectangular cross-section and/or the side wall segments and the front and the back wall segments are located on opposite sides of the package, respectively.
A further preferred embodiment of the inventive package, as regards repeatability and consistency of the opening and closing function, provides that the relative dimensions of the side wall segments and the closure segments are such that the side wall segments prevent opening of the package beyond a limited clearance between the further closure segment and the open side of the pocket. In particular, upon opening of the package end, the side wall segments straighten out along the crease lines and, when they are substantially straight, prevent further relative movement between the front wall and the back wall segments. This mechanical stop leaves a limited clearance between the further closure segment and the open side of the pocket, which is sufficient for inserting the further closure segment into the pocket. Typically, the clearance is dimensioned such that an end of the further closure segment slides on the wall segment of the package adjacent to the pocket so that insertion of the further closure segment into the pocket is more easily facilitated.
An important commercial aspect in the typical field of application of the present invention requires to provide a tamper evident closure mechanism of the package. To this end, at least one of the closure segments is provided with a tear strip.
In semi-automatic and automatic manufacturing and filling of the package, it has proven to be particularly efficient if the package further comprises a crash lock end. Preferably, the crash lock end is located at the bottom and the closure segments at the top of the package.
Many applications of the present invention require the package to hold goods which are sensitive as regards contamination. A particularly beneficial way to avoid contamination from the package material provides that the inventive package is, in accordance with a further preferred embodiment, made from a laminated compound blank material. This ebodiment of the present invention permits to provide a sterile inner compound. Additionally, this further embodiment permits to provide the outside of the inventive package with a layer of the desired aesthetic appearance while not compromising the carrier structure of the material in terms of strength and costs.
In the context of the present invention, terminologies such as “front” and “back” as well as “top” and “bottom” are used for the sake of simplification of the description and are not intended to limit the scope of the present invention, unless explicitly stated.
The inventive package blank referred to above preferably provides that the further closure segment is smaller than the remaining closure segments, to permit, upon complete insertion of the further closure segment into the pocket, abutment of the respective front and back wall segments. This abutment is provided by abutment of at least the edges of the wall segments from which the closure segments extend. Depending on the application of the present invention, the abutment thus provided can also be extended to cover an area of the respective wall segments.
Automatic manufacturing of the blank and the package from the blank requires high speed operations. To meet this requirement, the present invention advantageously further provides that the inventive blank is punched from one piece.
Those skilled in the art will be familiar with the methods of manufacture of the blanks of this invention, whether the blanks are made of plastic, paper or other suitable materials. They will also be able to select suitable methods of folding the blanks, possibly already about the product items to be packaged, and suitable ways of fixing the blank to form a package, which might be by means of adhesive if not welding or hot melt gluing.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention is described in greater detail in the following, by way of purely exemplary embodiments represented schematically in the following drawings, in which:
FIG. 1 shows a plan view of a package blank in accordance with the present invention;
FIGS. 2 to 4 show perspective views of the inventive package blank in sequential manufacturing steps; and
FIG. 5 shows a perspective view of the completed package in accordance with the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the following detailed description of preferred embodiments, similar reference signs are used throughout for the same or corresponding parts of the inventive package and the inventive package blank.
A shipping, presentation and end user package according to the present invention is shown in FIG. 1 in plan view in its configuration after manufacture of the blank. It comprises, in the center of FIG. 1 from the bottom to the top thereof, a front wall segment 10 , a side wall segment 12 , a back wall segment 14 , a further side wall segment 12 and a wall segment attachment flap 16 . To the left of the various wall segments, bottom closure segments 18 are connected by crease or fold lines 50 .
In this connection, it is to be noted that the crease lines or fold lines between the wall segments are adapted to enable folding of adjacent segments along these lines, substantially without deformation of the respective segments. A skilled person will be aware how to best embody this function.
Referring again to FIG. 1, an insertable closure segment 20 is connected to the front wall segment 10 by a crease line 22 . To the right of back wall segment 14 , a crease line 26 connects a pocket segment 24 which, in the completed package, forms the bottom of the pocket of the top closure of the package. A top pocket segment 28 is joined to the bottom pocket segment 24 by a crease line 30 and a pocket attachment segment 32 by a crease line 34 . A tear strip 36 extends, in FIG. 1 from the bottom, from pocket attachment segment 32 , connected to the latter by a perforation 38 . A further perforation 38 on the opposite side of the tear strip 36 connects a closure attachment flap 40 .
As is evident from FIG. 1, the various closure segments 20 , 24 , 28 , 32 are shaped substantially as isosceles rectangular triangles. This preferred embodiment permits easy operation of the package. However, the skilled reader will readily take from the concept described herein how to embody the present invention with different shapes. In particular, it is intended to carry out the inventive concept in trapezoidal and semi-circular configurations.
Turning again to FIG. 1, the skilled reader will note inverted Y-shaped fold lines 54 on the side wall segments 12 . Further crease lines 52 are located on the side wall segments 12 where the Y-shaped crease lines 54 meet the crease lines 56 , 58 ; 60 62 that join the respective side wall segments to the adjacent segments. By placing crease lines 52 appropriately on the side wall segments 12 , storage space within the package can be modified as desired to accommodate different goods to be packaged. The inverted Y-shape of crease lines 54 and their intersection at their bifurcated end with crease lines 52 on the one hand and crease lines 56 , 58 ; 60 62 on the other hand enables relative movement of the front wall segment 10 towards and away from the back wall segment 14 , as will be described in more detail below.
In this connection, it is to be noted that the inverted Y-shaped design permits this relative movement without affecting the storage space defined between crease lines 50 and 52 .
Now with reference to FIG. 2, an intermediate step of manufacturing the package 100 from the blank 1 is depicted. Relative to FIG. 1, the wall segment attachment flap 16 was folded along fold line 62 into a right angle relative to the adjacent side wall segment 12 which, in turn, was folded along crease line 60 into a right angle relative to back wall segment 14 . Similarly, the front wall segment 10 was folded along crease line 56 into a right angle relative to its adjacent side wall segment 12 which, subsequently, was folded along crease line 58 so that the free edge of front wall segment 10 overlies wall segment attachment flap 16 . Prior to folding, glue spots 68 were applied to front wall segment 10 to enable it to attach to wall segment attachment flap 16 (see FIG. 1 ). Although three spots of adhesive are depicted in FIG. 1, it is to be noted that the shape and arrangement of the “glue spots” can be modified as long as they serve the function of attachment. Naturally, in case a waterproof container is to be achieved, a skilled person will choose a means of attachment continuous and contiguous along the edge of front wall segment 10 . As previously mentioned, other means of attachment are also contemplated, for example welding, hot melt gluing or heat sealing.
In the disposition depicted in FIG. 2, the bottom closure segments 18 have also been provided with glue spots and folded into a bottom closure, in a conventional manner.
In the erected state of the package depicted in FIG. 2, it can clearly be seen that the insertable closure segment 20 is located above bottom pocket segment 24 . Arrows A in FIG. 2 indicate progress from the disposition shown in FIG. 2 to that shown in FIG. 3 .
In particular, arrows A indicate how the side walls 12 are pressed towards the interior of the package and fold along crease lines 54 , 52 to assume the shape depicted in FIG. 3 . The region of front wall 10 adjacent to the insertable closure segment 20 and the corresponding region of the back wall segment move towards one another until crease lines 22 and 26 contact one another in edge to edge abutment.
Referring now to FIG. 3, it is evident to the skilled reader that the insertable closure segment 20 overlies the bottom pocket segment 24 . The congruent shape of the insertable closure segment 20 and the bottom pocket closure segment 24 enables intimate surrounding contact in the closed disposition of the package. This intimate contact supplements the form-locking effect by means of congruent shapes with a force-locking effect by means of friction generated between the pocket segments 24 , 28 and the further closure segment 20 , so that the latter is securely held in the pocket, in the closed disposition of the package.
Arrow B in FIG. 3 indicates a subsequent manufacturing step progressing from the disposition show in FIG. 3 to that of FIG. 4 . In FIG. 3 the top pocket segment 28 is folded along its corresponding fold line ( 30 in FIG. 1) to lie in a coplanar manner on top of the insertable closure segment 20 . Top pocket segment 28 and insertable closure segment 20 are substantially free of any attachment means so that relative movement of the insertable closure segment 28 into and out of the pocket to be formed is enabled.
In FIG. 4, a subsequent manufacturing step is shown. In particular, glue spots 64 and 66 are applied to pocket attachment segment 32 and closure attachment flap 40 , respectively. Again, the skilled reader will readily be aware of different means of attachment.
Subsequently, pocket attachment segment 32 with tear strip 36 and closure attachment flap 40 are folded in the direction of arrow C along the corresponding crease line ( 34 in FIG. 1 ). The completed disposition of the package depicted in FIG. 5 results.
On account of glue spots 64 , pocket attachment segment 32 is attached to top pocket segment 28 and, consequently, completes by attachment the pocket between segments 24 and 28 in intimate contact around the insertable closure segment 20 . Further, on account of glue spot 66 , closure attachment flap 40 is attached to front wall 10 and, consequently, prevents the insertable closure segment 20 from sliding out of the pocket thus formed.
In order to open the package, tear strip 36 is gripped at its rounded gripping end 37 and torn off in the direction of arrow D which separates closure attachment 40 from pocket attachment segment 32 .
Consequently, the insertable closure segment 20 is free to be extracted from the pocket formed by bottom pocket segment 24 and top pocket segment 28 , by moving front wall segment 10 and back wall segment 14 toward and away from another. This relative movement is enabled by crease lines 54 and 52 in side wall segments 12 .
The dimensions, in the figures only schematically represented, of the side wall segments 12 relative to the insertable closure segment 20 and its corresponding pocket permit relative movement between the front wall and the back wall segments to an extent until the side wall segments 12 near crease lines 54 , 52 are straightened out. In this disposition, the tip of the insertable closure segment 20 is released from the top pocket segment 28 but still rests on the bottom pocket segment 24 or, alternatively, the back wall segment 14 . Consequently, the package can be fully opened and is accessible. For reclosing the package, the tip of the insertable closure segment 20 can be brought into contact with the back wall segment 14 or the bottom pocket segment 24 and easily slid back into the pocket.
Resilient materials properties of the package blank permit relative movement between the front wall and the back wall segments substantially without deformation thereof. Further, these properties assist in providing the inventive package with a pleasant aesthetic appearance so that, in the closed disposition of the package, the top closure segments are aligned perpendicularly to the bottom closure 18 and the inclined parts of the front wall and the back wall segment are arranged symmetrically.
Additional embodiments of the invention can be provided with e.g. tape on the extended part of closure segment 32 , which is glued onto a corresponding portion of the package, so that it is releasable in an easy manner for the consumer, as a tamper-proof closure. Other modifications of the tamper-proof closure could be provided by a slit or slot along crease line 22 , in which a tongue-like element at the margin of closure segment 32 is insertable, or a releasable glue spot between closure segments 20 and 28 . Naturally, other glue spots as illustrated can be provided on opposing package walls.
Further embodiments and advantages of the inventive package and the inventive package blank are defined in and by the various combinations of the following claims. | In order to provide a package which is inexpensive to manufacture, sufficiently stable to protect the contents of the package and repeatedly and consistently openable and closeable, a package and a blank therefor is disclosed. The blank comprises front wall ( 10 ) , back wall ( 14 ) and side wall ( 12 ) segments, and the front and the back wall segments extend into congruent closure segments ( 20, 24, 32, 28 ). At least two ( 24, 26 ) of the closure segments are arranged to be foldable on top of one another to form a pocket with one open side ( 26 ) At least a further one of the closure segments ( 20 ) is arranged to be insertable into the pocket from the open side thereof in such a manner as to permit repeatable opening and closing of an end of the package. | 1 |
BACKGROUND OF THE INVENTION
This invention relates to an improved filter aid material. More particularly, this invention relates to the composition and preparation of an improved filter aid comprised of expanded comminuted pumicite particulate. These particulates are to be used for clarifying and dehydrating the soiled solvent used in drycleaning operations.
Heretofore, the solvent used in drycleaning operations has been clarified and dehydrated by various means such as processes of filtration, the use of precipitation by various chemical reagents, or diassociation. Various experimental tests have shown, however, that in practically no case is the effluent perfectly free of moisture and foreign matter. Thus, the "washing" of the solvent results in only a partially clean solvent and, hence, subsequently there may be only a less than optimal drycleaning accomplished because the solvent itself is not free of foreign matter. Also in the past, various experiments and practices have endeavored to use centrifugal separators in order to separate suspended impurities and moisture. It was found, however, that a gelatinous residue would remain, this being formed by the moisture in the goods being cleaned emulsifying with a percentage of the soaps and oils liberated in numerous cases with the soap used in drycleaning. The residue would hold finely divided solids matter in colloidal state and removal of such residue by mechanical means was found to be substantially impossible.
Other improvements in the process of "washing" the solvent used in drycleaning operations has included the use of diatomaceous earths and compositions of diatomaceous earths which are constructed to filter the cleaning solvent. These compositions commonly are known to have various adsorbents prepared in conjunction with the diatomaceous earths and commonly include alumina, metal silicates, ground or fiberous asbestos, metal stearaets, sawdust, cellulose powder, starch and/or various powdered synthetic polymers.
In more recent times, commercial filter aids have been manufactured from particulates of naturally occuring glass of igneous origin that will expand when heated to yield a light, cellular particle. The heated and expanded form of this particulate is commonly known in the trade as "perlite". In strict geological usage, this term is restricted to a single variety or specie of volcanic glass. Perlite usually is brittle and friable. It rarely has a silica content greater than 70% and a combined water content is generally present in the range of 2 to 5%. Technically, acid volcanic glasses containing less combined water than perlite are classed as obsidians, and those containing more combined water are classed as pitchstone.
The manufacture of perlitic particles requires their introduction into a flame so as to cause expansion under a controlled temperature in the range of 1600° F., the subsequent softening of the glass being coincidental with the volatilization and release of the combined water causing the particles to quickly expand or puff up to an aggregate many times their original volume. However, dependent upon it's origin, the perlite minerals differ markedly in the time and temperature necessary for expansion, the controlled temperatures varying generally between 1400° and 1900° F. Likewise, the relative chemical constituancy of naturally occuring perlite is extremely variable with a wide range of temperatures necessary to accomplish expansion of the particulate. Due to the inconsistant and variable range of chemical composition in naturally occuring perlite, the ultimate particle that is produced is very inconsistant insofar as it's reliability for the purpose of solvent cleaning is concerned. It has been found, for example, that perlite, though being inconsistently satisfactory as a filter, that the clarity of the filtrate is inferior to the clarity of the filtrate obtained when other types of filter aids are used. Moreover, perlite filter products produced to date have been characterized by their inability to function as high flow rate filter aids. As a result, it is the common consensus that they have generally been commercially rejected in the drycleaning industry as an effective and reliable filter aid.
DESCRIPTION OF THE INVENTION
Pumicite Filter Aids
This invention pertains to the discovery and utilization of pumicite, a specie of rhyolite, as a compound additive for use in the drycleaning trade for "washing" the cleaning solvent.
In the drycleaning trade, the term "non-volatile matter" commonly refers to perspiration, salt, oil and grease and other dirt which is normally removed from the garments that are cleaned. Excessive non-volatile matter in the cleaning solvent occurs after it is continuously used. When this happens the non-volatile component in the solvent becomes a serious problem because it leads to longer drying time, odor in the garments and swale on some types of materials. Measuring and limiting the non-volatile in the cleaning solvent leads to satisfactory cleaning. It therefore becomes necessary to control the non-volatile residue in the cleaning solvent and although this has been attempted before, such as through the utilization of various filter aids, including the aforementioned perlite filter aids, satisfactory and commercially acceptable filter aids for reliably limiting the non-volatile matter in cleaning solvents has not been accomplished.
The present invention is directed to the use of a specie of volcanic ash for the purpose of cleaning the solvent. This volcanic ash, broadly termed rhyolite constitutes a volcanic, mostly effusive, glass like equivalent of granite. The glassy rhyolites include obsidian, pitchstone and pumice (or pumicite). Through microscopic examination it is shown that pumices are actually ash flows and thus better designated as tuffs. These ash flows or tuffs are characterized by a crystalline pattern which is generally thread like or fiberous in shape and are further indicated by thin partitions between the vesicles. Rhyolite and trachyte types of pumices are white and generally have a specific gravity of the glass in the range of 2.3 to 2.4. The crystalline shape of pumicite may be contrasted with perlite, for example, which is teardropped or concentrically onion shaped in form.
The rhyolites are known from all parts of the earth. Obsidian is well developed in Montana and the general locale. Pitchstone, of particular interest as a rock glass containing several percent of combined water, is found in Australia and other localities including Scotland. Pumicite, a frozen emulsion of air and lava of rhyolitic composition occurs in various areas of North America.
Small crystals of various minerals occur in many pumices; the most common are feldspar, augite, hornblend, and zircon. The cavities of pumices are generally elongate or tubular, as indicated above, this being due to their origination from a lava flow of constantly solidifying character. The chemical composition of rhyolite and trachyte pumices generally includes about 75% silica. For purposes of the invention described herein, however, it is desirable to use pumices containing silica content in the range of 80% or more. Specifically, expanded pumicite, which is described hereinafter, constitutes a volcanic dust comprised of a silicate rather than a silica. When expanded, the pumicite changes from it's flat irregular particles or shards to countless tiny glass-sealed hollow spheres or air cells increasing in volume from ten to fifteen times it's original size. The preferred pumicite composition includes silicon dioxide (SiO 2 ) in the range of 80% or more, iron oxide (Fe 2 O 3 ) in the range of 2% and trace quantities of sulfur trioxide (SO 3 ) and magnesium oxide (M g O) of about 3%. Moisture content comprises about 3% maximum. The physical form of pumicite is an extremely fine white powder and is chemically inert. It's thermal conductivity (K value) is less than .3 BTU per hour per square foot per degree Fahrenheit per in. (75° F. mean). It has a water absorption characteristic in the range of 700 to 800 pounds per 100 pounds. Pumicite, which is expanded in accordance with the explanation set forth hereafter, has a density of from 4.8 to 6 pounds per cubic foot. The expanded material does not require grinding since it is in the size range of 325 mesh, while retaining the micro-spherical configuration of the particle. The extremely fine pulverulent of pumicite substantially exceeds other forms of rhyolites including obsidian and pitchstone. Its pulverulence substantially exceeds perlite also. This is the case because pumices, as mentioned above, are actually ash flows and, by contrast to the other rhyolites, such as, obsidian and pitchstone are better designated technically as "tuffs". These tuffs are frequently so light as to be present in the atmosphere as volcanic dust.
In preparing the pumicite filter aid of the invention, the raw material or pumicite, is received in sand like form having uniform consistency and of mesh size in the area of 10 to 30. This raw material is introduced into a screw type drier having an internal temperature in the range of 600° F. The raw pumicite material moves through the drier so as to extract substantially all moisture content. The dried pumicite is then removed to a bin or other storage facility or in the alternative may be directly conveyed to the expander tube or "popper" as it is more commonly known. Here there is provided a feed pipe into the expander tube. Adjacent to the feed pipe is generally provided a gas jet directed into the expander tube. The flame of the gas jet should generally be in the temperature range of 2700° F. The raw pumicite material is introduced into the feed pipe and passed over the flame on it's way into the expander tube. Softening of the glass occurs coincidental with volatilization. Exposure to the elevated temperature produces the release of combined water in the particulate and immediately produces an expansion or puffing of the particulate up to an aggregate that is many times the original volume. During the expanding operation there is a substantial loss in density and the forming of a glassy type surface on the tiny hollow spheres. The expanded or bloated pumicite has a density in the range of 6 pounds per cubic foot. The heated material is then subjected to a fast cooling by permitting it to fall through a cooler, gaseous atmosphere so that the particles do not agglomerate while hot and plastic. Generally, the pumicite is dropped through a vertically directed flame and gathered in a collection system. The expanded material does not require grinding since it is in the size range of 300 mesh, the spherical configuration of the particles being retained.
As a filter aid, the expanded pumices or tuffs of the invention are markedly superior when compared to other commonly known solvent filter aids. By comparison to perlite, for example, the expended pumicite is characterized by the following specific advantages:
1. It makes distillation of the solvent unnecessary.
2. It can be used effectively in petroleum solvent or in perchlorethylene.
3. In substantially all experimental cases, it has increased the flow rate and reduced filter pressure more effectively than other filter aids.
4. It does not remove the soap charge from the cleaning solvent.
5. It removes rancid odor from solvent.
6. Expanded pumicite is found to remove objectionable fatty acids.
7. Expanded pumicite is further found to remove sufficient moisture to give clothes a softer feel, less wrinkles. Clothes are easier to press.
8. Expanded pumicite has been found, in experimental and actual use to reduce the NVR (Non-Volatile Ratio) to a safe operating level, well below the 11/2% recommended, when properly used. More particularly, there is found to exist an oil absorption characteristic in the range of 500 pounds per one hundred pounds.
It should be understood that variations and modifications to the specifics of the invention set forth may be made without departing from the spirit hereof. It is also to be noted that the scope of the invention is not to be interpreted as limited to the specific embodiments disclosed herein but only in accordance with the appended claims, when read in light of the foregoing description. | This invention relates to the use of a limited specie of glassy rhyolite, specifically pumicite as a filter aid for the cleaning of solvent in the drycleaning industry. The invention is particularly directed to the new and unexpected results accruing from the use of pumicite for accomplishing extremely low, non-volatile levels in the solvent and for also removing objectionable fatty acids and odor from the solvent while simultaneously making its distillation unnecessary and removing sufficient moisture to give clothes a softer feel, and fewer wrinkles. | 3 |
FIELD OF THE INVENTION
[0001] The invention relates to a bearing arrangement for supporting a shaft on a connecting structure, the bearing arrangement comprising a backup bearing.
BACKGROUND
[0002] In a bearing arrangement for supporting a shaft on a connecting structure the use of a backup bearing is known from experience, the backup bearing comprising a bearing ring, the bearing ring of the backup bearing forming a backup bearing gap with the shaft during the normal function of the bearing and in a load case, specifically in the event of failure of a bearing, comes into contact with the shaft. A housing with the bearing and the backup bearing is then fastened in the bore of a bearing support on a connecting structure. If the bearing—for example a magnetic bearing—fails, that is to say the load case occurs, the bearing ring of the backup bearing, which during the normal operation of the bearing includes the backup bearing gap in relation to the shaft, comes into contact with the shaft rotating at high speed, wherein high forces occur in the backup bearing which are concentrated on an only small section of the circumference of the bearing ring of the backup bearing. In this region, rolling elements or the running track of the bearing ring of the backup bearing can be damaged.
[0003] EP 1 395 759 B1 describes a bearing arrangement for supporting a shaft on a housing, comprising a magnetic bearing supporting the shaft, and a backup bearing, the bearing ring of the backup bearing including a backup bearing gap in relation to the shaft during the normal operation of the magnetic bearing. If the magnetic bearing fails, the shaft drops into an inner ring of the backup bearing. In order to avoid high axial and radial forces, a first intermediate element is fastened on the housing and a second intermediate element is fastened on an outer ring of the backup bearing, the second intermediate element having a radial groove in which engages a radial projection on the first intermediate element. Between the projection and the groove provision is made for damping elements which are to suppress a force transfer from the backup bearing to the rigid housing.
SUMMARY
[0004] It is the object of the invention to disclose a bearing arrangement with a backup bearing, in which the forces which occur in the backup bearing in the load case can be absorbed in a better way.
[0005] For the bearing arrangement which is referred to in the introduction this object is achieved according to the invention by provision being made in the housing for a slot which extends essentially in the circumferential direction and is formed as a penetration.
[0006] The penetration extends essentially in the circumferential direction so that a curved slot is formed. The penetration is directed for example essentially parallel to the axis of the bearing between axially spaced apart end faces of the housing.
[0007] The penetration effects a material weakening so that the shaft, which drops into the backup bearing, brings about an elastic yielding of the material of the housing between the penetration of the curved slot and the bearing ring of the backup bearing. The bearing ring of the backup bearing, dropping into the housing, is locally cushioned in the process in an elastically sprung manner in the region of the slot in the load case. In particular, that surface section in the circumferential direction of the bearing ring of the backup bearing which bears the weight of the shaft is increased so that the weight of shaft which drops into the backup bearing is distributed over an increased surface region of the bearing ring of the backup bearing, as a result of which localized peak loads of the backup bearing are suppressed. The penetration, which extends only sectionally in the circumferential direction, especially reduces the rigidity of the bearing arrangement in a directed manner.
[0008] As a result of the elastic yielding of the material of the housing between the penetration and the shaft in the load case a so-called backward whirl can also be suppressed, that is to say a wandering of the shaft along the bearing ring of the backup bearing which faces the shaft, during which the shaft at high rotational speed moves along the inner generated surface of the inner bearing ring of the backup bearing. While moving along, the bearing ring of the backup bearing which faces the shaft experiences a high acceleration so that high forces and also a slip can occur in the backup bearing, which in each case could damage said backup bearing.
[0009] It is preferably provided that the penetration of the slot is produced by wire-guided electrical discharge machining, laser jet cutting or water jet cutting so that the penetration can be formed as a linearly extending penetration of only small gap width. The gap width of the slot in this case is typically less than approximately 2.0 millimeters, for example only approximately 0.25 millimeters, and basically corresponds to the amount of deflection of the backup bearing with the shaft in the housing in the load case.
[0010] It is preferably provided that the backup bearing has a load direction, and that the penetration extends essentially symmetrically to the load direction. The load direction corresponds, for example, to the direction of the gravity force. If two or more load directions are to be assumed, more than one penetration may be provided, especially a penetration for each load direction in each case, the penetrations being arranged in a staggered manner along the circumference and also radially with regard to the rotational axis of the shaft.
[0011] It is preferably provided that the sectionally provided penetration extends over a circumferential angle of between approximately 50° and approximately 180°, especially of approximately 120°. Due to the larger circumferential angle, in the load case the force is distributed over a plurality of rolling elements or over a larger circumferential section of the bearing ring of the backup bearing, wherein especially high forces of the load case which are to be anticipated are absorbed by a penetration which extends over a large circumferential angle.
[0012] It is preferably provided that the penetration has an essentially constant distance from a rotational axis of the bearing ring of the backup bearing, the penetration being formed as a circular arc. It is understood, however, that other progressions of the penetration in the circumferential direction can also be provided so that the penetration, in a plan view of the bearing arrangement in the direction of the rotational axis of the shaft, can be formed as a polygonal progression or as a sine wave, for example.
[0013] It is preferably provided that in an overload case the walls of the penetration butt against each other. In this case, the maximum possible elastic deformation is utilized but at the same time a damaging plastic deformation of the housing is avoided. In this case, a load case in which an exceptionally high increase of impact occurs is to be understood by an overload case.
[0014] It is preferably provided that a gap width of the penetration of the slot increases towards at least one end section of the penetration. As a result of the increase of the gap width of the slot, an occurrence of notch stresses at the ends of the slot, which could damage the housing in the load case, is prevented.
[0015] It is preferably provided that the penetration at at least one end section is curved away from the shaft. The curvature of the slot also brings about a prevention of notch stresses in the load case.
[0016] Further advantages and features are gathered from the dependent claims and also from the subsequent description of a preferred exemplary embodiment of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] The invention is described and explained in more detail in the following text with reference to the attached drawings.
[0018] FIG. 1 shows a plan view of a housing which is part of an exemplary embodiment of a bearing arrangement according to the invention,
[0019] FIG. 2 shows in a detail a sectioned view of the housing from FIG. 1 along the line of intersection ‘A-A’ in FIG. 1 , and
[0020] FIG. 3 shows the detail ‘A’ from FIG. 2 in enlarged view.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0021] FIG. 1 shows a plan view of a housing 1 which is part of a bearing arrangement for the rotatable support of a shaft, which is not shown, on a connecting structure, which is not shown. In this case, an outer surface of the housing 1 is fastened in a bore of a bearing support. The shaft is rotatably supported in relation to the housing 1 and also in relation to the connecting structure by means of a bearing, especially by means of a magnetic bearing, which is not shown.
[0022] The bearing arrangement furthermore comprises a backup bearing, which is not shown, which is formed as a rolling bearing, the inner ring of which is fastened on the shaft and the outer ring of which includes a backup bearing gap in relation to an inner surface of the housing 1 , provided that the supporting of the shaft is ensured by means of the magnetic bearing. If the magnetic bearing fails, that is to say the load case occurs, the shaft drops under its own weight into the backup bearing so that the backup bearing is pressed by the outer ring onto an inner surface 15 of the housing 1 ( FIGS. 2 , 3 ), which in this case supports the shaft at least temporarily.
[0023] The basically circular housing 1 has a rear section 2 which is arranged beneath the plane of the paper, wherein in the rear section 2 provision is made for a circumferential sequence of blind holes, of which one is provided with the designation ‘ 3 ’. Fastened in the blind holes 3 are springs which act upon the outer ring of the backup bearing in the axial direction, that is to say in a direction which is perpendicular to the plane of the paper, so that the backup bearing, which is designed as a double-row angular-contact ball bearing with common inner ring for both running tracks of the spherical rolling elements, is mechanically pretensioned. The housing 1 has a front section 4 , located above the plane of the paper, in which provision is made for a similarly circumferential sequence of holes, of which one is identified by the designation ‘ 5 ’, the holes 5 being formed for the fastening of a cover. In the region of the front section 4 , provision is furthermore made for a circumferential sequence of ventilation holes, of which one is identified by the designation ‘ 6 ’, and also a circumferential sequence of fastening holes for the fastening of the housing 1 on the connecting structure, one of the fastening holes being identified by the designation ‘ 7 ’.
[0024] The circumferential sequence of the holes 5 , of the ventilation holes 6 , of the fastening holes 7 of the front section 4 and also of the blind holes 3 of the rear section 2 of the housing 1 is oriented in each case concentrically to a symmetry axis 8 , the symmetry axis 8 corresponding to the rotational axis of the shaft during normal, undisturbed operation of the magnetic bearing, and also corresponding to the rotational axis of the backup bearing.
[0025] In the body of the housing 1 , provision is made for a slot 9 which extends only sectionally in the circumferential direction of the circular housing 1 and is formed as a penetration, the penetration being directed parallel to the axis 8 , that is to say also parallel to the rotational axis of the magnetic bearing or of the backup bearing and, as a result, perpendicularly to the plane of the paper in FIG. 1 .
[0026] The slot 9 extends over a third of a circle, that is to say over a circumferential angle of 120°, the penetration of the slot 9 being produced by means of wire-guided electrical discharge machining (alternatively to this by means of laser jet cutting or water jet cutting, for example). The circumferential angle of the slot 9 could also assume other values, for example a value of between approximately 50° and approximately 180°.
[0027] The slot 9 has two end sections 10 , 11 , towards which a gap width of the penetration, that is to say of the distance between the opposite sides of the penetration, increases. The gap width of the slot 9 , over a length of approximately 95% of the extent in the circumferential direction, is approximately 0.2 millimeters and increases significantly towards the end sections 10 , 11 . Due to the only small gap width of approximately 0.2 millimeters, in an overload case, that is to say in a load case with a very high increase of impact, the walls of the penetration of the slot 9 butt against each other and therefore the slot 9 is blocked. When the penetration of the slot 9 is being produced, for example by wire-guided electrical discharge machining, the eroding wire is guided back at the end sections 10 , 11 in an arc towards the already produced slot section so that an approximately cylindrical material piece with a basically teardrop-shaped cross-sectional profile is cut out from the body of the housing 1 . It is understood that one of the two end sections 10 , 11 can be provided as an entry hole for the wire, for example as a hole into which the eroding wire is inserted. It is also understood that the wire can be guided back only incompletely when the wire-guided electrical machining is being carried out so that the result is a curved gap, pointing away from the axis 8 , which widens only slightly at the end sections.
[0028] The penetration of the slot 9 is formed inside a recess 12 so that the removal of material is reduced when the penetration is being formed.
[0029] The bearing arrangement with the backup bearing and the housing 1 has a preferred load direction which is provided by the direction of the gravity force acting upon the shaft and which in the view of FIG. 1 acts in the direction of the line of intersection A-A in the direction of the arrow 13 . The slot 9 with the penetration is formed symmetrically with regard to this load direction 13 .
[0030] The penetration of the slot 9 has a constant distance from the rotational axis 8 of the bearing ring of the backup bearing during normal operation of the magnetic bearing so that the slot 9 with the penetration is formed as a circular arc.
[0031] FIG. 2 and FIG. 3 show in each case the housing 1 from FIG. 1 in a detail in a view sectioned along the line A-A. The penetration of the slot 9 is realized from the bottom 14 of the recess 12 to a bottom of a recess on the axially opposite side of the housing 1 with regard to the axis 8 and is guided parallel to the axis 8 and also perpendicularly to the load direction 13 .
[0032] In the case of the previously described exemplary embodiment, in an overload case the walls of the penetration of the slot 9 , lying opposite with regard to the axis 8 , butt against each other. It is understood that provision can be made in the penetration for a filling material, for example a flexible film, which reduces the gap width of the slot or the space between the opposite walls, or a fluid which fills out the gap of the slot, the filling material absorbing the forces which occur in the load case.
[0033] In the case of the previously described exemplary embodiment, it was assumed that the backup bearing gap between the outer ring of the rolling bearing and the inner surface of the housing 1 is basically free. It is understood that a corrugated spring can be arranged between the bearing ring of the backup bearing and the housing 1 , the corrugated spring at least partially absorbing the forces which occur in the load case and being distributed over a larger surface section of the housing.
[0034] In the case of the previously described exemplary embodiment, the penetration of the slot 9 was formed as a circular arc which was also provided in the end sections 10 , 11 . It is understood that the slot in the end sections 10 , 11 can have a curvature pointing away from the shaft or from the axis 8 and in this respect can deviate from the contour of a circular arc.
[0035] Differing from the previously described exemplary embodiment, the slot can also have a progression in the circumferential direction of the housing 1 which deviates from a circular arc, for example the distance from the axis 8 can periodically vary in the circumferential direction so that the slot has a sine-shaped progression, for example. Again, alternatively to a periodic progression in the circumferential direction, the slot can be formed as a polygonal progression.
LIST OF REFERENCE NUMBERS
[0000]
1 . Housing
2 . Rear section of the housing 1
3 . Blind hole
4 . Front section of the housing 1
5 . Hole
6 . Ventilation hole
7 . Fastening hole
8 . Axis
9 . Slot
10 . End section
11 . End section
12 . Recess
13 . Load direction (arrow)
14 . Bottom
15 . Inner surface of the housing 1 | A bearing arrangement for mounting a shaft on a connection structure, the arrangement including a housing ( 1 ), a bearing which supports the shaft, and a backup bearing which includes a bearing ring that makes contact with the housing ( 1 ). According to the invention, the problem of providing a bearing arrangement which includes a backup bearing and allows the forces which arise in a loaded state to be better absorbed in the backup bearing, is solved by a slit ( 9 ) being provided in the housing ( 1 ), this slit being designed as an opening and extending substantially in a circumferential direction. | 5 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an image display apparatus, and more particularly to an image display apparatus which allows improvement in response speed at data writing for a display in a black level without being affected by constraint in area per pixel.
2. Description of the Related Art
Conventionally, proposals have been made to realize an image display apparatus provided with organic light-emitting diodes (OLEDs) which emit light by recombination of positive holes and electrons injected into a light emitting layer.
FIG. 14 is a diagram of a structure of a pixel-circuit corresponding to one pixel in the conventional image display apparatus. The pixel circuit of FIG. 14 includes an OLED 1 , a switching element 2 , a driver element 3 , a switching element 4 , a switching element 5 , a gate signal line 6 , a gate signal line 7 , a source signal line 8 , an electroluminescent (EL) power source line 9 , and a storage capacitor 1 Cs. It should be noted that in a first part of the description on the conventional image display apparatus, the pixel circuit does not include a capacitor 1 Ct (shown as surrounded by a broken line).
The OLED 1 has characteristics of emitting light when a potential difference equal to or higher than a threshold voltage is generated between an anode and a cathode to cause an electric current flow therein. Specifically, the OLED 1 includes at least an anode layer and a cathode layer formed from a material such as Al, Cu, and Indium Tin Oxide (ITO), and a light emitting layer formed from an organic material such as phthalcyanine, tris-aluminum complex, benzoquinolinolato, and beryllium complex, and functions to emit light by recombination of positive holes and electrons injected into the light emitting layer.
The switching elements 2 , 4 , and 5 , and the driver element 3 are thin film transistors (TFT).
In the pixel circuit with the above-described structure, in a data writing period the switching elements 4 and 5 are turned ON whereas the switching element 2 is turned OFF. Then, when a programming electric current i d is applied via the source signal line 8 , the electric current i d flows through a path formed by the EL power source line 9 , the driver element 3 , the switching element 4 , and the source signal line 8 in this order. A gate potential V G of the driver element 3 is determined according to the amount of the electric current i d flowing along the source signal line 8 . Thus, electric charges of an amount corresponding to the gate potential V G are accumulated in the storage capacitor 1 Cs.
In a light emitting period following the data writing period, the switching elements 4 and 5 are turned OFF whereas the switching element 2 is turned ON. Then, an electric current i d of the same amount as the programming electric current applied in the data writing period flows through the OLED 1 . If the amount of electric current i d flowing through the source signal line 8 changes in the data writing period, the amount of electric charges accumulated in the storage capacitor 1 Cs changes, thereby changing the amount of electric current i OL in the light emitting period to change the luminance of the OLED 1 .
When the OLED 1 performs an image display apparatus in a black level, for example, the amount of the electric current i d flowing through the source signal line 8 , i.e., an amount of an electric current for the black level display, is in the range of 1.5 nA to 29 nA. When the OLED 1 performs an image display apparatus in a white-level, the amount of the electric current i d flowing through the source signal line 8 , i.e., an amount of an electric current for the white level display, is approximately in the range of a few 100 nA to a few μA depending on an efficiency of the OLED 1 , panel luminance, and resolution.
The display in the black level with a small programming electric current i d causes rounding of the waveform of i d due to a time constant defined by a resistance of the driver element 3 and a parasitic floating capacitance of the source signal line 8 , whereby the amount of the electric current i d does not reach a predetermined level immediately. To deal with this inconvenience, the conventional image display apparatus is required to have a long data writing period, resulting in a slow response speed.
To eliminate such inconvenience, the gate of the driver element 3 and the gate of the switching element 4 of FIG. 14 may be connected (capacitance-coupled) via the capacitor 1 Ct (shown in broken line) to improve the response speed as is conventionally proposed.
With this proposed structure, in the data writing period the switching elements 4 and 5 are turned ON whereas the switching element 2 is turned OFF. Then, the electric current i d flows into the source signal line 8 . Specifically, the electric current i d flows along a path formed by the EL power source line 9 , the driver element 3 , the switching element 4 , and the source signal-line 8 , in this order.
In the subsequent light emitting period, the switching elements 4 and 5 are turned OFF whereas the switching element 2 is turned ON. Then, because of the presence of the capacitor 1 Ct, the gate potential V G of the driver element 3 changes according to the potential variation on the gate signal line 6 .
Variation ΔV G of the gate potential V G here can be represented as ΔV G =ΔV gg ×(C gs +Ct)/(C gs +Ct+Cs) where C gs represents a gate-to-source capacitance of the switching element 5 . Here, Ct is a capacitance of the capacitor 1 Ct, Cs is a capacitance of the capacitor 1 Cs, and ΔV gg is a variation in potential on the gate signal line 6 .
At the transition from the data writing period to the light emitting period, the potential on the gate signal line 6 rises to increase the gate potential V G of the driver element 3 . The amount of increase varies according to the three values of capacitance. Since C gs is determined based on the size and the structure of the switching element 5 , elements that actually control the amount of increase are the capacitor 1 Ct and the storage capacitor 1 Cs.
Further, the increase in the gate potential of the driver element 3 causes the drain current decrease. The drain current of the driver element 3 drops by an amount corresponding to the variation ΔV G . Hence, the amount of the electric current i OL flowing through the OLED 1 is smaller than a predetermined amount when the switching element 2 is turned ON.
In other words, a larger amount of the electric current i d than the predetermined amount is required to be applied to the transistor 3 in the data writing period in order to cause electric current flow of the predetermined amount in the OLED 1 in the light emitting period. The amount of the electric current i d can be increased if the storage capacitor 1 Cs is smaller or the capacitor 1 Ct is larger.
When the storage capacitor 1 Cs is smaller, the capacity to retain the electric charges decreases, which makes fluctuation in the gate potential V G of the driver element 3 more likely. Thus, since the smaller storage capacitor 1 Cs is not a realistic solution, the larger capacitor 1 Ct is preferable.
When the amount of the electric current i d flowing through the source signal line 8 increases, an apparent resistance of the driver element 3 can be reduced. Then, the time constant, which is a product of the resistance and the floating capacitance of the source signal line 8 , decreases, to shorten the time required for the change of the electric current i d to the predetermined amount in the data writing period, whereby the response speed can be improved.
FIG. 15 shows a relation between the electric current i d flowing through the source signal line 8 and the electric current i OL flowing through the OLED 1 at various capacitance values of capacitor 1 Ct, provided that the amplitude of the gate signal line 6 is 14 V. If the capacitance ratio ((C gs +Ct)/(C gs +Ct+Cs)) is 0.03, the amount of the electric current i d required to flow through the source signal line 8 is approximately five times the amount of the electric current i OL flowing through the OLED 1 . When the capacitance of 1 Ct is further increased, the ratio of the electric current i d flowing through the source signal line 8 to the electric current i OL flowing through the OLED 1 rises. If the capacitance ratio is 0.8, the amount of the electric current i d is 200 times the amount of the electric current i OL , and if the capacitance ratio is increased up to 0.9, the amount of the electric current i d is 500 times the amount of the electric current i OL .
With the increase in the amount of the electric current i d flowing through the source signal line 8 , the resistance of the driver element 3 decreases, and the time required for the attainment of the predetermined amount of electric current is shortened. Hence, a higher capacitance of 1 Ct results in more effective improvement of the response speed at data writing for the black level display.
The conventional technique as described above is disclosed, for example, in Japanese Patent Application Laid-Open No. 2003-140612.
As described above, in the conventional image display apparatus, a higher capacitance of 1 Ct is more effective for the improvement of the response speed at data writing for the black-level display. The higher capacitance of 1 Ct can be realized with a larger area of the capacitor 1 Ct.
In the conventional image display apparatus, however, since there is a limit to an area usable for one pixel, the size of the capacitor 1 Ct also is under a certain constraint. Hence, though the improvement in response speed is theoretically possible in the conventional image display apparatus, because of the actual manufacturing constraint, a remarkable improvement can hardly be achieved concerning the response speed at data writing for the black-level display.
SUMMARY OF THE INVENTION
An image display apparatus according to one aspect of the present invention includes a light emitting element that emits light depending on an injected electric current; a driver that includes at least a first terminal and a second terminal, and controls the light emitting element based on a potential difference, applied between the first terminal and the second terminal, of a level higher than a predetermined threshold; a storage capacitor that serves to retain a potential on the first terminal of the driver; and a controller that changes the potential on the first terminal via the storage capacitor at writing of electric data current corresponding to a display in a black level.
According to the image display apparatus of the present invention, the potential on the first terminal is changed via the storage capacitor at writing of electric data current for the black-level display. Thus, the amount of electric current for data writing increases, and unlike the conventional image display apparatus, the improvement in the response speed at data writing for the black-level display can be achieved without being affected by the area constraint per pixel.
A method according to another aspect of the present invention is of driving an image display apparatus which includes a light emitting element, a driver electrically connected to the light emitting element, and a capacitor having a first electrode and a second electrode which is connected to a gate of the driver. The method includes controlling a potential on the gate by changing a potential on the first electrode of the capacitor at writing of electric data current corresponding to a display in a black level.
The above and other objects, features, advantages and technical and industrial significance of this invention will be better understood by reading the following detailed description of presently preferred embodiments of the invention, when considered in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A is a circuit diagram of a pixel circuit corresponding to one pixel in an image display apparatus according to a first embodiment of the present invention, and FIG. 1B is a timing chart of the pixel circuit;
FIG. 2A is a diagram shown to describe a data writing operation in the first embodiment, and FIG. 1B is a timing chart of the pixel circuit in the data writing operation;
FIG. 3A is a diagram shown to describe a light emitting operation in the first embodiment, and FIG. 3B is a timing chart of the pixel circuit in the light emitting operation;
FIG. 4A is a diagram shown to describe a first phase of calculation of an average mobility parameter β ave in the first embodiment, and FIG. 4B is a timing chart of the pixel circuit in the first phase of the calculation;
FIG. 5A is a diagram shown to describe a second phase of calculation of the average mobility parameter β ave in the first embodiment, and FIG. 5B is a timing chart of the pixel circuit in the second phase of the calculation;
FIG. 6A is a diagram shown to describe a third phase of calculation of the average mobility parameter β ave in the first embodiment, and FIG. 6B is a timing chart of the pixel circuit in the third phase of the calculation;
FIG. 7A is a diagram shown to describe a fourth phase of calculation of the average mobility parameter β ave in the first embodiment, and FIG. 7B is a timing chart of the pixel circuit in the fourth phase of the calculation;
FIG. 8 is a graph of a relation between a electric data current i data and an electric current i OLED in the first embodiment;
FIG. 9A is a circuit diagram of a pixel circuit corresponding to one pixel in an image display apparatus according to a second embodiment of the present invention, and FIG. 9B is a timing chart of the pixel circuit;
FIG. 10A is a circuit diagram of a pixel circuit corresponding to one pixel in an image display apparatus according to a third embodiment of the present invention, and FIG. 10B is a timing chart of the pixel circuit;
FIG. 11A is a circuit diagram of a pixel circuit corresponding to one pixel in an image display apparatus according to a fourth embodiment of the present invention, and FIG. 11B is a timing chart of the pixel circuit;
FIG. 12A is a diagram shown to describe a data writing operation in the fourth embodiment, and FIG. 12B is a timing chart of the pixel circuit in the data writing operation;
FIG. 13A is a diagram shown to describe a light emitting operation in the fourth embodiment, and FIG. 13B is a timing chart of the pixel circuit in the light emitting operation;
FIG. 14 is a circuit diagram of a pixel circuit corresponding to one pixel in a conventional image display apparatus; and
FIG. 15 is a graph of a relation between an electric current flowing through a source signal line and an electric current flowing through an OLED in the conventional image display apparatus.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Exemplary embodiments of an image display apparatus and a method of driving the image display apparatus according to the present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the present invention is not limited to the embodiments.
FIG. 1A is a circuit diagram of a pixel circuit corresponding to one pixel in an image display apparatus according to a first embodiment of the present invention, and FIG. 1B is a timing chart of the pixel circuit. The pixel circuit in FIG. 1A includes, an OLED 10 , a switching element 11 , a driver element 12 , a switching element 13 , a switching element 14 , a gate signal line 15 , a gate signal line 16 , a source signal line 17 , a writing control line 18 , an EL power source line 19 , and a storage capacitor 10 Cs. The switching elements and the driver element, which are for example, transistors as shown in the drawings, are not clearly shown whether each element is an n-type or a p-type. However, they should be interpreted as either n-type or p-type according to the description below.
The OLED 10 , the switching element 11 , the driver element 12 , the switching element 13 , the switching element 14 , the gate signal line 15 , the gate signal line 16 , the source signal line 17 , the EL power source line 19 , and the storage capacitor 10 Cs in FIG. 1A correspond to the OLED 1 , the switching element 2 , the driver element 3 , the switching element 4 , the switching element 5 , the gate signal line 6 , the gate signal line 7 , the source signal line 8 , the EL power source line 9 , and the storage capacitor 1 Cs in FIG. 14 , respectively. The switching elements 11 , 13 , and 14 and the driver element 12 are p-type transistors.
The image display apparatus according to the first embodiment is different from the conventional image display apparatus in that the writing control line 18 is provided and connected to the storage capacitor 10 Cs as shown in FIG. 1A .
Next, a display in a black level will be described. Following operations are performed under control of a controller (not shown). For the display in the black level, a data writing operation is first performed corresponding to a data writing period t 1 of FIG. 2B . In the data writing period t 1 , the potential on the gate signal line 15 is at a high level, the potential on the gate signal line 16 is at a low level, and the potential on the writing control line 18 is at a low level (V L )
The switching element 11 is turned OFF as shown in FIG. 2A whereas the switching elements 13 and 14 are turned ON. The gate potential V g of the driver element 12 can be represented by Equation (1):
V g = V DD - V T - 2 i data β L ( 1 )
where V DD is a power source potential applied to the EL power source line 19 , V T is a threshold voltage corresponding to a driving threshold of the driver element 12 , β L is a value in proportion to carrier mobility in the driver element 12 (hereinafter referred to as a mobility parameter), and i data is an electric data current represented by Equation (2):
i data =α·i base (2)
The mobility parameter β L can be represented by Equation (3):
β L =( W×L )×μ eff ×C ox (3)
where W is a channel width of the driver element 12 , which is a transistor such as a Metal Oxide Semiconductor Field Effect Transistor (MOS FET), L is a channel length of the driver element 12 , μ eff is a carrier mobility, and C ox is a capacitance of a gate insulation film.
The electric data current i data represented by Equation (1) flows through a path formed by the EL power source line 19 , the driver element 12 , the switching element 13 , the source signal line 17 , and a power source 20 in this order. The electric data current i data is represented by Equation (2) where a is a coefficient, and i base is a black-level electric current.
Even if the electric data current i data is made larger, the electric current i OLED flowing through the OLED 10 at the light emission can be maintained at a level for the black level, since the potential on the writing control line 18 at the data writing is lower by an amount of δV r (described later in detail) than the potential on the writing control line 18 at the light emission of the OLED 10 in the previous process. As shown in FIG. 8 , for example, in the first embodiment the black level can be maintained even when the amount of i data is set to 10 μA, and the response speed is enhanced to approximately ten times that of the conventional image display apparatus (i d =approximately 1 μA; see FIG. 15 ).
Then, a light emitting operation is performed corresponding to a light emitting period t 2 of FIG. 3B . In the light emitting period t 2 , a signal on the gate signal line 15 attains a low level, a potential on the gate signal line 16 is at a high level, a potential on the source signal line 17 is at a high level, and a potential on the writing control line 18 is at a high level (V H ). The potential difference δV r on the writing control line 18 is represented by Equation (4):
δ V r = 2 i base β ave ( 4 )
where β ave is an average of the mobility parameter, i.e., an average value of the mobility parameter β L (see Equation (2)) described above, and i base is the black-level electric current as described above.
The value of δV r can be found as follows. The gate potential V g of the driver element 12 at light emission is found from Equation (5):
V
g
=
V
DD
-
V
T
-
2
i
data
β
L
+
δ
V
r
(
5
)
For the maintenance of the black level, the gate potential V g needs to be at the level of V DD −V T . Hence, a relation of δV r =(2×i data /β L ) 1/2 holds.
Here, since the electric data current i data to be written for the display in the black level is defined as i base , the above expression can be rewritten to another expression δV r =(2×i base /β L ) 1/2 . Since the mobility parameter β L is different for each driver element, a most appropriate value of δV r is also different for each pixel. Hence, theoretically it appears to be preferable to connect a separate writing control line 18 to each pixel and to separately assign a different value of δV r for each pixel. Then, however, the circuit structure of the control line 18 and hence, the manner of driving the same become extremely complicated. Thus, preferably the writing control line 18 is shared among pixels which are arranged in a same line or the writing control line 18 is commonly connected to all pixels so that δV r of the same value is assigned to all pixels.
In order to assign the same δV r to all pixels, the value of β L is also required to be same among all pixels. Hence, the mobility parameter β L of each pixel is replaced with β x . As a result, a relation (2×i base /β x ) 1/2 holds. Preferably the average value β ave of the mobility parameter β is employed as the value of β ave for all pixels as is shown by Equation (4). Alternatively, β x may be set in the range of 0.5β ave ≦β x ≦1.5β ave . Still alternatively, β x may preferably be set in the range of 0.9β ave ≦β x ≦1.1β ave .
As shown in FIG. 3A , the switching element 11 is turned ON, whereas the switching elements 13 and 14 are turned OFF, and the electric current i OLED represented by Equation (6) flows through a path formed by the EL power source line 19 , the driver element 12 , the switching element 11 , and the OLED 10 in this order.
i
OLED
=
β
L
2
(
V
sg
-
V
T
)
2
=
(
i
data
-
β
L
2
·
δ
V
r
)
2
=
(
i
data
-
β
L
β
ave
·
i
base
)
2
=
i
base
(
α
-
β
L
β
ave
)
2
(
6
)
In Equation (6), V sg is a source-to-gate voltage of the driver element 12 , V T is a threshold voltage corresponding to a driving threshold of the driver element 12 . When α is one and β ave is β L in Equation (6), with the substitution of these values into the last part of Equation (6), the value of the electric current i OLED can be given as zero, which means a display in a perfect black level.
As shown in FIGS. 4A and 4B , the average mobility parameter β ave is found after writing of a test electric current i test into all pixel circuits in the image display apparatus, light emission of the OLED 10 , temporal changes of potential on the writing control line 18 , and the calculation of the mobility parameter in each pixel circuit.
Specifically as shown in FIGS. 5A and 5B , when the switching elements 13 and 14 are turned ON and the switching element 11 is turned OFF, the test electric current i test flows through the source signal line 17 . Here, the gate potential V g of the driver element 12 can be represented by Equation (7):
V
g
=
V
DD
-
V
T
-
2
i
test
β
L
(
7
)
Then, when the switching elements 13 and 14 are turned OFF and the switching element 11 is turned ON as shown in FIGS. 6A and 6B , the test electric current i test (t) flows through the OLED 10 to cause light emission of the OLED 10 . Here, the gate potential V g of the driver element 12 can be represented by Equation (8):
V g = V DD - V T - 2 i test β L + δ V r ( t ) ( 8 )
where i test takes a value shown in FIG. 5A .
If, in the light emitting period, the potential difference δV r of the writing control line 18 is changed until the black level is attained at δV r (t) (see Expression (9)), in other words, if the test electric current i test (t) represented by Equation (10) is zero (see Equation (11)) and the OLED 10 does not emit light, the mobility parameter β L of the pertinent pixel circuit can be represented by Equation (12) where δV r (t) is a potential difference at an instant the black level is attained.
δ
V
r
(
t
)
≥
2
i
test
β
L
(
9
)
i
test
(
t
)
=
β
L
2
(
V
sg
-
V
T
)
2
=
(
i
test
-
β
L
2
·
δ
V
r
(
t
)
)
2
(
10
)
i
test
(
t
)
=
0
(
11
)
β
L
=
2
i
test
(
δ
V
r
(
t
)
)
2
(
12
)
In practice, distribution of potential differences dV r (t) (potential differences V1,1−Vn,m) at the transition to the black level can be obtained for each pixel circuit as shown in FIG. 7A . Then, with the substitution of each value of potential difference (V1,1−Vn,m) and a known value of the test electric current i test into δV r (t) of Equation (12), the mobility parameter β L for each pixel circuit is found. Thus, the distribution of the mobility parameter β L can be found for all pixel circuits as shown in FIG. 7B .
Then the average mobility parameter β ave is found based on the distribution of the mobility parameter β L . Specifically, each value (each of β1,1−βn,m) in the distribution of the mobility parameter β L is found and added, and the sum is divided by a number of all pixel circuits (sample number) to provide the average mobility parameter β ave .
As described above, in the first embodiment, the gate potential V g of the driver element 12 is changed via the storage capacitor 10 Cs at writing of electric data current for the display in the black level, to increase the amount of electric current i data for the data writing. Thus, unlike the conventional image display apparatus, the response speed at the data writing for the display in the black level can be improved without being affected by the area constraint per pixel.
In the description of the first embodiment above, the circuit with the structure of FIG. 1 is described. However, the circuit may take a structure shown in FIG. 9A . Hereinbelow, the exemplary circuit of FIG. 9A will be described as a second embodiment. FIG. 9A is a circuit diagram of a pixel circuit corresponding to one pixel in an image display apparatus according to the second embodiment of the present invention, and FIG. 9B is a timing chart of the pixel circuit. In FIG. 9A , the pixel circuit includes an OLED 40 , a switching element 41 , a driver element 42 , a switching element 43 , a switching element 44 , a gate signal line 45 , a gate signal line 46 , a source signal line 47 , a writing control line 48 , an EL power source line 49 , and a storage capacitor 40 Cs.
The OLED 40 , the switching element 41 , the driver element 42 , the switching element 43 , the switching element 44 , the gate signal line 45 , the gate signal line 46 , the source signal line 47 , the writing control line 48 , the EL power source line 49 , and the storage capacitor 40 Cs in FIG. 9 correspond with the OLED 10 , the switching element 11 , the driver element 12 , the switching element 13 , the switching element 14 , the gate signal line 15 , the gate signal line 16 , the source signal line 17 , the writing control line 18 , the EL power source line 19 , and the storage capacitor 10 Cs in FIG. 1 , respectively. The switching elements 41 , 43 , and 44 , and the driver element 42 are n-type transistors.
In the description of the second embodiment above, the circuit with the structure of FIG. 9A is described. However, the circuit may take a structure shown in FIG. 10A and its timing chart shown in FIG. 10B where the circuit does not include the switching element 41 and the gate signal line 46 (third embodiment).
In the description of the first embodiment above, the circuit with the structure of FIG. 1A is described. However, the circuit may take a current-mirror type structure shown in FIG. 11A . The exemplary circuit of FIG. 11A will be described below as a fourth embodiment. FIG. 11A is a circuit diagram of a pixel circuit corresponding to one pixel in an image display apparatus according to the fourth embodiment of the present invention, and FIG. 11B is a timing chart of the pixel circuit. In FIG. 11A , the pixel circuit includes an OLED 60 , a driver element 61 , a switching element 62 , a switching element 63 , a driver element 64 , a gate signal line 65 , a gate signal line 66 , a source signal line 67 , a writing control line 68 , an EL power source line 69 , a power source 70 , and a storage capacitor 60 Cs. The driver elements 61 and 64 form a current mirror circuit. The driver elements 61 and 64 , and the switching elements 62 and 63 are p-type transistors.
Next, the display in the black level will be described. At the display in the black level, a data writing operation is first performed corresponding to a data writing period t 1 in FIG. 12 . In the data writing period t 1 , a potential on the gate signal line 66 is at a low level, a potential on the gate signal line 65 is at a low level, and a potential on the writing control line 68 is at a low level (V L ).
Then, the gate potential V g of the driver element 64 can be represented by Equation (1) described above. The amount of electric data current i data flowing during this period is represented by Equation (2) described above. Similarly to the first embodiment, the electric data current i data flowing at data writing is as high as 10 μA as shown in FIG. 8 .
Next, a light emitting operation is performed corresponding to a light emitting period t 2 of FIG. 13B . In the light emitting period t 2 , a signal on the gate signal line 66 attains a high level, a potential on the gate signal line 65 is at a high level, a potential on the source signal line 67 is at a high level, and a potential on the writing control line 68 is at a high level (V H ). Here the potential difference δV r of the writing control line 68 can be represented by Equation (4) as described above. In addition, the electric current i OLED flowing through the OLED 60 can be represented by Equation (6′):
i
OLED
=
κβ
L
2
(
V
sg
-
V
T
)
2
=
κ
(
i
data
-
β
L
2
·
δ
V
r
)
2
=
κ
(
i
data
-
β
L
β
ave
·
i
base
)
2
=
κ
·
i
base
(
α
-
β
L
β
ave
)
2
(
6
'
)
Here, κ can be represented as κ=(Wb/Lb)/(Wa/La) where Wa and Wb are channel widths of driver elements 61 and 64 , and La and Lb are channel lengths thereof. The gate potential V g of the driver element 61 is represented by Equation (5) as described above.
As can be seen from the foregoing, the image display apparatus according to the present invention is useful for the improvement in the response speed at the display in the black level.
Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative embodiments shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents. | An image display apparatus includes a light emitting element that emits light depending on an injected electric current; a driver that includes at least a first terminal and a second terminal, and controls the light emitting element based on a potential difference, applied between the first terminal and the second terminal, of a level higher than a predetermined threshold; a storage capacitor that serves to retain a potential on the first terminal of the driver; and a controller that changes the potential on the first terminal via the storage capacitor at writing of electric data current corresponding to a display in a black level. | 6 |
BACKGROUND OF THE INVENTION
This invention relates to engine control systems in general and more particularly to determining barometric pressure using a manifold pressure sensor in an engine control system for an internal combustion engine.
Barometric pressure, the force per unit area due to the weight of the atmosphere, can be measured in a variety of ways. Currently, in automotive applications, the barometric pressure can be measured using a barometric pressure sensor mountable on any suitable place on the vehicle where it sees true atmospheric pressure. Such a sensor generates an output signal indicative of the atmospheric pressure. The barometric pressure reading is then used for a number of automobile controls. For example, barometric pressure is used for fuel management, exhaust gas recirculation, spark timing, shift control, idle speed compensation and coast-down throttle angles. However, barometric pressure sensors can be costly and it is always desirable, particularly in automotive applications, to minimize costs.
It is well known in automotive engine control systems to measure the manifold absolute pressure (MAP) using a MAP sensor. The manifold absolute pressure value is measured in automobiles because it is necessary for fuel delivery accuracy. The MAP supplies information on how much air is ingested during each cylinder intake stroke and this information is then used in base fuel calculations to determine how much fuel is needed for each cylinder.
It is also well known in the industry that at certain engine conditions such as wide open throttle (WOT), when the engine is keyed on and when the ignition is off, MAP is substantially equal to barometric pressure. Some prior systems have used this fact to determine barometric pressure at those particular engine conditions by using the manifold absolute pressure sensor rather than a separate barometric pressure sensor. However, these systems are ineffective for updating barometric pressure under certain vehicle operating conditions such as a long uphill climb. It would be desirable, then, to devise a method for using the manifold absolute pressure sensor to determine barometric pressure at all other engine conditions, including part throttle.
SUMMARY OF THE INVENTION
This invention provides for a determination of the barometric pressure at throttle positions in addition to WOT conditions using a manifold pressure sensor. This is cost efficient in automotive applications because manifold pressure is already measured for fuel delivery purposes.
In general, the subject invention provides a way to measure the barometric pressure based on the manifold absolute pressure even at part throttle conditions. This is accomplished by predicting the pressure offset between barometric pressure and manifold absolute pressure based on engine speed and throttle angle and then adding the offset value to MAP, the offset being the pressure drop in the intake system between atmosphere and the intake manifold. In the preferred embodiment of this invention, an accurate prediction of the offset value is obtained by interpolating between pressure offset values across the intake induction system between atmosphere and intake manifold, these offset values being calibrated at high altitude and at sea level. These pressure drop values are contained in lookup tables as functions of engine speed and throttle angle. The pressure drop value corresponding to measured values of engine speed and throttle angle can be added to the manifold absolute pressure to obtain a barometric pressure.
The foregoing and other objects of this invention may be best understood by reference to the following description of a preferred embodiment and the drawings in which:
FIG. 1 is a schematic and block diagram of an embodiment of this invention with a vehicle engine;
FIG. 2 illustrates a vehicle mounted computer which is a preferred embodiment of the control unit shown in FIG. 1; and
FIGS. 3A-3C are flow charts for the control unit of FIG. 1 which is suitable for use in the computer shown in FIG. 2.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, a motor vehicle engine 10 is shown, mountable in a motor vehicle in the normal manner, although the vehicle itself is omitted from the Figure. Engine 10 is of the internal combustion type having a rotating crankshaft, the rotations of which are sensed by a speed sensor 12. Speed sensor 12 may be any appropriate sensor of the type adapted to generate the signal indicative of the rotational speed of the crankshaft. An example of such a sensor is a magnetic pickup adjacent to the toothed flywheel of engine 10 coupled to a counter which counts pulses for unit time and supplies such counts on a regular basis. The output of the rotating crankshaft drives the transmission 14.
Engine 10 is also supplied with an air delivery system of the type wherein the intake air flows from the atmosphere at barometric pressure through an air filter 16 and past a throttle plate 18 which controls the regulation and flow of air into the intake manifold 20 from where it is supplied to the individual cylinders. Fuel can be delivered to a cylinder by any conventional means such as a fuel injection system, including fuel injectors for injecting fuel into the intake manifold 20.
Throttle actuation apparatus for carburetor 14 may be a standard accelerator pedal as included in most motor vehicles. Throttle position sensor 22 is adapted to determine what position throttle plate 18 is in. Such throttle position sensors are well known in control systems generally. Throttle position sensor 22 may be any appropriate sensor such as a potentiometer for providing a variable voltage or a voltage divider for generating a voltage representative of the position of the throttle.
Also associated with intake manifold 20 is a pressure sensor 24 for measuring manifold absolute pressure (MAP). MAP sensor 24 generates a signal indicative of the absolute pressure within the intake manifold 20 downstream of the throttle plate 18. The MAP signal can then be used in base fuel calculations to determine the correct amount of fuel to be supplied to each cylinder.
The vehicle powered by engine 10 includes an operator actuated braking system having a standard brake pedal 26 which, when pressed to actuate the brake, also actuates a brake switch 28 of the type normally used to illuminate the brake lights. Brake switch 28 therefor generates an output to indicate when the vehicle brakes are being applied.
The system further includes a control unit 30 adapted to receive inputs from the various switches and sensors described above, to control various engine functions such as fuel, spark ignition and EGR and to determine barometric pressure in accordance with the principles of this invention. It is understood that additional sensors or indicators and other control functions may be included in this system.
The preferred embodiment of the control unit 30 is a vehicle mounted digital computer which accepts the various input signals and processes them according to a predetermined program. Referring to FIG. 2, the digital computer basically comprises a central processing unit (CPU) 32 which interfaces in the normal manner with a random access memory (RAM) 34, a read only memory (ROM) 36, an input/output unit (I/0) 38, an analog-to-digital converter (A/D) 40, and a clock 42.
In general, the CPU 32 executes an operating program permanently stored in the ROM 36 which also contains stored lookup tables in accordance with the values of selected parameters as will be described. The RAM 34 provides a convenient memory into which data may be temporarily stored and from which data may be read at various address locations determined in accordance with the operating program stored in the ROM 36.
In the operation of the digital computer of FIG. 2, certain discrete input switches and signals such as the brake switch 28 and the engine speed signal from speed sensor 12 have binary output and so may be input directly to the input/output unit 38. Other signals such as the manifold absolute pressure (MAP) signal from the MAP sensor 24 and the throttle position signal from the throttle position sensor 22 are analog in nature and therefore are input to the A/D converter 40 to be converted to a digital signal before being input to the I/0 unit 38. The I/0 unit 38 outputs control signals for controlling exhaust gas recirculation (EGR), fuel injection, and spark timing.
The digital control unit 30 depicted in FIG. 2 may be any of a variety of suitable units programmable by anyone of ordinary skill in the art, according to the flow chart of FIG. 3.
Although the barometric pressure update program of FIG. 3 may be executed at any interval, in the preferred embodiment the barometric pressure update program is executed every 300 milliseconds.
Referring to FIG. 3, the barometric pressure update program is entered at step 44 and proceeds to step 46 where the throttle angle and engine speed values are read and stored in ROM designated memory locations in the RAM 34. The program continues to step 48 where a pressure drop between the atmosphere and the intake manifold, also termed an offset value, is obtained from a lookup table in the ROM 36 and is a function of the air flow rate, or engine speed. From step 48, the program proceeds to step 50 where the pressure drop through the intake system, comprising a pressure offset value obtained at step 48, is added to the MAP value. The value resulting from step 50 is used later in the program and is representative of the barometric pressure when the vehicle is operating at wide open throttle (WOT) or when the vehicle is off.
Thereafter, the program proceeds to a decision block 52 where the condition of the ignition switch is determined. If the ignition is OFF, the program proceeds to decision block 54 to determine whether a specified stabilization time or delay has occurred. When T1 is equal to zero that indicates that the required delay has expired, at which time the program proceeds to step 60 where a barometric pressure update is forced by clearing the memory location containing the current barometric pressure value. The purpose of step 60 is to force an update when the ignition has been turned off for a specified period of time because under that condition it is known that barometric pressure is equal to manifold absolute pressure, irregardless of the throttle angle, since there is little or no air flow. If the delay has not expired, T1 is decremented at step 56 with each execution of the barometric pressure update program until T1 is zero, thereby assuring that engine conditions have stabilized and barometric pressure can be updated.
Returning to decision block 52, if the ignition is ON, step 62 is executed to set the ignition off update delay T1 to a predetermined initial value before the program proceeds to decision block 58.
In decision block 58, it is determined whether the throttle 18 is in a wide open throttle (WOT) position. If the throttle 18 is wide open, the throttle position is irrelevant and barometric pressure is represented by the result of step 50. For wide open throttle condition, then, the program proceeds to decision block 68 to determine if the WOT flag has been set. If the WOT flag is not set that indicates that the engine was not operating at WOT during the previous execution of the program in which case the program is conditioned to force a barometric pressure update by clearing the old barometric pressure value at step 60. The effect then is to execute the steps subsequent to step 70 only in the first instance of WOT operation. If the throttle angle is not wide open, the program proceeds to step 64 where the wide open throttle flag is reset before the program proceeds to decision block 66.
In order to update the barometric pressure at part throttle conditions, three conditions must be met. First, the throttle angle must be within a calibratable part throttle window as determined by upper and lower throttle angle thresholds. The preferred embodiment of this invention operates within this window to obtain the most reliable barometric pressure values possible. If the throttle angle is high it approaches WOT in which case the WOT barometric pressure update is a more accurate update. If the throttle angle is quite low, a barometric pressure update would be unreliable and, thus, an update would be undesirable. The second and third conditions that must be satisfied before a part throttle barometric pressure update occurs relate to steady state engine operating conditions. The second condition requires the throttle angle to be substantially steady state while the third condition requires the engine speed to be substantially steady state. The purpose of requiring these three conditions is to obtain an accurate measurement of barometric pressure at part throttle conditions.
From step 64 or from decision block 68, if it is determined that the wide open throttle flag has been set, the program proceeds to decision blocks 66 and 72 to determine if the throttle angle is within a part throttle threshold window. In the preferred embodiment of this invention, part throttle updates of barometric pressure are allowed only when the part throttle value is within a given range so the computations derived from the part throttle update do not exceed the calibration range of the lookup tables.
If the throttle angle is within the calibratable part throttle range, as determined at decision blocks 66 and 72, the program proceeds to steps 76 through 86 to determine if the throttle angle and engine speed are substantially steady state. Steady state operation is indicated if the change in throttle angle and engine speed are each less than respective values for a predetermined time period (the initial value of timer T2 established at step 74).
Steps 78 and 80 first determine if the change in the throttle angle (the absolute value of the difference between the old and new values of throttle angle) is less than a predetermined threshold value. If not, the timer T2 is reinitialized at step 74. If the change is less than the predetermined threshold, steps 82 and 84 determine if the change in the engine speed (the absolute value of the difference between the old and new values of engine speed) is less than a predetermined threshold value. If not, the timer T2 is reinitialized at step 74.
If the changes in throttle angle and engine speed are both less than their respective thresholds, steps 84 and 86 determine if the condition has existed for the time period established by step 74. If step 74 determines the time period has not expired, the required steady state conditions of the throttle angle and engine speed have not been met and the time is decremented at step 86.
If the step 84 determines that the required steady state conditions are met, the program next proceeds to determine the barometric pressure. This procedure begins at step 90 where the manifold absolute pressure offset value at altitude is obtained from a three-dimensional lookup table in the ROM 36 containing a MAP offset schedule as a function of throttle angle and engine speed. Likewise, at step 92 a MAP offset value at sea level is obtained from a three-dimensional lookup table in the ROM 36, this offset value also a function of throttle angle and engine speed. Since the pressure offset between atmosphere and manifold absolute pressure changes depending on the atmosphere, use of the two lookup tables containing manifold absolute pressure values at the extremes provides a way of compensating for changes in altitude. At step 94 a linear interpolation is performed between the two offsets as a function of the current stored value of barometric pressure. Because the MAP offset is dependent on barometric pressure, an interpolation based on the last estimated value of barometric pressure provides an accurate estimation of the new MAP offset. The result of this interpolation is the final part throttle MAP offset. In accordance with this invention, step 96 sums the new MAP offset and the measured intake manifold absolute pressure, thereby computing a measure of the barometric pressure to be used later in the program.
At decision block 98, it is determined whether the exhaust gas recirculation (EGR) is ON which would cause a manifold pressure variation. If the exhaust gas recirculation is ON, the program proceeds to step 100 where the EGR is subtracted from the interpolated value computed at step 94. Having accounted for any manifold pressure variation due to exhaust gas recirculation, the program proceeds to decision blocks 102 and 104 where one final test is made before enabling a part throttle update. At decision block 102 it is determined whether the subtraction of the last computed barometric pressure from the computed barometric pressure of step 96 is equal to zero. If this value is zero, the program proceeds to decision block 88. If not, the program proceeds to decision block 104 where the computed barometric pressure is compared with the current barometric pressure to determine if the computed barometric pressure of step 96 is decreasing or increasing.
If the pressure is decreasing, the amount of decrease is compared at step 106 with a pressure decreasing threshold Kd below which part throttle barometric pressure updating is prevented. If the decrease is greater than Kd, a new estimate of barometric pressure is computed at step 110 by the first order lag filter expression
new BARO=current BARO-(ΔBARO * Md)
where Δ BARO is the difference between computed barometric pressure and current barometric pressure and Md is a decreasing pressure filter time constant having a value of unity or less. Similarly, if step 104 indicates pressure is increasing, the amount of increase is compared at step 108 with a pressure increasing threshold Ki above which part throttle barometric pressure updating is prevented. If the increase is less than Ki, a new estimate of barometric pressure is computed at step 112 by the expression
new BARO=current BARO+(ΔBARO * Mi)
where Δ BARO is the difference between computed and current barometric pressure and Mi is an increasing pressure filter time constant having a value of unity or less.
Smoother updates result when using a low delta barometric pressure threshold at steps 106 and 108 and small values of Md and Mi since this allows the current barometric pressure to approach the computed barometric pressure in a few small increments rather than in one large step.
Returning to decision block 88, it is determined whether the sum of the new MAP plus the offset value obtained at step 50 is greater than the last used barometric pressure value. It will be recalled that current barometric pressure was cleared at step 60 if the wide open throttle or ignition off barometric pressure update conditions existed. The existence of either of these conditions forces the execution of step 116 via step 88 wherein the new barometric pressure is set equal to the value determined at step 50.
After step 114, where the old throttle angle value is updated with the new throttle angle value determined at step 46 and stored in the RAM 34, the program proceeds to step 118 where the old engine speed value is likewise updated before exiting at step 120.
The foregoing description of a preferred embodiment of the invention for the purpose of illustrating the invention is not to be considered as limiting or restricting the invention since many modifications may be made by the exercise of skill in the art without departing from the scope of the invention. | A method for determining barometric pressure uses a manifold pressure sensor for measuring the manifold absolute pressure. A pressure drop between the atomosphere and the intake manifold is determined by utilizing stored lookup tables based on measured values of throttle angle and engine speed. Barometric pressure is then determined by summing the manifold absolute pressure and the pressure drop. | 5 |
This application is the national phase under 35 U.S.C. §371 of PCT International Application No. PCT/FI98/00531 which has an International filing date of Jun. 18, 1998, which designated the United States of America.
The present invention relates to an elevator and in particular, to a drive system for an elevator.
DESCRIPTION OF THE BACKGROUND ART
In elevator technology, several methods are used to produce the motive power for elevators. A common method is to use a traction sheave connected to a rotating motor hoisting the elevator car by means of ropes, with a counterweight placed on the opposite side of the traction sheave to balance the load. Another established solution is found in hydraulic elevators, in which the hoisting power to move the car is obtained from hydraulic cylinders either directly or via ropes. Most modern elevators are based on these solutions, of which many variations have been developed.
Although the above-mentioned elevator types have become established and are safe and reliable in operation, the solutions used in them comprise several factors that are objections of improvement and product development. For example, investigations are continuously being made to find ways of more effective utilisation of building space and reduction of energy consumption. For hydraulic elevators, the hoisting height is in practice limited to a few floors. By contrast, elevators with rope suspension have been installed in buildings as high as several hundred meters, in which case rope elongation and oscillation cause problems. Because of the rope suspension arrangements, the number of elevators in a shaft is practically limited to one.
In addition to rope-suspended and hydraulic elevators, several solutions for the use of a linear motor in an elevator have been proposed. In this case the electric motor is completely located in the shaft space. Most linear elevator motors have been based on the induction motor principle, although other motor types, such as a linear motor based on permanent magnets have also been presented. Several different solutions have been proposed, but as yet it has not been possible to produce a competitive elevator.
SUMMARY OF THE INVENTION
The object of the present invention is to achieve a new elevator in which several drawbacks encountered in prior art solutions are avoided.
The invention is based on a so-called switched reluctance linear motor or a variant developed from it, which makes use of the so-called microflux technique. In the switched reluctance motor, the windings of the linear motor are optionally placed either in a fixed primary circuit or in a movable secondary circuit. The motor is used to both move the car and support it by generating a force component in the direction of motion and a force component perpendicular to the direction of motion. The placement of the winding on the primary or secondary side can be selected separately for each application.
According to a preferred embodiment of the invention it is utilised the combined effect of a linear motor and pneumatic air gap regulation. The linear motor is used to both move the car and support it by generating a force component in the direction of motion and a force component perpendicular to the direction of motion. The air gap between the primary and secondary circuits of the linear motor is maintained by means of the perpendicular component and pressurised air.
According to a preferred embodiment of the invention, in a motor based on the microflux technique, called microflux motor, the windings are placed on both the primary and secondary sides, thus reducing the proportion of leakage flux and improving the power-to-weight ratio of the motor. The supply of current to the windings is so controlled that the magnetic flux will only pass through a minimal distance in the yoke part of the motor and that the flux loop will be completed in the first place via adjacent teeth.
According to a preferred embodiment, the power is supplied to the windings using control equipment disposed along the entire length of the track of the elevator and each winding is controlled separately. Alternatively, several windings can be combined to form a group with common control.
According to another alternative implementation of the invention, the pneumatic equipment comprises a source of pressurised air and a pipe system with nozzles, fitted substantially in the air gap between the primary and secondary circuits of the linear motor. The pressurised air keeps the air gap clean and generates a smooth air flow from the center of the air gap towards its edges.
The alternatives regarding the structural solutions of the invention are to dispose the linear motor and pneumatic equipment on one side of the elevator car or to dispose the linear motor and pneumatic equipment on two or more sides of the elevator car. The former solution provides more freedom regarding the placement of the elevator in the building and an independence of a traditional elevator shaft. The latter solution allows more freedom of variation of the physical dimensions of the elevator-specific motor.
In an embodiment of the invention relating especially to the structure of the linear motor, the tooth pitch of the primary and secondary circuits is effected by applying the vernier principle. The motor power can thus be uniformly distributed over the entire length of the active part of the motor, i.e. the movable secondary side.
According to a further embodiment, the primary circuit and/or secondary circuit is coated with a plastic film on the surface facing the air gap. The effective air gap of the linear motor can thus be adjusted without increasing the pneumatically regulated air gap at the same time.
The new type of motor solution of the invention provides several advantages in elevator technology. As the motor applies a lifting force directly to the elevator car, it eliminates the need for hoisting ropes, which are an object of regular maintenance and renewal. Readjustments due to rope elongation naturally become unnecessary. Correspondingly, no traction sheave and no diverting pulleys need to be installed. The counterweight and associated shaft equipment, such as counterweight guide rails, become superfluous. No separate machine room is needed, but the control and operating equipment can be placed in the elevator or in conjunction with the equipment at the landings. The travel of the elevator car in the elevator shaft is controlled by a pneumatic bearing system, so there are no conventional car guides and guide rails installed for them. Safety gears as used in current technology are also left out. The overall degree of utilisation of the elevator shaft is higher because the only equipment that needs to be installed in the elevator shaft in addition to the elevator car is the very flat magnetic circuits of the motor. The lifting height is unlimited without any special additional equipment or rigging necessitated by height.
The elevator can be implemented as a external installation in which the elevator climbs along the external wall of the building, thus allowing a further space saving inside the building. In the elevator solution of the invention it is further possible to use a light car construction because the magnitude of the friction does not limit the minimum car weight as in the case of traction sheave elevators. Based on the degrees of freedom of the elevator of the invention and the limitations of conventional elevators, this new solution provides advantages especially in the case of very high and very short elevator shafts. Furthermore, the elevator solution of the present invention makes it possible to develop multiple-car elevator shafts and also transport systems combining vertical and horizontal movement.
The switched reluctance motor has a considerably higher power-to-weight ratio than conventional motor solutions. In the microflux motor, the power-to-weight ratio can be further improved as compared even with the reluctance motor.
Further scope of the applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
In the following, the invention will be described in detail by the aid of some of its embodiments by referring to the attached drawings which are given by way of illustration only, and thus are not limitative of the present invention, and in which
FIG. 1 illustrates the principle of the elevator of the invention,
FIGS. 2 a and 2 b illustrate the principle of a switched reluctance motor, showing the motor as seen in side view and from the side of the air gap,
FIGS. 3 a and 3 b illustrate the principle of a microflux motor, showing the motor in lateral view and from the side of the air gap,
FIG. 4 illustrates the force effects of the motor,
FIG. 5 illustrates the principle of control of the motor of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The elevator of the invention (FIG. 1) moves along the surface of the primary circuit, i.e. stator 2 of a linear motor attached to a wall 1 of an elevator shaft fitted in a building. Although in FIG. 1 the elevator is depicted as moving in a shaft delimited by walls 1 , 3 and 5 , the implementation of the invention is not limited to a shaft, but instead the elevator, supported by its motor, can move along its stator, which is attached to the wall 1 or otherwise reliably fixed to the building, without side walls. A movable slide 4 with the secondary circuit, i.e. rotor of the linear motor fitted to it is attached to the elevator car 6 and it moves alongside the stator 2 , separated from it by an air gap, as described in more detail later on.
As illustrated by FIGS. 2 a and 2 b , the stator 2 comprises a plurality of component stators 8 attached to a supporting structure 7 of the stator and comprising a magnetic circuit 10 with teeth 12 pointing toward the rotor and a yoke part 14 connecting the teeth. The iron structure is substantially of the same order of thickness in the area of both the teeth and the yoke. Wound around the stator teeth 12 are coils 16 , and the current flowing in the coils generates a magnetic flux 18 passing via the teeth and the yoke part and further across the air gap 20 into the magnetic circuit 22 of the rotor fitted to the slide. The magnetic circuit 22 of the rotor consists of rotor teeth 24 and a yoke part 26 connecting adjacent rotor teeth 24 . In the embodiment presented in FIG. 2 a , the slot pitch of the component stators is identical with the slot pitch of the rotor, so the teeth of a given component stator are aligned with the rotor teeth opposite the component stator. Adjacent component stators have been removed through distance x in the direction of motion of the slide, which in the example in FIG. 2 a corresponds to ⅛ of the rotor slot pitch. Between the rotor and the stator, a force is developed which has a force component F x acting in the direction of the yoke of the slide, i.e. in the direction of motion, and a force component F y acting in a direction perpendicular to the direction of motion and attracting the rotor and stator to each other when a current is passed through the coil under appropriate control as described in detail below. The slide is provided with air channels 27 . At one end, the air channels terminate in a nozzle 21 in the air gap 20 of the motor and at the other end they are connected to a pipe system 23 with a pneumatic pressure source 25 connected to it. The entire pneumatic equipment can be mounted on the elevator car, in which case its drive motor is powered via a car cable or supply rails. Alternatively, the pneumatic pressure source can be immovably mounted in the building, in which case a pipe system 23 is provided under/beside the track of the elevator in a manner corresponding to a car cable. Using the pneumatic equipment, pressurised air is supplied into the air gap 20 of the motor so that the attractive force between the stator and rotor is cancelled and a constant air gap is maintained. The stator and rotor surfaces facing the air gap are of a smooth shape to ensure that the pressurised air is distributed in the air gap uniformly enough to maintain a constant air gap magnitude. The spaces between the stator windings and slots are filled with resin or some other material known in the art. Correspondingly, the slots between the rotor teeth are filled with resin or some other non-magnetic filler. Thus, the magnetic circuit consists of the stator and rotor teeth and the yoke parts connecting the teeth as well as the air gap between the stator and rotor.
An essential factor about the switched reluctance motor is that the magnetic flux must be so controlled that it will pass through two adjacent teeth and the yoke part connecting them on both the stator side and the rotor side. This ensures that the path of the magnetic flux is short and no massive iron frame is needed. In a rotor as shown in FIG. 2, placing the stator windings close to the air gap substantially reduces the stray flux, but some stray flux still appears on the side of the rotor teeth. To reduce the stray flux, in the alternative presented in FIG. 3, coils 28 have been wound around the rotor teeth 24 as well. Where applicable, the same reference numbers are used in FIG. 3 as in FIG. 2 for corresponding parts. In the microflux motor according to the embodiment illustrated by FIG. 3, ‘microflux motor’ being the designation used for this alternative in this context, the displacement x of the component stators of the stator is {fraction (1/21)} of the rotor slot pitch. Thus, there are twenty stator teeth for a length of 21 teeth of the entire rotor. In this manner, applying the vernier principle, a smoothness of the lifting force is achieved, which will be discussed in a later paragraph in conjunction with FIG. 4 . The magnetic circuit of the stator in the microflux motor presented in FIG. 3 comprises a continuous yoke provided with teeth in accordance with the slot pitch. Thus, the embodiments illustrated by FIGS. 2 and 3 differ structurally from each other and their control principles differ correspondingly from each other in certain details. In each embodiment, however, power is supplied to the stator windings in such a way that the main flux generated by each winding completes its loop via the tooth adjacent to the winding and does not pass further through the yoke. In the case illustrated by FIG. 3, the power supplied to the rotor windings serves to reduce the stray flux.
For the sake of clarity, FIG. 3 only depicts a part of the stator windings 16 and rotor windings 28 . The direction of the current (+or −) is shown in each slot and the magnetic fluxes completing their loops via the teeth 12 and 24 , yoke parts 14 and 26 and air gap 20 are depicted with solid and broken lines, respectively.
The force generated by the stator winding in the direction of motion varies in the manner illustrated by curve F xa as a rotor tooth is moving past a stator tooth T a . When it passes the next tooth T b , a force effect as illustrated by curve F xb is produced. The windings are switched on phased with a corresponding timing difference. As the stator and rotor teeth are additionally removed according to the vernier principle, a uniform total force F x in the direction of motion is achieved. The broken line F ya describes the mutual attractive force perpendicular to the direction of motion between the stator tooth and the rotor tooth. In the case of a certain dimensioning applied, force components of the indicated magnitude were formed on the ordinate axis, F y being over four times as high as F x .
The basic circuit arrangement of the microflux motor and its control in an elevator drive is presented in FIG. 5 . Mounted in the elevator shaft over its entire length is the stator, which comprises stator windings, i.e. shaft coils L 1 , L 2 , . . . LN, LN+ 1 ,LN+ 2 , . . . ,LM, fitted in the slots between the stator teeth as explained above, shifted in phase in relation to the rotor teeth. Coils L 1 , . . . ,LN are connected in series and power is supplied to them from a single constant current power source 30 . Along the total length of the elevator shaft there are several series-connected sets of shaft coils mounted one after the other, each set being fed by its own constant current power source. To enable each shaft coil to be switched on at the appropriate time, the elevator shaft is provided with detectors 32 which detect the position of the slide in the shaft and are used to switch on power to the appropriate portion of the shaft windings. It is not necessary to impose any exact requirements regarding the control of the shaft coils because it is enough to have the stator windings energised when the slide is over them. The constant current power sources for the shaft coils are fed from the electricity supply network by a mains bridge 34 via cables 36 mounted in the shaft. The current of the constant current power source 30 is also controlled by current adjusting equipment 38 via cables 40 mounted in the shaft. The control of the constant current power sources and therefore of the coils can be implemented in a manner known in itself and need not be described here in greater detail, but a person skilled in the art can design and construct the details of the equipment required by the invention in accordance with the principles taught by the invention.
Mounted on the elevator car is a slide 4 consisting of a toothed magnetic pack as illustrated by FIG. 3, which comprises e.g. ten rotor windings 28 . Each rotor winding is controlled by its own coil controller 42 , which are fed from the mains bridge 34 via car cables 44 . The coil controller is controlled using the speed reference and actual speed value of the elevator. The speed reference 46 is generated in accordance with the elevator control logic 48 and the actual speed value 50 is generated by means of speed or position detectors from the motion of the elevator car or the slide. The control signals of the coil controller are taken to the car via a control cable 52 . The coil controllers are so controlled that the force acting on the car is in accordance with the direction of motion and the car load.
The rotor windings can also be controlled using position and speed detectors. In this case, the elevator car is provided with a position detector for generating a position signal corresponding to the position of the elevator car and with an accelerometer for an acceleration controller. The coil controllers are controlled by the data provided by the position detector and the acceleration controller, so the position detector must provide sufficiently accurate position data to allow timely switching of the windings.
When the elevator is moving in the up direction, the motor windings must be so magnetised that, in addition to the perpendicular force between the stator and rotor that supports the car in the shaft, a force depending on the weight and velocity of motion of the car is generated. When the car is moving in the down direction, it can be braked electrically by supplying power into resistors or into the electricity supply network or into an energy reserve, such as a storage battery. However, the windings must produce a force between the stator and rotor that keeps the car fast on the shaft wall.
The control of a switched reluctance motor can be implemented in a corresponding manner, but the technical implementation differs considerably from that described above because only one of the motor halves is provided with windings and only these are controlled.
The supply of electricity of the shaft can be implemented in a partitioned fashion so that the coil controllers within each partition comprising a distance of a few meters have a separated power source connected to the electricity supply network.
The force F y acting on the car and slide in a direction perpendicular to the direction of motion is compensated and a constant air gap between the stator and rotor is maintained by supplying pressurised air into the air gap via a pipe system 27 . This technique is known from pneumatic bearing technology and according to it the pressure difference causes air to flow from the nozzle in the pipe to the edges of the motor.
The energy required for the lifting movement of the elevator is larger than in elevator solutions using a counterweight. To reduce the power taken from the electricity supply network, energy reserves are used into which the energy developed by the elevator car moving downward is loaded.
The energy needed by the rotor moving together with the elevator car can also be supplied to the car using means other than a car cable. It is possible to provide the shaft with conductor rails from which electricity is passed to car supply cables via current collectors. Alternatively, the energy can also be supplied inductively, via radiation or from an accumulator mounted on the elevator car and charged during stoppages.
The invention has been described above by the aid of one of its embodiments. However, the presentation is not to be regarded as constituting a limitation of the sphere of protection of the patent, but its embodiments may vary within the limits defined by the following claims. In addition to the embodiments presented as examples, there are numerous alternative solutions regarding electricity supply, elevator control, motor construction, regeneration of braking energy and safety device arrangements. Although the motor has been described as comprising only one air gap, it is possible to use a motor with several air gaps and a corresponding number of stator and rotor pairs defining the air gaps and placed on one side of the elevator car, on opposite sides of the elevator car or on two or more sides perpendicular to each other. Likewise, a plurality of motors can be disposed at different angles to each other even though they are on the same side or on different sides of the elevator car. | A drive system for an elevator includes a drive machine by means of which the for moving and supporting an elevator car. The primary circuit of a linear motor is permanently fitted to a wall of a building while its secondary circuit is fitted in conjunction with the elevator car and moves with the elevator car. Pressurized air is supplied between the primary and secondary circuits of the reluctance-type linear motor to maintain an air gap between them. | 7 |
FIELD OF THE INVENTION
The present invention relates to an anaerobic treatment process to convert organic materials to soluble and gaseous components.
BACKGROUND OF THE INVENTION
Anaerobic digestion is widely used industrially and municipally to convert organic materials to soluble and gaseous products. Typically, organic materials from industrial and municipal sources include soluble, colloidal and particulate constituents that have different hydrolysis rates. Some of the constituents of the organic materials will metabolize and be degraded more rapidly than other constituents. For example, acetic acid, as contained in condensates of sulfite pulping plants or glucose, as contained in sugar waste waters, are constituents that degrade rapidly. On the other hand, constituents that do not degrade so rapidly include particulate and colloidal materials, such as proteins, long chain fatty acids, fats, vegetable oils, tallow, bacterial and yeast cell walls, and celluloses.
The economic use of anaerobic digestion requires that a diverse symbiotic bacterial mass be maintained in contact with the organic material while promoting the hydrolysis of the particulate constituents and slowly metabolized materials. Consequently, a wide variety of anaerobic reactor designs have been developed that maintain biomass within a reactor. These reactor designs are characterized broadly as fixed film processes, anaerobic filters, sludge blanket reactors, carrier-assisted fluidized bed reactors, and anaerobic contact reactors. All of these processes provide the benefit of maintaining a large bacterial population within a reactor and thus reducing the size of the reactor. Nonetheless, when treating a stream of organic materials as described above containing rapidly hydrolyzed and degradable constituents and less rapidly hydrolyzed and degradable constituents, the hydrolysis of the less rapidly hydrolyzed constituents proceeds slowly compared to the other constituents. Accordingly, the hydrolysis of the less rapidly hydrolyzed constituents becomes the rate limiting step in the overall process since complete degradation can take place only after hydrolysis of all the nonsoluble constituents has occurred. In prior reactor designs achieving hydrolysis of all non-soluble constituents required large tank volumes, to accommodate for the entire substrate flow, regardless of concentration or varying substrate hydrolysis rates of the constituents.
Several previous investigators have noted this shortcoming and have addressed it in a number of different ways. For example, U.S. Pat. No. 4,559,142 to Morper and U.S. Pat. No. 4,551,250 to Morper et al. recognize that it is economically advantageous to process the more slowly hydrolyzable material in a reactor, separate from a reactor where the more rapidly hydrolyzed material is treated.
The rate of hydrolysis has typically been depicted as an innate quality of the substrate to be degraded. Prior investigators have modeled particulate hydrolysis as a first order reaction, independent of the concentration of bacteria. This basic approach to the rate of hydrolysis has limited many previous efforts to reduce the size of anaerobic reactors and thus improve the economic factors involved in the treatment process because again the reactors were sized to accommodate the entire substrate flow of less rapidly and more rapidly hydrolyzed constituents.
SUMMARY OF THE INVENTION
The present invention is an anaerobic process for converting organic slurries or waste materials, to precipitates, as well as soluble and gaseous products through a series of reactors or process steps. The organic influent that may be treated in accordance with the present invention is expected to be a mixed substrate including organic constituents that can be rapidly assimilated by anaerobic bacteria as well as organic constituents that are more slowly degraded or more slowly metabolized by the bacteria. These two types of constituents can generally be classified as being either soluble, colloidal, or particulate components.
The present invention in part is based upon applicant's observation that the rate of hydrolysis of various organic components is not solely a characteristic of the substrate itself, but is also dependent upon the concentration of the anaerobic bacteria, with their associated hydrolytic enzymes, and other environmental conditions including the concentration of the end products produced. As noted in the Background, in the past, the rate of hydrolysis was considered to be an innate quality of the substrate itself. Accordingly, particulate hydrolysis in the past has been modeled as a first order reaction, independent of the concentration of the bacteria. The present applicant has observed that the rate of substrate hydrolysis is a function of the contact rate, nature of the substrate, the bacterial population responsible for hydrolyzing the substrate, as well as end product concentration.
Applicant has devised a process comprising three sequential steps consisting of two anaerobic digestion steps and one liquid/solid separation step. The process involves the steps of first mixing an influent stream containing the organic material with first anaerobic bacteria from an anaerobic reactor. The organic material is maintained in contact with the anaerobic bacteria for a predetermined period to allow for the partial digestion of the organic material. The more rapidly hydrolyzed and metabolized constituents will tend to be the constituents that are digested in this first anaerobic reactor. The suspended colloidal constituents and particulate constituents, including bacteria and enzymes, are then separated mechanically (e.g., by flotation) or chemically from the partially digested influent stream. The separated suspended colloidal constituents and particulate constituents, including bacteria and enzymes, are then delivered to the second anaerobic reactor which preferably served as the source of anaerobic bacteria for the first reactor for further contact with the anaerobic bacteria. In this second anaerobic reactor, the more slowly hydrolyzed and degraded are maintained for a sufficient period of time with concentrated biomass to achieve the desired digestion. Because the volume of the suspended colloidal constituents and particulate constituents that are separated from the partially digested influent stream is less than the volume of the influent stream, the size requirements of the second anaerobic digester are reduced.
In a preferred embodiment, the first anaerobic reactor reduces the soluble constituents, or those constituents that cannot be removed by the separation device described above, to a level that meets the process effluent limitations and to remove particulate and colloidal constituents, or those constituents that can be removed by the separation device, to a level that benefits the separation device economics and the economics of the second anaerobic reactor. Thus, there are two goals to be met by the first reactor:
(1) Meet effluent limitations by removing those constituents that cannot be removed by the separator; and
(2) Remove as much of the particular and colloidal constituents as economically feasible to improve the economics of the separation process and the capacity of the second anaerobic digester.
In another aspect, the present invention relates to the removal of soluble products of digestion by elutriation of the anaerobic bacteria with the dilute influent stream or with dilution water. The advantage of elutriating these soluble products of digestion from the anaerobic bacteria is that it removes components that would otherwise inhibit the bacteria's desirable activity.
The process may be operated at both mesophilic or thermophilic temperatures. Use of a floation separation device will enhance organic acid removal through a gas bubble attachment if a thermophilic reactor temperature is maintained. For certain substrate materials, the process may be enhanced by maintaining the second reactor at a higher temperature to increase the hydrolysis of a particular substrate. Synthetic carriers for bacteria or fixed films within the first reactor may also be used to enhance removal of soluble constituents.
Processes carried out in accordance with the present invention take advantage of the natural anaerobic digestion mechanisms to produce a clean effluent while minimizing the capital and operating cost of anaerobic treatment facilities through reduction in reactor volume and total process retention times.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing aspects and many of the attendant advantages of this invention will become more readily appreciated as the same become better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein:
FIG. 1 is a schematic illustration of a preferred embodiment of an apparatus for carrying out the process of the present invention; and
FIG. 2 is a graph of hydrolysis rates.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention provides a process that takes advantage of the natural anaerobic digestive mechanisms to produce a clean effluent while minimizing the capital and operating cost of anaerobic treatment facilities through a reduction in reactor volume and total process retention time. The present invention also provides an apparatus as described below in more detail for carrying out the process.
The process achieves these functions by degrading a portion of the organic material in a first anaerobic reactor which is sized to provide a retention time suitable to rapidly convert the organic materials to soluble and gaseous components when contacted with a diverse and concentrated mass of hydrolyzing anaerobic bacteria, preferably from a second anaerobic reactor. In a preferred embodiment as described below in more detail, the first anaerobic or influent reactor is also sized to allow for elutriation or washing of soluble products from the anaerobic bacteria through contact with dilute influent stream or the addition of dilution water. By degrading a majority of the soluble and a portion of the particulate organic material in the first anaerobic reactor, the process is then able to concentrate the remaining organic material that has not been degraded and separate it from the soluble constituents for further treatment. This concentration/separation is accomplished in a separator that separates the suspended colloidal constituents and particulate constituents comprising colloidal and particulate unmetabolized solids, bacteria and inorganic precipitate products of digestion from the soluble components that comprise soluble inorganic solid products of digestion and soluble gas products of digestion. This separated stream of suspended colloidal constituents and particulate constituents is then directed to a second anaerobic reactor where they are contacted with anaerobic bacteria for further degradation as described below in more detail.
The goal of the first anaerobic reactor is to reduce the soluble constituents, or those constituents that cannot be removed by the separation device, to a level that meets the process effluent limitations and to remove particulate and colloidal constituents, or those constituents that can be removed by the separation device, to a level that benefits the separation economics and the economics of the second anaerobic reactor. There are two goals to be met by the first reactor. They are:
(1) Meet process effluent limitations by removing those constituents that cannot be removed by the separator. Once those constituents, assumed to be soluble, are removed, the separator can remove the remainder, thus the desired effluent limitations are met; and
(2) Remove as much of the particulate and colloidal constituents as economically feasible to improve the economics of the separation device and the second anaerobic digester capacity.
These process parameters will often be dictated by economics. The cost of separation is dictated by the total quantity of solids processed. The total quantity of solids dictates the cost of chemicals, such as polymer and the cost of pressurizing gas if flotation is used. The separation process is economically enhanced by removing as much of the particulate constituents as possible in the first anaerobic reactor. On the other hand, the cost of removing the solids in the first reactor is based on the detention time of the reactor (increased solids reduction means increased volume and therefore costs) and the quantity of solids recycled from the second reactor. The quantity necessary to recycle from the second reactor dictates the size and cost of the second reactor. In certain situations, the preferred economic decision point will be where the easily hydrolyzed solids are removed in the first reactor, with the soluble constituents or nonparticulate constituents, and the slowly hydrolyzed solids are removed in the second reactor with the stored bacteria.
Referring to FIG. 1, a schematic illustration of an apparatus for carrying out an aerobic treatment process in accordance with the present invention is provided. The apparatus includes a first influent anaerobic reactor 2, a second anaerobic reactor 7, and a separator 4 intermediate the first anaerobic reactor and the second anaerobic reactor.
Influent organic material comprising soluble, colloidal, and suspended particulate constituents having varying hydrolysis rates is delivered to influent anaerobic reactor 2 via line 1. In a preferred embodiment, influent anaerobic reactor 2 also receives biomass, i.e., anaerobic bacteria, from second anaerobic reactor 7 through line 8. It should be understood that although recycle of anaerobic bacteria from second anaerobic reactor 7 is preferred, it is not required. For instance, the biomass introduced into influent anaerobic reactor 2 can originate from an independent source of anaerobic bacteria. By way of example, if influent stream one contains about 2,500 mg/L of chemical oxygen demand, e.g., COD, with approximately 90% particulate COD (PCOD) and it has been determined through pilot testing of the substrate that about 50% of the PCOD can be removed in about 4 hours with about a 10:1 biomass recycle from the second reactor, which maintains biomass at a concentration of about 50,000 mg/L in about a 60,000 mg/L solid slurry, then the ratio of biomass recycled to influent flow will be 0.5 or 50%. The concentration influent to the separation device will be about 20,916 mg/L which can be concentrated to about 62,000 mg/L for return to the second anaerobic reactor.
Influent anaerobic reactor 2 is sized so that a portion of particulate organic constituents are rapidly coverted to soluble and gaseous components when contracted with the anaerobic bacteria. As described above, the goal of the first anaerobic reactor is to reduce the soluble constituents, or those constituents that cannot be removed, by the separation device, to a level that meets the process effluent limitations and to remove particulate and colloidal constituents, or those constituents that can be removed by the separation device, to a level that benefits the separation economics and the economics of the second anaerobic reactor as discussed above.
In a preferred embodiment, influent reactor 2 is also sized to allow for elutriation or washing of soluble products from the anaerobic bacteria through contact with a dilute influent stream from separator 4 as described below in more detail or the addition of dilution water via line 11. The volume of elutriation water required shall be sufficient to maintain the concentration of the products of anaerobic decompositions such as ammonia or sulfides below inhibitory values for the anaerobic bacteria. If desired, effluent may also be returned via line 10 to provide alkalinity if required to maintained proper pH within influent anaerobic reactor 2.
In a preferred embodiment, influent reactor 2 is also sized to allow for elutriation or washing of soluble products from the anaerobic bacteria through contact with a dilute influent stream. If anoxic gas flotation is used to provide the separation, certain soluble constituents that contain hydrophobic structures such as organic acids, proteins, and enzymes will be separated from the particulate matter due to attachment to the gas bubble surface. Increased removal of such constituents can be accomplished by increasing the gas bubble surface area through utilization of fine gas bubbles or increasing gas/solids ratios. It is preferred to hydrolyze and degrade as much of the influent organic material in the influent reactor as economically feasible in order to reduce the volume of concentrated solids that are removed from separator 4 and delivered to second anaerobic reactor 7 as described below in more detail. The reduction in the volume of the solids introduced into second anaerobic reactor results in a commensurate decrease in the size of second anaerobic reactor 7. In a preferred embodiment, influent anaerobic reactor 2 has a retention time of less than about 12 hours, more preferably less than about 8 hours, and most preferably less than about 2 hours.
The amount of bacteria from second anaerobic reactor 7, that is contacted with the influent stream in influent anaerobic reactor 2, should be sufficient to promote hydrolysis of the more rapidly metabolized colloidal and particulate constituents as well as promote the consumption of substantially all of the soluble constituents. It is possible that some adsorption and flocculation of colloidal material with the anaerobic bacteria may also take place. Such adsorption is not expected to be high since anaerobic bacteria do not flocculate well or adsorb substantial quantities of organic substrate. The anaerobic bacteria stream from second anaerobic reactor 7 will also contain soluble products of digestion that will be diluted by the influent, thus reducing the concentration of soluble digestion products. As discussed above, dilution water may be added to dilute, or elutriate the products of digestion from the bacteria. In accordance with the present invention, under these enriched bacterial conditions, a portion of the organic material in the influent will be substantially degraded in a short period of time as described above.
The effluent from influent anaerobic reactor 2, containing colloidal and particulate solids that have not been metabolized, anaerobic bacteria, inorganic precipitates generated through bacterial decomposition of the organic substrates, and soluble inorganic products of digestion are transferred via line 3 to a mechanical separation device 4, such as a gas floatation separator or centrifuge. It should be understood that other types of mechanical separators or chemically induced separators or chemically aided separation techniques can be employed provided there is no adverse impact on the anaerobic bacteria. The particular separation technique used provides an effluent that meets process effluent discharge criteria. Accordingly, it is preferred that the separation technique remove substantially all the suspended colloidal and particulate constituents, bacteria and precipitates from the soluble constituents in the partially digested stream from anaerobic reactor 2. Separation aids or chemicals may be used to accomplish the required separation and clarification. If gas floatation separation is used, the bubbles should be anoxic gas microbubbles capable of producing a clarified effluent substantially free of suspended solids. A floatation separator may also use a recycled effluent solution, or diluted effluent solution for elutriation of the anaerobic bacteria in separator 4. In addition, the recycled effluent can be used to carry dissolved gas back to separator 4. Dilute effluent may also be added to other mechanical separation devices to promote the desired elutriation. Floatation separation, using microbubbles, such as those produced with dissolved gas floatation, may also be structured to promote the removal of surface active constituents, having hydrophobic characteristics, such as organic acids, proteins, and extracellular enzymes. The high bacteria to substrate ratio will cause a more rapid hydrolysis of slowly metabolized constituents.
In order to assess the relationship between the hydrolysis rates and biomass concentration, two identical anaerobic reactors were operated in parallel for six months. Both reactors were fed semicontinuously the same, 5% to 6% solids, primary and waste activated sewage sludge. The biomass was concentrated in one reactor by means of anoxic gas flotation (AGF). The biomass was assumed to be directly proportional to the volatile solids content of each reactor. The AGF reactor had a volatile solids content of 43,175 mg/L. The conventional reactor had an average volatile solids content of 15,952 mg/L. The ratio of volatile solids content for the reactors was 2.52 which was presumed to be the biomass ratio for the respective reactors. Gas production was measured continuously and analyzed for methane content throughout the day. Each reactor was fed an average of 6 kilograms of sewage sludge of which about 85% was particulate chemical oxygen demand (COD). Methane gas production was recorded and converted to equivalent COD production based on 350 L of methane gas equaling 1.0 Kg of COD. As illustrated in FIG. 2, the hydrolysis rates were calculated for each reactor based on accumulated gas production. The hydrolysis rates for the AGF were almost twice (1.92), the rate of the conventional reactor. A solids concentration or biomass ratio of 2.52 resulted in a hydrolysis ratio of 1.92. An approximate doubling of the biomass resulted in an approximate doubling of the hydrolysis rates for identical influent streams.
Nonchemically aided gravity sedimentation is a separation process that is not considered to be within the scope of separation techniques that have application in the context of the present invention. The inapplicability of nonchemically aided gravity sedimentation is a function of the inability of this type of separation technique to effectuate satisfactory separation between suspended colloidal and particulate constituents from soluble constituents in the effluent from influent anaerobic reactor 2. It is possible that sedimentation techniques that are aided or induced by chemicals may be suitable to remove substantially all of the suspended, colloidal and particulate material from the influent stream, and thus be useful in the context of the present invention.
Separator 4 produces a clarified effluent containing primarily inorganic dissolved solids and gases which is removed from separator 4 via line 5. The effluent from separator 4 can be discharged for further treatment to remove the dissolved solids and gases. The suspended, colloidal and particulate constituents, bacteria and inorganic precipitates separated from the soluble constituents are removed from separator 4 and delivered to the second anaerobic reactor 7 via line 6. While not intending to be limited to any particular solids content, the concentrated solids in line 6 preferably comprise about 4 to about 10 wt. % solids. This is in comparison to the influent in line 1 which has a significantly lower solids content. It is preferable to have the solids content of the material in line 6 as high as possible because the more concentrated the solid feed stream from separator 4, the smaller the second anaerobic reactor 7, provided the higher concentration of solids does not inhibit the anaerobic activity of the bacteria by limiting mixing and the release of gaseous products of digestion. The desired solids concentration from separator 6 can be calculated using known formula that relate influent inorganic solids concentration with the desired solids retention time and anaerobic digester concentration. The desired anaerobic digestion concentration is expected to be limited by mixing in dispersion considerations.
The concentrated solids from separator 7 comprise biomass, organic particulate and colloidal solids that have not been hydrolyzed, and inorganic precipitates, such as metal sulfides, struvite, phosphates, and other complex precipitates produced through bacterial decomposition. The organic particulate and colloidal constituents in line 6 are the more slowly hydrolyzed and degraded materials that composed the influent stream 1. Accordingly, they were not materially hydrolyzed or metabolized in influent reactor 2. These organic particulate and colloidal constituents are contacted with anaerobic bacteria in the second anaerobic reactor 7 for a period sufficient to hydrolyze and metabolize these constituents. The second anaerobic reactor is sized to promote this degradation of the slowly metabolized constituents with a high concentration of cultured bacteria. The high bacteria to substrate ratio will cause a more rapid hydrolysis of slowly metabolized constituents In addition, the second anaerobic reactor 7 is sized to provide a bacterial mass required for influent anaerobic reactor 2. By reducing the volume of influent to anaerobic reactor 7, its size is reduced a commensurate amount compared to the size that would be required if the soluble constituents were not separated in separator 4 but rather were passed through second anaerobic reactor 7.
Byproduct soluble gas is vented from second anaerobic reactor 7 through line 12, and waste solids are removed via line 9.
Wasting of solids from second anaerobic reactor 7 may occur in order to prevent the accumulation of inorganic precipitates. The quantity to be wasted will be a function of the influent inorganic solids content and the desired solids level to be maintained in the second anaerobic reactor. It is preferred to limit the quantity of solids to be wasted since the wasting will reduce the solids retention time or time available for hydrolysis of the very slow hydrolyzable constituents.
The concentration of biomass stored in second anaerobic reactor 7 will effect its hydraulic retention time. The hydraulic retention time of second anaerobic 7 will be dictated by the rate of decomposition of the slowly metabolized particulates as well as the mass of bacteria required to hydrolyze the influent substrate in first anaerobic reactor 2. Since the hydrolysis rate of the influent particulate constituents is a function of the bacterial mass contacting the substrate, the rate of outflow stream 8 from second anaerobic reactor 7 will be established by the influent hydrolysis requirements of first anaerobic reactor 2 and the concentration of biomass maintained in second anaerobic reactor 7. The detention time of second anaerobic reactor 7 will be established by the hydrolysis of the slowly metabolized particulates as well as the concentration of the products of anaerobic decomposition, such as ammonia and sulfides which may limit the detention time.
Unlike conventional anaerobic digestion process wherein hydraulic retention times average on the order of 20 days, the present process is able to be practiced with hydraulic retention times on the order of 5 days or less. The present applicant has observed that waste activated sludge and primary sewage sludge, which when treated by conventional anaerobic digestion processes is considered to have hydrolysis half lifes of 4 to 5 days. In contrast, hydrolysis half lifes on the order of about 1 day or less are achieved when waste is treated in accordance with the anaerobic digestion process of the present invention.
While the preferred embodiment of the invention has been illustrated and described, it will be appreciated that various changes can be made therein without departing from the spirit and scope of the invention. For instance, the first anaerobic reactor can comprise a fixed film reactor and the entire anaerobic digestion process can be supplemented by a carrier-assisted process using a synthetic substrate for the anaerobic bacteria. | An anaerobic digestion process capable of converting organic slurries to precipitates, as well as soluble and gaseous products through a series of reactors or process steps. The organic material is processed through three sequential steps consisting of two anaerobic digestion steps and an intermediate liquid/solid separation step. The sequential steps consist of first degrading rapidly metabolized soluble and particulate constituents, contained in the influent, by mixing the influent to the first reactor with an effluent from a second reactor containing a high concentration of active biomass. Effluent from the first reactor is treated in a second step wherein the soluble and particulate components are mechanically separated from an effluent stream essentially free of particulate material but containing soluble products of digestion. The particulate stream is transferred to the second anaerobic reactor wherein the solely degrading materials are converted to soluble and gaseous products of digestion as well as precipitates. | 2 |
BACKGROUND OF THE INVENTION
The present invention relates to testing electronic components such as discrete, analog components, and more specifically, is directed to methods and apparatus for acquiring and graphically displaying component test data.
Passive components such as resistors and capacitors as well as semiconductor junctions can be tested by applying an appropriate stimulus signal to a device under test (DUT), and then measuring circuit parameters such as voltage and/or current. One problem in the prior art test equipment is the limited range of capacitance values that can measured. Because prior art devices, such as the Huntron instrument described below, use analog oscillators as a source of test stimulus signals, their stimulus frequency range is limited. Accordingly, high capacitance components cannot be tested without a high-voltage stimulus source which in many applications is not practical. Moreover, stimulus signals generated using analog oscillators have only a limited selection of discrete frequencies available.
Graphical display of component test data, such as Lissajous patterns, is particularly useful in many applications. In the prior art, however, complex and expensive equipment such as an oscilloscope is required to generate such patterns. For example, using an oscilloscope, an X-channel can be used to acquire voltage data while a Y-channel is used to acquire current data. By displaying X versus Y with a common trigger to synchronize the display, Lissajous patterns or the like may be generated. This is not possible in simpler, hand-held instruments such as a digital multimeter (DMM) which have only a single channel "front-end".
A semiconductor test instrument known commercially as the "Huntron Tracker" is described in U.S. Pat. No. 4,074, 195. It is used for determining operating states of a semiconductor junction, and displaying a trace representative of the characteristics of the junction. One of the problems with the Huntron type of apparatus is that it requires a multi-tap transformer and voltage dividers for providing a range of AC test stimulus signals. More specifically, the prior art teaches a transformer driving a set of vertical voltage dividers to provide test signals for vertical deflection of the display, together with a set of horizontal voltage dividers to provide test signals for horizontal deflection of the display. See FIG. 1 of the `195 patent and column 4. The `195 system therefore requires constant AC power for operation, a heavy transformer, and a two-channel (vertical and horizontal) high-voltage display system like an oscilloscope. That technology, therefore, is not useful in lightweight, portable test equipment which is desirable for field use, for example by a repair technician.
The need remains, therefore, to provide new methods and apparatus for component testing which do not require high power or bulky equipment, yet provides wide range and high accuracy, at minimum cost.
SUMMARY OF THE INVENTION
One object of the present invention is to provide a variable frequency, highly accurate source of test stimulus signals to allow a larger range of capacitance testing without the complications of high-voltage circuitry.
A further object of the invention is to provide graphical current vs. voltage displays for rapid in-circuit testing of passive components and p-n junctions using a small, portable test instrument.
Another object of the invention is to allow a user to select a desired frequency of a test stimulus signal.
A new paradigm for component test is described herein to provide improved accuracy, greater flexibility and at the same time obviate entirely the need for heavy transformers and high-voltage display systems. Moreover, the present invention includes a component test system that may be implemented in a portable digital multimeter type of test instrument to provide a new graphical display. The new methods and apparatus are compatible with the simple multimeter type of user interface - based on a large rotary function switch -that is familiar to many field technicians, repair persons and engineers. Accordingly, user training requirements are minimal.
Another aspect of the invention is to employ digital synthesis of test stimulus waveforms. This has the advantages of high accuracy and low power requirements, so that the invention can be embodied in a compact, portable, battery-operable test instrument, as disclosed herein. Digital synthesis allows a wide range of frequency of AC test stimulus signals, so that a wide range of components such as capacitors can be tested without high voltages.
A further aspect of the invention is to acquire both voltage and current test scan data using only a single channel "front-end". Prior art requires independent vertical and horizontal input channels, amplifiers, deflection circuits, etc. The two channels are synchronized by a common trigger, and operate in parallel, i.e., simultaneously, in the prior art to generate Lissajous displays. According to the present invention, most of this redundancy is eliminated by using only one "front end" channel. Vertical and horizontal scans, e.g., voltage and current scans, actually are performed one at a time. However, precise digital triggering is used to synchronize the acquired data, so produce Lissajous display patterns as though two channels were in use. More specifically, a test periodic stimulus waveform is synthesized digitally, and a trigger signal is provided by the synthesis circuitry to indicate, very accurately, a predetermined trigger point relative to the start of each cycle of the stimulus waveform. This trigger signal is used to start acquisition of voltage scan data. After the first scan is completed (and the data stored), the same trigger signal is used to retrigger acquisition of current scan data. The current scan therefore begins at the same trigger point relative to the start of a later cycle of the stimulus waveform. The acquired data is stored in digital form, and simultaneously displayed in orthogonal directions to form a Lissajous pattern.
Another aspect of the invention is a digital multimeter (DMM) that includes means for providing a graphic display of test data. In particular, the improved DMM includes a component test mode of operation in which it displays Lissajoustype patterns for fast component identification and screening without use of complicated equipment such as oscilloscopes and elaborate testing procedures. An electronics technician or repair person can quickly use the improved DMM in component test mode without special training or test setup. Component test mode can be selected using a rotary function switch in the same manner as conventional voltage or impedance measurements are taken. The resulting display patterns provide quick visual feedback for component identification or simple good/bad decisions for troubleshooting.
A further aspect of the invention is to provide methods and apparatus for testing high impedance reactive circuits or circuit elements by increasing the frequency of an AC test stimulus signal. This has the advantage of allowing use of low-voltage test signals without sacrificing range and accuracy. The test stimulus signal is digitally synthesized in the preferred embodiment, and its frequency thus can by selected by applying an appropriate frequency clock signal to the synthesizer circuitry. For example, in one embodiment described below, a test instrument according to the present invention can measure capacitance over several decades of range, e.g., from 7200 pF to 72 NF. Since the frequency of the stimulus waveform is varied, rather than its voltage, the instrument can be operating on a battery power supply for portability. The stimulus waveform has a fixed amplitude on the order of a few volts.
The present invention combines the foregoing aspects to provide a component test function that includes graphical output in a lightweight, portable test instrument otherwise similar to a DMM.
The foregoing and other objects, features and advantages of the invention will become more readily apparent from the following detailed description of a preferred embodiment which proceeds with reference to the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A and 1B form a simplified block diagram of a test instrument that embodies various aspects of the present invention in the currently preferred embodiment.
FIG. 2 is a partially schematic/partially block diagram showing the component test signal source 80 of the test instrument of FIG. 1A in greater detail.
FIG. 3 illustrates a test stimulus signal generated by the instrument of FIGS. 1A-1B and FIG. 2 in a component test mode of operation.
FIG. 4 illustrates a portion of the front panel of a test instrument, showing a graphic component test display generated according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
I. SYSTEM OVERVIEW
FIGS. 1A-1B together form a general block diagram of a test instrument that embodies aspects of the present invention. The test instrument is similar in several of its functions to a known digital multimeter. For example, the instrument can be used to measure voltage, current or impedance as explained below. Additionally, it incorporates new features, circuits and methods of operation, as explained below, directed specifically to component testing. Since the component test aspects are interrelated with the overall system apparatus and operation, the instrument is described generally at the outset. The instrument generally comprises a front end, a data acquisition section, a control/memory section and a display section, each of which is described in turn as follows.
Front End Section
Referring to FIG. 1A, the "front end" section of the test instrument includes a pair of terminals 36, 40 for coupling a device under test (DUT) to the instrument via appropriate test leads or probes (not shown), as is conventional. For example, to measure AC or DC voltage, one lead is connected to a selected circuit node or DUT and a second lead is connected between terminal 40 and circuit ground or the opposite side of the DUT. For DC voltage measurement, the input voltage presented at terminal 36 passes through a protection circuitry 34 (via either high voltage or low voltage path) to a DC input attenuation circuit 62. When the instrument is set to operate as a DC voltage meter, the attenuated DC input signal passes through a DC filter 64 and a multiplexer 66 to an analog-to-digital converter A/D 68 for conversion into digital form. Display of the results is discussed later.
For AC measurements, the input signal originating at terminal 36 is routed through protection circuit 34 to an AC input attenuation circuit 70. The output of attenuation circuit 70 is coupled through an RMS converter 72 into the multiplexer 66. During AC meter operations, multiplexer 66 couples the RMS AC signal to the A/D converter 68. For current measurements, one or more additional terminals, e.g., terminal 76 (rather than the common terminal 40), is used for connecting the second lead to current switching circuitry 52. Further description of input attenuation and of meter operations is omitted as such is unnecessary to understanding the present invention. The front end also includes a component test source circuit 80 for providing test stimulus waveforms as described in detail later.
Data Acquisition Section
The Data Acquisition Section is described next with emphasis on aspects pertinent to component testing. When the test instrument is switched to the component testing function, a component test source circuitry 80 is activated to provide a periodic test stimulus signal. The stimulus signal is output through protection circuit 34 to a DUT 38 (FIG. 2) through terminal 36. During a voltage scan (further described below), terminal 36 is coupled through the protection circuit 34 to the DC input attenuation circuit 62 for measuring voltage at the terminal. The output of attenuation circuit 62, labeled "DC", is coupled to a combination circuit 82 (see FIG. 1B). From the combination circuit 82, the DC signal is input to a filter circuit 84. AC input voltage or signals pass through the protection circuit 34 to the AC input attenuation circuit 70 (FIG. 1A), the output of which, labeled "AC", is coupled to the filter circuit 84 (FIG. 1B).
The combination circuit 82 and filter circuit 84 thus recombine the AC and DC voltage components of the terminal signal, and the combined signal is input to a flash A/D converter 60 for conversion to digital form. The flash A/D is driven by a relatively fast clock, further described below. The resulting digital values are transmitted over a data bus 90 for storage in an acquisition memory 92, also further described below.
Component testing also includes acquiring current measurement data as follows. During component test mode, common terminal 40 is coupled to a component test current-to-voltage conversion circuit 42. The resulting voltage (representing current)is coupled to both the DC input attenuation circuit 62 and the AC input attenuation circuit 70. In alternative embodiment, these voltages may be routed through the protection circuit 34 to the attenuation circuits. (it should be noted here that voltage and current measurements are not conducted simultaneously. Thus, portions of the front end are used for both functions.) The DC and the AC voltage signals then are combined, filtered and converted to digital form as described above in the case of component test voltage measurements. The resulting digital current data also is provided over data bus 90 for storage in the acquisition RAM 92. Acquisition RAM 92 is a random access memory having a total size, in the currently preferred embodiment, of 512 by 8 bits. Operation of the data acquisition section is described in greater detail below in part III.
Control and Memory Section
Referring to FIG. 1 B, a microprocessor 130 is coupled to an address bus 102 and a data bus 104. The acquisition RAM 92 also is coupled to the address and data buses. Under control of the microprocessor 130 and appropriate software, scan data temporarily stored in the acquisition RAM 92 is transferred over data bus 104 to a system memory SRAM 134. The address and data buses also are coupled to a status and control registers 95, EEPROM 136 and read-only memory (ROM) 132. The EEPROM and ROM are used for storing software further described below. The common address and data buses 102, 104 also are coupled to a LCD (liquid crystal display) controller 138 for displaying stored data on a LCD module 140 described next.
Display Section
In a preferred embodiment, a graphical display is provided by a liquid-crystal display device, a variety of which are commercially available. LCD have the advantages of ruggedness, low cost and low power requirements versus other display technologies. However, any pixel-addressable display means can be used. An LCD suitable for the present application may be transflective or reflective and optionally may be backlit. In one commercial embodiment of the invention in a portable test instrument, an LCD module 140 has a total of 200 pixels (vertical) by 240 pixels (horizontal). Only 128 pixels vertically are used for a graphical display such as a Lissajous pattern (vertical corresponds to volts). Accordingly, only the 7 most significant bits (msb) of data are used. This leaves space for display of other text or numeric information such as meter operating mode, scaling, etc. above or below the graphical portion of the display. As for the horizontal display, 256 levels (8 bits) are stored and displayed. In practice, however, the 240 horizontal pixels are adequate as the data does not reach full scale. The display is centered over approximately 80 percent of full scale. Thus, the graphical portion of the display measures 128 high by 180 pixels wide. Referring to FIG. 4, front panel 200 has a liquid crystal display 140 of the type described. A graphical portion 230 of the display shows a Lissajous pattern 240 formed as described above. Other features of the display are described later.
II. DIRECT DIGITAL SYNTHESIS OF TEST STIMULUS WAVEFORMS
Hardware
FIG. 2 is a diagram of selected portions of the test instrument of FIGS. 1A-1B, to illustrate implementation of direct digital synthesis of test stimulus waveforms. FIG. 2 generally corresponds to the "component test source" 80 of FIG. 1A. Digital synthesis is a technique for generating variable frequency, repetitive signals, such as a sine-wave. The disclosed apparatus may be used, however, to generate other waveforms such as a staircase or an arbitrary waveform.
Referring now to FIG. 2, a digital synthesis module 110 provides a test stimulus signal in digital form, i.e., as a series of digital values, to a digital to analog converter D/A 133. D/A 133 converts these values to form a corresponding analog test signal, which in turn is output to a device under test DUT 38 through terminal 36 as described above. In module 110, a clock input signal, called C-TEST CLOCK, is applied to an 8-bit counter 112. Counter 112 controls the entire stimulus generator circuitry as further described below. The C-TEST CLOCK has a frequency equal to 256 times a user-selected test stimulus signal frequency. (The C-TEST CLOCK source is described later.) Counter 112 is coupled to a control logic block 114, which in turn controls a 6-bit up/down counter 115, by selecting UP or DOWN counting modes. The up/down counter 115 receives the component test clock input signals via clock signal line 113. Accordingly, counter 112 and up/down counter 115 count at the same rate, but since counter 112 has two more bits, it has four more states. These four states correspond to the quadrants of the synthesized test stimulus signal.
The up/down counter 115 supplies a six-bit address to a look-up table 118, which can be stored in a memory such as a ROM or EPROM or other non-volatile memory. In the preferred embodiment, the lookup function is provided by combinatorial logic rather than a true memory. This strategy is advantageous for implementation in an integrated circuit such as a digital ASIC as it requires fewer gates than a true ROM table. The address bits from up/down counter 115 are used to sequentially access 64 predetermined values in the look-up table. For example, if the desired test waveform is a sine wave, the 64 stored values form one quadrant of the sine wave, starting at a zero crossing. In the preferred embodiment, the look-up table provides 64 words of 7-bits each, each word containing the seven least significant bits of the quarter sine-wave data. An overflow output of counter 112 provides the component test ("C-TEST") trigger signal. This signal is asserted once per cycle of the test stimulus waveform as further explained below. The C-TEST TRIGGER signal provides an exact trigger point for both current and voltage scans.
Lookup table 118 provides the series of 7-bit values to a digital complementor circuit 120. The digital complementor circuitry 120 complements or buffers the lookup table 118 output, depending on its input from the control logic 114. The resulting values, together with the inverted most significant bit from counter 112, are provided as inputs to the 8-bit digital-to-analog converter DAC 133. Referring now to FIG. 2 as well as FIGS. 1A-1B, interface circuitry indicated by dashed line 131 includes a DAC 133, as well as elements common to FIGS. 1A-1B. Thus, the protection circuit 34 and the terminal 36 are shown for coupling the synthesized test stimulus signal to DUT 38. The DUT also is coupled to input terminal 40. Current through the DUT is converted to voltage in the component test current to voltage conversion circuit 42 to form a representative voltage at node 144 during a current scan. The stimulus signal at terminal 36 also is coupled through a resistor 146 to present the stimulus voltage at node 148. Nodes 144 and 148 are coupled to respective inputs of the input multiplexer 149 for selecting one of these signals at a time. The selected signal is output from multiplexer 149 to a flash ND converter 60.
Operation of Digital Test Signal Synthesis
Referring now to FIGS. 2 and 3, an example of a digitally synthesized test signal waveform 150 is illustrated. During the first quadrant 152, counter 112 and up/down counter 115 synchronously count UP, with the most significant bit of counter 112 being zero (msb=0). Up/down counter 115 outputs a series of 64 addresses to the lookup table 118, and the resulting series of digital values are passed to the DAC 133 as noted previously. This series of values, converted to analog voltage levels, forms the first quadrant of waveform 150. Control logic 114 receives the msb of counter 112, and responsive thereto sets the digital complementor 120 off i.e., the input signals to the complementor are passed to the output (D/A 133) without complementation. This is true during the first and second quadrants.
During the second quadrant 154, the sine-wave has the same values as the first quarter, but they occur in reverse order. To accomplish this, Up/down counter 115 is controlled by control logic 114 to count DOWN. Again, the lookup values are not complemented but are passed to the DAC 133, thereby forming the second quadrant of the stimulus signal 150.
To generate the second half of the sine-wave, several changes must occur. First, the most significant bit (msb) of counter 112 is set (msb=1). This bit, when inverted and passed to the most significant bit of DAC 133, causes the DAC to use the lower half of its scale. Second, this bit enables the digital complementor 120 to complement the digital values from the lookup table. The complemented data causes DAC 133 to achieve the concave shape of this second half of the waveform 150. The up/down counter 115 counts up during this third quadrant 156. To summarize, during this quadrant, up/down counter 155 is again counting UP, the digital complementor is enabled, and DAC 133 is using the lower half of its scale.
Finally, during the last quadrant 158, the Up/down counter is switched to again count DOWN and the complementor remains on, thereby completing the digitally synthesized sine-wave. After the fourth quadrant, counter 112 overflows and the process starts over automatically, thereby generating a consistent, periodic stimulus signal. The circuitry disclosed has the advantage of minimizing the necessary circuitry because digital values need be stored in the lookup table for only one-fourth of each cycle of the desired waveform. Other periodic waveforms can be generated in the manner described.
Stimulus Signal Voltage
The component test stimulus waveform is coupled to the DUT at terminal 36 through a source channel of the protection circuit 34. This channel includes an op-amp (not shown) coupled to the output of D/A converter 133 (FIG. 2) to provide the stimulus signal. In a presently preferred commercial embodiment, the stimulus waveform has a peak voltage of 3.2 volts. An internal power supply provides a fixed 5 volts DC to power the instrument. The instrument can be powered by AC line voltage through a "battery eliminator" as is known, or by batteries for portable operation. For example, a series of approximately 6-8 "AA" size batteries can be used to provide raw power to the internal DC supply. Alternatively, a NiCad battery pack can be used to allow for recharging the supply. A suitable NiCad battery pack, commercially available, provides approximately 6-12 volts DC, depending on the charge level. The 3.2 volt peak fixed stimulus voltage is adequate for testing a wide range of reactive components, e.g., capacitors having values in a range of approximately 7200 pF to 72 μF, by selecting the stimulus waveform frequency over a range of 2 Hz to 20 kHz, as described below. The frequency is selected so that the resulting graphic display (such as a Lissajous pattern) is of appropriate size for easy visual inspection. This range of frequencies is available using the above digital synthesis technique. Accordingly, an advantage of the present invention is the ability to test components over a wide range of reactance, and obtain useful graphic displays of scan data, using a fixed, low-voltage stimulus signal source.
III. COMPONENT TEST OPERATION
Continuous Data Acquisition
In operation, when the instrument is switched to the component test mode of operation, the component test stimulus waveform generator described above is activated (by the control microprocessor 130) so that it continuously generates a periodic stimulus waveform such as a sine wave. The stimulus waveform is applied to the DUT as described above. Other sources of test waveforms could be used. For example, an external signal generator could provide the stimulus signal, as long as a trigger signal synchronized with the external signal is also provided for triggering data acquisition as will become apparent.
Measurement data is acquired continuously through the hardware as described above. More specifically, the acquisition control circuit 93 controls acquisition RAM 92 so as to write a data point into the RAM on each cycle of the retention clock, which is provided to the control circuit by a divide-by-n circuit 97 (FIG. 1B). In the currently preferred embodiment, 256 data points are acquired over each cycle of the test stimulus waveform. Note that the C-test clock runs at 256 times the test waveform frequency. Accordingly, the retention clock and the C-test clock in this case are the same. Divide-by-n circuit 97 receives a system clock signal having a frequency of, for example, 19.2 MHz, as provided by a crystal-based oscillator (not shown). Data points are stored sequentially into the RAM 92, which is arranged as a circular buffer. Thus, new data overwrites previously stored data once the buffer is full.
The user can select a desired test stimulus signal frequency. A value of "n" corresponding to the selected frequency is stored in a register for controlling the divider circuit 97 to provide the appropriate clock signal as both C-clock and the retention clock. Referring again to FIG. 4, front panel 200 includes a pixel-addressable display module 140 such as the LCD display described above. A row of "soft keys", for example soft keys 220, 222 may be used for selection of a desired frequency. "Soft keys" refers to hardware keyswitches (labeled 1-5 in the figure) which are used for different input functions depending on the present mode of operation of the instrument. Note the mode indicator 218 on the display screen indicating that the instrument is in the "Component test" mode. In that mode, soft keys 1-5 correspond to stimulus signal frequencies of 2 Hz, 20 Hz, 200 Hz, 2 kHz and 18.75 kHz respectively, as indicated along the bottom of the display at 224. One of the soft keys labeled 226 is highlighted or reverse video to indicate the currently selected value of 200 Hz.
Scan Triggering
Next, the microprocessor sets a flag (in status and control registers 95) to indicate start of a voltage scan. In response, the acquisition control circuit 93 enables a storage trigger. At the beginning of the next cycle of the test waveform (e.g., when counter 112 next overflows after the storage trigger is enabled), a voltage scan begins. Thus, the voltage scan is triggered by the start of the next test waveform cycle. At that time, the current value of the acquisition RAM address is stored in a register, so that it points to the start of the stored voltage scan data. Measurement data continues to be acquired and digital voltage samples stored in the acquisition RAM for exactly one cycle of the test stimulus signal. This completes one scan -referred to as a voltage scan where voltage is being acquired. The acquired sample data comprises a series of 256 digital data words or values. Once 256 values have been acquired, storage in the RAM is stopped so that it is not overwritten. The microprocessor then moves the acquired scan data into SRAM 134.
After the voltage scan is completed, the front end circuitry is switched to acquire current data as described previously. The microprocessor then sets a flag to initiate the start of the current scan. Again, data acquisition continues, with acquired current sample data being stored in RAM 92 in the same fashion as voltage data. As in the case of a voltage scan, the acquisition control circuit 93 enables a storage trigger. At the beginning of the next cycle of the test waveform, i.e., when counter 112 next overflows after the storage trigger has been set, a current scan begins. The present value of the acquisition RAM address is stored as a start address for the digital current scan data. Acquired data is stored over one cycle, i.e., 256 data points as with the voltage sample data. Subsequently, the stored current scan data is moved into SRAM 134.
Note that both current and voltage scans were triggered by exactly the same trigger point, namely the beginning or other predetermined phase point of a test stimulus waveform cycle. As a result, the stored voltage and current scan data are "synchronized" with respect to the periodic stimulus waveform, and therefore their phase relationship is maintained, just as if they had been acquired simultaneously. Although the foregoing operation described the voltage scan as preceding the current scan, the order of the scans can be reversed.
The stored digital voltage and current scan data are aligned in the SRAM. That is, they are stored as voltage -current data pairs, in the order acquired, starting from a common starting address in the SRAM. In this way, the data pairs are conveniently provided to the LCD controller 138 for concurrent display so as to form a Lissajous pattern on the display module 140.
While it is convenient to trigger on the rising zero-crossing of the periodic test waveform, any arbitrary phase point on the cycle can be used as the trigger point. It is essential only that the same trigger point be used for both voltage and current scans if Lissajous patterns are desired for display. Overflow of counter 112 conveniently provides a trigger signal corresponding to the positive zero-crossing of the test waveform. Any state of the counter, however, corresponding to any desired point on the test waveform could be decoded to provide the trigger signal. Other parts of the waveform generation circuit can also be used to generate the trigger circuit, such as the up/down counter 115.
Having illustrated and described the principles of my invention in a preferred embodiment thereof, it should be readily apparent to those skilled in the art that the invention can be modified in arrangement and detail without departing from such principles. I claim all modifications coming within the spirit and scope of the accompanying claims. | A "component test" function is provided in a low-power, portable test instrument like a digital multimeter. A test stimulus waveform is synthesized digitally, and a digital trigger signal from the synthesizing circuitry is used to trigger acquisition of measurement data. A single-channel front end acquires voltage scan data over one cycle of the test stimulus waveform following the trigger point. Current scan data is later acquired through the same acquisition circuitry beginning at the same trigger point relative to the start of a later cycle of the stimulus waveform, so that the voltage and current scan data, although acquired separately, are very closely synchronized relative to the stimulus waveform, as a result of which they maintain their phase relationship. Stored voltage and current scan data are aligned accordingly and concurrently displayed so as to form a Lissajous pattern on a small display. The invention thus provides improved component test capability in a small, portable instrument, including graphic display of test results. | 6 |
CROSS REFERENCE TO RELATED APPLICATIONS
The present application is related to four co-pending and commonly-owned applications filed on even date herewith, the disclosure of each is hereby incorporated by reference in their entirety, these four applications being respectively entitled:
(1) “SURGICAL INSTRUMENT INCORPORATING AN ARTICULATION MECHANISM HAVING ROTATION ABOUT THE LONGITUDINAL AXIS” to Kenneth S. Wales, Douglas B. Hoffman, Frederick E. Shelton IV, and Jeff Swayze; (2) “SURGICAL STAPLING INSTRUMENT INCORPORATING AN ARTICULATION JOINT FOR A FIRING BAR TRACK” to Douglas B. Hoffman; (3) “SURGICAL STAPLING INSTRUMENT HAVING ARTICULATION JOINT SUPPORT PLATES FOR SUPPORTING A FIRING BAR” to Kenneth S. Wales and Joseph Charles Hueil; and (4) “A SURGICAL INSTRUMENT WITH A LATERAL-MOVING ARTICULATION CONTROL” to Kenneth S. Wales.
FIELD OF THE INVENTION
The present invention relates in general to surgical stapler instruments that are capable of applying lines of staples to tissue while cutting the tissue between those staple lines and, more particularly, to improvements relating to stapler instruments and improvements in processes for forming various components of such stapler instruments that include an articulating shaft.
BACKGROUND OF THE INVENTION
Endoscopic surgical instruments are often preferred over traditional open surgical devices since a smaller incision tends to reduce the post-operative recovery time and complications. Consequently, significant development has gone into a range of endoscopic surgical instruments that are suitable for precise placement of a distal end effector at a desired surgical site through a cannula of a trocar. These distal end effectors engage the tissue in a number of ways to achieve a diagnostic or therapeutic effect (e.g., endocutter, grasper, cutter, staplers, clip applier, access device, drug/gene therapy delivery device, and energy device using ultrasound, RF, laser, etc.).
Positioning the end effector is constrained by the trocar. Generally these endoscopic surgical instruments include a long shaft between the end effector and a handle portion manipulated by the clinician, this long shaft enables insertion to a desired depth and rotation about the longitudinal axis of the shaft, thereby positioning the end effector to a degree. With judicious placement of the trocar and use of graspers, for instance, through another trocar, often this amount of positioning is sufficient. Surgical stapling and severing instruments, such as described in U.S. Pat. No. 5,465,895, are an example of an endoscopic surgical instrument that successfully positions an end effector by insertion and rotation.
More recently, U.S. Appl. Ser. No. 10/443,617, “SURGICAL STAPLING INSTRUMENT INCORPORATING AN E-BEAM FIRING MECHANISM” to Shelton et al., filed on 20 May 2003, describes an improved “E-beam” firing bar for severing tissue and actuating staples. Some of the additional advantages include affirmatively space the jaws of the end effector, even if slightly too much or two little tissue is clamped for optimal staple formation. Moreover, the E-beam firing bar includes engages the end effector and staple cartridge in a way that enables several beneficial lockouts to be incorporated.
Depending upon the nature of the operation, it may be desirable to further adjust the positioning of the end effector of an endoscopic surgical instrument rather than being limited to insertion and rotation. In particular, it is often desirable to orient the end effector at an axis transverse to the longitudinal axis of the shaft of the instrument. The transverse movement of the end effector relative to the instrument shaft is conventionally referred to as “articulation”. This articulated positioning permits the clinician to more easily engage tissue in some instances. In addition, articulated positioning advantageously allows an endoscope to be positioned behind the end effector without being blocked by the instrument shaft.
While the aforementioned non-articulating stapling and severing instruments have great utility and may be successfully employed in many surgical procedures, it is desirable to enhance their operation with the ability to articulate the end effector, thereby giving greater clinical flexibility in their use.
Approaches to articulating a stapling and severing tend to be complicated by integrating control of the articulation along with the control of closing the end effector to clamp tissue and firing (i.e., stapling and severing) the end effector within the small diameter constraints of an endoscopic instrument. Generally, the three control motions are all transferred through the shaft as longitudinal translations. For instance, U.S. Pat. No. 5,673,840 discloses an accordion-like articulation mechanism (“flex-neck”) that is articulated by selectively drawing back one of two connecting rods through the implement shaft, each rod offset respectively on opposite sides of the shaft centerline.
Another example of longitudinal control of an articulation mechanism is U.S. Pat. No. 5,865,361 that includes an articulation link offset from a camming pivot such that pushing or pulling longitudinal translation of the articulation link effects articulation to a respective side. Similarly, U.S. Pat. No. 5,797,537 discloses a similar rod passing through the shaft to effect articulation.
While these longitudinally controlled articulation mechanisms have provided certain advantages to surgical instruments such as for endoscopic stapling and severing, it is believed that an alternative articulation motion would provide additional design flexibility. In particular, advantageous approaches are described in the four above cross-referenced and co-pending applications wherein a rotational motion relative to a longitudinal axis of the shaft transfers an articulating motion to an articulation mechanism coupling the end effector to the shaft.
What would be further desirable is to retain the advantages of an E-beam firing bar in a surgical stapling and severing instrument in combination with a rotationally controlled articulation mechanism. Consequently, a significant need exists for such an instrument incorporating a firing beam that advantages severs clamped tissue, engages the jaws of the end effector for affirmatively-controlled stapling, yet is coupled for firing motion through an articulation mechanism.
SUMMARY OF THE INVENTION
The invention overcomes the above-noted and other deficiencies of the prior art by providing a firing bar that is effective in longitudinally actuating an end effector and also has a tapered proximal portion that is effective in flexing through an articulating shaft. Thereby, the clinical advantages of an articulating surgical instrument are realized without degrading consistent operation of the end effector.
On one aspect of the invention, a surgical instrument has a handle portion that produces an articulation motion and a firing motion that are transferred through a shaft having a longitudinal axis. An articulation mechanism coupling the shaft to an end effector and responsive to the articulation motion to rotate the end effector from the longitudinal axis of the shaft. A firing mechanism responds to the firing motion and is coupled for movement through the articulation mechanism and end effector. In particular, the firing mechanism has an actuating portion having a first thickness and positioned in the end effector and an articulation portion proximally attached to the actuating portion and having a second thickness less than the first thickness for articulating movement through the articulation mechanism. Thereby the firing mechanism is effective at both actuating the end effector and articulating through the articulation mechanism.
In another aspect of the invention, a surgical instrument has a handle portion that produces a firing motion, a closing motion, and an articulation motion, with all threw separately transferred down a shaft. An end effector is pivoted by an articulation mechanism responsive to the articulation motion. The end effector includes an elongate channel coupled to the shaft and including a channel slot. An anvil is pivotally coupled to the elongate channel and is responsive to the closing motion from the shaft and has an anvil channel. A firing device has a distally presented cutting edge longitudinally received between the elongate channel and the anvil and includes a thinned strip portion transitioning through the articulation mechanism.
In yet another aspect of the invention, a surgical instrument has a handle portion operably configured to produce a rotational articulation motion and a longitudinal firing motion, which are transferred through a shaft. An articulation mechanism responds to the rotational articulation motion to articulate an end effector. A firing bar responds to the longitudinal firing motion of the handle portion. The firing bar includes an elongate strip longitudinally positioned for movement through the articulation mechanism and has a firing bar head distally connected to the elongate strip and positioned for longitudinal movement in the end effector.
These and other objects and advantages of the present invention shall be made apparent from the accompanying drawings and the description thereof.
BRIEF DESCRIPTION OF THE FIGURES
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention, and, together with the general description of the invention given above, and the detailed description of the embodiments given below, serve to explain the principles of the present invention.
FIG. 1 is a perspective view of an articulating surgical instrument in a nonarticulated position.
FIG. 2 is a perspective view of an articulating surgical instrument in an articulated position.
FIG. 3 is a perspective view of an opened end effector of the articulating surgical instrument of FIGS. 1–2 .
FIG. 4 depicts a side elevation view in section of the end effector of FIG. 3 of the surgical instrument of FIG. 1 , the section generally taken along lines 4 — 4 of FIG. 3 to expose portions of a staple cartridge but also depicting the firing bar along the longitudinal centerline.
FIG. 5 depicts a side elevation view in section of the end effector of FIG. 4 after the firing bar has fully fired.
FIG. 6 depicts a side elevation view in section of a handle portion of a proximal end of the surgical instrument of FIG. 1 including a rotating articulation control.
FIG. 7 depicts a perspective, exploded view of the handle portion of the proximal end of the surgical instrument of FIG. 1 .
FIG. 8 depicts a perspective view looking downward, forward and to the right of a distal portion of the handle portion of the surgical instrument of FIG. 1 partially cutaway to expose a rotating articulation control mechanism.
FIG. 9 depicts a perspective view looking upward, rearward and to the right of the distal portion of the handle portion of FIG. 8 , partially cutaway to expose the rotating articulation control mechanism and have a rotating articulation control knob disassembled.
FIG. 10 depicts a top perspective detail view of a spur gear articulation mechanism and end effector of the surgical instrument of FIG. 1 with firing and frame portions removed.
FIG. 11 depicts a perspective, exploded view of an implement portion of the surgical instrument of FIG. 1 including a spur gear articulation mechanism.
FIG. 12 depicts a top sectional view of the spur gear articulation mechanism of FIG. 11 .
DETAILED DESCRIPTION OF THE INVENTION
Turning to the Drawings, wherein like numerals denote like components throughout the several views, FIGS. 1–3 depict a surgical instrument, which in the illustrative embodiment is more particularly a surgical stapling and severing instrument 10 , that is capable of practicing the unique benefits of the present invention. In particular, the surgical stapling and severing instrument 10 is sized for insertion, in a nonarticulated state as depicted in FIG. 1 , through a trocar cannula passageway to a surgical site in a patient for performing a surgical procedure. Once an articulation mechanism 11 and a distally attached end effector 12 are inserted through the cannula passageway, the articulation mechanism 11 may be remotely articulated, as depicted in FIG. 2 , by an articulation control 13 . Thereby, the end effector 12 may reach behind an organ or approach tissue from a desired angle or for other reasons. For instance, a firing mechanism, advantageously depicted as an E-beam firing bar 14 (depicted in FIG. 3 ), that severs clamped tissue, engages an elongate channel 16 and a pivotally attached anvil 18 .
The surgical and stapling and severing instrument 10 includes a handle portion 20 connected to an implement portion 22 , the latter further comprising a shaft 23 distally terminating in the articulating mechanism 11 and the end effector 12 . The handle portion 20 includes a pistol grip 24 toward which a closure trigger 26 is pivotally drawn by the clinician to cause clamping, or closing, of the anvil 18 toward the elongate channel 16 of the end effector 12 . A firing trigger 28 is farther outboard of the closure trigger 26 and is pivotally drawn by the clinician to cause the stapling and severing of clamped tissue in the end effector 12 . Thereafter, a release button 30 is depressed to release the clamped tissue.
An outmost closure sleeve 32 of the shaft 23 longitudinally translates in response to the closure trigger 26 to pivotally close the anvil 18 . Specifically, a distal portion, or closure ring 33 , of the closure sleeve 32 with respect to the articulation mechanism 11 is indirectly supported by a frame 34 of the implement portion 22 (partially visible at the articulation mechanism 11 ). At the articulation mechanism 11 , a proximal portion, or closure tube 35 , of the closure sleeve 32 communicates with the distal portion (closure ring) 33 . The frame 34 is flexibly attached to the elongate channel 16 via the articulation mechanism 11 , enabling articulation in a single plane. The frame 34 also longitudinally slidingly supports a firing drive member 36 that communicates a firing motion from the firing trigger 28 to the firing bar 14 . Only the firing bar 14 of the firing drive member 36 is depicted FIG. 3 , but the firing drive member 36 is described below further detail with regard to various versions of a rotationally controlled articulation mechanism 11 .
It will be appreciated that the terms “proximal” and “distal” are used herein with reference to a clinician gripping a handle of an instrument. Thus, the end effector 12 is distal with respect to the more proximal handle portion 20 . It will be further appreciated that for convenience and clarity, spatial terms such as “vertical” and “horizontal” are used herein with respect to the drawings. However, surgical instruments are used in many orientations and positions, and these terms are not intended to be limiting and absolute.
E-Beam Firing Bar
FIGS. 3–5 depict the end effector 12 employing the E-beam firing bar 14 to perform a number of functions. In FIG. 3 , the firing bar 14 is proximally positioned, allowing an unspent staple cartridge 37 to be installed into the elongate channel 16 . In particular, an upper pin 38 of the firing bar 14 resides within a recess, depicted as an anvil pocket 40 allowing the anvil 18 to be repeatedly opened and closed. With the end effector closed as depicted in FIG. 4 , the firing bar 14 is advanced in engagement with the anvil 18 by having the upper pin 38 enter a longitudinal anvil slot 42 . A lower most pin, or firing bar cap 44 , engaged a lower surface of the elongate channel 16 by having the firing bar 14 extend through a channel slot 45 . A middle pin 46 slidingly engages a top surface of the elongate channel 16 , cooperating with the firing bar cap 44 . Thereby, the firing bar 14 affirmatively spaces the end effector 12 during firing, overcoming pinching that may occur with a minimal amount of clamped tissue and overcoming staple malformation with an excessive amount of clamped tissue.
During firing, a distally presented cutting edge 48 between the upper pin 38 and middle pin 46 of the firing bar enters a proximally presented vertical slot 49 of the staple cartridge 37 , severing tissue clamped between the staple cartridge 37 and the anvil 18 . As shown in FIG. 4 , the middle pin 46 actuates the staple cartridge 37 by entering into a firing slot within the staple cartridge 37 , driving a wedge sled 41 into upward camming contact with staple drivers 43 that in turn drive a plurality of staples 47 out of staple apertures 51 in the staple cartridge 37 into forming contact with staple pockets 53 on an inner surface of the anvil 18 . FIG. 5 depicts the firing bar 14 fully distally translated after completing severing and stapling tissue.
Two-Axis Handle
With reference to FIGS. 6–7 , the handle portion 20 is comprised of first and second base sections 50 and 52 , which are molded from a polymeric material such as a glass-filled polycarbonate. The first base section 50 is provided with a plurality of cylindrical-shaped pins 54 . The second base section 52 includes a plurality of extending members 56 , each having a hexagonal-shaped opening 58 . The cylindrical-shaped pins 54 are received within the hexagonal-shaped openings 58 and are frictionally held therein for maintaining the first and second base sections 50 and 52 in assembly.
A housing cap 60 has a bore 62 extending completely through it for engaging and rotating the implement portion 22 about its longitudinal axis. The housing cap 60 includes an inwardly protruding boss 64 extending along at least a portion of the bore 62 . The protruding boss 64 is received within a longitudinal slot 66 formed at a proximal portion of the closure sleeve 32 such that rotation of the housing cap 60 effects rotation of the closure sleeve 32 . It will be appreciated that the boss 64 further extends through frame 34 and into contact with a portion of the firing drive member 36 to effect their rotation as well. Thus, the end effector 12 (not shown in FIGS. 3–4 ) rotates with the housing cap 60 .
A proximal end 68 of the frame 34 passes proximally through the housing cap 60 and is provided with a circumferential notch 70 that is engaged by opposing channel securement members 72 extending respectively from the base sections 50 and 52 . Only the channel securement member 72 of the second base section 52 is shown. The channel securement members 72 extending from the base sections 50 , 52 serve to secure the frame 34 to the handle portion 20 such that the frame 34 does not move longitudinally relative to the handle portion 20 .
The closure trigger 26 has a handle section 74 , a gear segment section 76 , and an intermediate section 78 . A bore 80 extends through the intermediate section 78 . A cylindrical support member 82 extending from the second base section 52 passes through the bore 80 for pivotally mounting the closure trigger 26 on the handle portion 20 . A second cylindrical support member 83 extending from the second base section 52 passes through a bore 81 of firing trigger 28 for pivotally mounting on the handle portion 20 . A hexagonal opening 84 is provided in the cylindrical support member 83 for receiving a securement pin (not shown) extending from the first base section 50 .
A closure yoke 86 is housed within the handle portion 20 for reciprocating movement therein and serves to transfer motion from the closure trigger 26 to the closure sleeve 32 . Support members 88 extending from the second base section 52 and securement member 72 , which extends through a recess 89 in the yoke 86 , support the yoke 86 within the handle portion 20 .
A proximal end 90 of the closure sleeve 32 is provided with a flange 92 that is snap-fitted into a receiving recess 94 formed in a distal end 96 of the yoke 86 . A proximal end 98 of the yoke 86 has a gear rack 100 that is engaged by the gear segment section 76 of the closure trigger 26 . When the closure trigger 26 is moved toward the pistol grip 24 of the handle portion 20 , the yoke 86 and, hence, the closure sleeve 32 move distally, compressing a spring 102 that biases the yoke 86 proximally. Distal movement of the closure sleeve 32 effects pivotal translation movement of the anvil 18 distally and toward the elongate channel 16 of the end effector 12 and proximal movement effects closing, as discussed below.
The closure trigger 26 is forward biased to an open position by a front surface 130 interacting with an engaging surface 128 of the firing trigger 28 . Clamp first hook 104 that pivots top to rear in the handle portion 20 about a pin 106 restrains movement of the firing trigger 28 toward the pistol grip 24 until the closure trigger 26 is clamped to its closed position. Hook 104 restrains firing trigger 28 motion by engaging a lockout pin 107 in firing trigger 28 . The hook 104 is also in contact with the closure trigger 26 . In particular, a forward projection 108 of the hook 104 engages a member 110 on the intermediate section 78 of the closure trigger 26 , the member 110 being outward of the bore 80 toward the handle section 74 . Hook 104 is biased toward contact with member 110 of the closure trigger 26 and engagement with lockout pin 107 in firing trigger 28 by a release spring 112 . As the closure trigger 26 is depressed, the hook 104 is moved top to rear, compressing the release spring 112 that is captured between a rearward projection 114 on the hook 104 and a forward projection 116 on the release button 30 .
As the yoke 86 moves distally in response to proximal movement of the closure trigger 26 , an upper latch arm 118 of the release button 30 moves along an upper surface 120 on the yoke 86 until dropping into an upwardly presented recess 122 in a proximal, lower portion of the yoke 86 . The release spring 112 urges the release button 30 outward, which pivots the upper latch arm 118 downwardly into engagement with the upwardly presented recess 122 , thereby locking the closure trigger 26 in a tissue clamping position.
The latch arm 118 can be moved out of the recess 122 to release the anvil 18 by pushing the release button 30 inward. Specifically, the upper latch arm 118 pivots upward about pin 123 of the second base section 52 . The yoke 86 is then permitted to move proximally in response to return movement of the closure trigger 26 .
A firing trigger return spring 124 is located within the handle portion 20 with one end attached to pin 106 of the second base section 52 and the other end attached to a pin 126 on the firing trigger 28 . The firing return spring 124 applies a return force to the pin 126 for biasing the firing trigger 28 in a direction away from the pistol grip 24 of the handle portion 20 . The closure trigger 26 is also biased away from pistol grip 24 by engaging surface 128 of firing trigger 28 biasing front surface 130 of closure trigger 26 .
As the closure trigger 26 is moved toward the pistol grip 24 , its front surface 130 engages with the engaging surface 128 on the firing trigger 28 causing the firing trigger 28 to move to its “firing” position. When in its firing position, the firing trigger 28 is located at an angle of approximately 45° to the pistol grip 24 . After staple firing, the spring 124 causes the firing trigger 28 to return to its initial position. During the return movement of the firing trigger 28 , its engaging surface 128 pushes against the front surface 130 of the closure trigger 26 causing the closure trigger 26 to return to its initial position. A stop member 132 extends from the second base section 52 to prevent the closure trigger 26 from rotating beyond its initial position.
The surgical stapling and severing instrument 10 additionally includes a reciprocating section 134 , a multiplier 136 and a drive member 138 . The reciprocating section 134 comprises a wedge sled, or wedge sled, in the implement portion 22 (not shown in FIG. 6-7 ) and a metal drive rod 140 .
The drive member 138 includes first and second gear racks 141 and 142 . A first notch 144 is provided on the drive member 138 intermediate the first and second gear racks 141 , 142 . During return movement of the firing trigger 28 , a tooth 146 on the firing trigger 28 engages with the first notch 144 for returning the drive member 138 to its initial position after staple firing. A second notch 148 is located at a proximal end of the metal drive rod 140 for locking the metal drive rod 140 to the upper latch arm 118 of the release button 30 in its unfired position.
The multiplier 136 comprises first and second integral pinion gears 150 and 152 . The first integral pinion gear 150 is engaged with a first gear rack 154 provided on the metal drive rod 140 . The second integral pinion gear 152 is engaged with the first gear rack 141 on the drive member 138 . The first integral pinion gear 150 has a first diameter and the second integral pinion gear 152 has a second diameter that is smaller than the first diameter.
Rotational Articulation Control
With reference to FIGS. 6–9 , the handle portion 20 advantageously incorporates the articulation control 13 that both rotates the implement portion 22 about the longitudinal axis of the surgical instrument 10 and articulates the end effector 12 to an angle with the longitudinal axis. A hollow articulation drive tube 200 is concentrically located within the closure sleeve 32 and is operably coupled to an actuation lever 202 such that rotation of actuation lever 202 rotates tube 200 about the longitudinal axis and causes perpendicular rotation or articulation of the closure ring 250 and end effector 12 . This articulation of the closure ring 250 corresponds to the degree and direction of rotation of actuator lever 202 viewed and manipulated by the clinician. In the illustrative version, the relationship is one to one, with the degree of rotation of the actuator lever 202 corresponding to the degree of articulation from the longitudinal axis of the shaft 23 , thus providing an intuitive indication to the clinician. It will be appreciated that other angular relationships may be selected.
The articulation control 13 includes a pair of mirrored articulation transmission housings 204 that are attached to the housing cap 60 . Moreover, the articulation transmission housing 204 includes longitudinally aligned external tabs 206 that a clinician twists to effect rotation of the articulation transmission housing 204 , and thus of the end effector 12 , about the longitudinal axis of the implement portion 22 . The actuator lever 202 is attached to a cylindrical articulation body 208 that resides within a cylindrical recess 210 opening generally upward and perpendicular to the shaft 23 . The lowermost portion of the articulation body 208 includes prongs 212 that snap fit into an opening 214 in the articulation transmission housing 208 near to the shaft 23 , the prongs 212 preventing the articulation body 208 from being withdrawn from the cylindrical recess 210 .
Annularly presented gear teeth 216 are located about the lower portion of the articulation body 208 and mesh with teeth 218 on an articulation yoke 220 . The articulation yoke 220 straddles an articulation rectangular window 222 formed in the closure sleeve 32 . Closure sleeve 32 is slidably moveable within the articulation control 13 (in the longitudinal direction) to close and open the end effector 12 . The articulation drive tube 200 moves longitudinally with the closure sleeve 32 relative to the fixed articulation control 13 . Window 222 provides clearance for a boss 224 inwardly presented from the articulation yoke 220 that passes through the rectangular window 222 to engage a slot 226 in the articulation drive tube 200 , longitudinally positioning the articulation drive tube 200 for rotational motion. The hollow articulation drive tube 200 extends longitudinally within the closure sleeve 32 from the articulation mechanism 11 and terminates distally before the locking tabs 227 of the closure sleeve 32 . The tabs 227 are inwardly bent behind the proximal face of the articulation drive tube 200 and thereby retaining the articulation drive tube 200 in the shaft 23 .
It should be appreciated that the articulation transmission housing 204 is operatively associated to the closure tube 35 of the shaft 23 . The housing cap 60 retains the articulation yoke 220 in the articulation transmission housing 204 and retains the articulation control 13 within the handle portion 20 by presenting proximally an outer diameter circular groove 228 that engages a circular inward lip 230 at the distal opening of the assembled base sections 50 , 52 .
FIGS. 10 and 11 depict the gear articulation mechanism 11 of FIGS. 1–2 in the form of a spur gear articulation mechanism 240 , which is generally the same as described above but with additional articulation driving components on the other side of the articulation mechanism 240 to thereby increase performance. Articulation mechanism 240 has a rotatable hollow articulation drive tube 242 that is concentrically located within closure sleeve 32 and has a distally projecting gear section 244 about a first circumference portion 246 . Gear section 244 meshes with a spur gear 248 attached to and proximally projecting from closure ring 250 which pivots about pins 253 extending through first and second pivot points 252 , 260 projecting distally from the closure sleeve 32 . Thus, an articulation pivot axis passes through both the first and second pivot points 252 , 260 and pins 253 rotatably couple closure ring 250 to the closure sleeve 32 . Rotation of drive 242 engages the gears 242 and 248 and articulates closure ring 250 about first and second pivot points 252 , 260 .
To increase the effective surface area of gear contact between the hollow articulation drive tube 242 and the closure ring 250 , a second circumference portion 254 of the hollow articulation drive tube 242 has a recessed distally projecting gear section 256 extending therefrom. Gear section 256 is operably coupled to a second spur gear 258 attached to and proximally projecting from an opposite lateral side of the closure ring 250 by a reversing gear 262 pivotally supported by the frame 34 . Reversing gear 262 engages both the recessed distally projecting gear section 256 on one side and the second spur gear 258 of the closure ring 250 on the other.
When the closure trigger 26 is actuated, both the hollow articulation drive tube 242 and pivotally attached closure tube 250 of the closure sleeve 32 are moved distally to close the anvil 18 . The closure tube 35 of the closure sleeve 32 is spaced away from the closure ring 33 by pivot points 252 , 260 pinned to pivot holes 264 and 266 centered in spur gears 248 , 258 , and a frame opening 268 that extends therethrough. The frame opening 268 provides clearance so that the proximal edges of the closure ring 33 and the distal edges of the closure tube 35 of the closure sleeve 32 do not collide during articulation.
FIG. 11 depicts in disassembled form an implement portion 270 that includes the spur gear articulation mechanism 240 . A frame 272 is longitudinally attachable to the handle portion 20 (depicted in FIGS. 1 and 2 ) with a bushing 274 on its proximal end for rotatingly engagement thereto. A frame trough 276 formed by an opening 278 longitudinally aligned with the center of the frame 272 is longer than a firing connector 280 that slides longitudinally within the frame trough 276 . The proximal end of the firing connector 280 rotatingly engages the distal end of the metal drive bar 140 (depicted in FIG. 6 ). The distal end of the firing connector 280 includes a slot 282 that receives a proximal end of the firing bar 14 , attached therein by pins 284 . A more distal portion of the firing bar 14 is positioned within a lower groove 286 in a firing bar slotted guide 288 that is distally engaged with an articulating frame member 290 and the frame 272 .
Articulating frame member 290 has a channel-anchoring member 292 that distally attaches to an attachment collar 294 of a proximal portion in the elongate channel 16 . The firing bar 14 passes through a lower slot 295 in the articulating frame member 290 . The articulating frame member 290 is spaced away from the distal end of the frame 272 by the firing bar slotted guide 288 and flexibly attached thereto for articulation by a resilient connector 296 . A widened proximal end 298 of the resilient connector 296 engages a distally communicating top recess 300 in the distal end of the frame 272 and a widened distal end 302 of the resilient connector 296 engages a proximally communicating top recess 304 in the articulating frame member 290 . Thereby, the elongate channel 16 is attached to the handle portion 20 , albeit with a flexible portion therebetween.
The elongate channel 16 also has an anvil cam slot 306 that pivotally receives an anvil pivot 308 of the anvil 18 . The closure ring 250 that encompasses the articulating frame member 290 includes a distally presented tab 310 that engages an anvil feature 312 proximate but distal to the anvil pivot 308 on the anvil 18 to thereby effect opening. When the closure ring 250 is moved forward, its distally presented closing face 314 contacts a ramped cylindrical closing face 316 , which is distal to tab 312 of the anvil 18 . This camming action closes the anvil 18 downward until the closing face 314 of the closure ring 250 contacts a flat cylindrical face 318 of the anvil 18 .
Tapered Firing Bar
FIG. 12 depicts the articulation mechanism 240 along the articulation pivot axis illustrating flexible support structures between the shaft 23 and the end effector 12 and a construction of the firing bar 14 that advantageously performs severing yet is flexible enough for articulation. The hollow articulation drive tube 242 engages the spur gear 248 of the closure ring 33 (only the spur gear 248 of the closure ring 33 being depicted). Omitted from this view are the proximal portion, or closure tube 35 , of the closure sleeve 32 that longitudinally position for articulation the spur gear 248 .
Resilient support in the articulation mechanism 240 allow articulation about the articulation pivot axis includes a pair of support plates 400 , 402 that provide lateral guides to a proximal portion of the firing bar, depicted as an elongate tapered firing bar strip 404 aligned for flexing about the articulation pivot axis. This tapered firing bar strip 404 transitioned to a thicker distal portion, depicted as a firing bar head 406 , that includes the cutting edge 48 , upper pin 38 , middle pin 46 and firing bar cap 44 . The thinner portion of firing bar strip 404 is easier to bend than the thicker portion 406 , thereby reducing the force to articulate the end effector. This thicker firing bar head 406 has increased thickness to resist deflection from tissue clamping loads during firing, thereby ensuring an effective severing and actuation of the staple cartridge 37 .
Operation
A closed end effector 12 and shaft 23 of an implement portion 22 of a surgical stapling and severing instrument 10 are inserted through a cannula passageway of a trocar to a surgical site for an endoscopic or laparoscopic procedure. The articulation control 13 is rotated as desired about the longitudinal axis of the shaft 23 to effect a corresponding rotation of the end effector 12 . Advantageously, the actuator lever 202 of the articulation control 13 is pivoted to create a rotation articulation motion in an articulation drive tube 200 , 242 that is converted into an articulation motion at a geared connection in an articulation mechanism 11 , 240 thereby positioning the end effector 12 in a desired position. The firing bar 14 is advanced through the implement portion 22 to actuate the end effector 12 , advantageously assisted through the articulation mechanism 11 , 240 by including the elongate tapered firing bar strip 404 that flexes with reduced resistance.
While the present invention has been illustrated by description of several embodiments and while the illustrative embodiments have been described in considerable detail, it is not the intention of the applicant to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications may readily appear to those skilled in the art.
The present invention has been discussed in terms of endoscopic procedures and apparatus. However, use herein of terms such as “endoscopic”, should not be construed to limit the present invention to a surgical stapling and severing instrument for use only in conjunction with an endoscopic tube (i.e., trocar). On the contrary, it is believed that the present invention may find use in any procedure where access is limited to a small incision, including but not limited to laparoscopic procedures, as well as open procedures.
For another example, although the E-beam firing beam 14 has advantages for an endoscopically employed surgical severing and stapling instrument 10 , a similar E-Beam may be used in other clinical procedures. It is generally accepted that endoscopic procedures are more common than laparoscopic procedures. Accordingly, the present invention has been discussed in terms of endoscopic procedures and apparatus. However, use herein of terms such as “endoscopic”, should not be construed to limit the present invention to a surgical stapling and severing instrument for use only in conjunction with an endoscopic tube (i.e., trocar). On the contrary, it is believed that the present invention may find use in any procedure where access is limited to a small incision, including but not limited to laparoscopic procedures, as well as open procedures.
For yet another example, although an illustrative handle portion 20 described herein is manually operated by a clinician, it is consistent with aspects of the invention for some or all of the functions of a handle portion to be powered (e.g., pneumatic, hydraulic, electromechanical, ultrasonic, etc.). Furthermore, controls of each of these functions may be manually presented on a handle portion or be remotely controlled (e.g., wireless remote, automated remote console, etc.).
As yet an additional example, although a simultaneous stapling and severing instrument is advantageously illustrated herein, it would be consistent with aspects of the invention rotationally controlled articulation with other types of end effectors, such as grasper, cutter, staplers, clip applier, access device, drug/gene therapy delivery device, and a energy device using ultrasound, RF, laser, etc.
For example, although a spur gear articulation mechanism 240 is illustrated herein, it that other articulation mechanisms may be included, such as those described in the aforementioned co-pending applications.
As an additional example, for articulation mechanisms that obstruct the longitudinal axis of the shaft, the support plates and tapered firing bar strip may be offset from the longitudinal axis. | A surgical stapling and severing instrument particularly suited to endoscopic articulates an end effector by having a geared articulation mechanism that converts rotational motion from a handle portion. A firing bar longitudinally translates between the handle portion and the end effector. The firing bar head is thickened in order to present an undistorted cutting edge and engagement features to the opposing jaws of the end effector. The firing bar also advantageously includes a thinned or tapered proximal portion in the form of a strip or band that negotiates the articulation mechanism. | 0 |
BACKGROUND OF THE INVENTION
This invention relates to molten aluminum containing molten salts and more particularly it relates to a method of removing finely divided particles of molten salts from molten aluminum.
In melting aluminum and transferring it, a considerable amount of impurities is often introduced into the melt. These impurities include gas (typically hydrogen from moisture in the atmosphere) non-metallic impurities (mostly being derived from the aluminum oxide film on the melt charge or that which forms on the surface of molten aluminum as it is melted and transported) together with sodium or other metallic impurities which can be introduced in the smelting process. It is important that these impurities be reduced to the minimum levels possible. Gases in the solidified metal produce a number of problems in fabricating and using aluminum products as does the presence of oxides. The gas content and oxide content seem to be related in that oxide particles tend to nucleate the formation of hydrogen filled discontinuities.
The presence of sodium interferes with certain fabrication procedures, especially hot rolling where any significant amount causes severe edge cracking during hot rolling reductions. This is especially significant in alloys containing magnesium, for instance 2 to 10% Mg, where edge cracking becomes very serious.
One example of difficulty in reducing the sodium content by chlorination is that the magnesium present in most aluminum alloy melts is ordinarily reacted simultaneously. This occurs even though chlorine, or the reaction product of chlorine with aluminum, aluminum chloride, react with sodium preferentially over magnesium at equilibrium conditions. From considerations of chemical reaction equilibria and the law of mass section, chlorine released in the melt would first be expected to largely form aluminum chloride because aluminum is by far the major component of the melt. Next in sequence, some of the aluminum chloride may encounter and react with magnesium in the melt to form magnesium chloride because magnesium is usually more concentrated than the other melt components capable of reacting with aluminum chloride. Finally, if contact with the metal is maintained long enough, the magnesium or aluminum chlorides encounter the trace amounts of sodium and react to form the final equilibrium product, sodium chloride. Rate of chlorination and magnesium concentration are factors determining how far and how rapidly reaction proceeds through this sequence to the final equilibrium product, sodium chloride. At commonly used chlorination rates, final equilibrium is difficult to achieve without using contact times which are unacceptable in a continuous commercial process. Accordingly, it has been difficult to achieve extremely low sodium levels under commercial production plant conditions which require comparatively large amounts of molten metal to be treated rather rapidly.
One of the difficulties in achieving extremely low levels of salts is that even after fluxing and filtering some of the molten salt formed can remain in very fine particle form or droplets suspended in the melt and as such becomes extremely difficult to separate by flotation or sedimentation in flowing streams of molten aluminum. Such suspended salt dispersions are of such a nature as to pass through molten metal filters and end up in the aluminum ingot with their attendant problems.
Thus, there is a great need for a process suitable for removing finely divided salt dispersion in molten aluminum. The present invention provides such a process wherein particles or droplets of salt, e.g., smaller than 225 microns, for example, can be effectively coalesced or amalgamated into droplets and which can then be brought to the surface by floatation and removed from the melt.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a flowsheet illustrating the step prior to and following the removal of finely divided salt.
FIG. 2 is a cross section of a vertical housing having a separator located therein for amalgamating or coagulating finely divided dispersions of molten salt particles into drops.
SUMMARY OF THE INVENTION
It is an object of the present invention to coalesce or agglomerate finely divided molten salt particles entrained in molten aluminum.
It is a further object of the present invention to provide a process for coalescing or amalgamating finely molten salt particles entrained in molten aluminum.
Yet a further object of the present invention is to provide an apparatus suitable for coalescing or amalgamating and removing finely divided salt particles or droplets entrained in molten metal.
And yet it is still a further object of the present invention to provide a process for coalescing or amalgamating finely divided salt particles entrained in molten aluminum to provide droplets which can float on the molten aluminum.
These and other objects of the invention will be apparent from the following description and accompanying drawings.
In accordance with these objects, there is provided a method for separating molten salt droplets from molten aluminum, the salt droplets having a size sufficiently small that they remain entrained or suspended in the molten aluminum. The method comprises providing a body of molten aluminum having finely divided salt particles entrained therein and passing a stream of the molten aluminum through an agglomerating medium which is essentially non-wettable by the molten salt. The finely divided particles collect on the medium where they agglomerate to a size which floats on the molten aluminum.
DETAILED DESCRIPTION OF THE INVENTION
In the process of the invention, a source of aluminum is provided (FIG. 1), melted in a melter and then transferred to a holding furnace. Normally, the molten metal is then subjected to a fluxing and/or filtering treatment. The filtering treatment removes entrained solid particles such as aluminum oxide particles, and the fluxing treatment is used to remove dissolved hydrogen as well as lowering the content of metals such as sodium, calcium, magnesium, etc. However, when chlorine or chlorine-containing reactants (i.e., salt injection) are used, the fluxing treatment, as noted earlier, can form salts such as magnesium chloride. A fraction of the salt in the melt can remain as a very finely divided suspension or in an uncoalesced form or state (sometimes referred to as immiscible second phase droplets or particles) and consequently is difficult to remove or separate from the molten aluminum by flotation or gravity separation. That is, even though the salt may have a lower density than the aluminum, it remains entrained in the molten aluminum and can pass through the filtering system with the resultant imperfections in the aluminum ingot. While reference is made to molten immersible second phase droplets or particles of salt, finely divided solid particles of oxide or salt may be included therewith for removal.
By way of illustration and not of limitation, the molten aluminum having salt particles dispersed therein enters a flow chamber of dimensions sufficient to lower the superficial metal velocity to approximately 1-2.5 cm/sec, this requires plan dimensions of about 20 in.×20 in. for a metal flow rate of 80,000 lbm/hr (V o =1.7 cm/sec). Since flow is in the Newton regime (C D =0.44), the smallest spherical salt droplet that would be expected to separate by body forces is given by the following formula: ##EQU1##
For this illustration, D d =0.224 mm or 224 microns. Thus, for this example, droplets approximately larger than 0.224 mm would be expected to separate to the metal surface, and salt droplets less than this size would be expected to remain entrained. Thus, the finely divided particles of salt, e.g., less than 224 microns, remain entrained or suspended in the molten aluminum, particularly when molten aluminum is under turbulent flow. These particles resist body force separation or molten metal surface separation, e.g., flotation or buoyant separation, because the particles are in a non-amalgamated or non-coalesced state. However, when a 2-inch thick phosphate bonded high alumina reticulated ceramic foam (pore diameter about 250 to 300 μm) was coated with boron nitride and the flow rate therethrough maintained as above through the chamber (FIG. 2), the subcritical diameter salt droplets consolidate to a size greater than 0.224 μm and collect on the surface of the aluminum. Aluminum ingot formed from the molten aluminum (AA5052) was found to be free of oxide patches which in such an alloy can contain MgO, MgAl 2 O 4 and salt. Particles or droplets of salt which tend to remain entrained have a size generally less than 750 microns, preferably less than 600 microns and are typically less than about 300 microns.
In treating molten aluminum, particularly when such aluminum contains magnesium or is alloyed with magnesium, a magnesium oxide dispersoid can form having a particle size of about 1 to 5 microns. It is believed that the dispersed salts and the magnesium oxide dispersoid-type particles form agglomerates. That is, the magnesium oxide-type particles associate with the salt dispersions or droplets to form agglomerates. Because such agglomerates can behave as a non-Newtonian fluid, the agglomerates are not readily removed from the molten aluminum by conventional filtration because the salt can function as a liquid vehicle for the oxides to migrate through the filtering process with its attendant problems. Thus, it is important to remove the salt from the melt.
With reference to FIG. 1, it will be seen that after the holding furnace, the molten metal is subjected to a fluxing treatment. It is after the fluxing treatment that the molten aluminum can be treated to remove salt dispersions in accordance with the invention. That is, the removal of the salt can be accomplished before the metal passes through the filtering step. However, there are certain instances where it is more expedient to remove the salt dispersions after the filtering step, and such is encompassed within the purview of the present invention.
For molten salt separation purposes from molten metal, e.g., molten aluminum, it is important to note where salt particles have a high form drag, i.e., the vertical terminal velocity of the particle is less than or equal to the local melt velocity, the particle is extremely difficult to separate from the melt by normal sedimentation or flotation. Thus, if separation is to occur, then the local metal velocity has to be low relative to the salt particle terminal velocity in order for the salt particle to separate by slip velocity when the salt particles have coalesced to a sufficiently large size. However, operations of this nature often require impractically large units which operate under laminar flow conditions.
In accordance with the invention, the finely divided salt droplets can be removed by passing the molten aluminum through a member, e.g., a plate or block on which the fine particles can collect and agglomerate, the member having many passages therein and preferably being non-wettable or only having low wettability by the salt. It should be noted that the salt particles do not normally penetrate the plate or block but are collected on the upstream surface where they agglomerate. However, a system may be devised where the salt particles collect and agglomerate on passages inside the plate or block and are collected in the down side stream, and such is contemplated within the purview of the invention. Or, the molten aluminum can be passed through a high porosity reticulated foam which is preferably non-wettable or only having low wettability by the finely divided molten salt particles which provides sites for the finely divided salt particles to collect and coalesce. The preferred plate or block member can be fabricated from boron nitride, alumina coated with boron nitride or zirconia coated boron nitride and can have a number of generally parallel passages therein which have low resistance to flow. Generally, the surface should be non-wetting to salt and be resistant to attack by molten aluminum. The tortuosity of the passages in the plate or block member should be about 1. The plate or block member can have generally parallel passages which are preferred because they offer low flow rate resistance.
For purposes of providing a substantially non-wetting surface for contacting with salt-containing melt, a bed, for example, comprised of Raschig rings, can be provided on which finely divided molten salt particles can collect and agglomerate.
By reference to FIG. 2, there is shown a treatment vessel for removal of entrained finely divided particles of molten salt. Molten aluminum containing entrained finely divided salt flows into chamber or vessel 10 through passage 20. Chamber 10 has mounted therein a plate o block member 30 having substantially parallel openings 32 therein. Molten aluminum leaves chamber 10 along passage 40. Finely divided molten salt particles entrained in the melt collect on surface 32 of member 30. After sufficient collection of droplets or subcritical diameter salt particles occur they agglomerate into drops 50 having a buoyancy which permits them to float to surface 7 of molten aluminum 5 where drops 50 collect as layer 52 and thus can be removed from the melt. Collection of the finely divided molten salt particles on surface 32 occurs as a result of salt/metal interface tension which resists drop formation. Drops 50 can float to the surface of the melt when the incoming velocity of the melt is controlled so as to be lower than the critical velocity which would carry drops 50 through the passages in plate member 30. While the molten metal is shown flowing generally downwardly through vertical passages 34 in horizontal member 30, the molten metal flow may flow horizontally through such passages or at an angle therebetween with similar results and such is contemplated within the purview of the invention. Also, while drops 50 are shown forming on member 30 and rising or floating against the flow of molten metal, the molten metal flow can be controlled so as to permit the finely divided salt particles to collect and form into drops on member 30 and carry the drops through passages 34 where they are thereafter collected as a layer of salt on the molten metal surface or separated by gravity.
While plate 30 is shown in vessel 10 as being horizontal with vertical passages, the plate may be provided in any number of configurations suitable in practicing the invention. In addition, plate or block 30 should be fabricated from a material which is not attacked by nor introduces contaminants to the molten metal. For treating molten aluminum, suitable plate materials are graphite, silicon carbide, carbon, alumina or other materials which do not contaminate molten aluminum. To provide a non-wetting surface, such material can be coated with boron nitride or a like material which provides a highly suitable surface on which the suspended subcritical liquid salt particles can collect and which surface facilitates the agglomeration of the subcritical liquid salt particles.
While the flow may be under turbulent flow conditions, it is not believed that laminar flow conditions are harmful to the separation required. But, it is important that separation or agglomeration can take place while under turbulent flow conditions, and accordingly, there is not believed to be restriction on the type of flow under which the present invention may be used. Accordingly, flow conditions can have Reynolds numbers above 2100 or 2300 with no observable detrimental effect. Counter current flow permits the agglomerate molten salt to collect on surface 7 of molten aluminum in vessel 10.
The size of passages 34 can vary but they should not be so small so as to impede flow of molten metal or become clogged with agglomerated salt. Thus, the size of the openings or passage can be 400 to 1200 microns in diameter, for example. However, this size is simply by way of example. The openings can be greater, if desired. It is important, though, that surface 32 as seen by the incoming molten metal be maximized so as to provide maximum sites for the liquid particles of salts to collect. The length of passages 34 can be short, e.g., 0.5 inch. However, if the passages have cone-shaped configurations so as to become wider in the direction of flow, this can aid in reducing flow restriction of the media.
Member 30 having passages 34 may be replaced with a high porosity reticulated foam on which the subcritical molten salt particles collect and agglomerate to form drops. The reticulated foam may be any material resistant to attack by molten aluminum and is preferably non-wetting by molten salt. Such material may be coated with boron nitride, or the like, which is non-wetting to the molten salt particles or has controlled wetting to the molten salt particles.
Thus, the present invention is useful in removing halide salts resulting from, for example, chloridization of molten aluminum including chloride salts of sodium, calcium, strontium, lithium and magnesium or eutectic, near eutectic or other molten compositions thereof. Typical of the salts that are removed are those which may not be removed by filtering. Typical of the filter beds suitable for removing oxides, other particles or materials such as salt particles not desired in the aluminum ingot is described in U.S. Pat. No. 4,390,364, incorporated herein by reference. Accordingly, the present invention is extremely useful in combination with the filtering processes for molten aluminum.
Thus, molten aluminum treated in accordance with this process is capable of removing the salts to a level which avoids oxide patches on the aluminum ingot.
While the invention has been described with respect to molten aluminum, it will be appreciated that the invention has application to other molten metal systems, such as steels where, for example, molten manganese sulfide can be a problem. Another example of a metal to which the invention can be applied includes magnesium where it is important to remove salt particles.
While the invention has been described in terms of preferred embodiments, the claims appended hereto are intended to encompass other embodiments which fall within the spirit of the invention. | A method of treating molten aluminum containing a suspension of finely divided salt particles remaining after filtering molten aluminum is disclosed. The method comprises providing a body of molten aluminum containing the suspension of molten salt particles entrained therein and passing the molten aluminum into a medium substantially unwettable by the molten salt particles. The particles of salt are collected on the medium and permitted to agglomerate so as to be removed to the surface of the molten aluminum by gravity. | 2 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] U.S. application Ser. No. 12/486,035 filed on Jun. 17, 2009 is hereby incorporated by reference in its entirety.
TECHNICAL FIELD
[0002] The present teachings relate to an electrically operated hydraulic control mechanism such as a solenoid valve.
BACKGROUND
[0003] Solenoid control valves for hydraulic control systems are used to control oil under pressure that may be used to switch latch pins in switching lifters and lash adjusters in engine valve systems. Valve lifters are engine components that control the opening and closing of exhaust and intake valves in an engine. Lash adjusters may also be used to deactivate exhaust and intake valves in an engine. Engine valves may be selectively deactivated or locked out to disable operation of some cylinders in an engine when power demands on an engine are reduced. By deactivating cylinders, fuel efficiency of an engine may be improved.
[0004] Engine deactivating solenoid control valves must operate with minimum response times to maximize engine efficiency. Valve response times include valve activation response times and deactivation response times. Solenoid control valves apply a magnetic force to an armature that moves a control valve stem by activating a coil to move the armature against a biasing force that is typically provided by a spring. The magnetic force applied by the solenoid to the armature and in turn to the control valve stem should be maximized to reduce response time. The magnetic force applied by the coil can be increased by increasing the size of the coil. However, cost and weight reduction considerations tend to limit the size of the coil. Deactivation response times are adversely impacted by valve closure biasing springs, the force of which must be overcome before the valve is opened. While this delay in response times in most applications is minimal, in variable valve actuation systems, the limited time window for valve activation and deactivation is critical and must be minimized.
SUMMARY
[0005] A hydraulic control valve is provided having a solenoid body, an energizable coil, and an armature positioned adjacent the coil. A valve stem extends from the armature. The coil is energizable to move the armature and the valve stem from a first position to a second position. The first position may be a deenergized, closed position, and the second position may be an energized, open position. The valve body, the armature and the valve stem are configured so that the armature and the valve stem are biased to the first position by pressurized fluid, allowing the armature to operate without a biasing spring. Thus, the armature is configured so that the net fluid forces contribute to closing the valve, providing a relatively quick valve actuation response time. If no biasing spring is used, cost and assembly time, as well as response time, are minimized. Additionally, the solenoid may be weaker, and therefore less expensive, as no spring biasing force needs to be overcome.
[0006] In one embodiment, the armature and the valve stem include a first poppet and a second poppet, and the valve body defines a supply chamber with a first seat, a second seat, and a control chamber between the first and second seats. The first poppet is configured to sit at the first seat and the second poppet is configured to be spaced from the second seat in the first position to prevent pressurized fluid flow past the first seat and to exhaust fluid from the control chamber past the second seat. The first poppet is configured to be spaced from the first seat and the second poppet is configured to sit at the second seat in the second position to permit flow of pressurized fluid from the supply chamber to the control chamber and prevent flow from the control chamber to the exhaust chamber.
[0007] The hydraulic control valve may be mounted to an engine such that the armature falls to the second position when the engine is off and the coil is not energized, thereby moving the first poppet off of the seat to open the supply chamber to the control chamber. Thus, due to gravity, the armature is in the same position as the energized, engine—on position when the engine is off and the coil is not energized. When the engine is subsequently restarted, with the coil still deenergized, air can thereby expel from the supply chamber to the control chamber, and further to the exhaust when the armature and valve stem move to the first position due to pressurized oil acting on the second poppet. Expelling any air in the system enables a quicker, more controlled response of the valve.
[0008] A hydraulic control circuit is provided with an electromagnetic actuator selectively actuatable to create a flux path, a valve body having a seat past which a fluid under pressure is selectively permitted to flow, and an armature that is selectively moved in a first direction by electromagnetic flux. The armature defines a poppet that is moved in the first direction relative to the seat from a closed position in which fluid flow past the seat is prevented to an open position in which fluid flow past the seat is permitted, the armature being biased to the closed position by operation of the fluid under pressure.
[0009] The above features and advantages and other features and advantages of the present teachings are readily apparent from the following detailed description of the best modes for carrying out the present teachings when taken in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 is a perspective view of a solenoid valve;
[0011] FIG. 2 is an exploded perspective view of the solenoid valve shown in FIG. 1 ;
[0012] FIG. 3 is a partial cross-sectional view taken along the plane of section line 3 - 3 in FIG. 1 showing the valve in a first, closed and deenergized position; and
[0013] FIG. 4 is a partial cross-sectional view similar to FIG. 3 of the valve in a second, open and energized position.
DETAILED DESCRIPTION
[0014] Referring to FIG. 1 , a solenoid valve 10 , for example, such as that used to deactivate lifters or operate a dual lift system in an internal combustion engine or diesel engine is illustrated. The solenoid valve 10 may also be referred to as an electromagnetic actuator. The solenoid valve 10 is installed in an engine 12 . The solenoid valve 10 includes a solenoid portion 16 and a valve body 18 .
[0015] Referring to FIGS. 2 and 3 , the solenoid valve 10 is shown to include a solenoid can 20 that houses a coil 22 that powers the solenoid valve 10 . A pole piece 24 is assembled within the solenoid can 20 . The pole piece 24 defines part of the flux path for the coil 22 . A flux collector insert 26 is disposed within the solenoid can 20 and also forms part of the flux path for the coil 22 .
[0016] An armature 28 is acted upon by the flux created by energizing the coil 22 to shift the solenoid valve 10 from a normally closed position as shown in FIG. 3 to the open position as shown in FIG. 4 . An air gap 30 is provided between a radially-extending face 31 of the pole piece 24 and a radially-extending face 33 of the armature 28 . The air gap 30 may be adjusted by adjusting the pole piece 24 relative to the armature 28 . A relief groove 34 , shown in FIG. 2 , is provided in the armature 28 that facilitates flow of oil under pressure axially across the armature 28 . The relief groove 34 is also referred to as a conduit. Alternatively, a conduit may be formed in the valve body 18 adjacent the armature 28 to provide flow of pressurized oil across the armature 28 . The flux collector insert 26 may be inserted adjacent to the coil 22 and the valve body 18 in a molded one-piece or multiple-piece body 40 .
[0017] The valve body 18 defines an oil intake chamber 41 , also referred to as a supply chamber, in which the armature 28 is disposed and that initially receives oil under pressure. The valve body also defines an intermediate chamber 42 , also referred to as a control chamber. A plurality of O-ring grooves 43 are provided on the exterior of the valve body 18 that each receives one of a plurality of seals 44 . The seals 44 establish a seal between the valve portion 18 and the engine 12 . The molded body 40 defines an internal coil receptacle 46 , or bobbin, that extends into the solenoid portion 16 . The coil 22 is shown only in part, but it is understood that the coil 22 fills the coil receptacle 46 . The body 40 may be formed as a one-piece integral plastic molded part, as illustrated, or could be formed in pieces and assembled together. The coil 22 is wrapped around the coil receptacle 46 .
[0018] A valve stem 48 has a portion 50 that is received within an opening 52 in the armature 28 . The position of the control valve stem 48 may be adjusted relative to the armature 28 by a threaded connection or by a press-fit between the stem 48 and the armature 28 . The armature 28 includes a poppet 54 that is moved relative to the valve seat 56 in response to pressure changes, as will be more fully described below. An exhaust poppet 60 is provided on one end of the control valve stem 48 to move relative to a valve seat 62 to open and close an exhaust port 70 .
[0019] A supply gallery 64 is provided in the engine 12 to provide pressure P i to the oil intake chamber 41 that is defined in the valve body 18 . A control gallery 68 is provided in the engine 12 that is normally maintained at control pressure P 2 . An exhaust gallery 71 , also provided in the engine, is in communication with the exhaust port 70 and is ported to ambient pressure and may be referred to as “P 0 ”. The intermediate chamber 42 goes to Pressure P 0 when the exhaust port 70 is opened.
[0020] Referring to FIG. 4 , the solenoid valve 10 is shown in the open position. The coil 22 is energized to retract the armature 28 toward the coil 22 . The poppet 54 opens the valve seat 56 to provide pressure P 1 from the oil intake chamber 41 to the intermediate chamber 42 , and the exhaust poppet 60 sits at seat 62 to close the exhaust port 70 .
[0021] Referring to FIGS. 2-4 , the valve body 18 includes a supply opening 63 that receives oil under pressure from a supply gallery 64 that is in communication with the oil intake chamber 41 and the valve seat 56 . When the valve seat 56 is open, the intake chamber 41 is in communication with the intermediate chamber 42 . Oil under pressure is provided through an outlet opening 66 , also referred to as a control port, and to a control gallery 68 . An exhaust port 70 is provided at the inboard end of the valve body 40 . Exhaust port 70 is in communication with exhaust gallery 71 .
[0022] In operation, the valve 10 is normally closed as shown in FIG. 3 and is shifted to its open position as shown in FIG. 4 by energizing the coil 22 . The coil 22 , when energized, reduces the air gap 30 formed between the pole piece 24 and the armature 28 . The armature 28 is shifted toward the pole piece 24 by electromagnetic flux created by the coil 22 . Oil in chamber 41 is in communication with the gap 30 through the relief groove 34 .
[0023] When in the normally closed position shown in FIG. 3 , the poppet 54 closes the valve seat 56 , isolating the oil intake chamber 41 , which is at P i , from the intermediate chamber 42 , which is at P 2 . The oil under pressure in the oil intake chamber 41 biases the poppet 54 against the valve seat 56 . The area of the armature 28 affected by P 1 biases the armature to the closed position as P 1 acts on the larger surface area of face 33 of the armature 28 at the gap 30 to provide biasing force in one direction (i.e., in a direction to seat the poppet 54 at the seat 56 , while pressurized fluid at P 1 acts on a smaller surface area 73 of the armature in the chamber 41 in an opposing direction. The biasing force applied to the poppet 54 is intended to eliminate the need for a spring. Alternatively, a spring (not shown) may be incorporated to increase the biasing force applied to the poppet 54 .
[0024] When the coil 22 is energized, flux through the pole piece 24 and flux collector insert 26 pulls the armature 28 toward the pole piece 24 , as shown in FIG. 4 . The face-to-face orientation of the armature 28 relative to the pole piece 24 subjects the armature 28 to exponentially greater magnetic force. Shifting the armature 28 causes the poppet 54 to open relative to the valve seat 56 , thereby providing pressure P i from the oil intake chamber 41 to the intermediate chamber 42 . The intermediate chamber 42 is normally maintained at pressure P 2 but is increased to P 1 when the poppet 54 opens the valve seat 56 and the poppet 60 closes valve seat 62 to close off the exhaust port 70 . Thus, P 1 acts on the surface area of face 33 of the armature 28 and the surface area 72 of the poppet 54 in one direction and on annular surface area 73 and surface area 74 of poppet 54 in an opposing direction. Because the affected surface area 33 is equal to the combined surface areas 73 and 74 , the net force is that on surface area 72 . This change in pressure increases the hydraulic pressure supplied to the engine valve system to P 1 . When the pressure provided to the engine valve system changes to P 1 , selected engine valves may be deactivated by latch pins, lash adjusters or another controlled device (not shown) to thereby deactivate selected cylinders of the engine.
[0025] When the coil 22 is subsequently deenergized, with the forces due to the flux removed (i.e., the net force pulling the armature 28 toward the pole piece 24 ), the net fluid pressure on surface area 33 drives the armature 28 to the normally closed, deenergized position of FIG. 3 . Thus, the armature 28 is configured so that the net fluid forces (i.e., net downward force acting on face 72 ) contributes to closing the valve 10 , with the chamber 42 exhausting to exhaust port 70 , thereby providing relatively quick valve actuation response time from the energized to the deenergized position.
[0026] The valve 10 is provided with an air purging and self-cleaning feature. Specifically, the armature 28 is formed with a bypass slot 53 , also referred to as a bypass channel, to permit a limited amount of oil to move from chamber 41 to chamber 42 when the valve 10 is closed, bypassing the seat 56 . Alternatively, the bypass slot may be provided in the body 18 adjacent the seat 56 . The slot 53 also allows particles of dirt to be expelled from chamber 41 with the oil, and thus functions as a “self-cleaning” feature of the valve. Additionally, air is purged from the chamber 41 through slot 53 , thus preventing an air cushion acting against valve 10 moving to the energized position of FIG. 4 when the coil 22 is subsequently energized. This allows quick transitioning from the deenergized to the energized position.
[0027] When the engine 12 is off so that no fluid pressure is provided in the valve 10 and the coil 22 is deenergized, assuming that the valve 10 is installed in the engine 12 with the armature 28 above the pole piece plug 24 (i.e., upside down with respect to the view shown in FIGS. 3 and 4 ), gravity will cause the armature 28 to fall to the energized position of FIG. 4 (although the coil is not energized). Thus, when the engine 12 is started, pressurized oil will come up the supply gallery 64 and force any air ahead of it out of the supply chamber 41 to the control chamber 42 , past the open seat 56 as the oil proceeds into chamber 41 and gap 30 , biasing the armature 28 to the closed, deenergized position of FIG. 3 . The air is expelled from chamber 42 to exhaust port 70 as the poppet 62 unseats.
[0028] While the best modes for carrying out the many aspects of the present teachings have been described in detail, those familiar with the art to which these teachings relate will recognize various alternative aspects for practicing the present teachings that are within the scope of the appended claims. | A hydraulic control valve is provided having a solenoid body, an energizable coil, and an armature positioned adjacent the coil. A valve stem extends from the armature. The coil is energizable to move the armature and the valve stem from a first position to a second position. The valve body, the armature and the valve stem are configured so that the armature and the valve stem are biased to the first position by pressurized fluid, allowing the armature to operate without a biasing spring. | 8 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to sticky darts.
2. Description of Prior Art
Sticky darts are already known and often used in children's games. The darts are generally benign and each have stem with a sticky nose at one end and feathers or flights at the other end. Many suitable sticky materials are known, and include Styrene-Ethylene-Butylene-Styrene Co-polymer emulsified in mineral oil. The sticky material is normally suitable for adherence, even sometimes only for a limited time after impact, to surfaces made of cardboard, plastics, glass and metal.
However because the nose of the sticky dart adheres to most materials it is difficult to store. Even in normal use, the nose will collect dust and debris and become contaminated to the point of becoming inoperative. Also, as conventional sticky darts are inherently very light, their aerodynamic performance is unpredictable and cannot be easily varied.
SUMMARY OF THE INVENTION
It is an object of the invention to overcome or at least reduce one or more of these problems.
According to the invention there is provided a sticky dart having a stem with a first end and a second end, including a nose at the first end of the stem, a layer of sticky material on a forward part of the nose and a housing surrounding the nose, with the layer of sticky material positioned beyond a remote open end of the housing in a first operable position, in which the nose is arranged to be movable with respect to the housing so that the layer of sticky material is positioned wholly within the housing in a second operable position.
The nose may be pivotably mounted to the housing and rotatable between the first and second operable positions.
The nose may be slidably mounted to the housing for sliding between the first and second operable positions. The nose may also be rotatably mounted in the housing and includes locking means that operates when the nose is in a predetermined rotational position relative to the housing to interlock with the nose and prevent the nose sliding in the housing between the first and second operable positions.
Preferably, a balance weight is provided on the stem adjacent said first end. The balance weight may be integrally formed with the housing.
The balance weight may be movable and locatable along the length of the stem.
The dart may have integrally formed flights mounted at the other end of the stem.
BRIEF DESCRIPTION OF THE DRAWINGS
Sticky darts according to the invention will now be described by way of example with reference to the accompanying drawings in which:
FIG. 1 is an exploded (or pre-assembly) isometric view of first sticky dart;
FIG. 2 is a sectional side view of the first sticky dart in a first operable position;
FIG. 3 is a part-section side view of the first dart in a second operable position;
FIG. 4 is an exploded isometric view of a second sticky dart;
FIG. 5 is a sectional side view of the second sticky dart in a first operable position;
FIG. 6 is a sectional side view of the second sticky dart in a second operable position;
FIG. 7 is an exploded isometric view of a third sticky dart;
FIG. 8 is a sectional side view of the third sticky dart in a first operable position; and
FIG. 9 is a sectional side view of the third sticky dart in a second operable position.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to the drawings, in FIGS. 1 and 3 the sticky dart has a threaded stem 10 and a nose 11 at a first end. A layer 12 of sticky material is mounted to a forward end of the nose and an open-ended housing 13 surrounds the nose 11. The nose 11 is pivotably attached to the housing 13 by opposing integrally formed stub axles 14.
A rear end of the nose is provided with a small compressible nipple 15 that can be located against a base member 16 (see FIGS. 2 and 3) inside the housing 13. The nipple releasably holds the nose in the first operable position, as shown in FIG. 2. The second operable position is shown in FIG. 3 and it will be appreciated that the nose 11 is moved by relative rotation from the first to the second operable position. Thus, the layer 12 can be moved from the position in FIG. 2, where the layer 12 extends beyond a remote end of the housing and where the layer 12 is prone to collecting dust, being damaged or otherwise contaminated, to the position in FIG. 3. In FIG. 3, the layer 12 is wholly surrounded by the housing 13, which prevents the layer 12 becoming contaminated and also facilitates handling during non-active use and for storage.
A balancing weight 17, formed in two halves that fix together, is mounted on the stem 10. The weight 17 has a central channel with a simple thread or follower 18 so that when the stem 10 is rotated with respect to the weight 17, the weight is caused to move along the stem. This enables the balance weight to be moved and positioned on the stem where desired to improve the aerodynamics of the sticky dart.
The stem and the other parts are normally made of molded plastics material and flights 19 at the other end of the sticky dart are preferably integrally formed.
In FIGS. 4 to 6, a second sticky dart is shown in which like-parts have the same numerals as in FIGS. 1 to 3. It will be clear from the FIGS. 4 to 6 that in order to change the dart from the first operating position to the second operating position (and vice versa), the stem 10 must be rotated relative to the weight 17. In this second sticky dart the weight 17 and the housing 13 are integrally formed. In the second operating position (FIG. 3), the layer 12 has been withdrawn within the housing 13 and although the layer 12 is still exposed to dust which may enter into the housing 13, the dart is readily more easy to store and the layer 12 is not prone to inadvertent touching or the picking up of debris and the like.
It will be appreciated that the weight 17 may be slidable along the stem 10 and held in the required positions by suitable dimples or grooves or even by frictional resistance, say.
In FIGS. 7 to 9, the third sticky dart is generally the same as the second sticky dart, although it is possible to make the housing 13 and the balancing weight as separate parts. This allows the weight 17 to move along the stem 10 independently of the housing 13 if desired. The housing 11 has integrally formed opposing wings 20 that can fit into one of two grooves 21 and 22 formed on the inside surface of the housing 13. A channel 23 that separates the two grooves is noncontinuous allowing the wings to pass from one of the grooves to the other. Thus, in the position shown in FIG. 7, the nose 11 can be slid forwards and backwards to allow the layer 12 to be withdrawn into the housing, say, when the dart is moved from its first operating position (FIG. 8) to its second operating position (FIG. 9). In FIGS. 8 and 9, the nose 11 has been turned 90° from the position shown in FIG. 7 so that the nose 11 is locked in position. That is to say, the nose 11 cannot move forwards or backwards within the housing 13 unless the nose is first turned to the relative position shown in FIG. 7. Thus the wings 20 and grooves 21 and 22 provide a locking means for retaining the nose in its two operative positions.
As before, the layer 12 can be withdrawn to substantially reduce any contamination when the dart is not in active use.
The balancing weights 17 may be in the form of a figurine or other decorative or otherwise aesthetic form, and display a company logo or trademark, for example. | A sticky dart has a stem, and a nose with a layer of sticky material pivotably connected to a housing. When not in use, the nose is swivelled around so that the layer moves within the housing so as to prevent the layer becoming contaminated and unserviceable. A balance weight is readily movable and locatable along the stem to improve the aerodynamics of the dart when required. | 5 |
FIELD OF THE INVENTION
[0001] The present invention pertains to the art of control systems and, more particularly, a system and method for controlling an automotive vehicle transmission in response to temperature changes in automatic transmission fluid passing through the transmission.
BACKGROUND OF THE INVENTION
[0002] Automotive vehicles often have an automatic transmission located in a powertrain that delivers power from an engine to traction wheels of the vehicle. When the vehicle accelerates from a standing start, the transmission automatically changes the relative ratio of a transmission input shaft that receives power from the engine and a transmission output shaft that delivers power from the transmission to downstream elements of the powertrain and eventually to the wheels. The ratio changes are generally performed by selectively braking components of interlinked planetary gear sets or selectively engaging components of the gear sets to other components of the gear sets by the use of friction elements. The gear sets are mounted in a housing that also contains actuators for the friction elements. A pump is used to supply automatic transmission fluid to the friction element actuators to enable them to perform the gear changing function and also provides fluid to the gear sets so that they are properly lubricated.
[0003] It is considered desirable in the art to ensure that automobile transmissions allow the complete powertrain to be as efficient as possible. However, because of adjustments required to properly manage transmission operation when the temperature of the automatic transmission fluid is elevated, efficiency can be compromised. The elevated temperature leads to lower viscosity in the automatic transmission fluid which, in turn, leads to reduced pump efficiency and to more fluid leakage as the fluid progresses around the transmission. In order to maintain a required lubrication flow and fluid pressure to supply the friction element actuators so that they may control the friction elements in a timely and effective manner, a minimum allowable pump speed must be increased. Since the pump usually obtains power from the engine, a minimum allowable engine speed must also be increased. Increasing the minimum allowable pump and engine speeds increases fuel consumption and worsens fuel economy.
[0004] Generally, prior art solutions to the problem of supplying sufficient automatic transmission fluid that has an elevated temperature were directed to requiring a minimum engine speed that would provide an adequate supply of fluid under worst-case temperature conditions. These solutions had the advantage of simplicity in that once the minimum allowable engine speed was set no further control was necessary. Also, the minimum engine speed required by other factors, such as drivability, vehicle noise and harshness, was frequently higher than the minimum required due to increased automotive fluid temperature so the increased temperature was not a major factor when trying to reduce engine speed. However, in order to reduce parasitic loss of power caused by the transmission fluid pump, transmission designers are reducing transmission pump displacements which, in turn, is requiring higher pump speeds. Thus, the need to provide an adequate supply of transmission fluid can become a controlling factor on minimum engine speed.
[0005] Other prior art solutions have been directed to increasing fuel efficiency by addressing different problems. For example, Japanese Patent Document JP 4066337 discloses an oil pump that is directly connected to an engine. The idle speed of the engine is increased when the oil temperature reaches a certain level. Basically, this arrangement is not concerned with setting a minimum engine speed during transmission gear ratio shifts, but rather focuses on adjusting engine idle speed.
[0006] Another prior art solution is set forth in U.S. Pat. No. 5,556,349 which discusses a known automatic transmission having a normal temperature shift pattern and a high temperature shift pattern. The goal is to have the automatic controller constantly monitor the transmission fluid temperature and prevent it from overheating by switching to the high temperature shift pattern. The high temperature shift pattern avoids heating the transmission fluid as much as the normal temperature shift pattern in that the high temperature pattern shifts to a higher gear at a higher speed than the normal temperature pattern. This increases torque converter average speed and reduces torque converter average torque, both of which changes reduce the amount of heat generated, particularly by an open torque converter.
[0007] As can be seen by the above discussion, there is a need in the art for a system that will effectively reduce the minimum allowable engine speed requirement during gear shifts, while still providing adequate amounts of automatic transmission fluid needed for lubrication and for friction element actuators.
SUMMARY OF THE INVENTION
[0008] The present invention is directed to a transmission fluid supply system method employed in a vehicle having an engine for providing power, a transmission including multiple gear ratios and friction elements with associated actuators for engaging and disengaging the friction elements to shift the transmission between gear ratios, and a pump driven by the engine. The system improves vehicle efficiency by regulating a minimum transmission input speed based on automatic transmission fluid temperature. The system includes a temperature sensor for sensing a temperature of the automatic transmission fluid and a controller for setting a minimum engine speed of the engine based on the temperature of the automatic transmission fluid. With this arrangement, the size of the pump may be reduced while the pump is still able to supply enough automatic transmission fluid to the friction elements and gear ratios to provide lubrication and to the actuators to enable the actuators to engage and disengage the friction elements in a timely and effective manner.
[0009] In accordance with a preferred embodiment of the invention, when the temperature of the automatic transmission fluid is below 210° F., the minimum engine speed is set to no greater than 900 revolutions per minute (rpm). When the temperature of the automatic transmission fluid is above 210° F., the minimum engine speed is set to no less than 1000 rpm. Therefore, the system operates by sensing a temperature of the automatic transmission fluid and setting a minimum engine speed of the engine based on the temperature of the automatic transmission fluid, whereby a size of the pump may be reduced as compared to known pump arrangements while still being able to supply the automatic transmission fluid to the friction elements and gear ratios to provide lubrication and to the actuators to enable the actuators to engage and disengage the friction elements in a timely and effective manner.
[0010] Additional objects, features and advantages of the present invention will become more readily apparent from the following detailed description of a preferred embodiment when taken in conjunction with the drawings wherein like reference numerals refer to corresponding parts in the several views.
BRIEF DESCRIPTION OF DRAWINGS
[0011] FIG. 1 is a diagram showing a vehicle incorporating a system for improving vehicle performance in accordance with the invention;
[0012] FIG. 2 is a schematic diagram of the system in FIG. 1 ;
[0013] FIG. 3 is a basic flowchart showing a control routine employed in the system of FIG. 1 according to a preferred embodiment of the invention;
[0014] FIG. 3A is a detailed flowchart showing another preferred embodiment of a control routine employed in the system of FIG. 1 ;
[0015] FIG. 4 is a graph showing a transmission upshift in accordance with the invention; and
[0016] FIG. 5 is a graph showing a transmission downshift in accordance with the invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0017] With initial reference to FIG. 1 , there is shown an automotive vehicle 10 having a body 11 and an engine 12 . Power from engine 12 is transmitted to a transmission 18 , then to the other portions of a powertrain 20 and eventually to drive wheels 22 . Vehicle 10 is shown as a rear wheel drive vehicle but any type of powertrain arrangement, including front wheel or all wheel drive systems, could be employed. In addition, although engine 12 is shown as an internal combustion engine, but other types of drive arrangements, including hybrid drive systems, could be utilized. A controller 25 is connected to engine 12 and transmission 18 by communication lines 27 and 28 respectively. In accordance with the invention, controller 25 functions to set a minimum engine speed based on automatic fluid temperature as more fully discussed below.
[0018] Transmission 18 is schematically illustrated in FIG. 2 with controller 25 , wherein ratio changes are controlled by friction elements CL/A-CL/E acting on individual gear elements. Torque from engine 12 is distributed to torque input element 30 of hydrokinetic torque converter 32 . An impeller 34 of torque converter 32 develops turbine torque on a turbine 36 in a known fashion. Turbine torque is distributed to a turbine shaft, which is also transmission input shaft 38 . Impeller 34 is connected to a relatively small oil pump assembly 39 .
[0019] Transmission 18 of FIG. 2 includes a simple planetary gearset 40 and a compound planetary gearset 41 . Gearset 40 has a permanently fixed sun gear S 1 , a ring gear R 1 and planetary pinions P 1 rotatably supported on a carrier 42 . Transmission input shaft 38 is drivably connected to ring gear R 1 . Compound planetary gearset 41 , sometimes referred to as a Ravagineaux gearset, has a small pitch diameter sun gear S 3 , a torque output ring gear R 3 , a large pitch diameter sun gear S 2 and compound planetary pinions. The compound planetary pinions include long pinions P 2 / 3 , which drivably engage short planetary pinions P 3 and torque output ring gear R 3 . Long planetary pinions P 2 / 3 also drivably engage short planetary pinions P 3 , while short planetary pinions P 3 further engage sun gear S 3 . Planetary pinions P 2 / 3 and P 3 of gearset 41 are rotatably supported on compound carrier 46 . Ring gear R 3 is drivably connected to a torque output shaft 48 , which is drivably connected to vehicle traction wheels 22 through a differential and axle assembly 50 shown in FIG. 1 . Gearset 40 is an underdrive ratio gearset arranged in series with respect to compound gearset 41 . Typically, transmission 18 preferably includes a lockup or torque converter bypass clutch, as shown at 58 , to directly connect transmission input shaft 30 to engine 12 after a torque converter torque multiplication mode is completed and a hydrokinetic coupling mode begins.
[0020] During operation in the first four forward driving ratios, carrier P 1 is drivably connected to sun gear S 3 through shaft 58 and forward friction element CL/A. During operation in the third ratio, fifth ratio and reverse, direct friction element CL/B drivably connects carrier 42 to shaft 59 , which is connected to large pitch diameter sun gear S 2 through shaft 60 . During operation in the fourth, fifth and sixth forward driving ratios, overdrive friction element CL/E connects turbine shaft 38 to compound carrier 46 through shaft 28 . Friction element CL/C acts as a reaction brake for sun gear S 2 during operation in second and sixth forward driving ratios. During operation of the third forward driving ratio, direct friction element CL/B is applied together with forward friction element CL/A. The elements of gearset 41 then are locked together to effect a direct driving connection between shaft 58 and output shaft 48 . If friction element CL/B is applied during third ratio operation when clutch A is applied and friction element CL/C is released, a downshift from the third ratio to the second ratio would be affected as friction element CL/C is applied in synchronism with release of friction element CL/B. If friction element CL/B is applied during third ratio operation when friction element CL/A is applied and friction element CL/B is released, an upshift from the third ratio to the fourth ratio is effected as friction element CL/E is applied in synchronism with release of friction element CL/B. The torque output side of forward friction element CL/A is connected through torque transfer element 54 to the torque input side of direct friction element CL/B, during forward drive. The torque output side of direct clutch CL/B, during forward drive, is connected to shaft 60 through torque transfer element 59 . Reverse drive is established by applying low-and-reverse friction element CL/D and friction element CL/B. More details of this type of transmission arrangement are found in U.S. Pat. No. 7,216,025, which is hereby incorporated by reference.
[0021] The friction elements CL (A-E) are powered by the automatic transmission fluid pumped by pump assembly 39 in accordance with instructions provided by controller 25 through communication lines 28 . Each friction element CL (A-E) has a corresponding communication channel A-E so that friction elements CL (A-E) may be controlled independently. Also, information from sensors on transmission 18 , such as an automatic fluid temperature sensor 62 , send information to controller 25 through communication lines 28 . More specifically, transmission control algorithms 70 are employed to control the shifting of gear ratios in transmission 18 , while engine control algorithms 72 operate in controller 25 in order to control engine 12 . Engine control algorithms 72 receive information from driver directed signals 75 , such as a desired speed and information from engine 12 , preferably engine speed in RPM from a speed sensor 77 and engine coolant temperature sensor, and communicate with transmission control algorithms 70 .
[0022] The operation of controller 25 can be further understood with reference to the basic flow chart shown in FIG. 3 . Initially, controller 25 determines minimum engine speeds at step 200 based on the temperature of the automatic transmission fluid. Preferably, the minimum engine speed is set to no greater than 900 rpm for temperatures below 210° F. and no less than 1000 rpm for temperatures above 210° F. However, it is desirable to prevent controller 25 from constraining the minimum engine speed unless absolutely necessary. Therefore, the minimum engine speed is preferably made a function of transmission oil temperature and engine coolant temperature, which may allow for a lower minimum engine speed as compared to a minimum engine speed determined based solely on automatic transmission fluid temperature. At step 210 , the temperature of the automatic transmission fluid is measured. Then, at step 220 , the temperature is compared to a predetermined temperature used to determine minimum engine speeds. With this information, the engine speed is altered by controller 25 during gear shifts to be at or above the minimum engine speed determined in step 200 . As a result of this method, the use of smaller oil pump assemblies with low drag is enabled. Additionally, the lower minimum engine speed results in improved fuel economy. Generally, a higher minimum engine speed required to protect transmission 18 will be invoked only when elevated transmission oil temperatures and their associated lower viscosity threaten to affect the operation of friction elements CL(A-E) or provide too little lubrication as further explained below.
[0023] FIG. 3A shows a more detailed flowchart showing the operation of controller 25 according to a second preferred embodiment of the invention. Initially, at step 300 , controller 25 determines the minimum vehicle speed at which an upshift into a higher gear or gear ratio may normally occur. The minimum vehicle speed is assigned a variable name such as “minimum_upshift_vehicle_speed”. The value determined to be the minimum vehicle speed is then stored as the variable “minimum_upshift_vehicle_speed”. Then controller 25 determines, at step 310 , whether or not the temperature of the automatic transmission fluid is high enough to require some type of shift modification. If the temperature is high enough, controller 25 proceeds to step 320 and calculates the minimum acceptable acceptable speed at which an upshift may occur in view of the measured temperature. As noted above, the variable “hot_minimum_upshift_vehicle_speed” could also be based on measuring the temperature of the automatic transmission fluid in combination with engine coolant temperature. Furthermore, the temperature used does not have to be directly measured but could also be estimated, modeled or projected. The resulting value is stored as the variable “hot_minimum_upshift_vehicle_speed”. At step 330 , controller 25 determines if “hot_minimum_upshift_vehicle_speed” is greater than “minimum_upshift_vehicle_speed” and, if so, the value for “minimum_upshift_vehicle_speed” is overwritten with the value for “hot_minimum_upshift_vehicle_speed”, which is the value that controller 25 uses for high temperature operation. The process then continues to step 350 where controller 25 determines if the current vehicle speed is greater than the “minimum_upshift_vehicle_speed” and, if so, an upshift is performed at step 360 . If not, the system does not perform an upshift and the process ends. If the transmission temperature is not high enough to require shift modification in step 310 , the process goes directly to step 350 . Likewise, if the “hot_minimum_upshift_vehicle_speed” is not greater than the “minimum_upshift_vehicle_speed” in step 330 , the process also goes directly to step 350 . Preferably, this process is conducted on a continuous basis, thus constantly monitoring the shifting process to adjust for temperature changes of the automatic transmission fluid. The process for a downshift is essentially a mirror image of the upshift strategy and therefore will not be discussed separately.
[0024] FIG. 4 is a graph representing an upshift from a lower gear ratio X to a higher gear ratio Y conducted while using the method shown in FIG. 3 . The vertical axis represents an average filtered vehicle speed before the shift, while the horizontal axis represents driver demand as derived from the position of an accelerator pedal or some other driver directed signal. A shift curve is shown that represents the transition where controller 25 will shift gears. For example, at a given driver demand, controller 25 will shift gears when the averaged filtered vehicle speed increased to above the shift curve. At a higher driver demand, the vehicle speed will be relatively higher before a shift occurs. The shift curve in accordance with the invention is significantly lower at low driver demand values than prior art shift curves, thereby enabling a lower minimum engine speed at normal automatic fluid temperatures. The prior art minimum is shown by a dashed line PA, the high temperature line H is shown just below the dashed line and the normal temperature line L is the lowest line in the graph. At high temperatures, the curve is clipped to maintain an engine speed that allows pump 42 to provide sufficient pressure to the friction elements CL (A-E) and lubrication to the transmission 18 .
[0025] FIG. 5 is a graph representing a downshift from a higher gear ratio X to a lower gear ratio Y conducted while using the method shown in FIG. 3 . The vertical axis represents driver demand as derived from the position of an accelerator pedal or some other driver detected signal, while the horizontal axis represents a predicted engine transmission speed after the gear shift. A shift curve is shown that represents the transition where controller 25 will shift gears. For example, at a given predicted engine speed after shift, controller 25 will shift gears when the driver demand increases to above the shift curve. At a higher predicted engine speed after the shift, the driver demand will be relatively higher before a shift occurs. The shift curve in accordance with the invention will always request downshifts at a minimum engine speed as represented by the dashed lines. At normal temperatures, the minimum speed is represented by dashed line L. That minimum engine speed will be higher shown by dashed lined H at higher transmission fluid temperatures to allow the pump to provide sufficient pressure to the friction elements and lubrication to the transmission.
[0026] Based on the above, it should be apparent that the present invention provides for a system that regulates a minimum engine speed based on automatic transmission fluid temperature to enable a smaller sized pump to be utilized and increases fuel economy. Although described with reference to a preferred embodiment of the invention, it should be readily understood that various changes and/or modifications can be made to the invention without departing from the spirit thereof. For instance, the way the minimum engine speed is enforced may be a change in shift points depending on measured temperature of the automatic transmission fluid or the controller may simply switch gear ratios when a certain engine speed is reached, regardless of what other inputs to the controller may suggest. In general, the invention is only intended to be limited by the scope of the following claims. | A system and method is employed to regulate a minimum transmission input speed based on automatic fluid temperature. The system includes a temperature sensor for sensing a temperature of the automatic transmission fluid and a controller for setting a minimum engine speed of the engine based on the temperature of the automatic transmission fluid. The size of a transmission pump may be reduced while the pump is still able to supply enough automatic transmission fluid to friction elements and gear ratios to provide lubrication and enable friction element actuators to engage and disengage the friction elements in a timely and effective manner. In a preferred form of the invention, when the temperature of the automatic transmission fluid is below 210° F., the minimum engine speed is set to no greater than 900 rpm; and when the temperature of the automatic transmission fluid is above 210° F., the minimum engine speed is set to no less than 1000 rpm. | 8 |
This application is the U.S. National Stage under 35 U.S.C. §371 of International Patent Application No. PCT/US2009/045490 filed May 28, 2009, which claims the benefit of U.S. Provisional Patent Application Ser. No. 61/057,110 filed May 29, 2008, entitled “Mechanism For Providing Controllable Angular Orientation While Transmitting Torsional Load.”
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not applicable.
FIELD OF THE INVENTION
The present invention relates in general to mechanisms for providing controllable angular orientation between an outer tubular element and a coaxial inner tubular element while transmitting torsional load between the outer and inner tubular elements. More particularly, the invention is directed to such mechanisms which can be incorporated in a downhole tool coupled within a drill string in a wellbore to provide controllable angular orientation between the sections of the string above and below the tool, while the mechanism is subjected to torsional load.
BACKGROUND OF THE INVENTION
In drilling a borehole (or wellbore) into the earth, such as for the recovery of hydrocarbons or minerals from a subsurface formation, it is conventional practice to connect a drill bit onto the lower end of a “drill string”, then rotate the drill string so that the drill bit progresses downward into the earth to create the desired borehole. A typical drill string is made up from an assembly of drill pipe sections connected end-to-end, plus a “bottomhole assembly” (“BHA”) disposed between the bottom of the drill pipe sections and the drill bit. The BHA is typically made up of sub-components such as drill collars, stabilizers, reamers and/or other drilling tools and accessories, selected to suit the particular requirements of the well being drilled.
In conventional vertical borehole drilling operations, the drill string and bit are rotated by means of either a “rotary table” or a “top drive” associated with a drilling rig erected at the ground surface over the borehole (or in offshore drilling operations, on a seabed-supported drilling platform or suitably-adapted floating vessel). During the drilling process, a drilling fluid (commonly referred to as “drilling mud” or simply “mud”) is pumped under pressure downward from the surface through the drill string, out the drill bit into the wellbore, and then upward back to the surface through the annulus between the drill string and the wellbore. The drilling fluid carries borehole cuttings to the surface, cools the drill bit, and forms a protective cake on the borehole wall (to stabilize and seal the borehole wall), in addition to other beneficial functions.
As an alternative to rotation by a rotary table or a top drive, a drill bit can also be rotated using a “mud motor” (alternatively referred to as a “downhole motor”) incorporated into the drill string immediately above the drill bit. The mud motor is powered by drilling mud pumped under pressure through the mud motor in accordance with well-known technologies. The technique of drilling by rotating the drill bit with a mud motor without rotating the drill string is commonly referred to as “slide” drilling, because the non-rotating drill string slides downward within the wellbore as the rotating drill bit cuts deeper into the formation. Torque loads from the mud motor are reacted by opposite torsional loadings transferred to the drill string.
Directional drilling operations using a mud motor require means for controlling the orientation of the mud motor relative to earth while the motor is down hole, in order to control the resulting direction of the curved or deflected wellbore. When drilling with a conventional string of drill pipe, mud motor orientation control can be accomplished by rotating the entire pipe string from surface. However, when drilling with coiled tubing, which cannot easily be rotated from surface, orientation control must be accomplished using means capable of controlling the angular orientation of the mud motor relative to the coiled tubing. It is desirable for this relative orientation to be controllable while drilling operations are in progress, to avoid any unexpected and undesired changes in orientation due to the unwinding and recoiling of the coiled tubing that can occur when drilling is interrupted.
Previous devices typically include an arrangement of lugs and spiral grooves, or an arrangement of lugs and circumferentially-spaced cam bodies, that convert axial motion of a piston into rotational motion of the lower string components. Such devices are generally very complicated in construction and operation, with large numbers of components. The devices also do not allow orientation to be controlled and adjusted while being subjected to torsional loads (such as under normal drilling conditions).
Accordingly, there remains a need for improved and less complicated apparatus for controlling and adjusting the angular orientation between coaxial tubular elements, particularly while under torsional loading. The present invention is directed to this need.
BRIEF SUMMARY OF THE INVENTION
The present invention provides a mechanism which can be incorporated into a tool located between the end of a tubing string and a mud motor, whereby the angular orientation of the mud motor relative to the tubing string can be adjusted without interrupting well-drilling operations, while maintaining effective transfer of torsional loads from the mud motor to the tubing string. In preferred embodiments, the mechanism includes a generally cylindrical mandrel having a central bore throughout its length (for passage of drilling fluid), a cylindrical central section, an upper section above the cylindrical central section, and a lower section below the cylindrical central section. The mandrel is positioned coaxially within a cylindrical tool housing such that the mandrel is rotatable relative to the housing but its axial position relative to the housing is substantially fixed. In a typical well-drilling application of the mechanism, a mud motor will be coupled to the lower end of the mandrel (either directly or through intermediary components).
A cylindrical central sleeve is disposed around the central cylindrical section of the mandrel, with the central sleeve having an internal diameter to provide a close but readily slidable fit with the central cylindrical section of the mandrel. The central sleeve is longitudinally slidable but substantially non-rotatable relative to the housing. In the preferred embodiment, this functionality is facilitated by forming the central sleeve with a plurality of longitudinally-oriented external splines slidingly received within complementary grooves formed in the inner surface of the housing. The upper and lower ends of the central sleeve each have a plurality of circumferentially-arrayed and equally-spaced ratchet teeth. In the preferred embodiment, each ratchet tooth has a first face that is parallel to the longitudinal axis of the mandrel, plus a second face that is angled relative to the first face (hereinafter these first and second faces will be referred to as “vertical faces” and “sloped faces” respectively).
The mechanism also includes generally cylindrical upper and lower ratchet members disposed, respectively, about the upper and lower sections of the mandrel; i.e., on either side of the central sleeve. The upper and lower ratchet members are mounted such that their axial positions relative to the mandrel are substantially fixed, but also such that they are independently rotatable relative to the mandrel within a limited angular range. In the preferred embodiment of the mechanism, this limited rotational functionality is facilitated by providing the inner cylindrical surfaces of the upper and lower ratchet members with longitudinal grooves configured to receive complementary external splines formed on the upper and lower sections of the mandrel, but with the ratchet member grooves being wider than the corresponding mandrel splines. In preferred embodiments, biasing means (such as bow springs) will be provided to bias the mandrel splines against one side face of the corresponding ratchet member grooves to facilitate torque transfer during drilling.
The lower end of the upper ratchet member has a plurality of circumferentially-arrayed and equally-spaced ratchet teeth configured for mating engagement with the ratchet teeth on the upper end of the central sleeve. Similarly, the upper end of the lower ratchet member has a plurality of circumferentially-arrayed and equally-spaced ratchet teeth configured for mating engagement with the ratchet teeth on the lower end of the central sleeve. The four pluralities of ratchet teeth have matching numbers of ratchet teeth, and, therefore, the same spacing (or angular interval) between adjacent ratchet teeth.
The upper and lower ratchet members are axially spaced such that the central sleeve can slide along the mandrel between:
an upper position in which the central sleeve's upper ratchet teeth are matingly engaged with the ratchet teeth of the upper ratchet member, with the central sleeve's lower ratchet teeth being clear of the ratchet teeth of the lower ratchet member; and a lower position in which the central sleeve's lower ratchet teeth are matingly engaged with the ratchet teeth of the lower ratchet member, with the central sleeve's upper ratchet teeth being clear of the ratchet teeth of the upper ratchet member.
When the central sleeve is in its upper position, its lower ratchet teeth will be offset relative to the ratchet teeth of the lower ratchet member, with the offset preferably being approximately one-half of the typical ratchet tooth spacing (or angular interval). In this configuration, torque from a mud motor connected to the bottom of the mandrel will be transferred from the mandrel to the upper ratchet member via the spline/groove connection therebetween, from the upper ratchet member to the central sleeve via the respective engaged ratchet teeth, and from the central sleeve to the tool housing via the spline/groove connection therebetween.
Similarly, when the central sleeve is in its lower position, its upper ratchet teeth will be offset relative to the ratchet teeth of the upper ratchet member, with the offset preferably being approximately one-half of the typical ratchet tooth spacing (or angular interval). In this configuration, torque from a mud motor connected to the bottom of the mandrel will be transferred from the mandrel to the lower ratchet member via the spline/groove connection therebetween, from the lower ratchet member to the central sleeve via the respective engaged ratchet teeth, and from the central sleeve to the tool housing via the spline/groove connection therebetween.
When the central sleeve is moved from its upper position toward its lower position, the central sleeve's upper ratchet teeth will begin disengaging from the ratchet teeth of the upper ratchet member, but torque transfer between the upper ratchet member and the central sleeve will remain effective until these two sets of ratchet teeth are fully disengaged, because their respective vertical faces will remain in load-transferring contact prior to full disengagement, and until such full disengagement there can be no rotation of the upper ratchet member relative to the sleeve.
However, as the central sleeve is moved from its upper position toward its lower position, the central sleeve's lower ratchet teeth will begin engaging the ratchet teeth of the lower ratchet member before the central sleeve's upper ratchet teeth are fully disengaged from the upper ratchet member. As well, due to the previously-noted offset between the central sleeve's ratchet teeth and the ratchet teeth of the lower ratchet member, the continued downward movement of the central section's ratchet teeth into the ratchet teeth of the lower ratchet member will force the lower ratchet member to rotate approximately one-half of a ratchet tooth interval relative to the mandrel, due to the tips of the central sleeve's lower ratchet teeth bearing downward against the sloped faces of the ratchet teeth of the lower ratchet member. This limited rotational displacement of the lower ratchet member is possible because, as previously noted, the splines in the lower splined section of the mandrel are narrower than the corresponding grooves in the lower ratchet member. During this limited rotational displacement, any springs or other biasing means associated with the lower ratchet member will be compressed or otherwise stressed as the mandrel splines move in an arcuate path within the lower ratchet member grooves.
As the central sleeve reaches its lower position, and as the central sleeve's upper ratchet teeth become fully disengaged from the upper ratchet member, torsional loads acting on the mandrel (e.g. from a mud motor) will cause a sudden angular displacement of the mandrel relative to the central sleeve, while concurrently relieving stresses induced in the biasing means (if present) during the movement of the central sleeve. The amount of this angular displacement will correspond to one-half of the ratchet tooth spacing. Because the central sleeve cannot rotate relative to the tool housing by virtue of the spline/groove connection therebetween, the effect of the angular displacement between the mandrel and the central sleeve is to create the same angular displacement between the tool housing and the mandrel—and therefore between the tool housing and any mud motor or other tool or appurtenance coupled to the mandrel.
In a fashion similar to that described above, upward movement of the central sleeve back to its upper position will induce a similar and additional angular displacement of the mandrel relative to the tool housing.
In alternative embodiments, the mechanism of the present invention may also be configured to internally drive the relative rotation that occurs during orientation in applications that are not subject to external torsional loads.
Although the present invention has particularly beneficial applications in association with directional drilling with coiled tubing, persons skilled in the art will appreciate that it may be also be readily adapted for use in other applications where controlled angular orientation between two or more coaxial components is required, with or without the presence of applied torsional load.
BRIEF DESCRIPTION OF THE DRAWINGS
Embodiments of the invention will now be described with reference to the accompanying figures, in which numerical references denote like parts, and in which:
FIG. 1 is a partial-cutaway elevation of a drill string incorporating an angular orientation mechanism in accordance with one embodiment of the present invention.
FIG. 1 a is an elevation of a mandrel suitable for use in accordance with one embodiment of the invention.
FIG. 2 is a partial cutaway view of the orientation mechanism in FIG. 1 , with the central sleeve in its upper position.
FIG. 3 is a transverse cross-section through the tool housing, cylindrical piston, upper ratchet member, and mandrel of the orientation mechanism in FIG. 2 .
FIG. 4 is a transverse cross-section through the tool housing, central sleeve, and mandrel of the orientation mechanism in FIG. 2 .
FIG. 5 is a transverse cross-section through the tool housing, lower ratchet member, and mandrel of the orientation mechanism in FIG. 2 .
FIG. 6 is a partial cutaway view of the orientation mechanism in FIG. 2 , with the central sleeve displaced slightly downward from its upper position, with its lower ratchet teeth beginning to engage the ratchet teeth of the lower ratchet member.
FIG. 7 is similar to FIG. 6 but with the central sleeve displaced further downward, with its lower ratchet teeth engaging the sloped faces of the ratchet teeth of the lower ratchet member so as to incrementally rotate the lower ratchet member in a counterclockwise direction.
FIG. 8 is a partial cutaway view showing the central sleeve after full downward displacement to its lower position, with its lower ratchet teeth in full mating engagement with the ratchet teeth of the lower ratchet member, and with its upper ratchet teeth fully disengaged from the upper ratchet member.
FIG. 9 is a transverse cross-section through the tool housing, lower ratchet member, and mandrel, as viewed during downward displacement of the central sleeve as in FIG. 7 .
FIG. 10 is a transverse cross-section through the tool housing, lower ratchet member, and mandrel, as viewed after full downward displacement of the central sleeve as in FIG. 8 .
FIG. 11 is a partial cutaway view of the orientation mechanism in FIG. 2 , with the central sleeve displaced slightly upward from its lower position, and with its upper ratchet teeth beginning to engage the ratchet teeth of the upper ratchet member.
FIG. 12 is similar to FIG. 11 but with the central sleeve displaced further upward, with its upper ratchet teeth engaging the sloped faces of the ratchet teeth of the upper ratchet member so as to incrementally rotate the upper ratchet member in a counterclockwise direction.
FIG. 13 is a partial cutaway view showing the central sleeve after full upward displacement back to its upper position, with its upper ratchet teeth in full mating engagement with the ratchet teeth of the upper ratchet member, and with its lower ratchet teeth fully disengaged from the lower ratchet member.
FIG. 14 is a transverse cross-section through the tool housing, cylindrical piston, upper ratchet member, and mandrel, as viewed during upward displacement of the central sleeve as in FIG. 12 .
FIG. 15 is a transverse cross-section through the tool housing, cylindrical piston, upper ratchet member, and mandrel, as viewed after full upward displacement of the central sleeve as in FIG. 13 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 illustrates an angular orientation mechanism 100 in accordance with one embodiment of the present invention, incorporated within a string of tubular elements constituting a downhole tool. FIG. 1 depicts one possible orientation of the downhole tool relative to a wellbore, with the tool comprising a cylindrical tool housing 20 (typically made up from a plurality of tool housing members) having an upper end 20 U which may be coupled to the lower end of a pipe string or coiled tubing string (not shown), or to other tools or components that are coupled to the lower end of the string. For convenience, the adjectives “upper” and “lower” are used in this patent specification in reference to various components as if mechanism 100 were at all times vertically oriented as in FIG. 1 . It will be appreciated, however, that these terms are used in a relative sense only, as the mechanism may be used in a variety of different orientations (such as during directional drilling operations).
Mechanism 100 includes a generally cylindrical mandrel member 14 with a central bore 30 to permit passage of drilling fluid (mud). FIG. 1 a illustrates one embodiment of a mandrel 14 adapted for use in mechanism 100 . Mandrel 14 is axially and radially supported within housing members 20 such that it is coaxially rotatable relative to housing 20 but its axial position relative to housing 20 is substantially fixed. Persons skilled in the art will appreciate that specific means for supporting mandrel 14 within housing 20 as described above may be readily devised, and the present invention is not limited to any particular means of providing such support.
Mandrel 14 includes a central section 31 having a smooth cylindrical outer surface, an upper splined section 32 above central section 31 , and a lower splined section 33 below central section 31 . As shown in FIG. 1 a , upper splined section 32 defines a plurality of longitudinally-oriented upper splines 141 spaced around the circumference of upper splined section 32 and projecting outward therefrom. Similarly, lower splined section 33 defines a plurality of longitudinally-oriented lower splines 142 spaced around the circumference of lower splined section 33 and projecting outward therefrom.
The lower end 14 L of mandrel 14 may be coupled to a mud motor (not shown) or other tool or other additional lower tubular elements that require controllable angular orientation relative to housing 20 (and relative to a pipe string or tubing string supporting housing 20 ). Additional or auxiliary elements or appurtenances may be coupled above mandrel 14 (for example, components that provide axial or radial support to mandrel 14 , or components involved in controlling the actuation of the mechanism 100 ). However, such additional elements do not form part of the broadest embodiments of the present invention, and other embodiments of the invention could take alternative forms without departing from the scope of the invention.
Mechanism 100 as illustrated is not limited to orientation relative to a wellbore as described above. In alternative embodiments, mechanism 100 may be inverted such that mandrel 14 is coupled to the lower end of the pipe string or coiled tubing string, or to other tools or components that are coupled to the lower end of the string, with housing 20 being coupled to a drilling tool or other additional lower tubular elements requiring angular orientation control.
In the embodiment illustrated in the FIGS. (and as will be explained in greater detail), torque-transmitting components of mechanism 100 are configured to resist torsional loading applied in the clockwise direction when viewed from above. In alternative embodiments adapted to resist counterclockwise torsional loading, the configurations of torque-transmitting components would be essentially the reverse of the illustrated configurations.
FIG. 2 is an enlarged detail illustrating the components of mechanism 100 in accordance with the embodiment of FIG. 1 . As shown, mechanism 100 includes a generally cylindrical central sleeve 10 with longitudinal external splines 101 , plus a generally cylindrical outer housing 11 coupled to the lower end of tool housing 20 , and having longitudinal internal grooves 111 configured to receive splines 101 of sleeve 10 in closely-fitting fashion as shown in FIG. 4 . The inner diameter of central sleeve 10 is slightly greater than the outer diameter of central section 31 of mandrel 14 , such that it may be coaxially disposed around central section 31 as shown in FIG. 4 , and will be free to rotate relative to mandrel 14 and free to slide longitudinally relative to mandrel 14 . Splines 101 on central sleeve 10 and grooves 111 on housing 11 prevent relative rotation between sleeve 10 and housing 11 , while allowing sleeve 10 to travel axially relative to housing 11 .
A generally cylindrical upper ratchet member 12 with internal grooves 122 is coaxially disposed around upper splined section 32 of mandrel 14 , such that splines 141 of mandrel 14 are received within grooves 122 . Grooves 122 are wider than splines 141 such that when a first vertical face 141 a of a given spline 141 is bearing against a first vertical face 122 a of the corresponding groove 122 , a vertical gap G- 1 will be formed between the second vertical face 122 b of groove 122 and the second vertical face 141 b of spline 141 , all as shown in FIG. 3 . The axial position of upper ratchet member 12 is substantially fixed relative to mandrel 14 , but upper ratchet member 12 is free to rotate coaxially relative to mandrel 14 , to the extent allowed by gaps G- 1 .
Preferred embodiments will include suitable biasing means such that when torque load is not present between upper ratchet member 12 and mandrel 14 , first vertical faces 141 a of splines 141 will be biased toward and against the corresponding first vertical faces 122 a of grooves 122 . As shown in FIG. 3 , such biasing means may be in the form of bow springs 15 disposed within the gaps G- 1 between second vertical faces 122 b and 141 b . However, the present invention is not limited to the use of this or any particular type of biasing means. Persons skilled in the art will appreciate that various functionally effective biasing means may be devised and provided in accordance with known technologies (e.g., torsion springs coupled between the mandrel and upper and lower ratchet members), without departing from the scope of the present invention, and the biasing means may be omitted in alternative embodiments.
A generally cylindrical lower ratchet member 13 with internal grooves 132 is coaxially disposed around lower splined section 33 of mandrel 14 , such that splines 142 of mandrel 14 are received within grooves 132 . Grooves 132 are wider than splines 142 such that when a first vertical face 142 a of a given spline 142 is bearing against a first vertical face 132 a of the corresponding groove 132 , a vertical gap G- 2 will be formed between the second vertical face 132 b of groove 132 and the second vertical face 142 b of spline 142 , all as shown in FIG. 5 . The axial position of lower ratchet member 13 is substantially fixed relative to mandrel 14 , but lower ratchet member 13 is free to rotate coaxially relative to mandrel 14 , to the extent allowed by gaps G- 2 . Preferred embodiments will include suitable biasing means such that when torque load is not present between lower ratchet member 13 and mandrel 14 , first vertical faces 142 a of splines 142 will be biased toward and against the corresponding first vertical faces 132 a of grooves 132 . As shown in FIG. 5 , such biasing means may be in the form of bow springs 21 disposed within the gaps G- 2 between second vertical faces 132 b and 142 b.
The lower end of upper ratchet member 12 has a circumferentially-arrayed plurality of ratchet teeth 121 , each having a vertical face 121 a and a sloped face 121 b . The upper end of lower ratchet member 13 has a similar plurality of ratchet teeth 131 , each having a vertical face 131 a and a sloped face 131 b . The upper end of central sleeve 10 has a plurality of ratchet teeth 102 , each having a vertical face 102 a and a sloped face 102 b , and configured to mate with ratchet teeth 121 on upper ratchet member 12 . Similarly, the lower end of central sleeve 10 has a plurality of ratchet teeth 103 , each having a vertical face 103 a and a sloped face 103 b , and configured to mate with ratchet teeth 131 on lower ratchet member 13 .
Upper ratchet member 12 and lower ratchet member 13 are positioned on mandrel 14 to permit a certain amount of axial movement of central sleeve 10 along mandrel 14 , such that when ratchet teeth 102 of central sleeve 10 are matingly engaged with ratchet teeth 121 of upper ratchet member 12 , ratchet teeth 103 of central sleeve 10 will be clear of ratchet teeth 131 of lower ratchet member 13 . Torque may thus be transmitted between central sleeve 10 and upper ratchet member 12 (i.e., by engagement of ratchet teeth 102 and 121 ) or between central sleeve 10 and lower ratchet member 13 (i.e., by engagement of ratchet teeth 103 and 131 ), depending on the axial position of central sleeve 10 during operation of mechanism 100 , as will be further explained below.
The incremental angular displacement that occurs during one index cycle is determined by the angular spacing between adjacent ratchet teeth, which is determined by the total number of ratchet teeth of each plurality of ratchet teeth. The tool may be configured with the required number of ratchet teeth per ratchet plurality to achieve a selected incremental angular displacement for each cycle. For example, a ratchet plurality comprising 24 teeth would result in an incremental angular rotation of 15 per index cycle.
The operation and function of mechanism 100 may be clearly understood with reference to the FIGS. and the foregoing description. FIG. 2 illustrates an embodiment of mechanism 100 with central sleeve 10 in its upper position (as previously defined), with ratchet teeth 102 of central sleeve 10 in mating engagement with ratchet teeth 121 of upper ratchet member 12 , and with ratchet teeth 103 of central sleeve 10 axially separated from ratchet teeth 131 of lower ratchet member 13 . Any torsional load (for example, due to drilling using a mud motor coupled to mandrel 14 ) is transmitted from mandrel 14 to housing 11 through splines 141 and grooves 122 , ratchet teeth 102 and 121 , and splines 101 and grooves 111 .
When adjustment is required with respect to the angular orientation of mandrel 14 relative to housing 11 , an index cycle is initiated by forcing central sleeve 10 downward toward its lower position (previously defined) using suitable central sleeve actuation means capable of providing sufficient force to overcome the friction between sliding or otherwise mechanically-engaged components (e.g., spline/groove arrangements; mating ratchet teeth) during indexing. In the illustrated embodiment, the central sleeve actuation means comprises:
a generally cylindrical piston 19 which is disposed above central sleeve 10 and is axially movable within an annular space between housing 11 and upper ratchet member 12 ; a cylindrical drive sleeve 17 which is disposed below central sleeve 10 and is axially movable within an annular space between housing 11 and lower ratchet member 13 ; and a helical return spring 16 disposed below and reacting against drive sleeve 17 in association with a drive sleeve retention ring 18 .
In this embodiment, piston 19 is actuated by exposure to fluid pressure (either liquid or gaseous) sufficient to force central sleeve 10 downward against drive sleeve 17 so as to compress return spring 16 . As return spring 16 is compressed, central sleeve 10 begins to travel axially along central section 31 of mandrel 14 , while ratchet teeth 102 of central sleeve 10 begin to move downward relative to ratchet teeth 121 of upper ratchet member 12 . During this phase of the indexing operation, however, vertical faces 102 a of ratchet teeth 102 remain in sliding contact with opposing vertical faces 121 a of ratchet teeth 121 (as may be seen in FIGS. 6 and 7 ), and thus remain capable of transmitting torsional load.
As illustrated in FIG. 6 , representative ratchet tooth 102 - 1 is initially located between adjacent ratchet teeth 121 - 1 and 121 - 2 . As central sleeve 10 continues to travel downward, sloped faces 103 b of ratchet teeth 103 begin to contact sloped faces 131 b of ratchet teeth 131 , as shown in FIG. 7 . Due to the angular inclination of sloped faces 103 b and 131 b , lower ratchet member 13 is thus forced to rotate relative to mandrel 14 opposite to the direction of torsional load (i.e., counterclockwise in the illustrated embodiment), while bow springs 21 compress and vertical faces 132 a of grooves 132 separate from vertical faces 142 a of splines 142 , as shown in FIG. 9 . Ratchet teeth 102 continue to separate from ratchet teeth 121 until they fully disengage. At this point, there is a sudden relative rotation between mandrel 14 and central sleeve 10 in the direction of torsional load. Concurrently, ratchet teeth 103 become fully engaged with ratchet teeth 131 as central sleeve 10 reaches its lower position, as shown in FIG. 8 . Rotation between mandrel 14 and central sleeve 10 continues until vertical faces 142 a of splines 142 contact vertical faces 132 a of grooves 132 , as shown in FIG. 10 . At this point of the index cycle, angular displacement between mandrel 14 and central sleeve 10 is approximately one-half of the total angular displacement of one full index cycle. In this position, ratchet teeth 102 and 121 are separated, and torsional load is transmitted from mandrel 14 to housing 11 through splines 142 and grooves 132 , ratchet teeth 103 and 131 , and splines 101 and grooves 111 .
To complete the index cycle, fluid pressure acting on piston 19 is sufficiently decreased such that return spring 16 forces central sleeve 10 to travel axially along mandrel 14 to return to its upper position. Ratchet teeth 103 begin to separate from ratchet teeth 131 while remaining torsionally engaged and capable of transmitting torsional load, with vertical faces 103 a of ratchet teeth 103 remaining in sliding contact with opposing vertical faces 131 a of ratchet teeth 131 as seen in FIGS. 11 and 12 . Because of the angular displacement between central sleeve 10 and mandrel 14 , as ratchet teeth 102 and 121 begin to reengage, ratchet tooth 102 - 1 is now located between ratchet teeth 121 - 2 and 121 - 3 . Contact between sloped faces 102 b of ratchet teeth 102 and sloped faces 121 b of ratchet teeth 121 , as shown in FIG. 12 , causes upper ratchet member 12 to rotate relative to mandrel 14 opposite to the direction of torsional load, while bow springs 15 compress and vertical faces 122 a of grooves 122 separate from vertical faces 141 a of splines 141 , as shown in FIG. 14 . Travel of central sleeve 10 continues until ratchet teeth 103 disengage from ratchet teeth 131 , and torsional load causes mandrel 14 to rotate relative to central sleeve 10 . Vertical faces 102 a of ratchet teeth 102 engage with vertical faces 121 a of ratchet teeth 121 , and vertical faces 141 a of splines 141 contact faces 122 a of grooves 122 , as shown in FIGS. 13 and 15 . Mechanism 100 has now returned to the initial position shown in FIG. 2 , but with ratchet teeth 102 and 121 having indexed one incremental amount, determined by the angular distance between adjacent teeth, and with mandrel 14 having rotated by this same amount relative to housing 11 . The index cycle is repeated until the desired orientation between elements above and below the tool is achieved.
Persons skilled in the art will appreciate that any of various means or mechanisms could be used to actuate piston 19 , and the present invention is not limited or restricted to the use of any particular means of actuating piston 19 . In alternative embodiments, piston 19 could be actuated by functionally effective means other than fluid pressure, without departing from the scope of the present invention. Furthermore, the invention is not limited or restricted to use of the central sleeve actuation means described and illustrated herein, or any other particular central sleeve actuation means. Persons skilled in the art will recognize that other functionally effective central sleeve actuation means can be readily devised and provided in accordance with known technologies, without departing from the scope of the invention.
In accordance with embodiments of the present invention as described above, applied torsional load drives the relative angular rotation that occurs during an index cycle. Mechanism 100 could alternatively be configured such that the relative angular rotation is internally driven. One way to achieve this would be to have strong enough biasing means between upper ratchet member 12 and mandrel 14 , and between lower ratchet member 13 and mandrel 14 , to induce enough torque to effect the relative rotation of mandrel 14 during the index cycle.
Another method would be to have upper ratchet member 12 and lower ratchet member 13 rotationally fixed to mandrel 14 . In that configuration, as central sleeve 10 translates axially on the downstroke or upstroke, contact between sloped faces 103 b and sloped faces 131 b , or between sloped faces 102 b and sloped faces 121 b , would provide the driving force to rotate mandrel 14 relative to housing 11 , so that indexing could be accomplished in the absence of an applied torsional load.
It will be readily appreciated by those skilled in the art that various modifications of the present invention may be devised without departing from the essential concept of the invention, and all such modifications are intended to come within the scope of the present invention. It is to be especially understood that the invention is not intended to be limited to illustrated embodiments, and that the substitution of a variant of a claimed element or feature, without any substantial resultant change in the working of the invention, will not constitute a departure from the scope of the invention. To provide one particular non-limiting example, the central sleeve actuation means could be provided in a variety of alternative forms, such as upper and lower gas-actuated or hydraulically-actuated pistons above and below the central sleeve, without a return spring being required.
In this patent document, the term “ratchet teeth” is not to be interpreted as being limited solely to ratchet teeth of form or configuration specifically as described and illustrated herein, but is also intended to encompass alternative means of torque-transferring engagement between the central sleeve and the upper and lower ratchet members in accordance with the described operative principles of the present invention. Similarly, the term “ratchet member” is to be understood as referring to a member incorporating means for torque-transferring engagement with the central sleeve, and such engagement means may but will not necessarily comprise ratchet teeth as such. Persons skilled in the art will recognize that alternative torque-transfer engagement means may be devised using known technologies without departing from the scope of the invention. To provide only one non-limiting example, the torque-transfer engagement means in an alternative embodiment of the present invention could comprise a series of circumferentially-spaced lugs on either end of the central sleeve, with each lug being operatively engageable with a ratchet-shaped slot along the circumference each of the upper and lower ratchet members.
In this patent document, any form of the word “comprise” is to be understood in its non-limiting sense to mean that any item following such word is included, but items not specifically mentioned are not excluded. A reference to an element by the indefinite article “a” does not exclude the possibility that more than one of the element is present, unless the context clearly requires that there be one and only one such element.
Any use of any form of the terms “connect”, “engage”, “couple”, “attach”, or any other term describing an interaction between elements is not meant to limit the interaction to direct interaction between the subject elements, and may also include indirect interaction between the elements such as through secondary or intermediary structure. Relational terms (such as but not limited to) “parallel”, “perpendicular”, “coaxial”, “coincident”, “intersecting”, and “equidistant” are not intended to denote or require absolute mathematical or geometrical precision. Accordingly, such terms are to be understood as denoting or requiring substantial precision (e.g., “substantially parallel”) unless the context clearly requires otherwise. | A mechanism for adjusting the relative angular orientation of two coaxial components includes a mandrel having a cylindrical central section between upper and lower splined sections, a sleeve rotatably and slidably disposed around the mandrel's central section, and generally cylindrical upper and lower ratchet members positioned, respectively, about the mandrel's upper and lower splined sections. The ratchet members have internal grooves which receive the mandrel splines for torsional load transfer while permitting limited rotation relative to the mandrel, but their axial positions relative to the mandrel are fixed. The upper and lower ends of the sleeve have circumferentially-arrayed ratchet teeth engageable, respectively, with corresponding teeth on the upper and lower ratchet members. The central sleeve has torque-transferring external splines slidable within matching grooves on the inner surface of a cylindrical tool housing enclosing the mechanism. The mandrel is rotatable relative to the housing, but its axial position is fixed. The teeth of the sleeve and ratchet members are configured such that movement of the sleeve from a position engaging the upper ratchet member to a position engaging the lower ratchet member, or vice versa, will effect an incremental angular shift of the mandrel relative to the tool housing, while maintaining effective transfer of torsional loads therebetween. | 4 |
This is a continuation of application Ser. No. 07/806,170, filed Dec. 12, 1991, now U.S. Pat. No. 5,373,381 issued Dec. 13, 1994 which is a division of application Ser. No. 07/382,752, filed Jul. 21, 1989, now U.S. Pat. No. 5,150,248.
BACKGROUND OF THE INVENTION
The present invention relates generally to optical systems and more particularly to optical computing, information and communication systems and logic elements for use therein which utilize the principle of cross-phase modulation (XPM).
When an intense ultrashort light pulse propagates through a non-linear material, it temporally distorts the atomic and molecular configuration of the material. This distortion of the non-linear material instantaneously results in a change in the refractive index of the material. This change in the index of refraction is directly proportional to the intensity of the propagating intense light pulse. The change in the refractive index of the non-linear material, in turn, causes a phase change in the propagating intense light pulse. The phase change causes a frequency sweep within the pulse envelope, typically resulting in a blue shift at the tail end of the pulse and a red shift at the front of the pulse. Typically, the effect is a spectral broadening of the pulse resulting in the generation of a supercontinuum. This spectral effect on the propagating intense light pulse is typically referred to as a self-phase modulation effect.
In addition to experiencing self-phase modulation, an intense light pulse propagating through a non-linear material will typically undergo self-focusing, that is, a narrowing of the cross-sectional diameter of the pulse. Self-focusing occurs because, typically, the intensity of a pulse of light is greatest at its center and weakest at its outer edges. Since n is directly proportional to the intensity of the pulse, the center or the pulse causes a greater change in refractive index of the non-linear material than the outer edges of the pulse. Consequently, the center of the pulse travels slower than its outer edges, causing the outer edges to bend in towards the center of the pulse. This effect causes the beam to focus.
In addition to experiencing self-phase modulation and self-focusing, an intense light pulse propagating through a non-linear material may also be used to induce the phase modulation of and/or the focusing of a co-propagating weak light pulse. These phenomena are typically referred to as cross-phase modulation and induced focusing, respectively.
Cross-phase modulation may result in either frequency shifting (i.e., blue shifting or red shifting) or spectral broadening (i.e., supercontinuum generation), the particular effect depending on the relative times at which the weak pulse and the intense pulse propagate through the non-linear material. For example, if the intense pulse has a greater wavelength than the weak pulse, the intense pulse will travel faster through the non-linear material. Therefore, if the intense and weak pulses are sent propagating into the non-linear material at the same time, the weak pulse will be exposed predominately to the change in refractive index caused by the tail end of the intense pulse. (This is referred to commonly as tail walk-off). The result of tail walk-off is a blue shift of the weak pulse. Analagously, if the weak pulse is sent propagating into the non-linear material ahead of the intense pulse, the weak pulse will feel the effects of the refractive index change due to the front end of the intense pulse (front walk-off). The result of front walk-off is a shift or the weak pulse to the red. Finally, if the weak and intense pulses are sent propagating into the non-linear material so that the weak pulse is subjected to the changes in the refractive index caused by both the tail end and the front end of the intense pulse (e.g. symmetric walk-off or no walk-off), the weak pulse broadens spectrally to both the red and the blue.
Spectral changes arising from cross-phase modulation may lead to changes in the temporal profile of the weak pulse when it propagates into a dispersive medium (i.e. an optical fiber) or a dispersive optical component (i.e. a grating or a prism). For example, if cross-phase modulation results in the spectral broadening of the weak pulse, a further propagation of the weak pulse through a grating pair may slow down its re-shifted frequencies (generated by XPM at the pulse front) with respect to its blues shifted frequencies (generated by XPM at the pulse back), and consequently reduces the pulse duration of the weak pulse.
Cross-phase modulation may also be used to change the spatial distribution of copropagating weak pulses. This effect occurs when the intense pulse generates a spatially-dependent non-linear refractive index. For example, a pump pulse with a Gaussian spatial distribution of its intensity generates a higher refractive index on the propagation axis of the weak pulse. As a consequence, the outer edges of the weak pulse bend in towards the center of the pulse, and the weak pulse focuses.
As a term of art, cross-phase modulation is frequently used generically to refer to both cross-phase modulation and induced focusing.
Non-linear materials are very well known in the art. Examples of non linear materials are BK-7 glass, CdSe, liquid CS 2 , NaCl crystal, doped glasses, semiconductor bulk and quantum structures, microcrystalline semiconductor particles in glasses polydiacetylene organic polymer and optical fibers.
SUMMARY OF THE INVENTION
The present invention is directed to optical computing and communication systems which rely on the phenomena of cross-phase modulation to alter and control, either or simultaneously, the spectral, temporal or/and spatial properties of ultrashort light pulses for processing of information with high speed (up to tens of terahertz regime) repetition rates. The present invention is also directed to a method for altering and controlling, either, or simultaneously, the spectral, temporal or/and spatial properties of ultrashort light pulses using cross phase modulation.
One optical communication system for transmitting information, which is constructed according to the teachings of the present invention and which involves frequency shifting (i.e. altering the spectral properties) comprises means for generating a first beam of laser light and a second beam of laser light, said first beam comprising a series of ultrashort pulses of a first frequency, said second beam comprising a series of ultrashort pulses of a second frequency, said pulses of said first beam being stronger in intensity than said pulses of said second beam, means for modulating said pulses in the first beam according to predetermined information, means for combining said modulated first beam and second beam to form a third beam, a non-linear material disposed along the path of said third beam for receiving said third beam and for producing a fourth beam, said fourth beam including pulses of said first frequency from said modulated first beam, pulses of said second frequency from said second beam, and pulses of a third frequency, said pulses of said third frequency resulting from XPM produced by copropagation of said first and second beams in said non-linear material, filter means disposed along the path of said fourth beam for filtering out pulses of said first frequency, a beamsplitter disposed along the path of said fourth beam on the output side of said filter means for splitting light passed by said filter means into a fifth beam and a sixth beam, filter means disposed along the path of said fifth beam for transmitting only pulses of said second frequency, detector means for detecting pulses passed by said filter means on the fifth beam, filter means disposed along the path of said sixth beam for passing only pulses of said third frequency, and detector means for detecting pulses passed by said filter means in the path of the sixth beam.
Another optical communication system for transmitting information, which is constructed according to the teachings of the present invention and which involves modulating the time duration and amplitude (i.e. the temporal properties) of ultrashort pulses comprises means for generating a first and second beams of laser light, said first beam comprising a series of ultrashort pulses of a first frequency bandwidth, said second beam comprising a series of ultrashort pulses of a second frequency bandwidth, said pulses of said first beam being stronger in intensity than said pulses of said second beam, said pulses of said second beam having a peak intensity p1, means disposed along the path of said first beam for modulating said pulses according to predetermined information, means for combining said first beam and second beam to form a third beam, a non-linear material disposed along the path of said third beam for receiving said third beam and for producing a fourth beam, said fourth beam including pulses of said first frequency bandwidth, pulses of said second frequency bandwidth and pulses of a third frequency bandwidth, said pulses of said third frequency bandwidth also having a peak intensity p1, said pulses of said third frequency bandwidth being a spectrally broadened version of said first frequency bandwidth caused by cross-phase modulation, filter means disposed along the path of said fourth beam for filtering out pulses of said first frequency bandwidth, means disposed along the path of said fourth beam for optically delaying longer light wavelengths relative to shorter light wavelengths and for producing a fifth beam, whereby said pulses of said second frequency bandwidth become temporally expanded and consequently less intense while said pulses of said third frequency bandwidth become temporally compressed and consequently more intense, and detector means disposed along the path of said fifth beam for measuring said pulses, said detector means set at a intensity detection threshhold level equal to p1.
Another optical communications system for transmitting information, which is constructed according to the teachings of the present invention and which involves controlling the spatial properties of ultrashort pulses comprises means for generating a first and second beams of laser light, said first beam comprising a series of ultrashort pulses of a first frequency, said second beam comprising a series of ultrashort pulses of a second frequency, said pulses of said first beam being greater in intensity relative to said pulses of said second beam, means disposed along the path of said first beam for splitting said first beam into third and fourth beams, means disposed along the path of said third beam for masking a portion of said third beam, means disposed along the path of said fourth beam for masking a portion of said fourth beam, the part of the third beam which is masked being different from the part of the fourth beam which is masked, means for modulating said third beam, means for modulating said fourth beam, means for combining said second, third and fourth beams to form a fifth beam, a non-linear material disposed along the path of said fifth beam for receiving said fifth beam and outputting sixth, seventh and eighth beams, each travelling along a different direction, the sixth beam containing pulses from said second beam, the seventh beam resulting from XPM and containing pulses from said second and third beams and the eighth beam resulting from XPM and containing pulses from said second and fourth beams, means disposed along the paths of said seventh beam for detecting only pulses from said third beam and means and means disposed along the paths of said eighth beam for detecting only pulses from said fourth beam.
An optical AND gate which is constructed according to the teachings of the present invention and which utilizes the principle of cross-phase modulation includes a beamsplitter for combining a pair of beams of light, a delay line for delaying one of the pair of beams so that the two beams overlap, a non-linear medium disposed along the path of the combined beam and a filter for filtering out certain frequencies in the beam passed through the non-linear medium.
An optical invertor which is constructed according to the teachings of the present invention and which utilizes the principle of cross phase modulation includes means for generating a light beam, a beamsplitter, a delay line, a non-linear medium and a filter.
In other embodiments of the invention the intense and weak beams have different polarizations rather than different frequencies.
It is an object of the present invention to provide an optical communication system that makes use of the principle of cross-phase modulation.
It is an object of this invention to provide a method for controlling either the spectral, temporal and spatial properties of ultrashort pulses that makes use of the principle of cross phase modulation.
It is another object of the present invention to provide an optical communication system utilizing an optical processor that has the has the capacity to process data streams in the GHZ to terahertz range.
It is another object of the present invention to provide an optical computing system utilizing an optical processor that has the has the capacity to process data streams in the GHZ to terahertz range.
It is yet still another object of the present invention to provide a new and novel optical processor.
It is a further object of this invention to provide a method for controlling the spectral, temporal and spatial properties of ultrashort pulses that makes use of the principle of cross phase modulation.
It is another object of this invention to provide an all optical system in which a plurality of sub-systems using the principle of cross-phase modulation are cascaded together.
It is still another object of this invention to provide mechanisms for a new and novel ultrafast optical information processor.
Various other features, objects and advantages will appear from the description to follow. In the description, reference is made to the accompanying drawings which form a part thereof, and in which are shown by way of illustration, specific embodiments for practicing the invention. These embodiments will be described in sufficient detail to enable those skilled in the art to practice the invention, and it is to be understood that other embodiments may be utilized and that structural changes may be made without departing from the scope of the invention. The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present invention is best defined by the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings in which like reference numerals or characters represent like parts and wherein:
FIG. 1 is a schematic representation of one embodiment of an optical system for transmitting information which is constructed according to the teachings of the present invention;
FIG. 1(a) is an illustration of a modification of modulator 18 in FIG. 1;
FIG. 2 is a schematic representation of another embodiment of an optical system for transmitting information which is constructed according to the teachings of the present invention;
FIG. 2(a) is a diagram showing the initial (i.e. before passing through the non-linear medium), expanded and compressed probe (i.e. weak) pulses in the FIG. 2 embodiment;
FIG. 3 is a schematic representation of a third embodiment of an optical system for transmitting information which is constructed according to the teachings of the present invention;
FIG. 4 is a graphic representation of the transmissivity of one of the masks in the FIG. 3 optical system, the transmissiveness of the mask being selected to make the intense beam profile triangular in shape;
FIG. 5 is an illustration showing how the profile of a pulse can be changed using the mask designed as in FIG. 4
FIG. 6 is a schematic of an optical computing system which includes an AND gate according to the teachings of this invention;
FIG. 7 is a truth table for the AND gate in FIG. 6.
FIG. 8 is a schematic of an optical computing system which includes an INVERTER according to this invention;
FIG. 9 is a truth table for the INVERTER IN FIG. 8.
FIG. 10 is a schematic of a modification of the system of FIG. 1;
FIG. 11 is a schematic of a miniaturized system according to this invention; and
FIG. 12 is a schematic of another embodiment of the invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Referring now to the drawings and more particularly to FIG. 1, there is illustrated a schematic view of one embodiment of an optical system for transmitting information, the optical system being constructed according to the teachings of the present invention and represented generally by reference numeral 11.
Optical system 11, which utilizes the spectral effects of cross phase modulation, includes an optical processor 12.
Processor 12 includes a laser system 13 which is used to produce an output beam 14-1. Beam 14-1 includes intense ultrashort pulses at a first frequency F1 and weaker ultrashort pulses at a second frequency F2. Laser system 13 may comprise a laser 13-1 and a second harmonic generating crystal 13-2. Laser 13-1 may be a mode locked Nd:YAG laser which is capable of emitting a beam of laser light having intense pulses at 1060 nm. Examples of other lasers which may be used are a Ti:sapphire Laser, an Alexandrite laser, a Forsterite laser, a laser diode, a dye laser or a free electron laser.
A dichroic beamsplitter 14-2 splits beam 14-1 into a first or pump beam 15, and a second or probe beam 17. Beamsplitter 14-2 is designed to transmit 90% at frequency F1 and 10% at frequency F2 and reflect 90% at frequency F2 and 10% at frequency F1. A narrow band filter 14-3 removes all frequencies except F1 from pump beam 15 and a narrow band filter 14-4 removes all frequencies except F2 from probe beam 17.
Processor 12 also includes means 18 disposed along the path of beam 15 for modulating beam 15 in accordance with predetermined information. Means 18 may comprise an optical Kerr shutter 19 which is designed to transmit the intense pulses of first beam 15 only when gating pulses, emitted from a laser 21, simultaneously arrive thereat. Thus, by controlling the emissions of laser 21, such as by a computer 23, it becomes possible through the operation of shutter 19 to effectively encode information obtained from computer 23 into the intense pulses of beam 15. Instead of a Kerrshutter and a laser, an electro-optical modulator 24-1 activated by a pulse generator 24-2 as shown in FIG. 1(a) or a photoconducting switch could be employed.
Processor 12 further includes a beamsplitter 25 for combining beams 15 and 17 and producing a third beam 27 containing both pulses at frequency F2 from beam 17 and pulses at frequency F1 from beam 15. Beam 15 passes into beamsplitter 25 after it is passed through an adjustable optical delay 24 while beam 17 passes directly into beamsplitter 25. Mirrors 28-1 and 28-2 are used to change the direction of beam 17 while adjustable optical delay 24 is used to adjust the path length of beam 15 so that the pulses in beam 15 and the pulses in beam 17 will overlap inside non-linear material X.sup.(3), identified by reference numeral 29. The length of material 29 is sufficient to produce "walk-off". Material 29 may be for example glass or an organic substance. If desired, the intensity modulating means 18 can be eliminated and the adjustable optical delay 24 used as a mechanism for temporally modulating the arrival time of the pulses in beam 15. As will hereinafter be explained, non-linear material 29 is used to modulate the frequency of the pulses at frequency F2 in beam 27 using the modulated copropagating pulses at frequency F1. The output from non-linear material 29 is a fourth beam 31 containing pulses at first frequency F1, pulses at second frequency F2 and pulses at a third frequency F3, the pulses at the third frequency F3 being pulses from the second beam 17 that are frequency shifted (an amount f) as a result of propagating through non-linear material 29 with pulses from beam 15.
More specifically, if a pulse in beam 17 copropagates through non-linear material 29 with a pulse from beam 15, the output will be the pulse from beam 15 and a pulse corresponding to a pulse from beam 17 frequency shifted an amount that is proportional to the peak power of the pulse from beam 15. On the other hand, if there is no pulse from beam 15 then the pulse from beam 17 will pass through non-linear material undistorted.
Processor 12 also includes a filter 33, which is diposed along the path of beam 31. Filter 33, is selected to block the transmission of the pulses at frequency F1.
System 11 further includes an optical transmission channel 34. A beamsplitter 35, which is also disposed along the path of beam 31 at the output side of filter 33, is used to split beam 31 into a fifth beam 37 and a sixth beam 39. A pair of filters 41 and 43 are disposed along the paths beams 37 and 39, respectively. Filter 41 is selected to pass only pulses at frequency F2 while filter 43 is selected to pass only pulses at frequency F3. A pair of photodiodes 45 and 47, are used to detect the light passed by filters 41 and 43, respectively. Photodiodes 45 and 47 are both electrically connected to a computer 49 which processes the signals received from each photodiode.
The operation of system 11 as a means for transmitting information is hereinafter described. Laser 13 is activated, causing the emission of an output beam from which is derived a first beam 15 of intense pulses at frequency F1 and a second beam of weak pulses at frequency F2. The information to be transmitted is sent from computer 22 to laser 21 causing the emission therefrom of gating pulses. Those intense pulses of beam 15 that arrive at shutter 19 at the same time that the gating pulses arrive undergo a change in their polarization, permitting their transmission through shutter 19. All other intense pulses are blocked from passing through shutter 19. Consequently, when beams 15 and 17 are combined into beam 27, there will usually be more weak pulses than intense pulses. Those weak pulses that arrive at non-linear material 29 without a corresponding intense pulse emerge from material 29 in beam 31 essentially unchanged. In contrast, those weak pulses that arrive at non-linear material 29 at approximately the same time as the intense pulses undergo cross-phase modulation and emerge from material 29 in beam 31 at a different frequency, the particular shift in frequency depending on whether the arrival of the weak pulses and the intense pulses is synchronized to result in tail walk-off or front walk-off and the extent of the shift depending on the relative intensity of the intense pulses. Beam 31, which contains pulses at frequency F1 at frequency F2 and pulses at frequency F3 is passed through filter 33. Filter 33 removes pulses at frequency F1. Beam 31 is then split into beams 37 and 39. Beam 37 is then passed through filter 41 which filters out the pulses at frequency F2. The modulated pulses are then detected by photodiode 45, and the signal is sent to computer 49. Beam 39 is passed through filter 43 which leaves only the non-modulated pulses to be detected by photodiode 47 and processed by computer 49. As can be appreciated, each signal received by photodiode 47 corresponds to a gating pulse whereas each signal received by photodiode 45 corresponds to the absence of a gating pulses. In this manner, binary information may be transmitted through system 11.
While, for the sake of convenience, source 13 has been represented as a single laser system which simultaneously generates pulses at different frequencies and intensities, it is to be understood that two separate lasers could easily be used if properly synchronized. Also, it is to be understood that while system 11 is designed specifically to process binary information, tertiary information or higher degrees of information could easily be transmitted by increasing the number of differing intense pulses (and the associated number of shutter mechanisms). It is also to be understood that shutter 19 could be replaced by an electro-optic shutter. Also, shutter 19 and laser 21 could be replaced by an electro-mechanical shutter. Furthermore, shutter 19 can be eliminated completely by triggering the emission of intense pulses from laser source 13 with electrical signals from computer 23.
Referring now to FIG. 2, there is shown another embodiment of an optical system for transmitting information constructed according to the teachings of the present invention and represented generally by reference numeral 51.
System 51, which utilizes the temporal effects of cross phase modulation to produce a pulse compression type switch, includes a laser system 13 for generating a beam 14-1 of ultrashort laser light pulses, beam 14-1 including intense pulses of one frequency F1 and weak pulses of another frequency F2, a dichroic beamsplitter 14-2, a pair of filters 14-3 and 14-4, a pair of deflection mirrors 28-1 and 28-2, an adjustable optical delay 24, a beamsplitter 25, modulating means 18, a nonlinear medium 30 and a filter 33, all arranged and functioning as in the FIG. 1 embodiment except that the length of non-linear medium 30 is such that there is effectively no "walk-off".
System 51 also includes a pair of parallel grating plates 53 and 55, which receive fourth beam 31 from filter 33 and produce a fifth beam 57. As will be explained later in greater detail, grating plates 53 and 55 are used to temporally resolve fourth beam 31 by optically delaying the longer wavelengths of light relative to the shorter wavelengths of light. A photodiode 59 or other light sensitive measuring device is disposed along the path of fifth beam 57. Finally, a computer 61 for processing the signals emitted by photodiode 59 is electrically connected to photodiode 59. For reasons to be discussed more fully below, computer 61 is programmed so that it will only process signals having an intensity above a predetermined threshold, the threshold being for example the intensity of weak pulses that pass through non-linear medium 29 without corresponding intense pulses.
Before discussing the operation of system 51, it is important to understand that, while for the sake of simplicity, the weak and intense pulses emitted from laser system 13 have been described as being of two different frequencies, the weak and intense pulses are actually of two different frequency bandwidths, each frequency bandwidth being for example a few tenths of a nanometer wide. Consequently, each pulse includes frequency components from across its entire bandwidth. However, these frequency components, while being spread over the spectral width of the pulse, are nonetheless homogeneously distributed over the entire temporal width of the pulse. In other words, at any point in time, the distribution of frequency components within each pulse is homogeneous.
With the above kept in mind, the description of the operation of system 51 is hereinafter set forth. Laser system 13 is activated, causing the emission therefrom of laser light including intense pulses of one frequency bandwidth within beam 15 and of weak pulses of another frequency bandwidth within beam 17. Instead of a laser system comprising single laser, two lasers could be employed, each emitting a separate beam. Information from computer 23 is then encoded into beam 15 using shutter 19 in the manner described above to eliminate certain intense pulses. Beams 15 and 17 are then combined using mirrors 28-1 and 28-2 and beamsplitter 25 to produce beam 27. Beam 27 now consists of weak pulses and intense pulses, synchronized using adjustable optical delay 24 so that they arrive simultaneously at non-linear material 30.
Beam 27 then travels across non-linear material 30, being transformed in the process by cross-phase modulation into beam 31. Beam 31 includes intense pulses and two varieties of weak pulses, namely, non-modulated weak pulses and modulated weak pulses. The non-modulated weak pulses are those weak pulses that propagated across material 29 without a corresponding, copropagating intense pulse. The non-modulated weak pulses are temporally and spectrally indistinguishable from the weak pulses in beam 27. The modulated weak pulses are those weak pulses that co-propagated through material 30 with intense pulses. The modulated weak pulses have a spectrally broader bandwith than the weak pulses in beam 27. Moreover, the modulated weak pulses are not spectrally homogeneous over time. Rather, the longer wavelength components are more concentrated towards the temporal fronts of the pulses and the shorter wavelength components are more concentrated towards the temporal tails of the pulses.
After emerging from non-linear material 30, beam 31 is then passed through filter 33 which filters out the intense pulses. The non-modulated weak pulses and the modulated weak pulses of beam 31 then arrive at grating plates 53 and 55. As discussed earlier, plates 53 and 55 optically delay in time the longer wavelengths of each pulse relative to the shorter wavelengths. This occurs because plate 53 disperses beam 31 into its frequency components (the longer wavelengths being deflected at a greater angle than the shorter wavelengths and, hence, traveling a greater distance to plate 55) while plate 55 receives the components and recombines them to form beam 57. The resultant effect of passing through grating plates 53 and 55 is as follows: For the weak non-modulated pulses, each of which is homogeneous in frequency distribution, passage through the plates results in temporal expansion. This occurs because the longer wavelengths slow down and go to the back of the pulse while the shorter wavelengths speed up and go to the front of the pulse. One consequence of temporal expansion is that the pulse becomes less intense. This occurs because while the temporal width of the pulse has increased, its energy has not. Consequently, the same amount of energy must be spread over a greater period of time.
In contrast, for the weak modulated pulses, each of which has longer wavelengths concentrated at the front of the pulse and shorter wavelength concentrated at the tail of the pulse, passage through the plates results in temporal compression. This occurs because the longer wavelengths at the front of the pulse are slowed down while the shorter wavelengths at the tail of the pulse are accelerated. The consequence of temporal compression is that the pulse becomes more intense. This occurs because while the temporal width of the pulse has decreased, its energy has not. Consequently, the same amount of energy must be spread over a shorter period of time.
Beam 57, including its compressed and expanded pulses, then arrives at photodiode 59. Both compressed signals and expanded signals trigger the emission of an electrical signal from photodiode 59 to computer 61. Because computer 61 is programmed to ignore signals of an intensity less than the modulated weak pulses in beam 27, only the compressed (i.e. modulated) pulses register. Because the compressed pulses are related to the intense pulses sent through shutter 19 which, in turn, correspond to the information to be transmitted, system 51 can so be used to transmit information.
FIG. 2(a) shows the shapes of an initial (i.e. before passing through non-linear medium 29) a compressed pulse and expanded probe pulse, the initial pulse being identified by reference numeral, 70-0, the compressed pulse being identified by reference numeral 70-1 and the expanded pulse by reference numeral 70-2.
In addition to being used as a system for transmitting information, system 51 may be used for intensity modulating pulses. In addition system 51 may be used as a pulse compression device by removing shutter 19, laser source 21, and computer 23 or as an pulse expansion device by removing shutter 19, source 21 and computer 23 and programming computer 61 to detect only expanded pulses.
Those modifications discussed in conjunction with system 11 are also applicable to system 51.
Instead of using a pair of gratings 53 and 55 for temporally resolving the fourth beam 31, a sequence of prisms or any optical component (or components) or material (i.e. optical fibers) which can produce by group-velocity dispersion the relative delay between short and long wavelengths may be employed.
Referring now to FIG. 3, there is shown a third embodiment of an optical system for transmitting information constructed according to the teachings of the present invention and represented generally by reference numeral 71.
As will be more fully explained below, system 71 is designed to exploit the principle of induced focusing and utilizes the spatial effects of cross-phase modulation to deflect a beam of light. Self-focusing occurs when a Gaussian shaped beam of intense light travels through a non-linear medium because the intensity of the beam across its cross-section is much greater at its center than around its outer edges. Consequently, the increase in the refractive index of the non-linear medium is also greatest in the center of the beam and weakest around the outer edges. This causes the center of the beam to move slower than the edges which, in turn, causes the edges to bend in towards the center. As a result, the beam narrows in cross-sectional diameter (i.e. focuses). Induced focusing is identical to self-focusing except that the change in the refractive index is applied to a weak beam that is copropagating with the intense beam.
As can be seen, system 71 has many of the same components as systems 11 and 51.
System 71 includes a processor 72. Processor 72 includes a laser system 13 for generating a beam 14-1 of ultrafast laser light, a beamsplitter 14-2 for splitting beam 14-1 into a pair of beams 15 and 17 and a pair of filters 14-3 and 14-4 for filtering beam 15 to contain only intense pulses of at frequency F1 and beam 17 to contain only weak pulses at another frequency F2. System 71 also includes a deflection mirror 72 for deflecting beam 15, a beamsplitter 73 for splitting beam 15 into two beams 73-1 and 73-2, a pair of modulators 18, one for modulating beam 73-1 and the other for modulating beam 73-2, a mask 73-4 disposed along the path of beam 73-1, a mask 73-5, disposed along the path of beam 73-2, a pair of deflection mirrors 73-61 and 73-62, and a pair of beamsplitters 73-8 and 73-9 for combining beams 73-1 and 73-2 with beam 17. Masks 73-4 and 73-5 are designed arranged to mask off different portions of their respective beams. Beamsplitters 73-8 and 73-9 combine the portions of beams 73-1 and 73-2 passed by their respective masks along the beams 15, identified by reference numerals 74-1 and 74-2 to produce a third beam 75.
Processor 72 further includes a non-linear material 29, which is disposed along the path of beam 75 and optical delays 72-1 and 72-2. As will be described later in more detail, non-linear material 29 receives beam 75 and produces a fourth beam 77, a fifth beam 79 and a sixth beam 80, fifth beam 79 and sixth beam 80 being angularly deflected, and by different amounts, relative to fourth beam 77. Filters 81, 82 and 83 are disposed along the path of beams 79 and 80, respectively to filter out the intense pulses present therein.
System 71 further includes photodiodes 85, 86 and 87 which are disposed further along the paths of beams 77, 79, and 80 receive beams 77, 79 and 80 and output corresponding electrical signals to a computer 91 for processing.
System 71 is operated first by activating laser 13, causing the emission therefrom of a beam of laser light having intense (i.e. pump) pulses of one frequency F1 and weak (i.e. probe) pulses of another frequency F2. The intense pulses are split into two beams 73-1 and 73-2 and modulated in accordance with the information from their respective modulators 18 to permit specific intense pulses to pass therethrough. Each beam 73-1 and 73-2 is partially masked by its respective mask 73-4 and 73-5 and then combined at beamsplitter 73-8 and 73-9, respectively with the weak pulses of beam 17 to produce a third beam 75. The intense pulses in beam 73-1 and 73-2 are synchronized with their corresponding weak pulses from beam 17 by using the optical delays so that they will arrive at non-linear material 29 at the proper time with the pulses of beam 17.
The propagation of beam 75 through non-linear material 29 results in the creation of beams 77 and 79 and 80. Beam 77, which was not subjected to induced focusing, consists of the weak pulses of beam 75 that traveled through non-linear material 29 without copropagating with intense pulses. Beam 79, which is angularly deflected by an angle A relative to beam 77 as a result of induced focusing, consists of the copropagating weak and intense pulses, the intense pulses being from beam 73-1. The reason why beam 79 is angularly deflected, rather than being reduced in cross-sectional diameter (the typical result of induced focusing), is that the masking of the intense pulses leads to an asymmetrical change in the refractive index of the non-linear medium. Consequently, this asymmetry causes the intense pulses (and their copropagating weak pulses) to be deflected in the direction of the masked portion of the intense beam.
Beam 80, is angularly deflected by an angle B, which is different from angle A, relative to beam 77. Beam 80 consists of copropagating weak and intense pulses, the intense pulses being from beam 73-2.
Beams 77 and 80 are then passed through filters 81 and 82, which remove the intense light pulses therefrom. The pulses in paths 77, 79 and 80 are converted into electrical signals by photodiodes 85. 87 and 88 and sent to computer 89 for processing.
While the above discussion makes it appear that beams 79 and 80 are collimated, the reality is that beams 79 and 80 actually emerge from non-linear medium 29 as diverging cones. However, most of the energy is concentrated in a small angle, the deflection angle. One way to eliminate the energy other than at this small angle is to make the beam profile of the intense beam triangular in shape. This may be done by designing masks 73-4 and 73-5 to mask off a part of the beam such that the intense beam profile becomes triangular. This may be done by varying the transmissivity of masks 73-4 and 73-5 over their cross-sectional area. A graph of transmissivity vs. radius for such a mask 73-4 is shown in FIG. 4. FIG. 5 shows the shape of a pulse without the mask of FIG. 4 and with the mask of FIG. 4; the pulse being gaussian shaped without the mask and triangularly shaped with the mask. Catastrophic self focusing and filament generation can be eliminated if the nonlinear medium is thin enough.
As can be appreciated, in the absence of a pump pulse from either beam 73-1 or beam 73-2, weak beam 17 will pass through non-linear medium 29 and emerge undeflected as beam 77. On the other hand, a pump pulse from beam 73-1 will cause a deflection of the emerging beam to beam path 79 and or pump pulse from beam 73-2 will cause a deflection of the emerging beam to beam path 80.
Also, apparatus 71 can be used, if desired, as a mechanism for altering the spatial distribution of light in a weak beam; i.e. beam 17.
As can be appreciated, the system in FIG. 3 can be easily modified to include more than two pump beams so as to be able to transmit more than two sources of information, or if desired, can be modified so as to have only one pump beam for use in transmitting information from a single source.
The modifications discussed in conjunction with system 11 are applicable to system 71.
Referring now to FIG. 6 there is shown an optical computing logic device system 91 constructed according to this invention, device 91 including an AND gate 93 which operates using the principle of cross-phase modulation and a detector 95. AND gate 93 includes an adjustable optical delay 97, a beamsplitter 99, non-linear medium 101 and a filter 103.
AND gate 93 is used to perform an AND function on a first beam 105 of intense pulses of one frequency f p and a second beam 107 of weak pulses of another frequency fo. Delay 97, delays beam 107 as necessary, so that beams 105 and 107 overlap. Beamsplitter 97 combines beams 105 and 107 to form a third beam 109 which is passed through non-linear medium 101. The output from non-linear medium 101 is a fourth beam 111 which may include pulses of frequency fp, pulses of frequency fo and pulses of a frequency (fo+Δf), the pulses having a frequency (fo+f) resulting from cross-phase modulation and where f is the change in frequency resulting from cross-phase modulation. Filter 103 removes pulses of frequency fp and pulses of frequency fo and allows only pulses of frequency (fo+Δf) to pass through. The light passed through filter 103, i.e. the pulses having a frequency (fo+Δf), is detected by detector 95. Detector 95 may be a photodiode.
AND gate 93 operates in the following manner. If there is a pulse from beam 105 and there is no pulse in beam 107, there will be no output from filter 103. If there is no pulse in beam 105 and there is a pulse in beam 107 there will be no output from filter 103. If there is a pulse in beam 105 and a pulse in beam 107, then there will be an output from filter 103, namely a pulse having a frequency (fo+Δf). A truth table for AND gate 93 is shown in FIG. 7.
Referring now to FIG. 8 there is shown an optical computing logic device 111 constructed according to this invention. Logic device 111 includes an INVERTER 113 which operates on the principle of cross phase modulation and a detector 115. INVERTER 113 includes a laser 117 for generating a weak beam 119 of ultrashort light pulses of frequency fo (i.e. probe pulses), an adjustable optical delay 118 a beamsplitter 121 for combining beam 119 with a signal or input beam 123 which is to be inverted by INVERTER 113 to form a third beam 125, input beam 123 being an intense beam of ultrashort pulses of frequency fp, (i.e. pump pulses), a non-linear medium 127 disposed along the path of beam 125, the light emerging from non-linear medium 127 including pulses of frequency fo, pulses of frequency fp and pulses of frequency (fo+Δf) where Δf is the change i.e. shift, in frequency fo as a result of cross-phase modulation and a filter 129 for removing pulses of frequency fp and pulses of frequency (fo+Δf) and allowing pulses of frequency fo to pass.
INVERTER 113 operates as follows. Laser 117 is continuously outputting pulses fo. If there is a pump pulse fp, there will be no output from filter 129, while if there is no pump pulse fp there will be an output from filter 129, namely, a pulse having a frequency fo. Thus, INVERTER 113 only provides an output in the absence of a pump pulse. A truth table for INVERTER 113 is shown in FIG. 9.
As can be appreciated, other logic elements using XPM can also be formed.
The embodiments of the present invention are intended to be merely exemplary and those skilled in the art shall be able to make numerous variations and modifications to it without departing from the spirit of the present invention. For example, the pump signals (in all embodiments) could be generated by all-optical processors and the output signals could be used in cascade as basic units of all-optical processors. Also, the optical processors may be miniaturized using diode laser technology and integrated optics. Also, instead of different frequencies, the pump and probe signals could have the same frequency but have different polarizations. All such variations and modifications are intended to be within the scope of the present invention as defined in the appended claims.
Referring now to FIG. 10 there is shown a system 131 which is similar to system 11 but wherein the pump and probe pulses have different polarizations rather than different frequencies. System 131 includes a laser system 133 having a laser 13-1 and a polarizer 135. The output beam from laser system 133 is split by beamsplitter 14-2 into an intense beam 15-1 and a weak beam 17-1. A quarter-wave plate 137 changes the polarization of weak beam 17-1 and a polarizer (analyzer) 139 removes intense beam 15-1 from the beam 31-1 emerging from non-linear medium 29.
All embodiments of this invention can be miniaturized using diode technology and integrated optics.
Referring now to FIG. 11 there is shown a system 141 similar to system 11 in FIG. 1 but that has been miniaturized using diode laser technology and integrated optics. System 141 includes a pair of diode lasers 143 and 145, a computer 147 an integrated optics modulator 149, a waveguide 151, a multiplexer 153, a waveguide 154, a demultiplexer 155, a non-linear material 157, a filter 158 and a pair of detectors 159 and 161.
Referring now to FIG. 12 there is shown an example of a system 171 in the form of an all-optical beam scanner remotely driven by an all optical processor 172. System 171 includes an INVERTOR 113 and AND gate 93 an optical amplifier 177, a frequency modulator 179, an OTC 181, a filter 183, an optical amplifier 185 and a beam scanner 187. Beam scanner 187 includes a laser system 13, a delay 72-2, a mirror 189, a beamsplitter 191 and a non-linear medium 29. | Optical communication systems, optical computing systems and optical logic elements which rely on the phenomina of cross-phase modulation to alter and control, either or simultaneously, the spectral, temporal or/and spatial properties of ultrashort light pulses for processing information with high speed repetition rates. A weak beam of ultrashort light pulses is modulated by an intense beam of ultrashort light pulses by copropagating both beams through a non-linear medium such that cross-phase modulation effects are realized. | 6 |
PRIORITY TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application No. 61/481,789, filed May 3, 2011, which is hereby incorporated by reference in its entirety.
FIELD OF THE INVENTION
The present invention relates to compounds useful as glucokinase activators for the treatment or prophylaxis of metabolic diseases and disorders.
BACKGROUND OF THE INVENTION
Glucokinase (GK), also referred to as Hexokinase IV, is one of four hexokinases that are found in mammals. Hexokinases catalyze the first step in the metabolism of glucose, i.e., the conversion of glucose to glucose-6-phosphate. GK has been found to have a critical role in whole-body glucose homeostasis. As such, activation of GK represents a potentially important therapeutic intervention point and small molecule GK activators have considerable potential for the treatment or prophylaxis of metabolic diseases and disorders, for example, Type II diabetes.
SUMMARY OF THE INVENTION
The present invention is directed in part to compounds of formula (I),
wherein:
R 1 is selected from the group consisting of: H, F, and CF 3 ; R 2 is selected from the group consisting of: isopropyl, cyclopropyl, cyclopentyl, cyclohexyl, and —CH 2 —S—CH 3 ; R 3 is
R 4 is selected from the group consisting of: H, Br, and —CH(OH)—CH 2 OH; and
R 5 is selected from the group consisting of: —CH(OH)—CH 2 OH, —CH 2 —C(CH 3 ) 2 —O—CH 3 , —CH 2 —CH 2 OH, —CH 2 —C(O)—O—C(CH 3 ) 3 , —(CH 2 ) 2 O—CH 3 , —CH 2 —COOH, —(CH 2 ) 2 —COOH, —(CH 2 ) 2 —C(O)—O—C(CH 3 ) 3 , —(CH 2 ) 2 —CH 2 OH, —(CH 2 ) 2 —O—CH(CH 3 ) 2 , and —CH 3 ;
and wherein,
when R 3 is
R 1 is CF 3 ; and
R 2 is selected from the group consisting of: isopropyl, cyclopentyl, and —CH 2 —S—CH 3 ; and (2) when R 3 is
R 1 is selected from the group consisting of: H, F, and CF 3 ; and
R 2 is selected from the group consisting of: cyclopentyl, cyclohexyl, and cyclopropyl;
or a pharmaceutically-acceptable salt thereof.
The compounds are useful as glucokinase activators for the treatment or prophylaxis of metabolic diseases and disorders, for example diabetes mellitus, including type II diabetes mellitus.
The present invention also relates to a process for the preparation of a compound according to formula (I) comprising the reaction of a compound of formula (VII),
with a compound of formula (VIII),
H 2 N—R 3 (VIII),
wherein R 1 , R 2 , and R 3 are as previously defined.
The present invention also relates to a compound according to formula (I), or a pharmaceutically-acceptable salt thereof, for use as a therapeutically active substance.
The present invention also relates to a pharmaceutical composition, comprising a compound according to formula (I), or a pharmaceutically-acceptable salt thereof, and a pharmaceutically-acceptable carrier.
The present invention also relates to the use of a compound according to formula (I), or a pharmaceutically-acceptable salt thereof, for the treatment or prophylaxis of a metabolic disease or disorder.
The present invention also relates to the use of a compound according to formula (I), or a pharmaceutically-acceptable salt thereof, for the preparation of a medicament for the treatment or prophylaxis of a metabolic disease or disorder.
The present invention also relates to a compound according to formula (I), or a pharmaceutically-acceptable salt thereof, for the treatment or prophylaxis of a metabolic disease or disorder.
The present invention also relates to a compound according to formula (I), or a pharmaceutically-acceptable salt thereof, prepared according to the aforementioned process for preparing said compound.
The present invention also relates to a method for activating glucokinase comprising administering to a patient a therapeutically-effective amount of a compound according to formula (I), or a pharmaceutically-acceptable salt thereof.
The present invention also relates to a method for the treatment or prophylaxis of a metabolic disease or disorder, which method comprises administering to a patient in need thereof a therapeutically-effective amount of a compound according to formula (I), or a pharmaceutically-acceptable salt thereof.
DETAILED DESCRIPTION OF THE INVENTION
It is to be understood that the terminology employed herein is for the purpose of describing particular embodiments and is not intended to be limiting. Further, although any methods, devices and materials similar or equivalent to those described herein can be used in the practice or testing of the invention, the preferred methods, devices and materials are now described.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the invention, suitable methods and materials are described below.
All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety.
The nomenclature used in this Application is based on IUPAC systematic nomenclature, unless indicated otherwise.
Any open valency appearing on a carbon, oxygen, sulfur or nitrogen atom in the structures herein indicates the presence of a hydrogen, unless indicated otherwise.
The definitions described herein apply irrespective of whether the terms in question appear alone or in combination. It is contemplated that the definitions described herein may be appended to form chemically-relevant combinations, such as e.g. “heterocycloalkyl-aryl”, “haloalkyl-heteroaryl”, “aryl-alkyl-heterocycloalkyl”, or “alkoxy-alkyl”. The last member of the combination is a radical which is substituted by the other members of the combination in inverse order.
The term “substituted” denotes that a specified group bears one or more substituents. Where any group may carry multiple substituents and a variety of possible substituents is provided, the substituents are independently selected and need not to be the same. The term “unsubstituted” means that the specified group bears no substituents. The term “optionally substituted” means that the specified group is unsubstituted or substituted by one or more substituents, independently chosen from the group of possible substituents. When indicating the number of substituents, the term “one or more” means from one substituent to the highest possible number of substitution, i.e. replacement of one hydrogen up to replacement of all hydrogens by substituents.
The term “compound(s) of this invention” and “compound(s) of the present invention” refers to compounds of formula I and stereoisomers, tautomers, solvates, and salts (e.g., pharmaceutically acceptable salts) thereof.
It will be appreciated, that the compounds of present invention may be derivatized at functional groups to provide derivatives which are capable of conversion back to the parent compound in vivo. Physiologically acceptable and metabolically labile derivatives, which are capable of producing the parent compounds of present invention in vivo are also within the scope of this invention.
The term “prodrug” denotes a form or derivative of a compound which is metabolized in vivo, e.g., by biological fluids or enzymes by a subject after administration, into a pharmacologically active form of the compound in order to produce the desired pharmacological effect. Prodrugs are described e.g. in “The Organic Chemistry of Drug Design and Drug Action”, by Richard B. Silverman, Academic Press, San Diego, 2004, Chapter 8 Prodrugs and Drug Delivery Systems, pp. 497-558.
The term “pharmaceutically acceptable salts” denotes salts which are not biologically or otherwise undesirable. Pharmaceutically acceptable salts include both acid and base addition salts.
The term “pharmaceutically acceptable acid addition salt” denotes those pharmaceutically acceptable salts formed with inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, carbonic acid, phosphoric acid, and organic acids selected from aliphatic, cycloaliphatic, aromatic, araliphatic, heterocyclic, carboxylic, and sulfonic classes of organic acids such as formic acid, acetic acid, propionic acid, glycolic acid, gluconic acid, lactic acid, pyruvic acid, oxalic acid, malic acid, maleic acid, maloneic acid, succinic acid, fumaric acid, tartaric acid, citric acid, aspartic acid, ascorbic acid, glutamic acid, anthranilic acid, benzoic acid, cinnamic acid, mandelic acid, embonic acid, phenylacetic acid, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, and salicyclic acid.
The term “pharmaceutically acceptable base addition salt” denotes those pharmaceutically acceptable salts formed with an organic or inorganic base. Examples of acceptable inorganic bases include sodium, potassium, ammonium, calcium, magnesium, iron, zinc, copper, manganese, and aluminum salts. Salts derived from pharmaceutically acceptable organic nontoxic bases includes salts of primary, secondary, and tertiary amines, substituted amines including naturally occurring substituted amines, cyclic amines and basic ion exchange resins, such as isopropylamine, trimethylamine, diethylamine, triethylamine, tripropylamine, ethanolamine, 2-diethylaminoethanol, trimethamine, dicyclohexylamine, lysine, arginine, histidine, caffeine, procaine, hydrabamine, choline, betaine, ethylenediamine, glucosamine, methylglucamine, theobromine, purines, piperazine, piperidine, N-ethylpiperidine, and polyamine resins.
The term “solvate” denotes crystal forms having either stoichiometric or nonstoichiometric amounts of a solvent incorporated in the crystal lattice. If the incorporated solvent is water, the solvate formed is a hydrate. When the incorporated solvent is alcohol, the solvate formed is an alcoholate.
Structures depicted herein are also meant to include compounds that differ only in the presence of one or more isotopically enriched atoms. For example wherein one or more hydrogen atoms are replaced by deuterium, or one or more carbon atoms are replaced by a 13C- or 14C-enriched carbon are within the scope of this invention.
Stereochemical definitions and conventions used herein generally follow S. P. Parker, Ed., McGraw-Hill Dictionary of Chemical Terms (1984) McGraw-Hill Book Company, New York; and Eliel, E. and Wilen, S., “Stereochemistry of Organic Compounds”, John Wiley & Sons, Inc., New York, 1994. In describing an optically active compound, the prefixes D and L, or R and S, are used to denote the absolute configuration of the molecule about its chiral center(s). The substituents attached to the chiral center under consideration are ranked in accordance with the Sequence Rule of Cahn, Ingold and Prelog. (Cahn et al. Angew. Chem. Inter. Edit. 1966, 5, 385; errata 511). The prefixes D and L or (+) and (−) are employed to designate the sign of rotation of plane-polarized light by the compound, with (−) or L designating that the compound is levorotatory. A compound prefixed with (+) or D is dextrorotatory.
The term “stereoisomer” denotes a compound that possesses identical molecular connectivity and bond multiplicity, but which differs in the arrangement of its atoms in space.
The term “chiral center” denotes a carbon atom bonded to four nonidentical substituents. The term “chiral” denotes the ability of non-superimposability with the mirror image, while the term “achiral” refers to embodiments which are superimposable with their mirror image. Chiral molecules are optically active, i.e., they have the ability to rotate the plane of plane-polarized light.
Compounds of present invention can have one or more chiral centers and can exist in the form of optically pure enantiomers, mixtures of enantiomers such as, for example, racemates, optically pure diastereoisomers, mixtures of diastereoisomers, diastereoisomeric racemates or mixtures of diastereoisomeric racemates. Whenever a chiral center is present in a chemical structure, it is intended that all stereoisomers associated with that chiral center are encompassed by the present invention.
The term “enantiomers” denotes two stereoisomers of a compound which are non-superimposable mirror images of one another.
The term “diastereomer” denotes a stereoisomer with two or more centers of chirality and whose molecules are not mirror images of one another. Diastereomers have different physical properties, e.g. melting points, boiling points, spectral properties, and reactivities.
The term “racemate” or “racemic mixture” refers to an equimolar mixture of two enantiomeric species, devoid of optical activity.
The term “alkyl” denotes a monovalent linear or branched saturated hydrocarbon group of 1 to 12 carbon atoms, in particular of 1 to 7 carbon atoms, more particular of 1 to 4 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, or tert-butyl.
The term “active pharmaceutical ingredient” (or “API”) denotes the compound in a pharmaceutical composition that has a particular biological activity.
The term “pharmaceutically-acceptable” denotes an attribute of a material which is useful in preparing a pharmaceutical composition that is generally safe, non-toxic, and neither biologically nor otherwise undesirable and is acceptable for veterinary as well as human pharmaceutical use.
The term “pharmaceutically-acceptable excipient” denotes any ingredient having no therapeutic activity and being non-toxic such as disintegrators, binders, fillers, solvents, buffers, tonicity agents, stabilizers, antioxidants, surfactants or lubricants used in formulating pharmaceutical products.
The term “pharmaceutical composition” (or “composition”) denotes a mixture or solution comprising a therapeutically effective amount of an active pharmaceutical ingredient together with pharmaceutically acceptable-excipients to be administered to a mammal, e.g., a human in need thereof.
The term “lyophilization” and variations thereof (e.g., “lyophilized”) refers to the process of freezing a substance and then reducing the concentration of water, by sublimation and/or evaporation to levels which do not support biological or chemical reactions.
The term “reconstituted composition” in connection with the composition according to the invention denotes a lyophilized composition which is re-dissolved by addition of reconstitution medium. The reconstitution medium comprises water for injection (WFI), bacteriostatic water for injection (BWFI), sodium chloride solutions (e.g. 0.9% (w/v) NaCl), glucose solutions (e.g. 5% glucose), surfactant comprising solutions (e.g. 0.01% polysorbate 20), or pH-buffered solution (e.g. phosphate-buffered solutions).
The term “sterile” denotes that a composition or excipient has a probability of being microbially contaminated of less than 10 −6 .
The term “buffer” denotes a pharmaceutically acceptable excipient, which stabilizes the pH of a pharmaceutical preparation. Suitable buffers are well known in the art and can be found in the literature. Particular pharmaceutically acceptable buffers comprise histidine-buffers, arginine-buffers, citrate-buffers, succinate-buffers, acetate-buffers and phosphate-buffers. Independently from the buffer used, the pH can be adjusted with an acid or a base known in the art, e.g. hydrochloric acid, acetic acid, phosphoric acid, sulfuric acid and citric acid, sodium hydroxide and potassium hydroxide.
The term “tonicity” denotes a measure of the osmotic pressure of two solutions separated by a semi-permeable membrane. Osmotic pressure is the pressure that must be applied to a solution to prevent the inward flow of water across a semi-permeable membrane. Osmotic pressure and tonicity are influenced only by solutes that cannot cross the membrane, as only these exert an osmotic pressure. Solutes able to freely cross the membrane do not affect tonicity because they will always be in equal concentrations on both sides of the membrane.
Tonicity in general relates to the osmotic pressure of a solution usually relative to that of human blood serum. A composition can be hypotonic, isotonic or hypertonic. An isotonic composition is liquid or liquid reconstituted from a solid form, e.g. from a lyophilized form, and denotes a solution having the same tonicity as some other solution with which it is compared, such as physiologic salt solution and the blood serum.
The term “surfactant” denotes a pharmaceutically acceptable excipient which is used to protect protein compositions against mechanical stresses like agitation and shearing. Examples of pharmaceutically acceptable surfactants include poloxamers, polysorbates, polyoxyethylene alkyl ethers (Brij), alkylphenylpolyoxyethylene ethers (Triton-X) or sodium dodecyl sulfate (SDS).
The term “poloxamer” denotes non-ionic triblock copolymers composed of a central hydrophobic chain of poly(propylene oxide) (PPO) flanked by two hydrophilic chains of poly(ethylene oxide) (PEO), each PPO or PEO chain can be of different molecular weights. Poloxamers are also known by the trade name Pluronics. Particular Poloxamer is Poloxamer 188, a poloxamer wherein the PPO chain has a molecular mass of 1800 g/mol and a PEO content of 80% (w/w).
The term “polysorbate” denotes oleate esters of sorbitol and its anhydrides, typically copolymerized with ethylene oxide. Particular polysorbates are Polysorbate 20 (poly(ethylene oxide) (20) sorbitan monolaurate, Tween 20) or Polysorbate 80 (poly(ethylene oxide) (80) sorbitan monolaurate, Tween 80).
The term “antioxidant” denotes pharmaceutically acceptable excipients, which prevent oxidation of the active pharmaceutical ingredient. Antioxidants comprise ascorbic acid, glutathione, cysteine, methionine, citric acid, EDTA.
The term “tonicity agent” denotes pharmaceutically acceptable excipient used to modulate the tonicity of a composition. Suitable tonicity agents comprise amino acids and sugars. Particular tonicity agents are trehalose, sucrose or arginine.
The term “sugar” denotes a monosaccharide or an oligosaccharide. A monosaccharide is a monomeric carbohydrate which is not hydrolysable by acids, including simple sugars and their derivatives, e.g. aminosugars. Examples of monosaccharides include glucose, fructose, galactose, mannose, sorbose, ribose, deoxyribose, neuraminic acid. An oligosaccharide is a carbohydrate consisting of more than one monomeric saccharide unit connected via glycosidic bond(s) either branched or in a chain. The monomeric saccharide units within an oligosaccharide can be identical or different. Depending on the number of monomeric saccharide units the oligosaccharide is a di-, tri-, tetra- penta- and so forth saccharide. In contrast to polysaccharides the monosaccharides and oligosaccharides are water soluble. Examples of oligosaccharides include sucrose, trehalose, lactose, maltose and raffinose.
The term “treating” or “treatment” of a disease state includes (1) preventing the disease state, i.e. causing the clinical symptoms of the disease state not to develop in a subject that may be exposed to or predisposed to the disease state, but does not yet experience or display symptoms of the disease state, (2) inhibiting the disease state, i.e., arresting the development of the disease state or its clinical symptoms, or (3) relieving the disease state, i.e., causing temporary or permanent regression of the disease state or its clinical symptoms.
The term “therapeutically effective amount” denotes an amount of a compound of the present invention that, when administered to a subject, (i) treats or prevents the particular disease, condition or disorder, (ii) attenuates, ameliorates or eliminates one or more symptoms of the particular disease, condition, or disorder, or (iii) prevents or delays the onset of one or more symptoms of the particular disease, condition or disorder described herein. The therapeutically effective amount will vary depending on the compound, disease state being treated, the severity of the disease treated, the age and relative health of the subject, the route and form of administration, the judgment of the attending medical or veterinary practitioner, and other factors.
The term “subject” denotes a vertebrate. In certain embodiments, the vertebrate is a mammal Mammals include humans, non-human primates such as chimpanzees and other apes and monkey species, farm animals such as cattle, horses, sheep, goats, and swine, domestic animals such as rabbits, dogs, and cats, laboratory animals including rodents, such as rats, mice, and guinea pigs. In certain embodiments, a mammal is a human. The term subject does not denote a particular age or sex.
In an embodiment of the present invention, provided are compound of formula (I):
wherein:
R 1 is selected from the group consisting of: H, F, and CF 3 ; R 2 is selected from the group consisting of: isopropyl, cyclopropyl, cyclopentyl, cyclohexyl, and —CH 2 —S—CH 3 ; R 3 is
R 4 is selected from the group consisting of: H, Br, and —CH(OH)—CH 2 OH; and
R 5 is selected from the group consisting of: —CH(OH)—CH 2 OH, —CH 2 —C(CH 3 ) 2 —O—CH 3 , —CH 2 —CH 2 OH, —CH 2 —C(O)—O—C(CH 3 ) 3 , —(CH 2 ) 2 O—CH 3 , —CH 2 —COOH, —(CH 2 ) 2 —COOH, —(CH 2 ) 2 —C(O)—O—C(CH 3 ) 3 , —(CH 2 ) 2 —CH 2 OH, —(CH 2 ) 2 —O—CH(CH 3 ) 2 , and —CH 3 ;
and wherein,
when R 3 is
R 1 is CF 3 ; and
R 2 is selected from the group consisting of: isopropyl, cyclopentyl, and —CH 2 —S—CH 3 ; and (2) when R 3 is
R 1 is selected from the group consisting of: H, F, and CF 3 ; and
R 2 is selected from the group consisting of: cyclopentyl, cyclohexyl, and cyclopropyl;
or a pharmaceutically-acceptable salt of said compound.
Compounds of formula (I) can have one or more asymmetric carbon atoms and can exist in the form of optically pure enantiomers, mixtures of enantiomers such as, for example, racemates, optically pure diastereoisomers, mixtures of diastereoisomers, diastereoisomeric racemates or mixtures of diastereoisomeric racemates. The optically active forms can be obtained for example by resolution of the racemates, by asymmetric synthesis or asymmetric chromatography (chromatography with a chiral adsorbents or eluant). The invention embraces all of these forms.
In the compound of formula I, the asterisk denotes an asymmetric carbon atom. The compound of formula I may be present as a racemate or in either the R or S configurations. In a particular embodiment of the present invention, the compound is in the S configuration.
In an embodiment, the compound is a compound of formula (I), wherein
R 3 is
In an embodiment, the compound is a compound of formula (I) selected from the group consisting of:
(S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-N-pyrazin-2-yl-propionamide; (S)—N-(5-bromo-pyrazin-2-yl)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[5-((S)-1,2-dihydroxy-ethyl)-pyrazin-2-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)—N-[5-((S)-1,2-dihydroxy-ethyl)-pyrazin-2-yl]-4-methylsulfanyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-butyramide; (S)-4-methyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-pentanoic acid pyrazin-2-ylamide; (S)-4-methyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-pentanoic acid [5-((S)-1,2-dihydroxy-ethyl)-pyrazin-2-yl]-amide;
and pharmaceutically-acceptable salts thereof.
In an embodiment, the compound is a compound of formula (I), wherein R 3 is
In an embodiment, the compound is a compound of formula (I) selected from the group consisting of:
(S)-3-cyclopentyl-N-(1-methyl-1H-pyrazol-3-yl)-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-hydroxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; {3-[(S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-acetic acid tert-butyl ester; {3-[(S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-acetic acid; (S)-3-cyclopentyl-N-[1-((R)-2,3-dihydroxy-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-((S)-2,3-dihydroxy-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-methoxy-2-methyl-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclohexyl-N-[1-(2-methoxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-methoxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopropyl-N-[1-(2-methoxy-2-methyl-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-isopropoxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(3-hydroxy-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-methoxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-methoxy-2-methyl-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-isopropoy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclohexyl-2-(4-fluoro-1-oxo-1,3-dihydro-isoindol-2-yl)-N-[1-(2-methoxy-ethyl)-1H-pyrazol-3-yl]-propionamide; 3-{3-[(S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-propionic acid tert-butyl ester; 3-{3-[(S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-propionic acid;
and pharmaceutically-acceptable salts thereof.
In an embodiment, the compound is a compound of formula (I), wherein R 1 is CF 3 .
In an embodiment, the compound is a compound of formula (I), selected from the group consisting of:
(S)-3-cyclopentyl-N-(1-methyl-1H-pyrazol-3-yl)-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-hydroxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; {3-[(S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-acetic acid tert-butyl ester; {3-[(S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-acetic acid; (S)-3-cyclopentyl-N-[1-((R)-2,3-dihydroxy-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-((S)-2,3-dihydroxy-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-methoxy-2-methyl-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-methoxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-N-pyrazin-2-yl-propionamide; (S)—N-(5-bromo-pyrazin-2-yl)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-isopropoy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; 3-{3-[(S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-propionic acid tert-butyl ester; 3-{3-[(S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-propionic acid; (S)-3-cyclopentyl-N-[5-((S)-1,2-dihydroxy-ethyl)-pyrazin-2-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)—N-[5-((S)-1,2-dihydroxy-ethyl)-pyrazin-2-yl]-4-methylsulfanyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-butyramide; (S)-4-methyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-pentanoic acid pyrazin-2-ylamide; (S)-4-methyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-pentanoic acid [5-((S)-1,2-dihydroxy-ethyl)-pyrazin-2-yl]-amide;
and pharmaceutically-acceptable salts thereof.
In an embodiment, the compound is a compound of formula (I), wherein R 2 is cyclopentyl.
In an embodiment, the compound is a compound of formula (I), selected from the group consisting of:
(S)-3-cyclopentyl-N-(1-methyl-1H-pyrazol-3-yl)-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-hydroxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; {3-[(S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-acetic acid tert-butyl ester; {3-[(S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-acetic acid; (S)-3-cyclopentyl-N-[1-((R)-2,3-dihydroxy-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-((S)-2,3-dihydroxy-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-methoxy-2-methyl-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-methoxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-isopropoxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(3-hydroxy-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-methoxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-methoxy-2-methyl-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-N-pyrazin-2-yl-propionamide; (S)—N-(5-bromo-pyrazin-2-yl)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-isopropoy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; 3-{3-[(S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-propionic acid tert-butyl ester; 3-{3-[(S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-propionic acid; (S)-3-cyclopentyl-N-[5-((S)-1,2-dihydroxy-ethyl)-pyrazin-2-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide;
and pharmaceutically-acceptable salts thereof.
In an embodiment, the compound is a compound of formula (I), wherein R 1 is H.
In an embodiment, the compound is a compound of formula (I), selected from the group consisting of:
(S)-3-cyclohexyl-N-[1-(2-methoxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-methoxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopropyl-N-[1-(2-methoxy-2-methyl-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-isopropoxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(3-hydroxy-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-methoxy-2-methyl-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide;
and pharmaceutically-acceptable salts thereof.
In an embodiment, the compound is a compound of formula (I), wherein R 1 is CF 3 , R 2 is cyclopentyl, and R 3 is
In an embodiment, the compound is a compound of formula (I) selected from the group consisting of:
(S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-N-pyrazin-2-yl-propionamide; (S)—N-(5-bromo-pyrazin-2-yl)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[5-((S)-1,2-dihydroxy-ethyl)-pyrazin-2-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide;
and pharmaceutically-acceptable salts thereof.
In an embodiment, the compound is a compound of formula (I), wherein R 1 is CF 3 , R 2 is cyclopentyl, and R 3 is
In an embodiment, the compound is a compound of formula (I) selected from the group consisting of:
(S)-3-cyclopentyl-N-(1-methyl-1H-pyrazol-3-yl)-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-hydroxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; {3-[(S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-acetic acid tert-butyl ester; {3-[(S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-acetic acid; (S)-3-cyclopentyl-N-[1-((R)-2,3-dihydroxy-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-((S)-2,3-dihydroxy-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-methoxy-2-methyl-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-methoxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; (S)-3-cyclopentyl-N-[1-(2-isopropoy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide; 3-{3-[(S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-propionic acid tert-butyl ester; 3-{3-[(S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-propionic acid;
and pharmaceutically-acceptable salts thereof.
In an embodiment of the present invention, there is provided a compound according to formula (I), or a pharmaceutically acceptable-salt thereof, for use as a therapeutically active substance, for example, for the treatment of a metabolic disease or disorder.
In another embodiment of the present invention, there is provided the use of a compound according to formula (I), or a pharmaceutically-acceptable salt thereof, for the treatment or prophylaxis of a metabolic disease or disorder.
The invention further provides the use of a compound according to formula (I), or a pharmaceutically-acceptable salt thereof, for the preparation of a medicament for the treatment or prophylaxis of a metabolic disease or disorder.
The invention further provides a compound according to formula (I), or a pharmaceutically-acceptable salt thereof, for the treatment or prophylaxis of a metabolic disease or disorder.
The present invention also relates to a method for the treatment or prophylaxis of a metabolic disease or disorder, which method comprises administering to a patient in need thereof a therapeutically-effective amount of a compound according to formula (I), or a pharmaceutically-acceptable salt thereof.
In an embodiment of the present invention, the compound according to formula (I), or a pharmaceutically-acceptable salt thereof, is administered at a dose that is within the range of from about 1 to about 1000 mg per day, in particular from about 1 mg to about 500 mg per day.
In the practice of the method of the present invention, a compound according to formula (I), or a pharmaceutically-acceptable salt thereof, is administered via any of the usual and acceptable methods known in the art, either singly or in combination. The compounds or compositions can thus be administered orally (e.g., buccal cavity), sublingually, parenterally (e.g., intramuscularly, intravenously, or subcutaneously), rectally (e.g., by suppositories or washings), transdermally (e.g., skin electroporation) or by inhalation (e.g., by aerosol), and in the form or solid, liquid or gaseous dosages, including tablets and suspensions. The administration can be conducted in a single unit dosage form with continuous therapy or in a single dose therapy ad libitum. The pharmaceutical composition can also be in the form of an oil emulsion or dispersion in conjunction with a lipophilic salt such as pamoic acid, or in the form of a biodegradable sustained-release composition for subcutaneous or intramuscular administration.
The present invention provides a pharmaceutical composition, comprising of a compound according to formula (I), or a pharmaceutically-acceptable salt thereof, and a pharmaceutically-acceptable carrier.
Useful pharmaceutically-acceptable carriers for the preparation of the compositions hereof, can be solids, liquids or gases. Thus, the compositions can take the form of tablets, pills, capsules, suppositories, powders, enterically coated or other protected formulations (e.g. binding on ion-exchange resins or packaging in lipid-protein vesicles), sustained release formulations, solutions, suspensions, elixirs, aerosols, and the like. The carrier can be selected from the various oils including those of petroleum, animal, vegetable or synthetic origin, e.g., peanut oil, soybean oil, mineral oil, sesame oil, and the like. Water, saline, aqueous dextrose, and glycols are preferred liquid carriers, particularly (when isotonic with the blood) for injectable solutions. For example, formulations for intravenous administration comprise sterile aqueous solutions of the active ingredient(s) which are prepared by dissolving solid active ingredient(s) in water to produce an aqueous solution, and rendering the solution sterile. Suitable pharmaceutically-acceptable excipients include starch, cellulose, talc, glucose, lactose, talc, gelatin, malt, rice, flour, chalk, silica, magnesium stearate, sodium stearate, glycerol monostearate, sodium chloride, dried skim milk, glycerol, propylene glycol, water, ethanol, and the like. The compositions may be subjected to conventional pharmaceutical additives such as preservatives, stabilizing agents, wetting or emulsifying agents, salts for adjusting osmotic pressure, buffers and the like. Suitable pharmaceutical carriers and their formulation are described in Remington's Pharmaceutical Sciences by E. W. Martin. Such compositions will, in any event, contain a therapeutically-effective amount of the compound according to formula (I), or a pharmaceutically-acceptable salt thereof and a pharmaceutically-acceptable carrier so as to prepare the proper dosage form for proper administration to the recipient.
Compounds of formula I can be prepared as outlined in the general scheme below. Compounds of formula II (where R 1 is F or CF 3 ) may be treated with hydrochloric acid in methanol at reflux to produce compounds of formula III. Compounds of formula III may then be treated with N-bromosuccinimide in carbon tetrachloride with catalytic benzoyl peroxide, at 80° C., to produce compounds of formula IV. Compounds of formula IV may then be treated with compounds of formula V and triethylamine in acetonitrile in a microwave reactor at 110° C. to produce a compound of formula VI. Alternatively, compounds of formula IV may be treated with ammonia in methanol to produce compounds of formula IX. Compounds of formula IX may be treated sodium hydride in tetrahydrofuran, followed by a compound of formula X, to produce a compound of formula VI. Compounds of formula VI may be saponified using lithium hydroxide in water/tetrahydrofuran to produce a compound of formula VII (where R 1 ═F or CF 3 ). Alternatively, compounds of formula VII (where R 1 ═H) can be prepared by treating phthalic dicarboxaldehyde (XI) with a compound of formula XII. The compound of formula VII may be treated with oxalyl chloride in dichloromethane with a catalytic amount of dimethylformamide followed by a compound of formula VIII in dichloromethane with 2,6-lutidine at room temperature to produce a compounds of formula I. Alternatively, compounds of formula VII may be treated with benzotriazole-1-yl-oxy-tris-(dimethylamino)-phosphonium hexafluorophosphate and N,N-diisopropylethylamine along with compounds of formula VIII in dichloromethane to produce a compounds of formula I.
Compounds of the present invention can be prepared beginning with commercially available starting materials and utilizing general synthetic techniques and procedures known to those skilled in the art.
Compounds of formula II (2-fluoro-3-trifluoromethyl-benzoic acid and 2-methyl-3-trifluoromethyl-benzoic acid) are commercially available (Oakwood, Alfa, Apollo). Compounds of formula (V) are commercially available (Aldrich, Sigma, Alfa, Bachem, Chemimpex) or can be prepared from the corresponding amino acid or protected amino acid derivatives using standard conditions. Amino acids (XII) can be purchased (Aldrich, Sigma, Alfa, Bachem, Chemimpex) or prepared using any number of standard methods. Compounds of formula X are commercially available (Aldrich, Pfaltz & Bauer, ArkPharm) or can be prepared by brominating the corresponding methyl ester using standard conditions. The corresponding methyl esters are commercially available (Aldrich, Pfaltz & Bauer, ArkPharm), or can be prepared from the corresponding acids using standard conditions. Phthalic dicarboxaldehyde (XI) is commercially (Sigma Aldrich). Compounds of formula VIII are commercially available (Matrix, Alfa, Oakwood) or can be prepared as described in US 20080021032 or WO2004052869.
In an embodiment of the present invention, there is provided a process for the preparation of a compound of formula (I) or a pharmaceutically-acceptable salt thereof comprising the reaction of a compound of formula (VII), as described above, with a compound of formula (VIII), as described above. R 1 , R 2 , and R 3 are as previously defined.
An embodiment of the present invention is a process for the preparation of a compound according to formula (I) comprising the reaction of a compound of formula (VII),
with a compound of formula (VIII), H 2 N—R 3 ,
wherein R 1 , R 2 , and R 3 are as previously defined.
In addition, the invention provides a compound of formula (I), or a pharmaceutically-acceptable salt thereof, manufactured according to the above process.
EXAMPLES
This invention will be more fully understood by reference to the following examples. They should not, however, be construed as limiting the scope of the invention.
Chemistry. All nonaqueous reactions were carried out under an argon or nitrogen atmosphere at room temperature, unless otherwise noted. All reagents and anhydrous solvents were used as obtained commercially without further purification or distillation, unless otherwise stated. Analytical thin-layer chromatography (TLC) was performed on EMD Chemicals silica gel 60 F254 precoated plates (0.25 mm) Compounds were visualized by UV light and/or stained with either p-anisaldehyde, iodine, or phosphomolybdic acid or KMnO 4 solutions followed by heating. Analytical high performance liquid chromatography (HPLC) and LC-MS analyses were conducted using the following two instruments and conditions. Method 1: Hewlett-Packard HP-1090 pump and HP-1090 PDA detector set at 215 nm with the MS detection performed with a Micromass Platform II mass spectrometer with electrospray ionization (ESI); Chromegabond WR C18 3 μm, 120 Å, 3.2×30 mm column; solvent A, H 2 O-0.02% TFA; solvent B, MeCN-0.02% TFA; flow rate: 2 mL/min; start 2% B, final 98% B in 4 min, linear gradient. Method 2: Waters 2795 pump and Waters 2996 photodiode array detector set at 214 nm with the MS detection performed with a Waters ZQ mass spectrometer (ESI); Epic Polar Hydrophilic 3 μm, 120 Å, 3.2×30 mm column; solvent A, H 2 O-0.03% HCO 2 H; solvent B, MeCN-0.03% HCO 2 H; flow rate) 2 mL/min; start 10% B, final 100% B in 3 min linear gradient, remaining for 1 min. Unless otherwise noted, compounds were purified using either of the following methods. Flash column chromatography was performed on EM Science silica gel 60 (particle size of 32-63 μm, 60 Å) or commercially available silica gel column cartridges from Biotage, ISCO or Analogix. Preparative reverse-phase high-pressure liquid chromatography (RP HPLC) was performed using one of the following systems: (A) a Waters Delta prep 4000 pump/controller, a 486 detector set at 215 nm, and a LKB Ultrorac fraction collector; or (B) a Sciex LC/MS system with a 150 EX single quad mass spec, a Shimadzu LC system, a LEAP autoinjector, and a Gilson fraction collector. The sample was dissolved in a mixture of acetonitrile/20 mM aqueous ammonium acetate or acetonitrile/water/TFA, applied on a Pursuit C-18 20×100 mm column and eluted at 20 ml/min with a linear gradient of 10%-90% B, where (A): 20 mM aqueous ammonium acetate (pH 7.0) and (B): acetonitrile or (A): water with 0.05% TFA and (B): acetonitrile with 0.05% TFA. The pooled fractions were concentrated under reduced pressure and lyophilized to afford the desired compounds. 1 H NMR spectra were recorded using a Varian Mercury 300 MHz or Varian Inova 400 MHz spectrometer. All peak listings for the NMR data were generated using ACD Labs 1D NMR Processor version 12.0. The chemical shifts are in parts per million (δ) referenced to DMSO-d5 (2.49 ppm) or CHCl 3 (7.26 ppm). High-resolution mass spectra (HRMS) were recorded on a Bruker Apex II FTICR mass spectrometers with a 4.7 T magnet (ES) or Micromass AutoSpec (EI) mass spectrometers. Optical rotations were measured on a Schmidt & Haensch electronic polarimeter. The wavelength was set at 589.45 nm which is the sodium D line. Temperature was ambient room temperature. Final compounds and intermediates were named using the Auto Nom2000 feature in the MDL ISIS Draw application.
Example 1
(S)-3-Cyclopentyl-N-(1-methyl-1H-pyrazol-3-yl)-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide
To a solution of 2-methyl-3-trifluoromethyl-benzoic acid (Apollo, 1 g, 4.90 mmol) in methanol (20 mL) was added concentrated sulfuric acid (0.5 mL) and the resulting mixture was heated to reflux overnight. The cooled reaction mixture was concentrated and diluted with water (25 mL) and a saturated sodium bicarbonate solution (25 mL). The mixture was extracted with ethyl acetate (50 mL), the organic phases combined, washed with water and dried over magnesium sulfate. The mixture was filtered and evaporated to give 2-methyl-3-trifluoromethyl-benzoic acid methyl ester (0.95 g, 4.35 mmol, 89%); 1 H NMR (300 MHz, CDCl 3 ) δ ppm 2.65 (s, 3H), 3.94 (s, 3H), 7.35 (t, J=7.85 Hz, 1H), 7.72-8.01 (m, 2H).
To a solution of 2-methyl-3-trifluoromethyl-benzoic acid methyl ester (0.95 g, 4.35 mmol) in benzene (10 mL) was added N-bromosuccinimide (0.77 g, 4.33 g) and benzoyl peroxide (0.052 g, 0.21 mmol) and the resulting mixture heated to reflux for 4 h, cooled and stirred at room temperature for 48 h. The mixture was filtered, the filter cake washed with diethyl ether and the filtrate washed with a 1 N sodium thiosulfate solution (10 mL), brine and dried over magnesium sulfate. The mixture was filtered and evaporated and the residue purified via automated flash chromatography (Analogix, SF25-80 g column, 5->10% ethyl acetate/hexane gradient) to give 2-bromomethyl-3-trifluoromethyl-benzoic acid methyl ester (1.04 g, 3.50 mmol, 81%) as an off white solid; 1 H NMR (300 MHz, DMSO-d 6 ) δ ppm 3.72-4.16 (m, 3H), 5.03 (s, 2H), 7.47-8.32 (m, 3H).
(S)-2-Amino-3-cyclopentyl-propionic acid (Chemimpex, 1.0 g, 6.36 mmol), methanol (15 mL) and concentrated hydrochloric acid (2 mL) was placed in a reaction flask and heated at 65° C. for 16 h. After such time, the reaction mixture was concentrated in vacuo and then dissolved in water. The resulting solution was then treated with a saturated aqueous sodium bicarbonate solution until pH ˜7-9. It was then extracted with ethyl acetate and the organic layers combined, dried over magnesium sulfate, filtered to remove the drying agent and the filtrate concentrated in vacuo to afford (S)-2-amino-3-cyclopentyl-propionic acid methyl ester (796 mg, 73%) as a clear colorless oil: HR-ES(+) m/e calcd for C 9 H 17 NO 2 [M+H] + 172.1332, observed 172.1332; 1 H NMR (300 MHz, DMSO-d6) δ ppm 3.60 (s, 3H), 3.25 (dd, J=6.04, 7.85 Hz, 1H), 1.34-1.96 (m, 9H), 0.92-1.14 (m, 2H).
A mixture of 2-bromomethyl-3-trifluoromethyl-benzoic acid methyl ester (695 mg, 2.34 mmol), (S)-2-amino-3-cyclopentyl-propionic acid methyl ester (400 mg, 2.34 mmol), triethylamine (358 μL, 2.57 mmol), and acetonitrile (20 mL) was heated at 82° C. for 7 h. The crude reaction mixture was treated with water (5 mL) and then concentrated in vacuo to remove the acetonitrile. The remaining solution was then diluted with water (10 mL) and extracted with ethyl acetate (3×20 mL), the combined organics were then dried over magnesium sulfate, filtered to remove the drying agent and the filtrate concentrated in vacuo. The residue was then purified via automated flash chromatography (12 g silica gel column, 10-40% ethyl acetate/hexanes) to afford (S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionic acid methyl ester (675 mg, 81%) as a clear colorless oil: [α] 25 D =−16.0°, (c=0.15, methylene chloride); HR-ES(+) m/e calcd for C 18 H 20 NO 3 F 3 [M+H] + 356.1468, observed 356.1466; 1 H NMR (300 MHz, DMSO-d6, ppm) δ 8.02 (t, J=8.00 Hz, 2H), 7.71-7.89 (m, 1H), 4.92 (dd, J=4.08, 10.41 Hz, 1H), 4.69 (s, 2H), 3.66 (s, 3H), 0.94-2.21 (m, 11H).
A solution (S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionic acid methyl ester (350 mg, 0.98 mmol) in tetrahydrofuran (5 mL) at room temperature was treated with a solution of lithium hydroxide monohydrate (82 mg, 1.96 mmol) in water (5 mL). The reaction mixture was then stirred at room temperature for 1 h. The reaction mixture was then acidified to pH=2 with a 1 N aqueous hydrochloric acid solution and extracted with ethyl acetate (3×20 mL). The combined organic layers were then dried over magnesium sulfate, filtered to remove the drying agent, and the filtrate concentrated in vacuo to afford (S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionic acid (293 mg, 88%) as a colorless oil: [α] 28 D =−5.3° (c=0.19, methylene chloride); HR-ES(+) m/e calcd for C 17 H 18 NO 3 F 3 [M+H] + 342.1312, observed 342.1310; 1 H NMR (300 MHz, DMSO-d6) δ ppm 13.13 (br. s., 1H), 8.02 (t, J=8.15 Hz, 2H), 7.68-7.85 (m, 1H), 4.82 (dd, J=4.23, 11.17 Hz, 1H), 4.69 (s, 2H), 1.02-2.20 (m, 11H).
A solution of (S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionic acid (100 mg, 0.29 mmol) in methylene chloride (2.9 mL) at 0° C. was treated with oxalyl chloride (0.03 mL, 0.34 mmol) followed by N,N-dimethylformamide (5 drops). The resulting solution was stirred at 0° C. for 30 min. At this time, the solution was warmed to room temperature and stirred for 30 min. The reaction was then concentrated in vacuo. The residue was re-suspended in methylene chloride (2×5 mL) and then concentrated in vacuo. The residue was then dissolved in methylene chloride (1 mL) and was added to a pre-cooled solution of 1-methyl-1H-pyrazol-3-ylamine (Matrix, 30 mg, 1.05 mmol) and 2,6-lutidine (0.05 mL, 0.47 mmol) in methylene chloride (3 mL) at 0° C. The reaction was allowed to gradually warm to room temperature and was stirred at room temperature overnight. After this time, the reaction was diluted with methylene chloride (50 mL) and was washed with a 1N aqueous hydrochloric acid solution (2×100 mL), a saturated aqueous sodium bicarbonate solution (2×100 mL) and water (1×100 mL), dried over sodium sulfate, filtered and concentrated in vacuo. Flash chromatography (50-75% ethyl acetate/hexanes) afforded (5)-3-cyclopentyl-N-(1-methyl-1H-pyrazol-3-yl)-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide (94 mg, 77%) as a white solid; ES − -HRMS m/e calcd for C 21 H 23 N 4 O 2 F 3 (M+H) + 421.1846 found 421.1844. 1 H-NMR (300 MHz, DMSO-d 6 ) δ ppm 10.87 (s, 1H), 8.01 (t, J=8.6 Hz, 2H), 7.68-7.81 (m, 1H), 7.54 (d, J=1.9 Hz, 1H), 6.39 (d, J=1.9 Hz, 1H), 5.02-5.15 (m, 1H), 5.03 (d, J=18.5 Hz, 1H), 4.71 (d, J=18.5 Hz, 1H), 3.73 (s, 3H), 0.98-2.12 (m, 11H).
Example 2
(S)-3-Cyclopentyl-N-[1-(2-hydroxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide
A solution of 1-[2-(tert-butyl-dimethyl-silanyloxy)-ethyl]-3-nitro-1H-pyrazole (prepared as in US 20080021032 Example 67, 6.34 g, 23.36 mmol) in ethanol (100 mL) was treated with concentrated hydrochloric acid (12 drops) and stirred for 1 h at room temperature. After this time, another portion of concentrated hydrochloric acid was added (12 drops) and it was stirred overnight at room temperature. After this time, the reaction mixture was concentrated in vacuo and then azeotroped with acetonitrile. The crude material was then purified by flash column chromatography (silica gel 60, 230-400 mesh, 80% ethyl acetate/hexanes) to afford 2-(3-nitro-pyrazol-1-yl)-ethanol (2.36 g, 94%) as a white solid: 1 H NMR (300 MHz, DMSO-d 6 ) δ ppm 8.00 (d, J=2.56 Hz, 1H), 7.03 (d, J=2.56 Hz, 1H), 5.00 (t, J=5.31 Hz, 1H), 4.26 (t, J=5.31 Hz, 2H), 3.77 (q, J=5.49 Hz, 2H).
A solution 2-(3-nitro-pyrazol-1-yl)-ethanol (3.46 g, 22.02 mmol) in ethanol (40 mL) was placed in a Parr shaker bottle and treated with 10% palladium on carbon (350 mg). The bottle was then put on the Parr shaker and charged with hydrogen to 50 psi and let shake for 1 h. After this time, the reaction mixture was filtered through celite and the celite washed with ethanol. The filtrate was then concentrated in vacuo and azeotroped with acetonitrile and then chloroform to afford 2-(3-amino-pyrazol-1-yl)-ethanol (3.02 g, >quant.) as a light yellow viscous oil: 1 H NMR (300 MHz, DMSO-d 6 δ ppm 7.26 (d, J=1.83 Hz, 1H), 5.34 (d, J=2.20 Hz, 1H), 4.76 (t, J=5.31 Hz, 1H), 4.50 (s, 2H), 3.78-3.88 (m, 2H), 3.62 (q, J=5.74 Hz, 2H).
A solution of (S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionic acid (50 mg, 0.15 mmol, prepared as in Example 1) in methylene chloride (5 mL) and N,N-dimethylformamide (1 drop) cooled to 0° C. was treated with a solution of oxalyl chloride in methylene chloride (2.0 M, 88 μL, 0.18 mmol) and stirred at 0° C. for 10 min. After this time, the reaction mixture was warmed to room temperature and then stirred for another 25 min. After this time, the reaction mixture was then concentrated in vacuo and the residue taken up in methylene chloride (2 mL) and added dropwise to a separate reaction flask containing a mixture of 2-(3-amino-pyrazol-1-yl)-ethanol (28 mg, 0.22 mmol) and 2,6-lutidine (32 μL, 0.29 mmol) in methylene chloride (5 mL) cooled to 0° C. The resulting reaction mixture was then allowed to warm to room temperature and stirred for 16 h. After such time, the reaction mixture was quenched with a saturated aqueous sodium bicarbonate solution (10 mL) and then extracted with methylene chloride (3×15 mL). The organic layers were then washed with a 1N aqueous hydrochloric acid solution (10 mL), dried over magnesium sulfate, filtered to remove the drying agent, and the filtrate concentrated in vacuo. The crude material was purified via automated flash chromatography (4 g silica gel column, 60-95% ethyl acetate/hexanes) to afford (S)-3-cyclopentyl-N-[1-(2-hydroxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide (57 mg, 86%) as a white foam: [α] 29 D =−28.5°, (c=0.26, methylene chloride); HR-ES(+) m/e calcd for C 22 H 25 N 4 O 3 F 3 [M+H] + 451.1952, observed 451.1950; 1 H NMR (300 MHz, DMSO-d 6 ) δ ppm 10.91 (s, 1H), 8.01 (t, J=8.50 Hz, 2H), 7.69-7.81 (m, 1H), 7.56 (d, J=2.27 Hz, 1H), 6.40 (d, J=2.27 Hz, 1H), 4.97-5.13 (m, 2H), 4.85 (t, J=5.29 Hz, 1H), 4.71 (d, J=18.51 Hz, 1H), 4.02 (t, J=5.67 Hz, 2H), 3.69 (q, J=5.67 Hz, 2H), 0.99-2.12 (m, 11H).
Example 3
{3-[(S)-3-Cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-acetic acid tert-butyl ester
A solution of (S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionic acid (100 mg, 0.29 mmol, prepared as in Example 1) in methylene chloride (4 mL) and N,N-dimethylformamide (4 drops) was treated with a solution of oxalyl chloride in methylene chloride (2.0 M, 150 μL, 0.30 mmol) and stirred for 15 min at room temperature. After this time, the reaction mixture was then concentrated in vacuo and the resulting residue was dissolved in methylene chloride (4 mL) and then added dropwise to a separate reaction flask containing a mixture of (3-amino-pyrazol-1-yl)-acetic acid tert-butyl ester (prepared as in US 20080021032, Example 3, 86 mg, 0.44 mmol) and 2,6-lutidine (100 μL, 0.87 mmol) in methylene chloride (3 mL) at room temperature. The resulting reaction mixture was then stirred at room temperature for 2 h. The reaction mixture was then quenched by the addition of methanol and then diluted with methylene chloride. The organic layer was then concentrated in vacuo with silica gel (2.0 g). The silica gel with absorbed material was placed in a SIM and purified via Biotage flash column chromatography (40 S silica gel column, 25% ethyl acetate/hexanes) to afford {3-[(S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-acetic acid tert-butyl ester (151 mg, 100%) as a white foam: HR-ES(+) m/e calcd for C 26 H 31 N 4 O 4 F 3 [M+H] + 521.2370, observed 521.2368; 1 H NMR (400 MHz, CHLOROFORM-d) δ ppm 8.49 (s, 1H), 8.08 (d, J=7.46 Hz, 1H), 7.81 (d, J=7.67 Hz, 1H), 7.63 (t, J=7.67 Hz, 1H), 7.33 (d, J=2.34 Hz, 1H), 6.73 (d, J=2.34 Hz, 1H), 5.02 (dd, J=7.03, 8.52 Hz, 1H), 4.70-4.81 (m, 1H), 4.53-4.69 (m, 3H), 1.10-2.25 (m, 20H).
Example 4
{3-[(S)-3-Cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-acetic acid
A mixture of {3-[(S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-acetic acid tert-butyl ester (133 mg, 0.26 mmol, prepared as in Example 3) and lithium hydroxide monohydrate (22 mg, 0.52 mmol) in tetrahydrofuran:water (1:1, 10 mL) at room temperature was stirred for 2 h. The reaction mixture was then concentrated in vacuo and partitioned between a 1 N aqueous hydrochloric acid solution and ethyl acetate. The organic layer was then dried over magnesium sulfate, filtered to remove the drying agent, and the filtrate concentrated in vacuo to afford {3-[(S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-acetic acid (118 mg, 98%) as a white foam: HR-ES(+) m/e calcd for C 22 H 23 N 4 O 4 F 3 [M+H] + 465.1744, observed 465.1744; 1 H NMR (400 MHz, DMSO-d6) δ ppm 10.93 (s, 1H), 8.01 (dd, J=7.67, 13.00 Hz, 2H), 7.69-7.80 (m, 1H), 7.59 (d, J=2.13 Hz, 1H), 6.45 (d, J=2.13 Hz, 1H), 4.95-5.12 (m, 2H), 4.81 (s, 2H), 4.72 (d, J=17.90 Hz, 1H), 1.09-2.11 (m, 11H).
Example 5
(S)-3-Cyclopentyl-N-[1-((R)-2,3-dihydroxy-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide
A solution of (S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionic acid (100 mg, 0.29 mmol, prepared as in Example 1) in methylene chloride (5 mL) and N,N-dimethylformamide (5 drops) was treated with a solution of oxalyl chloride in methylene chloride (2.0 M, 200 μL, 0.40 mmol) and stirred for 15 min at room temperature. After this time, the reaction mixture was then concentrated in vacuo and the resulting residue was dissolved in methylene chloride (5 mL) and then added dropwise to a separate reaction flask containing a mixture of (R)-3-(3-amino-pyrazol-1-yl)-propane-1,2-diol (prepared as in US 20080021032, Example 35, 70 mg, 0.45 mmol) and 2,6-lutidine (250 μL) in methylene chloride (3 mL) at room temperature. The resulting reaction mixture was then stirred room temperature for 2 h. The reaction mixture was quenched by the addition of methanol and then diluted with methylene chloride. The organic layer was then washed with a 1 N aqueous hydrochloric acid solution. The organic layer was then concentrated in vacuo with silica gel (2.0 g). The silica gel with absorbed material was placed in a SIM and purified via Biotage flash column chromatography (40 S silica gel column, 100% ethyl acetate to 10% methanol/ethyl acetate) to afford (S)-3-cyclopentyl-N-[1-((R)-2,3-dihydroxy-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide (98 mg, 69%) as a white foam: [α] 29 D =+12.0°, (c=0.15, methanol); HR-ES(+) m/e calcd for C 23 H 27 N 4 O 4 F 3 [M+H] + 481.2057, observed 481.2055; 1 H NMR (400 MHz, DMSO-d6) δ ppm 10.91 (s, 1H), 7.94-8.05 (m, 2H), 7.71-7.79 (m, 1H), 7.53 (d, J=2.34 Hz, 1H), 6.40 (d, J=2.13 Hz, 1H), 4.99-5.11 (m, 2H), 4.93 (d, J=5.33 Hz, 1H), 4.67-4.76 (m, 2H), 4.09 (dd, J=3.84, 13.85 Hz, 1H), 3.81-3.91 (m, 1H), 3.76 (br. s., 1H), 3.23-3.31 (m, 2H), 1.05-2.13 (m, 11H).
Example 6
(S)-3-Cyclopentyl-N-[1-((S)-2,3-dihydroxy-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide
A solution of (S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionic acid (100 mg, 0.29 mmol, prepared as in Example 1) in methylene chloride (5 mL) and N,N-dimethylformamide (5 drops) was treated with a solution of oxalyl chloride in methylene chloride (2.0 M, 200 μL, 0.40 mmol) and stirred for 15 min at room temperature. After this time, the reaction mixture was then concentrated in vacuo and the resulting residue was dissolved in methylene chloride (5 mL) and then added dropwise to a separate reaction flask containing a mixture of (S)-3-(3-amino-pyrazol-1-yl)-propane-1,2-diol (prepared as in US 20080021032, Example 34, 70 mg, 0.45 mmol) and 2,6-lutidine (250 μL) in methylene chloride (3 mL) at room temperature. The resulting reaction mixture was then stirred at room temperature for 2 h. The reaction mixture was quenched by the addition of methanol and then diluted with methylene chloride. The organic layer was then washed with a 1 N aqueous hydrochloric acid solution. The organic layer was then concentrated in vacuo with silica gel (2.0 g). The silica gel with absorbed material was placed in a SIM and purified via Biotage flash column chromatography (40 S silica gel column, 100% ethyl acetate to 5% methanol/ethyl acetate) to afford (S)-3-cyclopentyl-N-[1-((S)-2,3-dihydroxy-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide (99 mg, 69%) as a white foam: [α] 28 D =−12.0°, (c=0.15, methanol); HR-ES(+) m/e calcd for C 23 H 27 N 4 O 4 F 3 [M+H] + 481.2057, observed 481.2057; 1 H NMR (400 MHz, DMSO-d6) δ ppm 10.92 (s, 1H), 7.94-8.05 (m, 2H), 7.73-7.80 (m, 1H), 7.53 (d, J=2.13 Hz, 1H), 6.40 (d, J=2.13 Hz, 1H), 4.98-5.11 (m, 2H), 4.93 (d, J=5.33 Hz, 1H), 4.67-4.75 (m, 2H), 4.09 (dd, J=4.05, 13.64 Hz, 1H), 3.81-3.91 (m, 1H), 3.77 (br. s., 1H), 3.24-3.30 (m, 2H), 1.99-2.09 (m, 1H), 1.06-1.95 (m, 10H).
Example 7
(S)-3-Cyclopentyl-N-[1-(2-methoxy-2-methyl-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide
A solution of (S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionic acid (50 mg, 0.15 mmol, prepared as in Example 1) in methylene chloride (5 mL) and N,N-dimethylformamide (1 drop) cooled to 0° C. was treated with a solution of oxalyl chloride in methylene chloride (2.0 M, 88 μL, 0.18 mmol) and stirred at 0° C. for 10 min. After this time, the reaction mixture was warmed to room temperature and then stirred for another 25 min. After this time, the reaction mixture was then concentrated in vacuo and the residue taken up in methylene chloride (2 mL) and added dropwise to a separate reaction flask containing a mixture of 1-(2-methoxy-2-methyl-propyl)-1H-pyrazol-3-ylamine (prepared as in US 20080021032, Example 94, 37 mg, 0.22 mmol) and 2,6-lutidine (32 μL, 0.29 mmol) in methylene chloride (5 mL) cooled to 0° C. The resulting reaction mixture was then allowed to warm to room temperature and stirred for 16 h. After such time, the reaction mixture was quenched with a saturated aqueous sodium bicarbonate solution (10 mL) and then extracted with methylene chloride (3×15 mL). The organic layers were then washed with a 1N aqueous hydrochloric acid solution (10 mL), dried over magnesium sulfate, filtered to remove the drying agent, and the filtrate concentrated in vacuo. The crude material was purified via automated flash chromatography (4 g silica gel column, 50% ethyl acetate/hexanes) to afford (S)-3-cyclopentyl-N-[1-(2-methoxy-2-methyl-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide (51 mg, 71%) as a white foam: [α] 32 D =−41.1°, (c=0.09, methylene chloride); HR-ES(+) m/e calcd for C 25 H 31 N 4 O 3 F 3 [M+H] + 493.2421, observed 493.2419; 1 H NMR (300 MHz, DMSO-d6) δ ppm 10.95 (s, 1H), 8.01 (t, J=8.60 Hz, 2H), 7.68-7.81 (m, 1H), 7.49 (d, J=1.81 Hz, 1H), 6.44 (d, J=2.11 Hz, 1H), 4.97-5.17 (m, 2H), 4.71 (d, J=18.41 Hz, 1H), 3.92-4.08 (m, 2H), 3.06-3.22 (m, 3H), 0.93-2.16 (m, 17H).
Example 8
(S)-3-Cyclohexyl-N-[1-(2-methoxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide
A mixture of (S)-(+)-α-aminocyclohexanepropionic acid hydrate (5.00 g, 29.2 mmol) and phthalic dicarboxaldehyde (4.21 g, 31.3 mmol) in acetonitrile (120 mL) was refluxed for 20 h under nitrogen. The mixture was allowed to cool to room temperature and further cooled to 0° C. The solid was filtered off and washed once with cold acetonitrile (50 mL) to afford (6.54 g, 78%) (S)-3-cyclohexyl-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionic acid as a white solid: EI-HRMS m/e calcd for C 17 H 21 NO 3 (M + ) 287.1521, found 287.1521.
To a solution of (S)-3-cyclohexyl-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionic acid (60 mg, 0.21 mmol) and 1-(2-methoxy-ethyl)-1H-pyrazol-3-ylamine (prepared as in US 20080021032, Example 72, 0.031 g, 0.22 mmol) and benzotriazole-1-yl-oxy-tris-(dimethylamino)-phosphonium hexafluorophosphate (Chemimpex, 0.11 g, 0.25 mmol) in methylene chloride (3 mL) was added N,N-diisopropylethylamine (0.11 mL, 0.63 mmol) dropwise and the resulting solution stirred at room temperature over night. The solution was diluted with methylene chloride, washed with a 1 N hydrochloric acid solution (15 mL), a saturated sodium chloride solution (20 mL) dried over magnesium sulfate. The mixture was filtered and evaporated and the resulting material purified via automated flash chromatography (Analogix, SF4-40 g column, 70-100% ethyl acetate/hexanes) to give (S)-3-cyclohexyl-N-[1-(2-methoxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide (31 mg, 36%) as an off white solid: [α] 28 D =−69.7°, (c=0.31, chloroform); HR-ES(+) m/e calcd for C 23 H 30 N 4 O 3 [M+H] + 411.2391, observed 411.2389; 1 H NMR (300 MHz, DMSO-d 6 ) δ ppm 0.84-1.24 (m, 7H) 1.47-1.99 (m, 2H) 3.18 (s, 4H) 3.49-5.29 (m, 8H) 6.36 (s, 1H) 7.31-7.89 (m, 7H) 10.83 (s, 1H).
Example 9
(S)-3-Cyclopentyl-N-[1-(2-methoxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide
A solution of benzene-1,2-dicarbaldehyde (1.9 g, 14 mmol) and (S)-2-amino-3-cyclopentyl-propionic acid (2.0 g, 13 mmol) in acetonitrile was heated to reflux for 17 h. The solution was cooled to 4° C. for 3 h during which time a precipitate formed. The mixture was filtered and the solid washed with cold acetonitrile and dried under vacuum to give (S)-3-cyclopentyl-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionic acid (3.0 g, 86%) as a white solid: LR-ES(+) m/e calcd for C 16 H 19 NO 3 [M+H] + 274.15, observed 274.1; 1 H NMR (300 MHz, DMSO-d 6 ) δ ppm 0.89-2.29 (m, 11H), 4.23-5.12 (m, 3H), 7.20-7.99 (m, 4H), 13.00 (s, 1H).
To a solution of (S)-3-cyclopentyl-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionic acid (100 mg, 0.37 mmol) and 1-(2-methoxy-ethyl)-1H-pyrazol-3-ylamine (prepared as in US 20080021032, Example 72, 0.054 g, 0.38 mmol) and benzotriazole-1-yl-oxy-tris-(dimethylamino)-phosphonium hexafluorophosphate (Chemimpex, 0.19 g, 0.44 mmol) in methylene chloride (5 mL) was added N,N-diisopropylethylamine (0.19 mL, 1.1 mmol) dropwise and the resulting solution stirred at room temperature over night. The solution was diluted with methylene chloride, washed with a 1 N hydrochloric acid solution (15 mL), a saturated sodium chloride solution (20 mL) dried over magnesium sulfate. The mixture was filtered and evaporated and the resulting material purified via automated flash chromatography (Analogix, SF4-40 g column, 50-70% ethyl acetate/hexanes) to give (S)-3-cyclopentyl-N-[1-(2-methoxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide (94 mg, 65%) as an off white solid: [α] 29 D =−62.6°, (C=0.31, chloroform); HR-ES(+) m/e calcd for C 22 H 28 N 4 O 3 [M+Na] + 419.2053, observed 419.2055; 1 H NMR (300 MHz, DMSO-d 6 ) δ ppm 1.01-2.09 (m, 7H), 3.18 (s, 4H), 3.61 (t, J=5.28 Hz, 2H), 4.12 (t, J=5.13 Hz, 2H), 4.38-5.23 (m, 4H), 6.37 (d, J=2.11 Hz, 1H), 7.32-7.84 (m, 7H), 10.84 (s, 1H).
Example 10
(S)-3-Cyclopropyl-N-[1-(2-methoxy-2-methyl-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide
A solution of benzene-1,2-dicarbaldehyde (340 mg, 2.55 mmol) and (S)-2-amino-3-cyclopropyl-propionic acid (300 mg, 2.32 mmol) in acetonitrile (15 mL) was heated to reflux for 18 h. The solution was cooled, concentrated and the residue redissolved in methylene chloride (50 mL). The solution was extracted with a saturated sodium bicarbonate solution. The layers were separated and the aqueous phase was acidified (pH=2) with hydrochloric acid (3N), extracted with methylene chloride (2×50 mL). The organic phases were combined, dried over magnesium sulfate, filtered and evaporated to give (S)-3-cyclopropyl-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionic (170 mg, 30%) as a yellow solid: LR-ES(+) m/e calcd for C 14 H 15 NO 3 [M+H] + 246.29, observed 246.2; 1 H NMR (DMSO-d 6 ) δ7.24-7.94 (m, 4H), 4.83 (dd, J=10.6, 4.8 Hz, 1H), 4.54 (s, 2H), 3.16 (d, J=3.6 Hz, 1H), 1.90-2.16 (m, 1H), 1.54-1.79 (m, 1H), 0.65 (dd, J=7.8, 5.4 Hz, 1H), 0.29-0.48 (m, 2H), −0.01-0.19 (m, 2H).
To a solution of (S)-3-cyclopropyl-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionic acid (85 mg, 0.35 mmol) and 1-(2-methoxy-2-methyl-propyl)-1H-pyrazol-3-ylamine (prepared as in US 20080021032, Example 94, 64 mg, 0.38 mmol) and benzotriazole-1-yl-oxy-tris-(dimethylamino)-phosphonium hexafluorophosphate (Chemimpex, 0.18 g, 0.42 mmol) in methylene chloride (8 mL) was added N,N-diisopropylethylamine (0.18 mL, 1.0 mmol) dropwise and the resulting solution stirred at room temperature for 4 h. The solution was diluted with methylene chloride, washed with a 1 N hydrochloric acid solution (25 mL), a saturated sodium bicarbonate solution (25 mL) dried over magnesium sulfate. The mixture was filtered and evaporated and the resulting material purified via automated flash chromatography (Analogix, SF4-40 g column, 50-70% ethyl acetate/hexanes) to give (S)-3-cyclopropyl-N-[1-(2-methoxy-2-methyl-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide (46 mg, 34%) as an off white solid: [α] 30 D =−38.1°, (c=0.21, chloroform); HR-ES(+) m/e calcd for C 22 H 28 N 4 O 3 [M+H] + 397.2234, observed 397.2235; 1 H NMR (300 MHz, DMSO-d 6 ) δ ppm 0.03-1.69 (m, 9H), 2.00-2.28 (m, 1H), 3.15 (s, 4H), 3.99 (s, 2H), 4.36-5.39 (m, 4H), 6.42 (d, J=1.81 Hz, 1H), 7.25-7.88 (m, 6H), 10.80 (s, 1H).
Example 11
(S)-3-Cyclopentyl-N-[1-(2-isopropoxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide
To a solution of (S)-3-cyclopentyl-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionic acid (prepared as in Example 9, 94 mg, 0.35 mmol) and 1-(2-isopropoxy-ethyl)-1H-pyrazol-3-ylamine (prepared as in US 20080021032, Example 101, 70 mg, 0.41 mmol) and benzotriazole-1-yl-oxy-tris-(dimethylamino)-phosphonium hexafluorophosphate (Chemimpex, 0.18 g, 0.41 mmol) in methylene chloride (5 mL) was added N,N-diisopropylethylamine (0.18 mL, 1.0 mmol) dropwise and the resulting solution stirred at room temperature for 4 h. The solution was diluted with methylene chloride, washed with a 1 N hydrochloric acid solution (25 mL), a saturated sodium bicarbonate solution (25 mL) dried over magnesium sulfate. The mixture was filtered and evaporated and the resulting material purified via automated flash chromatography (Analogix, SF4-12 g column, 50% ethyl acetate/hexane) to afford (S)-3-cyclopentyl-N-[1-(2-methoxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide (110 mg, 75%) as an off white solid: [α] 31 D =−50.6°, (c=0.36, chloroform); HR-ES(+) m/e calcd for C 24 H 32 N 4 O 3 [M+H] + 425.2547, observed 425.2547; 1 H NMR (300 MHz, DMSO-d 6 ) δ ppm 0.77-2.18 (m, 17H), 3.40-5.25 (m, 8H), 6.39 (d, J=2.11 Hz, 1H), 7.26-7.91 (m, 5H), 10.86 (s, 1H).
Example 12
(S)-3-Cyclopentyl-N-[1-(3-hydroxy-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide
To a solution of (S)-3-cyclopentyl-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionic acid (prepared as in Example 9, 80 mg, 0.29 mmol) and 3-(3-amino-pyrazol-1-yl)-propan-1-ol (prepared as in US 20080021032, Example 23, 49 mg, 0.35 mmol) and benzotriazole-1-yl-oxy-tris-(dimethylamino)-phosphonium hexafluorophosphate (Chemimpex, 0.15 g, 0.35 mmol) in methylene chloride (8 mL) was added N,N-diisopropylethylamine (0.15 mL, 0.88 mmol) dropwise and the resulting solution stirred at room temperature for 4 h. The solution was diluted with methylene chloride, washed with a 1 N hydrochloric acid solution (25 mL), a saturated sodium bicarbonate solution (25 mL) dried over magnesium sulfate. The mixture was filtered and evaporated and the resulting material purified via automated flash chromatography (Analogix, SF4-12 g column, 50-70% ethyl acetate/hexanes) to afford (S)-3-cyclopentyl-N-[1-(3-hydroxy-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide (28 mg, 24%) as an off white solid: HR-ES(+) m/e calcd for C 22 H 28 N 4 O 3 [M+H] + 397.2234, observed 397.2233; 1 H NMR (300 MHz, DMSO-d 6 ) δ ppm 0.94-2.34 (m, 7H), 4.04 (t, J=6.79 Hz, 3H), 4.37-5.28 (m, 6H), 6.39 (s, 2H), 7.31-7.90 (m, 8H), 10.86 (s, 2H).
Example 13
(S)-3-Cyclopentyl-N-[1-(2-methoxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide
To a solution of (S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionic acid (prepared as in Example 1, 71 mg, 0.21 mmol) and 1-(2-methoxy-ethyl)-1H-pyrazol-3-ylamine (prepared as in US 20080021032, Example 72, 32 mg, 0.23 mmol) and benzotriazole-1-yl-oxy-tris-(dimethylamino)-phosphonium hexafluorophosphate (Chemimpex, 0.11 g, 0.25 mmol) in methylene chloride (5 mL) was added N,N-diisopropylethylamine (0.11 mL, 0.62 mmol) dropwise and the resulting solution stirred at room temperature over night. The solution was diluted with methylene chloride, washed with a 1 N hydrochloric acid solution (15 mL), a saturated sodium bicarbonate solution (20 mL) dried over magnesium sulfate. The mixture was filtered and evaporated and the resulting material purified via automated flash chromatography (Analogix, SF4-12 g column, 50-80% ethyl acetate/hexanes) to give (S)-3-cyclopentyl-N-[1-(2-methoxy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide (42 mg, 43%) as an off white solid: HR-ES(+) m/e calcd for C 23 H 27 N 4 O 3 F 3 [M+H] + 465.2108, observed 465.2107; 1 H NMR (300 MHz, DMSO-d 6 ) δ ppm 1.04-2.18 (m, 10H), 3.20 (s, 3H), 3.51-4.28 (m, 4H), 4.60-5.34 (m, 3H), 6.40 (d, J=1.81 Hz, 1H), 7.41-8.28 (m, 5H), 10.93 (s, 1H).
Example 14
(S)-3-Cyclopentyl-N-[1-(2-methoxy-2-methyl-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide
To a solution of (S)-3-cyclopentyl-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionic acid (prepared as in Example 9, 0.1 g, 0.37 mmol) and 1-(2-methoxy-2-methyl-propyl)-1H-pyrazol-3-ylamine (prepared as in US 20080021032, Example 94, 0.065 g, 0.38 mmol) and benzotriazole-1-yl-oxy-tris-(dimethylamino)-phosphonium hexafluorophosphate (0.19 g, 0.44 mmol) in methylene chloride (10 mL) was added N,N-diisopropylethylamine (0.19 mL, 1.10 mmol) and the resulting solution stirred at room temperature for 19 h. The solution was diluted with methylene chloride, washed with a 1 N hydrochloric acid solution (15 mL), a saturated sodium chloride solution, and dried over magnesium sulfate. The mixture was filtered and evaporated and the resulting material purified via automated flash chromatography (Analogix, SF15-40 g column, 50%-70% ethyl acetate/hexanes) to afford (S)-3-cyclopentyl-N-[1-(2-methoxy-2-methyl-propyl)-1H-pyrazol-3-yl]-2-(1-oxo-1,3-dihydro-isoindol-2-yl)-propionamide (0.063 g, 0.21 mmol, 41%) as an off white solid; [α 0 ] 29 D =−47.5° (c=0.28, chloroform); HR-ES(+) m/e calcd for C 24 H 32 N 4 O 3 [M+Na] + 447.2366, observed 447.2368; 1 H NMR (300 MHz, DMSO-d 6 ) δ ppm 10.88 (s, 1H), 7.70 (d, J=7.2 Hz, 1H), 7.62 (m, 2H), 7.48 (d, J=2.3 Hz, 1H), 7.45-7.54 (m, 1H), 6.43 (d, J=2.3 Hz, 1H), 5.05 (dd, J=10.7, 5.0 Hz, 1H), 4.87 (d, J=17.8 Hz, 1H), 4.53 (d, J=17.8 Hz, 1H), 3.99 (s, 2H), 3.15 (s, 3H), 1.07 (s, 3H), 1.06 (s, 3H), 0.98-2.10 (m, 11H).
Example 15
(S)-3-Cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-N-pyrazin-2-yl-propionamide
A solution of (S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionic acid (prepared as in Example 1, 160 mg, 0.47 mmol) in methylene chloride (10 mL) and N,N-dimethylformamide (1 drop) cooled to 0° C. was treated with a solution of oxalyl chloride in methylene chloride (2.0 M, 281 μL, 0.56 mmol) and stirred at 0° C. for 15 min. After this time, the reaction mixture was warmed to room temperature and then stirred for another 30 min. After this time, the reaction mixture was then concentrated in vacuo to ˜1 mL volume and an additional amount of methylene chloride (3 mL) was added. One half of this solution of prepared acid chloride (2 mL, 0.23 mmol) was added dropwise to a separate reaction flask containing a mixture of pyrazin-2-ylamine (33 mg, 0.35 mmol) and 2,6-lutidine (52 μL, 0.47 mmol) in methylene chloride (5 mL) cooled to 0° C. The resulting reaction mixture was then allowed to warm to room temperature and stirred for 16 h. After such time, the reaction mixture was quenched with a saturated aqueous sodium bicarbonate solution (10 mL) and then extracted with methylene chloride (3×10 mL). The organic layers were then washed with a 1N aqueous hydrochloric acid solution (10 mL), dried over magnesium sulfate, filtered to remove the drying agent, and the filtrate concentrated in vacuo. The crude material was purified via automated flash chromatography (12 g silica gel column, 25-75% ethyl acetate/hexanes and then a 4 g silica gel column, 40-60% ethyl acetate/hexanes) to afford (S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-N-pyrazin-2-yl-propionamide (39 mg, 40%) as a white foam: [α] 28 D =−65.0° (c=0.10, methylene chloride); HR-ES(+) m/e calcd for C 21 H 21 N 4 O 2 F 3 [M+H] + 419.1690, observed 416.1688; 1 H NMR (300 MHz, DMSO-d6) δ ppm 11.32 (s, 1H), 9.26 (s, 1H), 8.34-8.49 (m, 2H), 8.02 (t, J=8.45 Hz, 2H), 7.67-7.84 (m, 1H), 5.23 (dd, J=4.98, 10.41 Hz, 1H), 5.06 (d, J=18.41 Hz, 1H), 4.67-4.85 (m, 1H), 1.02-2.21 (m, 11H).
Example 16
(S)—N-(5-Bromo-pyrazin-2-yl)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide
A solution of (S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionic acid (prepared as in Example 1, 100 mg, 0.29 mmol) in methylene chloride (4 mL) and N,N-dimethylformamide (4 drops) was treated with a solution of oxalyl chloride in methylene chloride (2.0 M, 150 μL, 0.30 mmol) and stirred for 15 min at room temperature. After this time, the reaction mixture was then concentrated in vacuo and the resulting residue was dissolved in methylene chloride (4 mL) and then added dropwise to a separate reaction flask containing a mixture of 5-bromo-pyrazin-2-ylamine (76 mg, 0.44 mmol) and 2,6-lutidine (100 μL, 0.87 mmol) in methylene chloride (3 mL) at room temperature. The resulting reaction mixture was the stirred room temperature for 1.5 h. The reaction mixture was quenched by the addition of methanol and then diluted with methylene chloride and the organic layer was washed with a 1N aqueous hydrochloric acid solution. The organic layer was then dried, filtered and the filtrate concentrated in vacuo. The crude material was purified via Biotage flash column chromatography (40 S silica gel column, 25% ethyl acetate/hexanes) to afford (S)—N-(5-bromo-pyrazin-2-yl)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide (74 mg, 51%) as a white foam: HR-ES(+) m/e calcd for C 21 H 20 N 4 O 2 F 3 Br [M+H] + 497.0795, observed 497.0796; 1 H NMR (400 MHz, DMSO-d6) δ ppm 11.50 (s, 1H), 9.09 (d, J=1.07 Hz, 1H), 8.65 (d, J=1.28 Hz, 1H), 8.02 (dd, J=7.88, 10.44 Hz, 2H), 7.77 (t, J=7.67 Hz, 1H), 5.22 (dd, J=4.90, 10.66 Hz, 1H), 5.04 (d, J=18.33 Hz, 1H), 4.76 (d, J=18.11 Hz, 1H), 1.04-2.19 (m, 11H).
Example 17
(S)-3-Cyclopentyl-N-[1-(2-isopropoy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide
A solution of (S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionic acid (prepared as in Example 1, 160 mg, 0.47 mmol) in methylene chloride (10 mL) was treated with N,N-dimethylformamide (1 drop) and cooled to 0° C. It was then treated with a solution of oxalyl chloride (2.0 M in methylene chloride, 281 μL, 0.56 mmol) and stirred for 15 min at 0° C. and then warmed to room temperature and stirred for 30 min. After this time, the reaction mixture was concentrated in vacuo to about 1 mL and then methylene chloride was added (3 mL). Half of the resulting volume (˜2 mL, ˜0.235 mmol of the in situ generated acid chloride) was added to a flask containing 1-(2-isopropoxy-ethyl)-1H-pyrazol-3-ylamine (prepared as in US20080021032, Example 101, 60 mg, 0.35 mmol) and 2,6-lutidine (52 μL, 0.47 mmol) in methylene chloride (5 mL) at 0° C. The reaction mixture was then allowed to warm up to room temperature and stirred overnight for 16 h. After this time, the reaction mixture was quenched with an aqueous saturated sodium bicarbonate solution (10 mL) and extracted with methylene chloride (3×10 mL). The organic layers were then combined and washed with a 1N aqueous hydrochloric acid solution, dried over magnesium sulfate, filtered to remove the drying agent and the filtrate concentrated in vacuo. The crude material was purified using an Analogix Intelliflash 280 chromatography system (4 g silica gel column, 45-55% ethyl acetate/hexanes) to afford (S)-3-cyclopentyl-N-[1-(2-isopropoy-ethyl)-1H-pyrazol-3-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide (89 mg, 77%) as a white foam: HR-ES(+) m/e calcd for C 25 H 31 N 4 O 3 F 3 [M+H] + 493.2421, observed 493.2422; 1 H NMR (300 MHz, DMSO-d 6 ) δ 10.93 (s, 1H), 7.89-8.19 (m, 2H), 7.68-7.83 (m, 1H), 7.56 (d, J=2.11 Hz, 1H), 6.40 (d, J=2.11 Hz, 1H), 4.91-5.25 (m, 2H), 4.71 (d, J=18.41 Hz, 1H), 4.10 (t, J=5.28 Hz, 2H), 3.57-3.79 (m, 2H), 3.47 (td, J=6.15, 12.15 Hz, 1H), 0.89-2.17 (m, 17H).
Example 18
(S)-3-Cyclohexyl-2-(4-fluoro-1-oxo-1,3-dihydro-isoindol-2-yl)-N-[1-(2-methoxy-ethyl)-1H-pyrazol-3-yl]-propionamide
A solution of 3-fluoro-2-methyl-benzoic acid (Aldrich, 10.2 g, 66.17 mmol) in methanol (135 mL) at room temperature was treated with boron trifluoride etherate (15 mL) and was allowed to stir at room temperature. The reaction mixture was then concentrated in vacuo to remove the methanol and then diethyl ether (˜300 mL) was added. The solution was transferred to a separatory funnel and washed with water (200 mL) and a 5% aqueous sodium bicarbonate solution to pH>7.5. The organic layer was then dried over magnesium sulfate and concentrated in vacuo to afford 3-fluoro-2-methyl-benzoic acid methyl ester (9.74 g, 87%) as a light orange colored oil which was used without purification.
A solution of 3-fluoro-2-methyl-benzoic acid methyl ester (3.64 g, 21.67 mmol) in carbon tetrachloride (100 mL) was treated with N-bromosuccinimide (3.85 g, 21.63 mmol) and benzoyl peroxide (0.1 g). The reaction mixture was then heated at reflux temperature and after 3 h the heat was removed and it was stirred at room temperature over the weekend. The reaction was then filtered to remove the solids and concentrated in vacuo to yield a light yellow oil. The reaction was then repeated with the remaining 3-fluoro-2-methyl-benzoic acid methyl ester (6.1 g, 36.3 mmol) in carbon tetrachloride using N-bromosuccinimide (6.5 g, 36.5 mmol) and benzoyl peroxide (0.1 g) heating at reflux. The reaction mixture was then filtered and concentrated in vacuo. The two material from the two reactions was combined and purified by flash column chromatography (silica gel, 10% diethyl ether/hexanes) to afford 2-bromomethyl-3-fluoro-benzoic acid methyl ester (14.22 g, 99%) as a white solid.
A solution of (S)-2-amino-3-cyclohexyl-propionic acid methyl ester hydrochloride (Novabiochem, 500 mg, 2.25 mmol) in acetonitrile (20 mL) was placed in a flask and treated with 2-bromomethyl-3-fluoro-benzoic acid methyl ester (557 mg, 2.25 mmol) and triethylamine (660 μL, 4.74 mmol). The reaction mixture was then heated at reflux (82° C.) overnight for 16 h. After this time, the reaction mixture was diluted with water (5 mL) and concentrated in vacuo to remove the acetonitrile. The remaining material was then diluted with another portion of water (10 mL) and extracted with ethyl acetate (3×20 mL). The combined organic layers were then dried over magnesium sulfate, filtered to remove the drying agent and the filtrate concentrated in vacuo. The crude material was purified using an Analogix Intelliflash 280 chromatography system (RS-40 silica gel column, 10-25% ethyl acetate/hexanes) to afford (S)-3-cyclohexyl-2-(4-fluoro-1-oxo-1,3-dihydro-isoindol-2-yl)-propionic acid methyl ester (411 mg, 57%) as a clear colorless oil: [α] 30 D =−17.3° (c=0.30, methylene chloride); HR-ES(+) m/e calcd for C 18 H 22 NO 3 F [M+H] + 320.1657, observed 320.1656; 1 H NMR (300 MHz, DMSO-d 6 ) δ 7.54-7.63 (m, 2H), 7.42-7.54 (m, 1H), 4.96 (dd, J=4.53, 11.47 Hz, 1H), 4.49-4.65 (m, 2H), 3.63 (s, 3H), 1.48-1.99 (m, 7H), 0.74-1.23 (m, 6H).
A mixture of (S)-3-cyclohexyl-2-(4-fluoro-1-oxo-1,3-dihydro-isoindol-2-yl)-propionic acid methyl ester (311 mg, 0.97 mmol) in tetrahydrofuran (6 mL) at room temperature was treated with a mixture of lithium hydroxide monohydrate (82 mg, 1.95 mL) in water (6 mL). The reaction mixture was then stirred at room temperature until the reaction was complete by TLC (˜2 h). After this time, the reaction mixture was treated with 1N aqueous hydrochloric acid solution until the pH=2. The reaction mixture was then extracted with ethyl acetate (3×20 mL). The combined organic layers were then dried over magnesium sulfate, filtered to remove the drying agent and the filtrate was concentrated in vacuo to afford (S)-3-cyclohexyl-2-(4-fluoro-1-oxo-1,3-dihydro-isoindol-2-yl)-propionic acid (230 mg, 78%) as a white solid.
A solution of (S)-3-cyclohexyl-2-(4-fluoro-1-oxo-1,3-dihydro-isoindol-2-yl)-propionic acid (230 mg, 0.75 mmol) in methylene chloride (10 mL) was treated with N,N-dimethylformamide (1 drop) and cooled to 0° C. It was then treated with a solution of oxalyl chloride (2.0 M in methylene chloride, 452 μL, 0.91 mmol) and stirred for 15 min at 0° C. and then warmed to room temperature and stirred for 30 min. After this time, the reaction mixture was concentrated in vacuo to about 1 mL and then methylene chloride was added (5 mL). One third of the resulting volume (˜2 mL, ˜0.25 mmol of the in situ generated acid chloride) was added to a flask containing 1-(2-methoxy-ethyl)-1H-pyrazol-3-ylamine (prepared as in US20080021032, Example 72, 53 mg, 0.38 mmol) and 2,6-lutidine (55 μL, 0.50 mmol) in methylene chloride (5 mL) at 0° C. The reaction mixture was then allowed to warm up to room temperature and stirred overnight for 16 h. After this time, the reaction mixture was quenched with an aqueous saturated sodium bicarbonate solution (10 mL) and extracted with methylene chloride (3×10 mL). The organic layers were then combined and washed with a 1N aqueous hydrochloric acid solution, dried over magnesium sulfate, filtered to remove the drying agent and the filtrate concentrated in vacuo. The crude material was purified using an Analogix Intelliflash 280 chromatography system (4 g silica gel column, 40-60% ethyl acetate/hexanes) to afford (S)-3-cyclohexyl-2-(4-fluoro-1-oxo-1,3-dihydro-isoindol-2-yl)-N-[1-(2-methoxy-ethyl)-1H-pyrazol-3-yl]-propionamide (70 mg, 65%) as a white foam: [α] 28 D =−63.0° (c=0.10, methylene chloride); HR-ES(+) m/e calcd for C 23 H 29 N 4 O 3 F [M+H] + 429.2297, observed 429.2297; 1 H NMR (300 MHz, DMSO-d 6 ) δ 10.88 (s, 1H), 7.41-7.62 (m, 4H), 6.39 (d, J=2.11 Hz, 1H), 5.11 (dd, J=4.68, 10.72 Hz, 1H), 4.91 (d, J=17.81 Hz, 1H), 4.61 (d, J=17.81 Hz, 1H), 4.14 (t, J=4.98 Hz, 2H), 3.63 (t, J=4.98 Hz, 2H), 3.20 (s, 3H), 1.46-2.02 (m, 7H), 0.83-1.24 (m, 6H).
Example 19
3-{3-[(S)-3-Cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-propionic acid tert-butyl ester
A solution of (S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionic acid (prepared as in Example 1, 100 mg, 0.29 mmol,) in methylene chloride (4 mL) and N,N-dimethylformamide (4 drops) was treated with a solution of oxalyl chloride in methylene chloride (2.0 M, 150 μL, 0.30 mmol) and stirred for 15 min at room temperature. After this time, the reaction mixture was then concentrated in vacuo and the resulting residue was dissolved in methylene chloride (4 mL) and then added dropwise to a separate reaction flask containing a mixture of 3-(3-amino-pyrazol-1-yl)-propionic acid tent-butyl ester (prepared as in US 20080021032, Example 8, 92 mg, 0.44 mmol) and 2,6-lutidine (100 μL, 0.87 mmol) in methylene chloride (3 mL) at room temperature. The resulting reaction mixture was the stirred room temperature for 2 h. The reaction mixture was quenched by the addition of methanol and then diluted with methylene chloride and then washed with a 1 N aqueous hydrochloric acid solution. The organic layer was then dried over sodium sulfate, filtered and the filtrate was then concentrated in vacuo with silica gel (2.0 g). The silica gel with absorbed material was placed in a SIM and purified via Biotage flash column chromatography (40 S silica gel column, 25% ethyl acetate/hexanes) to afford 3-{3-[(S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-propionic acid tert-butyl ester (145 mg, 94%) as a white foam: HR-ES(+) m/e calcd for C 27 H 33 N 4 O 4 F 3 [M+H] + 535.2527, observed 535.2526; 1 H NMR (400 MHz, DMSO-d 6 ) δ 10.91 (s, 1H), 8.01 (dd, J=7.67, 12.79 Hz, 2H), 7.71-7.82 (m, 1H), 7.56 (d, J=2.13 Hz, 1H), 6.39 (d, J=2.13 Hz, 1H), 4.96-5.14 (m, 2H), 4.71 (d, J=18.33 Hz, 1H), 4.19 (t, J=6.50 Hz, 2H), 2.72 (t, J=6.61 Hz, 2H), 0.77-2.09 (m, 20H).
Example 20
3-{3-[(S)-3-Cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-propionic acid
A mixture of 3-{3-[(S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-propionic acid tert-butyl ester (prepared as in Example 19, 130 mg, 0.24 mmol) in methylene chloride (3 mL) at room temperature was treated with trifluoroacetic acid (1 mL) and stirred for 3 h at room temperature. The reaction mixture was then diluted with chloroform (3 mL) and washed with an aqueous semi-saturated sodium bicarbonate solution. The organic layer was then dried over magnesium sulfate, filtered to remove the drying agent, and the filtrate concentrated in vacuo to afford 3-{3-[(S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionylamino]-pyrazol-1-yl}-propionic acid (66 mg, 58%) as a white semi-solid: HR-ES(+) m/e calcd for C 23 H 25 N 4 O 4 F 3 [M+H] + 479.1901, observed 479.1901; 1 H NMR (400 MHz, DMSO-d 6 ) δ 10.88 (s, 1H), 8.01 (dd, J=7.67, 15.13 Hz, 2H), 7.75 (t, J=7.56 Hz, 1H), 7.53 (d, J=2.13 Hz, 1H), 6.33 (d, J=2.13 Hz, 1H), 4.97-5.11 (m, 2H), 4.70 (d, J=18.11 Hz, 1H), 4.06 (t, J=7.46 Hz, 2H), 2.25 (t, J=7.35 Hz, 2H), 1.05-2.09 (m, 11H).
Example 21
(S)-3-Cyclopentyl-N-[5-((S)-1,2-dihydroxy-ethyl)-pyrazin-2-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide
A solution of (S)-3-cyclopentyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionic acid (prepared as in Example 1, 125 mg, 0.37 mmol) in methylene chloride (10 mL) was treated with N,N-dimethylformamide (1 drop) and cooled to 0° C. It was then treated with a solution of oxalyl chloride (2.0 M in methylene chloride, 220 μL, 0.44 mmol) and stirred for 10 min at 0° C. and then warmed to room temperature and stirred for 30 min. After this time, the reaction mixture was concentrated in vacuo to about 1 mL and then it was added to a flask containing 5-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-pyrazin-2-ylamine (prepared as in WO2004052869, Example 54, 107 mg, 0.55 mmol) and 2,6-lutidine (81 μL, 0.73 mmol) in methylene chloride (10 mL) at 0° C. The reaction mixture was then allowed to warm up to room temperature and stirred overnight for 16 h. After this time, the reaction mixture was quenched with an aqueous saturated sodium bicarbonate solution (10 mL) and extracted with methylene chloride (3×10 mL). The organic layers were then combined and washed with a 1N aqueous hydrochloric acid solution (10 mL), dried over magnesium sulfate, filtered to remove the drying agent and the filtrate concentrated in vacuo. The crude material was purified using an Analogix Intelliflash 280 chromatography system (12 g silica gel column, 15-40% ethyl acetate/hexanes) to afford (S)-3-cyclopentyl-N-[5-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-pyrazin-2-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide (78 mg, 41%) as a white foam: [α] 27 D =−18.0° (c=0.15, methylene chloride); HR-ES(+) m/e calcd for C 26 H 29 N 4 O 4 F 3 [M+Na] + 541.2033, observed 541.2030; 1 H NMR (300 MHz, DMSO-d 6 ) δ 11.37 (s, 1H), 9.21 (d, J=1.21 Hz, 1H), 8.48 (d, J=1.21 Hz, 1H), 8.02 (t, J=8.00 Hz, 2H), 7.72-7.82 (m, 1H), 5.12-5.29 (m, 2H), 5.05 (d, J=17.81 Hz, 1H), 4.76 (d, J=18.11 Hz, 1H), 4.35 (dd, J=6.64, 8.45 Hz, 1H), 3.93 (dd, J=6.64, 8.45 Hz, 1H), 1.04-2.20 (m, 17H).
A mixture of (S)-3-cyclopentyl-N-[5-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-pyrazin-2-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide (74 mg, 0.14 mmol) in tetrahydrofuran (1.5 mL) was treated with a 1N aqueous hydrochloric acid solution (1.5 mL) and stirred at room temperature until there was no more starting material as indicated by TLC (overnight, ˜16 h). After this time, the reaction was treated with a saturated aqueous sodium bicarbonate solution and then extracted with ethyl acetate (3×20 mL). The organic layers were then combined and dried over magnesium sulfate, filtered to remove the drying agent and the filtrate concentrated in vacuo. The crude material was purified using an Analogix Intelliflash 280 chromatography system (4 g silica gel column, 100% ethyl acetate) to afford (S)-3-cyclopentyl-N-[5-((S)-1,2-dihydroxy-ethyl)-pyrazin-2-yl]-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-propionamide (49 mg, 72%) as a white foam: [α] 28 D =−41.6° (c=0.25, methylene chloride); HR-ES(+) m/e calcd for C 23 H 25 N 4 O 4 F 3 [M+H] + 479.1901, observed 479.1899; 1 H NMR (300 MHz, DMSO-d 6 ) δ 11.27 (s, 1H), 9.16 (s, 1H), 8.45 (d, J=0.91 Hz, 1H), 8.02 (t, J=8.45 Hz, 2H), 7.70-7.82 (m, 1H), 5.55 (br. s., 1H), 5.22 (dd, J=5.13, 10.26 Hz, 1H), 5.05 (d, J=18.11 Hz, 1H), 4.90-4.50 (br. s., 1H), 4.75 (d, J=18.11 Hz, 1H), 4.62 (t, J=5.13 Hz, 1H), 3.61-3.72 (m, 1H), 3.49-3.60 (m, 1H), 1.03-2.21 (m, 11H).
Example 22
(S)—N-[5-((S)-1,2-Dihydroxy-ethyl)-pyrazin-2-yl]-4-methylsulfanyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-butyramide
A mixture of (S)-2-amino-4-methylsulfanyl-butyric acid methyl ester hydrochloride (Aldrich, 199 mg, 1 mmol) and 2-bromomethyl-3-trifluoromethyl-benzoic acid methyl ester (prepared as in Example 1, 297 mg, 1 mmol) in acetonitrile (5 mL) and triethylamine (280 μL, 2 mmol) was placed in a microwave reaction vessel and sealed. The reaction mixture was then placed in a microwave reactor and heated at 115° C. for 15 min. After this time, the reaction mixture was cooled and concentrated with silica gel (2 g) in vacuo. The silica gel with absorbed material was placed in a SIM and purified via Biotage flash column chromatography (40 S silica gel column, 25% ethyl acetate/hexanes) to afford (S)-4-methylsulfanyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-butyric acid methyl ester (137 mg, 40%) as a colorless viscous oil: HR-ES(+) m/e calcd for C 15 H 16 NO 3 SF 3 [M+H] + 348.0876, observed 348.0874; 1 H NMR (400 MHz, CHLOROFORM-d) δ 8.07 (d, J=7.46 Hz, 1H), 7.83 (d, J=7.67 Hz, 1H), 7.64 (t, J=7.67 Hz, 1H), 5.25 (dd, J=4.69, 10.44 Hz, 1H), 4.79 (d, J=17.47 Hz, 1H), 4.53 (d, J=17.47 Hz, 1H), 3.77 (s, 3H), 2.38-2.62 (m, 3H), 2.16-2.31 (m, 1H), 2.13 (s, 3H).
A solution of (S)-4-methylsulfanyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-butyric acid methyl ester (134 mg, 0.39 mmol) in tetrahydrofuran/water (6 mL, 1:1) was treated with lithium hydroxide monohydrate (33 mg, 0.78 mmol) at room temperature. The reaction mixture was then stirred at room temperature for 2 h. After this time, the reaction mixture was concentrated in vacuo to remove the tetrahydrofuran. The resulting material was then diluted with a 1N aqueous hydrochloric acid solution and then extracted with ethyl acetate. The organic layers were combined and then dried over magnesium sulfate, filtered to remove the drying agent, and the filtrate was concentrated in vacuo to afford (S)-4-methylsulfanyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-butyric acid (126 mg, 97%) as a white foam: HR-ES(+) m/e calcd for C 14 H 14 NO 3 SF 3 [M+H] + 334.0719, observed 334.0717; 1 H NMR (400 MHz, CHLOROFORM-d) δ 8.07 (d, J=7.46 Hz, 1H), 7.83 (d, J=7.67 Hz, 1H), 7.59-7.71 (m, 1H), 5.25 (dd, J=4.48, 10.44 Hz, 1H), 4.79 (d, J=17.47 Hz, 1H), 4.56 (d, J=17.47 Hz, 1H), 2.41-2.66 (m, 3H), 2.20-2.35 (m, 1H), 2.13 (s, 3H).
A solution of (S)-4-methylsulfanyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-butyric acid (57 mg, 0.17 mmol) in methylene chloride (5 mL) and N,N-dimethylformamide (3 drops) at room temperature was treated with a solution of oxalyl chloride (2.0M in methylene chloride, 210 μL, 0.34 mmol) and stirred for 15 min. After this time, the reaction mixture was concentrated in vacuo and then diluted with methylene chloride (5 mL) and added to a flask containing a solution of 5-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-pyrazin-2-ylamine (prepared as in WO2004052869, Example 54, 67 mg, 0.34 mmol), 2,6-lutidine (64 μL, 0.34 mmol) in methylene chloride (2.5 mL) at room temperature. The reaction mixture was then stirred at room temperature for a period of 2 h. After this time, the reaction mixture was treated with methanol and then diluted with methylene chloride. The reaction mixture was then transferred to a separatory funnel and washed with a 1N aqueous hydrochloric acid solution. The organic layer was then dried over magnesium sulfate, filtered to remove the drying agent and the filtrate was concentrated with silica gel (2 g). The silica gel with absorbed material was placed in a SIM and purified via Biotage flash column chromatography (40 S silica gel column, 40%-60% ethyl acetate/hexanes) to afford (S)—N-[5-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-pyrazin-2-yl]-4-methylsulfanyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-butyramide (28 mg, 32%) as a colorless sticky solid.
A solution of (S)—N-[5-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-pyrazin-2-yl]-4-methylsulfanyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-butyramide (26 mg, 0.05 mmol) in tetrahydrofuran (1 mL) was treated with a 1N aqueous hydrochloric acid solution (1 mL) and stirred at room temperature overnight. The reaction mixture was then concentrated in vacuo to remove the tetrahydrofuran and the remaining material was partitioned between ethyl acetate and a saturated aqueous sodium bicarbonate solution. The organic layer was separated and dried over magnesium sulfate, filtered to remove the drying agent and the filtrate concentrated in vacuo to afford (S)—N-[5-((S)-1,2-dihydroxy-ethyl)-pyrazin-2-yl]-4-methylsulfanyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-butyramide (20 mg, 85%) as a pale yellow gum: HR-ES(+) m/e calcd for C 20 H 21 N 4 O 4 SF 3 [M+H] + 471.1309, observed 471.1306; 1 H NMR (400 MHz, DMSO-d 6 ) δ 11.15 (s, 1H), 9.16 (s, 1H), 8.44 (d, J=1.28 Hz, 1H), 8.02 (t, J=7.46 Hz, 2H), 7.71-7.81 (m, 1H), 5.55 (d, J=4.90 Hz, 1H), 5.18 (dd, J=5.01, 9.48 Hz, 1H), 4.93-5.02 (m, 1H), 4.77-4.87 (m, 1H), 4.72 (t, J=5.86 Hz, 1H), 4.58-4.66 (m, 1H), 3.61-3.71 (m, 1H), 3.55 (td, J=5.86, 11.29 Hz, 1H), 2.48-2.65 (m, 3H), 2.22-2.38 (m, 1H), 2.09 (s, 3H).
Example 23
(S)-4-Methyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-pentanoic acid pyrazin-2-ylamide
A mixture of (S)-2-amino-4-methyl-pentanoic acid methyl ester hydrochloride (Aldrich, 273 mg, 1.5 mmol) and 2-bromomethyl-3-trifluoromethyl-benzoic acid methyl ester (prepared as in Example 1, 445 mg, 1.5 mmol) in acetonitrile (5 mL) and triethylamine (420 μL, 3.0 mmol) was placed in a microwave reaction vessel and sealed. The reaction mixture was then placed in a microwave reactor and heated at 115° C. for 15 min. After this time, the reaction mixture was cooled and concentrated with silica gel (2 g) in vacuo. The silica gel with absorbed material was placed in a SIM and purified via Biotage flash column chromatography (40 S silica gel column, 20% ethyl acetate/hexanes) to afford (S)-4-methyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-pentanoic acid methyl ester (275 mg, 56%) as a colorless viscous oil.
A solution of (S)-4-methyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-pentanoic acid methyl ester (274 mg, 0.83 mmol) in tetrahydrofuran/water (12 mL, 1:1) was treated with lithium hydroxide monohydrate (70 mg, 1.66 mmol) at room temperature. The reaction mixture was then stirred at room temperature for 2 h. After this time, the reaction mixture was concentrated in vacuo to remove the tetrahydrofuran. The resulting material was then diluted with a 1N aqueous hydrochloric acid solution (10 mL) and then extracted with ethyl acetate. The organic layers were combined and then dried over magnesium sulfate, filtered to remove the drying agent, and the filtrate was concentrated in vacuo to afford (S)-4-methyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-pentanoic acid (254 mg, 97%) as a white solid.
A solution of (S)-4-methyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-pentanoic acid (95 mg, 0.30 mmol) in methylene chloride (5 mL) and N,N-dimethylformamide (5 drops) at room temperature was treated with a solution of oxalyl chloride (2.0M in methylene chloride, 200 μL, 0.36 mmol) and stirred for 15 min. After this time, the reaction mixture was concentrated in vacuo and then diluted with methylene chloride (5 mL) and added to a flask containing a solution of 2-aminopyrazine (Aldrich, 57 mg, 0.60 mmol), 2,6-lutidine (250 μL) in methylene chloride (2.5 mL) at 0° C. The reaction mixture was then stirred at room temperature for a period of 30 min After this time, the reaction mixture was treated with methanol and then diluted with methylene chloride. The reaction mixture was then transferred to a separatory funnel and washed with a 1N aqueous hydrochloric acid solution. The organic layer was then dried over magnesium sulfate, filtered to remove the drying agent and the filtrate was concentrated with silica gel (2 g). The silica gel with absorbed material was placed in a SIM and purified via Biotage flash column chromatography (40 S silica gel column, 25%-40% ethyl acetate/hexanes) to afford (S)-4-methyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-pentanoic acid pyrazin-2-ylamide (14 mg, 12%): HR-ES(+) m/e calcd for C 19 H 19 N 4 O 2 F 3 [M+H] + 393.1533, observed 393.1532; 1 H NMR (400 MHz, CHLOROFORM-d) δ 9.49 (s, 1H), 9.03 (br. s., 1H), 8.29-8.38 (m, 2H), 8.10 (d, J=7.67 Hz, 1H), 7.84 (d, J=7.88 Hz, 1H), 7.65 (t, J=7.67 Hz, 1H), 5.14 (dd, J=6.93, 8.84 Hz, 1H), 4.69-4.82 (m, 1H), 4.58-4.67 (m, 1H), 1.88-2.15 (m, 2H), 1.62 (td, J=6.87, 13.96 Hz, 1H), 1.01-1.10 (m, 6H).
Example 24
(S)-4-Methyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-pentanoic acid [5-((S)-1,2-dihydroxy-ethyl)-pyrazin-2-yl]-amide
A solution of (S)-4-methyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-pentanoic acid (prepared as in Example 23, 79 mg, 0.25 mmol) in methylene chloride (5 mL) and N,N-dimethylformamide (5 drops) at room temperature was treated with a solution of oxalyl chloride (2.0M in methylene chloride, 150 μL, 0.30 mmol) and stirred for 15 min. After this time, the reaction mixture was concentrated in vacuo and then diluted with methylene chloride (5 mL) and added to a flask containing a solution of 5-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-pyrazin-2-ylamine (prepared as in WO2004052869, Example 54, 98 mg, 0.50 mmol), 2,6-lutidine (100 μL, 0.50 mmol) in methylene chloride (2.5 mL) at room temperature. The reaction mixture was then stirred at room temperature for a period of 2 h. After this time, the reaction mixture was treated with methanol and then diluted with methylene chloride. The reaction mixture was then transferred to a separatory funnel and washed with a 1N aqueous hydrochloric acid solution. The organic layer was then dried over magnesium sulfate, filtered to remove the drying agent and the filtrate was concentrated with silica gel (2 g). The silica gel with absorbed material was placed in a SIM and purified via Biotage flash column chromatography (40 S silica gel column, 40% ethyl acetate/hexanes) to afford (S)-4-methyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-pentanoic acid [5-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-pyrazin-2-yl]-amide (54 mg, 44%) as a colorless sticky solid: HR-ES(+) m/e calcd for C 24 H 27 N 4 O 4 F 3 [M+H] + 493.2057, observed 493.2059; 1 H NMR (400 MHz, CHLOROFORM-d) δ 9.37 (d, J=1.28 Hz, 1H), 8.83 (s, 1H), 8.44 (s, 1H), 8.08 (d, J=7.46 Hz, 1H), 7.82 (d, J=7.67 Hz, 1H), 7.64 (t, J=7.78 Hz, 1H), 5.20 (t, J=6.50 Hz, 1H), 5.13 (dd, J=6.93, 8.84 Hz, 1H), 4.68-4.78 (m, 1H), 4.55-4.65 (m, 1H), 4.42 (dd, J=6.82, 8.52 Hz, 1H), 3.95 (dd, J=6.29, 8.42 Hz, 1H), 2.00-2.13 (m, 1H), 1.88-2.00 (m, 1H), 1.53-1.69 (m, 1H), 1.44-1.52 (m, 6H), 0.97-1.07 (m, 6H).
A solution of afford (S)-4-methyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-pentanoic acid [5-((S)-2,2-dimethyl-[1,3]dioxolan-4-yl)-pyrazin-2-yl]-amide (53 mg, 0.11 mmol) in tetrahydrofuran (1 mL) was treated with a 1N aqueous hydrochloric acid solution (1 mL) and stirred at room temperature overnight. The reaction mixture was then concentrated in vacuo to remove the tetrahydrofuran and the remaining material was partitioned between ethyl acetate and a saturated aqueous sodium bicarbonate solution. The organic layer was separated and dried over magnesium sulfate, filtered to remove the drying agent and the filtrate concentrated in vacuo to afford (S)-4-methyl-2-(1-oxo-4-trifluoromethyl-1,3-dihydro-isoindol-2-yl)-pentanoic acid [5-((S)-1,2-dihydroxy-ethyl)-pyrazin-2-yl]-amide (43 mg, 88%) as a cream colored foam: [α] 29 D =+22.9° (c=0.14, methanol); HR-ES(+) m/e calcd for C 21 H 23 N 4 O 4 F 3 [M+H] + 453.1744, observed 453.1744; 1 H NMR (400 MHz, DMSO-d 6 ) δ 11.26 (s, 1H), 9.16 (s, 1H), 8.45 (d, J=1.07 Hz, 1H), 8.02 (dd, J=7.67, 11.29 Hz, 2H), 7.67-7.85 (m, 1H), 5.55 (d, J=4.90 Hz, 1H), 5.28 (dd, J=5.11, 10.65 Hz, 1H), 5.05 (d, J=18.33 Hz, 1H), 4.66-4.78 (m, 2H), 4.62 (q, J=4.90 Hz, 1H), 3.67 (td, J=5.30, 10.92 Hz, 1H), 3.55 (td, J=5.78, 11.24 Hz, 1H), 1.95-2.09 (m, 1H), 1.71-1.88 (m, 1H), 1.49 (br. s., 1H), 0.90-1.00 (m, 6H).
Example 25
In Vitro Glucokinase Activity
The compounds of formula I, which include the compounds set forth in the Examples, were found to activate glucokinase in vitro by the procedure of this Example. In this manner, they increase the flux of glucose metabolism which causes increased insulin secretion. Therefore, the compounds of formula I are glucokinase activators useful for increasing insulin secretion.
Glucokinase In Vitro Assay Protocol:
Glucokinase (GK) was assayed by coupling the production of glucose-6-phosphate to the generation of NADH with glucose-6-phosphate dehydrogenase (G6PDH, 0.75-1 kunits/mg; Boehringer Mannheim, Indianapolis, Leuconostoc mesenteroides as the coupling enzyme (Scheme 2).
Recombinant human liver GK1 was expressed in E. coli as a glutathione S-transferase fusion protein (GST-GK) and was purified by chromatography over a glutathione-Sepharose 4B affinity column using the procedure provided by the manufacturer (Amersham Pharmacia Biotech, Piscataway, N.J.). Previous studies have demonstrated that the enzymatic properties of native GK and GST-GK are essentially identical.
The assay was conducted at 30° C. in a flat bottom 96-well tissue culture plate from Costar (Cambridge, Mass.) with a final incubation volume of 120 μL. The incubation reaction contained the following: 25 mM Hepes buffer (pH 7.1), 25 mM KCl, 5 mM D-glucose, 1 mM ATP, 1.8 mM NAD, 2 mM MgCl 2 , 1 μM sorbitol-6-phosphate, 1 mM dithiothreitol, test drug or 10% dimethylsulfoxide, ˜7 units/ml G6PDH, and GK (see below). All organic reagents were >98% pure and were from Boehringer Mannheim with the exceptions of D-glucose and Hepes which were from Sigma Chemical Co, St Louis, Mo. Test compounds were dissolved in dimethylsulfoxide and were added to the incubation reaction minus GST-GK in a volume of 12 μL to yield a final dimethylsulfoxide concentration of 10%. This mix was pre-incubated in the temperature controlled chamber of a SPECTRAmax 250 microplate spectrophotometer (Molecular Devices Corporation, Sunnyvale, Calif.) for 10 minutes to allow temperature equilibrium and then the reaction was started by the addition of 20 μL GST-GK.
After addition of enzyme, the increase in optical density (OD) at 340 nm was monitored spectrophotometrically to determine the rate of change (OD 340 per min). The GK activity (OD 340 /min) in control wells (10% dimethylsulfoxide minus GK activators) was compared with the activity in wells containing test GK activators, and the concentration of activator that produced a 50% increase in the activity of GK, i.e., the SC 1.5 , was calculated.
Table 1 below provides the in vitro glucokinase activity for the compounds in the Examples:
TABLE 1
Example
SC1.5 (μM)
1
0.187
2
0.186
3
0.244
4
0.439
5
0.074
6
0.119
7
0.032
8
3.526
9
1.6
10
20.625
11
2.091
12
1.857
13
0.328
14
1.242
15
0.176
16
0.062
17
0.179
18
0.962
19
0.334
20
0.457
21
0.255
22
14.914
23
1.422
24
2.966
Example 26
In Vivo Glucokinase Activity
Glucokinase Activator In Vivo Screen Protocol in Lean Mice:
Lean C57BL/6J mice were orally dosed via gavage with Glucokinase (GK) activator following a two hour fasting period. Blood glucose determinations were made at various (e.g. 0, 1, 2, 4 and 8 hours post-oral gavage) times during the study.
C57B1/6J mice were obtained from Jackson Laboratory (Bar Harbor, Me.) and were maintained in a light-dark cycle with lights on from 0600-1800 hr. For studies in lean mice, the mice were received at age ten weeks and given ad libitum access to control diet (LabDiet 5001 chow, PMI Nutrition, Brentwood, Mo.), and were at least age 11 weeks at the time of study. For studies in the DIO model, the mice were received at age five weeks and given ad libitum access to Bio-Sery F3282 High Fat Diet (Frenchtown, N.J.), and were at least age 16 weeks at the time of study. The experiments were conducted during the light phase of the light-dark cycle. Mice (n=6) are weighed and fasted for a two hour period prior to oral treatment. GK activators are formulated in Gelucire vehicle (Ethanol:Gelucire44/14:PEG400q.s. 4:66:30 v/w/v). For studies in lean mice, the mice were dosed orally with 5.0 μL per gram of body weight (i.e. 5 ml/kg×10.0 mg/ml formulation to equal a 50 mg/kg dose). For studies in DIO mice, the mice were dosed orally with 5.0 μL per gram of body weight (i.e. 5.0 ml/kg×5 mg/ml formulation to equal a 25 mg/kg dose). Immediately prior to dosing, a pre-dose (time zero) blood glucose reading was acquired by snipping off a small portion of the animal's tail and collecting 15 μL blood into a heparinized capillary tube for analysis. Following GK activator administration, additional blood glucose readings were taken at various time points post dose from the same tail wound. Results were interpreted by comparing the mean blood glucose values of vehicle treated mice with GK activator treated mice over the study period. Preferred compounds were considered to be those that exhibited a statistically significant (p≦0.05) decrease in blood glucose compared to vehicle for two consecutive assay time points.
Table 2 below provides data for % glucose lowering of a representative number of compounds of the present invention vs. control at 2 hours post 25 or 50 mg/kg dose in C57B6 mice:
TABLE 2
Exampl
% gluc lowering @ 2 H
Dose (mg/K)
1
−39.8
25
2
−38.8
25
5
−50.1
25
6
−48.3
25
7
−48.2
25
13
−45.2
50
15
−22.5
25
17
−40.2
25
18
−25.4
25
21
−36.6
25
It is to be understood that the invention is not limited to the particular embodiments of the invention described above, as variations of the particular embodiments may be made and still fall within the scope of the appended claims. | The present invention relates to compounds of the formula I,
as well as pharmaceutically-acceptable salts thereof, pharmaceutical compositions containing said compounds and methods of using said compounds in the treatment or prophylaxis of diseases and disorders. The compounds and compositions disclosed herein are glucokinase activators useful for the treatment or prophylaxis of metabolic diseases and disorders, for example diabetes mellitus, including type II diabetes mellitus. | 2 |
BACKGROUND OF THE INVENTION
The present invention relates to a protection mask for those who carry out electric arc welding, which mask automatically obscures the field of vision when the electric arc is lighted.
As is well-known, the electric arc emits an intense light having a high content of ultraviolet rays, and the eyes of the people carrying out the welding have to be protected against both the glare and the effect of the ultraviolet rays. At present time this is achieved by means of masks provided with a window of obscured glass which are manipulated manually by placing them before the face prior to welding. Such manipulation seriously hinders the work because of the total absence of visibility through the obscured glass between the moment in which the mask has been placed before the face and the moment in which the arc is lighted.
To try to find a remedy for this disadvantage, masks have been proposed in which the obscured glass may be manually displaced out of the visual field; this facilitates the welding operation, but does not allow one to avoid a period of lack of visibility and the possibility of injuries to the eyes in the case of delay in operating the obscuration. In any case, however, the fact that the operator must hold the mask as well as the welding gun at the same time and trail along the electric feeding cable constitutes a heavy hindrance and gives rise to dangers when the welding has to be carried out in not very accessible places, such as for instance wells, stairs and the like.
BRIEF SUMMARY OF THE INVENTION
The object of the present invention is to provide a mask which may be put on permanently, for example by connecting it to a helmet or support, without hindering the normal visibility, and which obscures automatically the visual field in those periods of time only, in which the electric arc is lighted. In this way, the free visibility is maintained up to the moment in which the arc is lighted, whereupon the visibility remains ensured even through the obscured glass, and the normal visibility is restored as soon as the arc is extinguished. Moreover, the disadvantages and dangers inherent in the necessity to hold the mask are avoided and it is also possible to avoid having to hold in one's hand the heavy cable of the welding machine, especially during the displacements thereof.
According to the present invention, the above object is achieved by means of an opaque mask provided with means for supporting it permanently before the operator's face and with a normally clear window whose field can be obscured by an absorption means controlled, directly or indirectly, by the welding current.
BRIEF DESCRIPTION OF THE DRAWINGS
One embodiment of the invention will now be described in detail herebelow with reference to the accompanying drawings, in which:
FIG. 1 is a side elevational cross-sectional view along line I--I of FIG. 2, showing the welding mask in its put-on condition;
FIG. 2 is a top cross-sectional view thereof, taken along line II--II of FIG. 1;
FIG. 3 is a cross-sectional view of a mask actuating device;
FIGS. 4 and 5 show details of a device for the connection of a flexible transmission cable;
FIGS. 6 and 7 are views showing on the enlarged scale two embodiments of a preloaded spring device serving to prevent overloads.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The welding mask according to the embodiment shown is formed by a shell, which may preferably be made of moulded plastic material and which comprises side elements 3 connected, by pivoting means 2, to a support cross 1 applicable to the operator's head indicated by dashed line at 0. This cross will not be described in detail, as it is well-known per se and can be found on the market. The shell of the mask is completed, between the side elements 3, by a central element 4 which extends before the operator's face and partly over it and below the chin, when the mask is in its operative position shown. However, thanks to its being pivoted at 2, the mask can be lifted and turned over the operator's head, without removing the cross 1, during the time intervals between the welding operations, thus leaving completely free the visual field of the operator.
At the level of the operator's eyes (when the mask is in its operative position), the shell of the mask is provided with a vision window limited by rims 5. At the level of the operator's mouth, the shell has also a channel-like recessing 6, extending towards the rear end, having centrally an aperture 7 and covered externally by a plate 8. The aperture 7 is located in such a manner as to receive operator's expiration, both from the nose and from the mouth, so that the air expired is conveyed outwards through the channel 6, thereby changing the air contained in the inner space of the mask.
Applied onto the side rims 5 of the vision window are support brackets 9, preferably made of metal, which support a pair of transverse bars 10 having hooked thereon, by means of profiled slots 11, a body 12 made of rubber or the like, provided with an almost rectangular window having restrained therein an inner glass 13. Preferably, this glass is treated by means of known processes in order to render it protective against infrared radiations.
Inserted from the outside into the vision window, between the rims which delimit the latter, is a frame of plastic material 14 which hooks itself in position by means of hooks 15 and retains in its interior, by means of a retainer member 16, an outer glass 17. Preferably, this latter glass is of a type, for instance containing iron ions, which is adapted to absorb the ultraviolet radiations. In this way, the operator is permanently protected (even during the periods of time which are not specifically reserved to the welding operations) both against the infrared radiations (thanks to the inner glass 13) and against ultraviolet radiations (thanks to the outer glass 17), without any hindrance of the vision. Thus, he cannot be injured by radiations emitted from adjacent working stations in which welding operations are carried out.
Housed in the closed chamber defined by rubber body 12 and frame 14 between the inner glass 13 and the outer glass 17 is a mobile frame 18 rigidly connected to a shaft 20 pivotally supported by the brackets 9, so that the frame 18 can move between a rest position shown by continuous lines in FIGS. 1 and 2 and an operative position shown by dashed lines in FIG. 1. The frame 18 carries, mounted on windows, a pair of small glasses 19, each of which corresponds to the visual field of one eye of the operator, when the frame 18 is in its operative position. The glasses 19 are of a type having a high degree of absorption of the rays of light, i.e. of the type which is usually employed for welding spectacles and masks. However, since the ultraviolet rays are absorbed already by the outer glass 17, said glasses 19 could also be made of a lighter material, as for instance a suitable plastic material, adapted to absorb the rays of light, but not the ultraviolet rays.
Keyed on an outer end of the shaft 20 by means of an adjusting member 21 is a short lever 22 having connected thereto an end of a flexible cable 23 whose sheath 24 is anchored in a suppport 25 rigidly connected to the side element 3 of the mask. These latter parts are shown by dashed lines in FIG. 1 because they are located in the mask portion which is removed by drawing the cross-section. Also hooked onto the lever 22 is a return spring 45, whose opposite end as well is fixed to the support 25. This return spring is disposed in such a way as to displace the frame 18, by means of the lever 22 and the shaft 20, towards the rest position, while cable 23 is connected in such a way that a traction exerted on it will move frame 18 towards the operative position.
The opposite ends of the flexible cable 23 and of the sheath 24 are connected to an actuating device, shown in FIG. 3. This device comprises a housing 26, which may for example be connected to the operator's belt or may be located at a fixed point in the vicinity of the operator's working place. Housing 26 contains an electromagnet 27 whose winding 28 is connected to two connections 29 and 30 protruding from the housing 26. The electromagnet 27 acts on a mobile keeper 31 which normally is maintained in a rest position by a return spring 32, but is shown in FIG. 3 as attracted by the electromagnet. Keeper 31 in turn acts on the end of the flexible cable 23 applying on it a traction, when the electromagnet 27 is excited.
The sheath 24 of the cable 23 rests on a stretcher 33 screwed into a ring nut 34, which stretcher serves for setting up the actuating device. Interposed between the sheath 24 and the stretcher 33 is a freely rotatable bush 35 which prevents sheath 24 from being accidentally twisted. The ring nut 34 is mounted on a neck 36 of the housing 26 and is fixed thereon by means of a bayonet joint engageable by a 90° rotation of the ring nut. Furthermore, the ring nut 34 extends internally with a neck 38, into the end of which there is inserted a slide 39, movable axially but not rotatable, coupled, by means of a preloaded spring 40, with a head 41 on which the end of the flexible cable 23 is anchored by means of a setscrew 42. Slide 39 is provided with shoulders 43, by means of which it may receive the thrust of the movable anchor 31, when it is in the operative position shown, but the slide 39 disengages from the anchor 31 when it is rotated by 90°. Therefore, disengagement of the bayonet joint 37 produces also the disengagement of the slide 39 from the anchor 31, and thus allows one to detach the ring nut 34 with all the parts connected to the cable 23, from the housing 26; moreover, owing to the arrangement, the coupling can take place in the correct position only.
Preferably, the neck 36 of the housing 26, and the ring nut 34, are sufficiently long to prevent any contact between the head 41 and the anchor 31 as long as the ring nut 34 is not mounted correctly onto the neck 36, whereby the insertion of the parts into one another can take place in the correct position only.
The connections 29 and 30 are inserted into the circuit of the welding machine used by the operator. Depending on the applications it may be suitable to insert such connections (and, consequently, the winding 28 of the electromagnet 27) in series with the cable which feeds the welding electrodes, or in parallel; obviously, the winding must be sized suitably. In any case, the electromagnet is excited during the periods of time in which the welding current is flowing, and remains de-energized when said current does not flow.
Therefore, when the operator, after having put on the mask, is on the point of carrying out a welding, he has a non obscured vision, because the frame 18 with the obscured glasses 19 is in a lifted rest position. As soon as, after the electrode has been brought into contact, the current begins flowing, the electromagnet 27 attracts the anchor 31 which actuates the slide 39 and, by means of the spring 40 (which prevents excessive stresses in case of high currents), pulls the cable 23, thereby lowering the frame 18 and obscuring the visual field of the operator. As soon as the welding electrode is detached, thereby switching off the current, the whole apparatus returns to the rest position and the operator immediately obtains again unobscured vision.
The preloaded spring, intended to prevent overloads, may generally be mounted in any point of the kinematic system, and for example also at 44, between the cable 23 and the lever 22, as shown partially and by dash lines in FIG. 1.
In FIG. 6 there is shown in detail, on an enlarged scale, a protection device having a preloaded compression spring. In this device, the head 41 having anchored thereon the flexible cable 23 by means of the setscrew 42, is attached in such a way as to be axially slidable along a limited path with respect to the slide 39, and the compression spring 40 is lodged in the compressed condition between said parts. It yields only in case of a stress higher than its preloading.
In the variant shown in FIG. 7, the slide 39' extends to form by itself the head 41' in the shape of a bracket, on which there is anchored the preloaded spring 40', which in this case is an extension spring, on which there is in turn anchored the flexible cable 23.
In any case, at some point on the cable 23 or on the elements connected to it, there is disposed a rotatable joint intended to prevent twisting of the cable.
In the cases in which the winding 28 has to be inserted in parallel to the welding circuit, for example in the case of continuous feed welding, it is advantageous to insert an incandescent lamp (diagrammatically shown at 46 in FIG. 3) in series with the winding, in order to allow the initial passage of a high actuating current and to successively limit the consumption, owing to the known characteristic of variation of the electric resistance of an incandescence lamp.
Obviously, instead of a lamp also other components or circuits may be used in view of obtaining this effect.
In accordance with possible modifications, the obscuration of the field could also be obtained by the cooperation of two crossing polarizing filters, one of which is fixed and the other is movable, or by means of an element whose transparency varies as a result of the application of a field or of an electric current. | A mask for carrying out electric arc welding by protecting the operator's eyes against both the glare and the ultraviolet rays during operation and reducing to a minimum the period of lack of visibility, which is embodied by an opaque shell with a vision window normally not obscured but provided with an oscurator means which is rendered operative upon flowing of electric current through an actuation apparatus connected to the electric welding circuit. | 5 |
BACKGROUND OF THE INVENTION
The present invention relates to a device for loading and unloading a load from a vehicle having a pivot frame mounted at one end of the vehicle so as to be pivotal about a horizontal axis oriented perpendicularly to the direction of vehicle length. A cantilever arm is pivotally connected to the other end of the pivot frame for pivotal motion about an axis parallel to the horizontal axis. The cantilever arm is angled upwardly from the vehicle (when viewed in the loaded position) and is swingable by a power device (such as hydraulic power cylinders) to a position where the cantilever arm engages an abutment of the pivot frame.
Such a device is known and is disclosed in German Offenlegungsschrift (non-examined published application) 2,325,866. This prior art device includes a hook at the free end of an angled cantilever arm, which engages the load and, by pivoting the cantilever arm over the rear end of the vehicle, can set down or hoist the load. Although the prior art device has favorable lever ratios which reduce the load acting on the hydraulic power cylinders, it is suitable only for the manipulation of certain large, box-like containers which can be emptied in a manner similar to that of a sliding dump truck body.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a loading and unloading device of the above-mentioned type with which differently shaped loads, such as containers, pallets, hutches (troughs) and also pontoons can be manipulated quickly and reliably without requiring excessive adaptation work.
This object and others to become apparent as the specification progresses, are accomplished by the invention, according to which, briefly stated, the vehicle-mounted load hoisting device includes a pivot frame mounted on the vehicle for pivotal motion about a first horizontal axis extending transversely to the vehicle length; a cantilever arm connected to the pivot frame for pivotal motion about a second horizontal axis extending parallel to the first axis; a pivot arm articulated to the cantilever arm for pivotal motion about a third axis oriented parallel to the first and second axes; a pulley mounted at an end of the pivot arm for supporting a cable or the like wound on a winch and attachable to the load; and an arrangement for locking the cantilever arm and the pivot frame together to form a rigid unit pivotal about the first axis. When forming the rigid unit, the cantilever arm is in contact with a stop face on the pivot frame and extends as a longitudinally aligned continuation of the cantilever arm.
It is an advantage of the invention that the requirement for simplification and greater uniformity in transportation as it is encountered, in particular, in current pioneering equipment, is met to the greatest possible extent. Additionally, the device according to the invention also overcomes the drawbacks encountered in the prior art devices for manipulating pontoons in that, when picking up the pontoon, the lifting cable need not be relocated from an upper engagement zone to a lower engagement zone.
The device of the invention can be employed with any vehicle (including tracked vehicles) that can be equipped with a flat bed and at most requires, for adaptation to different shapes of loads, easily and quickly performed conversion measures.
Additional features according to the present invention make it possible to omit the use of push boats when foldable pontoons are picked up out of the water. When picking-up pontoons (foldable in a W-shape) by prior art devices, the two outer flotation bodies would not fold automatically against the inner flotation bodies but had to be additionally pressed in by push boats. A sudden downward pivoting of the pivot arm, according to the invention, from a raised position simultaneously lowers the attached pontoon. The forces generated when the pontoon impacts on the water are sufficient to press the outer flotation bodies to the inner flotation bodies and simultaneously lock them together.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic side elevational view of a vehicle equipped with a preferred embodiment of the invention, with a pontoon load placed thereon.
FIG. 2 is a schematic side elevational view of the preferred embodiment, removed from the vehicle and drawn on an enlarged scale.
FIG. 3 is a schematic side elevational view of a vehicle equipped with the preferred embodiment, shown in the position before the pontoon is hoisted from the water.
FIG. 4 is a view similar to FIG. 3, showing the vehicle during the hoisting of the pontoon.
FIG. 5 is a schematic perspective view of a portion of the preferred embodiment, including components for performing conversion measures for the manipulation of various containers.
FIG. 6 is a schematic illustration of a hydraulic circuit associated with the power cylinder shown in FIG. 1.
FIG. 7 is a schematic side elevational view of a tackle block device serving as a winch for the hoisting cable shown in FIG. 1.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Turning to FIG. 1, a base frame 3 is fastened to the truck bed 1 and a pivot frame 4 is mounted thereon which is pivotal at one end about a horizontal axis 5 which extends transversely to the longitudinal direction of the truck 2 and which is situated at the rear end thereof. A cantilever arm 7 is hinged to the other end of the pivot frame 4 by an axis 6 which is parallel to the axis 5. The cantilever arm 7 has an integral terminal part 8 which is oriented at a right angle to the arm 7 and which, in the illustrated position, extends in an upward direction from the bed 1. A pivot arm 9 is articulated to the free end of the terminal part 8. The pivot frame 4 and the cantilever arm 7 are positioned in the longitudinal direction of the vehicle and, in the illustrated loaded state, lie horizontally and parallel on the base frame 3. At the free end of the pivot arm 9 a roller 10 is provided to guide a hoisting cable 11 connected to an upper location 13 of a load 12 and wound on a winch 14. The cable 11 is guided over a roller 15 which is coaxial with the pivot axis of pivot arm 9. The winch 14 is disposed on the terminal part 8 of the cantilever arm 7 on the side facing away from the load 12, that is, facing away from the axis 6 and thus oriented toward the driver's cab 16 of the vehicle 2. On the same side of the terminal part 8, at a higher level, a projection 17 is provided for supporting a hydraulic cylinder 18. The piston rod of the hydraulic cylinder 18 engages the pivot arm 9 at fulcrum 19.
The load 12 is guided on both sides along its lower outer edges 20 by three pairs of rollers 21, 22 and 23, each provided with wheel flanges on their exterior faces. The rollers of each pair are coaxial. Two centering cones 24 are rotatably mounted to the rear end of the vehicle 2 so as to engage the two lower edges 20 of the load 12 and prevent it from running off to the sides.
Turning now to FIG. 2 in which rollers 21, 22 and 23 have been omitted for the sake of clarity, the piston rods of two hydraulic cylinders 26 (only one is visible) are articulated to the cantilever arm 7 at an axis 25 which is spaced at a predetermined distance from and above the axis 6 where the cantilever arm 7 is pivoted to the pivot frame 4. The other ends of the piston rods are mounted at an axis 27 to the base frame 3. A pneumatic cylinder 28 is disposed on the cantilever arm 7 in the longitudinal direction of vehicle 2, with its piston rod 29 engaging a hook 30 which passes around a catch 31 which forms an extension of the pivot frame 4 beyond axis 6, in order to lock the pivot frame 4 to cantilever arm 7. In the locked state, the pivot frame 4 and the cantilever arm 7 are in a mutually flush position and form a rigid unit pivotal about axis 5 by hydraulic cylinders 26. In the unlocked state, the cantilever arm 7 is able to initially pivot about axis 6 until its frontal face 32 abuts a counterface 33 of a stop cam 34 forming part of the pivot frame 4. In the loading position, faces 32 and 33 are disposed approximately at a right angle to one another so that the cantilever arm 7 may pivot approximately 90°.
FIGS. 3 and 4 show the launching and hoisting of a pontoon 12, constituting a load. To launch (setting down) the pontoon 12, the cantilever arm 7 is lifted in its state locked to the pivot frame 4 as shown in FIG. 4. Rollers 21, 22 and 23 aid in the unloading of the pontoon as it is put into the water, and the cable 11 is released from pontoon 12 after it has been unloaded. Also, two bolt pin-type locks 35 (one visible in FIG. 1) which serves to prevent lateral displacement of the pontoon 12 during transportation, are released before launching. Then, in a known manner, pontoon 12 rocks over the end of the vehicle which itself may have been driven partially into the water, as may be observed in FIGS. 3 and 4. The pontoon 12 then unfolds automatically.
For hoisting the pontoon 12 from the water, cable 11 is attached at the point of attachment 13, which is disposed at the frontal portion of the pontoon at the lower end in the plane of symmetry and the pontoon is lifted by the pivotal arm 9 which forms a continuation of the cantilever arm 7. During this occurrence the two inner or center flotation bodies of pontoon 12 thus come to contact one another and are automatically locked to one another. Pontoon 12 is then lifted out of the water by pivoting pivot arm 9 into its end position shown by the dashed lines in FIG. 3, which is also visible in FIGS. 1 and 2, and is lowered suddenly due to a sudden depressurization of the hydraulic cylinder 18. This causes the inner sides of the outer flotation bodies of the pontoon to suddenly impact on the surface of the water, thus bringing the outer flotation bodies in contact with the already juxtaposed inner flotation bodies and automatically locking them at the same time. Then by the actuation of the winch 14 and the hydraulic cylinders 26 the pontoon 12 is again raised and pulled up over the rear end of vehicle 2, as shown in FIG. 4. Thus, the pontoon 12 can be pulled onto the vehicle without putting it down and without changing the position of the cable 11. While the pontoon 12 is being lifted out of the water, cantilever arm 7 is raised by hydraulic cylinders 26 to an angled, unlocked position with respect to the likewise raised pivot frame 4. The free end of the cantilever arm 7 projects beyond the end of vehicle 2 as shown in FIG. 3.
The sudden downward pivoting of pivot arm 9 from the raised position shown in FIG. 3 can be effected by means of a suitable hydraulic circuit as shown in FIG. 6. For this purpose, it is expedient to provide an appropriately dimensioned shutoff valve 44, with the circumvention of the valve block (not shown), directly in a large-sized suction conduit 45 connected to a pressurized fluid reservoir 46 and to both ends of the hydraulic cylinder 18. The double acting hydraulic cylinder 18 is as usual at both of its ends further provided with actuating conduits 47 and 48 which are connected to the valve block. If the conduit 47 is set under pressure for lifting purposes, the shutoff valve 44 is closed. For sudden downward pivoting of pivot arm 9 the valve 44 becomes opened thus permitting pressure compensation on both sides of the piston 49 of hydraulic cylinder 18.
In the pulled-up loaded state, as shown in FIG. 1, the frontal face of pontoon 12 facing the driver's cabin 16 lies against end stops 36 (only one shown) and is held in this position by bolt locks 35, and by tying down cable 11 by means of the winch 14.
FIG. 5 is a schematic representation illustrating the conversion of the device to accommodate standard containers according to ISO or DIN standards which are provided with two parallel longitudinal tracks along their undersides. For this purpose, a front guide wheel 37 is disposed on each side of cantilever arm 7, while a fork-like projection 38 is disposed at the rear end of the pivot frame 4. The projection is equipped with a tubular axle 39 which extends from both sides of projection 38 with respect to the base frame 3. A pair of rear guide wheels 40 can be placed on to axle 39. The axle 39 and two further axles 41 and 42 which are parallel to axle 39 are equipped with the guide rollers 23, 22 and 21 at their ends for hoisting a pontoon 12, as shown in FIG. 1. These guide rollers are removed during conversion. Two catch hooks 43 are provided at axle 41 in the region of the rails of the standard container. These hooks must be removed when transporting a pontoon or they may be folded down to such an extent that they no longer project over the loading plane.
FIG. 7 shows a tackle block device which can be used instead of the winch 14. This device comprises a hydraulic cylinder unit 51 connected to the terminal part 8 of the cantilever arm 7. The hoisting cable 11 is connected to a fixed point 52 at the piston side of the cylinder 51 and guided over two blocks 53 and 54 journalling parallel to each other at opposite ends of the hydraulic cylinder unit 51. Each of the blocks 53 and 54 comprises for instance five coaxial pulleys thus causing the hoisting cable 11 to move with a speed which is ten times the speed of the extending piston rod 55 of the hydraulic cylinder unit 51.
The present disclosure relates to the subject matter disclosed in Federal Republic of Germany Application No. P 37 23 604.0 filed July 17th, 1987, the entire specification of which is incorporated herein by reference.
It will be understood that the above description of the present invention is susceptible to various modifications, changes and adaptations, and the same are intended to be comprehended within the meaning and range of equivalents of the appended claims. | A vehicle-mounted load hoisting device includes a pivot frame mounted on the vehicle for pivotal motion about a first horizontal axis extending transversely to the vehicle length; a cantilever arm connected to the pivot frame for pivotal motion about a second horizontal axis extending parallel to the first axis; a pivot arm articulated to the cantilever arm for pivotal motion about a third axis oriented parallel to the first and second axes; a pulley mounted at an end of the pivot arm for supporting a cable or the like wound on a winch and attachable to the load; and an arrangement for locking the cantilever arm and the pivot frame together to form a rigid unit pivotal about the first axis. When forming the rigid unit, the cantilever arm is in contact with a stop face on the pivot frame and extends as a longitudinally aligned continuation of the cantilever arm. | 1 |
BACKGROUND OF THE INVENTION
[0001] 1. Technical Field
[0002] This invention relates to a counting device and, more particularly, an audio counter to determine when the defense can rush the passer during a pick-up game of football.
[0003] 2. Description of the Prior Art
[0004] One of the favorite sports in the United States is football. Throughout the season, millions of Americans either go to football games are watch the football games on television. Millions of younger people, and some not so young, engage in pick-up games of football. These pick-up games of football may be played in vacant lots, open spaces or in the backyards of the participants.
[0005] Normally in these pick-up games, the participants do not have pads and helmets or other protective gear to keep from getting hurt. As a result, these pick-up games are normally “touch” or “flag” football and do not involve tackling the runner with the ball. In probably its most common form, backyard football prohibits the quarterback from running with the ball. The game becomes entirely a passing game. In those cases, the number of players, which is usually less than the eleven per side as in a normal football game, are equally divided in number and/or skill level. In its most common form as played by millions of youth in America, the two teams line up and when the football is snapped, the defensive line has to wait for a predetermined amount of time before they can rush the quarterback. This gives the receivers a chance to run their routes before the quarterback has to throw the ball. A defensive line normally counts “1 Mississippi”, “2 Mississippi”, “3 Mississippi”, etc. Each “Mississippi” is normally one second. The typical period of time prior to rushing the quarterback is five seconds, but it could be expanded or reduced depending upon the desire of the players.
[0006] In this type of backyard football, disputes frequently erupt as to whether the defensive line rushed the quarterback too soon. Not everyone counts at the same speed. Hence if a slow counter provides the count the pass rush will be longer than if a fast counter provides the count. This results in frequent disputes between the two teams as to whether the pass-rush was too early.
[0007] There are many variations of this type of backyard football, including who is ineligible as a receiver or can the offense run the football. Typically, there is no “punting” of the football so the offense has four downs to either score or make a first down. First downs may even be eliminated depending upon the length of the field.
[0008] Applicant remembers when he was growing up and he would play backyard or sandlot football. There were always arguments about the pass rush with the offense saying “you rushed too soon” and the defense vehemently denying the allegations. As applicant has gotten older and watched his children play the same football game decades later, the same arguments still persist. The present invention is designed to reduce or eliminate those arguments.
BRIEF SUMMARY OF THE INVENTION
[0009] It is an object of the present invention to provide a football counting device.
[0010] It is another object of the present invention to provide a counting device to be used in pick-up or backyard football games to determine when the passer can be rushed by the defensive line.
[0011] It is another object of the present invention to provide a timing device that gives audible sounds to let the players know when the quarterback can be rushed in a game of backyard football.
[0012] The timing device has a generally flat football-shaped device with a flexible football-shaped cover there over. Under the football-shaped cover is a control circuit that includes a microcomputer powered by batteries or other suitable power source. By pressing a push-button switch, a timer is started and audible counts are given until the defensive line is told it can rush the passer. A visual signal can also be given as well as the audible signal.
[0013] The microcomputer may be preprogrammed with an audible voice or may have the option so the players can record their own audible voice. The timing sequence can then be set so that the players can rush after two seconds, three seconds, four seconds, five seconds, etc., as is determined by the participants in the football game.
[0014] Because the football counting device has its own internal microcomputer, commands given to the microcomputer can be done with individual switches or by a timing sequence of the single push-button switch. All that is necessary is there be an ON/OFF switch in combination with the push-button switch to start the count.
[0015] In the software program for the microcomputer, a player would select the desired pre-recorded voice sequence by pushing the push-button switch and holding it down until the numeric display identifies the desired voice selection. Next, the user selects the desired count while rapidly pushing the push-button switch until the numeric display indicates the desired value which can be anywhere from 1 to 7, representing 1 to 7 seconds.
[0016] Then, the player places the football counting device at the line of scrimmage. By pressing down on the top of the football-shaped cover of the football counting device, the push-button switch is activated which begins the preselected count. Simultaneously, the seconds are indicated in the numeric display and a red light turns ON until the count has been completed. When the preselected count sequence has been completed, (1) the audio sound changes to “RUSH” and (2) the red light turns to green.
[0017] After a pause for a few seconds, the football counting device resets and is ready for the next sequence.
[0018] If the football counting device has an optional custom voice recorder, the user gives appropriate commands through the push-button switch to get to the custom voice recording. An audio sound of “Say 1 Mississippi” will be given. At that time, the individual says “1 Mississippi” into the microphone which is recorded in the microcomputer. This is repeated until the individual has counted up to “7 Mississippi”. The recording will be completed with the audio sound of “RUSH”. Thereafter, the sequence is ended. The recordings by the individual are then used in the microprocessor to the provide the count prior to rushing the passer.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] FIG. 1 is an exploded perspective view of the football counting device with a flexible football-like cover being exploded from a base.
[0020] FIGS. 2 a - 2 e are left-end front side, right-end, top and bottom views, respectively of the football counting device.
[0021] FIG. 3 is a pictorial block diagram of major internal components of the football counting device.
[0022] FIG. 4 is a block diagram of the controls for the football counting device.
[0023] FIG. 5 is a logic flow diagram of software in a microcomputer of the football counting device.
[0024] FIG. 6 is an optional software routine for the microcomputer in a football counting device to provide a custom voice recording.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0025] Referring now to FIGS. 1 and 2 in combination, the football counting device is generally referred to with reference numeral 10 . The football counting device 10 has a flexible cover 12 that interlocks over base 14 with a flexible outer rim 16 . The base 14 has an outer retaining ring 18 (see FIG. 1 ) to receive the flexible outer rim 16 of the flexible cover 12 there over. The flexible cover 12 is made from a flexible, resilient material such as a polyurethane foam, also sometimes called foam rubber. The flexible cover 12 may be injection-molded with its external appearance and design resembling a football, complete with imitation football laces 20 , strips 21 , and other similar football imitating décor.
[0026] In one side of the flexible cover 12 is mounted an alpha-numeric display 22 that is constructed from low power light-emitting diodes. In the bottom of the base 14 is ON/OFF switch 24 that will turn ON or OFF the power sent to the control circuit 26 mounted on base 14 as pictorially shown in FIG. 1 .
[0027] Referring now to FIG. 3 , the control circuit 26 will be very broadly explained. A microcomputer is mounted inside of computer housing 28 . Connected to the microcomputer inside of housing 28 is the ON/OFF switch 24 and a power supply such as batteries 30 . Also connected to the microcomputer and computer housing 28 is the alpha-numeric display 22 and speakers 32 and 34 . Located above the computer housing 28 and connected to the microcomputer is a push-button switch 36 .
[0028] Generally, when using the football counting device 10 , the ON/OFF switch 24 is turned to the ON position and the football counting device 10 is placed at the line of scrimmage adjacent to where the football is located prior to being snapped at the start of another play. By pressing the flexible cover 12 , the push-button switch 36 is depressed, which through the microcomputer in the computer housing 28 will start the alpha-numeric display 22 so that it begins to count. Simultaneously, the speakers 32 and 34 will give an audible indication of “1 Mississippi”, “2 Mississippi”, “3 Mississippi”, up through the desired count, possibly as high as “7 Mississippi”. As the count is occurring, the alpha-numeric display 22 counts up and the back-lit portion indicates red. Once the desired count has been reached, the alpha-numeric display 22 and the back-lit portion will change to green and the count will stop. Simultaneously, the speakers 32 and 34 will give the oral command of “RUSH”. At that time, the defense can rush the quarterback. After a short time, the football counting device and the microcomputer will reset for the next play.
[0029] Referring now to FIG. 4 , the operation of the microcomputer 38 as it operates the control circuit 26 (see FIG. 3 ) is explained in more detail. The ON/OFF switch 24 will turn ON or OFF the microcomputer 38 by connecting it to the batteries 30 (see FIG. 3 ). Once the microcomputer 38 has been turned ON, push-button switch 36 may be pushed to start the sequence. Alpha-numeric display 22 will start the count with a red backlight 40 . Simultaneously, the audio processor 42 is sending the count of “1 Mississippi”, “2 Mississippi”, “3 Mississippi”, etc., to the speakers 32 and 34 . Once the count is reached, the alpha-numeric display 22 will hold that count, the red backlight 40 will go OFF and the green backlight 44 will come ON. Simultaneously, the microcomputer 38 will send a signal to the audio processor 42 to give the command “RUSH” to speakers 32 and 34 .
[0030] The microcomputer 38 , as explained in connection with FIG. 4 , has the capability of doing additional things for the football counting device 10 . Referring to FIGS. 4 and 5 in combination, FIG. 5 shows a program sequence for the microcomputer 38 . The push-button switch 36 may be pushed in a sequential order to allow the user to select a desired prerecorded voice sequence 46 . For example, the push-button switch 36 can be held down for a long time duration of several seconds and thereafter be momentarily pushed to move through a set of desired sequences. At one of the desired sequences, the user would select the desired prerecorded voice sequence as illustrated by block 46 . The user selecting the desired prerecorded voice sequence 46 is illustrated in both FIG. 5 and FIG. 4 . If desired, the momentary push-button switch 36 could be used to select the prerecorded voice versus going through the computer sequence as just described.
[0031] Next, the user will select the 1 through 7 “Mississippi” ascending set points 48 in the same manner the prerecorded voice sequence was selected. In other words, the push-button switch 36 is held down for a long period of time. Thereafter, by a momentarily pushing the push-button switch 36 , the microcomputer 38 is stepped through until the desired “Mississippi” count is reached. Again, the selecting of the “Mississippi” set point can be by a manual switch as pictorially illustrated in connection with FIG. 4 or by a computer sequence as illustration in connection with FIG. 5 .
[0032] After the prerecorded voice is selected and the count is set, the user places the football counting device 10 at the line of scrimmage as represented by block 50 in FIG. 5 . Thereafter, the user begins the sequence by pushing push-button switch 36 indicated by block 52 . The microcomputer 58 is programmed to (1) begin the audio sequence of counting up 54 , (2) incrementally increase the alpha-numeric display 56 and (3) turn ON the red backlight 58 . While the beginning of the audio sequence of counting up is representing in the logic diagram of FIG. 5 with the numeral 54 , it occurs through the audio processor 42 and speakers 32 and 34 as shown in FIG. 4 . Likewise, the incrementally increasing of the alpha-numeric display is indicated by logic block 56 in FIG. 5 , but occurs in the alpha-numeric display 22 as shown in FIG. 4 . Similarly, the turning ON of the red backlight is represented in FIG. 5 by logic block 58 . It occurs by turning ON the red backlight 40 of the alpha-numeric display 22 as shown in FIG. 4 .
[0033] As the microcomputer 38 counts up, it increments the counter until it reaches the user set point 60 as previously described in logic step 48 . When the counter has been incremented until it reaches the user set point 60 , a signal indicates that it has “reached end of sequence count up” 62 , which turns ON the green backlight 64 and announces “RUSH” 66 . Simultaneously, with turning ON of the green backlight 64 , the red backlight will be turned OFF. The announcing of RUSH 66 as shown in FIG. 5 occurs through the audio processor 42 and speakers 32 and 34 in FIG. 4 . At that time, the defense is rushing the quarterback as the quarterback attempts to throw the football.
[0034] Thereafter, the microcomputer 38 is programmed to pause for a certain number of seconds 68 then resets for the next down 70 . The amount of pause that occurs in step 68 can be programmed in the microcomputer 38 in the same manner as the user selects prerecorded voice sequence 46 or user selects 1 through 7 “Mississippi” 48 . For example, the user will hold down the push-button switch 36 for a predetermined length of time and thereafter sequence through steps until getting to the function that sets the length of pause as explained in connection with step 68 and then either extend or shorten the length of the pause.
[0035] Also, the microcomputer 38 can either have a prerecorded voice message of “1 Mississippi”, “2 Mississippi”, “3 Mississippi”, etc., and “RUSH” or as an option the user can record his or her voice. Again, as shown in FIGS. 6 and 4 in combination, the push-button switch 36 may be held down for a predetermined length of time and thereafter stepped through until the user gets custom voice record. Then the user presses custom voice record button 72 , which is represented in the function sequence in FIG. 6 , but requires pushing record voice 74 and using microphone 76 as shown in FIG. 4 . While the record voice 74 and the microphone 76 are not illustrated in FIGS. 1 and 2 , they could also be included in the base 14 . Thereafter, in the program set in the microcomputer 38 , it will control the audio processor 42 and speakers 32 and 34 so that it speaks “say 1 Mississippi” as indicated in logic step 78 . Then, the user speaks the phrase “1 Mississippi” 80 . The sequence will repeat until it reaches “7 Mississippi” 82 . After it reaches “7 Mississippi”, an end 84 will be indicated.
[0036] While not illustrated in a logic flow diagram, the same can be used for recording “RUSH” in the microcomputer 38 .
[0037] It should be realized that the setting of the individual functions in the microcomputer 38 may be done with sequential steps and timing as is commonly done with a clock to set date, time, alarm, or other functions. On the other hand, the various functions could be set in by manual switches. | The present invention is a football counting device that utilizes a microcomputer so that a proper count can be given for backyard or sandlot football games as to when the defense can rush the passer. A push-button switch will start the sequence and the microcomputer (1) controls an audio sound that counts “1 Mississippi”, “2 Mississippi” and (2) gives a visual display as to when the quarterback can be rushed. The length of time delay and the voice utilized can be selected by the players. The sequence repeats for each new down. | 0 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is based on and hereby claims priority to International Application No. PCT/EP2012/002092 filed on May 16, 2012 and German Application No. 10 2011 107 818.9 filed on Jul. 16, 2011, the contents of which are hereby incorporated by reference.
BACKGROUND
[0002] The invention relates to a method for determining the residual range of a motor vehicle which has an energy store for a drive which acts on at least one wheel of the motor vehicle and has an electric motor, as a function of residual energy in the energy store, and a motor vehicle.
[0003] Methods for automatically determining a residual range within a motor vehicle have already been known for a relatively long time. In this context, there is very frequently interaction with a navigation system which supplies route data about routes which will be traveled on in future by the motor vehicle. As a function of consumption observations it is then possible to predict how high the consumption will be on the various future route sections, with the result that if the residual energy is known it is possible to determine how far the motor vehicle can still travel on such a route. This can be displayed to a driver, in particular when the driver wishes to assess whether he can still end his journey without refueling or recharging energy in some other way, and in extended cases also whether the residual energy is even still sufficient for a return journey on the same route. In addition, range calculation methods are known which also check various possible future routes.
[0004] A method for determining a residual distance which can be covered and an associated arrangement are disclosed by DE 199 29 426 A1. In this context, it is assumed that there is an internal combustion engine, with the result that the residual energy corresponds to a fuel supply. The residual distance which can be covered with the fuel supply is determined from the quantity of the fuel supply and a determined fuel consumption, wherein situation-dependent consumption mean values are used. The core idea in said document is to determine road-class-dependent consumption mean values. Checking is then performed as to which class of road a route section is associated with, with the result that if the length thereof is known, consumption for the route section can be predicted as a function of the consumption mean values. Further classifications are also proposed in said document, for example for the state of charge of the vehicle, the positive gradient and/or a negative gradient of a route section and the like.
[0005] New drive concepts have recently been proposed for series production. The drive of the motor vehicle here has an electric motor which can be fed, for example, from a high voltage battery of the motor vehicle. Motor vehicles which have only at least one electric motor and which are frequently also referred to as electric vehicles are known. However, motor vehicles which comprise both an electric motor and an internal combustion engine to drive the vehicle (referred to as hybrid vehicles) have also been proposed. While in motor vehicles which have only one internal combustion engine the internal combustion engine also “pulls along” all the electric consumers (secondary consumers) which are provided in addition to the drive via the dynamo, this is no longer the case with an electric motor which is operated from a store for electrical energy, in particular a high-voltage battery, since the secondary consumers also contribute to the overall consumption from the electric energy store. Known concepts for calculating a residual range do not sufficiently take into account these secondary consumers in order also to make sufficiently reliable statements about the residual range even in the case of operation of an electric motor.
SUMMARY
[0006] One possible object relates to specifying a possible way of determining the residual range more precisely and in a more differentiated fashion.
[0007] The inventors propose a method of the type mentioned at the beginning in which
consumption values which describe the current consumption of the drive and of at least one secondary consumer are determined using at least one sensor, at least one drive prediction value which is assigned to the drive and describes the consumption over a predetermined distance is determined from the consumption values of the drive, and at least one secondary consumer prediction value which is assigned to the secondary consumers and describes the consumption over a predetermined distance is determined separately from the consumption values of the secondary consumers, and the residual range is determined for at least one distance which is to be traveled by the motor vehicle and which is described by route data taking into account the drive prediction value and the secondary consumer prediction value.
[0012] During the operation of an electric motor, the secondary consumers which contribute themselves to the consumption can therefore be taken into account separately, that is to say not only is a single prediction value determined (if appropriate for each classification) which describes the total consumption but instead at least two prediction values are determined, specifically a drive prediction value, which relates merely to the drive (specifically the electric motor), and at least one secondary consumer prediction value which attempts to predict consumption of secondary consumers for future route sections. This is based on the realization that the consumption values of the drive and secondary consumers are not always correlated and therefore separate consideration is appropriate in order to enable an ultimately more precise and, in particular, more differentiated calculation of the residual range. A more precise result is obtained overall. It is to be noted here that the method is, of course, carried out automatically within the motor vehicle, in particular by a correspondingly embodied control device.
[0013] It is particularly expedient here if the drive prediction value and the secondary consumer prediction value are determined with a different calculation method and/or a differently parameterized calculation method. This therefore means that the differentiated consideration of the drive and of the secondary consumers also takes the form of a different type of calculation of the corresponding prediction values, wherein the calculation methods or the parameterization can be selected in a way which is specifically matched to the secondary consumers and the drive, for example on the basis of empirical investigations. It is therefore conceivable, for example if different classes of ambient conditions and/or route sections are taken into account, to perform a different classification for the drive prediction values and the secondary consumer prediction values. It is also possible to use different filters or filter parameters, more details being given on this below.
[0014] In one advantageous refinement it can be provided that the drive prediction value and/or the secondary consumer prediction value are determined by filtering the profile of the consumption values using at least one filter. Therefore, ultimately the profile of the different consumption values is considered and analyzed, with the result that a specific history of the consumption values is always also taken into account solely by the filter effect, and consequently said history is included in the determination of the prediction values, which determination then ultimately also takes into account, in addition to the current consumption properties, as a function of the selected filter parameters, the consumption behavior (which for the most part is driver-initiated in the case of the secondary consumers) in the relatively recent part. This therefore means that the prediction values are continuously updated on the basis of the current consumption values, with the result that a better prediction is provided for the route sections which are to be traveled along in future.
[0015] In this context, it is also to be noted at this point that it is generally advantageous, in particular, to average out fluctuations in the consumption properties, and always to consider the consumption values averaged over a (short) distance, that is to say to form a mean value over 100 m in each case.
[0016] In this context PT filters, in particular PT2 filters, have proven to be particularly suitable filters, in particular with respect to the secondary consumer prediction value. Of course, other types of filtering are also conceivable, for example sliding mean value filtering or the like.
[0017] In one development of the method it is possible that two filters are used to determine the secondary consumer prediction value, wherein a first filter has high attenuation and a second filter has low attenuation, and an, in particular, weighted combination of the filter results is produced. It is therefore conceivable to use different filters to then combine the results. In one particularly advantageous embodiment, the weighting of the filter results can be carried out as a function of the residual energy. This therefore means that it is possible to use various filter characteristics which can then be weighted as a function of an operating parameter, specifically, for example, as a function of the residual energy.
[0018] Of course, when using a filter it is also generally possible to provide that at least one filter parameter is selected as a function of an operating parameter of the motor vehicle which is related to the drive, in particular as a function of the residual energy.
[0019] These two considerations—weighting the results of various filters as a function of the residual energy or adapting filter parameters as a function of an operating parameter, in particular the residual energy—which have just been mentioned and are particularly advantageous with respect to the secondary consumer prediction value, are based on the idea that, in particular, the residual energy constitutes a relevant criterion when the focus is on the time period which is considered when secondary consumers are used. This is because if the residual energy is already low, that is to say if a corresponding residual range can therefore also be expected to be rather small, current consumption developments during the use of secondary consumers have a relatively large, more relevant influence. If, for example in the case of very low residual energy, an air conditioning system is activated, the prediction value which relates to this secondary consumer should be increased more quickly than if relatively high residual energy is still available, according to which it is thus possible to react quickly to the changed, but highly relevant, situation since in the example of the air conditioning system said system constitutes a completely relevant consumer.
[0020] In one particularly preferred embodiment it is possible to provide that at least two secondary consumer prediction values are determined for at least one secondary consumer group comprising at least one secondary consumer. This means a more differentiated consideration is also possible with respect to the different secondary consumers themselves, with the result that, in particular also for such different secondary consumer groups, it is the case that the secondary consumer prediction values of different secondary consumer groups can be determined with different calculation methods and/or differently parameterized calculation methods. For example, differently parameterized filters can be used for determining the secondary consumer prediction values of different secondary consumer groups and the like.
[0021] It is therefore possible for example to provide that a secondary consumer group comprises all the secondary consumers which are under consideration and which are connected to an on-board power supply system with a low voltage, and a further secondary consumer group comprises at least one secondary consumer which is connected to an on-board power supply system with a relatively high voltage, in particular at least one secondary consumer which relates to the temperature management within the motor vehicle. Motor vehicles with an electric motor usually have a high-voltage power system and a low-voltage power system, which can be connected via a DC/DC converter. The high-voltage power system is fed by the high-voltage battery, which is also used as an energy store for the electric motor. The low-voltage power system can have a low-voltage battery, for example with an operating voltage of 12 V, wherein, of course, the high voltage is higher than the low voltage. It is then therefore conceivable to consider the low-voltage secondary consumers and the high-voltage secondary consumers separately, with the result that further, more precise differentiation can take place and consequently more precise calculation of the residual range is carried out. In particular, components of an air conditioning system are possible here as high-voltage secondary consumers with a marked influence, which can be considered separately. Generally, devices relating to the temperatures in the motor vehicle can be combined as a thermal management system.
[0022] It is also possible to provide that upper limits are used for the prediction values. This can be appropriate to avoid degeneration in various operating states.
[0023] In a further refinement it is possible to provide that drive prediction values and/or secondary consumer prediction values which are assigned to specific classes of route sections and/or ambient conditions are determined. In this context it is possible to use, for the drive prediction values, for example the method described by DE 199 29 426 A1 which was already cited at the beginning, wherein route sections are classified and each class is assigned a separate prediction value (consumption mean value in said document). Corresponding data for determining in which class of route sections the current location is, for example a road class, a speed limit, a positive gradient, a bend radius, traffic information and the like, can be supplied by a navigation system. It is also possible here to take into account classes for the secondary consumer prediction values which can also relate, for example, to ambient conditions, for example weather conditions or the like.
[0024] In a further refinement it is possible to provide that a control device of a combination display device is used to carry out the method, and/or the route data is made available by a control device of a navigation device. A navigation device can furthermore also supply information on the current location of the motor vehicle, which location can be determined, for example, by data of a GPS sensor and subsequent “map matching”. Route data, if appropriate data for classification and the current position of the motor vehicle, are then made available to the control device, which is intended to determine the residual range. This may preferably be a control device of a combination display device on which the residual range is then also to be displayed. Control devices of secondary consumers and of the drive can supply the current consumption values which can be determined, for example, by evaluating measured values of suitable sensors. The remaining residual energy can be made available by a corresponding battery control device, in particular by a battery management system.
[0025] If the prediction values are first known, for example, as consumption in kilowatt hours/100 km, the total consumption for various route sections, and therefore also the residual range, can be determined given knowledge of the route to be traveled along in future and by the route data by summing, wherein, if appropriate, classifications are to be taken into account.
[0026] In addition to the method, the inventors also propose a motor vehicle, having an energy store for a drive which acts on at least one wheel of the motor vehicle and has an electric motor, and a control device which is designed to carry out the method. The control device can particularly advantageously be here the control device of a combination display device. A navigation system and control devices of secondary consumers and the drive as well as of the energy store can supply further required information for determining the residual range. All the statements relating to the method apply analogously to the motor vehicle with which consequently more differentiated and consequently more precise calculation of the residual range is also possible.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] These and other objects and advantages of the present invention will become more apparent and more readily appreciated from the following description of the preferred embodiments, taken in conjunction with the accompanying drawings of which:
[0028] FIG. 1 shows a basic diagram of a proposed motor vehicle,
[0029] FIG. 2 shows a diagram showing the sequence of the proposed method, and
[0030] FIG. 3 shows various filter characteristics in the form of a response to an input signal.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0031] Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout.
[0032] FIG. 1 shows a basic diagram of a proposed motor vehicle 1 . This is an electric vehicle whose drive comprises an electric motor 2 to which a drive control device 3 is assigned. By a high-voltage power system (not shown in more detail in FIG. 1 for reasons of clarity), the electric motor 2 is supplied with energy by a high-voltage battery 4 , which constitutes an electric energy store 5 , and said electric motor 2 drives at least one wheel of the motor vehicle 1 . A battery control device 6 is also assigned to the high-voltage battery 4 .
[0033] Components of an air conditioning system 7 , to which a control device 8 is also assigned, are also operated by the high-voltage power system.
[0034] In addition to the high-voltage power system, in the motor vehicle there is also a low-voltage power system, which is likewise not shown in more detail for reasons of clarity. The low-voltage power system is fed by a low-voltage battery 9 , which is also monitored by the battery control device 6 , which therefore forms part of a battery management system.
[0035] Further secondary consumers, that is to say further consumers of electrical energy, are connected to the low-voltage power system in addition to the electric motor 2 of the drive, wherein purely by way of example an infotainment system 10 with an assigned control device 11 and a combination display device 12 with an assigned control device 13 are shown. In addition, the motor vehicle 1 is also provided with a navigation system 14 , to which a GPS sensor 15 is assigned. Of course, further secondary consumers are also conceivable; however, it is to be noted that the control devices 3 , 6 , 8 , 11 , 13 themselves also constitute secondary consumers which are operated via the low-voltage power system.
[0036] The various control devices and systems of the motor vehicle 1 communicate via a bus system 16 , here a CAN bus, as is generally known.
[0037] The control device 13 is now designed here to carry out the method. For this purpose, the control device 13 receives various data items about the bus system 16 , specifically route data about a route to be traveled along in future and the current position of the motor vehicle 1 from the navigation system 14 , information about the residual energy still present in the high-voltage battery 4 from the battery control device 6 and consumption values of the drive and of the secondary consumers, for example from the control devices 3 , 8 and 11 .
[0038] The consumption values are determined here by sensors (not illustrated in more detail in FIG. 1 ), for example in that the current and voltage at the input of the secondary consumer or electric motor 2 are measured, with the result that the power consumption can be determined. At this point it is also to be noted that the consumption values in the present exemplary embodiment are always considered averaged over a distance of 100 m, which means that a consumption value which is processed by the method relates to the average of a 100 m distance.
[0039] The consumption values are used to continuously update prediction values for the consumption of the drive and of the secondary consumers on a specific route length, 100 km here. This is to be explained in more detail by the illustration in FIG. 2 .
[0040] In this context the consumption values of the drive are shown as input values at 17 , the consumption values of high-voltage secondary consumers, here components of the air conditioning system 7 which are connected to the high-voltage power system, are shown at 18 , and consumption values of the other secondary consumers which are connected to the low-voltage power system are shown at 19 . It is possible to see the secondary consumers divided into two secondary consumer groups, specifically high-voltage secondary consumers and low-voltage secondary consumers.
[0041] Drive prediction values 20 a , 20 b and 20 c are derived from the consumption values 17 of the drive. This is already known in the related art; for example the procedure relating to the consumption mean values as described in DE 199 29 426 A1 can be adopted. The drive prediction values 20 a , 20 b and 20 c are assigned to various classes of route sections, for example “freeway”, “country road” and “town traffic”. The data of the navigation system 14 make it possible to determine which class the currently recorded consumption values 17 are to be assigned to. At this point it is to be noted that during the determination of secondary consumer prediction values 21 , 22 , which are determined separately, such classification is also conceivable; however, for the sake of simplicity an example is illustrated herein in which classification in this respect is not performed.
[0042] It is important for the method that a different calculation method and/or a differently parameterized calculation method is used for determining the secondary consumer prediction values 21 , 22 than for determining the drive prediction values 20 a , 20 b and 20 c . Other filters or filter characteristics can be used.
[0043] By way of example, the determination of the secondary consumer prediction value 21 for the secondary consumer group of the high-voltage consumers will firstly be explained in more detail, on the basis of the consumption values 18 . The box 23 represents the already described averaging over a specific, short distance, for example 100 m. The averaged consumption value 18 is then fed in parallel to two PT2 filters 24 , 25 . In this context, the PT2 filters 24 , 25 have different attenuation constants, as will be explained in more detail by FIG. 3 .
[0044] In FIG. 3 , firstly a profile of the consumption value plotted against the distance s traveled, consequently a time profile 27 , is shown in a first graph 26 . At one point 28 , there is clearly a jump in consumption, for example after a driver of the motor vehicle 1 has activated the air conditioning system 7 at this point 28 .
[0045] The graph 29 then shows the profile 30 which is filtered by the filter 24 with a high attenuation constant. The effect of the jump at the point 28 is clearly only extremely slow. In contrast, the profile 32 which is filtered by the filter 25 with a low attenuation constant, and which follows the original profile 27 significantly more quickly, is shown in the graph 31 .
[0046] The results of the filtering, which also, moreover, define through their parameterization the distances over which the historic consumption values 18 will have an effect, are added in a combiner 33 in a weighted fashion. The weighting takes place here as a function of the residual energy 34 in such a way that in the case of low residual energy levels the result of the filter 25 becomes more relevant, but in the case of high residual energy levels the result of the filter 24 becomes more relevant. This is due to the fact that in the case of low residual energy levels 34 , consequently in the case of low residual ranges, short-term changes in consumption can also be very relevant, with the result that it is then possible to react to them more quickly.
[0047] The result which is obtained is then the first secondary consumer prediction value 21 , which can specify, for example, how high the energy consumption is at 100 km on the basis of the profile of the consumption values 18 .
[0048] PT2 filters 35 and 36 , whose results are correspondingly combined in a combiner 37 , are also used for the group of low-voltage consumers, consumption values 19 . However, the filters 35 and 36 are parameterized differently than the filters 24 and 25 and the weighting as a function of the residual energy 34 also occurs in a different way, that is to say a differently parameterized calculation method is used. However, at this point it is also to be noted that different calculation methods, for example the use of different filters, can also be provided. Furthermore, the filters 24 , 25 , 35 and 36 do not have to be PT2 filters, but instead other filters can also be used, for example sliding mean value filters. A calculation method such as has been shown for the consumer prediction values 21 and 22 can, moreover, of course also be used in an analogous fashion, but parameterized differently, for the calculation of the drive prediction values 20 a , 20 b and 20 c.
[0049] If the current prediction values 20 a , 20 b , 20 c , 21 and 22 are then known, it is possible to determine a consumption for the route section by adding the corresponding values for a route section, combiner 38 , wherein, if appropriate, the class thereof has to be taken into account in the selection of the prediction value 20 a , 20 b or 20 c . Whenever the consumption has been predicted on the basis of the prediction values 20 a , 20 b , 20 c , 21 and 22 for a route section, this consumption is subtracted from the residual energy 34 . If this has dropped to zero, or even below zero, on a route section, the residual range 39 is determined for the corresponding route. It can then be displayed, for example, on the combination display device 12 .
[0050] Finally, it is also to be noted that it can be provided that upper limits are used for the prediction values 20 a , 20 b , 20 c , 21 and 22 in order to avoid incorrect calculations, in particular when there is little data available. In addition, it is to be noted that instead of the weighting in the combiners 33 and 37 it is alternatively or additionally also possible to change the filter parameters of the filters 25 , 24 , 35 and 36 as a function of the residual energy 34 .
[0051] The invention has been described in detail with particular reference to preferred embodiments thereof and examples, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention covered by the claims which may include the phrase “at least one of A, B and C” as an alternative expression that means one or more of A, B and C may be used, contrary to the holding in Superguide v. DIRECTV, 69 USPQ2d 1865 (Fed. Cir. 2004). | A method determines the remaining range of a motor vehicle which has an energy store for an electric motor drive which acts the wheels of the motor vehicle. Consumption values which describe the current consumption of the drive and of a secondary consumer are determined using a sensor. A drive prediction value which is assigned to the drive and describes the consumption over a predetermined distance is determined from the consumption values of the drive. A secondary consumption prediction value which is assigned to the secondary consumers and describes the consumption over a predetermined distance is determined separately from the consumption values of the secondary consumers, and the remaining range is determined for a distance which is to be travelled by the motor vehicle and is described by the route data, by taking into account the drive prediction value and the secondary consumption prediction value. | 8 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates to a process for drawing gel-spun polyethylene multi-filament yarns and to the drawn yarns produced thereby. The drawn yarns are useful in impact absorption and ballistic resistance for body armor, helmets, breast plates, helicopter seats, spall shields, and other applications; composite sports equipment such as kayaks, canoes, bicycles and boats; and in fishing line, sails, ropes, sutures and fabrics.
[0003] 2. Description of the Related Art
[0004] To place the invention in perspective, it should be recalled that polyethylene had been an article of commerce for about forty years prior to the first gel-spinning process in 1979. Prior to that time, polyethylene was regarded as a low strength, low stiffness material. It had been recognized theoretically that a straight polyethylene molecule had the potential to be very strong because of the intrinsically high carbon-carbon bond strength.
[0005] However, all then-known processes for spinning polyethylene fibers gave rise to “folded chain” molecular structures (lamellae) that inefficiently transmitted the load through the fiber and caused the fiber to be weak.
[0006] “Gel-spun” polyethylene fibers are prepared by spinning a solution of ultra-high molecular weight polyethylene (UHMWPE), cooling the solution filaments to a gel state, then removing the spinning solvent. One or more of the solution filaments, the gel filaments and the solvent-free filaments are drawn to a highly oriented state. The gel-spinning process discourages the formation of folded chain lamellae and favors formation of “extended chain” structures that more efficiently transmit tensile loads.
[0007] The first description of the preparation and drawing of UHMWPE filaments in the gel state was by P. Smith, P. J. Lemstra, B. Kalb and A. J. Pennings, Poly. Bull ., 1, 731 (1979). Single filaments were spun from 2 wt. % solution in decalin, cooled to a gel state and then stretched while evaporating the decalin in a hot air oven at 100 to 140° C.
[0008] More recent processes (see, e.g., U.S. Pat. Nos. 4,551,296, 4,663,101, and 6,448,659) describe drawing all three of the solution filaments, the gel filaments and the solvent-free filaments. A process for drawing high molecular weight polyethylene fibers is described in U.S. Pat. No. 5,741,451. The disclosures of these patents are hereby incorporated by reference to the extent not incompatible herewith.
[0009] Although gel-spinning processes tend to produce fibers that are free of lamellae with folded chain surfaces, nevertheless the molecules in gel-spun UHMWPE fibers are not free of gauche sequences as can be demonstrated by infra-red and Raman spectrographic methods. The gauche sequences are kinks in the zig-zag polyethylene molecule that create dislocations in the orthorhombic crystal structure. The strength of an ideal extended chain polyethylene fiber with all trans —(CH 2 )n— sequences has been variously calculated to be much higher than has presently been achieved. While fiber strength and multi-filament yarn strength are dependent on a multiplicity of factors, a more perfect polyethylene fiber structure, consisting of molecules having longer runs of straight chain all trans sequences, is expected to exhibit superior performance in a number of applications such as ballistic protection materials.
[0010] A need exists for gel-spun multi-filament UHMWPE yarns having increased perfection of molecular structure. One measure of such perfection is longer runs of straight chain all trans —(CH 2 )n— sequences as can be determined by Raman spectroscopy. Another measure is a greater “Parameter of Intrachain Cooperativity of the Melting Process” as can be determined by differential scanning calorimetry (DSC). Yet another measure is the existence of two orthorhombic crystalline components as can be determined by x-ray diffraction. It is among the objectives of this invention to provide methods to produce such yarns by drawing, and the yarns so produced.
SUMMARY OF THE INVENTION
[0011] The invention comprises a process for drawing a gel-spun multi-filament yarn comprising the steps of:
[0012] a) forming a gel-spun polyethylene multi-filament feed yarn comprising a polyethylene having an intrinsic viscosity in decalin at 135° C. of from about 5 dl/g to 35 dl/g, fewer than about two methyl groups per thousand carbon atoms, and less than about 2 wt. % of other constituents;
[0013] b) passing the feed yarn at a speed of V 1 meters/minute into a forced convection air oven having a yarn path length of L meters, wherein one or more zones are present along the yarn path having zone temperatures from 130° C. to 160° C.;
[0014] c) passing the feed yarn continuously through the oven and out of the oven at an exit speed of V 2 meters/minute wherein the following equations 1 to 4 are satisfied
[0000] 0.25≦ L/V 1 ≦20, min Eq. 1
[0000] 3≦ V 2 / V 1 ≦20 Eq. 2
[0000] 1.7≦( V 2 −V 1 )/L≦60, min −1 Eq. 3
[0000] 0.20≦2 L /( V 1 +V 2 )≦10, min. Eq. 4
[0015] The invention is also a novel polyethylene multi-filament yarn comprising a polyethylene having an intrinsic viscosity in decalin at 135° C. of from about 5 dl/g to 35 dl/g, fewer than about two methyl groups per thousand carbon atoms, and less than about 2 wt. % of other constituents, the multi-filament yarn having a tenacity of at least 17 g/d as measured by ASTM D2256-02, wherein filaments of the yarn have a peak value of the ordered-sequence length distribution function F(L) at a straight chain segment length L of at least 35 nanometers as determined at 23° C. from the low frequency Raman band associated with the longitudinal acoustic mode (LAM-1).
[0016] In another embodiment, the invention is a novel polyethylene multi-filament yarn comprising a polyethylene having an intrinsic viscosity in decalin at 135° C. of from about 5 dl/g to 35 dl/g, fewer than about two methyl groups per thousand carbon atoms, and less than about 2 wt. % of other constituents, the multi-filament yarn having a tenacity of at least 17 g/d as measured by ASTM D2256-02, wherein filaments of the yarn have a value of the “Parameter of Intrachain Cooperativity of the Melting Process”, v, of at least about 535.
[0017] In yet another embodiment, the invention is a novel polyethylene multi-filament yarn comprising a polyethylene having an intrinsic viscosity in decalin at 135° C. of from about 5 dl/g to 35 dl/g, fewer than about two methyl groups per thousand carbon atoms, and less than about 2 wt. % of other constituents, the multi-filament yarn having a tenacity of at least 17 g/d as measured by ASTM D2256-02, wherein the intensity of the (002) x-ray reflection of one the filament of the yarn, measured at room temperature and under no load, shows two distinct peaks.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 is the low frequency Raman spectrum and extracted LAM-1 spectrum of filaments of a commercially available gel-spun multi-filament UHMWPE yarn (SPECTRA® 900 yarn).
[0019] FIG. 2( a ) is a plot of the ordered sequence length distribution function F(L) determined from the LAM-1 spectrum of FIG. 1 .
[0020] FIG. 2( b ) is a plot of the ordered sequence length distribution function F(L) determined from the LAM-1 spectrum of a commercially available gel-spun multi-filament UHMWPE yarn (SPECTRA® 1000 yarn).
[0021] FIG. 2( c ) is a plot of the ordered sequence length distribution function F(L) determined from the LAM-1 spectrum of filaments of the invention.
[0022] FIG. 3 shows differential scanning calorimetry (DSC) scans at heating rates of 0.31, 0.62 and 1.25° K/min of a 0.03 mg filament segment taken from a multi-filament yarn of the invention chopped into pieces of 5 mm length and wrapped in parallel array in a Wood's metal foil and placed in an open sample pan.
[0023] FIG. 4 shows an x-ray pinhole photograph of a single filament taken from multi-filament yarn of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0024] In one embodiment, the invention comprises a process for drawing a gel-spun multi-filament yarn comprising the steps of:
[0025] a) forming a gel-spun polyethylene multi-filament feed yarn comprising a polyethylene having an intrinsic viscosity in decalin at 135° C. of from about 5 dl/g to 35 dl/g, fewer than about two methyl groups per thousand carbon atoms, and less than about 2 wt. % of other constituents;
[0026] b) passing the feed yarn at a speed of V 1 meters/minute into a forced convection air oven having a yarn path length of L meters, wherein one or more zones are present along the yarn path having zone temperatures from about 130° C. to 160° C.;
[0027] c) passing the feed yarn continuously through the oven and out of the oven at an exit speed of V 2 meters/minute wherein the following equations 1 to 4 are satisfied
[0000] 0.25≦ L/V 1 ≦20, min Eq. 1
[0000] 3≦ V 2 /V 1 ≦20 Eq. 2
[0000] 1.7≦(V 2 −V 1 )/L≦60, min −1 Eq. 3
[0000] 0.20≦2 L/(V 1 +V 2 )≦10, min. Eq. 4
[0028] For purposes of the present invention, a fiber is an elongate body the length dimension of which is much greater than the transverse. dimensions of width and thickness. Accordingly, “fiber” as used herein includes one, or a plurality of filaments, ribbons, strips, and the like having regular or irregular cross-sections in continuous or discontinuous lengths. A yarn is an assemblage of continuous or discontinuous fibers.
[0029] Preferably, the multi-filament feed yarn to be drawn comprises a polyethylene having an intrinsic viscosity in decalin of from about 8 to 30 dl/g, more preferably from about 10 to 25 dl/g, and most preferably from about 12 to 20 dl/g. Preferably, the multi-filament yarn to be drawn comprises a polyethylene having fewer than about one methyl group per thousand carbon atoms, more preferably fewer than 0.5 methyl groups per thousand carbon atoms, and less than about 1 wt. % of other constituents.
[0030] The gel-spun polyethylene multi-filament yarn to be drawn in the process of the invention may have been previously drawn, or it may be in an essentially undrawn state. The process for forming the gel-spun polyethylene feed yarn can be one of the processes described by U.S. Pat. Nos. 4,551,296, 4,663,101, 5,741,451, and 6,448,659.
[0031] The tenacity of the feed yarn may range from about 2 to 76, preferably from about 5 to 66, more preferably from about 7 to 51, grams per denier (g/d) as measured by ASTM D2256-97 at a gauge length of 10 inches (25.4 cm) and at a strain rate of 100%/min.
[0032] It is known that gel-spun polyethylene yarns may be drawn in an oven, in a hot tube, between heated rolls, or on a heated surface. WO 02/34980 A1 describes a particular drawing oven. We have found that drawing of gel-spun UHMWPE multi-filament yarns is most effective and productive if accomplished in a forced convection air oven under narrowly defined conditions. It is necessary that one or more temperature-controlled zones exist in the oven along the yarn path, each zone having a temperature from about 130° C. to 160° C. Preferably the temperature within a zone is controlled to vary less than ±2° C. (a total less than 4° C.), more preferably less than ±1° C. (a total less than 2° C.).
[0033] The yarn will generally enter the drawing oven at a temperature lower than the oven temperature. On the other hand, drawing of a yarn is a dissipative process generating heat. Therefore to quickly heat the yarn to the drawing temperature, and to maintain the yarn at a controlled temperature, it is necessary to have effective heat transmission between the yarn and the oven air. Preferably, the air circulation within the oven is in a turbulent state. The time-averaged air velocity in the vicinity of the yarn is preferably from about 1 to 200 meters/min, more preferably from about 2 to 100 meters/min, most preferably from about 5 to 100 meters/min.
[0034] The yarn path within the oven may be in a straight line from inlet to outlet. Alternatively, the yarn path may follow a reciprocating (“zig-zag”) path, up and down, and/or back and forth across the oven, around idler rolls or internal driven rolls. It is preferred that the yarn path within the oven is a straight line from inlet to outlet.
[0035] The yarn tension profile within the oven is adjusted by controlling the drag on idler rolls, by adjusting the speed of internal driven rolls, or by adjusting the oven temperature profile. Yarn tension may be increased by increasing the drag on idler rolls, increasing the difference between the speeds of consecutive driven rolls or decreasing oven temperature. The yarn tension within the oven may follow an alternating rising and falling profile, or it may increase steadily from inlet to outlet, or it may be constant. Preferably, the yarn tension everywhere within the oven is constant neglecting the effect of air drag, or it increases through the oven. Most preferably, the yarn tension everywhere within the oven is constant neglecting the effect of air drag.
[0036] The drawing process of the invention provides for drawing multiple yarn ends simultaneously. Typically, multiple packages of gel-spun polyethylene yarns to be drawn are placed on a creel. Multiple yarns ends are fed in parallel from the creel through a first set of rolls that set the feed speed into the drawing oven, and thence through the oven and out to a final set of rolls that set the yarn exit speed and also cool the yarn to room temperature under tension. The tension in the yarn during cooling is maintained sufficient to hold the yarn at its drawn length neglecting thermal contraction.
[0037] The productivity of the drawing process may be measured by the weight of drawn yarn that can be produced per unit of time per yarn end. Preferably, the productivity of the process is more than about 2 grams/minute per yarn end, more preferably more than about 4 grams/minute per yarn end.
[0038] In another embodiment, the invention is a novel polyethylene multi-filament yarn comprising a polyethylene having an intrinsic viscosity in decalin at 135° C. of from 5 dl/g to 35 dl/g, fewer than two methyl groups per thousand carbon atoms, and less than 2 wt. % of other constituents, the multi-filament yarn having a tenacity of at least 17 g/d as measured by ASTM D2256-02, wherein filaments of the yarn have a peak value of the ordered-sequence length distribution function F(L) at a straight chain segment length L of at least 40 nanometers as determined at 23° C. from the low frequency Raman band associated with the longitudinal acoustic mode (LAM-1).
[0039] In yet another embodiment, the invention is a novel polyethylene multi-filament yarn comprising a polyethylene having an intrinsic viscosity in decalin at 135° C. of from 5 dl/g to 35 dl/g, fewer than two methyl groups per thousand carbon atoms, and less than 2 wt. % of other constituents, the multi-filament yarn having a tenacity of at least 17 g/d as measured by ASTM D2256-02, wherein filaments of the yarn have a value of the “Parameter of Intrachain Cooperativity of the Melting Process”, v, of at least 535.
[0040] In a further embodiment, the invention is a novel polyethylene multi-filament yarn comprising a polyethylene having an intrinsic viscosity in decalin at 135° C. of from about 5 dl/g to 35 dl/g, fewer than about two methyl groups per thousand carbon atoms, and less than about 2 wt. % of other constituents, the multi-filament yarn having a tenacity of at least 17 g/d as measured by ASTM D2256-02, wherein the intensity of the (002) x-ray reflection of one filament of the yarn, measured at room temperature and under no load, shows two distinct peaks.
[0041] Preferably, a polyethylene yarn of the invention has an intrinsic viscosity in decalin at 135° C. of from about 7 dl/g to 30 dl/g, fewer than about one methyl group per thousand carbon atoms, less than about 1 wt. % of other constituents, and a tenacity of at least 22 g/d.
Measurement Methods
1. Raman Spectroscopy
[0042] Raman spectroscopy measures the change in the wavelength of light that is scattered by molecules. When a beam of monochromatic light traverses a semi-transparent material, a small fraction of the light is scattered in directions other than the direction of the incident beam. Most of this scattered light is of unchanged frequency. However, a small fraction is shifted in frequency from that of the incident light. The energies corresponding to the Raman frequency shifts are found to be the energies of rotational and vibrational quantum transitions of the scattering molecules. In semi-crystalline polymers containing all-trans sequences, the longitudinal acoustic vibrations propagate along these all-trans segments as they would along elastic rods. The chain vibrations of this kind are called longitudinal acoustic modes (LAM), and these modes produce specific bands in the low frequency Raman spectra. Gauche sequences produce kinks in the polyethylene chains that delimit the propagation of acoustic vibrations. It will be understood that in a real material a statistical distribution exists of the lengths of all-trans segments. A more perfectly ordered material will have a distribution of all-trans segments different from a less ordered material. An article titled, “Determination of the Distribution of Straight-Chain Segment Lengths in Crystalline Polyethylene from the Raman LAM-1 Band”, by R.G. Snyder et al, J. Poly. Sci. Poly. Phys. Ed., 16, 1593-1609 (1978) describes the theoretical basis for determination of the ordered-sequence length distribution function, F(L) from the Raman LAM-1 spectrum.
[0043] F(L) is determined as follows: Five or six filaments are withdrawn from the multi-filament yarn and placed in parallel alignment abutting one another on a frame such that light from a laser can be directed along and through this row of fibers perpendicular to their length dimension. The laser light should be substantially attenuated on passing sequentially through the fibers. The vector of light polarization is collinear with the fiber axis, (XX light polarization).
[0044] Spectra are measured at 23° C. on a spectrometer capable of detecting the Raman spectra within a few wave numbers (less than about 4 cm −1 ) of the exciting light. An example of such a spectrometer is the SPEX Industries, Inc, Metuchen, N.J., Model RAMALOG® 5, monochromator spectrometer using a He—Ne laser. The Raman spectra are recorded in 90° geometry, i.e., the scattered light is measured and recorded at an angle of 90 degrees to the direction of incident light. To exclude the contribution of the Rayleigh scattering, a background of the LAM spectrum in the vicinity of the central line must be subtracted from the experimental spectrum. The background scattering is fitted to a Lorentzian function of the form given by Eq. 5 using the initial part of the Raman scattering data, and the data in the region 30-60 cm −1 where there is practically no Raman scattering from the samples, but only background scattering.
[0000]
f
(
x
)
)
-
H
4
·
(
x
-
x
0
w
)
2
+
1
Eq
.
5
[0045] where: x 0 is the peak position
[0046] H is the peak height
[0047] w is the full width at half maximum
[0048] Where the Raman scattering is intense near the central line in the region from about 4 cm −1 to about 6 cm −1 , it is necessary to record the Raman intensity in this frequency range on a logarithmic scale and match the intensity recorded at a frequency of 6 cm −1 to that measured on a linear scale. The Lorentzian function is subtracted from each separate recording and the extracted LAM spectrum is spliced together from each portion.
[0049] FIG. 1 ( a ) shows the measured Raman spectra for a fibermaterial to be described below and the method of subtraction of the background and the extraction of the LAM spectrum.
[0050] The LAM-1 frequency, is inversely related to the straight chain length, L as expressed by Eq. 6.
[0000]
L
=
1
2
c
ω
L
(
Eg
c
ρ
)
1
2
Eq
.
6
[0051] where: c is the velocity of light, 3×10 10 cm/sec
[0052] ω L is the LAM-1 frequency, cm −1
[0053] E is the elastic modulus of a polyethylene molecule, g(f)/cm 2
[0054] ρ is the density of a polyethylene crystal, g(m)/cm 3
[0055] g c is the gravitational constant 980 (g(m)-cm)/((g(f)-sec 2 )
[0056] For the purposes of this invention, the elastic modulus E, is taken as 340 GPa as reported by Mizushima et al., J. Amer. Chem., Soc. 71, 1320 (1949). The quantity (g c E/ρ) 1/2 is the sonic velocity in an all trans polyethylene crystal. Based on an elastic modulus of 340 GPa, and a crystal density of 1.000 g/cm 3 , the sonic velocity is 1.844×10 6 cm/sec. Making that substitution in Eq. 6, the relationship between the straight chain length and the LAM-1 frequency as used herein is express by Eq. 7.
[0000]
L
=
307.3
ω
L
,
nanometers
Eq
.
7
[0057] The “ordered-sequence length distribution function”, F(L), is calculated from the measured Raman LAM-1 spectrum by means of Eq. 8.
[0000]
F
(
L
)
=
[
1
-
exp
(
-
hc
ω
L
kT
)
ω
L
2
I
ω
]
,
arbitrary
units
Eq
.
8
[0058] where: h is Plank's constant, 6.6238×10 −27 erg-cm
[0059] k is Boltzmann's constant, 1.380×10 −16 erg/° K
[0060] I ω is the intensity of the Raman spectrum at frequency ω L , arbitrary units
[0061] T is the absolute temperature, ° K
[0062] and the other terms are as previously defined.
[0063] Plots of the ordered-sequence length distribution function, F(L), derived from the Raman LAM-1 spectra for three polyethylene samples to be described below are shown in FIGS. 2( a ), 2 ( b ) and 2 ( c ).
[0064] Preferably, a polyethylene yarn of the invention is comprised of filaments for which the peak value of F(L) is at a straight chain segment length L of at least 45 nanometers as determined at 23° C. from the low frequency Raman band associated with the longitudinal acoustic mode (LAM-1). The peak value of F(L) preferably is at a straight chain segment length L of at least 50 nanometers, more preferably at least 55 nanometers, and most preferably 50-150 nanometers.
2. Differential Scanning Calorimetry (DSC)
[0065] It is well known that DSC measurements of UHMWPE are subject to systematic errors cause by thermal lags and inefficient heat transfer. To overcome the potential effect of such problems, for the purposes of the invention the DSC measurements are carried out in the following manner. A filament segment of about 0.03 mg mass is cut into pieces of about 5 mm length. The cut pieces are arranged in parallel array and wrapped in a thin Wood's metal foil and placed in an open sample pan. DSC measurements of such samples are made for at least three different heating rates at or below 2° K/min and the resulting measurements of the peak temperature of the first polyethylene melting endotherm are extrapolated to a heating rate of 0° K/min.
[0066] A “Parameter of Intrachain Cooperativity of the Melting Process”, represented by the Greek letter v, has been defined by V. A. Bershtein and V. M. Egorov, in “Differential Scanning Calorimetry of Polymers: Physics, Chemistry, Analysis, Technology”. P. 141-143, Tavistoc/Ellis Horwod, 1993. This parameter is a measure of the number of repeating units, here taken as (—CH 2 —CH 2 —), that cooperatively participate in the melting process and is a measure of crystallite size.
[0067] Higher values of v indicate longer crystalline sequences and therefore a higher degree of order. The “Parameter of Intrachain Cooperativity of the Melting Process” is defined herein by Eq. 9.
[0000]
ν
=
2
R
T
m
1
2
Δ
T
m
1
·
Δ
H
0
,
dimensionless
Eq
.
9
[0068] where: R is the gas constant, 8.31 J/° K-mol
[0069] T m1 is the peak temperature of the first polyethylene melting
endotherm at a heating rate extrapolated to 0° K/min, ° K
[0071] 66 T m1 is the width of the first polyethylene melting endotherm, ° K
[0072] ΔH 0 is the melting enthalpy of —CH 2 —CH 2 — taken as 8200 J/mol
[0073] The multi-filament yarns of the invention are comprised of filaments having a “Parameter of Intrachain Cooperativity of the Melting Process”, v, of at least 535, preferably at least 545, more preferably at least 555, and most preferably from 545 to 1100.
3. X-Ray Diffraction
[0074] A synchrotron is used as a source of high intensity x-radiation. The synchrotron x-radiation is monochromatized and collimated. A single filament is withdrawn from the yarn to be examined and is placed in the monochromatized and collimated x-ray beam. The x-radiation scattered by the filament is detected by electronic or photographic means with the filament at room temperature (˜23° C.) and under no external load. The position and intensity of the (002) reflection of the orthorhombic polyethylene crystals are recorded. If upon scanning across the (002) reflection, the slope of scattered intensity versus scattering angle changes from positive to negative twice, i.e., if two peaks are seen in the (002) reflection, then two orthorhombic crystalline phases exist within the fiber.
[0075] The following examples are presented to provide a more complete understanding of the invention. The specific techniques, conditions, materials, proportions and reported data set forth to illustrate the principles of the invention are exemplary and should not be construed as limiting the scope of the invention.
EXAMPLES
Comparative Example 1
[0076] An UHMWPE gel-spun yarn designated SPECTRA® 900 was manufactured by Honeywell International Inc. in accord with U.S. Pat. No. 4,551,296. The 650 denier yarn consisting of 60 filaments had an intrinsic viscosity in decalin at 135° C. of about 15 dl/g. The yarn tenacity was about 30 g/d as measured by ASTM D2256-02, and the yarn contained less than about 1 wt. % of other constituents. The yarn had been stretched in the solution state, in the gel state and after removal of the spinning solvent. The stretching conditions did not fall within the scope of equations 1 to 4 of the present invention.
[0077] Filaments of this yarn were characterized by Raman spectroscopy using a Model RAMALOG® 5, monochromator spectrometer made by SPEX Industries, Inc., Metuchen, N.J., using a He—Ne laser and the methodology described herein above. The measured Raman spectrum, 1 . and the extracted LAM-1 spectrum for this material, 3 , after subtraction of the Lorenzian, 2 , fitted to the Rayleigh background scattering are shown in FIG. 1( a ). The ordered-sequence length distribution function, F(L), for this material determined from the LAM-1 spectrum and equations 7 and 8 is shown in FIG. 2( a ). The peak value of the ordered-sequence length distribution function, F(L), was at a straight chain segment length L of approximately 12 nanometers (Table I).
[0078] Filaments of this yarn were also characterized by DSC using the methodology described hereinabove. The peak temperature of the first polyethylene melting endotherm at a heating rate extrapolated to 0° K/min. was 415.4° K. The width of the first polyethylene melting endotherm was 0.9° K. The “Parameter of Intrachain Cooperativity of the Melting Process”, V, determined from Eq. 9 was 389 (Table I).
[0079] A single filament taken from this yarn was examined by x-ray diffraction using the methodology described hereinabove. Only one peak was seen in the (002) reflection (Table 1).
Comparative Example 2
[0080] An UHMWPE gel-spun yarn designated SPECTRA® 1000 was manufactured by Honeywell International Inc. in accord with U.S. Pat. Nos. 4,551,296 and 5,741,451. The 1300 denier yarn consisting of 240 filaments had an intrinsic viscosity in decalin at 135° C. of about 14 dl/g. The yarn tenacity was about 35 g/d as measured by ASTM D2256-02, and the yarn contained less than 1 wt. % of other constituents. The yarn had been stretched in the solution state, in the gel state and after removal of the spinning solvent. The stretching conditions did not fall within the scope of equations 1 to 4 of the present invention.
[0081] Filaments of this yarn were characterized by Raman spectroscopy using a Model RAMALOG® 5, monochromator spectrometer made by SPEX Industries, Inc., Metuchen, N.J. using a He—Ne laser and the methodology described hereinabove. The ordered-sequence length distribution function, F(L), for this material determined from the LAM-1 spectrum and equations 7 and 8 is shown in FIG. 2( b ). The peak value of the ordered-sequence length distribution function, F(L), was at a straight chain segment length L of approximately 33 nanometers (Table I).
[0082] Filaments of this yarn were also characterized by DSC using the methodology described hereinabove. The peak temperature of the first polyethylene melting endotherm at a heating rate extrapolated to 0° K/min, was 415.2° K. The width of the first polyethylene melting endotherm was 1.3° K. The “Parameter of Intrachain Cooperativity of the Melting Process”, v, determined from Eq. 9 was 466 (Table I).
[0083] A single filament taken from this yarn was examined by x-ray diffraction using the methodology described hereinabove. Only one peak was seen in the (002) reflection (Table 1).
Comparative Examples 3-7
[0084] UHMWPE gel spun yarns from different lots manufactured by Honeywell International Inc. and designated either SPECTRA® 900 or SPECTRA° 1000 were characterized by Raman spectroscopy, DSC, and x-ray diffraction using the methodologies described hereinabove. The description of the yarns and the values of F(L) and v are listed in Table I as well as the number of peaks seen in the (002) x-ray reflection.
Example of the Invention
[0085] An UHMWPE gel spun yarn was produced by Honeywell International Inc. in accord with U.S. Pat. No. 4,551,296. The 2060 denier yarn consisting of 120 filaments had an intrinsic viscosity in decalin at 135° C. of about 12 dl/g. The yarn tenacity was about 20 g/d as measured by ASTM D2256-02, and the yarn contained less than about 1 wt. % of other constituents. The yarn had been stretched between 3.5 and 8 to 1 in the solution state, between 2.4 to 4 to 1 in the gel state and between 1.05 and 1.3 to 1 after removal of the spinning solvent.
[0086] The yarn was fed from a creel, through a set of restraining rolls at a speed (V 1 ) of about 25 meters/min into a forced convection air oven in which the internal temperature was 155±1° C. The air circulation within the oven was in a turbulent state with a time-averaged velocity in the vicinity of the yarn of about 34 meters/min.
[0087] The feed yarn passed through the oven in a straight line from inlet to outlet over a path length (L) of 14.63 meters and thence to a second set of rolls operating at a speed (V 2 ) of 98.8 meters/min. The yarn was cooled down on the second set of rolls at constant length neglecting thermal contraction. The yarn was thereby drawn in the oven at constant tension neglecting the effect of air drag. The above drawing conditions in relation to Equations 1-4 were as follows:
[0000] 0.25 [L/V 1 =0.59]≦20, min Eq. 1
[0000] 3≦ [V 2 /V 1 =3.95]≦20 Eq. 2
[0000] 1.7≦[( V 2 −V 1 )/ L= 5.04]≦60, min −1 Eq. 3
[0000] 0.20≦[2 L/(V 1 +V 2 )=0.24]≦10, min Eq. 4
[0088] Hence, each of Equations 1-4 was satisfied.
[0089] The denier per filament (dpf) was reduced from 17.2 dpf for the feed yarn to 4.34 dpf for the drawn yarn. Tenacity was increased from 20 g/d for the feed yarn to about 40 g/d for the drawn yarn. The mass throughput of drawn yarn was 5.72 grams/min per yarn end.
[0090] Filaments of this yarn produced by the process of the invention were characterized by Raman spectroscopy using a Model RAMALOG® 5, monochromator spectrometer made by SPEX Industries, Inc., Metuchen, N.J., using a He—Ne laser and the methodology described hereinabove. The ordered-sequence length distribution function, F(L), for this material determined from the LAM-1 spectrum and equations 7 and 8 is shown in FIG. 2( c ). The peak value of the ordered-sequence length distribution function, F(L), was at a straight chain segment length L of approximately 67 nanometers (Table I).
[0091] Filaments of this yarn were also characterized by DSC using the methodology described hereinabove. DSC scans at heating rates of 0.31° K/min, 0.62° K/min, and 1.25° K/min are shown in FIG. 3 . The peak temperature of the first polyethylene melting endotherm at a heating rate extrapolated to 0° K/min, was 416.1° K. The width of the first polyethylene melting endotherm was 0.6° K. The “Parameter of Intrachain Cooperativity of the Melting Process”, v, determined from Eq. 9 was 585 (Table I).
[0092] A single filament taken from this yarn was examined by x-ray diffraction using the methodology described hereinabove. An x-ray pinhole photograph of the filament is shown in FIG. 4 . Two peaks were seen in the (002) reflection.
[0000]
TABLE I
L, nm
No. of
Ex. or
at
ν,
(002)
Comp.
Identi-
Denier/
peak
dimension-
X-Ray
Ex. No.
fication
Fils
of F(L)
less
Peaks
Comp.
SPECTRA ®
650/60
12
389
1
Ex. 1
900 yarn
Comp.
SPECTRA ®
1300/240
33
466
1
Ex. 2
1000 yarn
Comp.
SPECTRA ®
650/60
28
437
1
Ex. 3
900 yarn
Comp.
SPECTRA ®
1200/120
19
387
1
Ex. 4
900 yarn
Comp.
SPECTRA ®
1200/120
20
409
1
Ex. 5
900 yarn
Comp.
SPECTRA ®
1200/120
24
435
1
Ex. 6
900 yarn
Comp.
SPECTRA ®
1300/240
17
467
1
Ex. 7
1000 yarn
Example
Inventive
521/120
67
585
2
Fiber
[0093] It is seen that filaments of the yarn of the invention had a peak value of the ordered-sequence length distribution function, F(L), at a straight chain segment length, L, greater than the prior art yarns. It is also seen that filaments of the yarn of the invention had a “Parameter of Intrachain Cooperativity of the Melting Process”, v, greater than the prior art yarns. Also, this appears to be the first observation of two (002) x-ray peaks in a polyethylene filament at room temperature under no load.
[0094] Having thus described the invention in rather full detail, it will be understood that such detail need not be strictly adhered to but that further changes and modifications may suggest themselves to one skilled in the art, all failing with the scope of the invention as defined by the subjoined claims. | Gel-spun multi-filament polyethylene yarns possessing a high degree of molecular and crystalline order, and to the drawing methods by which they are produced. The drawn yarns are useful in impact absorption and ballistic resistance for body armor, helmets, breast plates, helicopter seats, spall shields, and other applications; composite sports equipment such as kayaks, canoes, bicycles and boats; and in fishing line, sails. ropes, sutures and fabrics. | 3 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a cutting tool of a cutting machine having a base element and a chisel holder, wherein the chisel holder has a plug-in shoulder which is retained in a plug-in receptacle of the base element, and wherein the plug-in receptacle is spatially connected with its surroundings via one or several openings.
2. Discussion of Related Art
A cutting tool is known from German Patent Reference DE 43 22 401 C2. The cutting tool contains a chisel holder and a base element which is fastened to a cylinder-shaped cutting body of a cutting machine. For fastening the chisel holder on the base element, the base element has a plug-in receptacle with a V-guide, into which a plug-in shoulder of the chisel holder can be pushed. The chisel holder is fixed in place using a pressure screw. Thus the exact positioning of the chisel holder has particular importance, also in case of repeated assembly/disassembly and exchange.
For absorbing the forces occurring during the operation, the base element has a stop, on which the chisel holder is supported. So that the effects of the stop are maintained and stress on the plug-in shoulder and the plug-in receptacle is prevented to the greatest extent possible, the chisel holder is arranged offset by an adjusting space in the area around the plug-in receptacle.
It is disadvantageous in connection with such cutting tools which are employed, for example, in road construction, that the pulverized rock and water penetrate the area of the plug-in shoulder and the plug-in receptacle. Pulverized rock and water can cause the plug-in shoulder, as well as the pressure screw, to become caught in the plug-in receptacle. Thus, the chisel holder can only be released from the base element with increased effort. Often the parts are damaged during forcible separation, which results in a more cost-intensive replacement. Also, the pulverized rock results in increased wear in this area, which leads to reduced service life and therefore to higher operating costs. While releasing the pressure screw, dirt which becomes caught on the pressure screw from the interior, is worked into the threaded receptacle of the base element and damages it. A repair or replacement of the base element which must occur then can only be performed with added outlay, because customarily the base element is welded to the cutting cylinder tube and the adjacent base elements.
Dirt on the plug-in shoulder of the chisel holder and in the area of the plug-in receptacle of the base element is particularly disadvantageous. The particles adhering there are shattered during subsequent operation of the machine. Play is then created between the plug-in shoulder and the plug-in receptacle. The exactly fitted positioning of the chisel holder is then no longer assured. This has a negative effect, in particular during so-called fine milling. This method, which is gaining importance in actual use, is used to mill road surfaces to their final quality in one processing step. A prerequisite for this is that the chisel holders are exactly positioned. If one chisel holder does not meet these criteria, it causes a wrong spot in the milling pattern, which has an effect on the total result. Thus, a chisel holder which is seated loosely in the base element can decisively worsen the milling quality. Also, the loosely seated chisel can become completely separated from the base element and seriously damage the tool.
SUMMARY OF THE INVENTION
It is one object of this invention to provide a cutting tool of the type mentioned above but wherein the service life of the tool, in particular of the base element, is improved.
This object is achieved if at least one of the openings is at least partially closed by a sealing element.
The sealing element protects the transition area of the plug-in receptacle formed between the plug-in shoulder and the base element. It prevents the penetration of the plug-in receptacle by removed material and water in a simple and effective way. Once the chisel holder reaches its worn state, it can be pulled out of the plug-in receptacle. The reception chamber formed by the plug-in receptacle remains clean and substantially free of dirt. It is possible to position and fasten a fresh chisel holder with little loss of time. Thus, the sealing element forms a simple component, which permits a more effective tool change, and at the same time substantially increases the service life of the base element. The sealing element can also be formed by a grease layer.
Depending on the shape and arrangement of the sealing element, a reproducible and exactly fitting position of the chisel holder is possible.
In accordance with a preferred embodiment of this invention, the sealing element is arranged around the plug-in receptacle, at least in some areas between the chisel holder and the base element. With this an area is protected through which often massive amounts of dirt can enter.
Particularly effective sealing is achieved if the sealing element is embodied as a molded element having the contour of the circumference of the plug-in shoulder of the chisel holder. The design is particularly installation-friendly, because the sealing element can be placed on the plug-in shoulder of the chisel holder for mounting and can then be installed in the base element together with the chisel holder.
Because the base element has a circumferential bezel around the plug-in receptacle, which is used as a seat for the sealing element, the sealing element is immovably seated during operations. Also, the bezel provides the space into which the sealing element is definitely pressed when mounting without a possibility of being destroyed. An optimal sealing effect is thus achieved.
Permanent sealing of the area to be protected is achieved if the sealing element is made of a permanently elastic material, preferably of silicon, or of a thermoplastic elastomer.
In one embodiment, the chisel holder rests with its stop against the stop of the base element, the base element has a shoulder extending at an angle relative to the stop, a clearance acting as an adjusting space is formed between the shoulder of the base element and the side of the chisel holder facing the shoulder, and the sealing element is shaped so that it bridges this clearance. With this arrangement, pulverized rock and water cannot penetrate the plug-in receptacle through the adjustment space.
A particularly easy assembly and assured sealing effects are achieved if the sealing element is angled in a manner corresponding to the angle between the shoulder and the stop of the base element.
Good sealing of the different gap widths in the area of the stop and the adjustment space can be achieved if the sealing element has a section of an O-shaped cross section, which rests at least in part against the stop of the base element and has a section which is angled off relative to the base element, which rests against the shoulder of the base element and has a thickened cross section which bridges the clearance, at least partially.
In one embodiment, the angled-off section has a wedge-shaped sealing lip, which is matched to the shape of the adjustment space. Unevenness and production tolerances of the chisel holder and the base element are thus compensated.
A cost-effective manufacture, even in large numbers, as well as narrow tolerance and a design matched to the production process, are made possible if the sealing element is embodied as an injection-molded element, and the sprue nose is arranged in an area of or near the cross section which is thickened corresponding to the clearance. With this arrangement, the sprue nose does not hamper the sealing effect of the sealing element.
A simple and exactly fitting mounting of the chisel holder on the base element is achieved if the sealing element is drawn as a separate plastic component on the plug-in shoulder, or if the sealing element is injection-molded on the plug-in shoulder as a plastic component.
In one embodiment of this invention, the chisel holder of the cutting tool has a plug-in shoulder formed on a base body and the plug-in shoulder has a sealing element extending around the plug-in shoulder in at least partial areas of its outer circumference. Thus it is possible to preform the chisel holder with the plug-in shoulder and the sealing element as a structural unit, to stock it as a unit and to install it quickly and cost-effectively as a replacement part.
BRIEF DESCRIPTION OF THE DRAWINGS
This invention is explained in greater detail in view of exemplary embodiments represented in the drawings, wherein:
FIG. 1 is a lateral sectional view of a cutting tool with an exchangeable chisel holder in a partially assembled state;
FIG. 2 is a lateral sectional view of the cutting tool in accordance with FIG. 1 but with the chisel holder inserted;
FIG. 3 a is a sealing element in a top view; and
FIG. 3 b shows the sealing element in accordance with FIG. 3 a , in a lateral view.
DESCRIPTION OF PREFERRED EMBODIMENTS
The cutting tool ( 1 ) in FIG. 1 comprises a base element ( 20 ), into which an exchangeable chisel holder ( 10 ) can be inserted. The cutting tool ( 1 ) has a sealing element ( 30 ) and a pressure screw ( 40 ), which is used for fixing the chisel holder ( 10 ) in place in the base element ( 20 ).
The chisel holder ( 10 ) includes a base body ( 17 ) and on its lower end has a plug-in shoulder ( 15 ), which can be inserted into a corresponding plug-in receptacle ( 22 ) at the base element ( 20 ). The insertion movement of the chisel holder ( 10 ) into the base element ( 20 ) is limited in its rear area by a stop ( 11 ) at the chisel holder ( 10 ) and by a stop ( 24 ) on the base element ( 20 ) located opposite it. On its front edge, the plug-in shoulder ( 15 ) has at least one guide face ( 15 . 1 ), which is guided during insertion of the chisel holder ( 10 ) by a corresponding V-guide ( 22 . 1 ) in the plug-in receptacle ( 22 ).
Also, the chisel holder ( 10 ) has a chisel receptacle ( 12 ), into which a turning chisel, which is also easy to exchange, can be inserted. The longitudinal axis of the chisel receptacle ( 12 ) forms an acute angle with respect to the axis of the plug-in shoulder ( 15 ).
A sealing element ( 30 ) is drawn on the plug-in shoulder ( 15 ) which contour is matched to the prism-shaped cross-section of the plug-in receptacle ( 22 ) with its guide faces ( 15 . 1 ). The sealing element ( 30 ) can be angled, relative to the angle between the shoulder ( 21 ) and the stop ( 24 ) of the base element ( 20 ). Here, the sealing ( 30 ) has an O-shaped cross section ( 31 ) in the area of or near the stop ( 24 ) and a cross section, which is thickened in comparison with it, in the area of the shoulder ( 21 ). Here, this area is preferably formed as a wedge-shaped sealing lip ( 34 ).
In the area of or near the plug-in receptacle ( 22 ), the base element has a bezel ( 23 ) extending around the plug-in receptacle ( 22 ), which is used as a seating for the sealing element ( 30 ).
FIG. 2 shows the same cutting tool as shown in FIG. 1 in section with the chisel holder ( 10 ) completely inserted into the base element ( 20 ). Here, the pressure screw ( 40 ), which is preferably embodied as a stud screw and has a screw thread ( 41 ) and a flattened shaft ( 42 ), acts with its shaft ( 42 ) on a pressure face ( 14 ) formed by a V-shaped recess ( 13 ) on the side of the plug-in shoulder ( 15 ) located opposite the guide face ( 15 . 1 ).
When the pressure screw ( 40 ) is tightened, forces result which push the chisel holder ( 10 ) against the base element ( 20 ). During this, the stop ( 11 ) of the chisel holder ( 10 ) is supported on the stop ( 24 ) of the base element. During this, the sealing element ( 30 ) is seated with its area ( 31 ) of O-shaped cross section in the bezel ( 23 ) of the base element ( 20 ) designed as the sealing seat. The originally O-shaped cross section is pressed during this so that an optimum sealing effect is generated.
A clearance ( 16 ), acting as an adjustment space, is formed between the shoulder ( 21 ) in the front part of the base element ( 20 ) and the face of the chisel holder ( 10 ) located opposite the shoulder ( 21 ). With its cross section, which is thickened in this area, and the simultaneous embodiment as a wedge-shaped sealing lip ( 34 ), the sealing element ( 30 ) bridges the clearance ( 16 ), so that an optimal sealing effect is also thus achieved. With this arrangement, no waste material particles can penetrate into the area of the plug-in receptacle. This makes the exchange of the chisel holders ( 10 ) easier. At the same time, with this arrangement no water with waste material particles can penetrate the area of the shaft ( 42 ) and the pressure face ( 14 ) of the plug-in shoulder ( 15 ).
FIGS. 3 a and 3 b represent an embodiment of the sealing element ( 30 ) in a top view and in a lateral view, respectively.
The sealing element ( 30 ) is embodied as a molded part, having the contour of the circumference of the plug-in shoulder ( 15 ) of the chisel holder ( 10 ). The sealing element ( 30 ) is angled corresponding to the angle between the shoulder ( 21 ) and the stop ( 24 ) of the base element ( 20 ), wherein the sealing element ( 30 ) has at least one section of an O-shaped cross section, which rests against the stop ( 24 ) of the base element ( 20 ). The angled section ( 32 ) resting against the shoulder ( 21 ) of the base element ( 20 ) has a cross section which is thickened corresponding to the clearance ( 16 ). An angled section ( 32 ) embodied as a wedge-shaped sealing lip ( 34 ) increases the sealing effect.
In this case, the sealing element ( 30 ) is made of a permanently elastic material and is preferably designed as an injection-molded element. Silicons are used as the materials. Examples of this are so-called liquid silicon rubbers (LSR), for example SILOPREN® made by GE BAYER Silicones, which can be produced by the so-called liquid injector molding (LIM) process. Also suitable are thermoplastic elastomers, for example SANTOPRENE®, made by ADVANCED ELASTOMER SYSTEMS, which can be worked by the normal injection-molding process. The sprue, which is customary in connection with injection-molding processes, is displaced into the thickened area of the clearance ( 16 ), so that the sprue nose ( 33 ) does not hamper the sealing effect of the sealing element ( 30 ).
The sealing element ( 30 ) can be directly formed on the formed-on plug-in shoulder ( 15 ) of the chisel holder ( 10 ), and thus enclosing the exterior circumference of the plug-in shoulder ( 15 ) at least partially. In the same way, the sealing element ( 30 ) can be directly formed on the base element ( 20 ) in the area around or near the plug-in receptacle ( 22 ) and can enclose the exterior circumference of the plug-in receptacle ( 22 ), at least partially.
This invention is not limited to the cross-sectional shape of a plug-in shoulder ( 15 ) represented above and any arbitrary different cross-sectional variants are possible, such as round cross sections or plug-in shoulders of a conical shape, for example.
As shown in the drawings, the plug-in receptacle ( 22 ) in the base element ( 20 ) facing away from the chisel holder ( 10 ) is open. This opening is closed, together with the connected cutting cylinder tube, not represented in the drawings, by a weld seam connection. | A cutting tool of a cutting machine having a base part and a bit holder. According to this invention, the bit holder has a plug-in attachment, retained in a socket of the base part that has a stop against which the bit holder rests. To prevent the penetration of water and stone dust and to allow the bit holder to be easily detached from the base part, a sealing element is located between the bit holder and the base part, surrounding at least sections of the socket. | 4 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation of U.S. patent application Ser. No. 13/954,735, filed on Jul. 30, 2013, titled “DEVICES AND METHODS FOR CERVIX MEASUREMENT,” now U.S. Pat. No. 8,870,794, which is a continuation of U.S. patent application Ser. No. 13/747,331, filed on Jan. 22, 2013, titled “DEVICES AND METHODS FOR THE CERVIX MEASUREMENT,” now U.S. Pat. No. 8,517,960, which is a continuation of U.S. patent application Ser. No. 12/944,580, filed on Nov. 11, 2010, titled “DEVICES AND METHODS FOR CERVIX MEASUREMENT,” now U.S. Pat. No. 8,366,640, which claims priority to U.S. Provisional Patent Application No. 61/260,520, filed Nov. 12, 2009, entitled “DEVICES AND METHODS FOR CERVIX MEASUREMENT” and U.S. Provisional Patent Application No. 61/369,523, filed Jul. 30, 2010, titled “DEVICES AND METHODS FOR CERVIX MEASUREMENT.” These applications are herein incorporated by reference in their entirety.
INCORPORATION BY REFERENCE
All publications and patent applications mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference.
FIELD
The present invention relates to medical devices and methods of using such devices. More particularly, the invention relates to instruments and methods to measure the length of the cervix in the fornix vaginae and the dilation of the cervix uteri.
BACKGROUND
Preterm labor, or labor before 37 weeks gestation, has been reported in approximately 12.8 percent of all births but accounts for more than 85 percent of all perinatal complications and death. Rush et al., BMJ 2:965-8 (1976) and Villar et al., Res. Clin. Forums 16:9-33 (1994), which are both incorporated herein by reference. An inverse relationship between cervical length in the fornix vaginae and the risk of preterm labor has also been observed. Andersen et al., Am. J. Obstet. Gynecol. 163:859 (1990); Jams et al., N. Eng. J. Med. 334:567-72 (1996) and Heath et al., and Ultrasound Obstet. Gynecol. 12:312-7 (1998), which all are incorporated herein by reference. Accordingly, many physicians find it useful to examine the cervix in the fornix vaginae as part of normal prenatal care in order to assess risk of preterm labor.
It has long been known that the cervix normally undergoes a series of physical and biochemical changes during the course of pregnancy, which enhance the ease and safety of the birthing process for the mother and baby. For example, in the early stages of labor the tissues of the cervical canal soften and become more pliable, the cervix shortens (effaces), and the diameter of the proximal end of the cervical canal begins to increase at the internal os. As labor progresses, growth of the cervical diameter propagates to the distal end of the cervical canal, toward the external os. In the final stages of labor, the external os dilates allowing for the unobstructed passage of the fetus.
In addition to the physical and biochemical changes associated with normal labor, genetic or environmental factors, such as medical illness or infection, stress, malnutrition, chronic deprivation and certain chemicals or drugs can cause changes in the cervix. For example, it is well known that the in utero exposure of some women to diethylstilbestrol (DES) results in cervical abnormalities and in some cases gross anatomical changes, which leads to an incompetent cervix where the cervix matures, softens and painlessly dilates without apparent uterine contractions. An incompetent cervix can also occur where there is a history of cervical injury, as in a previous traumatic delivery, or as a result of induced abortion if the cervix is forcibly dilated to large diameters. Details of the incompetent cervix are discussed in Sonek, et al., Preterm Birth, Causes, Prevention and Management, Second Edition, McGraw-Hill, Inc., (1993), Chapter 5, which is incorporated by reference herein.
Cervical incompetence is a well recognized clinical problem. Several investigators have reported evidence of increased internal cervical os diameter as being consistent with cervical incompetence (see Brook et al., J. Obstet. Gynecol. 88:640 (1981); Michaels et al., Am. J. Obstet. Gynecol. 154:537 (1986); Sarti et al., Radiology 130:417 (1979); and Vaalamo et al., Acta Obstet. Gynecol. Scan 62:19 (1983), all of which are incorporated by reference herein). Internal os diameters ranging between 15 mm to 23 mm have been observed in connection with an incompetent cervix. Accordingly, a critical assessment in the diagnosis of an incompetent cervix involves measurement of the internal cervical os diameter.
There are also devices and methods to measure the diameter of the external cervical os. For example, cervical diameter can be manually estimated by a practitioner's use of his or her digits. Although an individual practitioner can achieve acceptable repeatability using this method, there is a significant variation between practitioners due to the subjective nature of the procedure. To address these concerns, various monitoring and measuring devices and methods have been developed. For example, an instrument for measuring dilation of the cervix uteri is described in U.S. Pat. No. 5,658,295. However, this device is somewhat large, leading to a risk of injury to the fundus of the vagina or cervical os. Additionally, it is not disposable and requires repeated sterilization. Another device for measuring cervical diameter is described, for example, in U.S. Pat. No. 6,039,701. In one version, the device described therein has a loop element which is secured to the cervix. The loop expands or contracts with the cervix and a gauge is coupled to the loop for measuring changes in the loop dimension. Such changes can then be detected by electronic means. Accordingly, this device is rather complex and expensive to manufacture.
Even if a woman is found to have an apparently normal internal cervical os diameter, there may nonetheless be a risk for preterm labor and delivery. Currently, risk assessment for preterm delivery remains difficult, particularly among women with no history of preterm birth. However, the findings that preterm delivery is more common among women with premature cervical shortening or effacement suggest that a measuring the length of the cervix would be predictive for preterm labor.
Currently, a physician has at least two options to measure the length of the cervix in the fornix vaginae. One such method involves serial digital examination of the cervix by estimating the length from the external cervical os to the cervical-uterine junction, as palpated through the vaginal fornix. Although this is useful for general qualitative analysis, it does not afford an easy nor accurate measurement of the length of the cervix from the external cervical os to the cervical-uterine junction (also described herein as the length of the cervix extending into the vagina) and, therefore, does not provide an accurate assessment of the risk of preterm labor. Despite the use of gloves, digital vaginal exams always carry with them the risk of transmitting infectious agents, especially to the fetal membranes, the lining and/or muscle of the uterus, or to the fetus itself.
Another method involves real-time sonographic evaluation of the cervix. This method provides relatively quick and accurate cervical dimensions. However, it requires expensive equipment, highly skilled operators, as well as skill in interpretation of results, which are all subject to human error. Additionally, there is a risk that the probe that must be inserted into the vagina as part of the procedure may cause injury if not inserted with care. Also, due to the expense of the procedure many women, especially those without proper health insurance, cannot afford to have a sonographic test performed.
It would be beneficial if there were an instrument a practitioner could use to measure the cervix quickly and accurately, and with little material expense. Although there are several instruments available for determining various dimensions of the uterus, there is no suitable instrument for measuring the length of the cervix in the fornix vaginae. For example, U.S. Pat. No. 4,016,867 describes a uterine caliper and depth gauge for taking a variety of uterine measurements, which although useful for fitting an intrauterine contraceptive device, is not capable of measuring the length of the cervix in the fornix vaginae due to interference by the caliper's wings. In fact, similar devices described in U.S. Pat. Nos. 4,224,951; 4,489,732; 4,685,474; and 5,658,295 suffer from similar problems due to their use of expandable wings or divergeable probe tips. These devices are also relatively sophisticated, making them expensive to manufacture and purchase. U.S. Pat. No. 3,630,190 describes a flexible intrauterine probe, which is particularly adapted to measuring the distance between the cervical os and the fundus of the uterus. The stem portion of the device has a plurality of annular ridges spaced apart from each other by a predetermined distance, preferably not more than one-half inch apart. However, this device is not adapted for accurately measuring the length of the cervix in the fornix vaginae because of the lack of an appropriate measuring scale and a stop for automatically recording the measurement.
There exists a need for a simple and inexpensive device that can be used to determine the length of the cervix in the fornix vaginae and, thus, predict the risk of preterm labor, as well as other conditions. There is also a need for such a device that can measure the dilation of the cervix uteri, to provide an overall assessment of the cervix and to determine the particular stage of labor. Ideally, the device should be adapted for use by a physician or obstetrician or even a trained nurse in the doctor's office or clinic. Preferably, the device should be sterile and disposable. In addition, it is desirable that device be able to lock after a measurement is taken to ensure that the measurement does not change between the time a user takes the measurement and removes the device from the patient to read the measurement. The present invention satisfies these needs and provides related advantages as well.
SUMMARY OF THE DISCLOSURE
In general, in one aspect, a device for measuring a length of a cervix includes an elongate measurement member, a hollow member, a flange, a handle, and a locking mechanism. The elongate measurement member extends along a longitudinal axis and includes a measurement scale thereon. The hollow member is coaxial with and disposed over the elongate measurement member. The flange is offset from the longitudinal axis and attached to a distal end of the hollow member. The handle is attached to a proximal end of the measurement member. The locking mechanism is configured, when locked, to fix the hollow member relative to the measurement member and, when unlocked to allow the hollow member to slide along the measurement member and rotate about the longitudinal axis so as to place the flange in a desired position without moving the measurement scale.
This and other embodiments can include one or more of the following features. The proximal end of the hollow member can be slideable into the handle. The flange can have an opening through which the measurement member can advance distally. The flange can have a flat surface perpendicular to the longitudinal axis. The locking mechanism can include a button, the button including a through-hole configured such that the hollow member can slide therethrough and a lock channel configured such that the hollow member cannot slide therethrough. The button can further include at least one lock ramp between the through-hole and the lock channel. The measurement scale can be a millimeter scale. The measurement scale can extend from 0 mm to 50 mm. The hollow member can be transparent. The measurement scale can include an opaque background. The device can further include an indicator line on the hollow member. The indicator line can be a color other than black.
In general, in one aspect, a method for measuring a length of a cervix includes: holding a handle of a device, the device further including an elongate measurement member having a measurement scale thereon, a hollow member coaxial with and disposed over the elongate measurement member, and a flange attached to a distal end of the hollow member; rotating the hollow member about the elongate measurement member so as to place the flange at a desired orientation without rotating the measurement scale; advancing the device distally within a vagina until the flange contacts a cervix at an external uterine opening; advancing the measurement member distally within the vagina until a distal end of the measurement member contacts a cervical uterine junction at a fornix vaginae; locking the measurement member relative to the hollow member by locking a locking mechanism on the handle; and observing a position of the hollow member with respect to the measurement member to determine a length of the cervix in the fornix vaginae.
This and other embodiments can include one or more of the following features. Advancing the measurement member distally can include sliding the hollow member into the handle. The flange can be offset from a longitudinal axis of the measurement member. The locking mechanism can include a button having a through-hole and a lock channel, and wherein locking the locking mechanism comprises pushing the button such that the hollow member moves into the lock channel and cannot slide through the through-hole. Observing the position can include observing an indicator line on the hollow member with respect to a measurement scale on the measurement member. The method can further include determining the risk of miscarriage based upon the length of the cervix in the fornix vaginae, wherein the length of the cervix in the fornix vaginae is inversely related to the risk of miscarriage. The method can further include predicting the ease of inducing labor, wherein the length of the cervix in the fornix vaginae is inversely related to the ease of inducing labor. The method can further include determining the risk of preterm labor based upon the length of the cervix in the fornix vaginae, wherein the length of the cervix in the fornix vaginae is inversely related to the risk of preterm labor.
BRIEF DESCRIPTION OF THE DRAWINGS
The novel features of the invention are set forth with particularity in the claims that follow. A better understanding of the features and advantages of the present invention will be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of the invention are utilized, and the accompanying drawings of which:
FIG. 1 a is an illustration of a measuring device, according to one embodiment.
FIGS. 1 b - 1 e are additional views of the measuring device of FIG. 1 a.
FIG. 2 a is an illustration of a measuring device, according to one embodiment.
FIGS. 2 b - 2 e are additional views of the measuring device of FIG. 2 a.
FIG. 3 a is an illustration of a measuring device, according to one embodiment.
FIGS. 3 b - 3 d are additional views of the measuring device of FIG. 3 a.
FIG. 4 a is an illustration of a measuring device, according to one embodiment.
FIGS. 4 b - 4 g are additional views of the measuring device of FIG. 4 a.
FIG. 5 a is an illustration of a measuring device, according to one embodiment.
FIGS. 5 b - 5 d are additional views of the measuring device of FIG. 5 a.
FIG. 6 a is an illustration of a measuring device, according to one embodiment.
FIGS. 6 b - 6 f are additional views of the measuring device of FIG. 6 a.
FIG. 7 a is an illustration of a measuring device, according to one embodiment.
FIGS. 7 b - 7 h are additional views of the measuring device of FIG. 7 a.
FIG. 8 is an illustration of a measuring device in use for measuring the vaginal cervix.
DETAILED DESCRIPTION
The present invention provides various devices and methods for determining dimensions of female reproductive organs. For example, the devices described herein are particularly adapted for determining the length of the cervix in the fornix vaginae, which, as described above, is related to the risk of preterm labor in an individual. The devices can also be suited for determining the dilation of the cervix uteri, for predicting the risk of preterm labor or the particular stage of delivery.
It is, however, contemplated herein, that the invention is not limited to determining various dimensions of female reproductive organs. For example, the invention can be usable for determining the dimension of any body cavity or passageway where such a device would be insertable, such as a vagina, uterus, mouth, throat, nasal cavity, ear channel, rectum, and also to any cavity created and opened by surgery, for example, during chest, abdominal or brain surgery.
The devices described herein are also preferably fabricated from relatively inexpensive materials and the measurement is quick to perform. This allows the practitioner to repeat the test over time and therefore to more closely monitor a woman's pregnancy and risk for preterm labor. It is also contemplated that the device can record the various measurements automatically, where the only input required by the practitioner is the proper insertion of the device into the body cavity or passageway. This can be accomplished by the use of a flange to stop progression of the hollow member of the device while still allowing the measurement member to be advanced within the body.
FIG. 1 a illustrates a measuring device 100 that includes an elongated measurement member 102 and an elongated hollow member 104 . The elongated measurement member 102 is adapted to be inserted into the hollow member 104 , and specifically into a lumen of the hollow member. Handle 106 can be positioned on a proximal portion of the measuring device, as shown in FIG. 1 a . In one embodiment, the handle is molded from the same material as the measurement member 102 . In other embodiments, the handle can be a rubber or foam component that is fitted on to and over the proximal end of the measuring device.
A measurement scale 108 can be disposed along a portion of the measurement member 102 . The measurement scale 108 can include any number of a series of visual markings on the measurement member 102 which relate a measurement or distance. In a particularly preferred embodiment, the measurement scale 108 includes a plurality of millimeter (mm) incremental markings and a plurality of centimeter (cm) incremental markings.
As shown in FIG. 1 a , the measurement scale 108 can be color-coded to indicate the relative risks of preterm delivery for a cervix length falling within each respective colored region. For example, in one embodiment, a first zone 132 can include the incremental markings less than 2 cm and can be coded in a first color, such as red, a second zone 134 can include the incremental markings from 2 to 3 cm and can be coded in a second color, such as yellow, and the third zone 134 can include the incremental markings from 3 to 5 cm and can be coded in a third color, such as green. In FIG. 1 a , the measurement scale is color-coded into three regions that each visually represents the relative risks of preterm delivery for a cervix length falling within the respective region. For instance, the first zone 132 indicates a shorter cervix, and therefore a higher risk of preterm delivery, than the second zone 134 , which indicates a cervix length that reflects a higher risk of preterm delivery than the green zone 136 .
A flange 110 that is shaped for non-abrasive contact with tissue can be disposed on a distal portion of measuring device 100 . The flange can be preferably flat and spherically or conically shaped. Alternatively, however, the flange may be any other non-abrasive shape to reduce irritation and scraping of the cervical canal, fundus of the vagina or perforation of the fundus of the uterus. The main body of the flange is also preferably offset from the longitudinal axis of the measuring device 100 . Additionally, the flange can include an opening 112 through, which measurement member 102 may be advanced distally after the flange contacts a bodily surface. Preferably, the flange is secured to the distal end of the hollow member 104 using a suitable attachment means, such as, e.g., an adhesive. Alternatively, the flange may be formed as an integral component of the hollow member 104 .
FIGS. 1 b - 1 d illustrate the operation of the measuring device 100 as it is used to measure the length of a cervix. When the distal end of the measurement member 102 is flush with the flange, as shown in FIG. 1 b , the device is in a starting configuration. The device 100 can be advanced into the vagina until the flange 110 is placed into contact with the end of the cervix at the external uterine opening. At this point, further forward progress of the hollow member 104 within the cervical canal or further within the body is prevented as a result of the contact between flange 110 and the end of the cervix at the external uterine opening. Since flange 110 is preferably offset from the longitudinal axis of measuring device 100 , in one embodiment the flange is placed both in contact with the end of the cervix and also covering the external uterine opening. As a result, the device can oriented so that measurement member 102 is still able to be progressed within the fornix, rather than being advanced through the uterus, since the body of flange 106 is, with this method, covering the external uterine opening.
Subsequently, as shown in FIGS. 1 c - 1 d , a distal portion of measurement member 102 can continue to be advanced through opening 112 of flange 110 until the distal end contacts a wall of the body, such as, e.g., the anterior fornix. When the distal end of the measurement member is advanced beyond the flange the device is in a measuring configuration. FIG. 1 c shows a side view of the measurement member in the measuring configuration, and FIG. 1 d shows a top down view of the device in the measuring configuration. It can be seen in FIG. 1 d , for example, that the measurement member has been advanced 4 cm beyond the flange. The length of the cervix can then be measured by observing the position of the proximal end of the hollow member 104 along the measurement scale 108 of the measurement member 102 . In another embodiment, a method of measurement comprises advancing the distal end of the measurement member 102 to the wall of the body, such as the anterior fornix, and then advancing the hollow member 104 so that the flange 110 is placed into contact with the end of the cervix at the external uterine opening.
Referring now to FIG. 1 e , a locking mechanism 114 can be located on the measuring device 100 that allows a user to secure the measurement member 102 within the hollow member 104 after the measurement of a body part, such as, e.g., the length of the cervix. In FIG. 1 e , the locking mechanism 114 includes button 116 , cantilever arm 118 , detents 120 , and opening 122 . When the locking mechanism is in the locked configuration, as shown in FIG. 1 e , the cantilever arm 118 engages detents 120 on the inside of hollow member 104 . The cantilever arm can be integral to the measurement member 102 , for example. To allow sliding of the measurement member within the hollow member, button 116 can be pressed inwards towards opening 122 , causing cantilever arm 118 to disengage detents 120 and allow sliding.
For example, to take a measurement of a body part, a user can insert the measuring device 100 into the patient. The user can then press the button 116 inwards to disengage the cantilever arm and allow the measurement member to slide within the hollow member. After the measurement of a body part is taken with the device, the user can release the button, causing the cantilever arm to engage the detents and lock the position of the measurement member 102 within the hollow member 104 . This allows the user to remove the device from the patient to read the measurement scale while ensuring that movement of the measurement member 102 proximally or distally within the hollow member 104 is prevented.
During a measurement procedure, a user can hold handle 106 with the dominant hand like a dart, and can hold the barrel of the hollow member 104 with the non-dominant hand. The user can activate button 116 with the dominant hand to temporarily unlock the measuring device, allowing the hollow member to slide with respect to the measurement member.
Referring now to FIG. 2 a , another embodiment of a measuring device 200 is shown. Measuring device 200 includes many of the features of measuring device 100 , described above and illustrated in FIGS. 1 a - 1 e . For example, measuring device 200 includes an elongated measurement member 202 slidably disposed within an elongated hollow member 204 . Handle 206 can be positioned on a proximal portion of the measuring device, and measurement scale 208 , such as a color-coded measurement scale, can be disposed on the measurement member 202 . The measuring device can further include a flange 210 on a distal portion of the device, and an opening 212 that allows the measurement member 202 to extend distally beyond the hollow member 204 .
As described above, the device 200 can have a starting configuration, as shown in FIG. 2 b , and a measuring configuration, as shown in FIG. 2 c . The measuring device 200 can further include a locking mechanism 214 . The locking mechanism allows a user to lock the measurement member 202 within the hollow member 204 , to prevent movement of the measurement member with respect to the hollow member after a measurement is taken. In the embodiment shown in FIGS. 2 a - 2 e , the locking mechanism 214 is disposed on the hollow member 204 .
Referring now to FIG. 2 d , which is a side view of the locking mechanism 214 , and FIG. 2 e , which is a cross sectional view of the locking mechanism 214 , the locking mechanism can further include pads or buttons 216 , tabs 218 , and detents 220 . The buttons 216 and tabs 218 can be integral to the hollow member 204 , and the detents 220 can be integral to the measurement member 202 , for example. In the embodiment shown in FIGS. 2 d - 2 e , the locking mechanism includes two buttons 216 . However, in other embodiments, the locking mechanism can include only a single button, or alternatively, can include more than two buttons.
When the locking mechanism 214 is in a locked configuration, as shown in FIG. 2 d , the tabs engage detents 220 , preventing any movement of the measurement member with respect to the hollow member 204 . However, when the buttons 216 are depressed inwards by a user, as shown in FIG. 2 e , the tabs 218 can be squeezed outwards, as indicated by arrows 224 , causing them to disengage from detents 220 . This allows a measurement to be taken by sliding the measurement member 202 within the hollow member 204 .
To take a measurement of a body part, a user can insert the measuring device 200 into the patient. The user can then press the button or buttons 216 inwards to cause the tabs 218 to squeeze outwards disengaging detents 220 , thereby allowing the measurement member to slide within the hollow member. After the measurement of a body part is taken with the device, the user can release the buttons, causing the tabs to engage the detents and lock the position of the measurement member 202 within the hollow member 204 . This allows the user to remove the device from the patient to read the measurement scale while ensuring that movement of the measurement member 202 proximally or distally within the hollow member 204 is prevented.
During a measurement procedure, a user can hold handle 206 with the dominant hand like a dart, and can hold the barrel of the hollow member 204 with the non-dominant hand. The user can activate button 216 with the non-dominant hand to temporarily unlock the measuring device, allowing the hollow member to slide with respect to the measurement member.
Referring now to FIG. 3 a , yet another embodiment of a measuring device 300 is shown. Measuring device 300 includes many of the features of measuring device 100 , described above and illustrated in FIGS. 1 a - 1 e . For example, measuring device 300 includes an elongated measurement member 302 slidably disposed within an elongated hollow member 304 . Handle 306 can be positioned on a proximal portion of the measuring device, and measurement scale 308 , such as a color-coded measurement scale, can be disposed on the measurement member 302 . The measuring device can further include a flange 310 on a distal portion of the device, and an opening 312 that allows the measurement member 302 to extend distally beyond the hollow member 304 .
As described above, the device 300 can have a starting configuration, as shown in FIG. 3 b , and a measuring configuration, as shown in FIG. 3 c . In addition, a locking mechanism 314 can be located on the measuring device 300 that allows a user to secure the measurement member 302 within the hollow member 304 after the measurement of a body part, such as, e.g., the length of the cervix.
In FIG. 3 d , the locking mechanism 314 includes button 316 , cantilever arm 318 , and detents 320 . When the locking mechanism is in the locked configuration, as shown in FIG. 3 d , the cantilever arm 318 engages detents 320 on the outside of measurement member 302 . The cantilever arm can be integral to the hollow member 304 , for example. To allow sliding of the measurement member within the hollow member, button 316 can be pressed inwards, causing cantilever arm 318 to disengage detents 320 and allow sliding.
For example, to take a measurement of a body part, a user can insert the measuring device 300 into the patient. The user can then press the button 316 inwards to disengage the cantilever arm and allow the measurement member to slide within the hollow member. After the measurement of a body part is taken with the device, the user can release the button, causing the cantilever arm to engage the detents and lock the position of the measurement member 302 within the hollow member 304 . This allows the user to remove the device from the patient to read the measurement scale while ensuring that movement of the measurement member 302 proximally or distally within the hollow member 304 is prevented.
During a measurement procedure, a user can hold handle 306 with the dominant hand like a dart, and can hold the barrel of the hollow member 304 with the non-dominant hand. The user can activate button 316 with the non-dominant hand to temporarily unlock the measuring device, allowing the hollow member to slide with respect to the measurement member.
Referring now to FIG. 4 a , another embodiment of a measuring device 400 is shown. Measuring device 400 includes many of the features of measuring device 100 , described above and illustrated in FIGS. 1 a - 1 e . For example, measuring device 400 includes an elongated measurement member 402 slidably disposed within an elongated hollow member 404 . Handle 406 can be positioned on a proximal portion of the measuring device, and measurement scale 408 , such as a color-coded measurement scale, can be disposed on the measurement member 402 . The measuring device can further include a flange 410 on a distal portion of the device, and an opening 412 that allows the measurement member 402 to extend distally beyond the hollow member 404 .
As described above, the device 400 can have a starting configuration, as shown in FIG. 4 b , and a measuring configuration, as shown in FIG. 4 c . In contrast to the embodiments described above, the hollow member 404 of the measuring device 400 in FIGS. 4 a - 4 e slides into the handle 406 when a measurement is taken. The measurement member 402 remains fixed in position with respect to the handle, which allows the measurement member to extend distally beyond the flange 410 during measurements.
The measuring device 400 can further include a locking mechanism 414 . The locking mechanism allows a user to lock the hollow member 404 within the handle 406 , to prevent movement of the hollow member with respect to the measurement member after a measurement is taken. In the embodiment shown in FIGS. 4 a - 4 e , the locking mechanism 414 can comprise a button 416 with a through-hole (not shown). In FIG. 4 d , the device is shown in an unlocked configuration, in which the through-hole is aligned with the hollow member 404 to allow the hollow member to travel therethrough. When the device is in a locked configuration, as shown in FIG. 4 e , the through-hole pushes against the hollow member, preventing movement of the hollow member with respect to the measurement member.
FIG. 4 f shows a cross-sectional view of locking mechanism 414 , button 416 , and hollow member 404 . The button geometry is designed to operate smoothly with a low actuation force to engage the locking mechanism. The open channel 418 of the button allows the hollow member 404 to slide freely into the handle when a measurement is being taken. When the button is depressed, the lock ramps 420 are forced to slide over the hollow member 404 , which provides tactile and audible feedback that the device is in the locked position. The design of the lock ramps, including height and ramp angle affects the effort levels required to activate the button. The width of the lock channel 422 is designed to be narrower than the overall outside diameter of the hollow member 404 , so that the interference between the two surfaces provides a retention force to maintain the measurement while the device is removed from the patient. In some embodiments, the locking mechanism does not include the lock ramps 420 . In other embodiments, the lock channel 422 can be tapered to provide a frictional, locking fit for hollow member 404 when button 416 is depressed, as shown in FIG. 4 g.
For example, to take a measurement of a body part, a user can insert the measuring device 400 in an unlocked configuration (e.g., where the through-hole is aligned to allowed movement of the hollow member) into the patient. After the measurement of a body part is taken with the device, the user can press the button 416 , causing the through-hole to press against the hollow member to prevent movement of the hollow member. This allows the user to remove the device from the patient to read the measurement scale while ensuring that movement of the measurement member 402 proximally or distally within the hollow member 404 is prevented.
During a measurement procedure, a user can hold handle 406 with the dominant hand like a dart, and can hold the barrel of the hollow member 104 with the non-dominant hand. After taking a measurement, the user can activate button 416 with the dominant hand to lock the measuring device, preventing the hollow member from sliding with respect to the measurement member.
Referring now to FIG. 5 a , another embodiment of a measuring device 500 is shown. Measuring device 500 includes many of the features of measuring device 100 , described above and illustrated in FIGS. 1 a - 1 e . For example, measuring device 500 includes an elongated measurement member 502 slidably disposed within an elongated hollow member 504 . Syringe-style handle 506 can be positioned on a proximal portion of the measuring device, and measurement scale 508 , such as a color-coded measurement scale, can be disposed on the measurement member 502 . The measuring device can further include a flange 510 on a distal portion of the device, and an opening 512 that allows the measurement member 502 to extend distally beyond the hollow member 504 .
As described above, the device 500 can have a starting configuration, as shown in FIG. 5 b , and a measuring configuration, as shown in FIG. 5 c . Similar to the embodiment of measuring device 400 described above and illustrated in FIGS. 4 a - 4 e , the hollow member 504 of the measuring device 500 in FIGS. 5 a - 5 d slides into the handle 506 when a measurement is taken. The measurement member 502 remains fixed in position with respect to the handle, which allows the measurement member to extend distally beyond the flange 510 during measurements.
The measuring device 500 can further include a locking mechanism 514 . The locking mechanism allows a user to lock the hollow member 504 within the handle 506 , to prevent movement of the hollow member with respect to the measurement member after a measurement is taken. In the embodiment shown in FIG. 5 d , the locking mechanism 514 can comprise a button 516 with a through-hole (not shown). Similar to the embodiments described above in FIGS. 4 a - 4 e , the device can have an unlocked configuration, in which the through-hole is aligned with the hollow member 504 to allow the hollow member to travel therethrough. The device can also have a locked configuration, in which the through-hole pushes against the hollow member thereby preventing movement of the hollow member with respect to the measurement member.
To take a measurement of a body part, a user can insert the measuring device 500 in an unlocked configuration (e.g., where the through-hole is aligned to allowed movement of the hollow member) into the patient. After the measurement of a body part is taken with the device, the user can press the button 516 , causing the through-hole to press against the hollow member to prevent movement of the hollow member. This allows the user to remove the device from the patient to read the measurement scale while ensuring that movement of the measurement member 502 proximally or distally within the hollow member 504 is prevented. In FIG. 5 d , the measurement scale is read at point 526 on the handle when taking the measurement, for example.
During a measurement procedure, a user can hold syringe-style handle 506 with the dominant hand like a syringe, and can hold the barrel of the hollow member 504 with the non-dominant hand. After taking a measurement, the user can activate button 516 with the dominant or non-dominant hand to lock the measuring device, preventing the hollow member from sliding with respect to the measurement member.
Referring now to FIG. 6 a , another embodiment of a measuring device 600 is shown. Measuring device 600 includes many of the features of measuring device 100 , described above and illustrated in FIGS. 1 a - 1 e . For example, measuring device 600 includes an elongated measurement member 602 slidably disposed within an elongated hollow member 604 . Handle 606 can be positioned on a proximal portion of the measuring device, and measurement scale 608 , such as a color-coded measurement scale, can be disposed on the measurement member 602 . The measuring device can further include a flange 610 on a distal portion of the device, and an opening 612 that allows the measurement member 602 to extend distally beyond the hollow member 604 .
As described above, the device 600 can have a starting configuration, as shown in FIG. 6 b , and a measuring configuration, as shown in FIG. 6 c . The measuring device 600 can further include a locking mechanism 614 . The locking mechanism allows a user to lock the measurement member 602 within the hollow member 604 , to prevent movement of the measurement member with respect to the hollow member after a measurement is taken. In the embodiment shown in FIGS. 6 a - 6 f , the locking mechanism 614 is disposed on the hollow member 204 .
Referring now to FIG. 6 d , which is a cross sectional view of the locking mechanism 614 , the locking mechanism can further an annular snap 628 . The measurement member 602 also has an annular snap 630 that corresponds to the annular snap 628 on the locking mechanism. When the locking mechanism is in an unlocked configuration, as shown in FIG. 6 d , the annular snaps 628 and 630 are not in contact, so there is some play between the locking mechanism 614 and the measurement member 602 , which allows the measurement member to slide freely within the hollow member 604 . As a user rotates the locking mechanism, as shown in FIG. 6 e , the annular snaps contact each other, providing the user with tactile feedback of locking. In FIG. 6 f , the locking mechanism is shown in a locked configuration, with the annular snaps contacting each other on both sides. When the annular snaps are in contact as shown in FIG. 6 f , there is no play between the hollow member and the measurement member, which prevents movement of the hollow member with respect to the measurement member.
To take a measurement of a body part, a user can insert the measuring device 600 into the patient in the unlocked configuration. After the measurement of a body part is taken with the device, the user can rotate the locking mechanism 614 , causing the annular snaps to engage each other on both sides to lock the position of the measurement member 602 within the hollow member 604 . This allows the user to remove the device from the patient to read the measurement scale while ensuring that movement of the measurement member 602 proximally or distally within the hollow member 604 is prevented.
During a measurement procedure, a user can hold handle 606 with the dominant hand like a dart, and can hold the locking mechanism 614 with the non-dominant hand. After taking a measurement, the user can rotate the locking mechanism with the non-dominant hand until the annular snaps engage each other to lock the measuring device, preventing the hollow member from sliding with respect to the measurement member. The user can also hold steady the locking mechanism 614 with the non-dominant hand and rotate the handle 606 with the dominant hand until the annular snaps engage each other to lock the measuring device. The relative motion of the locking mechanism 614 and the handle 606 is what engages the locking mechanism, regardless of which is held in place and which is rotated.
Referring now to FIG. 7 a , another embodiment of a measuring device 700 is shown. Measuring device 700 includes many of the features of measuring device 100 , described above and illustrated in FIGS. 1 a - 1 e . For example, measuring device 700 includes an elongated measurement member 702 slidably disposed within an elongated hollow member 704 . The measuring device can further include a flange 710 on a distal portion of the elongated hollow member 704 , and an opening 712 that allows the measurement member 702 to extend distally beyond the hollow member 704 . Handle 706 can be positioned on a proximal portion of the measuring device and can be attached to the measurement member and measurement scale 708 can be disposed on the measurement member 702 . As shown in FIG. 7 f , the measurement scale can be a millimeter sale, with markings from 0-50 mm, marked in 5 mm increments. Moreover, the background 732 for the measurement scale 708 can be opaque. For example, the measurement member 702 can be composed of an opaque material or an opaque coating can cover the portion of the measurement member 702 on which the measurement scale 708 is printed. An opaque background for the measurement scale can allow for easier readability of the numbers on the scale. Further, the hollow member 704 can be transparent and include an indicator line 734 that is colored, e.g., blue, to help contrast it from the measurement scale. Contrasting the indicator line 734 with the measurement scale allows for easier readability of the final measurement.
As described above, the device 700 can have a starting configuration, as shown in FIG. 7 b , and a measuring configuration, as shown in FIG. 7 c . Similar to the embodiment of measuring device 400 described above and illustrated in FIGS. 4 a - 4 e , the hollow member 704 of the measuring device 700 in FIGS. 7 a - 7 d slides into the handle 706 (or, alternatively, the handle 706 slides over the hollow member 704 ) when a measurement is taken. The measurement member 702 remains fixed in position with respect to the handle, which allows the measurement member to extend distally beyond the flange 710 during measurements. As shown in FIGS. 7 g and 7 h , the elongated hollow member 704 can be free to rotate with respect to the handle 706 and the measurement member 702 ( FIG. 7 g shows the flange 710 extending parallel to the page, while FIG. 7 h shows the flange 710 extending out of the page). Such free rotation allows for the accommodation of any measurement technique, e.g. right or left-handed measurements, while still allowing for proper placement of the flange 710 . That is, rotation of the hollow member 702 to place the flange 710 in a desired position allows the measurement scale to remain in place, i.e., facing the user. Maintaining the measurement scale directed towards the users ensures that the user is more easily able to read and determine the measured length.
The measuring device 700 can further include a locking mechanism 714 . The locking mechanism allows a user to lock the hollow member 704 within the handle 706 , to prevent rotational or longitudinal movement of the hollow member with respect to the measurement member after a measurement is taken. In the embodiment shown in FIG. 7 d , the locking mechanism 714 can comprise a button 716 with a through-hole (not shown). Similar to the embodiments described above in FIGS. 4 a - 4 e , the device can have an unlocked configuration, in which the through-hole is aligned with the hollow member 704 to allow the hollow member to travel therethrough. The device can also have a locked configuration, in which the through-hole pushes against the hollow member thereby preventing movement of the hollow member with respect to the measurement member.
To take a measurement of a body part, a user can hold the handle 706 with the dominant hand and can hold the hollow member 704 with the non-dominant hand. The user can orient the measuring scale 708 such that it faces the user and can then rotate the hollow member 704 such that the flange 710 is properly oriented with respect to the patient. Because the hollow member 704 is transparent, the measuring scale 708 can be viewed through the hollow member 704 .
The measuring device 700 can be inserted in an unlocked configuration (e.g., where the through-hole is aligned to allowed movement of the hollow member) into the patient. After the measurement of a body part is taken with the device, as described above, the user can press the button 716 , causing the through-hole to press against the hollow member to prevent movement of the hollow member. This allows the user to remove the device from the patient to better read the measurement scale while ensuring that movement of the measurement member 702 proximally or distally within the hollow member 704 is prevented.
Referring to FIG. 8 , the devices described herein can be used to measure the vaginal cervical length. The flange 810 (representing any of the flanges described herein) can be placed against the proximal wall of cervix 802 , while the measurement member 702 (representing any of the measurement members described herein) can be extended along the lateral wall of the cervix 802 until it is stopped by the vaginal fornix 804 . The measurement member 702 and the flange 810 can then be locked with respect to one another such that the device's measurement scale can be used to determine the length as described above.
As for additional details pertinent to the present invention, materials and manufacturing techniques may be employed as within the level of those with skill in the relevant art. The same may hold true with respect to method-based aspects of the invention in terms of additional acts commonly or logically employed. Also, it is contemplated that any optional feature of the inventive variations described may be set forth and claimed independently, or in combination with any one or more of the features described herein. Likewise, reference to a singular item, includes the possibility that there are plural of the same items present. More specifically, as used herein and in the appended claims, the singular forms “a,” “and,” “said,” and “the” include plural referents unless the context clearly dictates otherwise. It is further noted that the claims may be drafted to exclude any optional element. As such, this statement is intended to serve as antecedent basis for use of such exclusive terminology as “solely,” “only” and the like in connection with the recitation of claim elements, or use of a “negative” limitation. Unless defined otherwise herein, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The breadth of the present invention is not to be limited by the subject specification, but rather only by the plain meaning of the claim terms employed. | A device for measuring a length of a cervix includes an elongate measurement member extending along a longitudinal axis and including a measurement scale thereon, a hollow member coaxial with and disposed over the elongate measurement member, a flange offset from the longitudinal axis and attached to a distal end of the hollow member, a handle attached to a proximal end of the measurement member, and a locking mechanism on the handle. The hollow member is freely rotatable about the longitudinal axis relative to the measurement member to place the flange in a first position and in a second position perpendicular to the first position without moving the measurement scale. The locking mechanism is configured, when locked, to fix the hollow member relative to the measurement member and, when unlocked, to allow the hollow member to slide axially along the measurement member in the first and second positions. | 0 |
TECHNICAL FIELD
[0001] The invention relates to variants of yeast NDI1 gene, proteins encoded by the variants, and the uses of the variant genes, transcribed RNA and proteins in the treatment of disease, especially neurodegenerative disease.
INTRODUCTION
[0002] Leber hereditary optic neuropathy (LHON) is a maternally inherited disorder affecting 1/25,000 people, predominantly males 1 . Loss of central vision results from the degeneration of the retinal ganglion cell (RGC) layer and optic nerve 2 . In over 95% of patients the genetic pathogenesis of LHON involves mutations in genes encoding components of the mitochondrial respiratory NADH-ubiquinone oxidoreductase complex 3 (complex I), which is involved in transfer of electrons from NADH to ubiquinone (coenzyme Q). Complex I is composed of forty-six subunits, seven of which are encoded by the mitochondrial genome, ND1-6 and ND4L. Mutations in five of the mitochondrially encoded subunits of complex I, ND1, ND4, ND4L, ND5 and ND6, are associated with LHON (http://www.mitomap.org/MITOMAP). There is growing evidence that mitochondrial dysfunction may be involved in a wide range of neurodegenerative disorders such as Alzheimer disease (AD), Huntington disease and dominant optic atrophy as well as multifactorial diseases including dry and wet age related macular degeneration (AMD), diabetic retinopathies and glaucoma 4 . It is perhaps not surprising that a tissue such as retina, with the most significant energy requirements of any mammalian tissues, may be particularly vulnerable to mitochondrial dysfunction. However, it is notable that such a dependency on energy metabolism in principle may provide an opportunity for the development of therapeutic interventions for such high energy-dependent tissues where a shift in energy metabolism may potentially provide substantial beneficial effects. Complex I dysfunction results in an increase of reactive oxygen species (ROS) and a decreased energy supply 6 . In mitochondria, ATP synthesis is coupled to oxygen consumption by the proton electrochemical gradient established across the mitochondrial inner membrane in the process termed oxidative phosphorylation 7 (OXPHOS). Mitochondrial complex I mutations leading to respiratory chain dysfunction are hence linked to reduced oxygen consumption; a reliable measure of overall mitochondrial activity.
[0003] Interestingly, many LHON mutations are not fully penetrant, it seems that the appearance of the pathological features of the disorder may be influenced by genetic and environmental modifiers. For example, it has been observed that the T14484C mutation in the ND6 subunit tends to be associated with a better clinical outcome and at times recovery in visual function 8 . Furthermore, there has been some suggestion that certain mitochondrial genetic backgrounds may render patients more or less susceptible to a variety of disorders including LHON and that this may be linked to variations in oxygen consumption, the efficiency of electron transport and ATP production 9 . For example, the G11778A and T14484C LHON mutations on a mitochondrial haplogroup J or K background have been associated with an increased risk of visual loss 10 . Nuclear modifier genes can influence LHON progression and severity, for example, an x-linked modifier locus has been reported 11 . Additionally, smoking has been suggested as one of the environmental factors which can influence disease penetrance 12 . In addition, the male prevalence (5:1) of LHON may at last in part be influenced by oestrogens 13 . An interplay between the primary mutation, modifying nuclear genes, the mtDNA genetic background and environmental factors may collaborate to determine overall risk of visual loss for a given LHON patient.
[0004] While significant progress has been made with regard to understanding the genetic pathogenesis of LHON, development of gene therapies for LHON has been impeded by the need to deliver therapies to the mitochondria of RGCs. In addition, intragenic heterogeneity has made development of therapies complex. Allotopic or nuclear expression of mitochondrial genes is being explored as a potential therapeutic avenue for some mitochondrial disorders including ND4-linked LHON, although modifications may be required to facilitate import of expressed proteins into mitochondria 14,15,16 . A nuclear complementation approach using NDI1 has been considered as a potential therapy for Parkinson disease (PD) 17 . Additionally, recombinant adenoassociated virus (AAV) serotype 5 delivery of NDI1 into the optic layer of the superior colliculus of the brain, has recently been shown to provide significant benefit in a chemically-induced rat model of LHON using functional and histological readouts 18 . Whereas this represents an exciting and innovative strategy making use of transkingdom gene therapy, the mode of delivery may not be readily translatable to human LHON patients.
[0005] It is an object of the invention to overcome at least one of the above-referenced problems.
STATEMENTS OF INVENTION
[0006] The invention relates to variants of the yeast NDI1 gene of SEQ ID NO: 1 which are codon optimised to provide for improved expression in mammalian cells, and/or modified to encode an immune optimised functional variant of NDI1 protein. Codon optimisation involves replacing codons which are common to yeast cells and uncommon to mammalian cells with synonomous codons which are common to mammalian cells. These are known as “silent changes” as they do not result in an amino acid change in the encoded protein. Codon optomisation provides for improved expression of the nucleic acid in mammalian cells and/or conveys less immunogenicity. Immune optimisation involves substitution of one or more amino acids (i.e. see Table 1b), for example from one to ten amino acids, in the protein to provide a variant protein that exhibits reduced immunogenicity in-vivo in humans compared to yeast NDI1 protein. Examples of possible amino acid changes include conservative amino acid changes at one or more of the following positions:
[0007] L195, K284, K10, S143, L502, L403, A387, S86, F90, L94, K196, L19, K214, K373, L259, K511, L159, R479, L483, I82, F90, L89, V266, K214, L481, L202, L259, L195, L150, R85, Y151, Y482, S488, V45, L483, S80, K196, for example one or more of the following amino acid changes:
[0008] L195F, K284E, K10R, S143N, L502M, L4031, A387S, S86K, F90H, L94M, K196E, L19M, K214E, K373E, L259F, K511E, L159M, R479Q, L483M, I82V, F90Y, L89I, V266I, K214E, L481I, L202M, L259V, L195I, L150M, R85K, Y151F, Y482F, S488T, V45I, L483M, S80T, K196T.
[0009] In a first aspect, the invention provides an isolated nucleic acid sequence encoding the yeast NDI1 protein of SEQ ID NO: 542 or a functional variant thereof having at least 90% sequence identity with SEQ ID NO: 542, wherein the nucleic acid comprises at least 50 codons which are codon optimised compared with the sequence of yeast NDI1 gene of SEQ ID NO: 1.
[0010] Examples of codon optimised variants of yeast NDI1 gene are provided in SEQ ID NO'S: 2-62, 75-145, 165-243, 264-341, 362-441, 462-541, and 705-1004.
[0011] In a second aspect, the invention provides an isolated codon optimised nucleic acid sequence encoding an immune optimised functional variant of the yeast NDI1 protein of SEQ ID NO: 542 comprising at least one conservative amino acid change at a residue selected from the group consisting of:
[0012] L195, K284, K10, S143, L502, L403, A387, S86, F90, L94, K196, L19, K214, K373, L259, K511, L159, R479, L483, I82, F90, L89, V266, K214, L481, L202, L259, L195, L150, R85, Y151, Y482, S488, V45, L483, S80, K196, for example one or more of the following amino acid changes:
[0013] L195F, K284E, K10R, S143N, L502M, L4031, A387S, S86K, F90H, L94M, K196E, L19M, K214E, K373E, L259F, K511E, L159M, R479Q, L483M, I82V, F90Y, L89I, V266I, K214E, L481I, L202M, L259V, L195I, L150M, R85K, Y151F, Y482F, S488T, V45I, L483M, S80T, K196T, wherein the nucleic acid comprises at least 50 codons which are codon optimised compared with the sequence of wild-type yeast NDI1 gene of SEQ ID NO: 1.
[0014] Examples of immune and codon optimised variants of yeast NDI1 gene are provided in SEQ ID NO'S: 75-145, 165-243, 264-341, 362-441, 462-541, 566-584, 705-824, 835-884, 895-944 and 955-1004.
[0015] In a third aspect, the invention provides an isolated nucleic acid sequence encoding an immune optimised functional variant of yeast NDI1 protein of SEQ ID NO: 542 in which the variant comprises at least one conservative amino acid change at a residue selected from the group consisting of:
[0016] L195, K284, K10, S143, L502, L403, A387, S86, F90, L94, K196, L19, K214, K373, L259, K511, L159, R479, L483, 182, F90, L89, V266, K214, L481, L202, L259, L195, L150, R85, Y151, Y482, S488, V45, L483, S80, K196, for example one or more of the following amino acid changes:
[0017] L195F, K284E, K10R, S143N, L502M, L4031, A387S, S86K, F90H, L94M, K196E, L19M, K214E, K373E, L259F, K511E, L159M, R479Q, L483M, I82V, F90Y, L89I, V266I, K214E, L481I, L202M, L259V, L195I, L150M, R85K, Y151F, Y482F, S488T, V45I, L483M, S80T, K196T,
[0018] In an additional aspect of the invention the NDI1 gene and encoded protein are immune optimized employing amino acid substitution(s) at one or more key NDI1 positions as defined by K10, L19, V45, S80, I82, R85, S86, L89, F90, L94, S143, L150, Y151, L159, L195, K196, L202, K214, L259, V266, K284, K373, A387, L403, R479, L481, Y482, L483, S488, L502, K511.
[0019] Examples of immune optimised variants of yeast NDI1 gene (without codon optimisation) are provided in SEQ ID NO'S: 63-74 and 547-565 (one amino acid change), 146-164 and 585-605 (two amino acid changes), 244-263 and 606-640 (three amino acid changes), 641-675 (four amino acid changes), 342-361 and 676-696 (five amino acid changes), 697-703 (six amino acid changes), 704 (seven amino acid changes) and 442-461 (ten amino acid changes).
[0020] Typically, the nucleic acid sequence of the invention encodes a functional variant of the yeast NDI1 protein of SEQ ID NO: 542 having at last 90% sequence identity with SEQ ID NO:542. Preferably, the functional variant comprises at least 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% sequence identity with SEQ ID NO: 542.
[0021] Preferably, the nucleic acid sequence of the invention encodes a yeast NDI1 protein that includes at least 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 amino acid changes. Typically, from 1-20, 1-15, or ideally from 1-10, amino acids are changed. The changes are suitably conservative changes made to one or more of the residues identified above, for example one or more of: L195F, K284E, K10R, S143N, L502M, L4031, A387S, S86K, F90H, L94M, K196E, L19M, K214E, K373E, L259F, K511E, L159M, R479Q, L483M, I82V, F90Y, L89I, V266I, K214E, L481I, L202M, L259V, L195I, L150M, R85K, Y151F, Y482F, S488T, V45I, L483M, S80T, K196T.
[0022] Preferably, the nucleic acid sequence of the invention encodes a yeast NDI1 protein that includes at least 2, 3, 4, 5, 6, 7, 8, 9, or 10 amino acid changes. Typically, from 1-20, 1-15, or ideally from 1-10, amino acids are changed, and the changes are suitably selected at NDI1 positions from the group: K10, L19, V45, S80, I82, R85, S86, L89, F90, L94, S143, L150, Y151, L159, L195, K196, L202, K214, L259, V266, K284, K373, A387, L403, R479, L481, Y482, L483, S488, L502, K511.
[0023] Suitably, the variant protein includes at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or all of the amino acid changes selected from: L195F, K284E, K10R, S143N, L502M, L4031, A387S, S86K, F90H, L94M, K196E, L19M, K214E, K373E, L259F, K511E, L159M, R479Q, L483M, I82V, F90Y, L89I, V266I, K214E, L481I, L202M, L259V, L195I, L150M, R85K, Y151F, Y482F, S488T, V45I, L483M, S80T, K196T.
[0024] Ideally, the variant protein includes an amino acid change selected from: L195F, K284E, K10R, S143N, L502M, L4031, A387S, S86K, F90H, L94M, K196E, L19M, K214E, K373E, L259F, K511E, L159M, R479Q, L483M, I82V, F90Y, L89I, V266I, K214E, L481I, L202M, L259V, L195I, L150M, R85K, Y151F, Y482F, S488T, V45I, L483M, S80T, K196T.
[0025] Preferably, at least 90, 100, 150, 200, 250, 300, 320, or 329 codons are codon optimised for use in a mammal. In one embodiment, 1-100, 100-200, 200-300, or 300-329 codons are optimised. Ideally, 329 codons are optimised (see SEQ ID NO's 62, 134-145, 225-243, 324-341, 422-441, 522-541, 566-584 and 705-824).
[0026] In another embodiment 1-100, 100-200, 200-300, or 300-329 NDI1 codons are optimised for use in mammals and the nucleic acid sequence encodes a yeast NDI1 protein that includes at least 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 amino acid changes. Typically, from 1-20, 1-15, or ideally from 1-10, amino acids are changed, and the changes are suitably selected at NDI1 positions from the group: K10, L19, V45, S80, I82, R85, S86, L89, F90, L94, S143, L150, Y151, L159, L195, K196, L202, K214, L259, V266, K284, K373, A387, L403, R479, L481, Y482, L483, S488, L502, K511.
[0027] Preferably, the nucleic acid of the invention encodes a variant protein having at least 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% sequence identity with SEQ ID NO: 542.
[0028] The invention also relates to a nucleic acid construct comprising a nucleic acid sequence of the invention and a nucleic acid sequence encoding a mitochondrial localisation sequence. This may be, but are not limited to, sequences such as MLSKNLYSNKRLLTSTNTLVRFASTRS (SEQ ID NO: 1006) or MSVLTPLLLRGLTGSARRLPVPRAKIHSL (SEQ ID NO: 1007).
[0029] The invention also relates to a nucleic acid construct encoding a protein of the invention. The nucleic acid may be a DNA or RNA nucleic acid. The nucleic acid of the invention may use modified nucleic acids to optimise delivery and or increase stability and or increase longevity and or reduce immunogenicity 22,23.
[0030] In one aspect the invention relates to delivery of RNA encoding the protein and or protein variants of the invention.
[0031] The invention also relates to a protein encoded by a nucleic acid construct of the invention.
[0032] The term “nucleic acid sequence of the invention” as employed hereafter should be understood to mean either or both of the nucleic acid sequences of the invention and the nucleic acid constructs of the invention.
[0033] The invention also relates to a nucleic acid sequence selected from SEQ ID NO's: 1-541 and 547-1004.
[0034] The invention also relates to a protein encoded by a nucleic acid sequence of the invention. The protein may also include one or more mitochondrial localisation signal(s). This may be but not limited to sequences such as MLSKNLYSNKRLLTSTNTLVRFASTRS (SEQ ID NO: 1006) or MSVLTPLLLRGLTGSARRLPVPRAKIHSL (SEQ ID NO: 1007).
[0035] The invention also relates to a vector suitable for use in gene therapy and comprising a nucleic acid sequence of the invention. Suitably the vector is a viral vector, typically an adeno-associated virus (AAV), preferably AAV virus serotype 2, although other AAV serotypes and other types of vectors may be employed such as for example other viral vectors, non-viral vectors, naked DNA and other vectors, examples of which are listed in Table 5. Typically, the nucleic acid of the invention is expressed singly from the vector (single delivery vehicle). In another embodiment, the nucleic acid of the invention is expressed together with another gene either from the single delivery vehicle or using two delivery vechicles, for example, a gene that enhances cell survival and or cell function such as a neurotrophic factor, a growth factor, an anti-apoptotic agent, an antioxidant, a cytokine, a hormone or others, examples of which are described in Table 6. Genes may be delivered at the same time and/or before and/or after each other. Ideally, the second gene is a neurotrophic factor, examples of which are described in Table 6.
[0036] The invention also relates to a kit comprising a vector of the invention in combination with a second vector comprising a gene that enhances cell survival and or cell function such as a neurotrophic factor, a growth factor, an anti-apoptotic agent, an antioxidant, a cytokine, a hormone or others, examples of which are described in Table 6. Ideally, the second vector comprises a gene encoding a neurotrophic factor.
[0037] In an additional aspect additional gene sequences may be expressed in the same vector as the nucleic acid of the invention from a component such as an internal ribosome entry site (IRES) and or may be expressed using two or multiple promoter sequences.
[0038] Typically, the vector of the invention comprises a promotor wherein the nucleic acid of the invention is expressed from the promotor. Preferably, the promotor is one that is preferentially or specifically expressed in retinal ganglion cells (RGC's) wherein expression of the nucleic acid of the invention is under the control of the promotor. Examples of such promotors are described in Table 4. In an alternative embodiment, the vector of the invention comprises a promotor known to be expressed at low levels in RGC's.
[0039] In a further embodiment, the promotor is one that is known to be expressed in multiple cell types, examples of which are described in Table 4.
[0040] In an additional aspect, the nucleic acid of the invention is expressed from an inducible and/or conditional promotor.
[0041] In a further embodiment, the promotor is a tissue specific and/or cell specific promotor targeting mammalian cells other than RGC's such as the rhodopsin promotor which expresses in rod photoreceptor cells. Suitably, the vector comprises tissue specific and/or cell specific promotors combined with an inducible promotor system to control expression of the nucleic acid.
[0042] The promotors may control expression of the nucleic acid of the invention in combination with additional genes, as described above. Alternatively, the vector may comprise different promotors for expressing the nucleic acid of the invention and the other genes, for example, a gene encoding a neurotrophic agent.
[0043] The invention also relates to a method for the treatment and/or prevention of a neurodegenerative disease, especially LHON, which method comprises a step of delivering a nucleic acid of the invention to an individual by means of intraocular, ideally intravitreal, delivery. In one aspect a nucleic acid of the invention is delivered to an individual by means of systemic administration.
[0044] Preferably, the step of delivering the nucleic acid of the invention involves delivering a vector of the invention to the individual.
[0045] The invention also relates to the use of a nucleic acid of the invention, or a protein encoded by a nucleic acid of the invention, or a vector of the invention, as a medicament.
[0046] The invention also relates to a nucleic acid sequence of the invention, or a protein encoded by a nucleic acid sequence of the invention, or a vector of the invention, for use in the treatment of a disease or condition associated with mitochondrial dysfunction, for example a neurodegenerative disease, especially Leber Hereditory Optic Neuropathy (LHON). Typically, the treatment is symptomatic or prophylactic treatment.
[0047] The invention also relates to a method of treating a disease, for example a disease associated with mitochondrial dysfunction, for example a neurodegenerative disease, in an individual comprising a step of administering an active agent to the individual, typically administering the active agent to the eye, ideally to the retinal ganglion cells, photoreceptor cells or other eye cells, in which the active agent includes a nucleic acid sequence of the invention, a protein encoded by the nucleic acid sequence of the invention, or a vector of the invention. The treatment may be symptomatic or prophylactic treatment.
[0048] Typically, the active agent is administered by intra-ocular, ideally intra-vitreal and/or subretinal, administration. The active agent may include an additional agent, for example a gene or protein or compounds that enhances cell survival and or cell function such as a neurotrophic factor, a growth factor, an anti-apoptotic agent, an antioxidant, a cytokine, a hormone or others, examples of which are described in Table 6. The active agent and the additional agent, for example an additional gene, may be delivered at the same time or before or after each other.
[0049] Ideally, the additional agent is a gene encoding a neurotrophic factor, examples of which are described in Table 6. The active agent may be delivered by means of a vector, or by means of separate vectors, or by direct delivery of the additional agent. The active agent may be delivered to other parts of the body involving mitochondrial dysfunction, for example, to the brain for the treatment of neurodegenerative diseases such as Alzheimer's disease, Parkinson's disease or dementia, or to photoreceptor cells for the treatment of Retinitis Pigmentosa or Age-related macular degeneration, or to muscle cells to treat muscle weakness and/or degeneration.
[0050] Further, the nucleic acid sequence of the invention, its protein product, or a vector of the invention, may be delivered to the target cell or tissue at the same time or at a different time to the additional agent.
[0051] The invention also relates to a cell, for example a stem cell or progenitor cell, RGC or RGC precursor cell that is transformed with a nucleic acid of the invention. Cells of the invention may be delivered to the eye via subretinal and/or intravitreal injection to treat cells of the eye affected by mitochondrial dysfunction such as RGC dysfunction. Alternatively, cells of the invention may be delivered to other parts of the body involving mitochondrial dysfunction, for example to the brain for the treatment of neurodegenerative diseases such as Alzheimer disease, Parkinsons disease or dementia, or to photoreceptor cells for the treatment of Retinitis Pigmentosa or Age-related macular degeneration, or to muscle cells to treat muscle weakness and/or degeneration.
[0052] Thus, the invention also relates to a transformed cell of the invention for use as a medicament. The invention also relates to a method of treating a disease or condition involving mitochondrial dysfunction, typically a neurodegenerative disease, suitably LHON, comprising a step of delivering cells of the invention to the individual.
[0053] The invention also provides a pharmaceutical formulation comprising an active agent selected from a nucleic acid of the invention, a protein encoded by the nucleic acid of the invention, a vector of the invention, or a cell of the invention, in combination with a pharmaceutically acceptable carrier.
[0054] Suitably, the formulation is provided in the form of a slow release capsule adapted to release the active agent following subretinal and or intravitreal injection, or following delivery to or close to a target tissue type/cell type (see examples in Table 7).
[0055] In an additional embodiment encapsulated cell technology is employed for delivery of the therapy.
[0056] In one embodiment the invention provides a transgenic organ, or a transgenic non-human animal, comprising the nucleic acids and vectors of the invention.
[0057] In another embodiment the invention may be delivered to cells with mutations in the nuclear genome which lead to disease phenotypes which are similar to disease phenotypes related to mitochondrial mutations. For example the disease phenotypes described in Table 8 may all result from nuclear mutations or mitochondrial mutations and hence may benefit from the invention. The invention would need to be delivered to the appropriate affected cell or tissue type. Typically these nuclear mutations affect cell types that require high levels of energy such as neurons and muscle cells. Hence these disorders, resulting from mutations in the nuclear genome and affecting these high energy requiring cell types may also benefit from additional energy provided by the invention.
[0058] In a further aspect, the invention relates to a method for the treatment or prevention of a neurodegenerative disease, especially LHON, which method comprises a step of delivering a yeast NDI1 gene, or a variant thereof such as a nucleic acid of the invention, to an individual by means of intraocular delivery, ideally intravitreal and/or subretinal delivery.
[0059] In a yet further aspect, the invention relates to a method for the treatment or prevention of a neurodegenerative disease, especially LHON, which method comprises a step of delivering a yeast NDI1 gene, or a variant thereof such as a nucleic acid of the invention, and an agent that enhances cell survival and or cell function such as a neurotrophic factor, a growth factor, an anti-apoptotic agent, an antioxidant, a cytokine, a hormone or others (examples of which are described in Table 6) to an individual. Treatment may be symptomatic or prophylactic.
[0060] In a yet further aspect, the invention relates to a method for the treatment or prevention of a neurodegenerative disease, especially LHON, which method comprises a step of delivering a yeast NDI1 gene, or a variant thereof such as a nucleic acid of the invention using an AAV vector, and delivery of an agent, using the same or a separate AAV vector, that enhances cell survival and or cell function such as a neurotrophic factor, a growth factor, an anti-apoptotic agent, an antioxidant, a cytokine, a hormone or others (examples of which are described in Table 6) to an individual. Treatment may be symptomatic or prophylactic.
[0061] The term “yeast NDI1 gene” refers to the wild-type Saccharomyces cerviscae NDI1 gene shown in SEQ ID NO: 1.
[0062] The term “variant of yeast NDI1 gene” means a variant of yeast NDI1 gene which differs from the wild-type gene due to at least codon optimisation, immune optimisation, or both.
[0063] The term “conservative amino acid change” should to be understood to mean that the amino acid being introduced is similar structurally, chemically, or functionally to that being substituted. In particular, it refers to the substitution of an amino acid of a particular grouping as defined by its side chain with a different amino acid from the same grouping.
[0064] The term nucleic acid means deoxyribonucleic acid (DNA), ribonucleic acid (RNA), and artificial nucleic acid analogs such as peptide nucleic acid (PNA), morpholino- and locked nucleic acid, glycol nucleic acid and threose nucleic acid. Artificial nucleic acid analogs differ from DNA and RNA as they typically contain changes to the backbone of the molecule. Nucleic acids incorporating chemical modification(s) to DNA and RNA to optimise delivery and or increase stability and or increase longevity and or reduce immunogenicity are also contemplated by the term nucleic acid. Modifications, such as phosphorothioates, boranophosphate, 2′-Amino, 2′-Fluoro, 2′-Methoxy have been made to nucleic acids to modulate parameters such as resistance to nuclease degradation, binding affinity and or uptake. Exemplary nucleic acid molecules for use are phosphoramidate, phosphothioate and methylphosphonate analogs of DNA and or RNA. Modifications include but are not limited to inclusion of 5-fluorouracil, 5-bromouracil, 5-chlorouracil, 5-iodouracil, hypoxanthine, xantine, 4-acetylcytosine, 5-(carboxyhydroxylmethyl)uracil, 5-carboxymethylaminomethyl-2-thiouridine, 5-carboxymethylaminomethyluracil, dihydrouracil, beta-D-galactosylqueosine, inosine, N6-isopentenyladenine, 1-methylguanine, 1-methylinosine, 2,2-dimethylguanine, 2-methyladenine, 2-methylguanine, 3-methylcytosine, 5-methylcytosine, N6-adenine, 7-methylguanine, 5-methylaminomethyluracil, 5-methoxyaminomethyl-2-thiouracil, beta-D-mannosylqueosine, 5′-methoxycarboxymethyluracil, 5-methoxyuracil, 2-methylthio-N6-isopentenyladenine, uracil-5-oxyacetic acid (v), wybutoxosine, pseudouracil, queosine, 2-thiocytosine, 2′-O-methyl, 5-methyl-2-thiouracil, 2-thiouracil, 4-thiouracil, 5-methyluracil, uracil-5-oxyacetic acid methylester, uracil-5-oxyacetic acid (v), -5-methyl-2-thiouracil, 3-(3-amino-3-N-2-carboxypropyl)uracil, (acp3)w, and 2,6-diaminopurine, 2-thiourdine, 5-methyl-cytidine amongst others.
[0065] The term “codon optimised” means that a codon that expresses a bias for yeast (i.e. is common in yeast genes but uncommon in mammalian genes) is changed to a synonomous codon (a codon that codes for the same amino acid) that expresses a bias for mammals. Thus, the change in codon does not result in any amino acid change in the encoded protein.
[0066] The term “immune optimised” as applied to a variant of yeast NDI1 gene means that the gene variant encodes a variant NDI1 protein which elicits a reduced immune response when expressed in a mammal compared to the wild-type yeast NDI1 gene.
[0067] The term “yeast NDI1 protein” should be understood to mean the wild-type Saccharomyces cerviscae NDI1 protein shown in SEQ ID NO: 542. The “functional variant” should be understood to mean a variant of SEQ ID NO: 542 which retains the functionality of yeast NDI1 protein, for example, comparable oxygen consumption measurements in the presence of rotenone (see methods below/ FIG. 2 ). Typically, the functional variants of yeast NDI1 protein will have at least 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% sequence identity with SEQ ID NO: 542. In this context, a polypeptide sequence that shares 90% amino acid identity with SEQ ID NO: 542 is one in which any 90% of aligned residues are either identical to, or conservative substitutions of, the corresponding residues in SEQ ID NO: 542. The “percent sequence identity” of two amino acid sequences is determined using the algorithm of Karlin and Altschul Proc. Natl. Acad. Sci . USA 87:2264-68, 1990, modified as in Karlin and Altschul Proc. Natl. Acad. Sci . USA 90:5873-77, 1993. Such an algorithm is incorporated into the NBLAST and XBLAST programs (version 2.0) of Altschul, et al. J. Mol. Biol. 215:403-10, 1990. BLAST protein searches can be performed with the XBLAST program, score=50, wordlength=3 to obtain amino acid sequences homologous to the protein molecules of the invention. Where gaps exist between two sequences, Gapped BLAST can be utilized as described in Altschul et al., Nucleic Acids Res. 25(17):3389-3402, 1997. When utilizing BLAST and Gapped BLAST programs, the default parameters of the respective programs (e.g., XBLAST and NBLAST) can be used.
[0068] The term “neurodegenerative disease” should be understood to mean a disease characterised by neuronal injury or death, or axonal degeneration, and includes diseases such as motor neuron disease; prion disease; Huntington's disease; Parkinson's disease; Parkinson's plus; Tauopathies; Chromosome 17 dementias; Alzheimer's disease; Multiple sclerosis (MS); hereditary and acquired neuropathies; retinopathies and diseases involving cerebellar degeneration.
[0069] In the context of the present invention, the term “gene therapy” refers to treatment of individual which involves insertion of a gene into an individual's cells for the purpose of preventing or treating disease. Insertion of the gene is generally achieved using a delivery vehicle, also known as a vector. Viral and non-viral vectors may be employed to deliver a gene to a patients' cells. Other types of vectors suitable for use in gene therapy are described below.
[0070] The term “neurotrophic agent” should be understood to mean a protein that induces the survival, development and function of neurons. Examples include nerve growth factor (NGF) and brain-derived neurotrophic factor (BDNF). Other examples are provided below.
[0071] Retinal ganglion cells (RGCs) are types of neurons located close to the inner surface (the retinal ganglion layer) of the retina of the eye. They collectively image forming and non-image forming visual information from the retina to several regions in the thalamus, hypothalamus, and mid-brain.
[0072] It will be appreciated that the nucleci acids of the invention may include one or more polyadenylation signals, typically located at the 3′-end of the molecule. In addition, the nucleic acid may include a leader sequence and/or a stop codon. It will also be appreciated that the nucleci acids of the invention may include one or more signals to facilitate import of proteins into mitochondria.
[0073] Proteins and polypeptides (including variants and fragments thereof) of and for use in the invention may be generated wholly or partly by chemical synthesis or by expression from nucleic acid. The proteins and peptides of and for use in the present invention can be readily prepared according to well-established, standard liquid or, preferably, solid-phase peptide synthesis methods known in the art (see, for example, J. M. Stewart and J. D. Young, Solid Phase Peptide Synthesis, 2nd edition, Pierce Chemical Company, Rockford, Ill. (1984), in M. Bodanzsky and A. Bodanzsky, The Practice of Peptide Synthesis, Springer Verlag, New York (1984).
[0074] Apart from the specific delivery systems embodied below, various delivery systems are known and can be used to administer the therapeutic of the invention, e.g., encapsulation in liposomes, microparticles, microcapsules, recombinant cells capable of expressing the Therapeutic, receptor-mediated endocytosis (see, e.g., Wu and Wu, 1987, J. Biol. Chem. 262:4429-4432), construction of a therapeutic nucleic acid as part of a retroviral or other vector, etc. Methods of introduction include but are not limited to intradermal, intramuscular, intraperitoneal, intraocular, intravenous, subcutaneous, intranasal, epidural, and oral routes. The compounds may be administered by any convenient route, for example by infusion or bolus injection, by absorption through epithelial or mucocutaneous linings (e.g., oral mucosa, rectal and intestinal mucosa, etc.) and may be administered together with other biologically active agents. Administration can be systemic or local. In addition, it may be desirable to introduce the pharmaceutical compositions of the invention into the central nervous system by any suitable route, including intraventricular and intrathecal injection; intraventricular injection may be facilitated by an intraventricular catheter, for example, attached to a reservoir, such as an Ommaya reservoir. Pulmonary administration can also be employed, e.g., by use of an inhaler or nebulizer, and formulation with an aerosolizing agent. In addition, naked DNA can be used for delivery.
[0075] In one aspect of the invention, agents such as surfactants may be included in formulations to minimize aggregation of the therapeutic of the invention, whether viral and/or non-viral vectors, proteins or polypeptides and/or cells.
[0076] In a specific embodiment, it may be desirable to administer the pharmaceutical compositions of the invention locally to the area in need of treatment; this may be achieved, for example, by means of an implant, said implant being of a porous, non-porous, or gelatinous material, including membranes, such as sialastic membranes, or fibers.
[0077] In another embodiment, the therapeutic can be delivered in a vesicle, in particular a liposome (see Langer, Science 249:1527-1533 (1990); Treat et al., in Liposomes in the Therapy of Infectious Disease and Cancer, Lopez-Berestein and Fidler (eds.), Liss, New York, pp. 353-365 (1989); Lopez-Berestein, ibid., pp. 317-327; see generally ibid.)
[0078] In yet another embodiment, the therapeutic can be delivered in a controlled release system. In one embodiment, a pump may be used (see Langer, supra; Sefton, CRC Crit. Ref. Biomed., Eng. 14:201 (1987); Buchwald et al., Surgery 88:75 (1980); Saudek et al., N. Engl. J. Med. 321:574 (1989)). In another embodiment, polymeric materials can be used (see Medical Applications of Controlled Release, Langer and Wise (eds.), CRC Pres., Boca Raton, Fla. (1974); Controlled Drug Bioavailability, Drug Product Design and Performance, Smolen and Ball (eds.), Wiley, New York (1984); Ranger and Peppas, J. Macromol. Sci. Rev. Macromol. Chem. 23:61 (1983); see also Levy et al., Science 228:190 (1985); During et al., Ann. Neurol. 25:351 (1989); Howard et al., J. Neurosurg. 71:105 (1989)). In yet another embodiment, a controlled release system can be placed in proximity of the therapeutic target, thus requiring only a fraction of the systemic dose (see, e.g., Goodson, in Medical Applications of Controlled Release, supra, vol. 2, pp. 115-138 (1984)). Other controlled release systems are discussed in the review by Langer (Science 249:1527-1533 (1990)).
[0079] The present invention also provides pharmaceutical compositions comprising a nucleic acid of the invention and/or a protein encoded by the nucleic acid. Such compositions comprise a therapeutically effective amount of the therapeutic, and a pharmaceutically acceptable carrier. In a specific embodiment, the term “pharmaceutically acceptable” means approved by a regulatory agency of the Federal or a state government or listed in the U.S. Pharmacopeia or other generally recognized pharmacopeia for use in animals, and humans. The term “carrier” refers to a diluent, adjuvant, excipient, or vehicle with which the therapeutic is administered. Such pharmaceutical carriers can be sterile liquids, such as water and oils, including those of petroleum, animal, vegetable or synthetic origin, such as peanut oil, soybean oil, mineral oil, sesame oil and the like. Water is a preferred carrier when the pharmaceutical composition is administered intravenously. Saline solutions and aqueous dextrose and glycerol solutions can also be employed as liquid carriers, particularly for injectable solutions. Suitable pharmaceutical excipients include starch, glucose, lactose, sucrose, gelatin, malt, rice, flour, chalk, silica gel, sodium stearate, glycerol monostearate, talc, sodium chloride, dried skim milk, glycerol, propylene glycol, water, ethanol and the like.
[0080] The composition, if desired, can also contain minor amounts of wetting or emulsifying agents, or pH buffering agents. These compositions can take the form of solutions, suspensions, emulsion, tablets, pills, capsules, powders, sustained-release formulations and the like. The composition can be formulated as a suppository, with traditional binders and carriers such as triglycerides. Oral formulation can include standard carriers such as pharmaceutical grades of mannitol, lactose, starch, magnesium stearate, sodium saccharine, cellulose, magnesium carbonate, etc. Examples of suitable pharmaceutical carriers are described in “Remington's Pharmaceutical Sciences” by E. W. Martin. Such compositions will contain a therapeutically effective amount of the therapeutic, preferably in purified form, together with a suitable amount of carrier so as to provide the form for proper administration to the patient.
[0081] In a preferred embodiment, the composition is formulated in accordance with routine procedures as a pharmaceutical composition adapted for intravenous administration to human beings. Typically, compositions for intravenous administration are solutions in sterile isotonic aqueous buffer. Where necessary, the composition may also include a solubilizing agent and a local anesthetic such as lignocaine to, ease pain at the, site of the injection. Generally, the ingredients are supplied either separately or mixed together in unit dosage form, for example, as a dry lyophilized powder or water free concentrate in a hermetically sealed container such as an ampoule or sachette indicating the quantity of active agent. Where the composition is to be administered by infusion, it can be dispensed with an infusion bottle containing sterile pharmaceutical grade water or saline. Where the composition is administered by injection, an ampoule of sterile water for injection or saline can be provided so that the ingredients may be mixed prior to administration.
[0082] The amount of the therapeutic of the invention which will be effective in the treatment of a particular disorder or condition will depend on the nature of the disorder or condition, and can be determined by standard clinical techniques. In addition, in vivo and/or in vitro assays may optionally be employed to help predict optimal dosage ranges. The precise dose to be employed in the formulation will also depend on the route of administration, and the seriousness of the disease or disorder, and should be decided according to the judgment of the practitioner and each patient's circumstances.
Nucleic Acid Sequences of the Invention
[0083] The sequence listing below provides a number of nucleic acid sequences according to the invention, specifically:
[0084] SEQ ID NO: 1—Yeast NDI1 gene—0 amino acid changes—0 codon changes
[0085] SEQ ID NO'S 2-21 and 825-834—Yeast NDI1 gene—0 amino acid changes—100 codon changes
[0086] SEQ ID NO'S 22-41 and 885-894—Yeast NDI1 gene—0 amino acid changes—200 codon changes
[0087] SEQ ID NO'S 42-61 and 945-954—Yeast NDI1 gene—0 amino acid changes—300 codon changes
[0088] SEQ ID NO 62—Yeast NDI1 gene—0 amino acid changes—329 codon changes
[0089] SEQ ID NO'S 63-74 and 547-565—Yeast NDI1 gene—1 amino acid changes—0 codon changes
[0090] SEQ ID NO'S 75-94 and 835-844—Yeast NDI1 gene—1 amino acid changes—100 codon changes
[0091] SEQ ID NO'S 95-114 and 895-904—Yeast NDI1 gene—1 amino acid changes—200 codon changes
[0092] SEQ ID NO'S 115-134 and 955-964—Yeast NDI1 gene—1 amino acid changes—300 codon changes
[0093] SEQ ID NO'S 134-145 and 566-584—Yeast NDI1 gene—1 amino acid changes—329 codon changes
[0094] SEQ ID NO'S 146-164 and 585-605—Yeast NDI1 gene—2 amino acid changes—0 codon changes
[0095] SEQ ID NO'S 165-184 and 845-854—Yeast NDI1 gene—2 amino acid changes—100 codon changes
[0096] SEQ ID NO'S 185-204 and 905-914—Yeast NDI1 gene—2 amino acid changes—200 codon changes
[0097] SEQ ID NO'S 205-224 and 965-974—Yeast NDI1 gene—2 amino acid changes—300 codon changes
[0098] SEQ ID NO'S 225-243 and 705-725—Yeast NDI1 gene—2 amino acid changes—329 codon changes
[0099] SEQ ID NO'S 244-263 and 606-640—Yeast NDI1 gene—3 amino acid changes—0 codon changes
[0100] SEQ ID NO'S 264-283 and 855-864—Yeast NDI1 gene—3 amino acid changes—100 codon changes
[0101] SEQ ID NO'S 284-303 and 915-924—Yeast NDI1 gene—3 amino acid changes—200 codon changes
[0102] SEQ ID NO'S 304-323 and 975-984—Yeast NDI1 gene—3 amino acid changes—300 codon changes
[0103] SEQ ID NO'S 324-341 and 726-760—Yeast NDI1 gene—3 amino acid changes—329 codon changes
[0104] SEQ ID NO'S 641-675—Yeast NDI1 gene—4 amino acid changes—0 codon changes
[0105] SEQ ID NO'S 865-874—Yeast NDI1 gene—4 amino acid changes—100 codon changes
[0106] SEQ ID NO'S 925-934—Yeast NDI1 gene—4 amino acid changes—200 codon changes
[0107] SEQ ID NO'S 985-994—Yeast NDI1 gene—4 amino acid changes—300 codon changes
[0108] SEQ ID NO'S 761-795—Yeast NDI1 gene—4 amino acid changes—329 codon changes
[0109] SEQ ID NO'S 342-361 and 676-696—Yeast NDI1 gene—5 amino acid changes—0 codon changes
[0110] SEQ ID NO'S 362-381 and 875-884—Yeast NDI1 gene—5 amino acid changes—100 codon changes
[0111] SEQ ID NO'S 382-401 and 935-944—Yeast NDI1 gene—5 amino acid changes—200 codon changes
[0112] SEQ ID NO'S 402-421 and 995-1004—Yeast NDI1 gene—5 amino acid changes—300 codon changes
[0113] SEQ ID NO'S 422-441 and 796-816—Yeast NDI1 gene—5 amino acid changes—329 codon changes
[0114] SEQ ID NO'S 697-703—Yeast NDI1 gene—6 amino acid changes—0 codon changes
[0115] SEQ ID NO'S 817-823—Yeast NDI1 gene—6 amino acid changes—329 codon changes
[0116] SEQ ID NO 704—Yeast NDI1 gene—7 amino acid changes—0 codon changes SEQ ID NO 824—Yeast NDI1 gene—7 amino acid changes—329 codon changes
[0117] SEQ ID NO'S 442-461—Yeast NDI1 gene—10 amino acid changes—0 codon changes
[0118] SEQ ID NO'S 462-481—Yeast NDI1 gene—10 amino acid changes—100 codon changes
[0119] SEQ ID NO'S 482-501—Yeast NDI1 gene—10 amino acid changes—200 codon changes
[0120] SEQ ID NO'S 502-521—Yeast NDI1 gene—10 amino acid changes—300 codon changes
[0121] SEQ ID NO'S 522-541—Yeast NDI1 gene—10 amino acid changes—329 codon changes
[0122] SEQ ID NO: 542—Yeast NDI1 protein—0 amino acid changes
BRIEF DESCRIPTION OF THE FIGURES
[0123] FIG. 1 . Diagrammatic representation of the core construct designs. A: OphNDI1; OphNDI1 (yeast NDI1 gene which has been codon optimized and/or immune optimized) was expressed from the CMV (cytomegalovirus) immediate early promoter. A minimal polyadenylation signal was located at the 3′ end of the NDI1 gene. B: AAV-GDNF; GDNF (glial cell line derived neurotrophic factor) was expressed from the short ubiquitin promoter. The neurturin polyadenylation signal was located at the 3′ end of the GDNF gene. C: AAV-OphNDI1_GDNF; OphNDI1 was expressed from the CMV immediate early promoter. A minimal polyadenylation signal was located at the 3′ end of the NDI1 gene. 3′ to this GDNF was expressed from the short ubiquitin promoter. The neurturin polyadenylation signal was located at the 3′ end of the GDNF gene. D: OphNdiI expressed from a CMV promoter with a 3′ minimal polyadenylation signal. In this construct GDNF is expressed from an IRES and also contains the neurturin Polyadenylation signal.
[0124] Notably OphNDI1 may contain 0-10 amino acid substitutions to modulate and immune response or 1-329 altered codons, which are expressed more frequently in mammalian cells than the wild type codons in NDI1 (Table 1a & 1b and Sequence Listing). In addition the CMV and ubiquitin promoters may be substituted for any of the promoters indicated in Tables 2-4 and the GDNF gene may be substituted for any gene indicated in Table 6. Sequences for these core construct designs are presented in Table 1a & 1b and the attached Sequence Listing. Notably, different polyadenalation signals may also be utilised in the constructs described.
[0125] FIG. 2 . Localisation, function and mRNA expression of NDI1. Western blot analysis of mitochondrial protein isolated from pAAV-NDI1 transfected and untransfected (Ctrl) HeLa cells (A). Top panel shows NDI1 protein expression (56 KDa) and bottom panel shows VDAC1 protein expression (31 KDa, mitochondrial loading control; n=3). B. Bar chart represents oxygen consumption measurements from pAAV-NDI1 transfected (black columns) and pAAV-EGFP transfected (Ctrl, white columns) HeLa cells with (+) and without (no) 5 μmol rotenone (n=6). C. Bar chart represents percentage rotenone insensitive respiration in pAAV-NDI1 transfected (black columns) and pAAV-EGFP transfected (control, white columns) HeLa cells (n=6). D. Retinal NDI1 mRNA expression from adult wild type mice intravitreally injected with 3×10 8 vp AAV-NDI1 or 3×10 8 vp AAV-EGFP (Ctrl) and analysed by RT-PCR two weeks post-injection (n=6). Rot insensitive resp (%): Percentage rotenone insensitive respiration, w: water blank, M: size marker; KDa (A), by (D). Error bars represent SD values and *: p<0.001.
[0126] FIG. 3 . Oxygen consumption measurements from NDI1 transfected HeLa cells. Oxygen consumption measurements from HeLa cells transfected with pAAV-NDI1 (A) and pAAV-EGFP (B) in the presence of 5 μmol rotenone. Oxygen consumption measurements from HeLa cells transfected with pAAV-NDI1 (C) and pAAV-EGFP (D) in the absence of rotenone (control).
[0127] FIG. 4 a . Oxygraphs for NDI1 constructs. Traces showing oxygen concentration (blue line) and oxygen consumption (red line) in media treated with 5 μmol rotenone and untransfected HeLa cells (negative control, A), cells transfected with ophNDI1-I82V (B), containing codon-optimisation at 329 codons and the I82V substitution and cells transfected with NDI1-I82V (C). Representative graphs for each are presented. Similarly HeLa cells were transfected with V45I constructs either the codon optimised hNDI1-V45I construct (D) or the wild type NDI1 construct containing the V45I substitution (NDI1-V45I; E). In addition V266I constructs, both NDI1-V266I (F) and hNDI1-V266I (G) were evaluated. The NDI1-F90Y (H) and hNDI1-F90Y (I) construct was also tested in HeLa cells treated with rotenone.
[0128] FIG. 4 b . Bar charts of the data sets measuring the change in oxygen consumption from the experiments in FIG. 4 a are presented. A statistically significant retention in oxygen consumption was observed between cells transfected with either the NDI1 variant or the hNDI1 variant constructs with p values ranging from p<0.05 (*) to <0.01 (**). A significant difference was observed between the rotenone insensitive respiration achieved with I82V and V45I constructs versus that achieved with the F90Y construct (I82V versus F90Y p<0.02 and V45I versus Y90Y p<0.002). No significant differences were observed between NDI1 treated cells and cells treated with NDI1-I82V, hNDI1-I82V or V45I constructs. However F90Y transfected cells differed significantly compared to NDI1 transfected cells, the latter showing a better retention of oxygen consumption.
[0129] FIG. 5 . Histology of NDI1 treated retinas following rotenone insult. Adult wild type mice were intravitreally injected into contralateral eyes with 3×10 8 vp AAV-NDI1 (A) and 1×10 8 vp AAV-EGFP, to facilitate localisation of transduced regions of the retinas, or 3×10 8 vp AAV-EGFP (B) alone (n=4). Three weeks post-injection, 1.5 nmol of rotenone was administered intravitrally to both eyes. Three weeks post-rotenone treatment eyes were enucleated, fixed, cryosectioned (12 μm) and processed for immunocytochemistry using NeuN primary and Cy3-conjugated secondary antibodies. Nuclei were counterstained with DAPI. A and B: representative sections show NeuN labelling (red) and nuclear DAPI (blue) signals overlaid. OS: photoreceptor outer segments; ONL: outer nuclear layer; INL: inner nuclear layer; GCL: ganglion cell layer. Scale bar: 20 μm. C: Bar chart representing mean ganglion cell counts per 100 μm. Blue and white columns represent values corresponding to AAV-NDI1+rotenone (NDI1) and AAV-EGFP+rotenone (EGFP), respectively. Error bars represent SD values and ***: p<0.001.
[0130] FIG. 6 . Ultra-structural analysis of NDI1 treated optic nerves following rotenone insult. Adult wild type mice were intravitrally injected into contralateral eyes with AAV-NDI1 (B) or AAV-EGFP (C and D) (n=3). Three weeks post-injection, 1.5 nmol of rotenone was administered intravitreally to both eyes. Three weeks later eyes were enucleated and optic nerves collected, post-fixed, processed and analysed by transmission electron microscopy. At low magnification electron dense structures (arrow heads, B and C) were less frequent in the AAV-NDI1+rotenone (B) treated samples compared to the AAV-EGFP+rotenone treated samples (C). AAV-EGFP+rotenone treated samples at higher magnification (D). These were not apparent in the untreated samples (A). E: Bar chart representing mean number of membrane debris. Black and white columns represent AAV-NDI1+rotenone (NDI1) and AAV-EGFP+rotenone (EGFP), respectively. F: Bar chart representing mean optic nerve diameter measurements. Optic nerves from identically injected mice were taken nine months post-rotenone treatment, fixed, cryosectioned (12 μm) and the thickness of the optic nerve measured using light microscopy. Black and white columns represent AAV-NDI1+rotenone (NDI1) and AAV-EGFP+rotenone (EGFP), respectively. Error bars represent SD values and **: p<0.01. Scale bars: 10 μm (A, B and C) and 2 μm (D).
[0131] FIG. 7 . Functional analysis of AAV-NDI1 and AAV-NSG treated optic nerves following rotenone insult. Adult wild type mice were intravitreally injected into the right eye with AAV-NDI1 (n=10) or AAV-NSG (n=6). Three weeks later, AAV-NDI1 (n=10) or AAV-NSG (n=6) injected mice received 1.5 nmol rotenone in the right eye. A further group of adult wild type mice received either DMSO (vehicle control, n=16) or 1.5 nmol rotenone intravitreally injected into the right eye (n=16). Two weeks post rotenone, or DMSO, treatment each mouse was intravitreally injected with 40 μg manganese chloride and manganese enhanced magnetic resonance imaging (MEMRI) carried out 2 hrs later. Pseudo-coloured T1-weighted images: Signal enhancement of the mouse visual pathway in oblique sections (36°) from DMSO (A), rotenone alone (B), AAV-NDI1+rotenone (C) and AAV-NSG+rotenone (D) are presented. E: Bar chart representing mean lg signal intensities in the region of the optic chiasm calculated using Image J® software. a.u.: arbitrary unit. Error bars represent SD values and ** represent p<0.01.
[0132] FIG. 8 . Analysis of spatial vision in NDI treated mice following rotenone insult. Adult wild type mice were intravitrally injected into contralateral eyes with 3×10 9 vp AAV-NDI1 or 3×10 9 vp AAV-EGFP. Three weeks post-injection, 1.5 nmol of rotenone was administered intravitreally to both eyes; control mice were not administered with rotenone. Three months post-rotenone treatment optokinetic responses were measured using a virtual optokinetic system. Bar chart represents the mean spatial frequency threshold established for each eye. Black and white columns represent values corresponding to AAV-NDI1+rotenone (NDI1) and AAV-EGFP+rotenone (EGFP), respectively in rotenone treated (+Rotenone) and control (No Rotenone) mice. Error bars represent SD values and ***: p<0.001.
[0133] FIG. 9 a . A representative western blot of proteins extracted from HeLa cells transiently transfected with plasmids expressing OphNDI1 and NDI1. A polyclonal antibody for Ndi1 was used to detect OphNDI1 and Ndi1 protein expressed in transfected cells. Lane 1; Ndi1 protein expressed from the original wild type NDI1 construct, Lane 2; Ndi1 with a C-terminal HA tag, Lane 3; Ndi1 protein expressed from OphNDI1, a humanized NDI1 construct with 329 optimised codons, Lane 4; Ndi1 protein expressed from OphNDI1-HA, a humanized Ndi1 with a HA tag. Lane 5; untransfected HeLa cells.
[0134] FIG. 9 b : Bar chart showing normalized expression of humanized and wild-type Ndi1 protein as measured by western blot. HeLa cells were transfected with humanized and wild-type Ndi1. Cells were harvested 48 hours post-transfection and protein was extracted and western blotted using a polyclonal anti-Ndi1 primary antibody. Four independent blots were performed and images were captured and analysed with ImageJ® software to measure relative expression. For each blot, the relative expression level of wild-type Ndi1 was taken as a reference and the expression level of humanized Ndi1 was directly compared to it. Paired t-test performed on the non-normalized values indicate that humanized Ndi1 expresses significantly more highly than wild-typeNdI1 (P<0.005). a.u.:arbitrary unit
[0135] FIG. 10 . Expression from AAV vectors expressing variants of NDI1 AAV vectors were intravitreally injected into wild type mice. AAV vectors contained unmodified NDI1, NSG (expressing both unmodified NDI1 and a GDNF gene), modified NDI1 with a V266I modification, humanised NDI1 (hNDI1), or hNDI1 with a I82V modification. Two weeks post-injection retinas were harvested and total RNA extracted. Real time RT PCRs were performed on RNA samples using primers NDI1F and NDI1R and hNDI1F and hNDI1 R.
[0136] A, Levels of NDI1 expressed from unmodified vector (NDI1) and from NSG, which expresses both an unmodified NDI1 gene and a GDNF gene, were compared by real time RT-PCR. Levels of expression (y-axis) are expressed in copy number per unit of the housekeeping gene, β-actin.
[0137] B, Levels of humanised NDI1 (hNDI1) expressed in mouse retina delivered invitreally using AAV2/2 vectors were compared to levels of unmodified NDI1 delivered also using AAV2/2. Levels of expression are expressed in copy number per unit of the housekeeping gene β-actin. As expression levels in FIGS. 5A and 5B are expressed in copy number per unit of the housekeeping gene β-actin, expression levels may be compared directly.
[0138] C, RT-PCR samples performed on RNA samples extracted from wild type mice which were intravitreally injected with AAV2/2 vectors expressing variants of the NDI1 gene and run on 3% agarose gels. Lanes 1 and 8, GeneRuler 100 bp DNA size ladder (Fermentas). The two lower bands of the ladder represent 100 and 200 bp. Lane 2, NDI1; Lane 3, NSG; Lane 4, NDI1 with V266I modification; Lane 5, NSG; Lane 6, humanised NDI1; Lane 7 Humanised NDI1 with I82V modification. NDI1 amplification product is 87 bp and humanised NDI1 amplification product is 115 bp. Equal amounts of PCR products were loaded into each well. The hNDI1 and NSG vectors resulted in visibly higher levels of expression than the unmodified NDI1 vector mirroring the findings in FIGS. 10 a and 10 b.
[0139] FIG. 11 . Immunogenicity predictions of each 9-mer peptide fragment in NDI1, via in silico modelling of antigen presentation using the MHC class I predictor alone ( FIG. 11 a ) or employing the MHC-I pathway using the IEDB proteasomal cleavage/TAP transport/MHC class I combined predictor ( FIG. 11 b ). Immunogenicity scores and amino acid positions are presented.
[0140] FIG. 12A . Oxygraphs for NSG constructs Trace showing oxygen concentration (blue line) and oxygen consumption (red line) in media containing untransfected cells (negative control A), cells transfected with wild-type Ndi1 (B) and cells transfected with NSG, a construct expressing both wild-type NDI1 and GDNF (C). In each case, cells were analysed without rotenone and a steady respiration level measured. Once respiration stabilized and a measurement taken, 5 μmol rotenone was added and a measurement of rotenone-insensitive respiration taken once oxygen consumption stabilized.
[0141] FIG. 12B : A bar chart of the data from NSG and NDI1 transfected HeLa cells is presented. NSG and NDI1 transfected HeLa cells did not differ significantly from each other p=0.6, however, both significantly retained oxygen consumption compared to untransfected controls (NSG p<0.05 and NDI1 p<0.01).
DETAILED DESCRIPTION OF THE INVENTION
[0142] In the present invention delivery of NDI1 constructs ( FIG. 1 ) has been used to protect cells in the presence of a complex I inhibitor, rotenone, ( FIGS. 2-8 and 12 ), HeLa cells and retinal ganglion cells (RGCs) were protected in the presence of NDI1 delivered as a wild type construct or as codon-optimised and immuno-optimised constructs ( FIGS. 2-4 ). For example, RGCs, the cells primarily affected in LHON, were protected in a rotenone-induced murine model of LHON. Recombinant AAV serotype 2 (AAV2/2) expressing wild type NDI1 from a CMV promoter (AAV-NDI1, FIG. 1A ) was administered to mice using a single intravitreal injection. AAV2/2 administered through this route has been shown to infect RGCs efficiently. Moreover, intravitreal injection typically results in a broad area of retinal transduction as the vitreous contacts the entire underlying retinal surface 32 . Intravitreal injection of AAV provides a route of administration for the gene therapy which is directly applicable to human patients and is routinely used to administer drugs such as Avastin and Lucentis for treatment of wet AMD. In this study, intravitreal injection of AAV-NDI1 was utilised for the first time and was shown significantly to reduce RGC death and optic nerve atrophy seen in untreated eyes in response to rotenone administration and moreover, led to a preservation of retinal function as assessed by manganese enhanced magnetic resonance imaging (MEMRI) and optokinetic responses (OKR; FIGS. 5-8 ).
[0143] In the present Application, intravitreal injection of AAV-NDI1 provided substantial protection against rotenone-induced insult, as assessed by a variety of assays ( FIGS. 5-8 ). Notably, histological analyses demonstrated significant protection of both RGCs and the optic nerve ( FIGS. 5 and 6 ). Furthermore, MEMRI indicated that AAV-NDI1 treatment preserved optic nerve function by enabling active transport of manganese ions through the optic nerve using voltage-gated calcium channels and hence provided evidence of the improved functional integrity of the optic nerve tissue in AAV-NDI1 treated eyes compared to control eyes ( FIG. 7 ). Evaluation of visual function by optokinetics showed that the protection of RGCs and optic nerve integrity afforded by AAV-NDI1 led to preservation of mouse vision in the presence of the complex I inhibitor rotenone ( FIG. 8 ). The results highlight the potential therapeutic value of NDI1-based therapies for LHON when intravitreally delivered using AAV2/2.
[0144] Following the successful delivery of AAV-NDI1 to RGCs using intravitreal injection, NDI1 was codon optimised so that codons which are used more frequently in mammalian cells were introduced to the NDI1 yeast gene. Codon modifications from 1-329 codons can be implemented to optimize expression of NDI1 in mammals while maintaining wild type amino acids. The maximal number of codons that can be altered in NDI1 to align codons with those most frequently used in mammals is 329 codons and these alterations were employed to generate a construct termed OphNDI1 and also known as humanized NDI1 (hNDI1). Plasmids containing OphNDI1 (hNDI1) or wild type NDI1, both expressed from a cytomegalovirus (CMV) promoter and containing a minimal polyadenylation (PolyA) signal, a modified rabbit beta-globin polyadenylation signal, were transiently transfected into HeLa cells using lipofectamine. Levels of NDI1 protein expression from NDI1 and hNDI1 constructs were compared using Western Blot analysis. hNDI1 (OphNDI1) was determined to express more highly than wild type NDI1 indicating that codon optimising the NDI1 gene has indeed enhanced expression in mammalian cells ( FIGS. 9 a , 9 b and 10 ). A statistically significant difference in levels of expression was obtained between wild type and optimized NDI1 constructs ( FIGS. 9 a and 9 b ). The results obtained for NDI1 protein ( FIGS. 9 a and 9 b ) are mirrored by those obtained at the RNA level in mice intravitreally injected with AAV wild type and optimized NDI1 constructs using real-time RT PCR as the assay ( FIG. 10 ).
[0145] In addition both the wild type and the codon-optimised NDI1 constructs have been immuno-optimised by introducing one or more amino acid changes to modulate the immune response(s) (Table 1a & 1b and Sequence Listing). Amino acid modifications were undertaken subsequent to in silico analyses for potential immunogenic sites within NDI1 (see FIGS. 11 a and 11 b , material and methods). Immuno-optimised constructs were generated for both the wild type NDI1 construct and for the codon-optimised hNDI1 construct. Modified codon-optimised and immuno-optimised NDI1 constructs were generated as high titre AAV2/2 vectors (1-5×10 11 vg/ml) using triple plasmid transfection methods in 293 cells followed by cesium chloride gradient purification of virus. Representative immuno-optimised NDI1 and immuno-optimised hNDI1 constructs inter alia V45I, I82V, L89I, I90Y, V266I, L481I, L483M were generated as plasmids and or AAV vectors. All nucleated mammalian cells present peptide fragments bound to MHC-I molecules on their cell surface. These fragments are derived from the degradation of proteins in the cytoplasm. As such, MHC-I presentation offers a snapshot of the pool of proteins being produced within each cell. Cytotoxic T-cells inspect the peptide fragments presented by cells and can induce apoptosis in cells presenting non-self proteins, which is usually an indicator of viral infection. HeLa cells were transfected with NDI1, hNDI1 and immuno-optimised constructs and levels of rotenone insensitive respiration evaluated ( FIGS. 2-4 , 12 ). Significant retention of oxygen consumption was observed in cells transfected with NDI1, codon-optimised and immuno-optimised constructs ( FIGS. 2-4 , 12 ), when compared to untransfected control cells.
[0146] In addition, to codon-optimized and immuno-optimized NDI1 constructs, a dual component construct was generated containing the CMV promoter driven NDI1 gene together with a ubiquitin promoter driven glial derived neurotrophic factor (GDNF) gene (NSG), the latter employing a neurturin polyA signal ( FIG. 1 ) and generated as an AAV2/2 vector (AAV-NSG). Significantly higher levels of expression of NDI1 were achieved from this vector in vivo in mice after intravitreal injection compared to AAV-NDI1 as evaluated by real time RT-PCR assays ( FIGS. 10 a and 10 c ). GDNF expression from AAV-NSG was confirmed in mouse retinas by real time RT-PCR. Furthermore, intravitreally delivery of AAV-NSG resulted in preservation of cell function as evaluated by oxygen consumption measurements in rotenone treated HeLa cells ( FIG. 12 ) and functional preservation in vivo using MRI analyses of wild type mice intravitreally injected with AAV-NSG vector ( FIG. 7 ). Mean MRI signal intensity for DMSO was 2.38±0.04, for rotenone alone was 2.30±0.06, for AAV-NDI1 plus rotenone was 2.35±0.07 and for AAV-NSG plus rotenone was 2.37±0.07, significant differences were found between the rotenone alone treated mice and those treated with rotenone and either AAV-NDI1 or AAV-NSG; for both rotenone versus AAV-NDI1 and rotenone versus AAV-NSG comparisons, p<0.01 (**). Indeed AAV-NDI1 (plus rotenone) or AAV-NSG (plus rotenone) treated mice did not differ significantly from wild type control mice treated with DMSO alone. Notably these MRI results were established using a 4-fold lower titre of AAV-NSG than AAV-NDI1 (5.99×10 11 vp/ml versus 2.5×10 11 vp/ml) Suggesting that less AAV-NSG is required to mediate an equivalent beneficial effect.
[0147] Cohorts of adult wild type mice were intravitreally injected with 3 ul of AAV2/2 vectors expressing either NDI1, hNDI1, immuno-optimised hNDI1 I82V, immuno-optimised NDI1 V266I or AAV-NSG. Two weeks post-injection retinas were harvested from treated mouse eyes and total RNA extracted. Levels of expression from AAV vectors in mouse retinas were evaluated by real time RT-PCR ( FIG. 10 ). Levels of expression from different vectors could be directly compared as expression was evaluated by absolute copy number per unit of β-actin (the housekeeping control) for each vector. The standard curves were generated using plasmid DNA standards with known copy number. Expression levels achieved after AAV intravitreal injection of vectors were greater in mouse eyes treated with AAV-hNDI1 or AAV-NSG treated eyes compared to AAV-NDI1 injected eyes ( FIG. 10 ).
[0148] All gene therapies which deliver non-human proteins risk activation of cytotoxic T-cell responses following presentation of peptide fragments derived from the transgenic protein. It is therefore important to the success of the treatment that immunogenicity of the transgenic protein is modulated. One of the most effective ways this can be done is by searching the sequence of the protein for fragments which are likely to strongly bind MHC-I, increasing the likelihood that they will be presented on the cell surface and so induce an immune reaction.
[0149] This approach is complicated somewhat by the presence of many different MHC-I alleles in the human population, each of which may have slightly different binding affinities for different peptides.
[0150] There are established bioinformatics methods for predicting the MHC-I binding affinity of a particular peptide, several of which are available as downloadable tools. For our purposes, the consensus prediction method of Nielsen et al (Protein Sci. 2003 May; 12(5):1007-17) was most suitable, in addition to having excellent experimentally-validated accuracy. These tools were adapted and supporting software generated to enable prediction of affinity for a wide variety of MHC-I alleles. The computational tool thus generated may be applied and modified to predict other types of immune responses.
[0151] All potential peptide fragments that could be derived from the Ndi1 protein were assayed by the consensus prediction method for binding affinity to all well-characterised human MHC-I proteins.
Methods
[0152] Vector Construction and AAV Production
[0153] Yeast NDI1 (Accession No: NM — 001182483.1) was cloned as described 53 . Briefly, NDI1 was PCR amplified from total yeast DNA extracted from S288c using the following primers F: TTCTCGAGGTAGGGTGTCAGTTTC (SEQ ID NO: 543) and R: AAAGCGGCCGCAGTGATCAACCAATCTTG (SEQ ID NO: 544) and cloned into XhoI and NotI sites of pcDNA3.1- (Invitrogen, Paisley, UK). A minimal poly-adenylation signals 4 was cloned downstream of NDI1 using NotI and EcoRV. The CMV immediate early promoter (present in pcDNA3.1-), the NDI1 gene and poly-adenylation signal were isolated on a MluI and EcoRV fragment, end filled and cloned into the NotI sites of pAAV-MCS (Agilent Technologies, La Jolla, Calif., USA) to create pAAV-NDI; FIG. 1 . pAAV-EGFP was cloned as previously described 19 .
[0154] The entire human GDNF coding sequence from the atg start codon (nucleotides 201-836 of accession number NM — 000514) was cloned 3-prime of a 347 bp human Ubiquitin promoter (nucleotides 3557-3904 of accession number D63791) and a human Neurturin polyA consisting of nucleotides 1057-1160 of accession number AL161995 was cloned down-stream of the GDNF gene. This entire ubiquitin-driven GDNF cassette, including Neurturin polyA was cloned downstream of the CMV-driven NDI1 (including the rabbit b-globulin polyA).
[0155] Codon optimized NDI1 sequences and/or with amino acid changes to reduce immunogenicity profiles were synthesized by Geneart Inc. These were isolated on a XbaI and XhoI fragment and cloned into pAAV-MCS (Agilent Technologies, La Jolla, Calif., USA) and pcDNA3.1- (Invitrogen, Paisley, UK) plasmids with a CMV immediate early promoter and minimal polyA and verified by DNA sequencing.
[0156] Recombinant AAV2/2 viruses, AAV-ND1, AAV-NSG, pAAV-NDI1 V266I, AAV-huNDI1, pAAV-huNDI1 182V and AAV-EGFP were prepared as described 20 , with a modified cesium chloride gradient as described 19 Additional AAV-ND1, AAV-NSG recombinant AAV2/2 viruses were generated by the Gene Vector production Center of Nantes. Genomic titres (DNase-resistant viral particles per milliliter; vp/ml) were determined by quantitative real-time-polymerase chain reaction (qRT-PCR) according to the method of Rohr et al. 21
Cell Culture
[0157] Human cervical carcinoma cells (HeLa, ATCC accession no. CCL-2) were transfected with pAAV-NDI1 or pAAV-EGFP using Lipofectamine 2000 reagent, according to the manufacturer's instructions (Invitrogen, Carlsbad, Calif., USA). 5×10 5 cells per well were seeded onto 6-well plates containing 1 ml Dulbecco's modified Eagle medium supplemented with 10% calf serum, 2 mM glutamine and 1 mM sodium pyruvate and incubated overnight at 37° C. Media was then aspirated and the cells were washed twice with phosphate-buffered saline (PBS). Each well was transfected with 1 μg pAAV-NDI1 or 1 μg pAAV-EGFP in triplicate. Cells were harvested 48 hrs later and the cells from each triplicate pooled for an individual experiment, each experiment was repeated in triplicate.
Mitochondrial Isolation and Western Blot Analysis
[0158] Mitochondria were isolated from HeLa cells using Anti-TOM22 microbeads (Mitochondria isolation kit, Miltenyi Biotec GmbH, Germany). Isolated mitochondria were washed twice in PBS and homogenised in 100 μl radioimmunoprecipitation assay (RIPA) buffer (150 mM NaCl, 1% Triton X-100, 0.5% sodium deoxycholate, 0.1% SDS, 50 mM TrisCl pH 8.0 and 1 protease inhibitor cocktail tablet/10 mls (Roche, Mannheim, Germany)). The homogenate was centrifuged at 10,000 g for 20 min at 4° C. and the supernatant removed for analysis. Normalised protein samples were separated on 12% polyacrylamide gels and electrophoretically transferred to PVDF membranes (Bio-Rad, Berkley, Calif., USA). The PVDF membrane was blocked with 5% non-fat milk in tris buffered saline (TBS, 0.05M Tris, 150 mM NaCl, pH 7.5) and 0.05% (vol/vol) Tween 20 for 1 hr at room temperature. Rabbit polyclonal antibodies to NDI1 (1:500, Cambridge Research Biochemicals, Cleveland, UK) and VDAC1 (1:1000, Abcam, Cambridge, UK) were diluted in 5% milk and incubated overnight at 4° C. Membranes were washed twice with TBS and incubated with a secondary anti-rabbit (IgG) horseradish peroxidise-conjugated antibody (1:2500, Sigma-Aldrich, St. Louis Mo., USA) for 2 hr at room temperature, exposed to Super-Signal chemiluminescent substrate and enhancer (Pierce Biotechnology, Rochford, Ill., USA) and signal detected using X-ray film (Kodak, Rochester, N.Y., USA). All Western blots were repeated three times.
Respiratory Analysis
[0159] Respiratory measurements were performed in DMEM at 37° C. on an Oxygraph-2k (OROBOROS® INSTRUMENTS GmbH, Innsbruck, Austria) according to the manufacturer's instructions. Briefly, each chamber was calibrated with 2 mls DMEM and stirred (200 rpm) for 1 hr to saturate the media with oxygen. Parallel experiments were run in the two chambers of the Oxygraph-2k using 1×10 6 pAAV-NDI1 or 1×10 6 pAAV-EGFP transfected HeLa cells. Following the addition of cells to the oxygen saturated media the chamber size was reduced to 2 ml to remove air. Continuous readings were taken to establish the fully oxygenated baseline. 2 ul 5 mM rotenone (5 μM in 100% ethanol) was added to 1×10 6 pAAV-NDI1 or 1×10 6 pAAV-EGFP transfected HeLa cells prior to transfer to the requisite chambers and continuous post-rotenone readings taken. Continuous readings were taken both with and without rotenone until oxygen consumption stabilised. Readings were taken from three independent transfections for each construct.
Animals and Intravitreal Injections
[0160] Wild type 129 S2/SvHsd (Harlan UK Ltd, Oxfordshire, UK) mice were maintained under specific pathogen free (spf) housing conditions. Intravitreal injections were carried out in strict compliance with the European Communities Regulations 2002 and 2005 (Cruelty to Animals Act) and the Association for Research in Vision and Ophthalmology (ARVO) statement for the use of animals. Briefly, adult mice were anaesthetised and pupils dilated as described 57 . Using topical anaesthesia (Amethocaine), a small puncture was made in the sclera. A 34-gauge blunt-ended microneedle attached to a 10 μl Hamilton syringe was inserted through the puncture, and 0.6 μl 2.5 mM rotenone (1.5 nmol) in dimethyl sulfoxide (DMSO, vehicle), 0.6 μl DMSO alone or 3 μl 1×10 12 vp/ml AAV2/2 was slowly, over a two minute period, administered into the vitreous. Following intravitreal injection, an anesthetic reversing agent (100 mg/10 g body weight; Atipamezole Hydrochloride) was delivered by intraperitoneal injection. Body temperature was maintained using a homeothermic heating device. All animal studies have been approved by the authors' Institutional Review Board.
RNA Extraction and PCR Analysis
[0161] Adult wild type mice (n=6) were intravitrally injected with 3×10 9 vp AAV-NDI1 while fellow eyes received 3×10 9 vp AAV-EGFP. Retinas were harvested two weeks post-injection and total RNA extracted using the Qiagen RNeasy kit according to the manufacturers specification. In vivo expression of NDI1 from AAV-NDI1 was confirmed by reverse transcription PCR (RT-PCR) on a 7300 Real Time PCR System (Applied Biosystems, Foster City, Calif., USA) using a QuantiTect SYBR Green RT-PCR kit (Qiagen Ltd., Crawley, UK) and resulting amplification products separated and sized on 2.5% agarose gels. The following primers were used: NDI1 forward primer 5′ CACCAGTTGGGACAGTAGAC 3′ (SEQ ID NO: 545) and NDI1 reverse primer: 5′ CCTCATAGTAGGTAACGTTC 3′ (SEQ ID NO: 546). Humanised forms of NDI1 transcript were RT-PCR amplified with hNDI1 forward primer 5′ GAACACCGTGACCATCAAGA 3′ and hNDI1 reverse primer 5′ GCTGATCAGGTAGTCGTACT 3′ β-actin was used as an internal control as described (ref). RT-PCRs were performed twice in triplicate or quadruplicate. Levels of NDI1 or humanised NDI1 expression were determined by real time RT PCR using the Quantitect SYBR green RT PCR kit (Qiagen). Briefly, the copy number of two plasmid DNA preparations containing either NDI1 or humanized NDI1 was determined by spectraphotometry on a NanoDrop and serial dilutions of these plasmid DNA preparations were prepared containing between 10e2-10e7 copies/μl. These standard curves were included in 96-well plates that also included RNA samples to be analysed. Hence expression levels from all constructs, whether humanized or not, could be compared using absolute copy number, even though the primer pairs used for non humanized and humanized PCR amplification were not the same. Expression levels were normalized using the internal housekeeping gene β-actin.
Histology
[0162] Eyes and optic nerves were fixed in 4% paraformaldehyde in PBS (pH 7.4) overnight at room 4° C. washed three times with PBS and cryoprotected using a sucrose gradient (10%, 20%, 30%). 10 μm sections were cut on a cryostat (HM 500 Microm, Leica, Solms, Germany) at −20° C. Nuclei were counterstained with 4′,6-diamidino-2-phenylindole (DAPI). Specimens were analysed with a Zeiss Axiophot fluorescence microscope (Carl Zeiss, Oberkochen, Germany). Corresponding microscope images taken with different filters were overlaid using Photoshop v. 10 (Adobe Systems Europe, Glasgow, UK). For ganglion cell (GCL) counts the ganglion cells were labelled using NeuN (Abcam, Cambridge, UK) immunohistochemistry as previously described. The primary antibody was diluted 1:100 and visualised using cy3-conjugated anti-mouse-IgG secondary antibody (Jackson ImmunoResearch Europe, Suffolk, UK). Four retinal sections per eye from four mice per group were analysed (n=4). The sections were taken approximately 150 μm apart in the central retina (600 μm span in total); 2 counts per section i.e. 8 counts per eye in total, were made using the count tool in Photoshop (Adobe systems). The diameter of the optic nerves was determined at approximately 5 mm from the optic nerve head from 3 animals per group (n=3). Three measurements per nerve were made approximately 150 μm apart using the ruler tool in Photoshop (Adobe Systems). Procedures for TEM were as previously described. Briefly, three weeks post-rotenone injection optic nerves were fixed in 4% paraformaldehyde in phosphate-buffered solution and fixed in 2.5% glutaraldehyde in 0.1M cacodylate buffer (pH 7.3) for 2 hr at room temperature. Washed specimens were post-fixed in buffered 2% osmium tetroxide, dehydrated and embedded in araldite. Ultrathin cross-sections were cut on a vibratome (Leica VT 1000 S), analysed using a Tecnai 12 BioTwin transmission electron microscope (FEI, Eindhoven, Holland) and imaged with a SIS MegaView III surface channel charge-coupled device (SCCD) camera (Olympus Soft Imaging Solutions, Münster, Germany). The total number of membrane debris particles in the images was counted in 5 cross sections per optic nerve from 3 animals per group (n=3).
Magnetic Resonance Imaging
[0163] Optic nerve integrity in experimental and control mice was assessed by Manganese (Mn 2+ ) enhanced magnetic resonance imaging (MEMRI) technique using a 7 T Bruker Biospec 70/30 magnet (Bruker Biospin, Etlingen, Germany). MEMRI demarcates active regions of the brain due to the ability of Mn 2+ ions to enter excitable cells through voltage-gated calcium channels, thus analysis of Mn 2+ transport through the optic nerve provides a good measure of its integrity. Two hours prior to scanning, mice were anaesthetised and intravitreally injected, as described above, with 2 μl of 20 mg/ml manganese chloride solution. For image acquisition, mice were maintained under sedation with ketamine (375 μg/10 g body weight) and placed on an MRI-compatible cradle which maintains the animal's body temperature at 37° C. (respiration and temperature were monitored for the duration of experiment). The cradle was positioned within the MRI scanner and an initial rapid pilot image acquired to ensure accurate positioning of the mouse. Oblique coronal T 1 -weighted 2D images were acquired using FLASH sequence (TR/TE:150/2.5 ms; Matrix: 128×128; Field of View: 20×20 mm 2 ; Flip Angle 50°; number of averages: 40, the pixel resolution was 0.156 mm/pixel). In the oblique coronal orientation (36°), 20 slices, each measuring 0.35 mm in thickness with 0.45 mm inter slice gap, were recorded for an acquisition time of 9 min 36 sec. MRI scans corresponding to the area immediately superior to the optic chiasm provided more consistent images compared to the optic nerve itself due to the variations in physically positioning each animal. Log signal intensities in this region were quantified using Image J© software (http://imagej.nih.gov/ij/).
Optokinetics
[0164] Optokinetic response (OKR) spatial frequency thresholds were measured blind by two independent researchers using a virtual optokinetic system (VOS, OptoMotry, CerebralMechanics, Lethbridge, AB, Canada). OptoMotry 36 measures the threshold of the mouse's optokinetic tracking response to moving gratings. Briefly, a virtual-reality chamber is created with four 17 inch computer monitors facing into a square and the unrestrained mouse was placed on a platform in the centre. A video camera, situated above the animal, provided real-time video feedback. The experimenter centred the virtual drum on the mouse's head and judged whether the mouse made slow tracking movements with its head and neck. The spatial frequency threshold, the point at which the mouse no longer tracked, was obtained by incrementally increasing the spatial frequency of the grating at 100% contrast. A staircase procedure was used in which the step size was halved after each reversal, and terminated when the step size became smaller than the hardware resolution (˜0.003 c/d, 0.2% contrast). One staircase was presented for each direction of rotation to measure each eye separately, with the two staircases being interspersed.
Statistical Analysis
[0165] Data sets of treated and untreated samples were pooled, averaged and standard deviation (SD) values calculated. Statistical significance of differences between data sets was determined by either Student's two-tailed t-test or ANOVA used with Tukey's multiple comparison post hoc test. In addition, the Kruskall-Wallis one-way analysis of variance was applied to the MRI data set and Mann Whitney U-tests were undertaken on all other data sets to establish that statistical significance was maintained using nonparametric statistical models. Analysis was performed using Prism v. 5.0 c (GraphPad Software, La Jolla, Calif., USA); differences with p<0.05 were considered statistically significant
Predictions of Immunogenic Codons
[0166] All potential peptide fragments that could be derived from the Ndi1 protein were assayed by the consensus prediction method for binding affinity to all well-characterised human MHC-I proteins. All epitopes displaying a high affinity for MHC-I (defined as a predicted IC50<500 nM) were noted, along with the corresponding MHC-I allele to which they had displayed high binding affinity. Each potential peptide fragment was then assigned an ‘immunogenicity score’, defined as the sum of the frequencies of all MHC-I alleles in the global human population for which it had a high binding affinity. The highest-scoring fragments were then selected for potential modification to reduce immunogenicity. All possible single amino acid mutations for each of these immunogenic fragment sequences were generated, and each was assayed for immunogenicity by the above methods. In addition, the BLOSUM62 matrix was used to calculate the sequence similarity between the original and mutated sequences. For each fragment, an optimal immunogenicity-reducing mutation was chosen. This was done by taking the set of all potential mutations for that fragment and eliminating all fragments which had an immunogenicity score greater than half of the immunogenicity score of the original fragment. The sequence with the highest sequence similarity to the original fragment (as defined by the BLOSUM62 matrix) was selected as the optimal substitution for that position.
[0167] In addition to the analyses described above using information regarding MHC-1 alone, immunogenicity estimation and reduction in Ndi1 was achieved via in silico modelling of antigen presentation via the MHC-I pathway using the IEDB proteasomal cleavage/TAP transport/MHC class I combined predictor.
[0168] As fragments of 9 amino acids in length are the most commonly presented fragments by MHC-I, all possible sequences of 9 consecutive amino acids that could be derived from Ndi1 were listed and passed to the IEDB predictor for analysis. For every 9-mer peptide P and MHC-I allele i, an immunogenicity value G p,i was generated which is proportional to the amount of that fragment that would be displayed on the cell surface by a given MHC-I allele, taking into account proteasomal degradation, transport and binding by MHC-I.
[0169] An overall immunogenicity factor F p for the 9-mer peptide was then calculated as
[0000]
F
p
=
∑
i
G
p
,
i
N
i
[0000] where N i is the estimated prevalence of each allele in the global human population as a fraction of the total pool of alleles, calculated using population frequency data from The Allele Frequency Net Database (Gonzalez-Galarza et al, 2011). In other words, F p represents the mean amount of that fragment that would be displayed on the surface of a cell for all MHC-I alleles, weighted by how frequently each allele occurs in the human population.
[0170] Each amino acid position A in the Ndi1 peptide was then assigned an immunogenicity score S A defined as the sum of the immunogenicity factors for all 9-mer peptides containing that amino acid. All positions whose immunogenicity score was less than one-fifth of the highest score were not considered further, as mutations at these positions would not be able to significantly affect the overall immunogenicity of the protein.
[0171] For each of the remaining positions, a BLOSUM matrix (Henikoff and Henikoff, 1992) was used to identify potential mutations that would not be overly disruptive to the structure or function of Ndi1. A BLOSUM matrix is calculated by aligning homologous protein sequences from many species against each other, and comparing the frequency with which each amino acid is replaced by every other amino acid.
[0172] For two amino acids x and y, the BLOSUM score B x,y is defined as the log-likelihood of the amino acid x replacing y or vice-versa in a given position in homologous peptides. As a direct consequence of this definition, B x,y =B y,x for all x and y (in other words, all BLOSUM matrices are symmetric).
[0173] A high BLOSUM score for an amino-acid pair indicates that mutations changing one of those amino acids to the other are more likely to be observed in homologous proteins, indicating that such changes are less likely to severely disrupt protein structure. A BLOSUM score can also be calculated between each amino acid and itself (B x,x ), indicating the likelihood that that amino acid will remain constant between homologous proteins.
[0174] For all possible mutations at a given position, ΔB was defined as the change in the BLOSUM score for that mutation. More formally, given an initial amino acid x and a candidate replacement amino acid y, ΔB=B x,x −B x,y . All mutations for which ΔB was greater than 4 were considered too disruptive to protein function and not analysed further.
[0175] For all remaining candidate mutations, immunogenicity factors F and scores S were recalculated for the post-mutation peptide using the IEDB predictor. The reduction in immunogenicity ΔS was then determined, defined as the difference between the score S for that position in the original peptide versus the new score S after mutation.
[0176] All possible mutations were then ranked by the metric
[0000]
Δ
S
Δ
B
.
[0000] High values of
[0000]
Δ
S
Δ
B
[0000] represent mutations which are likely to cause a large reduction in immunogenicity with a relatively small predicted impact on protein function. Outputs with predicted amino acids and scores are provided in Table X.
[0177] The invention is not limited to the embodiments hereinbefore described which may be varied in construction and detail without departing from the spirit of the invention.
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[0000]
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5. Ames A 3 rd . CNS energy metabolism as related to function. Brain Res Brain Res Rev. 34:42-68 (2000).
6. Yen M Y, Wang A G, Wei Y H. Leber's hereditary optic neuropathy: a multifactorial disease. Prog Retin Eye Res. 25 (4):381-396 (2006).
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9. Marcuello A, Martinez-Redondo D, Dahmani Y, Casajús J A, Ruiz-Pesini E, Montoya J, López-Pérez M J, Díez-Sánchez C. Human mitochondrial varienats influence on oxygen consumption. Mitochondrion. 9:27-30 (2009).
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11. Shankar S P, Fingert J H, Carelli V, Valentino M L, King T M, Daiger S P, Salomao S R, Berezovsky A, Belfort R Jr, Braun T A, Sheffield V C, Sadun A A, Stone E M. Evidence for a novel x-linked modifier locus for leber hereditary optic neuropathy. Ophthalmic Genet. 29 (1):17-24 (2008).
12. Tsao K, Aitken P A, Johns D R. Smoking as an aetiological factor in a pedigree with Leber hereditary optic neuropathy. Br J. Ophthalmol. 83 (5):577-581 (1999).
13. Giordano C, Montopoli M, Perli E, Orlandi M, Fantin M, Ross-Cisneros F N, Caparrotta L, Martinuzzi A, Ragazzi E, Ghelli A, Sadun A A, d'Amati G, Carelli V. Oestrogens ameliorate mitochondrial dysfunction in Leber's hereditary optic neuropathy. Brain. 134 (Pt 1):220-234 (2011).
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APPENDIX
[0201]
[0000]
TABLE 1a
Nucleic acid and amino acid sequences of the Invention.
Amino Acid
Nucleic Acid
Gene
Substitution
Sequence
Yeast NDI1
FYLWRILYL
SEQ ID NO: 1
Yeast NDI1 codon
FYLWRILYL
SEQ ID NO: 62
optimised
Yeast NDI1 + 1amino
FYLWRILYL →
SEQ ID NO: 63
acid change
FYLWRILYM
Yeast NDI1 codon
FYLWRILYL →
SEQ ID NO: 134
optimized + 1 amino
FYLWRILYM
acid change
Yeast NDI1 + 2 amino
FYLWRILYL →
SEQ ID NO: 146
acid change
FYLWRILYM
FLKEIPNSL →
FFKEIPNSL
Yeast NDI1 codon
FYLWRILYL →
SEQ ID NO: 225
optimized + 2 amino
FYLWRILYM
acid change
FLKEIPNSL →
FFKEIPNSL
[0000]
TABLE 1b
Immunochange/
Initial
Position
New
Immunoscore
Immunochange
Blosumchange
Blosumchange
I
82
V
2.569262982
1.002693684
2
0.501346842
F
90
Y
1.926170105
1.497108683
3
0.499036228
L
89
I
2.104411858
1.253907982
3
0.417969327
V
266
I
0.667339713
0.362552877
1
0.362552877
K
214
E
0.712950213
0.70677809
4
0.176694523
L
481
I
0.885723713
0.498012741
3
0.166004247
L
202
M
0.608956047
0.315494717
2
0.157747359
L
259
V
0.594189679
0.469145841
3
0.156381947
L
195
I
0.565666654
0.465061673
3
0.155020558
I
81
V
0.852520887
0.266903644
2
0.133451822
L
150
M
0.656551833
0.259100799
2
0.129550399
R
85
K
2.714843954
0.43039463
4
0.107598657
Y
151
F
0.686249712
0.397772899
4
0.099443225
Y
482
F
0.891857027
0.37332648
4
0.09333162
S
488
T
0.562058188
0.361418691
4
0.090354673
S
80
T
0.674070843
0.301172594
4
0.075293149
K
196
E
0.618739275
0.284207587
4
0.071051897
R
206
K
0.780227471
0.247789757
4
0.061947439
R
490
K
0.590906411
0.237769694
4
0.059442424
S
145
T
0.67224222
0.225480169
4
0.056370042
V
147
T
0.671708207
0.210263616
4
0.052565904
R
479
K
1.226655337
0.210156887
4
0.052539222
A
489
S
0.587738848
0.201645996
4
0.050411499
L
212
V
0.717379457
0.144498379
3
0.048166126
R
492
K
0.564269712
0.191259766
4
0.047814941
L
262
M
0.596470347
0.084255646
2
0.042127823
Q
149
E
0.656724126
0.167775872
4
0.041943968
T
207
S
0.779275641
0.162365948
4
0.040591487
Y
476
F
1.203763001
0.154940174
4
0.038735043
S
201
T
0.598628015
0.145693616
4
0.036423404
S
86
A
2.752011125
0.111576956
4
0.027894239
M
473
L
0.621739886
0.108503212
4
0.027125803
E
265
Q
0.583898093
0.099401686
4
0.024850422
E
264
Q
0.583540076
0.086415603
4
0.021603901
S
148
A
0.642943664
0.069504199
4
0.01737605
A
261
S
0.592734437
0.053926096
4
0.013481524
A
209
S
0.725497927
0.039698254
4
0.009924564
E
213
Q
0.71301777
0.004330404
4
0.001082601
Initial: The amino acid at this position in the native protein
Position: Position in the protein
New: Replacement amino acid suggested by the program
Immunoscore: Immunoscore for this locus in the native protein.
Immunochange: Change in immunoscore between the native and the modified locus.
Blosumchange: The change in BLOSUM score between the native and the modified position (a measure of how conservative the change is, lower numbers being more conservative)
Immunochange/Blosumchange: The change in immunogenicity divided by the blosum change.
[0000]
TABLE 1c
Output from immunogenicity analyses
position
totalscore
mhcscore
tapscore
proteasomescore
0
0.000165143
11.14069809
0.44351918
9.06162E−05
1
0.041457346
11.40019829
2.86360034
0.003448543
2
0.002426595
15.73665433
7.707479979
5.46497E−05
3
0.002526801
24.94091632
4.435191796
6.27721E−05
4
0.005897232
16.1032081
6.122268966
0.000162811
5
0.00032745
12.79123286
1.221553255
5.69915E−05
6
7.91604E−05
15.37844434
0.168621289
8.22938E−05
7
0.000166722
13.39406509
0.702930528
4.84144E−05
8
0.000109826
14.68630033
0.533227336
3.79468E−05
9
0.000316701
11.14069809
1.308917895
5.83262E−05
10
0.123430476
22.74638603
6.264874929
0.002349837
11
0.097134418
17.65681657
2.552186489
0.005899826
12
0.048628469
20.27273789
7.532036315
0.000863136
13
0.046499396
20.74495061
21.22816259
0.000286354
14
0.001693195
20.74495061
0.926642906
0.000243003
15
2.94196E−05
11.40019829
0.150283882
4.66216E−05
16
0.000555893
11.14069809
0.845108374
0.000157342
17
0.062993668
16.4783
9.055499382
0.001146233
18
0.000129314
12.79123286
0.212281626
0.000129245
19
0.000372025
11.93747308
1.250006885
6.79306E−05
20
0.000170764
11.40019829
0.656012939
6.24617E−05
21
0.017125463
13.39406509
2.437319175
0.00142792
22
8.29984E−05
14.68630033
0.360505924
4.22373E−05
23
0.000159095
14.02530793
0.558357566
5.49707E−05
24
3.85269E−05
12.50006885
0.222286151
3.77629E−05
25
0.000126872
14.68630033
0.533227336
4.48928E−05
26
0.000210364
11.14069809
0.970314241
5.24778E−05
27
5.09001E−05
9.929157627
0.352299807
4.009E−05
28
0.000168829
8.070722319
1.537844434
3.71193E−05
29
0.000363844
10.16043742
0.671293443
0.000146293
30
2.06189E−05
11.66574302
0.127912329
3.82109E−05
31
0.022132896
17.65681657
16.1032081
0.000209655
32
0.027879223
8.84937105
2.494091632
0.003429894
33
0.000123359
11.14069809
0.641080261
4.68999E−05
34
0.000806311
20.74495061
1.891961982
5.6086E−05
35
0.000356829
11.14069809
1.806809666
4.82049E−05
36
0.00055883
18.4889567
1.308917895
6.21902E−05
37
0.00163762
14.68630033
2.734717094
0.00010891
38
0.000115249
22.22861507
0.336443704
4.12917E−05
39
0.000191343
7.88701025
1.765681657
3.74729E−05
40
0.000491116
6.712934432
1.537844434
0.000129807
41
0.000677471
18.06809666
1.166574302
8.70739E−05
42
3.36856E−05
11.14069809
0.207449506
3.88118E−05
43
0.00014483
21.22816259
0.377496044
4.85281E−05
44
0.003264254
7.360586237
2.93030216
0.000402442
45
0.000140007
7.707479979
1.402530793
3.521E−05
46
3.62244E−05
11.40019829
0.232762174
3.73826E−05
47
0.000348616
16.1032081
1.339406509
4.33022E−05
48
0.004074612
34.42804843
3.774960444
8.44971E−05
49
0.001131584
11.66574302
2.122816259
0.000123023
50
0.002085286
19.81127403
3.213012427
8.89479E−05
51
4.51837E−05
10.39710441
0.32878531
3.62723E−05
52
3.03008E−05
14.68630033
0.114001983
4.98593E−05
53
3.76548E−05
10.88710484
0.261163455
3.596E−05
54
0.001659218
2.79123286
4.139161818
8.50937E−05
55
0.000149148
14.02530793
0.545647796
5.22381E−05
56
0.004171506
12.50006885
1.166574302
0.000776349
57
0.006443566
14.35199932
2.611634549
0.000465797
58
3.34281E−05
14.68630033
0.133940651
4.56139E−05
59
0.037127736
11.93747308
16.1032081
0.00052448
60
0.00663909
19.81127403
3.952868849
0.000229639
61
0.006458684
9.266429059
2.494091632
0.000758499
62
0.000340528
20.27273789
0.702930528
6.40334E−05
63
0.002881924
17.65681657
2.494091632
0.000178119
64
7.61656E−05
14.68630033
0.336443704
4.10584E−05
65
0.000209237
7.88701025
1.140019829
6.41994E−05
66
0.005967534
9.703142406
3.364437037
0.000493477
67
0.001955737
9.266429059
2.552186489
0.000221532
68
0.017604909
20.27273789
29.98557666
7.89816E−05
69
8.35826E−05
11.14069809
0.558357566
3.65261E−05
70
0.002594439
19.36031438
2.172263001
0.000165466
71
3.00088E−05
16.86212891
0.122155325
3.90383E−05
72
0.000919044
11.66574302
2.027273789
0.000106306
73
0.000624075
10.88710484
2.494091632
6.17683E−05
74
6.33881E−05
11.40019829
0.249409163
6.13181E−05
75
0.000697186
9.929157627
2.672467333
7.11732E−05
76
0.015140398
10.39710441
7.360586237
0.000539173
77
6.53066E−05
16.86212891
0.19811274
5.41402E−05
78
0.312040853
26.72467333
42.35575283
0.000759428
79
0.344490583
12.79123286
27.98416838
0.002643626
80
0.178480054
26.11634549
5.210895997
0.003561048
81
1.717661138
12.21553255
21.72263001
0.017177042
82
0.001404259
20.74495061
0.671293443
0.000273623
83
0.000277344
13.39406509
1.468630033
3.83701E−05
84
0.145284018
12.50006885
5.98290911
0.005274918
85
0.052307569
15.73665433
7.532036315
0.001198564
86
0.000858248
9.482271919
2.274638603
0.000108393
87
0.007596331
13.39406509
0.172548984
0.008925249
88
0.000542897
16.86212891
0.992915763
8.77791E−05
89
0.000238301
8.258713592
1.686212891
4.70592E−05
90
0.006680505
9.929157627
1.502838821
0.001238526
91
6.22969E−05
15.73665433
0.267246733
4.00927E−05
92
0.000881673
23.81839017
0.702930528
0.000142668
93
0.011560202
14.35199932
1.725489835
0.001248935
94
5.48864E−05
22.22861507
0.184889567
3.67735E−05
95
6.20843E−05
13.70605295
0.32878531
3.78829E−05
96
0.000404981
8.84937105
2.552186489
4.90042E−05
97
2.28667E−05
14.35199932
0.122155325
3.5317E−05
98
0.000413407
14.02530793
1.891961982
4.16191E−05
99
0.000498189
9.266429059
2.611634549
5.58373E−05
100
7.19144E−05
15.37844434
0.313987533
4.02088E−05
101
0.000134928
8.070722319
1.250006885
3.66345E−05
102
0.001767121
10.16043742
1.84889567
0.000253395
103
0.000489226
16.4783
1.686212891
4.78379E−05
104
0.000140668
17.25489835
0.464421595
4.76012E−05
105
0.489070827
0.68403046
29.3030216
0.001466533
106
0.001456535
13.39406509
1.016043742
0.000286335
107
0.031214534
14.68630033
3.862890569
0.001494362
108
0.000379244
6.264874929
1.725489835
9.6805E−05
109
0.002898725
11.66574302
1.686212891
0.000399516
110
0.014553946
9.482271919
2.437319175
0.001712156
111
7.03894E−05
12.21553255
0.423557528
3.71112E−05
112
9.96662E−05
13.08917895
0.584672147
3.58761E−05
113
0.001309179
11.66574302
2.552186489
0.000120062
114
0.000377961
15.73665433
0.864793477
7.53049E−05
115
0.164165075
20.272737893
7.74960444
0.000583111
116
0.070071877
12.791232863
7.74960444
0.000394384
117
0.000102335
18.4889567
0.377496044
4.00326E−05
118
0.000736796
13.39406509
0.825871359
0.00018023
119
8.86678E−05
21.22816259
0.299855767
3.78003E−05
120
0.000604388
12.50006885
1.088710484
0.000120905
121
0.000474711
16.4783
1.166574302
6.72969E−05
122
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12.21553255
25.52186489
0.000112607
361
0.004583891
16.4783
4.752393632
0.000158805
362
0.000214841
7.360586237
1.468630033
5.37078E−05
363
0.007450718
18.91961982
2.494091632
0.000428744
364
0.106193293
10.88710484
3.364437037
0.008050725
365
6.36614E−05
12.50006885
0.368903185
3.78588E−05
366
3.36424E−05
15.02838821
0.157366543
3.92244E−05
367
6.81265E−05
10.63928408
0.453850068
3.83103E−05
368
6.02667E−05
10.16043742
0.344280484
4.64704E−05
369
0.015366884
10.88710484
2.93030216
0.001306252
370
0.041789394
19.36031438
25.52186489
0.000230784
371
0.000222478
15.73665433
0.864793477
4.34986E−05
372
0.005150502
17.25489835
2.494091632
0.000326126
373
8.00509E−05
9.482271919
0.360505924
6.48627E−05
374
6.63686E−05
22.22861507
0.212281626
3.81911E−05
375
7.50907E−05
12.21553255
0.44351918
3.70893E−05
376
0.001539591
13.39406509
1.468630033
0.000212993
377
0.130153448
18.4889567
29.3030216
0.000651829
378
0.012114767
18.06809666
0.992915763
0.001833678
379
7.85619E−05
10.63928408
0.413916182
4.87707E−05
380
0.001795076
16.86212891
3.2878531
8.70516E−05
381
0.000130478
8.451083744
1.039710441
4.08208E−05
382
0.00011804
7.029305285
1.114069809
4.04629E−05
383
0.001199255
11.14069809
0.864793477
0.000337446
384
0.00076988
16.4783
1.537844434
8.24444E−05
385
0.000328129
11.66574302
1.402530793
5.43864E−05
386
0.001878249
23.27621742
1.806809666
0.000121176
387
0.000949237
22.74638603
0.948227192
0.000119569
388
0.000322352
11.93747308
0.686929876
0.000108257
389
9.70649E−05
10.88710484
0.686929876
3.58878E−05
390
5.56156E−05
21.22816259
0.184889567
3.84766E−05
391
0.000301138
14.02530793
0.825871359
7.01035E−05
392
0.00023197
19.36031438
0.464421595
6.96021E−05
393
0.086167577
13.08917895
42.35575283
0.000428099
394
0.00320585
20.74495061
4.752393632
8.8303E−05
395
0.000356753
14.02530793
1.140019829
6.04461E−05
396
0.003535662
11.66574302
2.611634549
0.000315439
397
0.00014032
16.4783
0.386289057
5.92625E−05
398
0.004866363
12.50006885
14.68630033
7.28681E−05
399
0.000158366
23.81839017
0.273471709
6.59099E−05
400
0.001939939
8.647934772
3.2878531
0.000185328
401
0.074518819
16.1032081
1.936031438
0.006598619
402
0.000368539
16.4783
0.970314241
6.18047E−05
403
0.00019918
8.070722319
1.725489835
3.91329E−05
404
0.0023339
14.35199932
3.52299807
0.000125363
405
0.000307937
10.16043742
2.074495061
3.99055E−05
406
4.35479E−05
8.070722319
0.344280484
4.25484E−05
407
0.009636643
10.63928408
15.37844434
0.000162331
408
0.000704922
12.79123286
1.64783
9.09555E−05
409
0.082073394
13.39406509
3.139875335
0.005307281
410
0.000172874
11.14069809
0.612226897
6.78625E−05
411
0.002590415
20.74495061
5.713633843
5.95983E−05
412
2.14123E−05
10.16043742
0.114001983
5.01741E−05
413
1.79079E−05
12.50006885
0.103971044
3.74308E−05
414
0.015229974
16.4783
7.532036315
0.000340591
415
0.001564252
5.456477959
2.93030216
0.000265267
416
7.42737E−05
24.94091632
0.232762174
3.46397E−05
417
0.002017239
12.50006885
2.437319175
0.000179922
418
0.001073996
14.02530793
3.2878531
6.32416E−05
419
0.000103914
24.37319175
0.321301243
3.60307E−05
420
0.00227239
15.02838821
5.210895997
7.79872E−05
421
0.003094582
17.65681657
5.846721472
8.01705E−05
422
0.026822594
11.14069809
24.37319175
0.000263402
423
8.06153E−05
17.25489835
0.321301243
3.90039E−05
424
6.65435E−05
15.02838821
0.313987533
3.80554E−05
425
8.68244E−05
12.50006885
0.413916182
4.61813E−05
426
5.02296E−05
9.482271919
0.377496044
3.7914E−05
427
0.005633169
13.39406509
15.73665433
7.26803E−05
428
0.053561311
10.88710484
2.611634549
0.005001157
429
0.000211193
7.360586237
1.981127403
3.98133E−05
430
0.128441705
12.50006885
15.02838821
0.001895798
431
0.00032307
9.482271919
1.537844434
6.04888E−05
432
0.010134136
23.81839017
16.4783
6.92222E−05
433
7.69896E−05
13.70605295
0.377496044
4.06321E−05
434
0.000135597
22.22861507
0.377496044
4.37181E−05
435
0.001444653
14.68630033
4.644215946
5.67292E−05
436
8.44475E−05
14.02530793
0.336443704
4.85387E−05
437
0.000172682
15.02838821
0.788701025
4.02947E−05
438
0.043302564
22.22861507
4.334234505
0.001237471
439
0.00083712
19.81127403
1.140019829
0.000100867
440
0.110359565
17.25489835
23.81839017
0.000713841
441
0.00239921
15.02838821
3.139875335
0.000138022
442
5.51714E−05
11.40019829
0.299855767
4.43098E−05
443
2.73416E−05
13.70605295
0.119374731
4.57706E−05
444
7.76194E−05
13.39406509
0.32878531
4.81237E−05
445
0.01841864
18.06809666
8.451083744
0.000326235
446
0.00091319
13.70605295
1.435199932
0.00012658
447
0.005087454
18.06809666
4.538500684
0.000169647
448
0.001545552
16.86212891
0.970314241
0.000258749
449
0.000120989
10.39710441
0.584672147
5.2939E−05
450
0.000949163
15.73665433
2.222861507
7.37358E−05
451
0.003519884
15.37844434
6.869298762
9.09167E−05
452
2.91528E−05
10.63928408
0.184889567
3.93474E−05
453
0.000259943
12.50006885
0.497636704
0.000114874
454
0.069613956
9.929157627
4.044942993
0.004814647
455
0.011539164
13.39406509
8.84937105
0.000266971
456
0.000245616
15.37844434
0.992915763
4.32175E−05
457
0.064510667
18.91961982
27.98416838
0.000328666
458
0.019758322
16.1032081
38.62890569
8.50784E−05
459
0.000992578
10.39710441
0.926642906
0.000279497
460
0.000162264
13.70605295
0.377496044
8.49288E−05
461
8.60808E−05
14.68630033
0.395286885
3.95986E−05
462
0.000100838
10.16043742
0.5210896
5.101E−05
463
0.026273224
22.74638603
6.712934432
0.000467224
464
0.003758225
13.70605295
3.52299807
0.000209698
465
0.000251714
14.02530793
0.948227192
5.16242E−05
466
0.210714099
20.74495061
15.37844434
0.001793468
467
0.015124482
16.86212891
18.4889567
0.000130494
468
0.001275927
18.91961982
2.381839017
7.7579E−05
469
0.005514392
20.74495061
2.494091632
0.000288274
470
0.156586151
18.4889567
6.410802613
0.003538119
471
0.186229111
14.35199932
2.998557666
0.011991882
472
0.042285785
28.6360034
5.210895997
0.000773999
473
0.650258534
12.21553255
44.35191796
0.003257705
474
0.144329762
25.52186489
5.210895997
0.002904785
475
0.002158857
16.4783
0.184889567
0.001965935
476
0.006971615
20.27273789
2.86360034
0.000330172
477
0.00402333
9.929157627
3.774960444
0.00029246
478
0.033812192
17.25489835
5.98290911
0.000880456
479
0.00023843
15.02838821
0.249409163
0.000173268
480
0.001645208
19.36031438
1.308917895
0.000179905
481
0.0484191
11.93747308
7.532036315
0.001430588
482
9.55314E−05
18.4889567
0.184889567
7.59792E−05
483
0.041845605
11.93747308
9.703142406
0.000984742
484
0.019450519
19.81127403
5.456477959
0.000480395
485
0.026711018
8.647934772
2.798416838
0.002995786
486
0.002357911
18.4889567
2.437319175
0.000142909
487
0.421294865
33.64437037
25.52186489
0.001344337
488
0.025919091
16.1032081
30.68403046
0.000141309
489
0.00481277
27.34717094
0.433423451
0.001102531
490
0.005726208
9.266429059
5.98290911
0.000280416
491
0.016151725
15.37844434
3.862890569
0.000738517
492
0.000487614
7.360586237
3.442804843
5.22113E−05
493
0.061733956
29.3030216
6.410802613
0.000885952
494
0.001663264
19.81127403
1.502838821
0.000152943
495
0.066165089
11.40019829
19.81127403
0.000798045
496
0.014395555
15.37844434
14.68630033
0.000170788
497
0.009138115
16.4783
2.381839017
0.000638927
498
0.105623599
15.02838821
7.029305285
0.002777924
499
0.000110394
28.6360034
0.279841684
3.7797E−05
500
0.044368613
9.703142406
24.37319175
0.000512563
501
0.092445553
13.39406509
27.34717094
0.000694007
502
0.24858678
10.39710441
4.235575283
0.015327737
503
0.000134276
11.40019829
0.509228152
6.18108E−05
504
0.003680974
26.11634549
3.862890569
9.72953E−05
[0000]
TABLE 2
Genes expressed predominately in the Retinal Ganglion Cell
Layer (RGL). Genes expressed at least at 10 fold higher
levels in the GCL than in other parts of the retina, as
identified both by SAM and t-test, and grouped by putative function.
Promoter sequences belonging to any of these genes would in
drive high and preferential gene expression in GCL
and may hence be utilised to drive expression of OphNDI1
contemplated in this patent application. In addition, additional
genes expresses in addition to OphNDI1 such as those
described in Table 6 may be expressed from any of these promoters.
Table adapted from Kim et al., Mol Vis 2006; 12:1640-1646
Transcriptional regulation and RNA
binding molecules
ECM organisation
EBF
CTHRC1
ERF5A2
LAMA4
ELAVL2
SERPINE2
ELAVL4
Neuronal development
FKBP1B
CRTAC1
KIAA1045
GAP43
POU4F1
NRG1
RBPMS
NRN1
RBPMS2
Fatty acid metabolism
TGFB1I1
FABP3
Cytoskeleton/Neurofilaments
LSS
EPPK1
Signal transduction
KEF5A
GPR54
MAP1A
RGS1
MICAL2
RGS5
NEF3
RIT2
NEFH
Apoptosis
NEFL
IER3
PRPH
LGALS1
TMSB10
TNFRSF21
Endocytosis/neurotransmitter
Miscellaneous
transport/synaptic transmission
ANXA2
GGH
AP1G1
HBA2
CHRNB3
HHL
CPLX1
HLA-DPA1
GNAS
LMO2
QPRT
MT3
RAB13
PECAM1
STMN2
PPP2R2C
STXBP6
UCHL1
SYNGR3
Cell adhesion
Ion/Anion transport
FAT3
ATP1B1
FN1
KCNA2
GJA1
KCNJ8
PCDH7
SCN1A
SRPX
SCN1B
THY1
SCN4B
SLC17A6
SLC4A11
GABRB3
[0000]
TABLE 3
Transcripts detected at very high levels by gene array analyses
of the human retinal ganglion cell layer (GCL). The genes listed
here are likely to represent highly abundant
transcripts of the ganglion cell layer. Promoter
sequences belonging to any of these genes
would in theory drive very high levels of gene
expression in GCL and may hence be utilised
to drive expression of OphNDI1 and the
contemplated in this patent application. In addition,
additional genes expresses in addition to
OphNDI1 such as those described in Table 6 may be
expressed from any of these promoters.
Table adapted from Kim et al., Mol Vis 2006;12:1640-1646
TF
H3F3A
TUBA3
COX7A2
NEFH
RTN1
GABARAPL3
CALM2
TUBB
MAFF
GLUL
INA
UBB
PGK1
NEFL
AF1Q
EIF3S6IP
YWHAB
PGAM1
SUI1
LDHA
DDAH1
RTN4
EIF4A2
HINT1
MAP1B
LDHB
NDUFB8
PGR1
K-ALPHA-1
EEF1A1
STK35
PTPRO
NEF3
SNAP25
TMSB10
FTH1
DRLM
EEF1D
MGC14697
SKP1A
FTL
BEX1
CSRP2
HSPA8
SRP14
PCP4
CYCS
PARK7
BNIP3
MAP4
LAMP1
ACTG1
WIF1
CDIPT
MDH1
VAMP1
NARS
SMT3H2
OAZ1
EEF1G
STOM
COX5A
GNAS
SPARCL1
NGFRAP1
UBC
DBI
KARS
TSC22
C6orf53
ATP6V0E
VEGF
FDFT1
COX4I1
SAT
STMN2
ATP5A1
NPM1
MTCH1
APP
HIG1
CIRBP
GPX3
B2M
CFL1
DP1
MYL6
LAPTM4B
SNCG
[0000]
TABLE 4
Exemplary universal promoters, inducible/conditional promoters,
enhancer elements and epigenetic elements
Promoters
Reference
chicken β-actin promoter
Miyazaki et al., Gene. 1989
July 15; 79(2):269-77.
SV40 promoter
Byrne et al., Proc Natl Acad
Sci USA. 1983
February; 80(3):721-5.
CMV promoter
Thomsen et al., Proc Natl
Acad Sci USA. 1984
February; 81(3):659-63.
Schmidt et al., Mol Cell. Biol.
August 1990 vol.10 no.8
4406-4411.
Furth et al., Nucl Acids Res.
(1991) 19(22):6205-6208.
Ubiquitin promoter
Schorpp et al., Nucl. Acids
Res. (1996) 24 (9):1787-
1788.
PGK promoter
McBurney et al., Dev Dyn.
August 1994; 200(4):278-93.
Inducible Promoters
Reference
tetR
Steiger et al., 2007
Enhancer Element
Reference
Chicken ovalbumin upstream
Eguchi et al., Biochimie
promoter transcription factor II
89(3):278-88, 2007
Mouse dystrophin muscle
Anderson et al., Mol. Ther.
promoter/enhancer
14(5):724-34, 2006
Tobacco eIF4A-10
Tian et al., J. Plant Physiol.
promoter elements
162(12):1355-66, 2005
Immunoglobulin (Ig)
Frezza et al., Ann. Rheum.
enhancer element HS1, 2A
Dis. Mar. 28, 2007
Col9a1 enhancer element
Genzer and Bridgewater
Nucleic Acids Res.
35(4):1178-86, 2007
Gata2 intronic enhancer
Khandekar et al.,
Development Mar. 29, 2007
TH promoter enhancer
Gao et al., Brain Res.
1130(1):1-16, 2007
CMV enhancer
InvivoGen cat# pdrive-cag
05A13-SV
Woodchuck hepatitis virus
Donello et al., J. Virol.
posttranscriptional
72(6):5085-92, 1998
regulatory element
Woodchuck hepatitis virus
Schambach et al., Gene Ther.
posttranscriptional
13(7):641-5, 2006
regulatory element
IRBP
Ying et al., Curr. Eye Res.
17(8):777-82, 1998
CMV enhancer and
InvivoGen cat# pdrive-cag
chicken β-actin promoter
05A13-SV
CMV enhancer and chicken
InvivoGen cat# pdrive-cag
β-actin promoter and 5'UTR
05A13-SV
CpG-island
Antoniou et al., Genomics
82:269-279, 2003
Epigenetic elements
Reference
Mcp Insulators
Kyrchanova et al., Mol. Cell Biol.
27(8):3035-43, 2007
CpG-island region of
Williams et al., BMC Biotechnol.
the HNRPA2B1 locus
5:17, 2005
Chicken b-globin
Kwaks and Otte 2006 Trends in
5'hypersensitive site 4 (cHS4)
Biotechnology 24:137-142
Ubiquitous chromatin
Kwaks and Otte 2006 Trends in
opening elements (UCOEs)
Biotechnology 24:137-142
Matrix associated
Kwaks and Otte 2006 Trends in
regions (MARs)
Biotechnology 24:137-142
Stabilising and antirepressor
Kwaks and Otte 2006 Trends in
elements (STAR)
Biotechnology 24:137-142
Human growth
Trujillo MA et al. 2006 Mol
hormone gene silencer
Endocrinol 20:2559
[0000]
TABLE 5
Exemplary Vectors
Viral Vectors
Delivery Method
Serotype
Reference
AAV (ssAAV
All serotypes,
Lebkowski et al., Mol. Cell
or scAAV)
including
Biol. 8(10):3988-96, 1988
but not limited to
Flannery et al., Proc. Natl.
1, 2, 3, 4, 5, 6, 7,
Acad. Sci. U.S.A.
8, 9, 10, 11, 12,
94(13):6916-21, 1997
Lentivirus (for example
VSV-G
Pang et al., Mol. Vis. 12:
but not exclusively
Rabies-G
756-67, 2006
Feline-FIV,
Further
Takahashi Methods Mol.
Equine-EIAV,
serotypes**
Biol. 246:439-49, 2004
Bovine-BIV
Balaggan et al., J. Gene
and Simian-SIV).
Med. 8(3):275-85, 2006
Adenovirus
Bennett et al., Nat. Med.
2(6):649-54, 1996
Simian papovirius
Kimchi-Sarfaty et al., Hum.
SV40
Gene Ther. 13(2):299-310,
2002
Semliki Forest Virus
DiCiommo et al., Invest.
Ophthalmol. Vis. Sco.
45(9):3320-9, 2004
Sendai Virus
Ikeda et al., Exp. Eye Res.
75(1):39-48, 2002
The list provided is not exhaustive; other viral vectors and derivatives,
natural or synthesized could be used in the invention.
Non Viral Vectors or Delivery Methods
Delivery Method
Reference
Cationic liposomes
Sakurai et al., Gene Ther. 8(9):677-86, 2001
HVJ liposomes
Hangai et al., Arch. Ophthalmol. 116(3):342-8,
1998
Polyethylenimine
Liao and Yau Biotechniques 42(3):285-6, 2007
DNA nanoparticles
Farjo et al., PloS ONE 1:e38, 2006
Dendrimers
Marano et al., Gene Ther. 12(21):1544-50,
2005
Bacterial
Brown and Giaccia Cancer Res. 58(7):1408-16,
1998
Macrophages
Griffiths et al., Gene Ther. 7(3):255-62, 2000
Stem cells
Hall et al., Exp. Hematol. 34(4):433-42, 2006
Retinal transplant
Ng et al., Chem. Immunol. Allergy 92:300-16,
2007
Marrow/Mesenchymal
Kicic et al., J. Neurosci. 23(21):7742-9, 2003
stromal cells
Chng et al., J. Gene Med. 9(1):22-32, 2007
Implant (e.g.,
Montezuma et al., Invest. Ophthalmol. Vis. Sci.
Poly(imide)uncoated
47(8):3514-22, 2006
or coated)
Electroporation
Featherstone A. Biotechnol. Lab. 11(8):16,
1993
Targeting peptides
Trompeter et al., J. Immunol Methods. 274(1-
(for example but
2):245-56, 2003
not exclusively Tat)
Lipid mediated
Nagahara et al., Nat. Med. 4(12):1449-52, 1998
(e.g., DOPE, PEG)
Zeng et al., J. Virol. 81(5):2401-17, 2007
Caplen et al., Gene Ther. 2(9):603-13,
1995Manconi et al., Int. J. Pharm. 234(1-
2):237-48, 2006
Amrite et al., Invest. Ophthalmol. Vis. Sci.
47(3):1149-60, 2006
Chalberg et al., Invest. Ophthalmol. Vis. Sci.
46(6):2140-6, 2005
[0000]
TABLE 6
Exemplary neurotrophic factors, anti-apoptotic agents and antioxidants.
Neurotrophic factor genes, anti-apoptotic agents or antioxidants
which may be used in conjunction with the optimised NdiI therapy
contemplated in this patent application. These genes may be delivered
at the same time as the NdiI therapy or at a different time, using the
same vector as the NdiI therapy or a different one. Neurotrophic factor,
anti-apoptotic agents or antioxidants genes may be expressed from
ubiquitously expressed promoters such as CMV and Ubiquitin (Table 4)
or from one of the promoters described in Tables 2 and 3.
Neurotrophic factor
Reference
NGF
Carmignoto et al., 1989
b-NGF
Lipps 2002
NT-3
Lu et al., 2011
NT4
Krishnamoorthy et al., 2001
BDNF
Krishnamoorthy et al., 2001; DiPolo et al.,
1998; Garcia and Sharma 1998; Carmignoto
et al., 1989
GDNF
Wu et al., 2004, Frasson et al., 1999,
Gregory-Evans et al., 2009
NTN (Neurturin)
Koeberle et al 2002
aFGF and bFGF
Faktorovich et al. 1900; LaVail et al.,
1991, 1992 Perry et al., 1995; McLaren and
Inana 1997; Akimoto et al., 1999; Uteza et
al., 1999; Lau et al., 2000
LIF
Joly et al., 2008, Rhee and Yang, 2010
CNTF
Sieving et al., 2006, Thanos et al., 2009, Li et
al., 2011
Hepatocyte growth factor
Tönges et al., 2011
PDGF
Akiyaman et al., 2006
VEGF
Trujillo et al., 2007
PEDF
Cayouette et al., 1999
RdCVF
Leveillard et al., 2004
Chondroitinase ABC
Liu 2011
Erythropoietin
Rex et al., 2009, Rong et al., 2011, Gong et al
2011, Hu et al., 2011, Sullivan et al., 2011
Suberythropoietc Epo
Wang et al., 2011
Anti-apoptotic agents
Reference
Calpain inhibitor I
McKenan et al., 2007
Calpain inhibitor II
McKenan et al., 2007
Calpeptin
McKenan et al., 2007
PARP
Norgestrel
Doonan et al., 2011
Antioxidant
Reference
Vitamin C
www.nei.nih.gov/amd
Vitamin E
www.nei.nih.gov/amd
Beta-carotene
www.nei.nih.gov/amd
SOD2 +/− catalase
Jung et al., 2007, Usui et al., 2009, Doonan
al., 2009
Rosiglitazone
Doonan et al., 2009
Sestrin-1
Budanov et al., 2002, 2004
PPAR
Aoun et al., 2003, Zhao et al., 2006
Tomita et al., 2005, Komeina et al., 2006, 2007
Lutein
Li et al., 2010
[0000]
TABLE 7
Disease phenotypes and genotypes associated with mitochondrial disease.
Clinical Phenotypes (non-LHON) Associated with mtDNA Polypeptide Gene Mutations
(http://www.mitomap.org/bin/view.pl/MITOMAP/ClinicalPhenotypesPolypeptide)
Nucleotide
Syndromes
Locus
Disease*
Allele
Change
AA Change
Dystonia
MTND
Adult-Onset Dystonia
A3796G
A-G
T164A
1
Dystonia, Leigh
MTND
LS/Dystonia
T14487C
T-C
M63V
Syndrome
6
Dystonia, Leigh
MTND
LDYT/LS
G14459A
G-A
A72V
Syndrome
6
Leigh Syndrome
MTND
LS
T10158C
T-C
S34P
3
Leigh Syndrome
MTND
LS-like/ESOC
T10191C
T-C
S45P
3
Leigh Syndrome
MTND
LS
C11777A
C-A
R340S
4
Leigh Syndrome
MTND
LS
T12706C
T-C
F124L
5
Leigh syndrome
MTATP
LS/FBSN
T9176C
T-C
L217P
6
Leigh Syndrome
MTATP
LS
T9176G
T-G
L217R
6
Leigh Syndrome
MTATP
LS
T9185C
T-C
L220P
6
Leigh Syndrome
MTATP
LS
T9191C
T C
L222P
6
Leigh Syndrome
MTATP
LS/NARP
T8993C
T-C
L156P
6
Neurogenic
MTATP
NARP
T8993G
T-G
L156R
Muscle Weakness
6
Ataxia and
Retinitis
Pigmentosa
Leigh Syndrome
MTCO3
LS-like
C9537ins
C-CC
Q111frameshift
C
Encephalomyopathy,
MTND
MELAS
T3308C
T C
M1T
MELAS
1
Encephalomyopathy,
MTND
MELAS/LHON
G3376A
G-A
E24K
MELAS
1
Encephalomyopathy,
MTND
MELAS
G3697A
G-A
G131S
MELAS
1
Encephalomyopathy,
MTND
MELAS
G3946A
G-A
E214K
MELAS
1
Encephalomyopathy,
MTND
MELAS
T3949C
T-C
Y215H
MELAS
1
Encephalomyopathy,
MTND
MELAS
A11084G
A-G
T109A
MELAS
4
Encephalomyopathy,
MTND
MELAS
A12770G
A-G
E145G
MELAS
5
Encephalomyopathy,
MTND
MELAS/LHON/LS
A13045C
A-C
M237L
MELAS
5
overlap syndrome
Encephalomyopathy,
MTND
MELAS/LS
A13084T
A-T
S250C
MELAS
5
Encephalomyopathy,
MTND
MELAS/LS
G13513A
G-A
D393N
MELAS
5
Encephalomyopathy,
MTND
MELAS
A13514G
A-G
D393G
MELAS
5
Encephalomyopathy,
MTND
MELAS
G14453A
G-A
A74V
MELAS
6
Encephalomyopathy,
MTCY
MELAS/PD
14787del
TTAA-
I14frameshift
MELAS
B
4
del
Epilepsy
MTCO1
Therapy-resistant
C6489A
C-A
L196I
Epilepsy
Encephalomyopathy,
MTCO1
Multisystem Disorder
G6930A
G-A
G343Ter
Multisystem
Disorder
Encephalomyopathy,
MTCOI
Myopathy and Cortical
6015del5
Del 5 bp
Frameshift, 42
Multisystem
Lesions
peptide
Disorder
Encephalomyopathy
MTCO2
Encephalomyopathy
T7587C
T-C
M1T
Encephalomyopathy,
MTCO2
Multisystem Disorder
G7896A
G-A
W104Ter
Multisystem
Disorder
Encephalomyopathy,
MTCO2
Lactic Acidosis
8042del2
AT-del
M153Ter
Lactic
Acidosis
Encephalomyopathy
MTCO3
Encephalomyopathy
G9952A
G-A
W248Ter
Encephalomyopathy,
MTCO3
MELAS/PEM/NAION
T9957C
T-C
F251L
MELAS
Encephalomyopathy,
MTATP
Lactic Acidosis/
9205del2
TA-del
Ter227M
Lactic
6
Seizures
Acidosis
Encephalomyopathy,
MTCY
Multisystem Disorder
A15579G
A-G
Y278C
Lactic
B
Acidosis
Encephalomyopathy,
MTCY
Septo-Optic Dysplasia
T14849C
T-C
S35P
Septo-Optic
B
Dysplasia
MM, Exercise
MTCY
EXIT
G14846A
G-A
G34S
Intolerance
B
Mitochondrial
MTCY
MM
G15059A
G-A
G190Ter
Myopathy
B
MM, Exercise
MTCY
EXIT
G15084A
G-A
W113Ter
Intolerance
B
MM, Exercise
MTCY
EXIT
G15150A
G-A
W135Ter
Intolerance
B
MM, Exercise
MTCY
EXIT
G15168A
G-A
W141Ter
Intolerance
B
MM, Exercise
MTCY
EXIT
T15197C
T-C
S151P
Intolerance
B
MM, Exercise
MTCY
EXIT/
G15242A
G-A
G166Ter
Intolerance
B
Encephalomyopathy
MM, Exercise
MTCY
EXIT
G15497A
G-A
G251S
Intolerance
B
MM, Exercise
MTCY
EXIT
15498del24
24 bp
251GDPDNYT
Intolerance
B
deletion-
L-del258
MM, Exercise
MTCY
EXIT
G15615A
G-A
G290D
Intolerance
B
MM, Exercise
MTCY
EXIT
G15723A
G-A
W326Ter
Intolerance
B
Mitochondrial
MTCY
MM
G15762A
G-A
G339E
Myopathy
B
MM, CPEO
MTND
CPEO
T11232C
T-C
L140P
4
MM, Exercise
MTND
EXIT
G11832A
G-A
W358Ter
Intolerance
4
MM, Exercise
MTCO1
EXIT/Myoglobinuria
G5920A
G-A
W6Ter
Intolerance
Mitochondrial
MTCO1
MM &
G6708A
G-A
G269Ter
Myopathy
Rhabdomyolysis
Mitochondrial
MTCO2
MM
T7671A
T-A
M29K
Myopathy
MM, Exercise
MTCO2
EXIT/Rhabdomyolysis
T7989C
T-C
L135P
Intolerance
Mitochondrial
MTCO3
Myopathy and
9487del15
Del 15 bp
Removed 5 aa
Myopathy
Myoglobinuria
Hypertrophic
MTCY
HCM
G15243A
G-A
G166E
Cardiomyopathy
B
Hypertrophic
MTCY
HCM
G15498A
G-A
G251D
Cardiomyopathy
B
Deafness
MTCO1
DEAF
A7443G
A-G
Ter514G
Deafness
MTCO1
DEAF
1A7445C
A-C
Ter514S
Deafness-Sensory
MTCO1
SNHL/LHON
G7444A
G-A
Ter514K
Neural Hearing
Loss
Deafness-Sensory
MTCO1
SNHL
A7445G
A-G
Ter514Ter
Neural Hearing
Loss
Deafness-Sensory
MTCO2
SNHL
A8108G
A-G
I175V
Neural Hearing
Loss
Deafness-Sensory
MTND
SNHL
C14340T
C-T
V112M
Neural Hearing
6
Loss
Diabetes Mellitus
MTND
NIDDM/PEO
G3316A
G-A
A4T
1
Diabetes Mellitus
MTND
DM
A12026G
A-G
I423V
4
Alzheimer &
MTND
ADPD
A3397G
A-G
M31V
Parkinson Disease
1
Alzheimer &
MTND
AD
G5460A
G-A
A331T
Parkinson Disease
2
Alzheimer &
MTND
AD
G5460T
G-T
A331S
Parkinson Disease
2
Idiopathic
MTCO1
SIDA
T6721C
T-C
M273T
Sideroblastic
Anemia
Idiopathic
MTCO1
SIDA
T6742C
T-C
I280T
Sideroblastic
Anemia
Abbreviations
♦Plasmy: Ho, homoplasmy; He, heteroplasmy
*Disease: AD, Alzheimer's Disease; ADPD, Alzheimer's Disease and Parkinsons's Disease; CPEO, Chronic Progressive External
Ophthalmoplegia; EXIT, exercise intolerance; LHON Leber Hereditary Optic Neuropathy; LS, Leigh Syndrome; MELAS,
Mitochondrial Encephalomyopathy, Lactic Acidosis, and Stroke-like episodes; MM, mitochondrial myopathy; NAION Nonarteritic
Anterior Ischemic Optic Neuropathy; NARP, Neurogenic muscle weakness, Ataxia, and Retinitis Pigmentosa; NIDDM, Non-Insulin
Dependent Diabetes Mellitus; SIDA, sideroblastic anemia; SNHL, Sensorineural Hearing Loss.
** Status: Cfrm, considered confirmed by multiple reports in the literature; Prov, provisional isolated report(s), not yet confirmed by
multiple labs; P.M., reported originally in the literature at pathogenic but now generally considered to be a polymorphic variant.
Clinical Phenotypes (non-LHON) Associated with mtDNA rRNA & tRNA Mutations (http://www.mitomap.org/bin/view.pl/
MITOMAP/ClinicalPhenotypesRNA)
Syndromes
Locus
Disease*
Allele
RNA
Encephalomyopathy,
MTTV
LS
C1624T
tRNA Val
Leigh Syndrome
Encephalomyopathy,
MTTV
Adult LS
G1644T
tRNA Val
Leigh Syndrome
Encephalomyopathy
MTTW
MILS
A5537insT
tRNA Trp
Leigh Syndrome
Encephalomyopathy
MTTK
MERRF
A8344G
ItRNA Lys
MERRF
Encephalomyopathy
MTTK
MERRF
T8356C
tRNA Lys
MERRF
Encephalomyopathy
MTTK
MERRF
G8361A
tRNA Lys
MERRF
Encephalomyopathy
MTTK
MERRF/MICM+
G8363A
tRNA Lys
MERRF
DEAF/Autism
Encephalomyopathy
MTTL1
MERRF/KSS overlap
G3255A
tRNA Leu
MERRF
( UUR)
Encephalomyopathy
MTTF
MERRF
G611A
tRNA Phe
MERRF
Encephalomyopathy
MTTD
MEPR
A7543G
tRNA
Myoclonus and
Asp
Psychomotor
Regression
Encephalomyopathy
MTTV
AMDF
G1606A
tRNA Val
Ataxia, Myoclonus
and Deafness
Encephalomyopathy
MTTH
MERRF-MELAS/
G12147A
tRNA His
MERRF
Cerebral edema
Encephalomyopathy
MTTL1
MELAS
A3243G
tRNA Leu
MELAS
(UUR)
Encephalomyopathy
MTTL1
MELAS
G3244A
tRNA Leu
MELAS
(UUR)
Encephalomyopathy
MTTL1
MELAS
A3252G
tRNA Leu
MELAS
(UUR)
Encephalomyopathy
MTTL1
MELAS
C3256T
tRNA Leu
MELAS
(UUR)
Encephalomyopathy
MTTL1
MELAS/Myopathy
T3258C
tRNA Leu
MELAS
(UUR)
Encephalomyopathy
MTTL1
MELAS
T3271C
tRNA Leu
MELAS
(UUR)
Encephalomyopathy
MTTL1
MELAS
T3291C
tRNA Leu
MELAS
(UUR)
Encephalomyopathy
MTTV
MELAS
G1642A
tRNA Val
MELAS
Encephalomyopathy
MTTQ
MELAS/
G4332A
tRNA Gln
MELAS
Encephalopathy
Encephalomyopathy
MTTF
MELAS
G583A
tRNA Phe
MELAS
Encephalomyopathy
MTRNR
MELAS
C3093G
16S
MELAS
2
rRNA
Encephalomyopathy
MTTL1
PEM
T3271delT
tRNA Leu
(UUR)
Encephalomyopathy
MTTI
Progressive
T4290C
tRNA Ile
Encephalopathy
Encephalomyopathy
MTTI
(Mitochondria
C4320T
tRNA Ile
Encephalo-
cardiomyopathy
Encephalomyopathy
MTTW
Encephalomyopathy
G5540A
tRNA Trp
Encephalomyopathy
MTTC
Encephalopathy
T5814C
tRNA Cys
Encephalomyopathy
MTTS1
PEM/AMDF
C7472insC
tRNA Ser
(UCN)
Encephalomyopathy
MTTS1
PEM/MERME
T7512C
tRNA Ser
(UCN)
Encephalomyopathy
MTTK
Encephalopathy
C8302T
tRNA Lys
Encephalomyopathy
MTTK
Mitochondrial
G8328A
tRNA Lys
Encephalopathy
Encephalomyopathy
MTTG
PEM
T10010C
tRNA Gly
Encephalomyopathy
MTATT
Encephalomyopathy
G15915A
tRNA Thr
Encepehaolmyopathy
MTRNR
Rett Syndrome
C2835T
rRNA
Rett Syndrome
2
16S
Multisystem Disease
MTTI
Varied familial
G4284A
tRNA Ile
presentation
Encephalomyopathy
MTTG
GER/SIDS
A10044G
tRNA Gly
Gastrointestinal
Reflux and Sudden
Infant Death
Syndrome
Mitochondrial
MTTF
MM
T582C
tRNA Phe
Myopathy
Mitochondrial
MTTF
MM
T618C
tRNA Phe
Myopathy
Mitochondrial
MTTL1
MM
G3242A
tRNA Leu
Myopathy
(UUR)
Mitochondrial
MTTL1
MM/CPEO
A3243G
TRNA
Myopathy
Leu(UUR)
Mitochondrial
MTTL1
MM
A3243T
tRNA
Myopathy
Leu(UUR)
Mitochondrial
MTTL1
MM/CPEO
T3250C
tRNA Leu
Myopathy
(UUR)
Mitochondrial
MTTL1
MM
A3251G
tRNA Leu
Myopathy
(UUR)
Mitochondrial
MTTL1
MM
C3254G
tRNA Leu
Myopathy
(UUR)
Mitochondrial
MTTL1
Myopathy
A3280G
tRNA Leu
Myopathy
(UUR)
Mitochondrial
MTTL1
Myopathy
A3288G
TRNA
Myopathy
Leu(UUR)
Mitochondrial
MTTL1
MM
A3302G
tRNA Leu
Myopathy
(UUR)
Mitochondrial
MTTI
MM
A4267G
tRNA Ile
Myopathy
Mitochondrial
MTTQ
Myopathy
T4370AT
tRNA Gln
Myopathy
Mitochondrial
MTTM
MM
T4409C
tRNA
Myopathy
Met
Mitochondrial
MTTM
MM
G4450A
tRNA
Myopathy
Met
Mitochondrial
MTTW
MM
G5521A
tRNA Trp
Myopathy
Mitochondrial
MTTS1
MM
T7480G
tRNA Ser
Myopathy
(UCN)
Mitochondrial
MTTS1
MM
G7497A
tRNA Ser
Myopathy
(UCN)
Mitochondrial
MTTK
Myopathy
T8355C
tRNA Lys
Myopathy
Mitochondrial
MTTK
Myopathy
T8362G
tRNA Lys
Myopathy
Mitochondrial
MTTG
Myopathy
G10014A
tRNA Gly
Myopathy
Mitochondrial
MTTL2
MM
A12320G
tRNA Leu
Myopathy
(CUN)
Mitochondrial
MTTE
MM + DM
T14709C
tRNA Glu
Myopathy
Mitochondrial
MTTT
MM
T15940delT
tRNA Thr
Myopathy
Mitochondrial
MTTP
MM
C15990T
tRNA Pro
Myopathy
Mitochondrial
MTTY
Exercise Intolerance
T5874G
tRNA Tyr
Myopathy, Exercise
Intolerance
Mitochondrial
MTTL1
CPEO
C3254T
tRNA Leu
Myopathy, CPEO
(UUR)
Mitochondrial
MTTI
CPEO
T4274C
tRNA Ile
Myopathy, CPEO
Mitochondrial
MTTI
CPEO
T4285C
tRNA Ile
Myopathy, CPEO
Mitochondrial
MTTI
CPEO/MS
G4298A
tRNA Ile
Myopathy, CPEO
Mitochondrial
MTTI
CPEO
G4309A
tRNA Ile
Myopathy, CPEO
Mitochondrial
MTTA
CPEO
T5628C
tRNA Ala
Myopathy, CPEO
Asn
Mitochondrial
MTTN
CPEO/MM
T5692C
tRNA
Myopathy, CPEO
Asn
Mitochondrial
MTTN
CPEO/MM
G5698A
tRNA
Myopathy, CPEO
Asn
Mitochondrial
MTTN
CPEO/MM
G5703G
tRNA
Myopathy, CPEO
Asn
Mitochondrial
MTTK
CPEO + Myoclonus
G8342A
tRNA Lys
Myopathy, CPEO
Mitochondrial
MTTL2
CPEO
G12294A
tRNA Leu
Myopathy, CPEO
(CUN)
Mitochondrial
MTTL2
CPEO/Stroke/CM
A12308G
tRNA Leu
Myopathy, CPEO
(CUN)
Mitochondrial
MTTL2
CPEO
T12311C
tRNA Leu
Myopathy, CPEO
(CUN)
Mitochondrial
MTTL2
CPEO
G12315A
tRNA Leu
Myopathy, CPEO
(CUN)
Mitochondrial
MTTL1
Ocular myopathy
T3273C
tRNA Leu
Myopathy, Ocular
(UUR)
Myopathy
Mitochondrial
MTTL1
KSS
G3249A
tRNA Leu
Myopathy, KSS
(UUR)
Mitochondrial
MTTY
Mitochondrial
A5843G
tRNA Tyr
Myopathy
Cytopathy/
Cytopathy
FSGS
Mitochondrial
MTTK
Mitochondrial
A8326G
tRNA Lys
Myopathy
cytopathy
Cytopathy
Mitochondrial
MTTP
Mitochondrial
G15995A
tRNA Pro
Myopathy
cytopathy
Cytopathy
Mitochondrial
MTTF
Myoglobinuria
A606G
TRNA
Myopathy with
Phe
Myoglobinuria
Mitochondrial
MTTW
Gastrointestinal
G5532A
tRNA Trp
Myopathy,
Syndrome
Gastrointestinal
Syndrome
Mitochondrial
MTTK
MNGIE
G8313A
tRNA Lys
Myopathy,
Mitochondrial
Neurogastrointestinal
Encephalomyopathy
Mitochondrial
MTTG
CIPO
A10006G
tRNA Gly
Myopathy with
Chronic Intestinal
Pseudoobstruction
Mitochondrial
MTTS1
CIPO
C12246G
tRNA Ser
Myopathy with
(AGY)
Chronic Intestinal
Pseudoobstruction
Mitochondrial
MTTF
Tubulointerstitial
A608G
tRNA Phe
Myopathy with
nephritis
Renal Dysfunction
Mitochondrial
MTTT
LIMM
A15923G
tRNA Thr
Myopathy Lethal
Infantile
Mitochondrial
Myopathy
Mitochondrial
MTTT
LIMM
A15924G
tRNA Thr
Myopathy Lethal
Infantile
Mitochondrial
Myopathy
Mitochondrial
MTTL1
MMC
A3260G
tRNA Leu
Myopathy and
(UUR)
cardiomyopathy
Mitochondrial
MTTL1
MMC
C3303T
tRNA Leu
Myopathy and
(UUR)
cardiomyopathy
Maternaly Inherited
MTTI
MHCM
A4295G
tRNA Ile
Hypertrophic
Cardiomyopathy
Maternally Inherited
MTTI
MICM
A4300G
tRNA Ile
Cardiomyopathy
Cardiomyopathy
MTTK
Cardiomyopathy
A8348G
tRNA Lys
Maternally Inherited
MTTG
MHCM
T9997C
tRNA Gly
Hypertrophic
Cardiomyopathy
Maternally Inherited
MTTH
MICM
G12192A
tRNA His
Cardiomyopathy
Cardiomyopathy
MTTL2
Dilated
T12297C
tRNA Leu
Cardiomyopathy
(CUN)
Fatal Infantile
MTTI
FICP
A4269G
tRNA Ile
Cardiomyopathy
Plus (MELAS)
Fatal Infantile
MTTI
FICP
A4317G
tRNA Ile
Cardiomyopathy
Plus (MELAS)
Deafness
MTRNR
DEAF
A827G
12S
1
rRNA
Deafness
MTRNR
DEAF
T961C
12S
1
rRNA
Deafness
MTRNR
DEAF
T961delT+C(n)ins
12S
1
rRNA
Deafness
MTRNR
DEAF
T961insC
12S
1
rRNA
Deafness
MTRNR
DEAF
T1005C
12S
1
rRNA
Deafness
MTRNR
SNHL
T1095C
12S
Sensory Neural
1
rRNA
Hearing Loss
Deafness
MTRNR
DEAF
A1116G
12S
1
rRNA
Deafness
MTRNR
DEAF
C1494T
12S
1
rRNA
Deafness
MTRNR
DEAF
A1555G
12S
1
rRNA
Deafness
MTTS1
SNHL
T7510C
tRNA Ser
Sensory Neural
(UCN)
Hearing Loss
Deafness
MTTS1
SNHL
T7511C
tRNA
Sensory Neural
Ser(UCN)
Hearing Loss
Deafness
MTTS1
Deafness and Cerebellar
7472insC
tRNA
cerebellar
Dysfunction
Ser(UCN)
dysfunction
Deafness
MTTH
DEAF + RP
G12183A
tRNA His
Deafness Ataxia and
MTTE
Deafness, Mental
14709G
tRNA Glu
MR
Retaration,
Cerebellar Dysfunction
Diabetes Mellitus
MTRNR
DM
C1310T
12S
1
Diabetes Mellitus
MTRNR
DM
A1438G
12S
1
Diabetes Mellitus &
MTTL1
DM/DMDF
A3243G
tRNA Leu
Deafness
(UUR)
Diabetes Mellitus
MTTL1
DM
T3264C
tRNALeu
(UUR)
Diabetes Mellitus
MTTL1
DM
T3271C
tRNA Leu
(UUR)
Diabetes Mellitus
MTTI
Metabolic Syndrome &
T4291C
tRNA Ile
Metabolic
Hypomagnesemia
Syndrome
Diabetes Mellitus &
MTTK
DMDF/MERRF/HCM
A8296G
tRNA Lys
Deafness &
Cardiomyopathy
Diabetes Mellitus &
MTTS2
DMDF
C12258A
tRNA Ser
Deafness and
(AGY)
Retinitis Pigmentosa
Movement Disorder
MTTV
Movement Disorder
T1659C
tRNA Val
Alzheimer &
MTRNR
ADPD
G3196A
rRNA
Parkinson Disease
2
16S
Alzheimer &
MTTQ
ADPD/Hearing loss and
T4336C
tRNA Gln
Parkinson Disease
migraine
Deafness &
Migraine
Dementia and
MTTW
DEMCHO
G5549A
tRNA Trp
Chorea
Abbreviations
Plasmy: Ho, homoplasmy; He, heteroplasmy
*Disease: AD, Alzheimer's Disease; ADPD, Alzheimer's Disease and Parkinsons's Disease; CIPO Chronic Intestinal
Pseudoobstruction with myopathy and Ophthalmoplegia; CPEO, Chronic Progressive External Ophthalmoplegia; DEMCHO,
Dementia and Chorea; DM, Diabetes Mellitus; DMDF Diabetes Mellitus & Deafness; EXIT, exercise intolerance; FBSN Familial
Bilateral Striatal Necrosis; FICP Fatal Infantile Cardiomyopathy Plus, a MELAS-associated cardiomyopathy; HCM, Hypertrophic
CardioMyopathy; LS, Leigh Syndrome; MELAS, Mitochondrial Encephalomyopathy, Lactic Acidosis, and Stroke-like episodes;
MERRF Myoclonic Epilepsy and Ragged Red Muscle Fibers; MHCM Maternally Inherited Hypertrophic Cardiomyopathy; MICM
Maternally Inherited Cardiomyopathy; MM, mitochondrial myopathy; NAION Nonarteritic Anterior Ischemic Optic Neuropathy;
NARP, Neurogenic muscle weakness, Ataxia, and Retinitis Pigmentosa; NIDDM, Non-Insulin Dependent Diabetes Mellitus; SNHL,
Sensorineural Hearing Loss.
**Status: Cfrm, considered confirmed by multiple reports in the literature; Prov, provisional isolated report(s), not yet confirmed by
multiple labs; P.M., reported originally in the literature at pathogenic but now generally considered to be a polymorphic variant.
[0000]
TABLE 8
Disease phenotypes which are associated with
mitochondrial mutations and where similar phenotypes may be caused
by genomic mutations. Patients with these phenotypes,
whether due to mitochondrial or genomic mutations,
may benefit from OphNDI1 treatment. Possible target tissues
for therapies directed to these disorders are indicated.
Disease phenotype
Possible target tissue type
Encephalomyopathy
Brain, Muscle
Cardiomyopathy
Muscle
Myopathy
Muscle
Migraine
Brain
Gastrointestinal Reflux and
Brain
Sudden Infant Death Syndrome
Lactic Acidosis
Muscle
Muscle Weakness
Muscle
Deafness
Neurons
Alzheimer
Brain
Dementia
Brain
Epilepsy
Brain
Septo-Optic Dysplasia
Brain, Optic Nerve, Pituitary
Parkinson Disease
Brain
Anemia
Bone marrow
Dystonia
Brain
Ataxia
Brain
Sensory Neural Hearing Loss
Neurons in ear
Chorea
Brain
Retinitis Pigmentosa
Photoreceptor cell in retina
Exercise Intolerance
Muscles
Diabetes
Pancreas
Age related macular degeneration
Photoreceptor cell in retina | An isolated nucleic acid sequence encoding the yeast NDI1 protein of SEQ ID NO: 542 or a functional variant thereof is described. The nucleic acid sequence comprises at least 50 codons which are codon optimised compared with the sequence of yeast NDI1 gene of SEQ ID NO: 1. | 0 |
CROSS REFERENCE TO RELATED APPLICATION(S)
[0001] This application claims the benefit of U.S. Provisional Patent Application No. 61/426,680, filed Dec. 23, 2010, entitled CATHODIC ARC VAPOR DEPOSITION COATINGS FOR DIMENSIONAL RESTORATION OF SURFACES.
BACKGROUND
[0002] The present disclosure relates to a process for dimensionally restoring surfaces on a workpiece using a near non-line of sight technique such as cathodic arc vapor deposition technique.
[0003] Cathodic arc deposition was developed to apply simple coatings, such as titanium nitride, as a hard coat for workpieces such as drill bits. Cathodic arc deposition has been used to apply wear resistant and corrosion resistant coating systems on workpieces.
[0004] In use, some workpieces, such as turbine engine components, suffer loss of desired dimensions. It thus becomes necessary to repair them by performing dimensional restoration. Conventional thermal sprays require moderate to near-normal angle of approach to the substrate to achieve adherence, limiting applications where only shallow angle of approach is available. Such repairs have been difficult to perform on certain portions of the workpieces with limited line-of-sight (LLOS) such as hook attachments, seal grooves, and bolt holes. Current methods for LLOS dimensional restoration are restricted to plating processes or recoil directed thermal sprays. Plating materials with high temperature capability such as those operating at temperatures greater than 1000° F., are not commercially available. Choice of plating materials for titanium is much more restricted. Welding is frequently not an option because of mechanical property debits and distortion.
[0005] Near non-line of sight (NLOS) dimensional restoration approaches for repair are currently dominated by plating processes; however, electroless nickel, electrolytic nickel and chrome (Cr-III or Cr-VI) plates are limited on parts with service temperatures over 800° F. for chrome and electroless nickel and to 1000° F. for electrolytic nickel
[0006] Certain bolts used on turbine engines are used to align and tie the high pressure compressor cases together. These are press-installed in to tight tolerance, heavily loaded holes in each stage case. These holes can wear beyond limits with no known repair other than flange replacement. Local weld repair of the holes induces too much distortion on the other holes in the flange or leaves unacceptable levels of residual stress and fatigue property debit from the weld process.
[0007] Repair of worn and damaged cases with seal slot lands requires removal of the rear flange to access the repair area with plasma spray. The flange is subsequently restored by electron beam welding on a new flange. Such repairs have had limited success because the post-weld heat treatment frequently results in irreparable distortion. Vane hooks are similarly weld repaired when worn but may not have sufficient strength after extensive weld repair.
[0008] Other applications push the acceptable temperature limits of nickel plate, but only at reduced allowable stresses on the plate. These include diffuser case stator hooks and turbine disk shoulder snap diameters. Also note that use of chrome plate is increasingly hampered by EH&S restrictions world-wide and its viability as a repair technique is more and more becoming a method of last resort.
SUMMARY
[0009] Cathodic arc vapor deposition provides an alternative approach for performing dimensional restoration of a part, such as a hole, in a case used on a turbine engine. In particular, cathodic arc vapor deposition enables one to coat down the sides of the holes or to both faces of a hook. Further, coating down the inner diameter of tubes is also possible, particularly where the restoration of material near the end of the tube where the largest wear takes place is of concern.
[0010] In accordance with the present disclosure, there is provided a process for repairing a workpiece which broadly comprises the steps of: providing a workpiece having at least one interior surface requiring restoration; providing a source of repair material; and depositing the repair material onto the at least one interior surface using a technique which is a near non-line of sight technique.
[0011] Other details of the cathodic arc vapor deposition coatings for dimensional restoration of surfaces are set forth in the following detailed description and the accompanying drawings wherein like reference numerals depict like elements.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 is a schematic representation of a cathodic arc vapor deposition apparatus being used to coat a hole in a workpiece;
[0013] FIG. 2 is a schematic representation showing a mask placed over a portion of the workpiece;
[0014] FIGS. 3( a )- 3 ( i ) are photomicrographs showing build-up of a coating along a hole area in a diffuser case.
DETAILED DESCRIPTION
[0015] Cathodic arc vapor deposition is a method of applying coatings that do not require full line of sight. Cathodic arc vapor deposition can coat areas not accessible via thermal spray coatings and can apply coatings that result in little or no base material debit. Cathodic arc vapor deposition can coat parts to near-net shapes without requiring subsequent machining. Cathodic arc can be applied without introducing structural lifing debits as part of the surface preparation or coating processes.
[0016] While cathodic arc vapor deposition has been used as a means to install wear resistant and corrosion resistant coatings onto a surface of smaller parts in OEM, cathodic arc vapor deposition has not been used in repair techniques for dimensional restoration of an object. The LLOS advantages of cathodic arc coating have not yet been utilized.
[0017] Cathodic arc vapor deposition is a process which uses electrical biasing and inert gas pressure to enhance coverage to include areas of limited accessibility or that lack line-of-sight. Coating composition is flexible and can be made from any material. Coatings are fully dense and metallurgically bonded with bond strength capability in excess of 9 ksi. Coating compositions have an operating temperature capability equal to or better than base allow substrate.
[0018] As shown in FIG. 1 , cathodic arc vapor deposition can be used to restore the dimensions of a workpiece, such as the walls 11 of a hole 10 in a case 12 . The hole 10 may have a diameter less than 0.25 inches. The case 12 is placed within a chamber 14 and spaced from a source 16 of the coating material by a distance “d”. The distance “d” can be varied as desired. The source 16 is a cathode having an evaporative surface.
[0019] Prior to being placed in the chamber 14 , the walls 11 and other areas of the workpiece to be coated may be subjected to a treatment to remove any deleterious material, such as engine run contaminants and oxides, and provide a clean surface for the coating.
[0020] The coating material forming the source 16 may comprise a supply of any desired coating material. The coating material may comprise a restoration alloy having desirable strength properties, desirable wear properties, desirable lubrication properties, desirable electronic properties, desirable corrosion resistance properties, or a metal which closely matches the metal forming the case 12 . By “closely match”, it is meant that the restoration alloy is formed of a composition similar to or the same as the parent material from which the case 12 is formed. Examples of such materials include nickel-based alloys, nickel-based superalloys, titanium, titanium-based alloys, cobalt alloys, cobalt superalloys, stainless steels, corrosion resistant steels, i.e. Greek Ascaloy steel, and high temperature steels, i.e. Thermospan steel.
[0021] The source/cathode 16 is connected to a negative lead of a direct current power supply (not shown) and the positive lead of the power supply is attached to an anodic member. An inert gas such as Argon is introduced into the chamber 14 . An arc-initiating trigger, at or near the same electrical potential as the anode, contacts the cathode and subsequently moves away from the cathode. When the trigger is still in close proximity to the cathode, the difference in electrical potential between the trigger and the cathode causes an arc of electricity to extend therebetween. As the trigger moves further away, the arc jumps between the cathode and the anodic chamber. The cathode material vaporizes into a plasma containing atoms, molecules, ions, electrons, and particles. Positively charged ions liberated from the cathode are attracted toward the negatively charged workpiece 12 and the walls 11 of the hole 10 and are deposited thereon.
[0022] The amperage (source) and bias (case) needed to obtain the desired coating 18 down the hole (a limited line of sight), are dependent on “d” and the aspect ratio of the hole being coated.
[0023] If desired, as shown in FIG. 2 , masking 20 may be added to keep the coating 18 off certain areas of the workpiece or case 12 . With masking, no bridging is observed using cathodic arc vapor deposition. The use of masking also enables the restorative build-up to take place only at the intended location, rather than over the entire workpiece.
[0024] In one test of a cathodic arc vapor deposition repair technique, a hole area in a diffuser case was coated down the sides of a hole. FIGS. 3( a )- 3 ( i ) illustrate the coating which was deposited on the sides of the hole using a cathodic arc vapor deposit. FIGS. 3( a ) and 3 ( c ) show the sides of the hole closest to the source. FIGS. 3( d ) and 3 ( i ) show the sides of the hole farthest from the source.
[0025] Using cathodic arc vapor deposition to effect dimensional repairs has a number of advantages. First, it is a near non-line of sight coating technique. Second, restored materials deposited using this method have a high bond strength. Third, it allows the use of coating materials, such as Stellite-31 base material. Such materials are desirable because they are thermally stable well beyond the highest allowable service temperatures for nickel or chrome plates. Fourth, cathodic arc vapor deposition results in no grit blast fatigue debit like thermal spray coatings and no hydrogen pick-up fatigue debit as per most electrolytic applied plating. Fifth, cathodic arc deposition may allow for as-applied surfaces to be released without subsequent machining.
[0026] Use of cathodic arc deposition for dimensional restoration can extend to holes and to hooks, but can also be considered for seal ring grooves such as on turbine seal plates or on bearing housings, i.e. a trough-like shape where out on the sides of the groove is the critical dimension. There is also a potential use as an alternate to Chrome plate.
[0027] The cathodic arc repair technique is advantageous in that it can be used to coat holes having a depth greater than 0.060 inches. Further, it can be used to repair slots in workpieces that have a width less than 0.25 inches and/or a depth greater than 0.060 inches.
[0028] Although the process described herein has been shown and described with respect to detailed embodiments thereof, it will be understood by those skilled in the art that various changes in form and detail thereof may be made without departing from the spirit and the scope of the instant disclosure. | A process for repairing a workpiece includes the steps of: providing a workpiece having at least one interior surface requiring restoration; providing a source of repair material; and depositing the repair material onto the at least one interior surface using a technique which is a near non-line of sight technique. | 5 |
PRIORITY CLAIM
This application discloses and claims an Improvement over the invention disclosed and claimed in our application Ser. No. 10/053,998, filed Jan. 24, 2002, to be issued as U.S. Pat. No. 6,604,306 on Aug. 12, 2003.
SUMMARY OF THE INVENTION
According to the invention an expandable stitchery frame has visible markings placed at the longitudinal center of each of its side and end pieces. Tension is applied from the frame to the fabric directly in the plane of the fabric by expanding the spacings between side pieces and end pieces. While doing so, the expansion movement is controlled so that a center point in the fabric remains substantially aligned with all four visible markers.
According to the presently preferred embodiment of the invention the end portions of all of the side and end pieces are of substantially identical configuration. When one of the frame members is inverted relative to another and they are arranged to form a right angle, their adjoining ends have tongue and groove structures which are interengaged, and each frame member may be moved away from the other associated frame member along the longitudinal axis of the other without interrupting the interengagement.
DRAWING SUMMARY
FIG. 1 is a perspective view of an expandable flame in accordance with the invention;
FIG. 2 is a fragmentary perspective view showing how when one member is inverted, end portions of two of the members may be slidingly interengaged; and
FIG. 3 is a fragmentary cross sectional view of the end portions of two interengaged frame members showing expansion screws adapted to selectively drive them apart.
DETAILED DESCRIPTION
FIGS. 1 - 3
In the assembled frame of FIG. 1, the two side pieces are identified as A while the two end pieces are identified as B. Visible center markings on the side pieces and end pieces are identified as V. Fabric supported within the frame is identified as F.
Each end of each side piece and each end of each end piece has at one side thereof a transversely extending recess 10 . A first tongue portion 12 borders the recess 10 and is parallel to it. A transverse groove 14 borders the other side of tongue 12 and is parallel to recess 10 . A second tongue 16 is on the other side of groove 14 .
The width of groove 14 is at least equal to the thickness of first tongue 12 , so that the first tongue 12 of one of the side or end pieces may be slideably inserted into groove 14 of another.
When one frame member is inverted relative to another and their ends arranged to form a right angle, the second tongue 16 of one may occupy the recess 10 of the other, and the first tongue 12 of the one may occupy groove 14 of the other. See FIG. 2 .
The end portion of each side piece and each end piece has a hole or opening 18 through its first tongue portion 12 . An expansion screw 20 with an allen wrench opening is inserted into and through opening 18 from the outer side of the frame member. A nut 22 embedded in the tongue portion on its inner surface (see FIG. 3) allows the screw to be rotatably driven for expanding the frame. A pressure plate 24 in the bottom of groove 14 receives axial pressure from the expansion screw 20 .
While the frame may be square with side pieces and end pieces being of equal length, it may be preferred to have a rectangular frame in which the side pieces are longer than the end pieces. While the screw opening 20 is presently shown in tongue portion 12 , it may if desired be in tongue 16 instead.
Method of Operation
According to the present invention the method of stitching a piece of fabric such as congress cloth, linen, or needlepoint canvas that is supported within a rectangular frame having side and end pieces is accomplished as follows. A visible marker is placed at the longitudinal center of each side and end piece. The fabric is placed within the frame. The corresponding fabric edges are attached. Tension is then applied from the frame to the fabric directly in the plane of the fabric by expanding the spacing between the side pieces and concurrently expanding the spacing between the end pieces. While expanding the spacings, the visible markers are observed and the movements of the end pieces and the side pieces are controlled so that a center point in the fabric remains substantially aligned with all four visible markers. Thereafter, stitches are added into the fabric while maintaining the tension thus applied to the fabric; and the spaces between the end pieces and side pieces of the frame are again expanded. | A stitchery frame which is progressively expanded while in use to keep the fabric taut. Centerline markers are provided on side and end pieces of the frame to aid the process. | 3 |
CROSS-REFERENCE TO RELATED PATENT APPLICATIONS
This application claims priority from Provisional Application U.S. Application 60/740,110, filed Nov. 28, 2005, incorporated herein by reference in its entirety.
BACKGROUND OF THE INVENTION
This invention is directed to a system for shelf mounting, more particularly, to a system and method for mounting shelves on integrated hangers in a mobile truck body.
Mobile truck bodies are typically modular in design and include at least two side packs. These side packs each include one or more storage compartments, suitably configured to enclose tools, equipment, and the like. The most common side packs are pre-configured with installed-shelving, which is not adjustable by the end user. When adjustable shelving is offered to the end user, the adjustable shelves require substantial effort to raise, lower, or remove the shelves. Hence, shelf hangers typically require independent installation onto the walls of the compartments in the body side packs.
Thus, there is a need for a system and method for mounting adjustable shelves in mobile truck body applications that would be more convenient for the end user, require less effort for installation, and be suited for commercial use.
SUMMARY OF THE INVENTION
There is provided a system and method for mounting adjustable shelves.
Further, there is provided a system and method for mounting adjustable shelves onto the walls of compartments in a mobile truck body using integrated hangers.
Still further, there is provided a system and method for integrating attachment means into the walls of compartments in a body side pack so as to provide predetermined positions for shelving to a user.
There is provided a system for mounting adjustable shelves in mobile truck body applications. The mobile truck body comprises at least one storage compartment that includes a first interior space and at least one first upstanding panel that at least partially defines the first interior face. The system comprises a first attachment means including at least two first hanger components. The first attachment means is adapted to be integrated into the at least one first upstanding panel such that the at least two first hanger components are disposed transversely at a predetermined distance from each other. The at least two first hanger components extend into the first interior space. The system also comprises at least one first cross-member including at least two slots therethrough disposed correspondingly to the at least two first hanger components. The system further comprises at least one shelf member having at first and a second opposed periphery surface. The at least one shelf member includes at least two slots therethrough disposed along the first periphery surface correspondingly to the at least two first hanger components. The first attachment means is adapted to receive and engage the at least one first cross-member, which is adapted to receive the at least one shelf member. The respective slots included in the at least one shelf member and in the at least one first cross-member are adapted to receive a corresponding fastener, which extends therethrough and is adapted to secure the at least one shelf member to the at least one first cross-member.
There is also provided a vehicle comprising a support platform. A support member coupled to the support platform and configured to engage a surface. A storage compartment coupled to the support platform, the storage compartment including a first interior space and at least one first upstanding panel at least partially defining the first interior space. The storage compartment including at least two first hanger components configured to be integrated into the one first upstanding panel and disposed transversely at a predetermined distance from each other and extending into the first interior space. A first cross-member defining at least two slots therethrough disposed correspondingly to the two first hanger components. A shelf member having a first and a second opposed periphery surface, the shelf member comprising at least two slots therethrough disposed along the first periphery surface correspondingly to the two first hanger components. Wherein the two first hanger components are configured to receive and engage the cross-member. Wherein the cross-member is adapted to receive the shelf member. Wherein the respective slots included in the shelf member and in the cross-member are configured to receive a corresponding fastener, which extends therethrough and is configured to secure the shelf member to the cross-member.
At least one storage compartment further comprises at least one second upstanding panel opposed to the at least one first upstanding panel to form the first interior space. The system for shelf mounting further comprises a second attachment means including at least two second hanger components. The second attachment means is adapted to be integrated into the at least one second upstanding panel such, that the at least two second hanger components are disposed transversely correspondingly to the at least two first hanger components extending thereby, into the first interior space. The system also comprises at least one second cross-member including at least two slots therethrough disposed correspondingly to the at least two second hanger components. The at least one shelf member further includes at least two slots therethrough disposed along the second periphery surface correspondingly to the at least two second hanger components. The second attachment means is adapted to receive and engage the at least one second cross-member, which is adapted to receive the at least one shelf member. The respective slots included along the second periphery surface in the at least one shelf member and in the at least one second cross-member are adapted to receive a corresponding fastener, which extends therethrough and is adapted to secure the at least one shelf member to the at least one second cross-member.
Still further, the first hanger components and the second hanger components, preferably, have a substantially L shaped cross-section. The hanger components are integrated into respective upstanding panels such that a portion of each hanger component extends substantially orthogonally from the respective upstanding panel into the first interior space, wherein another portion of each hanger component is substantially parallel to a surface of the respective upstanding panel. The integral extending portions of the first and second hanger components that extend substantially orthogonally from the respective upstanding panels form a weather stripping. It will be appreciated by a skilled artisan that the at least one storage compartment, preferably, includes at least one door upstanding panel.
The at least one second upstanding panel serves as a divider panel to form at least one storage compartment. In this embodiment the system further comprises a third attachment means including multiple hanger components. The third attachment means is adapted to be integrated into the at least one second upstanding panel such as to extend into the second interior space. As it will be appreciated by those skilled in the art, at least one dimension the first interior space and at least one dimension the second interior space corresponds to at least one dimension of the at least one shelf member.
As will be understood by those skilled in the art, the at least one storage compartment is, preferably, a side pack storage compartment of the mobile truck body.
Still other aspects of the system for shelf mounting will become readily apparent to those skilled in this art from the following description, simply by way of illustration of one of the best modes suited for to carry out the invention. As it will be realized by those skilled in the art, the system is capable of other different embodiments and its several details are capable of modifications in various obvious aspects. Accordingly, the drawing and descriptions will be regarded as illustrative in nature and not as restrictive.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings incorporated in and forming a part of the specification, illustrate several aspects of the system for shelf mounting. In the drawings:
FIG. 1 is an isometric view of a side pack for a mobile truck body including an exemplary embodiment of a system for shelf mounting.
FIG. 2 is a isometric view of integrated hanging components of the system for shelf mounting in the mobile truck body illustrated in FIG. 1 .
FIG. 3 is a schematic view of a vehicle with a side pack including a system for shelf mounting according to an exemplary embodiment.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
This invention is directed to a system for shelf mounting in a mobile truck body. In particular, to a system for mounting shelves on integrated hangers in mobile truck body applications. The mounting system and method includes hanger components, which are integrated into panels that make up the compartments of a side pack of a truck body. The system and method also include a drop-in mounting bar and shelf, which enable quick and easy installation of the shelves at predetermined positions by the user. The system and method eliminate the need for shelf hangers to be independently installed onto the walls of the compartments in a body side pack.
Referring to FIG. 1 , there is shown an isometric view of a side pack 100 for a mobile truck body. The side pack 100 includes a plurality of storage compartments, with storage compartment 102 being used herein for illustrating and example purposes. It should be understood that each or any of the storage compartment 102 may include a door. The storage compartment 102 is advantageously formed from a plurality of upstanding panels 106 . The side pack 100 also includes hanger components 104 , which are integrated into the upstanding panels 106 .
As shown in FIG. 1 , the hanger components 104 are disposed along the vertical door jams and proximate the back corners of the storage compartment 102 . The storage compartment 102 advantageously includes a door panel (not shown in the drawing). It will be appreciated by those skilled in the art that the hanger components 104 situated adjacent to the door jams are part of, and integrally formed into the upstanding panels 106 which form the vertical panel components of the storage compartment 102 . In accordance with one embodiment an upstanding panel 108 serves as a divider panel to divide the storage compartment 102 into a first and second adjacent vertical storage compartments having a first and second adjacent interior space 110 , 112 , respectively.
The hanger components 104 , preferably, have a substantially L shaped cross-section and are integrated into the respective upstanding panels 106 , 108 such that a portion of each hanger component 104 extends substantially orthogonally from the respective upstanding panel 106 , 108 into the respective interior space 110 , 112 . Another portion of each hanger component 104 is substantially parallel to the surface of the respective upstanding panel 106 , 108 . It will be appreciated by those skilled in the art that the hanger components 104 are advantageously formed into the respective upstanding panel 106 , 108 in one embodiment the hanger components 104 are welded to the divider panel 108 . In another embodiment the hanger component 104 is formed during the manufacture of the upstanding panel 108 , for example by a purchased brake process. The integral portions of respective hanger portions of respective hanger components 104 that extend substantially orthogonally from the respective upstanding panels 106 , 108 , advantageously form a weather stripping. The side pack 100 for a mobile truck body is not limited to a particular number and/or orientation of storage compartments. Thus, the embodiment illustrated in FIG. 1 also includes storage compartments 114 , 116 with hanger components 104 integrated into respective upstanding panels 118 , 120 , which define the storage compartments 114 , 116 .
Referring to FIG. 2 , there is shown a detailed isometric view of an exemplary embodiment of a hanger component mounting system. The detailed view of FIG. 2 shows a compartment 200 formed in a side pack 100 . The system uses a cross-member 202 , also referred to as a drop-in-mounting bar, which is received by respective hanger components 104 . The cross-member 202 advantageously engages the hanger components 104 running along the upstanding panel 106 . Once the cross-member 202 is suitably engaged with the hanger components 104 , a shelf member 206 is placed on top of the cross-member 202 . It will be appreciated by those skilled in the art that both sides of the compartment 102 include hanger components 104 upon which a corresponding cross-member 202 is actively engaged.
The shelf 206 is secured to the cross-member 202 via fasteners 208 extending through slots 204 . The skilled artisan will appreciate that the slots 204 advantageously align with slots located in the shelf member 206 . the fasteners 208 are then secured via any means known in the art such that the shelf 206 is securely attached to the side body pack 100 . Suitable fasteners 208 include, for example and without limitation, nuts, bolts, screws, and the like. The skilled artisan will appreciate, that the side body pack 100 is advantageously constructed from any suitable material known in the art, including, for example and without limitation, aluminum, steel, high-density plastic, or the like. Preferably, the hanger components 104 are constructed so as to support weights in excess of 250 pounds distributed on the shelf FIG. 206 .
Referring to FIG. 3 , a vehicle 10 is shown according to an exemplary embodiment. Vehicle 10 is a truck that includes a side pack 100 , a support structure 15 (e.g., frame, bed, platform, chassis, etc.), one or more support members 20 , and a cab 25 . According to various exemplary embodiments, support members 20 may be wheels, tracks, or any other members that are in communication with both the ground and the support structure 15 . Support structure 15 provides a structure to which side pack 100 and cab 25 are coupled. Cab 25 provides a compartment for one or more occupants where one of the occupants is a driver. Side pack 100 includes a plurality of storage compartments 102 . Hanger components 104 are provided on walls of storage compartments 102 to support cross-members or mounting bars 202 . Shelves 206 are coupled to mounting bars 202 . While vehicle 10 is shown as a truck with a single rear axle, it should be understood that vehicle 10 may have more than one rear axle. According to other exemplary embodiments, vehicle 10 may not be self-propelled and may be a platform, trailer or other structure that is towed or otherwise propelled by a truck.
For purposes of this disclosure, the term “coupled” means the joining of two components (electrical or mechanical) directly or indirectly to one another. Such joining may be stationary in nature or movable in nature. Such joining may be achieved with the two components (electrical or mechanical) and any additional intermediate members being integrally formed as a single unitary body with one another or with the two components or the two components and any additional member being attached to one another. Such joining may be permanent in nature or alternatively may be removable or releasable in nature
The foregoing description of a preferred embodiment of the invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Obvious modifications or variations are possible in light of the above teachings. The embodiment was chosen and described to provide the best illustration of the principles of the invention and its practical application to thereby enable one of ordinary skill in the art to use the invention in various embodiments and with various modifications as are suited to the particular use contemplated. All such modifications and variations are within the scope of the invention as determined by the appended claims when interpreted in accordance with the breadth to which they are fairly, legally and equitable entitled. | A system for mounting adjustable shelves ( 206 ) in mobile truck body-applications. The system includes integrated attachment means adapted to receive a cross-member ( 202 ) for affixing thereto. The integrated attachment means are integrated into the panels forming the compartments ( 102,112,114,116 ) of the body side pack. The system further includes one or more shelves ( 206 ), which include at least two slots, disposed along the periphery surface of the shelf ( 206 ) so as to receive a corresponding fastener ( 208 ). The cross-member ( 202 ) includes at least two slots, corresponding to the slots in the shelf ( 206 ), such that a fastener ( 208 ) extends through the slots to secure the shelf to the panel of the compartment. | 1 |
CROSS-REFERENCE
[0001] This application claims the benefit of U.S. Provisional Patent Application Ser. No. 61/840,116, filed Jun. 27, 2013 (pending), the disclosure of which is incorporated by reference herein in its entirety
TECHNICAL FIELD
[0002] The present invention relates generally to garments and, more particularly, to garments configured to protect an electronic device from exposure to water.
BACKGROUND
[0003] The use of personal electronic devices, such as cellular telephones, digital audio players, and other electronic devices, is increasing in popularity. Many users enjoy listening to music, communicating with others, accessing the Internet, or viewing photos or videos during leisure or sport activities. In some environments, such as at or near a pool or beach, the use of electronic devices presents a danger that the device may become damaged if exposed to water. To protect electronic devices from exposure to water and other liquids, and to avoid the need for users of electronic devices to constantly hold their electronic devices while enjoying such sport or leisure activities, there is a need for a garment that allows users access to, and enjoyment of, their electronic devices while also permitting them to participate in sport or leisure activities where there is a risk of exposure to water.
SUMMARY
[0004] The present invention overcomes the foregoing and other shortcomings and drawbacks associated with the need for a garment that allows users access to and enjoyment of their electronic devices while also permitting them to participate in sport or leisure activities where there is a risk of exposure to water. While the invention will be described in connection with certain embodiments, it will be understood that the invention is not limited to these embodiments. On the contrary, the invention includes all alternatives, modifications and equivalents as may be included within the spirit and scope of the present invention.
[0005] In one aspect in accordance with the principles of the present disclosure, an article of swimming apparel includes a swimsuit adapted for wear in a wet environment, and a waterproof receptacle coupled with the swimsuit for receiving a personal electronic device and protecting the personal electronic device against exposure to water or other liquids. The receptacle may include a waterproof speaker that facilitates transmitting audio signals from a personal electronic device disposed within the receptacle.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and, together with a general description of the invention given above, and the detailed description given below, serve to explain the invention.
[0007] FIG. 1 is a schematic illustration depicting an exemplary garment including a waterproof electronic device receptacle in accordance with the principles of the present invention.
[0008] FIG. 2 is a front view of an exemplary waterproof electronic device receptacle in accordance with the principles of the present invention.
[0009] FIG. 3A is a front view an alternative embodiment of an exemplary waterproof electronic device receptacle in accordance with the principles of the present invention.
[0010] FIG. 3B is a rear view of the exemplary waterproof electronic device receptacle of FIG. 3A .
[0011] FIG. 4 is a front view of the exemplary waterproof electronic device receptacle of FIG. 3A , with an electronic device disposed within the reservoir.
[0012] FIG. 5 is a front view of yet another exemplary waterproof electronic device receptacle, illustrating an output connection.
[0013] It should be understood that the appended drawings are not necessarily to scale, presenting a somewhat simplified representation of various features illustrative of the basic principles of the invention. The specific features disclosed herein, including, for example, any specific dimensions, orientations, locations, and shapes of various illustrated components, will be determined in part by the particular intended application and use environment. Certain features of the illustrated embodiments may have been enlarged or distorted relative to others to facilitate visualization and provide a clear understanding.
DETAILED DESCRIPTION
[0014] FIG. 1 depicts an exemplary garment 10 , in the form of swim trunks, which may be worn by a user during the enjoyment or performance of sport or leisure activities where the user and garment 10 may be exposed to water. A waterproof electronic device receptacle 12 is coupled with the garment 10 for receiving and containing a personal electronic device 14 such as a cellular telephone, a digital audio player, or any other electronic device. The receptacle 12 may be provided in a pocket 16 of the garment 10 , or may be attached to an inner surface or an outer surface of the garment 10 , or at any other suitable location on the garment 10 . The receptacle 12 may be selectively removably coupled to the garment 10 , such as by buttons, zippers, snaps, hook-and-loop type fasteners (such as Velcro®), or by any other suitable method. Alternatively, the receptacle 12 may be permanently coupled with the garment 10 , such as by stitching, riveting, or other suitable methods. The receptacle 12 may also be attached to the garment 10 by a flexible tether to facilitate limited movement of the receptacle 12 relative to the garment 10 , while still securing the receptacle 12 to the garment 10 .
[0015] FIGS. 2-4 depict different embodiments of waterproof electronic device receptacles 12 , 12 a in accordance with the principles of the present invention. With continued reference to FIG. 1 , and referring further to FIGS. 2 , 3 A, 3 B, and 4 , the waterproof electronic device receptacle 12 , 12 a comprises a flexible enclosure 20 having an interior reservoir 22 sized to receive the personal electronic device 14 . In the embodiment shown, the receptacle 12 , 12 a has a generally rectangular shape. However, it will be appreciated that the receptacle 12 , 12 a may have various other shapes suitable for receiving a personal electronic device 14 and for being coupled with a garment 10 . At least one end of the receptacle 12 , 12 a includes an opening 24 that provides access to the interior reservoir 22 for receiving and removing the personal electronic device 14 . A selectively sealable closure 26 is provided adjacent the opening 24 to thereby seal the interior reservoir 22 against the intrusion of water, so that a personal electronic device 14 disposed therein is protected from exposure to water or other liquids. The sealable closure 26 may comprise a zipper-type seal, or various other structures suitable to facilitate sealing the enclosure 20 against intrusion of water or other liquids.
[0016] The waterproof electronic device receptacle 12 , 12 a may further include a waterproof speaker 30 , 30 a coupled with the flexible enclosure 20 . In the embodiments shown, the speaker 30 , 30 a is depicted on a side panel of the enclosure 20 . However, it will be appreciated that the speaker 30 , 30 a may be located on various other portions of the enclosure 20 , as may be desired. The receptacle 12 , 12 a further includes a speaker input connection 32 coupled with the speaker 30 and configured to be connected with an electronic device 14 disposed within the reservoir 22 . When the electronic device 14 is disposed in the reservoir 22 and sealed with the closure 26 , a user may operate the electronic device 14 whereby the speaker 30 , 30 a transmits audio signals from the electronic device 14 such that the audio signals can be heard by the user during enjoyment of leisure or sports activities in and around water. Controls may be provided on the speaker 30 , or other suitable structure, for adjusting the volume of sound transmitted by speaker 30 or for performing various other functions. In the embodiment shown in FIG. 3B , the speaker 30 a includes controls in the form of a button 34 for controlling the volume of sound, and a button 36 for controlling power to the speaker 30 a. The waterproof electronic device receptacle 12 , 12 a may further include a pocket 38 or other structure (best seen in FIGS. 3A and 3B ) for receiving one or more batteries (not shown) within the interior reservoir 22 to provide power to speaker 30 .
[0017] In another embodiment, the waterproof electronic device receptacle 12 b may further include a waterproof output connection, or jack, communicating with the exterior of the reservoir 22 and configured to receive a corresponding connection to waterproof headphones, ear buds, or other suitable components that can play audio signals from the electronic device 14 disposed within the interior reservoir 22 . FIG. 5 depicts an exemplary embodiment of a waterproof electronic device receptacle 12 b having a waterproof output connection 40 that can be coupled with an electronic device 14 disposed in the reservoir 22 , and also with headphones, ear buds, or other suitable components (not shown) outside the receptacle 12 b. In this embodiment, the waterproof electronic device receptacle 12 b does not include a speaker as described above. However, it will be appreciated that other embodiments of a waterproof electronic device receptacle 12 b having an output connection 40 may also include a waterproof speaker as described above.
[0018] In some embodiments, the waterproof electronic device receptacle 12 , 12 a, 12 b may be constructed of materials that facilitate manipulation and operation of the electronic device 14 disposed in the interior reservoir 22 , such as, but not limited to, thermoplastic urethane (TPU), polyvinyl chloride (PVC), or other suitable materials. For example, at least a portion of the flexible enclosure 20 may comprise a material that facilitates actuation and operation of an electronic device 14 having touch screen functionality while the device 14 is disposed within the interior reservoir 22 of the receptacle 12 , 12 a, 12 b. In another embodiment, at least a portion of the flexible enclosure 20 may comprise a material that is transparent, or at least translucent, so that the electronic device 14 may be operated to take photographs while disposed within the interior reservoir 22 and while the waterproof electronic device receptacle 12 , 12 a, 12 b is underwater. Advantageously, the waterproof electronic device receptacle 12 , 12 a, 12 b enables users to operate the electronic device 14 without having to access the device 14 through the opening 24 .
[0019] In another embodiment, the speaker 30 , 30 a may be adapted to receive audible commands from a user and transmit corresponding signals to the electronic device 14 disposed within the interior reservoir 22 , such as by speaker input connection 32 or other suitable connections with the electronic device 14 . Alternatively, the receptacle 12 , 12 a, 12 b may further include a separate microphone (not shown) adapted to receive audible commands from a user and transmit corresponding signals to an electronic device 14 disposed within the interior reservoir 22 .
[0020] While the garment 10 has been shown and described herein as comprising swim trunks, it will be appreciated that the garment 10 may alternatively be styled in the form of a bikini, a tank top, or various other garments intended for use in and around a wet environment. In another embodiment, the garment 10 may further include a waterproof lining coupled with the garment 10 and sized to receive the waterproof electronic device receptacle 12 , 12 a, 12 b therein.
[0021] While the present invention has been illustrated by a description of one or more embodiments thereof, and while these embodiments have been described in considerable detail, they are not intended to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications will readily appear to those skilled in the art. Moreover, it should be appreciated that the various features, applications, and devices disclosed herein may also be used alone or in any combination. The invention in its broader aspects is therefore not limited to the specific details, representative apparatus and method, and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the scope of the general inventive concept. | An article of swimming apparel includes a swimsuit adapted for wear in a wet environment and a waterproof receptacle coupled with the swimsuit for receiving a personal electronic device and protecting the personal electronic device against exposure to water or other liquids. The receptacle includes a waterproof speaker that facilitates transmitting audio signals from a personal electronic device disposed within the receptacle. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a urea-formaldehyde resin composition, to methods of manufacturing the resin and using it, and to products prepared using the resin. More particularly, the invention relates to a urea-formaldehyde resin composition which cures quickly and exhibits low formaldehyde emission. The resin is useful, for example, in a binder composition for making glass fiber mats, such as roofing shingles.
2. Description of Related Art
Often, products containing fibrous or particulate materials are manufactured by binding the materials together by use of a binder composition. Such compositions typically are known as "binders". Binders not only retain the fibrous or particulate materials in the desired orientation or shape, but also impart certain physical characteristics to the product. For example, mats of glass fibers bound together have a variety of forms and uses, such as support sheets for vinyl and other types of composite flooring, roofing shingles, or siding.
Preferred characteristics of binders used to bind glass fibers may be different from preferred characteristics of binders used to bind other particulates. For example, it may be desirable to use a binder that after setting is soluble in a preselected solvent so that the bound material is released into that solvent. It may be desirable to make the set or cured binder freely soluble in some solvent, affording quick release of the bound material, or to make the binder only sparingly soluble, thus delaying release of the material. Because the characteristics exhibited by the binder contribute to the overall characteristics of the product, the binder must be carefully selected.
Typical binders used to bind glass fiber mats include urea-formaldehyde resins, phenolic resins, melamine resins, bone glue, polyvinyl alcohols, and latexes. These binder materials are impregnated directly into the fibrous mat and set or cured by heating to provide the desired integrity for the glass fibers. The most widely used glass mat binder is ureaformaldehyde because it is relatively inexpensive.
Glass fibers also have been used by themselves and in combination with other types of fibers in the production of paper-like sheet materials. Glass fibers have been used as a supplemental fiber in specialty, synthetic, fiberboard, pulp, and composite papers, and are finding a use in glass fiber paper, a substitute for papers made of asbestos fiber. Also, there has been and continues to be increasing use of a nonwoven, sheet-like mat of glass fibers (particularly chopped glass fibers or strands, and combinations thereof) as a replacement for organic felts such as cellulose mats in roofing shingles and buildup roofing systems (BUR systems).
Use of the glass fiber mats in the roofing industry provides several advantages. These advantages include: reduction in the amount of asphalt necessary for the roofing products, reduction in the weight of the roofing products, increased production rates for producing roofing products, superior rot resistance, longer product life, and improved fire ratings. These nonwoven, sheet-like mats usually are produced in a process in which glass fibers (chopped fibers, chopped fiber strands, strands, and combinations thereof) are dispersed in an aqueous medium and the resulting slurry is formed into a mat. The nonwoven, sheet-like mat product is fixed in form by contacting the mat of glass fibers with a resinic binder. An example of such a process is the "wet-laid process". Descriptions of the wet-laid process may be found in a number of U.S. patents, including U.S. Pat. Nos. 2,906,660, 3,012,929, 3,050,427, 3,103,461, 3,228,825, 3,760,458, 3,766,003, 3,838,995 and 3,905,067, all of the teachings of which are incorporated herein by reference.
The wet-laid process involves forming, usually with agitation in a mixing tank, an aqueous slurry of glass fibers, typically chopped fibers or chopped strands of suitable length and diameter. Other forms of glass fibers, such as continuous strands, also may be used. Generally, fibers having a length of about 1/4 inch to 3 inches and a diameter of about 3 to 20 microns are used. Each bundle may contain from about 20 to 300, or more, of such fibers, which may be sized or unsized, wet or dry, as long as they can be suitably dispersed in an aqueous dispersant-containing medium. The bundles are added to the medium to form an aqueous slurry. Any suitable dispersant known in the art, e.g., polyacrylamide, hydroxyethyl cellulose, ethoxylated amines, and amine oxides, may be used. The dispersant is employed in relatively small amounts, e.g. 0.2-10 parts in 10,000 parts of water.
The fiber slurry is agitated to form a workable, well-dispersed slurry having a suitable consistency. The aqueous slurry, often referred to as slush, is processed into the wet-laid, nonwoven, sheet-like mat by such machines as cylinder or Fourdrinier machines. More technologically-advanced machinery, such as the StevensFormer, RotoFormer, InverFormer, DeltaFormer, and the VertiFormer machines, also are used. The slush is deposited in some manner from a head box onto a moving wire screen or onto the surface of a moving wire-covered cylinder. On route to the screen, the dispersion usually is diluted with water to a lower fiber concentration. The slurry on the screen or cylinder is processed into the sheet-like mat by the removal of water, usually by suction and/or vacuum devices, followed by the application of a polymeric binder. Binder composition is applied by soaking the mat in an excess of binder solution, or by impregnating the mat surface by means of a binder applicator, for example, by roller or spray. The primary binder applicator for glass mat machines is the falling film curtain coater. Suction devices often are utilized for further removal of water and excess binder and to ensure a thorough application of binder through the glass mat.
Thus-incorporated binder is thermally cured, typically in an oven at elevated temperatures. Generally, a temperature of at least about 200° C. is used during curing. Normally, this heat treatment alone will effect curing. Catalytic curing, such as is accomplished with an acid catalyst (for example, ammonium chloride or p-toluene sulfonic acid), generally is a less desirable, though an optional, alternative.
Typically, when urea-formaldehyde resins are used as a binder component they release formaldehyde into the environment during cure. Formaldehyde also can be released subsequently from the cured resin, particularly when the cured resin is exposed to acidic environments. Such formaldehyde release is undesirable, particularly in enclosed environments. In such environments, formaldehyde is inhaled by workers and comes into contact with the eyes, the mouth, and other parts of the body. Formaldehyde is malodorous and is thought to contribute to human and animal illness.
Various techniques have been used to reduce formaldehyde emission from urea-formaldehyde resins. Use of formaldehyde scavengers and various methods for resin formulation, including addition of urea as a reactant late in the resin formation reaction, are techniques often used to reduce formaldehyde emission. However, use of formaldehyde scavengers often is undesirable, not only because of the additional cost, but also because it affects the characteristics, or properties, of the resin. For example, using ammonia as a formaldehyde scavenger often reduces the resistance of the cured resin to hydrolysis (degradation). Later addition of urea to reduce free formaldehyde concentration in the resin generally yields a resin that must be cured at a relatively low rate to avoid smoking. Resin stability also can be adversely effected by such treatments.
U.S. Pat. No. 2,260,033 describes a method which purportedly reduces the amount of free formaldehyde in a urea-formaldehyde resin. In the disclosed process, triethanolamine is added to a mixture of urea and formaldehyde having a 1:1 to 1.5:1 formaldehyde to urea mole ratio in an amount sufficient to neutralize its pH. The mixture is then reacted at 30° C. The resin is used to make molded objects, laminated material and films.
U.S. Pat. No. 2,626,251 describes the preparation of a water soluble, cationic urea-formaldehyde resin. The resin is disclosed as having a high degree of water resistance when cured and is suggested for use in textile applications and for adding wet strength to paper. The preferred resin is prepared by initially reacting urea and formaldehyde at a formaldehyde to urea mole ratio of at least 2.0 but less than 3.0 together with triethanolamine in a urea to triethanolamine mole ratio of 2.0 to not more than 3.0. The resin thus-formed then is made cationic by acidifying it to a pH below 2.5, and preferably at least 1.5, with a strong inorganic acid such as hydrochloric, sulfuric or nitric acid, followed by prompt neutralization to a pH of 6 to 7. A pH above 7 is discouraged as this purportedly retards the cure of the resin.
U.S. Pat. No. 3,882,462 to Pearson, describes a urea-formaldehyde resin prepared by reacting sequentially aqueous formaldehyde, a catalyzing acid, triethanolamine and urea. The aqueous resin is taught for use in coatings, adhesives and textile finishes. The preferred resin is prepared using 30 moles of formaldehyde, 2 moles of acid, preferably phosphoric acid, 2 moles of triethanolamine and 12 moles of urea. The various reactants are said to react, without applied heat, as rapidly as the materials are mixed together. In U.S. Pat. No. 4,119,598, said to be an improvement on the '462 patent, the formaldehyde, urea and triethanolamine are mixed before addition of the acid and the molar quantities, based on about 30 moles of formaldehyde, are changed to 0.13 mole acid, 1.6 mole triethanolamine and 9.9 moles urea. In yet another improvement patent, U.S. Pat. No. 4,370,442, melamine is included in the reaction mix to expand the resin's water dilutability and storage stability. Finally, in U.S. Pat. No. 4,663,239, Pearson describes including ammonium hydroxide, ammonium chloride and ammonium formate in the composition to reduce formaldehyde emissions.
U.S. Pat. No. 4,492,699 describes a urea-formaldehyde resin adhesive for wood composites, such as particle board, purportedly characterized by slow formaldehyde emission. The patent indicates that by increasing the level of methylene linkages in the resin, instead of dimethylene ether linkages and methylol end groups, hydrolytic degradation, which contributes to increased formaldehyde emission, is reduced. To accomplish this goal, the resin is prepared in a process having two stages of condensation and two stages of methylolation. In a first condensation stage, urea is added to a highly acidic formaldehyde solution (pH of 0.5 to 2.5) at a formaldehyde to urea mole ratio of 2.5 to 4.0. The initial stage is very exothermic and proceeds without the application of heat. The reaction can be controlled to a temperature in the range of 50° C. to 99° C. by adding the urea incrementally. Thereafter, the resin solution is neutralized and additional urea is added. Triethanolamine is one of several bases mentioned for neutralizing the resin and a combination of sodium hydroxide and triethanolamine is preferred. After the second stage, the cumulative formaldehyde to urea mole ratio is within the range of 1.5:1.0 to 2.5:1.0. The second step is conducted at a temperature of 50° C. to 80° C. to permit methylolation to proceed slowly. The resin then is switched again to an acidic pH, heated to reflux and reacted to a desired viscosity. Finally, the resin is neutralized to slight alkalinity (pH of 7.3-7.5) and additional urea is added to provide a cumulative formaldehyde to urea mole ratio of 1.1:1.0 to 2.3:1.0. Methylolation is said to proceed thereafter during storage. Finally, the resin can be cured later to an infusible state during use by adding ammonium chloride and heating at 115° C. for 15 minutes.
U.S. Pat. No. 4,968,773 describes preparing a urea-formaldehyde resin purportedly having a low extractable formaldehyde content by first methylolating urea under alkaline conditions (pH of 6-11) at a formaldehyde to urea mole ratio within the range of 2:1 to 3:1, followed by condensation at a low (highly acidic) pH (pH of 0.5-3.5), then neutralizing the resin (PH of 6.5-9) and adding additional urea to yield a final formaldehyde to urea mole ratio of 1.8:1 or less.
U.S. Pat. 5,362,842 describes the preparation of a U/F resin suitable for use in a glass binder composition. The resin is prepared by initially reacting, at an alkaline pH (preferably 8 to 8.4) and at an elevated temperature (preferably 95° C.), a mixture of urea, formaldehyde and triethanolamine TEA), optionally containing ammonia, to methylolate the urea. The reaction typically takes less than 30 minutes, and as it progresses the pH falls to about 6.8 and 7.3. The initial F/U mole ratio is broadly between 1.5 and 4 (preferably 2.75 to 4.0), the TEA/U mole ratio is between 0.001 and 0.1 and the preferred NH 3 /U mole ratio is 0 to 0.5. The mixture then is acidified, generally to a pH of about 5 (i.e., 4.9 to 5.2), additional urea is added, generally in several doses, to reduce the F/U mole ratio to within the range of from 1.5 to 2.5 and the reaction is continued for 1.5 to 2 hours. Finally, the resin is neutralized.
SUMMARY OF THE INVENTION
The present invention is based on the discovery of a urea-formaldehyde resin and of a method for making the resin. The resin is prepared by reacting urea and formaldehyde in at least a two step and optionally a three-step process. In the first step, conducted under alkaline reaction conditions, urea and formaldehyde are reacted in the presence of ammonia, at an F/U mole ratio of between about 1.2:1 and 1.8:1. The ammonia is supplied in an amount sufficient to yield an ammonia/urea mole ratio of between about 0.05:1 and 1.2: 1. The mixture is reacted to form a cyclic triazone/triazine polymer which forms the building block for the ultimate resin.
Thereafter, a thermosetting resin is formed from the triazole/triazine resin building block by adding additional formaldehyde to yield a higher cumulative F/U mole ratio of between about 1.5:1 and 3.0:1. The pH is adjusted low enough to control the rate of condensation and the reaction is continued under this mildly acidic condition (second step). During this reaction, the pH is lowered to about 4.3 to 4.9 and the resin viscosity advances. Once the desired viscosity endpoint is reached, the reaction mixture is cooled and the resin is used promptly or the resin is neutralized (third step) with, for example, sodium hydroxide to enhance its storage stability for later use and/or distribution.
DETAILED DESCRIPTION OF THE INVENTION
The invention is based on the discovery that a prepolymer formed by a first step reaction of formaldehyde, urea, and ammonia can be converted to a crosslinked polymer matrix that exhibits improved control of formaldehyde emissions and a faster rate of cure than similar polymers made using conventional methods. The polymer is prepared by reacting urea and formaldehyde in at least a two step and optionally a three-step process.
In the first step, a cyclic triazone/triazine polymer is formed. Urea and formaldehyde are mixed in the presence of ammonia under an alkaline reaction condition, at an F/U mole ratio of between about 1.2:1 and 1.8:1. The ammonia is supplied in an amount sufficient to yield an ammonia:urea mole ratio of between about 0.05:1 and 1.2:1, preferably between about 0.2:1 and 0.8:1. The alkalinity of the reaction mixture is maintained at a pH of about 8.0 to 10.0, preferably about 8.7 to 9.3. The alkalinity can be maintained by adding an alkali metal hydroxide such as sodium, lithium or potassium hydroxide, preferably sodium hydroxide, or other compounds such as alkali metal carbonates, alkaline earth hydroxides, organic amines.
The mixture is heated quickly to a temperature of about 85° to 105° C., preferably about 95° C., and the mixture is maintained at that temperature for a time sufficient for the reaction to form the cyclic triazone/triazine polymer. The amount of a time sufficient for the reaction to proceed to the desired extent varies depending on the particular reaction conditions, but is usually about 45 to 135 minutes, and particularly about 90 minutes.
In the second step, a thermosetting polymer is formed from the cyclic polymer. The reaction mixture containing triazole/triazine polymer formed in step one is cooled to a temperature of between about 60° to 90° C., preferably about 85° C., and then additional formaldehyde is added, preferably with additional urea, to yield a higher cumulative F/U mole ratio of between about 1.5:1 to 3.0:1, preferably between about 1.9:1 and 2.7:1. A sufficient amount of mild acid is also added to adjust the pH to a value low enough to permit good control of the rate of condensation with a preferred pH being about 6.0 to 6.4. Mild acids include a dilute mineral acid, an organic acid or an acid salt, such as ammonium chloride, ammonium sulfate, etc., or alum that is diluted to a controlled concentration and can be added for pH adjustment before or after the formaldehyde. The reaction is then continued under this mildly acidic condition at a temperature of between about 70° to 105° C., preferably about 85° C. for a time sufficient to form the thermosetting polymer. A typical, but not limiting, reaction time is about 10 to 90 minutes, most often about 45 minutes, to ensure proper advancement of polymer condensation reaction.
The polymer then is cooled to an appropriate temperature, for example, to a temperature of about 80° C. The polymer may be cooled in stages, for example, the polymer may be cooled first to about 80° C. over about 15 minutes and then to about 75° C. The cooling time and temperature may be varied and selection of particular conditions is within the skill of the art by routine testing. As the polymer cools, the pit falls to about 4.3 to 4.9, preferably about 4.5, and the viscosity of the polymer increases. Once the desired viscosity is reached, for example, 100 to 225 centipoise, the resin is cooled to room temperature. The resin can be used promptly or is further treated and stored.
If the resin is not used immediately, a third neutralization step should be employed. In this step, the resin is neutralized with, for example, an alkali metal hydroxide such as sodium, lithium, or potassium hydroxide, preferably sodium hydroxide, to enhance its storage stability. Other neutralizing agents include alkali metal carbonates, alkaline earth hydroxides and organic amines.
Skilled practitioners recognize that the reactants are commercially available in many forms. Any form which can react with the other reactants and which does not introduce extraneous moieties deleterious to the desired reaction and reaction product can be used in the preparation of the urea-formaldehyde resin of the invention.
Formaldehyde is available in many forms. Paraform (solid, polymerized formaldehyde) and formalin solutions (aqueous solutions of formaldehyde, sometimes with methanol, in 37 percent, 44 percent, or 50 percent formaldehyde concentrations) are commonly used forms. Formaldehyde also is available as a gas. Any of these forms is suitable for use in the practice of the invention. Typically, formalin solutions are preferred as the formaldehyde source.
Similarly, urea is available in many forms. Solid urea, such as prill, and urea solutions, typically aqueous solutions, are commonly available. Further, urea may be combined with another moiety, most typically formaldehyde and urea-formaldehyde, often in aqueous solution. Any form of urea or urea in combination with formaldehyde is suitable for use in the practice of the invention. Both urea prill and combined urea-formaldehyde products are preferred, such as Urea Formaldehyde Concentrate or UFC 85. These types of products are disclosed in, for example, U.S. Pat. No. 5,362,842 and 5,389,716.
Skilled practitioners also recognize that ammonia is available in various gaseous and liquid forms, particularly including aqueous solutions at various concentrations. Any of these forms is suitable for use. However, commercially-available aqueous ammonia-containing solutions are preferred herein. Such solutions typically contain between about 10 and 35 percent ammonia. A solution having 35% ammonia can be used providing stability and control problems can be overcome. An aqueous solution containing about 28 percent ammonia is particularly preferred. Anhydrous ammonia may also be used.
Use of ammonia and/or late additions of urea are commonly used prior art techniques to reduce free formaldehyde levels in urea-formaldehyde polymer systems. The former technique suffers from reducing the cured polymers resistance to hydrolysis. The latter technique suffers from a tendency to produce a polymer system that releases smoke during the cure cycle. This invention reduces or eliminates both of these problems, yet still significantly reduces free formaldehyde levels during cure and in the cured product.
The reactants may also include a small amount of a resin modifier such as ethylenediamine (EDA). Additional modifiers, such as melamine, ethylene ureas, and primary, secondary and triamines, for example, dicyanodiamide can also be incorporated into the resin of the invention. Concentrations of these modifiers in the reaction mixture may vary from 0.05 to 5.00%. These types of modifiers promote hydrolysis resistance, polymer flexibility and lower formaldehyde emissions.
Further urea additions for purposes of scavenging formaldehyde or as a diluent also may be used although should not normally be needed.
The resin of the invention also is advantageously used in the preparation of glass fiber mats to be used, for example, in the manufacture of roofing shingles. For example, glass fibers are slurried into an aqueous dispersant medium. The glass slurry is then dewatered on a perforated surface to form a mat. The binder resin of the invention is then applied to the mat before the mat passes through a drying oven where the mat is dried and the incorporated binder resin is cured. Glass fiber mats so-produced with the resin of this invention exhibit low formaldehyde emission and exhibit good dry and hot wet tensile strength, as well as good tear strength. For instance, 20-25% increases in hot wet tensile strength and 25-30% increases in tear strength have been observed relative to a control without the cyclic prepolymer.
The following examples are for purposes of illustration and are not intended to limit the scope of the claimed invention.
EXAMPLES
Example 1
The following reactants were used to prepare a urea-formaldehyde resin.
______________________________________Reactant moles______________________________________formalin solution, 50% CH.sub.2 O 14.5EDA 0.3Urea (first charge) 12.1NH.sub.4 OH, 28% 6.1UFC 85:water 14.4HCHO 34.5UREA 7.2Urea (second charge) 3.5Alum 50% 0.2NaOH 25% 0.02latent catalyst 0.02Water 1.6______________________________________
A resin was prepared by charging the 50% formalin, EDA (ethylenediamine) and urea into a reactor and heating the mixture to 45° C. to dissolve the urea. Then NH 4 OH was added which caused the mixture to exotherm to a temperature of 83° C. The reaction mixture was then heated further to 95° C. and maintained at that temperature for 90 minutes. A cyclic polymer was formed in this initial phase of the chemical reaction. (The triazone concentration can be over 50% of the total polymer mix at this time of the synthesis depending on the molar ratios of the ingredients.) The pH of the mixture was monitored and maintained between 8.7 and 9.3 by adding 25% NaOH as needed at spaced intervals. A total of 0.4 moles were added. The reaction mixture then was cooled to 85° C. UFC 85 (25% urea, 60% formaldehyde and 15% water) and a second charge of urea then were added to the reaction mixture. The temperature was thereafter maintained at 85° C. for 10 minutes. The pH was adjusted to from about 6.2 to 6.4 by adding a total of 0.2 mole of alum in increments over a course of 25 minutes. The reaction mixture was cooled to 80° C., and after 15 minutes, further cooled to 75° C. After 7 minutes, the reaction mixture was cooled to 55° C., 26.9 g 25% NaOH was added, and then the mixture was further cooled to 35° C. A latent catalyst was added and the reaction mixture was cooled to 25 ° C. The pH was finally adjusted to 7.6 to 8.2 with 25% NaOH.
The fresh free formaldehyde level of the so-produced resin was 0.59%. After 24 hours the free formaldehyde level had dropped to 0.15%. The resin's viscosity was 573 cp.
Example 2
About 1.2 moles formaldehyde (50% solution), about 1.0 moles urea, and about 0.5 moles ammonia as 28% ammonium hydroxide were added to a glass reactor and heated to 95° C. The pH was maintained at 8.3 to 8.6 for 90 minutes with 25% sodium hydroxide. Then about 2.4 moles of formaldehyde and about 0.9 moles of urea were added as UFC 85 and urea. The pH of the solution was adjusted to 4.9 to 5.1 with 50% aluminum sulfate and reacted to a Gardner-Holdt viscosity of "K". The polymer solution was then neutralized to pH 7.4 with 25% sodium hydroxide and cooled to 25° C. The final Brookfield viscosity was 200 cps with a free formaldehyde level of about 0.5%.
Example 3
About 1.2 moles formaldehyde (50% solution), about 0.0003 moles triethanolamine, about 1.0 moles urea, and about 0.5 moles ammonia as 28% ammonium hydroxide were added to a glass reactor and heated to 95° C. The pH was maintained at 8.3 to 9.1 for 90 minutes with 25% sodium hydroxide. Then about 2.4 moles of formaldehyde and about 0.9 moles of urea were added as UFC 85 and urea. The temperature was adjusted to 90° C. and the pH of the solution was adjusted to 5.1 to 5.3 with 50% aluminum sulfate and reacted to a Gardner-Holdt viscosity of "K". The polymer solution was then adjusted to a pH of 6.8 with 25% sodium hydroxide and cooled to 25 ° C. The final Brookfield viscosity was 245 cps with a free formaldehyde level of about 0.7%. | A urea-formaldehyde resin useful as a binder for making a variety of products, and a method for making the resin. The resin is prepared by reacting formaldehyde, urea, and ammonia in at least a two under alkaline conditions and optionally neutralizing the resin in a third step. The urea-formaldehyde resin thus produced has good resistance to hydrolysis, cures quickly, and is characterized by low formaldehyde emissions (release). | 2 |
This application claims the benefit of U.S. Provisional Patent Application No. 60/150,443 filed Aug. 24, 1999.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the polishing and planarization of integrated circuit surfaces, particularly those comprising silicon dioxide films (TEOS, thermal oxide or BPSG), low-K ILD films, silicon nitride films, metal films (lines) and the mixtures of these.
2. Discussion of Related Art
CMP is an enabling technology used in the semiconductor industry to remove/planarize various thin films from the surface of semiconductor substrates during the production of IC. Various types of abrasives have been used for CMP. The polishing pad, typically made of polymer materials, is another important part in the CMP process. Particles of silicon dioxide, metal oxide (alummina, ceria, titania and ziconia etc.) or a mixture of the like are typically used as the abrasive in CMP slurries.
Achieving IC wafer planarization with smooth, scratch-free and low defect surfaces is greatly challenged by the presence of abrasive particles and the micro-asperities of the polymer pads. A CMP slurry which is not properly formulated will generate scratches and residues on the polished surfaces. The scratches may result from the trace tracks of the particles (slurry abrasives and residue from removed materials), while the residue coating may come from the gelled slurries and the re-deposition of the removed materials (metal oxide in the case of metal CMP and silanol or silicates in the case of silicon oxide CMP.) The dense scratching texture will heavily contribute to the higher level of roughness on the wafer surfaces. It has been observed that the slurry coating and re-deposition of residue will preferentially occur in the dense pattern areas, especially small features and interconnection lines in areas where the surface energy is high and the residue can be readily accommodated.
U.S. Pat. No. 5,704,987 addresses the problem of removing residual slurry particles adhered to a wafer surface after chemical-mechanical polishing. Proposed is a two step cleaning operation. The first step uses a basic aqueous solution of a nonionic polymeric surfactant; the second step uses purified water.
U.S. Pat. No. 5,783,489 discusses the use of surfactants, stabilizers, or dispersing agents to promote stabilization of a polishing slurry including oxidizing agents against settling, flocculation and decomposition. Surfactants may be anionic, cationic, nonionic, or amphoteric. It was found that the addition of a surfactant may be useful to improve the within-wafer-non-uniformity (WTWNU) of the wafers, thereby improving the surface of the wafer and reducing wafer defects.
The present invention provides compounds that can be used in CMP slurries to prevent scratching, minimize surface roughness, and eliminate coating of gelled slurries or residue on the IC wafer surfaces. The chemical compounds listed in this patent work effectively with abrasive particles including, but not limited to, silicon dioxide, metal oxides and any other inorganic oxides, and mixtures of the like. The slurries of this invention work effectively on CMP processes for sheet wafers, pattern wafers with the films/lines of silicon dioxide (TEOS, BPSG, thermal oxide), low K polymers, silicon nitride and metals, as well as mixtures of the like.
SUMMARY OF THE INVENTION
A composition is provided which is useful for the polishing of a semiconductor wafer substrate comprising an organic polymer having a backbone comprised of at least 16 carbon atoms, the polymer having a plurality of moieties with affinity to surface groups on the semiconductor wafer surface.
Another composition is provided which is useful for the polishing of a semiconductor wafer substrate comprising a surfactant having a carbon chain backbone comprised of at least 16 carbon atoms.
A further aspect of this invention is the method of polishing a semiconductor wafer substrate, wherein the substrate is pressed against a polishing pad, the substrate and the pad are moved relative to each other, and a polishing composition is applied to the pad during the polishing operation, the polishing composition comprising an organic polymer having a backbone comprised of at least 16 carbon atoms, the polymer having a plurality of moieties with affinity to surface groups on the semiconductor wafer surface.
Yet another aspect of this invention is the method of polishing a semiconductor wafer substrate, wherein the substrate is pressed against a polishing pad, the substrate and the pad are moved relative to each other, and a polishing composition is applied to the pad during the polishing operation, the polishing composition comprising a surfactant having a carbon chain backbone comprised of at least 16 carbon atoms.
The compositions of this invention may optionally further comprise one or more of the following: submicron abrasive particles, a dispersing agent, an oxidizing agent, and a complexing agent.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 shows the effects of the addition of PVP on surface roughness.
FIG. 2 shows the effects of the addition of PVP on slurry or debris re-deposition.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Coating of polished IC wafer surfaces by preferentially adsorbed surfactants or polymers can significantly eliminate scratching and redeposition of residue. The coating layer, however, should be weakly bonded to the wafer surfaces, and be readily swept away by abrasion during CMP process, so that the materials removal rate will not be significantly reduced. The coating layers should also be readily rinsed off by DI water, or alkaline solutions in the post-CMP cleaning processes. It has been discovered that the addition of a type of surfactant or a type of polymer into the CMP slurries can effectively serve the purposes outlined above providing the additive has a carbon chain length greater than about 16. A surfactant should have a hydrophobic end containing CxH2x+1 with x>16, or have ethylene oxide chains (OCH2CH2)n with n>8, or the mixture of both. The other end of the surfactant comprises functional hydrophilic moieties attached to the hydrophobic chain described above. These moieties have affinity to surface groups (i.e., silanol, siloxane, or hydroxylized metal films or lines) contained on wafer surfaces. These functional end groups are commonly polar moieties, such as, but not limited to, hydroxyl, ether, amine oxide, phosphine oxide, sulphoxide, carboxy, carbonyl, alkoxy, sulphonyl, sulphate and phosphonyl. The polymer may be a high molecular weight organic polymer containing a carbon backbone with functional moieties extending from the backbone. The functional moieties interact strongly with the wafer surface so as to provide a protective layer. The mechanism of interaction between the functional moieties and the hydroxyl surface is most likely, though not limited to, that observed in the hydrogen bonding of polar species (such as the interaction of hydroxyl groups). The polymer compound is further defined as a high molecular weight organic material, having a degree of polymerization of at least 5 (i.e., 5 repeating monomeric units), more preferably more than 10, and most preferably greater than 50. The carbon chain backbone of the polymer should have a carbon chain length of about 16 or greater. The polymer compound comprises a plurality of moieties having affinity to surface groups (i.e., silanol, siloxane, hydroxylized metal films or lines etc.) contained on wafer surfaces. These groups are commonly polar moieties, such as, but not limited to, hydroxyl, ether, amine oxide, phosphine oxide, sulphoxide, carboxy, carbonyl, alkoxy, sulphonyl, sulphate and phosphonyl. The ratio of the number of the wafer surface affinity functional groups to the number of carbons in the backbone chain shall be between 1:1 to 1:200, preferably from 1:1 to 50, and most preferably from 1:1 to 1:10. It is also observed that block co-polymers of the above defined polymers have the same functions for the above mentioned applications. Examples of this type of molecule include, but not limited to, poly-vinyl alcohol, poly-vinylpyrrolidone, poly-methyl methacrylate, poly-formaldehyde, poly-ethylene oxide, poly-ethylene glycol, poly-methacrylic acid and the mixture of the like.
The slurries of this invention may optionally comprise a dispersant. Aqueous CMP slurries contain submicron abrasive particles. The size of these particles is important to the performance of the slurry as well as to the resultant surface quality. If the abrasive particles agglomerate, the polishing removal rates may change and the surface quality may deteriorate. Dispersants can be included in the slurry formulation to prevent this agglomeration of abrasive particles. Dispersants can be anionic, cationic, or nonionic. The selection of the proper dispersant depends on many factors including the surface characteristics of the abrasive particles and the ionic nature of the slurry formulation. Some examples of ionic surfactants include sodium lauryl sulfate, cetyl-trimethyl ammonium bromide. Amino alcohols are also used as dispersants in slurries for CMP.
An oxidizing agent may also be present in the compositions of the present invention. Examples of common oxidizing agents are nitrates, iodates, chlorates, perchlorates, chlorites, sulphates, persulphates, peroxides, ozonated water, and oxygenated water. Oxidizing agents can be used in slurries for CMP at concentrations of about 0.01% to about 7% by weight. Generally they are used at concentrations of about 1% to about 7% by weight. An iodate is a preferred oxidizing agent.
Any metal oxide or other polishing abrasive (such as alumina, ceria, zirconia, silica, titania, barium carbonate, or diamond) may be used in the slurries of this invention.
In the examples presented below, we demonstrate the reduction of wafer surface tension resulting from the adsorption of the above mentioned additives in the slurries. Examples of the surface roughness improvement and prevention of slurry/residue redeposit are also given.
EXAMPLE 1
Wafer Surface Tension Reduction by Additives in Slurries
A Cruise K-12 Tensiometer was used to determine surface tension. For surface tension measurements, the density of the slurry is measured and recorded. Wafers, cut into square sections and cleaned via torch method, are measured to determine their thickness' and widths, and then placed in a clean area for future use. The instrument is turned on and the balance is zeroed. Wafers, are attached to the balance via a clasp holder, and 80 ml of slurry is added to the appropriate sample container. During experimentation, the sample container will rise until the wafer is immersed in the slurry to a given depth. The data generated by the instrument is calculated based on weight differences experienced by the wafer as it penetrates the surface of the slurry. To determine surface tension, the surface tension software is opened, the plate method is selected, and sample parameters are entered. (e.g. Thickness, and width of the wafer, density of the slurry, and immersion depth.) The instrument is started and surface tension is calculated.
As seen in Table 1, the addition of PVP into the slurry reduces the surface tension on both TEOS and BPSG wafer surfaces, indicating that the PVP adsorbed on the surface and formed a protection layer along the surfaces.
TABLE 1
Effect of additives on surface tension of wafers
Surface Tension
Surface Tension
on TEOS
on BPSG
Solution
(Dyne/cm)
(dyne/cm)
D.I. Water at 25 C.
54.3
68
Sample A without PVP
54.3
56
Sample B: Sample A + 0.2
41.5
44
wt % PVP
EXAMPLE 2
Wafer Surface Roughness Reduction
AFM images were taken of wafers from samples A & B. A Digital Instruments Dimension 5000 AFM was used to image the wafers. A 10×10 μm scan size was chosen. RMS (root mean square) roughness was measured as well as P-V (peak to valley) for all surface points. Center and edge points on the wafer were sampled.
As shown in FIG. 1, the addition of PVP improved the surface roughness significantly. Scratches were eliminated by addition of PVP.
EXAMPLE 3
Prevention of Slurry/residue Re-deposition
To illustrate the effects of PVP on extreme surface roughening and slurry residue re-deposition, an underconditioned OXP-3000 was used in a slower table and platen speed process. Sample A without PVP was used as the polishing slurry under the given conditions. This was followed by Sample B with PVP. TEOS sheet wafers were polished, buffed with DIWater, cleaned with an ammonium hydroxide solution on an OnTrak DSS-200 scrubber, and reviewed under a Leica defect review optical microscope. The Leica was set at 5× objective, which translates to a 143× total screen magnification. Normarski prism mode was used to enhance contrast.
As seen in FIG. 2, slurry deposition or polishing debris re-deposition was eliminated by adding PVP into the polishing slurries, indicating that the PVP coating layer on the wafer prevented slurries or debris from directly depositing on wafer surface.
EXAMPLE 4
Prevention of Slurry/residue Re-deposition
Several polymers and surfactants were used in this Example in which slurry/residue re-deposition was measured as in Example 3. It was surprisingly found that the polymers and surfactants which prevent the re-deposition of slurry/residue must have a carbon chain length of at least about 16. We cannot generally say that all polymers and surfactants containing the functional moieties mentioned above will be effective. The molecules must be large enough to form a film thick enough to be a preventative to the slurry/residue re-deposition.
For the following slurry/redeposition tests, TEOS wafers were polished on a Strsbaugh 6DS-SP polisher under the following conditions. ILD1300 polishing slurry available from Rodel, Inc., Newark, Del. was used with 0.2% by weight of the surfactant or polymer additive.
TABLE 2
Effect of carbon chain length.
Approximate
Carbon
Slurry/residue
Additive
Manufacturer
Type
Chain Length
re-deposition
Polyvinylpyrrolidone
Sigma/Aldrich
Polymer
180
No
(Mw˜10,000)
Polyvinylalcohol
Air Products
Polymer
1600+
No
(Mw˜40,000)
Amphoterge KJ-2
Lonza
Amphoteric
9-5
Yes
Surfactant
BRIJ-58
ICI Surfactants
Nonionic
56
No
Surfactant
Zonyl FSP
Dupont
Anionic
4-16
Yes
Surfactant
Table 2 shows that the carbon chain length must be about 16 or greater for the additive to be effective in preventing slurry/residue redeposition. It has also been found that suitable additives are particularly effective when used with a polishing pad with a relatively hard surface such as an OXP3000 pad available from Rodel, Inc., Newark, Del. | A composition is provided which is useful for the polishing of a semiconductor wafer substrate comprising an organic polymer having a backbone comprised of at least 16 carbon atoms, the polymer having a plurality of moieties with affinity to surface groups on the semiconductor wafer surface. Another composition is provided which is useful for the polishing of a semiconductor wafer substrate comprising a surfactant having a carbon chain backbone comprised of at least 16 carbon atoms. | 2 |
BACKGROUND
Many ideas for improvements in the world's energy usage focus on increasing the efficiency of existing types of engines. Most heat engines are limited in their efficiency by the theoretical efficiency of the Carnot cycle, which requires an increase in operating temperature in order to increase operating efficiency. A typical application for a heat engine is to generate electricity by boiling water to create superheated steam and using the expansion of the steam to drive a turbine attached to a generator. This works very well if two temperature reservoirs can be created with a large temperature difference between them to facilitate a large expansion ratio of the superheated steam as it cools. Other gaseous working mediums having different specific heats and boiling points may be used, but in all cases the maximum efficiency of the heat engine is defined by the increase in temperature which can be achieved in the heat source over the temperature of the heat sink.
If, however, one wishes to harvest a source of thermal energy with a low temperature relative to any available cooling reservoir, then low efficiencies and low power output must be accepted when using currently available heat engine technologies. Accordingly, additional methods of harvesting energy from relatively low temperature sources of thermal energy are desirable.
Some heat engines using phase change materials, such as Nickel-Titanium alloys known as nitinol, have been designed in which the engine efficiency does not depend on the difference in temperature between the heat source and the heat sink. These engines are theoretically capable of utilizing relatively low-temperature sources of heat. These engines, however, tend to be rather inefficient and do not take advantage of the full phase change expansion that nitinol undergoes. Many of the existing designs do not fully insulate the heat source from the heat sink and therefore do not efficiently use the available heat. Accordingly, there is a need for a more efficient engine that utilizes a phase change material.
SUMMARY
The following embodiments and aspects thereof are described and illustrated in conjunction with systems, tools and methods which are meant to be exemplary and illustrative, not limiting in scope. In various embodiments, one or more of the above-described problems have been reduced or eliminated, while other embodiments are directed to other improvements.
In a first separate aspect, the present invention may take the form of a heat-driven engine that includes a thermally conductive path into the engine, from a heat source and a working medium of a working medium phase change material, having a low-to-high temperature of transformation and a high-to-low temperature of transformation, positioned adjacent to the thermally conductive path. Also, a heat pump of phase change material is positioned adjacent to the working medium and an actuator is controlled to apply stimulus to the heat pump, causing a phase change and an associated release of thermal energy, to drive the working medium above its low-to-high temperature of transformation and controlled to alternatingly remove the stimulus from the heat pump, causing the phase change to reverse, and an associated intake of thermal energy, to drive the working medium below its high-to-low temperature of transformation. Also, heat flow through the thermally conductive path maintains the working medium at a temperature range that permits the heat pump to drive the working medium temperature, in the manner noted previously.
In a second separate aspect, the present invention may take the form of a method of operating a heat-driven engine that utilizes a heat spreader, to permit a heat path into the engine, from a heat source, a working medium of phase change material, having a low-to-high temperature of transformation and high-to-low temperature of transformation, positioned adjacent to the thermally conductive path and a heat pump of phase change material positioned adjacent to the working medium. A stimulus is applied to the heat pump, causing a phase change and an associated release of thermal energy, to drive the working medium above its low-to-high temperature of transformation. Alternately the stimulus is removed from the heat pump, causing a reverse phase change and an associated intake of thermal energy to drive the working medium below its high-to-low temperature of transformation. Also, heat flow is permitted through the thermally conductive path to maintain the working medium at a temperature range that permits the heat pump to drive the working medium temperature above and below its temperature triggers.
In a third separate aspect, the present invention may take the form of a heat-driven engine that includes a thermally conductive path into the engine, from a heat source; a working medium of phase change material, having a low-to-high temperature of transformation and a high-to-low temperature of transformation, positioned adjacent to the thermally conductive path; a heat pump of phase change material positioned adjacent to the working medium. A stimulus is applied to the heat pump, causing a phase change and the associated release of thermal energy, to drive the working medium above its low-to-high temperature of transformation and then the stimulus is removed from the heat pump causing the phase change to reverse, along with an associated intake of thermal energy, to drive the working medium below it high-to-low temperature of transformation. Further causing heat flow through the thermally conductive path and maintaining the working medium at a temperature range that permits the heat pump to so drive the working medium temperature. Also, the thermally conductive path includes a heat flow constricting element, to avoid heat flow that does not conform to desired characteristics.
In a fourth separate aspect, the present invention may take the form of a cam assembly, for translating rotary movement of a first cycle type and producing from it linear movement having a second cycle type. The assembly includes a slider plate, supported by a pair of linear bushings and defining an aperture having a non-round shape; a first shaft being driven rotationally through movement of the first cycle type; and a cam-following projection joined to the first shaft by a crank that is fit into the aperture and follows the outline of the aperture as the first shaft moves through the first cycle type, causing the slider plate to move through its second cycle type.
In addition to the exemplary aspects and embodiments described above, further aspects and embodiments will become apparent by reference to the drawings and by study of the following detailed descriptions.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a proof-of-concept heat engine, according to the present invention.
FIG. 2 is a perspective view of the interior elements of the heat engine of FIG. 1
FIG. 3 is a sectional view of the shaft of the interior elements of FIG. 2 , taken at line 3 - 3 of FIG. 2 .
FIG. 4 is a schematic side view of a heat engine, according to the present invention.
FIG. 4A is a schematic view of a heat engine that is similar to that of FIG. 4 , except for that shape memory alloy elements have been replaced by cylinders containing phase change materials.
FIG. 5 shows a sectional view of the engine of FIG. 4 , taken along line 5 - 5 of FIG. 4 .
FIG. 5A is a sectional view of the engine of FIG. 4 , taken from the same perspective as FIG. 5 , showing a heat throttle mechanism that could be used with any of the embodiments.
FIG. 6 is a schematic side view of an alternative embodiment of a heat engine according to the present invention.
FIG. 7 is a sectional view of the engine of FIG. 6 , taken along line 7 - 7 .
FIG. 8 is a schematic side view of an additional alternative embodiment of a heat engine, according to the present invention.
FIG. 8A is a schematic side view of a heat engine, similar to that of FIG. 8 , but wherein the shape memory alloy starter has been replaced by a starter of a differing form.
FIG. 9 is a sectional view of the engine of FIG. 8 , taken along line 9 - 9 of FIG. 8 .
FIG. 10 is a sectional view of a variant of the engine of FIG. 8 , taken along line 9 - 9 of FIG. 8 .
FIG. 11 is a sectional view of the engine of FIG. 4 , taken from the same perspective as FIG. 5 , showing a heat reservoir that could be used with any of the embodiments.
FIG. 12 is a schematic side view of the engine of FIG. 4 , showing a cam mechanism that could be used with any of the embodiments to alter the timing of the motion created by the engine, thereby making this motion useful as an engine input.
FIG. 13 is a top view of a pair of heat engines, joined together to achieve improved performance.
FIG. 14 is a graph of temperature and heat flow between the major elements of the present invention.
Exemplary embodiments are illustrated in referenced drawings. It is intended that the embodiments and figures disclosed herein are to be considered illustrative rather than restrictive.
DETAILED DESCRIPTION
Referring to FIG. 1 , a proof-of-concept preferred embodiment of a heat engine 10 includes a working mechanism 12 , which is rigidly attached at either end to a set of four support columns 14 . Referring to FIGS. 2 and 3 , a central shaft 16 , includes thermally insulating portions 18 , thermally conductive heat spreader 20 and thermally insulating core 22 . Between conductive heat spreader 20 and insulator 22 four pairs of a shape memory alloy (SMA) working medium 30 and an SMA heat pump 32 are arranged. Working medium 30 moves moveable clamp 28 and heat pump 32 is held by a stationary clamp 26 . By applying heat to conductive portion 20 , the working mediums 30 expand and contract, causing a magnetically permeable core (not shown) to move back and forth within a solenoid 24 , mounted on solenoid mounting plate 25 , to generate electricity. This movement is explained below, with reference to FIGS. 4 , 5 and 14 .
A preferred embodiment of a heat engine 110 uses a working medium 30 , made of nitinol, to convert heat energy into kinetic energy. An adjacent heat pump 32 , also made of nitinol, is kept above its temperature of transformation (lower than that of the working medium 30 ). Stationary clamps 34 keep working medium 30 and heat pump 32 fixed in position at one end, whereas moveable clamps 36 permit motion on the other end. A heat spreader 44 , is driven by heat source 46 ( FIG. 5 ) and periodically warms working medium 30 , as described further below. Thermal insulation 47 prevents heat from escaping into the environment. Referring to FIG. 14 , at time T 0 , both working medium temperature (curve 52 ) and heat pump temperature (curve 54 ) are below the working medium low-to-high trigger temperature. The heat pump 32 is then stressed by actuator 40 , forcing heat pump 32 into its pliable, Martensite, low-enthalpy state, and releasing heat energy (shown by a heat pump-to-working medium heat flow shaded area 56 ) that had been stored in the crystalline structure of the nitinol. Heat pump 32 heats up, and heat flow from heat pump 32 to working medium 30 begins. This causes the temperature of the working medium 30 to pass the low-to-high trigger 50 , causing the working medium 30 to change phases into its shorter, Austenite, high-enthalpy state. As the working medium 30 contracts, it exerts mechanical force that is harvested by kinetic energy harvesting mechanism 42 .
While the transition of working medium 30 to its shortened, high-enthalpy state progresses, the temperature of the heat pump 32 and working medium 30 continue to rise, until the heat pump 32 transition to its low enthalpy state is largely complete. The transition of working medium 30 to its high-enthalpy state, continues (this transition began after the start of the transition of heat pump 32 ), causing medium 30 to absorb its latent heat of transformation, which is stored in its high-enthalpy crystalline structure. This phenomenon begins to cool down both working medium 30 and heat pump 32 .
While heat pump 32 is in its low-enthalpy Martensite state, it has the physical characteristic of a spring in tension, exerting force on actuator 40 . At time T 3 , to push the temperature of working medium 30 below its high-to-low enthalpy trigger 62 , the actuator 40 of heat pump 32 , permits itself to be pulled by heat pump 32 , thereby permitting heat pump 32 to transition to its shorter, Austenite, high-enthalpy state, absorbing its latent heat of transformation, thereby and causing its temperature to plunge and drawing heat from working medium 30 . Energy may be harvested from the heat pump 32 at this time, compensating in part for the expenditure of kinetic energy at time T 0 . Soon, the temperature of working medium 30 falls below the working medium high-to-low trigger 62 , which causes working medium 30 to undergo the phase change to its pliable, Martensite, low-enthalpy state. Mechanism 42 exerts a relatively small force on working medium 30 , causing it to elongate and resetting it for the purpose of creating productive work against mechanism 42 during the next cycle. While the temperature of working medium 30 is below the temperature of the heat spreader 44 , medium 30 is warmed by the heat spreader 44 (shown in FIG. 14 by a heat source-to-working medium heat flow shaded area 64 ), and in turn heats heat pump 32 . Moreover, as working medium 30 transitions to its pliable, Martensite, low-enthalpy phase, it releases its latent heat of transformation (less the thermal energy which has been converted to mechanical work), also contributing to the warming of medium 30 and heat pump 32 . This leads the heat and transformation cycle back to the starting point, at which point heat pump 32 is pulled, beginning the cycle over again.
Referring to FIG. 4A , In an alternative preferred, either 30 or the heat pump 32 can comprise an expandable cylinder that is filled with a phase-change material that undergoes a phase change, from liquid-to-gas, from liquid-to-solid or from solid-to-gas. In all of these cases (with the exception of water) the phase change material is compressed or cooled to cause phase-change to a lower volume phase, and is expanded or heated to cause phase change to a higher volume phase.
More specifically, in the case of a working medium 30 , incorporating a liquid-to-vapor phase change material, the cycle begins with the working medium 30 in its liquid phase, at a relatively low pressure and a temperature at the operating temperature of the engine 110 . Heat energy from heat spreader 44 together with heat from actuating the heat pump 32 , causes a rapid vaporization (a flash boil), which causes the working medium cylinder to expand, thereby doing work against mechanism 42 . This expansion causes the temperature of working medium 30 to fall and heat absorption from a de-actuated heat pump causes the temperature of medium 30 to fall below the condensation point, causing contraction of cylinder 30 , and bringing the mechanism back to the beginning of the cycle. If heat pump 32 is also a liquid-to-vapor expandable cylinder, it is actuated by a sudden contraction, causing a rapid expression of heat, and heat pump 32 is de-actuated by a sudden expansion, causing its temperature to drop and causing it to absorb heat from working medium 30 .
Skilled persons will recognize that this same principal of operation could be used with an expandable cylinder filled with a material that expands during a solid-to-liquid transformation or a solid-to-gas transformation for either working medium 30 or heat pump 32 or both. If water, or some other material that contracts when transforming from solid-to-liquid is used, the mechanism is constructed to accommodate this difference.
Referring to FIG. 5 , a heat source 46 sends heat into heat spreader 44 , but is partially isolated from working medium 30 , by area of lower total thermal conductivity 48 , to limit any back flow of heat from working medium 30 into heat source 46 , when working medium 30 is at its hottest, and to limit the heat flow from the heat source 46 to no more than that which can be converted to mechanical energy. Referring to FIG. 5A , other devices, such as a mechanical shutter 150 , adapted to decrease heat flow in a partially closed or closed position, could also be used to limit the heat flow to and from the heat source 46 . A sensing and control assembly reads the temperature in the heat spreader 44 and places shutter 150 in a further closed position if the heat spreader is too hot. In an alternative preferred embodiment, element 150 schematically represents a variable-conductance heat pipe, controlled responsively to the temperature of heat spreader 44 , heat source 46 , and to the requirement for output of mechanical energy or the actual contemporaneous output of mechanical energy. Additionally, in one preferred embodiment, more than one heat source is connected, each by way of a separate variable-conductivity heat pipe, to heat spreader 44 . In an example of such an embodiment a first heat source is a solar collector and a second heat source is a backup fuel-burning heat source. When the fuel-burning heat source is in use, the variable-conductivity heat pipe to the solar collector can be set to lowest conductivity, to prevent the heat from the fuel-burning heat source from flowing to the solar collector. In yet another alternative, a thermal diode is used to prevent heat flow from heat spreader 44 back to a heat source 46 , or in the case of multiple heat sources, from one heat source to another. Referring to FIG. 6 , in an alternative embodiment of a heat engine 210 , working medium 130 is warmed and cooled by a heat pump 132 that is magneto-caloric, and is caused to change phase by the application of a magnetic field, by electromagnet 140 , serving as the actuator for heat pump 132 and separated from pump 132 by insulator 136 . Alternatively, heat pump 132 is pyro-electric, with electric field generator 140 actuating it by creating an electric field, and insulator 136 again providing physical separation. Element 142 both harvests kinetic energy from working medium 130 and powers and controls field generator 140 . FIG. 7 shows heat source 146 , area of lower total thermal conductivity 148 and heat spreader 144 , which perform in similar manner to the like elements of FIG. 5 .
Referring to FIG. 8 , an embodiment of a heat engine 310 is shown which, unlike the embodiment of FIG. 5 , includes a starter element 250 , intended for use in designs where the working medium 30 and heat pump 32 may increase in temperature above the desired operating temperature during time periods when the heat engine 310 is not operating, resulting in more difficult heat engine starting. The starter element thereby relieves the design requirement that the heat pump 32 be sized adequately to start the engine cycle by absorbing the extra heat required to lower the system temperature to less than the low-enthalpy to high-enthalpy transition temperature of the working medium 30 . Starter 250 , typically also made of nitinol shape memory alloy, is kept in tension in its low-enthalpy pliable state by the latch 252 during periods when the engine is not operating. When it is desired to start the engine cycle, element 250 is released by latch 252 , thereby transforming to its shortened high-enthalpy state, absorbing its latent heat of transformation and causing a drop in temperature in itself, working medium 30 and heat pump 32 . This causes working medium 30 to undergo a transformation from its high-enthalpy, shortened state, to its low-enthalpy, pliable state. In this embodiment, working medium 30 and heat pump 32 are linked by a power transmitting element, as will be explained further below in reference to FIG. 12 . The forces applied to working medium 30 and heat pump 32 by actuators 40 and 42 are further controlled arbitrarily by a timing device, one example of which will be explained further below in reference to FIG. 12 . Accordingly, when working medium 30 becomes pliable and is caused to elongate, this causes, after a delay, heat pump 32 to be pulled into its elongated, low-enthalpy state, causing a release of heat. The engine cycle is now in a state approximately equal to T 1 in FIG. 14 , and the cycle is now self-perpetuating with heat flowing through starting element 250 to working medium 30 , as shown in FIG. 9 . FIG. 10 shows, however, that the starting element 250 , working medium 30 and heat pump 32 can be arranged in any one of a number of different configurations, some of which avoid the necessity of heat flowing through starting element 250 , to reach working medium 30 .
FIG. 8A depicts a heat engine 110 ′, similar to engine 110 of FIG. 8 , but wherein starter element 250 can take any one of several different forms including one or more magneto-caloric elements, stimulated by a magnetic field producing actuator 252 ; one or more pyro-electric elements, stimulated by an electric-field producing actuator 252 ; an electro-mechanical heat pump, controlled by an actuator 252 in the form of an electrical switch; or a volume adjustable cylinder filled with a phase change material, such as water. Any cooling device which, when brought into thermal contact directly or indirectly, will absorb enough thermal energy to lower the temperature of the working medium down to a starting temperature can serve as a starting element 250 . In the volume-adjustable cylinder embodiment a starting element actuator 252 pulls on starter element cylinder 250 , causing a sudden drop in temperature of element 250 , which in turn causes a drop in temperature of working medium 30 , which starts heat engine 110 ′. Alternatively starting element 250 takes the form of a fluid passageway and actuator 252 is a cold-fluid blower, which creates a stream of cold fluid that cools working medium 30 and starts engine 110 ′.
Referring to FIG. 11 , in an instance in which a heat source, such as source 46 is inconstant, a thermal mass or other sort of heat stabilizer 370 , can be used to provide a constant-temperature heat source to engine 310 at a temperature close to the operating temperature of the engine 310 . In one embodiment stabilizer 370 includes a medium having a relatively large specific heat or a medium which undergoes a phase change (thus absorbing or releasing a relatively large latent heat) at a temperature near the operating temperature of the engine. Examples of these mediums could be cast iron or a large volume of water, having a large capacity to absorb heat. Further examples may include eutectic salts or organic chemicals having a phase change at approximately the operating temperature of engine 310 . Heat transfer into and out of the stabilizer 370 may be assisted by a heat exchange device, composed of, alternately, a solid finned structure, pipes through which liquid is pumped, or a series of evacuated heat pipes.
Referring to FIG. 12 , which shows an embodiment of a heat engine 410 in which working medium 30 is mechanically linked to heat pump 32 , in such a manner that after engine 410 is started heat pump 32 is mechanically driven by working medium 30 so that heat pump 32 is pulled, causing elongation and a release of heat, a fixed delay after working medium 30 has reached its maximum length and heat pump 32 is permitted to shorten, causing absorption of heat, a fixed delay after working medium 30 has reached its shortest length.
Working medium 30 drives a shaft 440 hinged at the top and connected by hinge 444 to both a clockwise rotating flywheel and a counterweight 446 that supports a cam follower 448 . Cam follower 448 is constrained in its movement by cam aperture 450 , which is defined by a slider plate 452 , supported and permitted to slide by linear bushings 454 . A driving shaft 456 , which is driven by plate 452 alternatingly pulls and pushes heat pump 32 .
FIG. 12 shows heat engine 410 at time T 3 in FIG. 14 , with working medium 30 in its shortened high-enthalpy Austenite phase and heat engine 32 constrained to be in its lengthened, low enthalpy Martensite phase by the pressure of the cam follower 448 on the inside of cam aperture 450 . As the inertia of flywheel 440 causes it and the cam follower 448 to continue their clockwise rotation, cam follower 448 slips into a first notch 460 and the circular path of the cam follower 448 allows the slider plate 452 to move upwards under the influence of the force exerted on it through shaft 456 by heat pump 32 , which displays, at this phase in the cycle, characteristics similar to those of a spring held in tension. This causes the phase change and rapid cooling of heat pump 32 , which also cools the working medium 30 as shown on FIG. 14 between T 3 and T 4 . Further constriction of heat pump 32 , allowed by working medium 30 crossing its high-to-low trigger temperature 62 and undergoing the phase change to its low-enthalpy, pliable state, causes cam follower 448 to follow the upper curve of cam aperture 450 until it enters second notch 462 . This is approximately time T 0 on FIG. 14 . At this point the inertia of the flywheel 442 causes cam follower 448 to enter second notch 462 and exert force downward on slider plate 452 , causing the elongation of heat pump 32 and the release of its latent heat of transformation; thus driving the temperature of working medium 30 above its low-to-high trigger 50 and causing working medium 30 to undergo a phase change to its constricted, high-enthalpy state and the cycle to begin anew. In a preferred embodiment, over a complete cycle, the thermal energy converted to kinetic energy by the working medium 30 , is greater than the net kinetic energy input into the heat pump 32 , thereby creating a self-sustaining cycle.
FIG. 13 shows two heat engines 410 mechanically linked together and with their cycles arranged out of phase so that each one complements the other. Further, there may be more heat engines 410 mechanically linked in like manner, arranged with their cycles at various phase relationships to each other.
There are two criteria which are critical for choosing a nickel-titanium (nitinol) alloy for use as the shape memory allow material. The first is the relationship of the Austenite start temperature to the operating temperature of the engine. The Austenite start temperature (As) is the temperature at which the phase change in the nickel-titanium crystalline structure from Martensite (the low-enthalpy state) to Austenite (the high-enthalpy state) begins to take place.
Nitinol is an alloy of nickel and titanium with approximately 50% Nickel and 50% Titanium by atomic count. The As of a nitinol can be reduced by increasing the ratio of nickel to titanium, and increased by reducing the ratio of nickel to titanium. As can be further affected by the heat treatment applied to the alloy during fabrication. Increasing the aging time and temperature of the heat treatment depletes nickel from the Ni—Ti lattice, thus increasing As. Using these methods, the Austenite start for the working medium 30 and heat pump 32 can be set to a temperature which allows for the operation of the heat engine.
The average mechanical work output by the working medium 30 is determined by the average rate of heat flow from the heat spreader 44 into the working medium 30 . This rate of heat flow is determined by the difference between the temperature of the heat source and As of the Working Medium. If the operating temperature of the heat source is known, the As of the working medium 30 (and the proportion of Ni to Ti) can be specified so as to balance the heat input to the working medium 30 with the mechanical work output (plus inefficiencies).
The As of the heat pump 32 is specified in a different fashion; the heat pump 32 alloy is superelastic, undergoing the stress-induced transformation rather than a temperature-induced transformation. In order to satisfy this condition, the Heat Pump alloy must have an As lower than any temperature it will be subjected to during the operation of the heat engine, such that it will always be in the high-enthalpy state unless subjected to enough stress to cause it to transition to the low-enthalpy state.
The second criteria by which the nickel-titanium alloy should be chosen is the hysteresis temperature. The hysteresis temperature is defined as the difference between the Austenite start temperature and the Martensite start temperature (Ms). The Martensite start temperature is the temperature at which the temperature-induced transformation of the Nitinol crystalline structure from Austenite to Martensite begins to occur.
The hysteresis temperature of the working medium 30 should be as small as is practical, because the thermal energy required to raise or lower the temperature of the Working Medium by the hysteresis temperature is wasted heat energy, which must be absorbed and released by the heat pump 32 in order to cause the working medium 30 to change phase. A larger hysteresis temperature requires a larger heat pump 32 , and increased inefficiencies in the total system.
One method of reducing the hysteresis temperature of nitinol is to add a small amount of a third element to the alloy; often this third element is copper.
The present device and method provide broader applicability for a process of converting thermal energy to mechanical energy by eliminating the requirement for a “cold reservoir”. The elimination of the step of cold reservoir cooling of a working medium also yields a significant increase in efficiency. Thermal energy from the heat source 46 is converted directly into mechanical energy by working medium 30 during its phase change from the low-enthalpy state to the high-enthalpy state. That portion of the latent heat of transformation of working medium 30 which is not so converted is released by working medium 30 during its phase change from the high-enthalpy state to the low-enthalpy state, and is absorbed by heat pump 32 during its phase change from the low-enthalpy state to the high-enthalpy state. The thermal energy thus absorbed by heat pump 32 is released again and flows back to working medium 30 during its phase change from the low-enthalpy state to the high-enthalpy state. Disregarding system inefficiencies such as heat loss to the environment through insulated or non-insulated portions of the device, all thermal energy that might otherwise be “waste heat” is thus recycled into working medium 30 in the course of one cycle, making a “cold reservoir” to receive waste heat unnecessary. As long as the thermal energy flowing from the heat source into the working medium 30 can be limited to the quantity that is converted to mechanical energy while the engine is operating plus losses due to system inefficiencies, the device will continue to operate as designed. The conversion of thermal energy to mechanical energy occurs during a phase change in which the crystalline structure of the working medium 30 changes from a low-entropy state to a high-entropy state, and the mechanical energy acts on the environment as work. The thermal energy so converted is no longer contained within the working medium 30 , and is therefore not absorbed by heat pump 32 . Thus over the course of a cycle of operation, entropy increases. No claim is made that would violate the Clausius Inequality by any of the embodiments of a heat engine according to the present invention.
While a number of exemplary aspects and embodiments have been discussed above, those possessed of skill in the art will recognize certain modifications, permutations, additions and sub-combinations thereof. It is therefore intended that the following appended claims and claims hereafter introduced are interpreted to include all such modifications, permutations, additions and sub-combinations as are within their true spirit and scope. | A heat-driven engine includes a thermally conductive path into the engine, from a heat source and a working medium of a thermostrictive material, having a first temperature of transformation, positioned adjacent to the thermally conductive path. Also, a heat pump of phase change material is positioned adjacent to the working medium and an actuator is controlled to apply stimulus to the heat pump, causing a phase change and an associated release of thermal energy, to drive the working medium above its low-to-high temperature of transformation and controlled to alternatingly remove the stimulus from the heat pump, causing the phase change to reverse, and an associated intake of thermal energy, to drive the working medium below its high-to-low temperature of transformation. Also, heat flow through the thermally conductive path maintains the working medium at a temperature range permitting the heat pump to drive the working medium temperature, in the manner noted. | 5 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to packaging, and particularly to storage containers for storing food condiments. More particularly, the present invention relates to such a storage container having a selectively openable cap structured to wipingly engage the surface of food articles which are inserted therethrough, thereby restricting the amount of material dispensed therefrom when the food article is withdrawn.
2. Description of the Background Art
Several types of disposable condiment storage containers are known and are in use today. Many of the known types of disposable storage containers are pillow shaped, are made of flexible material such as paper or plastic, and are opened by tearing off a generally flattened end portion. Other types of condiment storage containers have a generally cup-shaped plastic base with a flexible paper or foil lid sealably attached to the base, and are opened by peeling the flexible lid off the base.
What follows is a listing of some previously issued patents relating generally to packaging.
U.S. Pat. No. 2,122,299 to Sloan discloses a resilient dispensing top for a glass bottle or similar container. The top includes a flexible cover member formed of rubber or other resilient material, and having a central slit formed therein. The flexible cover member is held on the top of the bottle by a cap which fits over the cover member. A boss which is attached to an edge of the flexible cover member extends through an opening in the cap, and may be pressed inwardly to open the cover member, along the slit, to dispense contents of the container.
U.S. Pat. No. 2,257,823 to Stokes discloses a method and apparatus for producing containers. The containers are fed continuously from a web, and are formed in a double-walled, substantially tubular shape.
U.S. Pat. No. 3,349,972 to Whiteford discloses a dispenser closure for toothpaste or the like, which includes a body having a cup-shaped member at its upper end, and a marquise-shaped aperture is formed in a top wall of the cup-shaped member. The cup-shaped member has a rotatable elliptical collar permanently attached thereto, and when the collar is rotated, the collar causes the marquise-shaped aperture to open or close depending on the direction and extent of the rotation.
U.S. Pat. No. 2,813,799 to Bender et al discloses a method and apparatus for manufacturing individual condiment dispensers. The dispensers are small envelope-like enclosures, each with a dispensing neck protruding from one side of the envelope, and a tearing flap on one side of the neck to facilitate tearing the neck open to form a dispensing spout.
Although various types of containers are available today, a need still exists in the art for a food article dipping condiment storage container which restricts the amount of condiment adhering to a food item as it is withdrawn from from the container after having been dipped thereinto in order that condiment waste and mess is minimized.
SUMMARY OF THE INVENTION
The present invention provides a food article dipping and wiping container for storing and dispensing a condiment, the container including a cap which is constructed and arranged to provide a wiping action on a food article, thereby limiting the amount of condiment adhering to the food article as it is withdrawn from from the container after having been dipped thereto.
The condiment container according to the present invention, generally, includes a hollow body and a substantially flat cap which is sealably attached to an upper edge of the hollow body around the perimeter thereof. A tear-away strip is attached to the cap, wherein the tear-away strip is formed from a thin strip of substantially strong, flexible material. The tear-away strip is structured with respect to the cap for a user to pullingly tear the tear-away strip through the cap so as to thereby form a narrow slit in and across the cap which thereby opens the container and provides access to the contents thereof.
In operation, the tear-away strip is torn through the cap of a condiment container to thereby form a slit in the cap, the slit having mutually opposed slit edges on opposite sides thereof. A portion of a food article is inserted through the slit in the cap and into a quantity of condiment stored inside the container, wherein the opposed slit edges of the cap wipingly engage the food article. As the food article is removed from the condiment container, the opposed slit edges of the cap wipingly remove excess condiment adhering to the food article as the food article is pulled therepast, thereby avoiding mess as the food article is handled and eaten.
Accordingly, it is an object of the present invention to provide a food wiping condiment container which automatically wipes excess condiment from a surface of a food article which has been partially dipped therein as the article is withdrawn therefrom.
It is a further object of the present invention to provide a food wiping condiment container having a cap with a tear-away strip which creates a slit when torn off of the cap, the cap having mutually opposed slit edges on opposite sides of the slit which wipingly restrict the thickness of the layer of condiment adhering to a food article as the food article is withdrawn from the condiment container after the food article has been partially dipped into the condiment contained therein.
It is yet a further object of the present invention to provide a method for dipping a food article into a condiment, wherein the thickness of the condiment adhering to the food article is limited upon the food article being withdrawn from the condiment.
These, and additional objects, advantages, features and benefits of the present invention will become apparent from the following specification, which should be read in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a food wiping condiment container according to the present invention, shown being hand held with a food article being withdrawn therefrom after having been partially dipped into the condiment contained there.
FIG. 2 is a cut-away side view of the condiment container according to the present invention, showing the contents thereof.
FIG. 3 is a perspective view of the condiment container according to the present invention, showing a tear-away strip being partially torn away therefrom.
FIG. 4 is a partly cut-away end view of of the condiment container according to the present invention, where a food article is shown about to be dipped thereinto.
FIG. 5 is a partly cut-away end view of of the condiment container according to the present invention, wherein the food article is shown partially dipped thereto.
FIG. 6 is a partly cut-away end view of of the condiment container according to the present invention, wherein the food article is shown being withdrawn therefrom.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawings, FIG. 1 generally depicts a food wiping condiment container 10 according to the present invention, shown in operation with respect to a food article 12. In this regard, as the food article 12 is being withdrawn from the condiment container 10, after having been dipped into a reservoir of condiment located inside the condiment container, the surface of the food article is being wiped so as to reduce the thickness of the condiment 18 clinging to the withdrawn surface of the food article, while inside the container the condiment being wiped off the food article falls back into the reservoir of condiment therewithin.
The condiment container 10 has a hollow, generally tubular body 14 which surrounds and houses a storage volume 16 therein (see FIG. 2). The body 14 is preferably formed from an inexpensive flexible material such as paper or plastic, but the material used should be suitable for storing fluid suspensions or emulsions for extended time periods. Accordingly, where paper is used, it is preferably lined with either foil or plastic. A reservoir of condiment 18, such as for example ketchup, mustard, mayonnaise, tarter sauce, etc., is stored in the storage volume 16 as shown in FIG. 2. The body 14 has an upper edge 20 which lies substantially in a plane, and a lower edge 22 distally remote from the upper edge 20. In the preferred embodiment, the upper edge is provided with an annular bead 20a, and the lower edge 22 is sealed in a flattened linear seam 24. Those in the relevant art will realize that other equivalent ways of closing off the lower edge 22 of the body 14 could be used.
The condiment container 10 also includes a substantially flat cap 26 having an upper surface 28 and an opposite lower surface 30. The cap 26 is composed of a thin layer of flexible, fluid impermeable material such as coated paper, plasticized foil, plastic or combination thereof. Preferably, the cap 26 is generally flexibly deformable, yet relatively strong. The cap 26 has an outer rim 32 which defines a perimeter therearound. The cap 26 is sealably attached to the annular bead 20a of the upper edge 20 of the body 12 along the outer rim 32 thereof. The annular bead is desireably sufficiently structurally strong to resist deformation when handled, and could be composed of a suitable material attached to the upper edge of the body, such as a plastic ring.
A tear-away strip 34 is attached to the cap 26, at the lower surface 30 thereof. The tear-away strip 34 is structured with respect to the cap 26 for being pulled with respect to the cap whereupon the tear-away strip tears through the cap to thereby create a slit 36 across all, or substantially all, the cap. To facilitate the tearing action, the tear-away strip 34 is securely attached to the cap 26, preferably, though not necessarily, at the lower surface 30 thereof; also, the cap may be locally weakened by being made thinner at the tear-away strip 34, or by being pre-stressed in the local area of the tear-away strip, to thereby predispose the cap to tear in the form of a narrow strip therealong as the tear-away strip is pulled tearringly therethrough. The tear-away strip 34 is substantially linear and is made up of a thin strip or filament of substantially strong, flexible material, such as for example polyester cord, wherein the material of the tear-away strip is significantly stronger than the material of the cap 26 and which will maintain structural integrity under the stress of being pulled while the material of the cap rips. To facilitate a user grabbing the tear-away strip to being the tearing process, an ample length thereof overhangs the cap 26, as shown by FIG. 2. In order the cap 26 be torn thereacross as described herein, the tear-away strip 34 is preferably attached to the cap in an outstretched line L across the cap, preferably crossing the center thereof (see FIG. 3). The end of the tear-away strip 34 opposite the free end may or may not be attached permanently to the cap 26.
A more detailed description of the aformentioned food article wiping action will now be discussed.
As the tear-away strip 34 is pulled, mutually opposing slit edges 38, 40 of the cap 26 form in the cap as the slit 36 forms. The cap 26 locally deforms to accommodate a food article 12, such as the french fry depict in the Drawing, being thrust into the slit 36, wherein the deformation results in the edges 38, 40 pressing against the surface 42 of the food article. Thusly, the edges 38, 40 thereupon wipingly engage the surface 42 of the food article 12 and thereby restrict the thickness of condiment 18 which is allowed to pass therebetween as the food article is withdrawn from the condiment container 10 after having been dipped into the condiment. The pressing of the edges 38, 40 against the surface 42 of the food article 12 is facilitated by the cap 26 being tautly attached to the body 14 (held taut by the structural resistance to deforming by the annular bead 20a even when the slit is formed therein), and/or by the cap being composed of resilient material.
The tear-away strip and cap are mutually configured and structured to provide a slit of predetermined width that wipes food articles of known shape and size ranges (such as french fries) and predetermined condiment viscosities to thereby provide a selected range of thickness of the layer of condiment clinging to the food article after having been withdrawn from the slit.
An example of making of a food wiping condiment container 10 now be given. A substantially tubular material is fed from a roll thereof. Then a seam is formed in the substantially tubular material which is transverse to the longitudinal axis thereof, the seam defining the aforesaid lower edge 24. Next, a portion of the substantially tubular material is separated from the roll at a section which is parallel to and spaced apart from the seam to define the aforesaid upper edge 20, and thereby the body 12 of the condiment container 10. The aforementioned cap 26 is formed such as by a die cutting process and a forming process whereby the outer rim thereof is provided, and the aforementioned tear-away strip 34 is attached such as by sonic welding, adhesive or lamination process, to the lower surface of the cap. Thereupon, the cap is sealably affixed to the upper edge of the body at an outer rim of the cap. Other manufacturing processes known in the food container art may be utilized to make the condiment container according to the present invention.
Operation of the food wiping condiment container 10 according to the present invention will now be detailed.
The user grasps the body 14 of the condiment container 10, as generally depicted by FIG. 1. To open the condiment container, the user grasps the free end of the tear-away strip 34 and then pulls thereupon transversely with respect to the cap 26 to thereby cause the tear-away strip to tear through the cap. As the tear-away strip is pulled, a narrow slit 36 results across the cap, wherein the cap has mutually opposing slit edges 38, 40. The user then grasps a food article 12 and then inserts a portion thereof through the slit so as to cause the food article to dip into condiment within the condiment container and thereby coat upon the surface 42 of the food article. When the user extracts the food article from the condiment container, the slit edges of the cap wipingly engage the surface of the food article to thereby cause wiping removal of excess, mess generating condiment on the surface of the food article. Thus, the layer of condiment which does remain on the food article is not prone to dripping and messy handling of the food article after having been pulled through the slit.
Although the present invention has been described herein with respect to a specific embodiment thereof, the foregoing description is intended to be illustrative, and not restrictive. To those skilled in the art to which this invention appertains, the above described preferred embodiment may be subject to change or modification. For example, the tear-away strip may or may not be associated with a cap, but rather with a body of the condiment container, being operable to wipe food articles as generally recounted hereinabove. Further for example, the slit may be wider or narrower depending upon the deformation property of the selected material and configuration of the condiment container to thereby provide optimum wiping action of food article. Further, while a tear-away strip is the preferred agent to provide the silt, other slit forming agents known in the packaging arts may be used to form the slit. Such change or modification can be carried out without departing from the scope of the invention, which is intended to be limited only by the scope of the appended claims. | A food wiping condiment container for removing excess condiment from a food article after being dipped thereinto. The condiment container has a body, a thin, flexible cap sealingly attached to the body, and a tear-away strip attached to the cap. When the tear-away strip is torn from the cap, a slit is formed in the cap with mutually opposed slit edges. When a food article is partially inserted into the condiment container through the slit, the slit edges of the cap wipe against the food article. Accordingly, after the food article is partially dipped into a condiment stored inside the condiment container, the slit edges of the cap wipe against the food article to limit the thickness of condiment adhering to the food article as it is moved therepast. | 1 |
FIELD OF INVENTION
The invention concerns a method and apparatus for operating a vehicle, in particular a passenger automobile, with a driving motor consisting of an internal combustion engine and a flywheel following the engine for equalizing the non-unformity of the engine output torque.
BACKGROUND
Throughout much of the operational time of a vehicle, in particular a passenger automobile, the engine runs without driving the vehicle. For example, during intermittent shorttime stopping of the vehicle, e.g., due to traffic conditions, the engine, with the transmission in neutral, will continue to turn at the idling speed. Also, during deceleration and coasting, not only is the engine not driving the vehicle but it will itself be driven at a higher speed by the vehicle's forward momentum acting through the wheels of the car and transmission. Such coasting or deceleration occurs not only on driving downhill but whenever during travel the driver releases the gas pedal.
In both operating conditions, deceleration as well as idling, fuel delivered to the engine is wasted inasmuch as it is not utilized to drive the vehicle. In some cases of coasting and deceleration, braking by the engine is desirable for reasons of safety to boost the main foot brake, since the engine is used to dissipate kinetic energy. In cases other than travel down a steep incline, however, the fact that the engine continues to run when not powering the vehicle constitutes an extremely unprofitable utilization of fuel, a resource becoming scarcer and scarcer.
SUMMARY OF THE INVENTION
This invention relates to a method of operating a vehicle which offers a more effective utilization of fuel, and to a vehicle operated in accordance with such method.
More particularly, the present invention relates to an engine having a flywheel coupled to the engine for equalizing the non-uniformity of the engine output torque. In accordance with the invention, at operating conditions in which both the engine does not drive the vehicle and the flywheel rotates above a predetermined minimum speed, the coupling between the engine and the flywheel is automatically interrupted and the engine is stopped, and on termination of such operating conditions, the flywheel is again coupled to the engine to restart the engine. Due to the fact that the connection between the engine and the flywheel will be interrupted at certain operating states, e.g., on idling or coasting, and the engine thus stopped, the fuel otherwise uselessly consumed in these operating conditions can be saved. The interruption of the connection between the engine and the flywheel, which in a vehicle operated in accordance with this method may be by means of a controllable clutch interposed therebetween, moreover offers the possibility of easily starting the engine again after termination of the idling or coasting operating conditions, with the help of the flywheel which continues to rotate throughout. In many engines, e.g. the common four-cylinder four-stroke engine, the crank mechanism is acted on only temporarily by the gas forces, and the moment of inertia alone is not sufficient for uniform continuation of the rotation. Thus, the interruption of the connection between the engine and the flywheel on idling will be itself sufficient to stop the engine. However, if the engine is such that it will not stop by itself on uncoupling of the flywheel, an ignition circuit cutoff or a control signal interrupting the fuel supply may be used to assist.
The interruption and re-establishment of the connection between the driving motor and the flywheel, as well as the stopping of the engine, may be controlled as a function of parameters characterizing the operating state of the vehicle. Suitable control quantities which may be used, for example, are the engine output, the rotational speed of the flywheel, the speed of the vehicle, the operating position of the transmission, or the inclination of the vehicle. Utilization of the inclination of the vehicle is desirable so that the automatic interruption of the coupling between the engine and the flywheel, which would otherwise take place during coasting, is prevented when the vehicle is going downhill, and thereby the engine will remain connected to the drive train to help with braking the vehicle.
In accordance with this invention, automatic disengagement of the main clutch, which will be arranged between the flywheel and the transmission, may be provided at certain operating conditions of the vehicle, for example when the accelerator pedal is released or the brake pedal is depressed. Thus, during periods of deceleration, coasting, and stopping due to traffic, the flywheel, since it will be disconnected from the transmission and thus the slowing down or stopped drive wheels as well as the stopped engine, will continue to rotate freely. The flywheel will continue to store kinetic energy until it is again desired to start the engine, in which case the driver need only depress the accelerator pedal to reconnect the engine and flywheel.
The advantages attained by the invention consist above all in a substantial decrease in fuel consumption and in noise, as well as in the elimination of noxious substances in the exhaust gas of the automobile. The decrease in fuel consumption is attained not only because the engine is turned off during deceleration and certain idling states, thus using no fuel, but also because the method in accordance with the invention, as a controlled freewheel system, promotes the increased use of more efficient engine operating states. This results because internal combustion engines inherently operate more efficiently at higher loads. In place of operating continuously at partial loads, the vehicle may instead be operated intermittently at higher loads, having the engine run subsequently in the idling or deceleration state. Moreover, the starting process can be substantially improved in that, through suitable operation of the clutches, initially only the flywheel is accelerated to its starting speed by the starter motor. Thereafter, through engagement of the clutch arranged between the flywheel and the engine, the engine will be started. With the help of such an improved starting system, sure starting may be achieved even at low outside temperatures because of the higher starting rotational speed provided, while the starting device is simplified at the same time, e.g., in the form of diminished size of the starter, protection of the battery from peak currents, no need for heater plugs in diesel engines, and reduction of the fuel used during cold starting. Even if the engines in question are used for stationary aggregates, e.g., heat pumps, advantages are attained in that, for example, for starting, the customary electric starter with starter battery and battery charger or generator need not be present. Instead, it is now possible to operate with a relatively small starter motor supplied through the power system and such a motor, due to its limited current consumption, cannot overload supply systems with low-voltage protection, such as dwellings.
BRIEF DESCRIPTIONS OF THE DRAWINGS
For a better understanding of the invention, reference is made to the accompanying drawings, and the detailed description thereof, in which:
FIG. 1 is a schematic diagram of a vehicle which may be operated by the method in accordance with the invention;
FIG. 2 is a longitudinal section view through a structural unit including a flywheel, a main clutch, and a flywheel clutch according to the present invention; and
FIG. 3 is a detailed view of a portion of the flywheel clutch on a larger scale.
DETAILED DESCRIPTION
In FIG. 1, a motor vehicle has an engine 1, e.g., a four-cylinder four-stroke Otto engine, which drives the driving wheels 5 of the automobile by means of a transmission 4 and a differential axle gear 4a. Coupled to the engine crankshaft 2, and arranged between the engine 1 and transmission 4, is a flywheel 3 which equalizes the non-uniformities of the engine torque. The customary main clutch 6 is arranged between the flywheel 3 and the transmission 4 which is actuated for the purpose of interrupting the tractive connection between the engine 1 and the transmission 4 in order to shift gears.
In accordance with the invention, there is furthermore arranged between the engine 1 and the flywheel 3 a second controllable clutch or flywheel clutch 7 which at certain operating conditions of the automobile, in particular on idling and deceleration, is used to disconnect the engine 1 from the successive elements. This flywheel clutch 7 may be actuable in any suitable manner, for example, hydraulically, the action on the clutch by the hydraulic mechanism being controlled by a valve 10, the valve 10, in turn, being connected with a control device 15 for delivery of control signals causing the engagement and disengagement of the clutch. The control device 15 processes several parameter signals delivered by signal generators and characterizing the operating condition of the automobile. For example, a signal generator 16 may be provided for delivery of a load-dependent control signal; another signal generator 17 delivers a speed-dependent signal; a signal generator 18 delivers a gear position-dependent signal; signal generator 19 detects the speed of the flywheel 3 and generates a signal to the control device 15; a signal transmitter 20 detects the inclination of the vehicle; and finally, a switch 21, which can be actuated manually, is provided which when activated disconnects the automatic control of the flywheel clutch 7 to retain the flywheel clutch 7 in the engaged position regardless of the operating state of the engine. In cases where disengagement of the flywheel 3 from the engine 1 will not assure that the engine will stall (due to its non-uniform torque), or as an additional assurance that the engine will in fact stop when the flywheel is disengaged, a relay 22 may be connected into the ignition circuit of the engine 1 or a fuel cut-off valve in the fuel line, and may be acted on through the control device 15 by means of a signal for interruption of the ignition or the fuel feed, respectively.
FIG. 1 also illustrates the delivery system of the hydraulic fluid to the flywheel clutch 7, including a supply pump 11, a supply line 12 leading to the clutch 7, a nonreturn valve 13 and a pressure reservoir 14 inserted into the said line ahead of the hydraulic control valve 10. A fluid line 23 branching off behind the supply pump 11 may be used to supply fluid to other components.
In accordance with the invention, the flywheel clutch 7 arranged between the engine 1 and the flywheel 3 is actuated automatically, i.e., without any action by the passenger or driver, and is disengaged for the purpose of disconnecting the mechanical coupling between the motor 1 and the flywheel 3 whenever the motor 1 is in decelerating or idling operation. Both these operating conditions are indicated by the position of the accelerator pedal which determines the engine load and is actuated during operation by the driver. If in case of a normally running engine the accelerator pedal is released, the engine will be in one of two operating states, either deceleration or idling. The former is distinguished in that the engine is not rotating at its idling speed, but at a speed determined by the traveling speed of the vehicle and the particular transmission gear engaged. In order to detect these operating conditions, the signal generator 16 may be a switch connected to the gas pedal and delivering to the control device 15 a signal as long as the gas pedal is in its released (idle) position. In place of the gas pedal, the control quantity used could also be the position of the intake throttle which will be actuated through the gas pedal.
The disengagement of the flywheel clutch 7 and stopping of the engine during operation of the vehicle is advantageous only as long as the flywheel 3 has a sufficient rotational velocity to restart the engine when re-connected to the engine 1 at the termination of the idling or deceleration condition. Thus, the signal of transmitter 19 is used for purposeful control of the actuation of the flywheel only when the flywheel is rotating above a predetermined minimum speed. The control device 15 then forwards a signal for actuation (disengagement) to the control valve 10 whenever both the signal generator 16 indicates that the accelerator pedal is in its released position and the signal generator 19 indicates a speed of the flywheel 3 which is above a predetermined value.
In addition to a determination of the speed of the flywheel 3 as provided by the signal generator 19, the speed of travel together with the position of the transmission gears 4 may be determined and a signal corresponding thereto provided by transmitters 17 and 18. In such a case, the control device 15 would be designed to effect uncoupling through the control valve 10 only above a minimum travel speed, unless the transmission is in the idling position.
At certain times, for example, during extended downhill travel over inclined roads, it is desirable to use the braking effect of the engine to assist the vehicle's foot brakes. In order to make use of the braking effect of the engine in support of the foot brake, which may become heavily stressed thermally, a signal transmitter 20 detecting the inclination of the vehicle may be provided in accordance with the invention. Such a signal transmitter would provide a signal such that on inclinations above a prescribed threshold valve, e.g. 6%, the control device will not emit a signal for disengagement of the flywheel clutch 7. The signal transmitter in question may be a gradient switch fixed on a stationary, non-deformable part of the vehicle body. In place of such a gradient switch, or in addition thereto, a manually operated switch 21 may likewise be provided. Using this switch 21, the driver can disconnect the entire clutch disengagement control, and the vehicle will operate in the customary manner, the driving motor 1 and the flywheel 3 being permanently rigidly connected as long as that switch 21 is actuated.
The vehicle may also have a mechanism, independent of the manually operated switch 21 or the gradient switch 20, which will permit the driver to choose whether the vehicle is to be operated with or without actuation of the control clutch, i.e., disconnection of the driving motor, when the accelerator pedal is in the idling position. This may be done by having an accelerator pedal mechanism which has a two stage idling position. Thereby, the automatic uncoupling of the engine is obtained at complete release of the gas pedal by a switch acting on the control device 15, whereas upon partially depressing the gas pedal, that is, to the second stage idling position, the customary idling or deceleration operation, without disengagement of the engine from the flywheel, is obtained. In the case of a vehicle with a gas pedal designed in this manner, the driver must thus bring back the pedal beyond the second stage idling position in order to attain the driving stage with a disengaged and stopped engine in the deceleration mode.
In accordance with the invention, it is further provided that the engine 1 is stopped after uncoupling of the flywheel 3. A four-stroke reciprocating piston engine with four or fewer cylinders will stall by itself when the flywheel is uncoupled, since, with an engine of this type having non-uniform torque applied by the pistons, the flywheel effect of the rotating engine is not sufficient to keep it going. With engines having a larger number of cylinders, or if otherwise necessary, the engine may be stalled, and thus the fuel savings achieved, by temporarily interrupting the ignition spark or fuel delivery in the case of Otto engines, or of interrupting the fuel injection mechanism in the case of a diesel engine. Towards such end, a relay 22 is provided in the embodiment as per FIG. 1, which is arranged in the ignition circuit of the engine 1 (Otto engine), such relay 22 being actuated by the control device 15 synchronous with the control valve 10 for temporary interruption of the ignition. Inasmuch as the engine, on stopping, will cool off only slowly, especially if the water pump has likewise been stopped, the engine remains in continuous operating readiness and can be put under full load immediately after resumption of running without any difficulty or danger.
As a rule, the pressure and lubricant supply pump 11 driven by the engine stops simultaneously with the engine. However, the fluid pressure then still available is generally sufficient in order to supply lubricant to the various engine components. Optionally, it may also be possible in case of lack of sufficient fluid pressure to engage again the control clutch 7 in order to start the engine and/or make available during a prescribed period a residual oil pressure from a pressure reservoir for the lubricating points of the engine prior to its restarting.
In the vehicle shown in FIG. 1, the main clutch 6 is designed as a customary control clutch which can be operated at will when changing gears in the mechanical manually operated transmission 4. Evidently, the invention may also be applied to automatic transmissions, in which a hydrodynamic converter takes the place of the main clutch 6.
In a further refinement of the invention, the connection of the flywheel 3 with the driving wheels 5 is interrupted at certain operating states through automatic disengagement of the main clutch so that the flywheel continues to run separated both from the engine 1 and from the driving wheels 5 with relatively small frictional losses. To control this process, the speed of the flywheel 3 may again be used which on exceeding of a prescribed limit effects the disengagement of the main clutch 6. The automatic disengagement of the main clutch 6 may also be associated with the actuation of the foot brake or the release of the accelerator pedal. By means of this measure, it would be obtained that the vehicle on deceleration and also on stopping, e.g., due to traffic conditions, could be maintained ready to operate with the engine 1 disconnected and the flywheel 3 in rotation. This would result in a considerable decrease in fuel consumption and emission of exhaust gases, advantageous particularly in city traffic with its frequent stop and go traffic resulting in acceleration and deceleration at short intervals. As is known, the customary engines produce considerable quantities of exhaust gases during the stopping and starting processes.
FIGS. 2 and 3 show an example of an embodiment for the structural shaping of an aggregate flywheel 3, main clutch 6 and flywheel clutch 7. A clutch disk 31 is fixed on an enclosing flywheel housing 32 which, in turn, is supported by a bearing 33 on the crankshaft 2 protruding from the engine, not shown in this figure. On the outer periphery of the flywheel housing 32 a toothing 34 is provided for engagement of the pinion, not shown, of a starter motor.
The flywheel clutch 7 is housed in a portion of the flywheel housing 32 and has a driving plate 25 rigidly connected to the crankshaft 2. Due to its corrugated form, the plate 35 has little axial flexibility. Clutch linings 36 are arranged in the vicinity of the outer periphery of the driving plate 35 between one end face of a clutch disk 31 and a pressure plate 37 and which on presence of an axial compression force caused by a plate spring 38 produce a friction connection between the crankshaft 2 and the flywheel 3. The plate spring 38 at the same time provides play-free force transmission from the crankshaft 2 to the flywheel 3 by being engaged, as shown by the structural detail in FIG. 3, with its spring tongs 44, arranged on its end faces, in conically tapering recesses 45 on the flywheel housing 32 and, respectively, the pressure plate 37.
The disengagement of the flywheel clutch 7 is effected by an actuating piston 39 which slides in an actuating cylinder 40 connected with the flywheel housing 32 and acts on the plate spring 38 by way of a butt plate 42 and a joining element 43. The pressure cavity 41 formed in the actuating cylinder 40 is connected with the supply line 12 from the control valve 10, the supply line 12 extending at least partly within the crankshaft 2. Upon opening of the control valve 10 by the control device 15, the control clutch 7 will be disengaged, whereas upon closing of the control valve 10, the clutch will once again be engaged through spring force. This design ensures faultless and safe operation of the vehicle, since, upon the failure or breakdown of the control device or upon loss of fluid pressure, the vehicle will continue to operate with the flywheel and engine continually engaged. Evidently, the control actions on the flywheel clutch 7 may also occur in reverse, i.e., the engagement may be obtained through spring force and the disengagement through oil pressure. In case of such a design, starting of the driving engine could be obtained in an especially simple manner in that the starting motor would have to rotate only the flywheel uncoupled from the engine. In the event that this simplification is to be obtained for the embodiment shown in the drawing, too, the clutch would first have to be disengaged by means of oil pressure, requiring a separately driven pump with an associated reservoir.
In contrast to the embodiment shown in the drawing, the control clutch 7 may also be designed as a purely mechanically operating clutch, in which case the servo forces used for automatic actuation will be provided for outside of the clutch proper.
In addition to the flywheel clutch 7, in the embodiment as per FIG. 2 the main clutch 6 is also combined with the flywheel 3 so as to form a single structural unit. The main clutch 6 consists of an entraining disk 46 fixed on a gear primary shaft 8. A lining support disk 47 is fixed on the entraining disk 46 with clutch linings 48 arranged on either side. The clutch linings 48 are placed between a pressure plate 49 and the end face of the clutch disk 31 facing away from the control clutch 7. A diaphragm spring 50, which is fixed by rivets 52 on a holding ring 51 fastened to the flywheel housing 32, applies pressure to the pressure plate 49. On its radially inner end, the annular diaphragm spring 50 is provided with spring tongs 53 which in the customary manner can be acted on by a clutch thrust bearing 54 axially for disengagement at will of the main clutch.
As mentioned above, the main clutch 6 could be designed in the same manner as the control clutch 7 for automatic disengagement by means of hydraulic, pneumatic or electric-servo forces. In such a case, the automatic disengagement could likewise be controlled by a control device as a function, e.g., of the rotational velocity of the flywheel, the position of the accelerator pedal, the speed of travel of the automobile, the gear position and/or the brake actuation, in order to facilitate at periods of stopping or deceleration of the vehicle a continued rotation of the flywheel as an energy reservoir for a subsequent energy-saving starting of the driving motor.
A time function element may also be incorporated into the control device 15. This element would operate so that at only momentary occurrences of idling and deceleration states, such as during gear shifting processes, the control clutch and the main clutch are not automatically actuated. In such a case, the control or switching signals are transmitted to the control valve or other control devices, e.g., for interruption of the ignition for the fuel supply only after an extended presence of the control conditions. In order to prevent the flywheel, after extended rotation in the doubly disengaged state, from reaching a decreased speed insufficient to restart the engine, the control device 15 is designed so that should the speed fall below a preset minimum, the flywheel is again connected with the engine 1 or is again caused to rotate at a higher speed by other driving means, e.g., the starter motor acting on the flywheel.
Although the invention has been illustrated and described herein with reference to specific embodiments thereof in the form of apparatus and methods it will be understood that such embodiments are susceptible of modification and variation without departing from the inventive concepts embodied therein. All such modifications and variations, therefore, are intended to be encompassed within the spirit and scope of the appended claims.
Finally the practical operation of a motor vehicle equipped with an apparatus in accordance with the invention will be described as follows. To start the motor vehicle the flywheel in the doubly disengaged state initially is rotated by means of the starter motor to a speed sufficient to start the engine. The automatical operation of the clutches is then caused by depressing the gas pedal by the driver engaging first the flywheel clutch and subsequently the main clutch, so that the engine now can drive the wheels of the vehicle in the usual manner.
But if the gas pedal is completely released by the driver, for example during periods of deceleration, coasting, and stopping due to traffic the clutches are once more caused to be automatically disengaged and the engine is caused to turn off. Thus only the flywheel continues to rotate freely storing kinetic energy and avoiding useless consumption of fuel and decreasing the noise and the elimination of noxious substances in the exhaust gas of the automobile. If thereby the rotating flywheel runs the risk to reach a decreased speed insufficient to restart the engine, then for a short time the flywheel is again connected with the engine or with the starter motor to be caused to rotate at a higher speed.
In order to terminate that freewheel operating condition and to start again the engine, the driver only has to depress the gas pedal thus causing to engage the clutches and to drive the vehicle by the engine.
At last it is pointed out to the fact, that the flywheel used in the system according to the invention, substantially is the same as used in the conventional automobile engines for equalizing the non-uniformity of the engine output torque. Only by arranging an automatically operated clutch between the flywheel and the engine there is achieved a very simple and effective storing system for kinetic energy, which is in the position to bridge operating conditions of the automobile with poor efficiency, such as idling or coasting, in continuous operating readiness. | A motor vehicle and a method of operation thereof. The method and apparatus relate to motor vehicles having an internal combustion engine for driving the vehicle and a flywheel coupled to the engine for equalizing the non-uniformity of the engine output torque. In accordance with the invention, at operating conditions wherein both the engine does not drive the vehicle and the flywheel rotates above a predetermined minimum speed, the coupling between the engine and the flywheel is automatically interrupted and the engine is stopped. Upon termination of these operating conditions, the flywheel is re-coupled to the engine to restart the engine. The coupling is preferably a controllable clutch arranged between the engine and flywheel, and the interruption of the coupling between the engine and flywheel is controlled as a function of one or more parameters representative of the operating state of the vehicle. | 5 |
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