description stringlengths 2.98k 3.35M | abstract stringlengths 94 10.6k | cpc int64 0 8 |
|---|---|---|
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to fluid pressure devices which can be used either as pumps or motors.
2. Prior Art
Various fluid devices utilizing a swash plate principle of actuation have been advanced. Some of these have attempted to provide load reducing couplings for the pistons and the cylinders. Examples of such connections are shown in U.S. Pat. Nos. 2,157,692 to Doe et al; 3,245,354 to Gregor; and 2,146,133 to Tweedale.
U.S. Pat. No. 3,479,963, issued to Randa et al, and U.S. Pat. No. 3,246,577 issued to MacIntosh show devices for resiliently biasing a rotating cylinder carrier against a valving surface.
Other swash plate fluid devices have mounted the plates on the shafts with limited pivotal movement being provided. Examples of this type of drive for the variable cam or swash plate are shown in U.S. Pat. Nos. 2,095,316 issued to Davis; 1,118,799 issued to Prott; and 3,319,874 issued to Welsh et al. Further showings occur in U.S. Pat. Nos. 2,465,510 issued to Bonnafe; 3,292,554 issued to Hessler; and 2,231,100 issued to Wahlmark.
Additionally, U.S. Pat. No. 2,661,695 discloses, in FIGS. 3 and 6, an arrangement for minimizing noise by precharging or prefilling the cylinders as the units are rotated from the low to the high pressure ports. However, a very complex arrangement is disclosed to accomplish this end, and the structure is much different from that utilized in the present device. U.S. Pat. No. 3,699,845, issued to Ifield, shows a pump which has a port plate that has small passageways which are used to avoid rapid changes in pressure in the passageways associated with the port as the pump is operated. The small passageways permit limited flow before full communication of the ports and associated passageways.
SUMMARY OF THE INVENTION
The present invention relates to a fluid device that can be used as a pump or motor and which includes a rotating shaft carrying a plurality of piston pumps mounted on a "swash" plate control. A control cam can be changed in inclination relative to the axis of rotation of the shaft to cause greater or less actuation of piston type pumps carried by the swash plate. Each of the piston pumps comprises a piston slidably mounted in its respective cylinder. The cylinders are mounted in a cylinder carrier that rotates with the shaft and which has universal swiveling ball sockets for mounting ball ends on the cylinders to the carrier. Likewise, the pistons, which are mounted to the cam plate, are mounted in a universally swiveling ball and socket arrangement so that when operated, the pistons and cylinders will not tend to bind, and will easily accommodate different adjustments.
The cam operated plate carrying the pistons is mounted on the shaft through thrust bearings to carry thrust loads.
The cylinder carrier has separate ports thereon open to each of the cylinders and these ports will alternately communicate with one of a pair of inlet and outlet ports, respectively formed in a valve plate, against which the cylinder carrier rotates. The noise normally associated with this type of fluid device is also minimized by providing means for opening the cylinders and pistons to a restricted passageway leading to the high pressure ports prior to the time they are fully opened to the high pressure port so that violent changes in pressure are avoided.
The major thrust loads are carried by a thrust bearing from the shaft mounting the piston pumps to the housing to minimize the likelihood of wear.
Resilient spring washers are used between each of the cylinders and the cylinder carrier to provide a resilient force urging the cylinder carrier against the valve plate and thus exert a sealing force that will compensate for slight wear to minimize problems with excessive leakage from minor wearing of parts.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is an end view of a fluid device made according to the present invention;
FIG. 2 is a sectional view taken as on line 2--2 in FIG. 1;
FIG. 3 is a sectional view taken as on line 3--3 in FIG. 2;
FIG. 4 is a sectional view taken as on line 4--4 in FIG. 1;
FIG. 5 is a sectional view taken along the line 5--5 in FIG. 2;
FIG. 6 is a fragmentary view taken along line 6--6 in FIG. 2; and
FIG. 7 is a fragmentary sectional view taken on line 7--7 in FIG. 5.
DESCRIPTION OF THE PREFERRED EMBODIMENT
A fluid power device comprising a fluid pump or motor is illustrated generally at 10. If the fluid device is to be operated as a pump, a shaft 11 is driven from a power source, and serves to drive the pump components, while if it is to be used as a motor, the shaft 11 would be the power output shaft and fluid under pressure will be provided to the motor to drive the device in opposite operation from that which is described herein.
For sake of explanation, the present discussion will describe the operation as a pump. The mechanism, as is well known, can operate in either manner.
The pump or motor 10 as shown has an outer main housing 10A which, as can be seen in FIGS. 2 and 3, has an interior chamber 12. The chamber 12 is closed with a port block 13 at one end thereof, and an end cap 14 at the opposite end. The port block 13, as shown in FIG. 3, mounts a bearing 15 for the shaft 11 which extends through the port block. A thrust bearing 16 is positioned between a collar 17 and a radial surface formed in a recess in the port block 13. The collar 17 also fits within the recess, and is driven with the shaft through a key and is held axially on the shaft with suitable snap ring 18. A seal holder cap 21 can be mounted on the port block and used for mounting a seal for the shaft 11.
The shaft 11 as shown has an external splined end portion 22 for driving (power output or input), and an intermediate spline 23 is also formed on shaft 11 toward the interior chamber 12 of the housing 10A from the port block 13. The spline 23 drivably mounts an internally splined cylinder carrier ring 24. The cylinder carrier ring 24, as will be more fully explained, bears against the interior surface of a valve port plate 19 which in turn bears against a surface 13A of the port block 13.
A shoulder 25 is formed on the shaft 11 and a cylinder seat retaining ring 27 is seated against the shoulder 25. The shaft 11 has an opposite end portion 28 that is rotatably mounted in a bearing 29 in the end cap 14. The shaft 11 has a slot formed therein as shown at 31 between shoulder 25 and end 28, which is best seen in FIG. 3. The shaft 11 also has a reduced diameter section 32 which is turned down to provide clearance for pivoting the "swash plate", as will be explained. A disk member 35 has central portions 35A that slidably fit within the slot 31. The disk 35 has a pair of annular surfaces 35B adjacent its outer edges, and thrust bearings 39 are mounted on these surfaces and engage the sides of slot 31.
The disk 35 is mounted on a cross pin 37 that is perpendicular to the plane of the disk 35 and extends into provided cross holes in the shaft 11. The pin 37 is mounted in bearings 38 in the cross holes in shaft 11 (FIG. 3).
The disk member 35 has an opening therethrough having an axis centered on the central plane of the disk. A pin 36 is mounted in this opening in the disk and extends outwardly from the edges of the disk member 35. The pin 36 is smaller in diameter than pin 37 and also passes through an opening in pin 37. As shown in FIG. 2, the ends of pin 36 which extend beyond the disk 35 drive a hub 40 which surrounds the shaft 11 and which rotates with the shaft 11. The ends of pin 36 are mounted in suitable bearings carried by the hub.
A nonrotating pivoting housing member 41 has an open center surrounding shaft 11 and a bearing 42 is mounted therein. One end of hub 40 is rotatably mounted in bearing 42. The pivotal mounting of the housing 41 to the main housing 10A will be subsequently more fully explained. A piston mounting ring or piston carrier 43 is internally splined and drivably mounts over splines on the periphery of the hub 40. The piston carrier 43 encircles the hub 40 and thus overlies both ends of the pin 36. A snap ring 44 is used for removably holding the piston carrier 43 in place on the hub 40. A thrust bearing 46 is positioned between an end surface of the piston carrier 43 and the housing 41. Thus it can be seen that the disk 35, the pin 36 which it carries, the hub 40 and the piston carrier 43 will all rotate with the shaft 11, and because of the mounting through the bearings 42 and 46, these members may rotate with respect to the housing 41. The assembly just described comprises the swash plate for controlling pump output.
The hub 40 and therefore the piston carrier 43 are universally coupled to the shaft 11. The disk 35 and hub 40 may pivot about the axis of pin 37, and the hub 40 may also pivot about the axis of pin 36. The main adjustment of pump output is accomplished by the pivoting about pin 37, while the ability to pivot about pin 36 permits movements to compensate for small misalignments and the like.
Referring specifically to FIG. 3, it can be seen that the cam or swash plate housing 41 has side support members 50 formed integrally therewith. These side plates 50 are mounted through bushings to suitably pivot pins 51, fixed to opposite sides of the housing 10A. The pins 51 form pivots for the swash plate housing 41 which permit it to pivot about an axis which is substantially coincidental with the axis of pin 37 and which passes through the axis of rotation of the shaft 11 at right angles thereto.
The side members 50 further have swash plate adjustment rollers 52 mounted therein, which adjustment rollers are on opposite sides of the chamber 12, and which are controlled by the use of small hydraulic pistons as shown at 53 in FIG. 4, acting against spring loaded piston members 54 on the opposite side of the respective rollers. The pressure on the pistons may be derived by adjusting a relief valve 55 which controls bypass of fluid under pressure from a pressure passageway 56 leading from the pressure port. The pistons 53 on both sides of the unit may be controlled by a common pressure supply in a known manner. The spring pistons will tend to bias the swash plate assembly to maximum output. The balancing pressure on piston 53 modulates the output in accordance with the desired adjustment.
The device for adjusting the angle of the swash plate housing 41, and thus also the angle of the hub 40 and piston carrier 43, about the axes of the pins 51 and 37 are not shown in detail because it does not form a part of the invention. Mechanical adjusting devices can be utilized if desired, or other known forms of adjusting devices can be used so that the displacement of the pump can be varied by changing the angle of the swash plate assembly and thus changing the rotational plane of the piston carrier 43 with respect to the axis of the shaft 11.
The pump utilizes a series of individual linear piston pump assemblies indicated generally at 57 (FIGS. 2 and 3) for providing fluid power. Each of the pump assemblies includes a piston 58, which as shown has a part spherical end member 59 that is seated in a part spherical seat indicated generally at 60 on the piston carrier 43. In the form of the invention shown there are seven such linear pump assemblies 57, and thus there are seven hemispherical seats 60 defined in the piston carrier ring 43, for the seven pistons 58. The part spherical or ball member ends 59 are each held in place with a suitable retaining member 61 that keeps the respective end 59 seated in the hemispherical surfaces 60. The retainer 61 can be held in place on the piston carrier 43 with small cap screws.
The pistons 58 each comprise an elongated cylindrical tubular member that has an end orifice passageway 62 that leads to and opens to the end of the respective ball member 59. It should also be noted that the outer end of the ball members 59 are flattened off so that there is a pocket formed between the end of each ball member and its seat 60. The passageway 62 serves to provide lubrication for the ball member in its hemispherical seat by permitting fluid under pressure to bleed to the seat 60 through the restricted orifice.
The outer surfaces of the piston members are cylindrical and they are slidably disposed within an interior chamber or opening of corresponding cylinder members 63. There are seven of the cylinder members 63 in the fluid device. The ends of the cylinder members opposite from the pistons 58 have end portions 64 that have part spherical outer surfaces of larger diameter than the main portion of the cylinders. The part spherical outer surfaces of the ends 64 are seated against washer-like seats 65 which in turn are mounted into individual receptacles 66 on the cylinder carrier 24. A corrugated or wavy spring washer or other suitable bias means indicated generally at 70 is positioned between the end surface of each receptacle 66 and the respective seat 65. The cylinder seats are sealed with a suitable seal 71 to the outer surface of the receptacle 66. The cylinder ends 64 are held against the seats 65 by retainers 65A which are suitably located partially in receptacles in the carrier 24 and also in the retainer ring 27. The retainer 27 is held against shoulder 25.
Each of the cylinders opens to a port 72 which faces the valve plate 19. The end surface of the cylinder carrier 24 indicated at 74 seats against a complementary surface 75 on the valve plate 19. The cylinders 63 are therefore held in the seats 65 and retainer 65A by the ring 27 held by shoulder 25. Force is reacted through shaft 11, snap ring 18, collar 17, and thrust bearing 16 to port block 13. The reactive force from the cylinders is carried by wavy washers 70 to carrier 24 and then to plate 19 and to port block 13. The cylinder carrier 24 rotates relative to valve plate 19 during operation so a sliding seal is necessary between the two mating surfaces. The force with which these two surfaces contact must be controlled and the wavy washers aid in regulating the sealing force.
The retainer ring 27 has openings through which the cylinders 63 extend and the openings permit the cylinders 63 to tilt or swivel a limited amount in seats 65 and retainers 65A during use without interfering with the retainer ring 27.
Referring now specifically to FIGS. 3 and 5, it can be seen that the port block 13 has a first port 80, comprising a pressure port, defined therein, that leads to the exterior of the pump or motor and also has a port 81 defined therein which comprises a return or intake port. The ports 80 and 81 are shown open on opposite sides of port block 13 and curve toward and open to the surface 13A. The valve plate 19 rides against surface 13A and has part annular (kidney shaped) ports defined therethrough spaced radially to be in alignment with the ports 80 and 81. The valve plate 19 is held from rotating relative to port block 13, by the use of tubular spring pins 82 which project partially into openings 84 in the valve plate 19. The passageways 83 provide drainage to and from the cavity in valve block 13 in which bearing 16 is mounted and also insure lubrication of the bearing.
Referring specifically to FIG. 5, which provides an end view of the valve plate 19, looking at it in a direction from the cylinder carrier 24 toward the valve plate, a part annular, slot-like valving port, which is indicated generally at 85, is positioned so that it is open to the pressure port 80. The valving port 85 extends through the plate 19 in a part annular path starting at about 261/2 ° from a vertical center line, and terminating clockwise approximately 161/2° from the vertical center line at its lower end.
A part annular port 86 comprising the intake valving port as shown starts at its lower end approximately 261/2 ° from the vertical center line, and terminates in clockwise direction at its upper end approximately 161/2 ° from the vertical center line. The valving port 86 in the valve plate 19 is open to the intake port 81, as also shown in FIG. 5.
The valve plate 19 is provided with a small opening 87 through the plate adjacent to the rotationally leading end of the valving port 85, that is, with the shaft 11 rotating clockwise as shown by the arrow in FIG. 5, and also a small opening 88 is provided adjacent the rotationally leading end of the valve port 86. The opening 87, as can be seen in FIG. 6, is fluidly connected with a small recess or slot 87A to the end of the port 85. This recess 87A is typical, and a similar recess 88A is provided connecting the lower opening 88 to the port 86. Recess 88A is shown in dotted lines in FIG. 5. The recesses 87A and 88A are closed on one side by surface 13A.
The ports 85 and 86 are divided with port bars 85A and 85B, as well as port bars 86A and 86B. These port bars are for strength purposes, and as can be seen typically in FIG. 7, they do not divide the ports into chambers, in that the bars are recessed below the general plane of the surface 75 of the valve plate 19 in contact with the cylinder carrier. Pressure in one portion of the port 85, for example, will be present in all portions of the port, and likewise the fluid pressure in any portion of the port 86 will be the same in other portions of the port 86 throughout its arcuate length.
Assuming that the shaft 11 is rotating in a clockwise direction as viewed in FIG. 5 and shown by the arrow, and with the swash plate assembly in the position as shown in FIG. 2, when the individual pump assemblies are at a top of their cycle, that is, the reference piston is nearly centered on the vertical center line shown in FIG. 5 and up near the top of the valve plate 19, that piston will be expanded from its cylinder a maximum amount and will have been charged with fluid from the intake valving port 86. The reference pump will have been in communication with port 86 and the port 72 will be sealed on surface 75, as shown in FIG. 2. The reference position of the port 72 is shown at 72A in FIG. 5. As the pump continues to rotate clockwise the piston will be tending to compress. The pump will rotate so that the port 72 for that pump will open to the opening 87 as represented at 72B in FIG. 5.
Pressure that is present in the pressure valving port 85 will be bled through the opening 87 and passageway 87A into the pump to precharge the piston and cylinder to equalize pressure. Because the opening 87 and its associated passageway 87A are controlled in size, they form a pressure drop orifice that presents a sudden surge of pressure into the pump (which is under low pressure) that is coming into position to open to the pressure valving port 85. This gradual precharge of pressure minimizes the noise of operation. As the cylinder and piston carrier continues to rotate, the port 72 for the reference pump will come into full communication with the valving port 85. As the shaft 11 rotates, the swash plate assembly including the piston carrier 43 which rotates in a plane at an angle to the cylinder carrier 24, will cause the piston to be pushed inwardly relative to its respective cylinder to force the fluid in the cylinder out through port 72 and into the valving port 85 under pressure, and thus out through the port 80 to the high pressure outlet. The rotation of the individual linear pumps is continuous, so there will be additional cylinders opening to the port 85 at the same time the reference pump cylinder is open to the port. Then, as the reference pump reaches the lower end of the port 85 the port 72 will seal against the surface 75, which is the surface of valve plate 19 facing the viewer in FIG. 5, and will be closed off from the pressure valving port 85. The reference cylinder assembly will be fully collapsed as shown in FIG. 2 at the lower portion of the figure. That is, the piston will be collapsed into its cylinder at this point of travel, and as the reference pump continues to rotate the cylinder will open to the opening 88, which is connected through the passageway 88A to the intake valving port 86 so that any differentials in pressure will be bled off. This will prevent any residual pressure in the reference cylinder from suddenly affecting the suction from other cylinder assemblies which are open to the intake valving port 86.
As the reference pump comprising a cylinder and piston assembly continues to rotate, the piston will be pulled outwardly from the cylinder, causing a partial vacuum, and therefore the cylinder will fill with fluid from the intake valving port 86 and port 81 until the reference pump again reaches the upper end of port 86 where the port 72 will again be closed off from port 86 and the cycle will repeat.
Each of the cylinder assemblies operates in this cycle, so that fluid under pressure is supplied to the port 80, through the pressure valving port 85, and hydraulic fluid is taken into the cylinder assemblies through the port 81 and the port 86.
The use of a separate valve plate 19 permits grinding the surfaces of the valve plate to close tolerances to insure adequate sealing capabilities, and as can be seen, the valve plate is easily held in place with the tubular spring pins 82 that also provide for drain passageways for the thrust bearing cavity in the cap 21.
It should again be noted that the cylinder openings leading to the respective ports 72 are the same diameter as the outside diameter of the piston. This opening continues without restriction all the way to the output end of the cylinder assemblies, even through the part spherical end portion 64, so that there is no restriction in the outlet of the cylinder that wastes power and reduces the output pressure. Further, intake flow is unrestricted as the cylinders are charged.
The pistons may have suitable grooves formed on their outer surfaces to reduce leakage and minimize binding.
Also, the valve plate may have an annular collector and drain passageway shown partially in FIG. 6 to permit leaking fluid to be collected and drained from between the sealing surfaces through radial passageways. As noted, the springy or wavy washers 70 will insure an axial sealing force between surfaces 74 and 75, and will take up any wear, and will compensate for slight movement of the cylinder assemblies during use to maintain adequate seals during operation.
The universal action swivel for the hub 40 and piston carrier ring is easily constructed, and is securely mounted in thrust bearings on the opposite sides of the disk 35 inside the slot 31 in shaft 11 so that wear problems are greatly reduced. The main thrust load from the pressure exerted on the cylinders and pistons is carried through the shoulder 25 integrally formed on the shaft, and then back to the snap ring 18 to the thrust bearing 16 so that the shaft 11 contains most of the reactive load from the cylinder assemblies.
It should be noted that the thrust bearings 46, 39 and 16 are all roller thrust bearings as distinguished from thrust collars that carry sliding members. The roller thrust bearings disclosed carry higher loads with less wear and friction than thrust collars, and there is no need for forced lubrication with the thrust bearings, particularly in regard to bearing 46 which transmits the thrust loads from the piston and piston carrier ring to the nonrotating housing 41.
Likewise, bearings 38, 42 and the bearings supporting the ends of pin 36 are roller or needle bearings, and not bushings.
The ball and socket type couplings at the ends of the pistons and cylinders minimize binding or cocking of the pistons as they move in the cylinders, and thus there is no need for placing bushings in the cylinders, or rigidly attaching the cylinders to the shaft. | A fluid pressure device comprising a pump or motor having a rotating internal assembly comprising linear pistons and cylinders operated through a "swash" plate to actuate the pistons to provide output pressure. The swash plate is mounted to the drive shaft through a universal connection and the cylinder and piston assemblies are coupled to their component parts through universal swiveling ball and socket connections. Special spring washers are provided for insuring a sliding seal between the internal cylinders and a valving plate, and the valve ports are designed for noise minimization. | 5 |
BACKGROUND OF THE INVENTION
Typically, when constructed, an offshore platform has the jacket legs, pile sleeves, and conductor pipes sealed to prevent water leakage therein to facilitate towing operations and platform installation. With the jacket legs, pile sleeves, and conductor pipes sealed against water leakage, the offshore platform is usually placed on barges to be transported to the installation site or may be towed while floating to the desired site. At the installation site the offshore platform is positioned on the sea bottom by the controlled flooding of the jacket legs and, possibly, pile sleeves.
In some instances it is desirable to preinstall the piles which are used to anchor the offshore platform to the floor of the body of water in the jacket legs and pile sleeves before the platform is transported to the installation site. When the piles are pre-installed in the jacket legs or pile sleeves, they must also be sealed against water leakage thereinto.
Various types of prior art plugs which are usable to seal the jacket legs, pile sleeves and conductor pipes of offshore platforms are illustrated in U.S. Pat. Nos. 3,434,293; 3,577,737; 4,142,371; 4,160,612; 4,178,967; 4,184,515; 4,215,951; 4,249,576; 4,262,702; 4,286,629; 4,292,004; 4,412,559; 4,421,138; 4,421,139; and 4,432,419.
Several of the prior art plugs use linkage mechanisms to control or facilitate the release of the locking members retaining the plugs in position within either the jacket leg, pile sleeve or conductor pipe. Examples of such prior art plugs using linkage mechanisms from the above group of prior art plugs are illustrated in U.S. Pat. Nos. 3,577,737; 4,160,612; 4,178,967; 4,215,951; 4,292,004; 4,412,559; 4,421,138; 4,421,139; and 4,432,419.
Other prior art plugs use shear pin arrangements to control or facilitate the release of the plugs or locking members retaining the plugs in position within either the jacket leg, pile sleeve or conductor pipe. Examples of such prior art plugs using shear pin arrangements are illustrated in U.S. Pat. Nos. 3,434,293; 4,184,515; 4,249,576; 4,262,702; and 4,286,629.
However, when linkage mechanisms are used to control or facilitate the release of the locking members retaining the plugs in position, to accomodate the variations in the roundness of the members in which they are installed the linkages must either be adjustable or be manufactured for specific plugs to be used in specific members.
Also, when shear pin arrangements are used to control or facilitate the release of the plugs or locking members, it is desirable to have the shear pins shear when desired and at a reasonable level of loading. This is not always possible since large diameter plugs and/or plugs used to withstand large pressure differentials thereacross may require large diameter shear pins having high shear loading levels.
It is also desirable to have a plug which will withstand pressure loadings from either direction thereacross, which may be easily installed in a member in which it is to be used, and which may be removed without requiring the running of permanently installed lines to the surface of the offshore platform.
STATEMENT OF THE INVENTION
The present invention is directed to an improved reusable plug for sealing hollow cylindrical members such as the jacket legs, pile sleeves, pilings, conductor pipes, or other similar members of offshore platforms. The plug of the present invention utilizes an improved dog locking sleeve arrangement, will hold fluid pressure from either direction, may be easily installed in a hollow cylindrical member and utilizes an overshot retrieving assembly to remove the plug from the member in which it is installed thereby eliminating permanently installed lines from the plug to the surface of the offshore platform.
The plug of the present invention comprises a packer mandrel assembly, packer member, packer setting assembly, dog locking sleeve assembly, pressure equalization plug assembly and overshot retrieving assembly.
BRIEF DESCRIPTION OF THE INVENTION
FIG. 1A is a cross-sectional view of the overshot retrieving assembly unsecured to the pressure equalization plug body of the plug of the present invention in an annular cylindrical member.
FIG. 1B is a cross-sectional view of the plug of the present invention in an annular cylindrical member with the packer member in an unset position.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1A and 1B, the preferred embodiment of the plug assembly 10 of the present invention is shown in an annular cylindrical member 1.
The plug assembly 10 comprises a packer mandrel assembly 12, packer member 14, packer setting assembly 16, dog locking sleeve assembly 18, pressure equalization plug assembly 20 and overshot retrieving assembly 22.
The packer mandrel assembly 12 comprises packer mandrel body 24, upper locking dogs 26, upper locking dog supports 28, lower locking dogs 30, lower locking dog supports 32, dished head 34 having, in turn, collet sleeve 36 retained therein, dished head support ring 38, upper packer member retaining member 40, packer mandrel end ring 42, a plurality of lower dog locking sleeve stops 44, and upper dog locking sleeve lift retaining ring 45.
The packer mandrel body 24 comprises an annular cylindrical member having a plurality of rectangular elongated slots 46 therein through which locking dogs 26 extend and are movable into the interior thereof, having a plurality of rectangular elongated slots 48 therein through which portions of the packer setting assembly 16 extend, having a plurality of threaded apertures 50 therein which releasably, threadedly receive the plurality of dog locking sleeve stops 44 therein, having upper packer member retaining member 40 secured thereto on the exterior thereof at any suitable position by any suitable means, having dished circular head 34 and dished head support ring 38 secured thereto on the interior thereof at any suitable position by any suitable means, and having packer mandrel end ring 42 secured to one end thereof on the exterior thereof by any suitable means. The packer member retaining member 40 may be of any suitable configuration to retain one end of packer member 14 from movement when the packer member 14 is installed on the packer mandrel body 24.
The collet sleeve 36 retained in dished head 34 comprises an elongated cylindrical annular member having an annular recess 52 therein, having annular seal recesses 54 having, in turn, annular elastomeric seals 56 therein which may be of any suitable type elastomeric seal means and having threaded exterior portion 58 on one end thereof. Threadedly secured to exterior portion 58 of collet sleeve 36 is collet member 70 which comprises an annular member having a plurality of collet fingers 72 thereon, each finger 72 having, in turn, an enlarged head 74 thereon.
The dished head 34 may be of any suitable spherical or elliptical cross-sectional configuration. By utilizing a dished head 34 rather than a flat member the dished head 34 may be constructed of thinner thickness material thereby reducing the weight and cost of the plug assembly 10.
The locking dogs 26 are rotatably mounted on pins 60 which extend between adjacent locking dog supports 28 being secured thereto and rotatably extend through slots 46 in packer mandrel body 24. Each locking dog 26 is formed having an inwardly extending angular surface 62 on the interior thereof which terminates in vertical surface 64. Each locking dog 26 is further formed with angular face 66 on the exterior portion thereof which mates with upper plug body retaining ring 2.
The packer member 14 comprises any suitable compression set elastomeric packer member.
The packer setting assembly 16 comprises packer setting mandrel 68 having collet member 80 secured thereto on one end thereof, having ratchet threaded portion 86 thereon, packer setting ratchet nut 88 secured to the other end thereof, and packer setting sleeve assembly 90.
The collet member 80 comprises an annular member having a plurality of fingers 82 thereon, each finger having, in turn, an enlarged head 84 thereon.
The packer setting sleeve assembly 90 comprises packer setting sleeve mandrel 92 having a plurality of radial spokes 94 secured thereto having, in turn, packer setting sleeve rim 96 secured thereto having, in turn, a plurality of packer setting pins 98 received in apertures 100 in rim 96 which pins extend through slots 48 in packer mandrel 24 and are threadedly secured in threaded apertures 102 in packer setting ring 104 which has lower packer end ring 106 secured thereto.
The packer setting ratchet nut 88 comprises ratchet housing 108 having frusto-conical bore 110 therethrough, ratchet retainer 112 threadedly, releasably secured to ratchet housing 108 and a split ratchet nut 114 which mates with ratchet threaded portion 86 of packer setting mandrel 68.
The dog locking sleeve assembly 18 comprises cylindrical annular dog locking sleeve 120 having an annular recess 122 therein and a plurality of threaded apertures 124 therein, cylindrical annular dog locking sleeve body 126 having a plurality of lifting lugs 128 secured thereto having, in turn, apertures 130 therein, a plurality of radial supports 132 each support 132 having one end thereof secured to dog locking sleeve 120 and the other end thereof secured to dog locking sleeve body 126, annular cylindrical dog locking sleeve stiffener 134 and a plurality of shearable threaded fasteners 136 which threadedly, releasably engage threaded apertures 124 in dog locking sleeve 120.
The pressure equalization plug assembly 20 comprises pressure equalization plug body 138, a plurality of lifting lugs 140, each lug 140 having aperture 142 therein, plug lifting shackles 144, dog locking sleeve shackles 146 and a plurality of dog lifting cables 148, each cable 148 having one end thereof secured to plug lifting shackle 144 and the other end thereof secured to dog locking sleeve shackle 146.
The pressure equalization plug body 138 comprises an elongated cylindrical member having first annular chamfered surface 150, first cylindrical surface 152 which retains the enlarged heads 84 of collet member 80 into annular recess 52 of collet sleeve 36, second annular chamfered surface 154, second cylindrical surface 156, which slidingly, sealingly engages annular elastomeric seals 56 in collet sleeve 36, third cylindrical surface 158, third annular chamfered surface 160, fourth cylindrical surface 162 which retains enlarged heads 74 of collet member 70 in annular recess 122 of dog locking sleeve 120, and which has annular recess 167 therein which, in turn, receives a portion of shearable threaded fasteners 136 therein, fifth cylindrical surface 166 and frusto-conical surface 168. Since fifth cylindrical surface 166 is larger than fourth cylindrical surface 162, the combination of frusto-conical surface 166 and fifth cylindrical surface 164 form head 170 on plug body 138.
The overshot retrieving assembly 22 comprises guide 180, guide locking sleeve 182, a plurality of guide supports 184 and retrieving ring assembly 186.
The guide 180 comprises an annular frusto-conical member.
The guide locking sleeve 182 comprises an elongated annular cylindrical member having a cylindrical exterior surface 188, having one end 190 thereof secured to guide 180, having bore 192 therethrough into which head 170 of equalization plug body 138 is slidably received having, in turn, annular recess 194 therein containing a plurality of locking members 196 therein, each locking member 196 resiliently biased inwardly into bore 192 by resilient means 198, and having the other end thereof 200 secured to one end 202 of guide supports 184.
Each guide support 184 comprises an elongated rectangular member having one end 202 thereof secured to guide locking sleeve 182 and the other end 204 thereof secured to the interior of retrieving ring 206.
The retrieving ring assembly 186 comprises annular cylindrical retrieving ring 206, a plurality of retrieving ring lugs 208, each lug 208 having an aperture 220 therein, a plurality of retrieving shackles 212 and retrieving cable 214.
OPERATION OF THE INVENTION
Still referring to FIGS. 1A and 1B, to install the plug assembly 10 in a cylindrical member 1, the upper plug assembly retaining ring 2 is secured in position in the cylindrical member 1. Subsequently, the plug assembly 10 is moved into position within the cylindrical member 1 having upper locking dogs 26 engaging upper plug assembly retaining ring 2. At this time, lower plug assembly retaining ring 3 is secured in position in the cylindrical member 1 abutting or engaging lower locking dogs 30. To secure the plug assembly 10 in position in the cylindrical member 1 the dog locking sleeve assembly 18 is positioned within packer mandrel 24 having dog locking sleeve body 126 abutting vertical surface 64 of the upper locking dogs 26 and the pressure equalization plug body 138 is inserted through dog locking sleeve 120 thereby causing the enlarged heads 74 of collet sleeve 70 to be retained within annular recess 122 in sleeve 120 and is inserted into collet sleeve 36 having the fingers 82 having enlarged heads 84 thereon of collet member 80 inserted therein thereby causing the enlarged heads 84 to be retained within annular recess 52 of collet sleeve 36 and second cylindrical surface 156 of plug 138 to slidingly sealingly engage annular elastomeric seals 56 in annular recesses 54 of collet sleeve 36. To secure pressure equalization plug body 138 in position in dog locking sleeve 120 shearable threaded fasteners 136 are threaded through apertures 124 in dog locking sleeve 120 so that a portion of each fastener engages annular recess 164 in pressure equalization plug body 138. At this time, the plug assembly 10 is prevented from axial movement within cylindrical member 1 by upper 2 and lower 3 plug assembly retaining rings engaging upper locking dogs 26 and lower locking dogs 30, the upper locking dogs 26 being prevented from movement by dog locking sleeve assembly 18 while the lower locking dogs 30 are prevented from movement inwardly by lower plug assembly retaining ring 3, the dog locking sleeve assembly is prevented from movement by the enlarged head 74 of fingers 72 of collet member 70 engaging annular recess 122 of dog locking sleeve 120 being retained therein by pressure equalization plug body 138, and pressure equalization plug body 138 is prevented from movement by shearable threaded fasteners 136 engaging annular recess 164 in plug body 138 and apertures 124 in dog locking sleeve 120.
To compress the packer member 14 into engagement with the cylindrical member 1 a hydraulic jack or other device is attached to the threaded end portion 86 of packer setting mandrel 68 to apply sufficient force to the packer setting sleeve assembly 16 via packer setting ratchet nut 88 to compress the packer member 14 to seal the annulus between the plug assembly 10 and cylindrical member 1. During the packer member setting process the packer member 14 is compressed between upper packer member retaining member 40 and lower packer end ring 106. As the packer member 14 is compressed to seal the annulus between the plug assembly 10 and cylindrical member 1, the packer setting ratchet nut 88 is advanced along ratchet threaded portion 86 of packer setting mandrel 68 so that when the hydraulic jack or other device is removed, the ratchet blocks 114 are forced into engagement with ratchet threaded portion 86 of packer setting mandrel 68 by frusto-conical bore 110 of ratchet housing 108 thereby retaining packer setting sleeve mandrel 92 in position on packer setting mandrel 68. The packer setting mandrel 68 is prevented from movement by enlarged head 84 of fingers 82 of collet member 90 secured to the packer setting mandrel 68 being held in annular recess 52 of collet sleeve 36 by pressure equalization plug body 138.
Any forces applied from below the plug assembly 10 will tend to compress the packer member 14 tighter in the annulus between the plug assembly 10 and cylindrical member 1 once the packer member 14 is compressed, the axial loading of the plug assembly 10 is carried by the retaining rings 2 and 3, and fluid entering collet sleeve 36 is prevented from flowing therethrough by pressure equalization plug body 138 sealingly engaging annular elastomeric seals 56 in collet sleeve 36.
To remove the plug assembly 10 from the cylindrical member 1 overshot retrieving assembly 22 is used. The overshot retrieving assembly 22 is lowered through cylindrical member 1 until the guide 180 slides over head 170 of pressure equalization plug body 138 guiding the head 170 into bore 192 of guide locking sleeve 182 and past locking members 196 therein which are then resiliently biased into engagement with fourth cylindrical surface 162 of body 138. When an upward force is placed upon overshot assembly 22, the locking members 196 engage the annular surface 165 formed between fourth cylindrical surface 162 and fifth cylindrical surface 166 of pressure equalization plug body 138 thereby causing a force to be placed upon body 138. When the force on pressure equalization plug body 138 is sufficient, shearable threaded fasteners 136 are sheared or severed thereby causing the body 138 to be removed from dog locking sleeve 120 and collet sleeve 36. It should be noted that dog lifting cables 148 are sufficient to allow the movement of the lower end of pressure equalization plug body 138 past the enlarged heads 74 on fingers 72 of collet member 70 to allow release of the collet member 70 from dog locking sleeve 120 before any movement of the dog locking sleeve assembly 18 in the packer mandrel assembly 12.
When the pressure equalization plug body 138 moves upwardly, the collet member 80 is released initially from collet sleeve 36 thereby allowing the packer member 14 to disengage sealing engagement with cylindrical member 1 allowing fluid to flow thereby. Continued upward movement of the pressure equalization plug body 138 allows fluid to flow through collet sleeve 36 when second cylindrical surface 156 no longer engages annular elastomeric seals 56 in collet sleeve 36, allows collet member 70 to disengage annular recess 122 in dog locking sleeve 120 and cause dog locking sleeve body 126 of dog locking sleeve assembly 18 to disengage locking dogs 26. When the dog locking sleeve body 126 abuts or engages upper dog locking sleeve lift retaining ring 45, since upper locking dogs 26 are free to rotate inwardly through slots 46 in packer mandrel 24 and lower locking dogs 30 may rotate inwardly when the plug assembly 10 is moved upwardly in cylindrical member 1, the continued movement of the pressure equalization body plug 138 by overshot retrieving assembly 22 upwardly in cylindrical member 1 will cause the upper locking dogs 26 to disengage upper plug assembly retaining ring 2 and lower locking dogs 30 to disengage lower plug assembly retaining ring 3 and move past upper plug assembly retaining ring 2 thereby allowing the removal of plug assembly 10 from cylindrical member 1.
From the foregoing it can be easily seen that the plug assembly 10 of the present invention uses an improved dog locking sleeve arrangement using a collet sleeve 36 and collet member 70 to retain the same in the plug assembly 10, will hold pressure from either direction since upper 26 and lower 30 locking dogs are used and may be easily installed in a cylindrical member 1. | An improved reusable plug for sealing hollow cylindrical members, in particular, the jacket legs, pile sleeves, pilings, conductor pipes, or other similar members of offshore structures, the improved reusable plug comprising a packer mandrel assembly, packer member, packer setting assembly, dog locking sleeve assembly, pressure equalization plug assembly, and overshot retrieving assembly. | 4 |
[0001] This application is a continuation of U.S. application Ser. No. 11/881,237, filed on Jul. 25, 2007, which is a divisional of U.S. application Ser. No. 10/774,848, filed on Feb. 9, 2004, now U.S. Pat. No. 7,272,991 B2.
[0002] The invention relates to shaving razors, and blade subassemblies therefor and methods of manufacture.
[0003] Shaving razors often include a plurality of blades that are secured in a desired position in a plastic housing. The housing is often provided with a guard with fins or other skin engaging structures made of elastomeric material in front of the blades, and a cap on which the skin can slide behind the blades. A shaving aid (e.g., a lubricant agent dispensing mechanism) can be incorporated into the cap and, in some cases, the guard. The blades can be stationary or movable, and the housing can be fixed to a handle or movably mounted on the handle, to, e.g., assist in following the contours of the skin during shaving.
[0004] Examples of some different types of shaving razors are described in U.S. Pat. Nos. 5,313,706; 5,369,885; 5,416,974; 5,546,660; 6,032,372; 6,145,201; 6,161,288; 6,216,345; 6,216,561; and 6,397,473.
SUMMARY OF THE INVENTION
[0005] In one aspect, the invention features, in general, a subassembly for a shaving razor that includes a plurality of elongated metal blades that are secured to each other as an integral unit. The plural blades have cutting edges defining a shaving surface, and are secured to each other by weld connections at their respective longitudinal ends.
[0006] Particular embodiments of the invention may include one or more of the following features. In particular embodiments, the longitudinal ends of the blades are bent and are transverse to the cutting edges. In some embodiments, the unit includes two metal plates, and one set of longitudinal ends are connected by first weld connections to a first metal plate, and the other set of longitudinal ends are connected by second weld connections to a second metal plate. The plates can have a stainless steel base and an aluminum cladding thereover. In some other embodiments, one set of longitudinal ends of the blades overlap and are welded to adjacent ends at one side of the unit, and the other set of longitudinal ends of the blades overlap and are welded to adjacent ends at the other side of the unit. In some embodiments each blade includes an elongated cutting member having a cutting edge and an elongated support to which the elongated cutting member is attached, with the longitudinal ends of the elongated support being welded to each other at the two sides. In some other embodiments, each blade includes an elongated cutting member portion having a cutting edge and an integral elongated support portion bent downward from the cutting member portion, with the longitudinal ends of the elongated support portion being welded to each other at the two sides. In still other embodiments, each blade includes an elongated cutting member having a cutting edge, and the longitudinal ends of the elongated cutting member are welded to each other at the two sides. The subassembly can have two blades, three blades, four blades or five blades or more. The cutting edges can be located in a common plane. The subassembly can have a snap-fitting structure for connection to a housing of a shaving razor.
[0007] In another aspect the invention features, in general, a shaving razor including a subassembly as already described, and a housing having a recess in which the subassembly is secured.
[0008] In another aspect the invention features, in general, a method of making a shaving razor that includes providing a plurality of elongated metal razor blades having cutting edges and first and second longitudinal ends, positioning the cutting edges parallel to each other and spaced from adjacent cutting edges so as to define a shaving surface, connecting the first longitudinal ends to each other and the second longitudinal ends to each by welding while the cutting edges are maintained parallel to each other.
[0009] Particular embodiments of the invention may include one or more of the following features. In particular embodiments a fixture is used to align the blades in parallel planes and to position the cutting edges at desired positions. The fixture has slots to align the blades and stop surfaces to position the cutting edges. The integral unit of blades is positioned into a recess in a housing. The recess can be open to the top, with, e.g., the integral blade unit being lowered into the recess and held in place by clips or by snap-fitting, or the recess can open to the bottom, with the integral blade unit being raised into the recess.
[0010] Embodiments of the invention may include one or more of the following advantages. Automated assembly of razor blade cartridges can be simplified by installing all of the blades as a unit in a single step. The geometry of the cutting edges with respect to each other can be set prior to assembly, e.g., with a fixture, and tightly controlled and varied, if desired. The subassembly of blades can be removably mounted in a housing and replaced with a new subassembly as the blades become spent, thereby decreasing the parts that are disposed and reusing more parts. Also, integrated blade unit subassemblies can be manufactured with a variety of different blade geometries, with, e.g., different blade tangent angles, exposures, and/or spans, and the different subassemblies can all be used with a common design for the rest of the cartridge into which they are inserted, simplifying part count and tooling at the same time that a variety of different geometries can be easily implemented.
[0011] Other advantages and features of the invention will be apparent from the following description of particular embodiments thereof and from the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 is a partial, perspective view of a shaving razor.
[0013] FIG. 2 is an exploded, partial, perspective view of the FIG. 1 shaving razor.
[0014] FIG. 3 is a perspective view of a blade subassembly of the FIG. 1 shaving razor.
[0015] FIG. 4 is a plan view of the FIG. 3 blade subassembly.
[0016] FIG. 5 is a front elevation of the FIG. 3 blade subassembly.
[0017] FIG. 6 is a side elevation of the FIG. 3 blade subassembly.
[0018] FIG. 7 is a perspective view of a blade of the FIG. 3 blade subassembly.
[0019] FIG. 8 is a partial diagrammatic plan view illustrating blade and side plate components of the FIG. 3 blade subassembly.
[0020] FIG. 9 is a diagrammatic side view of fixture used in the manufacture of the FIG. 3 blade subassembly.
[0021] FIG. 10 is a diagrammatic, partial, exploded view of an alternative embodiment of a blade subassembly that does not have side plates.
[0022] FIG. 11 is an elevation of an alternative embodiment of a blade subassembly that is replaceable.
[0023] FIGS. 12-13 are perspective views of alternative, one-piece blade constructions.
[0024] FIGS. 14-16 are a perspective view of two-, three- and four-blade alternative subassemblies, respectively, for use in the FIG. 1 shaving razor.
DETAILED DESCRIPTION
[0025] Referring to FIG. 1 , shaving razor 10 includes plastic housing 12 , blades 14 secured in housing 12 , cap 16 (including a lubricating strip), handle 18 , connecting piece 19 (which is pivotally connected to housing 12 and removably connected to handle 18 ), and elastomeric guard 20 which has fins 22 . There are five blades 14 having cutting edges 28 (see FIG. 7 ) that define a shaving surface. As appears from FIG. 2 , blades 14 are provided in an integrated blade subassembly 13 that mounts in recess 21 in housing 12 from the top and is held in place by two clips 23 , only one of which is shown in FIG. 2 .
[0026] Referring to FIGS. 3-8 , blade subassembly 13 includes five blades 14 and two side plates 24 . Plates 24 have a stainless steel base and an aluminum cladding thereover for corrosion resistance. However, corrosion resistance can be achieved by other means and materials, such as by the contact with a separate cartridge component that acts as a sacrificial anode such as an aluminum clip or a separate zinc component.
[0027] Each blade 14 includes an elongated cutting member 26 having cutting edge 28 and elongated support 30 to which cutting member 26 is attached by spot welds 32 . Elongated support 30 has an angled section along its length, with a short upper portion 34 and longer base portion 36 . The longitudinal ends 38 of base portion 36 are bent 90°, and are secured to side plates 24 by spot welds 40 .
[0028] Alternatively, the elongated cutting members could be one-piece constructions having a cutting edge portion and an integral bent base portion, as shown, e.g., for one-piece complex member 39 in FIG. 12 , or not even have a bent base portion, as shown, e.g., for one-piece simple cutting member 41 in FIG. 13 .
[0029] Referring to FIG. 9 , fixture 42 is used to position blades 14 while they are welded to side plates 24 by spot welds 40 . Fixture 42 has base member 44 that includes slots 46 that receive base portions 36 of elongated supports 30 of blades 14 . Bladder 47 provides an upward force to the bottoms of base portions 36 , to cause cutting members 26 to abut angled surfaces 48 of alignment block 50 , and cutting edges 28 to contact comers 52 , thereby placing the cutting edges 28 in the desired position to define a shaving surface, and providing the desired blade tangent angle for cutting members 26 . With blades 14 properly positioned in slots 46 and biased upward against surfaces 48 and comers 52 , side plates 24 are welded to bent longitudinal ends 38 , resulting in an integral blade subassembly 30 , that can then be simply inserted into recess 21 and moved into position in housing 12 and secured therein by clips 23 ( FIGS. 1 , 2 ). Alternatively, the blades could also be rear mounted into a cartridge housing that has a recess 21 that opens from the bottom. Also, if desired, alignment block 50 can allow for different blades to have different blade tangent angles, exposures and/or spans by different positions for angled surfaces 48 and corners 52 of alignment block 50 .
[0030] Referring to FIG. 10 , alternative blade subassembly 60 (shown prior to attachment of the last blade 62 ) differs from blade subassembly 30 in that it does not have side plates 24 , but instead has offset extensions 64 on the longitudinal ends 66 that overlap and are welded to portions 68 of the prior blade 62 by welds 70 .
[0031] Referring to FIG. 11 , alternative blade subassembly 76 has angled side plates 78 that are snap-fit into housing 12 and held in housing 12 without the need for clips 23 . When the blades need to be replaced, instead replacing the entire cartridge (including housing 12 and connecting piece 19 as well as the blades) one pushes the used subassembly 76 out from the bottom, and simply snaps in a new subassembly 76 , permitting the housing 12 and connecting piece 19 to be used multiple times. Alternatively, side plates 78 could be slidably mounted in guide slots (not shown) in the housing to allow the blades to be floating, sliding up and down, in the cartridge.
[0032] Other embodiments of the invention are within the scope of the appended claims. For example, other techniques (such as elastomeric materials, magnetism, solenoids, and springs) can be used in place of bladder 47 to bias the blades 14 into the proper position. Other structures or shapes can be used in place of angled surfaces 48 and comers 52 to align the blades. Oval spots and dual spots can be used in place of the round spot welds 40 and 70 .
[0033] There can be any number of blades, (e.g., 2, 3, 4, 5, 6, 7, etc). Two-, three- and four-blade subassemblies 80 , 82 , 84 , respectively, are shown in FIGS. 14-16 , respectively. Also, the cartridge and handle may be integral parts such as a disposable razor.
[0034] As discussed above in the Summary section, the recess can be open to the top, with the integral blade unit being lowed into the recess and held in place by clips or by snap-fitting, or alternatively the recess can open to the bottom, with the integral blade unit being raised into the recess.
LISTING OF REFERENCE NUMERALS
[0035] shaving razor 10
[0036] plastic housing 12
[0037] integrated blade subassembly 13
[0038] blades 14
[0039] cap 16
[0040] handle 18
[0041] connecting piece 19
[0042] elastomeric guard 20
[0043] recess 21
[0044] fins 22
[0045] clips 23
[0046] side plates 24
[0047] cutting member 26
[0048] cutting edge 28
[0049] elongated support 30
[0050] spot welds 32
[0051] short upper portion 34
[0052] longer base portion 36
[0053] longitudinal ends 38
[0054] one-piece complex cutting member 39
[0055] spot welds 40
[0056] one-piece simple cutting member 41
[0057] fixture 42
[0058] base member 44
[0059] slots 46
[0060] angled surfaces 48
[0061] alignment block 50
[0062] corners 52
[0063] alternative blade subassembly 60
[0064] last blade 62
[0065] offset extensions 64
[0066] longitudinal ends 66
[0067] prior blade portions 68
[0068] welds 70
[0069] alternative blade subassembly 76
[0070] angled side plates 78
[0071] Two-blade subassembly 80
[0072] Three-blade subassembly 82
[0073] Four-blade subassembly 84 | A subassembly for a shaving razor that includes a plurality of elongated metal blades that are secured to each other as an integral unit. The plural blades have cutting edges defining a shaving surface, and are secured to each other by weld connections at their respective longitudinal ends. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to an internal gear pump which may be constructed both as ring gear pump and as filling piece pump.
2. Description of the Prior Art
Such internal gear pumps must pass through a very wide speed range. They should have good volumetric efficiency at low speed and must therefore be made with narrow leak gaps. At the same time, however, at high speeds they should, as far as possible, not cause any cavitation noises due to vapour and air bubble cavitation on passage of the pumping medium from the suction side to the pressure side of the pump. These gear pumps are preferably employed as lubricating, delivery and shift or control pumps in internal-combustion engines and automatic transmissions in which in particular cavitation noises are found to be very annoying.
As a rule these gear pumps have a critical speed of rotation above which the delivery line deviates from the linear path and becomes increasingly flatter. The diagram according to the attached FIG. 1 shows the delivery stream QH (ordinate) as a function of the speed n (abscissa) and the deviation of the delivery line from the linear region from a critical speed n krit . The delivery line then becomes increasingly flatter.
From the critical speed n krit onwards, the filling degree therefore becomes smaller than 1 and consequently there is a delivery medium shortage in the teeth chambers compared with the geometric delivery volume. The shortage space is partially filled with vapour of the delivery medium, partially with air separated from the medium and partially with "false air" sucked in through leakage points. This critical speed is fundamentally defined by a critical peripheral speed in the toothing region at which in accordance with Bernoulli's Law the static pressure in the liquid is increasingly absorbed by the velocity pressure (dynamic pressure). If the static pressure drops below the vapour pressure of the liquid, bubbles are formed which are subjected to the reduced static pressure and do not condense again until the static pressure of the bubble has risen above the vapour pressure.
It is remarkable that the critical speed of the gear pumps being considered here is almost independent of the viscosity of the medium. Normally, it would be expected that the critical speed would be substantially lower in the case of a very viscous medium than in the case of a thinly liquid medium. This is however not the case. A plausible explanation of this phenomenon is seen in that the dynamic pressure is linearly dependent only on the specific mass and is dependent upon the square of the velocity. Consequently, in similar pumps having about the same peripheral velocity the critical speed is also fairly exactly at the same point irrespective of the viscosity and the design of the pump (i.e. whether with or without filling piece). In practically no case has it proved possible to influence substantially the critical speed above which the pumps become appreciably louder by modifying the tooth flank forms or the inlet passage in the housing or by other constructional steps.
In a particularly simple design of such a pump the pinion has only one tooth less than the ring gear, i.e. the pump is a so-called gerotor pump in which each tooth of the pinion permanently cooperates in sealing manner with the toothing of the ring gear. In this case, fundamentally any form of toothing may be employed which is suitable for a gerotor pump and ensures adequate sealing between the teeth of the pinion and ring gear even in the pressure region of the pump. Particularly suitable for such a gerotor pump is a pure cycloid toothing in which the teeth heads and gaps of the gears have the profile of cycloids which are formed by rolling of roll circles on fixed circles extending concentrically to the respective gear axes, the teeth heads of the pinion and the teeth gaps of the ring gear each having the form of epicycloids which are formed by rolling of a first roll circle, the teeth gaps of the pinion and the teeth heads of the ring gear each having the form of hypocycloids which are formed by rolling of a second roll circle, and the sum of the circumferences of the two roll circles being equal in each case to the tooth pitch of the gears on the fixed tooth circles thereof. Examples of such toothings are described in German published specification 39 38 346.6 and German patent application P 42 00 883.2-15.
However, the difference between the teeth numbers of the pinion and ring gear may also be greater than 1. It should however not be large in order to ensure that a relatively small average teeth number is sufficient and consequently large displacement cells are retained. It is therefore preferred for the teeth number difference not to be greater than three.
If the teeth number difference is greater than one, in the region opposite the point of deepest tooth engagement usually a filling piece must be provided which fills at least the peripherally centre portion of the free space between the head circles of the two gears and thus ensures the necessary sealing there. This type of pump is distinguished by particularly good running quietness.
Such pumps are suitable for example for feeding hydraulic systems. In particular, such pumps are used however as oil or hydraulic pumps for motor vehicle engines and/or transmissions. Motor vehicle engines and transmissions are operated in a wide speed range. The speed basic values may be in the ratio of 12:1 or more.
The desired delivery of the lubricating pump of an internal-combustion engine, which in automatic transmissions must additionally perform the function of supplying pressure to the hydraulic shift elements and the converter filling for protection against cavitation, both in the case of the engine and in the case of the transmission, is proportional to the speed only in the lower third of the operating range. In the upper speed range the oil requirement increases far less than the speed of the engine. It is therefore desirable to have a drive-regulated lubricating or hydraulic pump or one having a displacement adjustable in dependence upon the speed.
The most common form of a hydraulic, oil and/or lubricating pump is the gear pump because it is simple, cheap and reliable. A disadvantage is that the theoretical delivery per revolution is constant, i.e. proportional to the speed.
Hitherto, the only practicable way of avoiding the unnecessary pump performance from a certain pump speed onwards with low losses was to control the suction. Since the flow resistances increase overproportionally with increasing liquid velocity, with a throttle in the suction conduit with increasing speed the static pressure increasingly drops in the intake opening of the gear chamber until the so-called cavitation pressure threshold is reached, i.e. until the pressure drops below the vapour pressure of the oil. The displacement cell content then consists partly of liquid oil, partly of oil vapour, and partly of inspired air and is subjected to a static pressure lying appreciably beneath the atmospheric pressure. It is a simple matter, for example by correspondingly narrow suction conduits or by an orifice or alternatively in controllable manner by a suction slide valve to define or control the flow resistances in the suction conduit in such a manner that extensive adaptation of the useful displacement of the gear pump to the requirement line of the consumption is achieved.
A disadvantage with this control is once again the cavitation which occurs. For if the cell content consisting of liquid and gas subjected to a low absolute pressure is suddenly transferred to zones of higher pressure, as is inherent in the system of such pumps, the gaseous constituents of the cell content implode so violently that undesired noises, and even worse destruction of the cell walls, are the result.
To avoid these implosions, by shortening the outlet mouth in the region of the diminishing displacement cells the cell content is given enough time by gradual compression to increase the static pressure by an adequate extent so that when a cell comes into communication with the outlet passage no implosions of gas bubbles can take place therein because due to gradual reduction of the cell volume said gas bubbles have already condensed to liquid again or have dissolved in the liquid. The diminishing displacement cells must be sealed so well with respect to each other here that the expulsion pressure through the gap between the two teeth separating two consecutive displacement cells from each other cannot propagate itself to any appreciable extent against the displacement direction. The prevention of extremely high squeeze oil pressures at low speed is ensured constructionally in that on the displacement side of the pump the cells come into communication with the displacement pressure space so that if the cell is not filled completely with liquid the displacement pressure cannot become active therein. If however the cells are already completely filled with liquid on the suction side, which is the case in the lower speed range, the higher squeeze pressure in the cell opens the check valve in the direction towards the pressure displacement space so that the displaced oil can flow into the pressure space with only a slightly increased cell pressure compared with the displacement pressure, corresponding to the opening pressure of the check valve and the flow resistance thereof.
Such a construction is known from DE-PS 3,005,657. In the latter axial bores leading to the outlet passage extend over the entire pressure half of the pump in the housing and contain check valves which are spaced from the gear chamber and which open only when the pressure of the cell lying in front of the respective bore exceeds the pressure in the outlet passage.
This pump has a correspondingly large axial extent. The spring valve used can break. Also, the inconstant connection of the displacement cells to the outlet passage is disadvantageous. Finally, the pressure distribution in the pump is disadvantageous as regards avoiding cavitation-induced implosions and the pump is loud in operation.
Considerably more advantageous is the gerotor pump known from German patent 3,933,978 in which the problem of the squeeze oil removal in the diminishing displacement cells at low speed with cavitation-free operation is solved in that in the teeth of at least one gear passages connecting displacement cells adjacent the respective tooth are provided in which check valves are located which permit a flow through the respective passage only in the displacement direction. However, this pump is also undesirably loud in operation at higher speeds.
SUMMARY OF THE INVENTION
The problem underlying the present invention is to reduce appreciably the noises caused by cavitation in an internal gear pump of the type indicated.
This problem is solved by an internal gear pump for a wide speed range comprising
a housing containing a gear chamber,
a ring gear in the housing,
a pinion which has one tooth or only a few teeth less than the ring gear, meshes with the ring gear and is arranged in the latter,
the teeth of which form together with the teeth of the ring gear increasing and again diminishing consecutive displacement cells for the working liquid and seal said cells with respect to each other,
inlet and outlet passages passing through the housing for the supply and discharge of the operating liquid,
which open into the gear chamber on both sides of the point of deepest tooth engagement,
said mouths being passed over by the displacement cells,
and furthermore the end of the mouth of the outlet passage lying remote from the point of deepest tooth engagement is located so close to the point of deepest tooth engagement that between it and the point at which the displacement cells start to diminish there is always more than one displacement cell,
wherein
in the region of diminishing displacement cells in the wall of the gear chamber peripherally spaced from the mouth of the outlet passage at least one opening is located over which alternately displacement cells and teeth defining said cells pass,
in which the opening is connected via a connecting passage to the outlet passage, and
the opening on each passage of a tooth thereover is covered by said tooth completely or at least to a major degree.
Expedient embodiments are defined by the features of the subsidiary claims.
The advantages obtained with the invention are based on the following mode of operation: the period of time of static pressure increase in the displacement cells is increased in the peripheral direction to an adequate extent to ensure that the pressure gradient dp/dt becomes smaller. As a result, the bubbles have enough time to dissolve again or condense whilst still in the low-pressure region. The feared violent implosion of the bubbles under high pressure, leading to noises and cavitation damage, is thereby avoided. This extension of the compression phase must not however lead to squeezing occurring with 100% filling of the cells with compact liquid, i.e. in the low speed range. This would then lead to noises of a different type and to power losses.
In such a pump, squeeze oil can flow off into an outlet passage through an opening from the diminishing displacement cells. If the pump is running at low speed, all the displacement cells in the suction region of the pump are fully filled with operating liquid. Before they can be appreciably diminished, these full displacement cells intersect the opening or openings in the pressure region. During the diminishing of the displacement cells which then occurs, the squeeze oil flows through a connection passage into the outlet passage. If the speed further increases until the occurrence of cavitation in the inlet mouth and the region of the enlarging displacement cells, the flow in the connection passage to the outlet passage slows down and comes to a stop on further increase of the speed, finally even being reversed. This reversed flow of operating liquid from the outlet passage into the diminishing displacement cells remains however small because due to the alternating opening and closing of the opening or openings by the teethepassing thereover, becoming increasingly fast with increasing speed, the operating liquid column in the connecting passage must be continuously retarded to zero and accelerated again and this leads to a very high apparent flow resistance in said passage at high speed of the pump. The thus remaining weak liquid flow from the outlet passage into the diminishing displacement cells containing cavitation bubbles is too small to allow these cavitation bubbles to collapse abruptly on the path from the start of the displacement cell diminishing up to the mouth of the outlet passage and consequently the slow pressure rise avoiding the feared cavitation damage and cavitation noises is retained.
At low speed of the pump the apparent resistance generated by the continuous acceleration and retardation of the liquid column in the connecting passage no longer plays any part because here the processes take place correspondingly more slowly. The squeeze oil can flow off through the opening(s) and the connecting passage. The transition from one state to the other in the connecting passage is a gradual one.
Each opening is covered completely, or at least to a major extent, each time a tooth passes thereover.
The connecting passage preferably leads via the outlet mouth into the outlet passage.
According to a preferred embodiment, the opening is kept small in comparison with the mouth of the outlet passage and the cross-section of the connecting passage is kept small in comparison with that of the outlet passage. The smaller the opening and the cross-section of the connecting passage, the greater the hydraulic apparent resistance will be. The ratio of the size of the opening to that of the mouth of the outlet passage and of the cross-section of the connecting passage to that of the outlet passage may for example be 5% or 10%. To retain the dependence of the flow apparent resistance on the speed of the pump utilized in the invention, a certain length of the connecting passage is of course also required. This is however obtained automatically because the opening must of course have a certain distance from the outlet passage mouth. Generally, it may be stated that the length of the connecting passage should be a multiple of the characteristic length of its cross-section.
The magnitude of the apparent resistance may also be influenced by the arrangement of the opening in the radial direction. The closer the opening lies to the foot circle of the gear, the greater the period of time in which the opening is covered by teeth compared with the period of time in which the opening lies opposite teeth gaps, i.e. is open towards displacement cells.
It is therefore preferred for the opening to be formed as a groove in the end wall of the gear chamber extending in the peripheral direction near the foot circle of the toothing of the pinion, or rather ring gear. The formation in the region of the foot or root circle of the ring gear is preferred because more room is available here for the provision of the opening and the connecting passage. By forming the opening as a groove extending in the peripheral direction in an end wall of the gear chamber, the opening can be easily dimensioned as desired with regard to the impedance effect.
The extent of the opening in the radial direction is preferably one fifth to one third of the height of the teeth passing thereover.
The connecting passage can for example open directly into the outlet passage and be cast as tubular passage into the wall of the pump housing. It is however preferred for the connecting passage to be formed as a groove in the wall of the gear chamber covered by the body of the gear carrying the teeth passing thereover. Said groove is advantageously located in the end wall of the .gear chamber and not in the peripheral wall. The latter would be more complicated in the mechanical formation of the groove.
If the mean tooth number of the pump is small, i.e. if only one or two displacement cells not open towards the mouth are always located in the region of diminishing displacement cells in front of the mouth, then no more than one opening will be required. With a relatively large tooth number with which the number of diminishing displacement cells in front of the mouth of the outlet passage is relatively high, it is advisable to provide several openings offset in the peripheral direction since to enable the opening to serve an adequate number of cells said opening would otherwise have to be so long that the apparent resistance would in turn become too small because an at least approximately complete covering of the opening would no longer be possible.
Generally, it can be stated that the number of openings is preferably at the most one smaller than the maximum number of closed displacement cells between the starting point of the displacement cell diminishing and the start of the pressure mouth.
If several openings are provided, they may advantageously be arranged in series in the peripheral direction and have a spacing in said direction of about 1/2 of the tooth pitch. This does not refer to the spacing of the opening centres but in each case to the spacing of the opposing opening edges from each other.
Basically, each opening, the number of which will in any case not be large in practice in pumps for motor vehicle engines and transmissions, maybe connected via a separate connecting passage to the outlet passage. Preferably, however, the openings are connected via a common connecting passage to the outlet passage.
In a preferred embodiment of the internal gear pump with the teeth number difference 1, the spacing of the opening from the mouth of the outlet passage in the peripheral direction is substantially equal to half the spacing between the end of the mouth of the inlet passage and the end of the mouth of the outlet passage.
If the teeth number difference is greater than 1, i.e. the pump has a filling piece in a space between a head circle of the ring gear and a head circle of the pinion opposite the point of deepest tooth engagement, the spacing of the opening from the pressure side end of the filling piece measured in the conveying direction is preferably substantially equal to zero.
A preferred embodiment of the internal gear pump according to the invention comprises a suction control with a fixed or variable throttle provided in the inlet passage. The advantages described above of a suction control can therefore be integrated in this manner into the internal gear pump according to the invention.
Preferably, the extent of the openings in the peripheral direction is substantially equal to the thickness of the teeth passing thereover at the radial height of the opening. This ensures at low speed adequate squeeze oil flow and at high speed adequately high throttling.
The arrangement of the opening in the peripheral direction is also of significance. Preferably, the distance of the opening from the mouth of the outlet passage in the peripheral direction is substantially equal to the tooth pitch.
BRIEF DESCRIPTION OF THE DRAWINGS
Hereinafter the invention will be explained in detail with reference to two preferred embodiments illustrated as examples in the drawings, wherein:
FIG. 1 is a delivery stream/speed diagram for a gear pump;
FIG. 2 is a plan view of the end wall, formed as housing, of the gear chamber of an internal gear pump;
FIG. 3 illustrates schematically a gerotor pump according to the invention in which the housing cover is removed and for greater clarity the gears are only partly shown;
FIG. 4 is a diagram similar to FIG. 3 showing a further embodiment of a pump according to the invention in which the pinion has two teeth less than the ring gear and is therefore provided with a filling piece;
FIG. 5 illustrates the delivery flow QH as a function of the speed n for a pump according to the invention;
FIG. 6 shows the leakage oil flow QL in the connecting passage as a function of the speed n for such a pump;
FIG. 7 shows the suction pressure PS in the inlet mouth as a function of the speed n for such a pump; and
FIG. 8 shows the intermediate pressure PI and the pressure difference PI-PH as a function of the speed n for such a pump.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In FIG. 2 the end wall of the cylindrical gear chamber is shown constructed as housing. On the right side of FIG. 2 there is the kidney-shaped inlet mouth 11 formed as a trough in the cover; the flow direction in the inlet mouth 11 is indicated by an arrow. On the left side of the housing shown in FIG. 2, denoted by the reference numeral 20, is the outlet mouth or kidney 20 likewise formed as trough in the housing wall. Beneath the mouth 20, the connecting passage 33 formed there is indicated and the opening 30 thereof at its end opposite the flow direction.
The pump illustrated schematically in FIG. 3 comprises a pump housing 1 from which the cover is removed so that the cylindrical gear chamber 2 is open and can be seen; in said chamber a ring gear 3 is mounted with its periphery on a peripheral wall 8 of the gear chamber 2. Also located in the gear chamber 2 is a pinion 4 which is carried by a drive shaft 10 of the pump. In this respect other mountings are also possible. The pinion has ten teeth and the ring gear 2 has eleven teeth. The toothing is of the type in which all the teeth of the pinion 4 are in permanent engagement with the toothing of the ring gear 3. As a result, all the displacement cells 13 and 17 formed by the teeth gaps of pinion and ring gear are permanently adequately sealed with respect to adjacent displacement cells. The direction of rotation of the pump is clockwise, as indicated by the arrow on the shaft 10.
The toothing of the gears is a pure cycloid toothing. In the latter the teeth heads and teeth gaps both of the ring gear and of the pinion have the profile of cycloids which are formed by the rolling of small roll circles, the periphery of each of which is equal to half the tooth pitch, along the reference circle of the respective gear. The teeth heads of the pinion and the teeth gaps of the ring gear each have the form of epicycloids whilst the teeth gaps of the pinion and the teeth heads of the ring gear each have the form of hypocycloids. The diameters of the roll circles forming the epicycloids are equal to the diameter of the roll circles forming the hypocycloids. Such a toothing is described in detail in DE-OS 3,938,346.
In the end wall 22 of the gear chamber 2 lying behind the plane of the drawing in FIG. 3 an intake opening 11 is provided which in FIG. 3 is partially covered by the gears 3 and 4 shown broken away. The tooth contour of the two gears is illustrated in FIG. 1 in dot-dash line over the remaining periphery. The centre of the ring gear 3 is indicated at 5 and the centre of the pinion 4 at 6.
The point of deepest tooth engagement is indicated at 7; the point 23 of the tooth apex contact is diametrically opposite the point 7.
In the right half of the Figure, in the end wall 22 of the gear chamber 2 facing the observer, the mouth 11 of the supply passage 12 can be seen in said end wall as depression, an orifice 14 serving for suction control being inserted into said passage 12. The mouth 11 is also referred to as suction kidney. It extends in the peripheral direction from a point near the point 7 of deepest tooth engagement up to close to the point 23 of apex contact.
In the left figure half of FIG. 3 the mouth 20 of the outlet passage 21 is located and is likewise formed as depression in the visible end wall 22 of the gear chamber 2. As can be seen, the outlet mouth or kidney 20 is substantially smaller than the inlet mouth 11. Whereas the end of the outlet mouth 20 lying in the direction of rotation has substantially the same spacing from the point 7 of deepest tooth engagement as the inlet mouth 11, the end of the outlet mouth 20 lying opposite the direction of rotation is spaced from the point 7 of deepest tooth engagement a distance of only about 80°.
As described so far within the framework of the example of embodiment the construction of the pump housing is known.
In FIG. 3, on the path from the point 23 of the tooth apex contact up to the start of the outlet mouth 20 three displacement cells 17, 17.1 and 17.2 surrounded by dot-dash lines can be seen, which convey liquid migrating in the clockwise sense from the inlet mouth 11 to the outlet mouth 20. In the path of the displacement cells, close to the tooth foot circle of the ring gear 3, corresponding to the relatively large tooth number, in the end wall 22 of the gear chamber 2 two openings 30 and 31 are provided which extend in the peripheral direction in said end wall. The openings 30 and 31 extend close to the foot circle of the toothing of the ring gear 3 within said foot circle. Each of the two openings 30 and 31 is connected via a short radially outwardly extending passage piece to the connecting passage 33 extending in peripheral direction and connected to the mouth 20 of the outlet passage. The radial passage portions, the openings 30, 31 and the connecting passage 33 are formed as grooves in the end wall 22 of the gear chamber 2. They may for example have a rectangular cross-section with rounded corners, the depth being about equal to the width of the groove indicated. The connecting passage 33 is continuously covered by the annular portion of the ring gear 3 bearing the teeth.
Since shortly after leaving the point 23 of the tooth apex contact the displacement cells are still gradually diminishing, the end of the first opening 30 facing said point may have a relatively large angular distance in the peripheral direction from said point, said distance here being substantially equal to two-thirds of the tooth pitch of the ring gear passing over said opening, measured in angular units. Compared therewith, the end of the opening 31 lying in the conveying direction is substantially further remote from the opposing end of the outlet opening 20, that is slightly more than one tooth pitch, so that whenever a displacement cell looses contact with the opening 31 it immediately starts to open into the outlet opening 20. The spacing of the opposing ends of the two openings 30 and 31 is so large that the two openings 30 and 31 are never connected by a displacement cell; it may however also be somewhat larger if the openings are narrow.
When designing the openings 30 and 31 account is also to be taken of the radial position of said openings. Thus, to obtain equal opening and closing times the extent of the openings 30, 31 in the peripheral direction must be the smaller the greater the distance of the opening from the tooth foot circle of the ring gear 3. To indicate this, the opening 30 is shown lying radially somewhat further inwardly than the opening 31, being however then also somewhat shorter than the latter. The two openings are relatively short in the example shown. In many cases it will also be possible to make them somewhat longer.
In operation of the ring gear pump according to FIG. 3 at low speed the squeeze oil flow QL through the passage 33 corresponds to the displacement volume of the displacement cells 17, 17.1 and 17.2. Now, with increasing speed the flow resistance to the flow through the passage 33 also increases because the opening times for the openings 30 and 31 become increasingly shorter. Accordingly, the pressure PI in the cells 17, 17.1 and 17.2 increases with a simultaneous drop of the squeeze oil flow QL through the conduit 33. These conditions however apply only up to the speed at which no cavitation takes place in the intake mouth 11, i.e. in the displacement cells 13. In the cavitation range at higher speed, where the delivery line (FIG. 5) has accordingly passed from the linearly rising curve to an approximately horizontal line, the pressures PI in the displacement cells drop to close to atmospheric pressure. Since the intake pressure is kept constant with the speed, the QL curve now passes through the zero point and even becomes slightly negative. This means that oil flows to a slight extent from the outlet opening 20 through the connecting passage 33 back into the displacement cells 17, 17.1 and 17.2. At very high speed, which is not employed in practice, the negative leakage oil flow QL from the outlet opening 20 to the openings 30 and 31 would again approach the zero line due to the increase in the apparent flow resistance (FIG. 6).
FIG. 7 shows the corresponding suction pressure PS in the inlet mouth as a function of the speed whilst FIG. 8 represents the intermediate pressure PI and the pressure difference PI-PH as a function of the speed n for such a pump.
Many modifications of the examples shown are possible. Thus, for example, the openings 30, 31 and the passage may be formed by a single serpentine-like groove which extends (clockwise) in FIG. 3 from the right end of the opening 30 to the left end thereof, then horizontally to the left into the passage 33 and follows the latter until it extends substantially perpendicularly upwardly to the lower end of the opening 31, follows the latter up to the upper end and from the latter end finally again leads to the left into the passage 33 which it follows up to the opening 20. Also, for example, the openings 30, 31 may be made to extend spirally or circularly.
Like the pump according to FIG. 3, the pump shown in FIG. 4 has a housing 41 in which a ring gear 43 is mounted which meshes with a pinion 44. An intake 52 in which an orifice 54 is provided for suction control feeds an intake mouth 51 whilst an outlet mouth 60 is connected to an outlet passage 61. However, in contrast to the pump according to FIG. 3 the pinion 44 here has two teeth less than the ring gear 43 so that opposite the point of deepest tooth engagement, i.e. at the bottom in FIG. 4, a filling piece must be arranged in order to provide the necessary sealing there. As apparent from the foregoing, in this case as well the direction of rotation of the pump is clockwise.
As apparent from the drawings, the filling piece 60 is shortened at both ends because an excessively thin tapering of the already narrow filling piece would lead to undesirable fluttering. The ends of the filling piece are cut off so that in each case one tooth of the pinion and one tooth of the ring gear come simultaneously into and out of engagement with the filling piece.
The toothing is so constructed that the teeth come out of engagement and into engagement with each other just before the start of the filling piece and just after the end of the filling piece respectively. This means that the points of disengagement and engagement of the toothing lie close to the intersection points of the head circles of the two gears. Before and after these intersection points, i.e. in FIG. 4 roughly stated within the two upper thirds of the orbital path of the gears, each tooth of the pinion is permanently in engagement with the toothing of the ring gear. Now, according to the invention here as well two openings 70 and 71 are provided in the region between the end of the filling piece 60 lying in the delivery direction and the end of the outlet mouth 60 lying opposite the delivery direction. The two openings 70 and 71 are connected via the connecting passage 73 to the mouth 60 of the outlet passage 61. As regards the function and mode of operation of this construction, essentially the same applies as to the pump according to FIG. 3. The only difference is that here the region of the diminishing displacement cells to be relieved through the openings 70 and 71 at low speed of the pump extends only between the left end of the filling piece 60 in FIG. 4 and the lower end of the outlet mouth 62.
Otherwise, the application of the principle of the invention is the same as with the pump according to FIG. 3. | In an internal gear pump, which can also be constructed as pump with suction control, to reduce the undesired cavitation effects in the pressure region and to permit the oil to flow off from the diminishing displacement cells between the teeth of the gears, and impedance-controlled overflow passage is provided, the openings of which towards the moving displacement cells are alternately opened and closed by the teeth of at least one of the gears. | 5 |
RELATED APPLICATION
The priority application Number Japanese Patent Application 2010-224973 upon which this application is based is hereby incorporated by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an electrophotographic image forming apparatus such as copiers, printers, facsimiles and combined machines thereof.
2. Description of the Related Art
It is a common practice in the electrophotographic image forming apparatus such as copiers, printers, facsimiles and combined machines thereof that the developing device supplies the toner to an electrostatic latent image formed on the image carrier so as to form thereon a toner image corresponding to the electrostatic latent image.
After the toner image thus formed on the image carrier is transferred by the transfer device to the transfer receiving material such as a recording medium or an intermediate transfer belt, the toner recovery device recovers from the surface of the image carrier the toner remaining thereon after the transfer of the toner image. There is also known an apparatus which employs the toner return device for returning to the developing device the toner recovered by the toner recovery device so that the recovered toner is put to effective use.
The above developing device includes a developing device of a single component development system using a toner alone as the developer and a developing device of a two-component development system using a developer containing the toner and the carrier. The developing device of the two-component development system using the developer containing the toner and the carrier is superior in terms of quick and adequate toner charging for facilitating high-speed image formation.
In the above-described developing device of the two-component development system, the developer containing the toner and the carrier is mixingly agitated to charge the toner by contact with the carrier. The developer containing the charged toner is retained on the developer carrier having the magnet member equipped with the magnetic poles mounted on the inner periphery thereof. The developer carrier is rotated to deliver the retained developer to the image carrier.
The toner of the developer retained on the developer carrier is supplied to the image carrier by applying the developing bias voltage from the bias voltage source between the developer carrier and the image carrier. Thus, the toner image corresponding to the electrostatic latent image is formed on the surface of the image carrier.
In a case where the developer is decreased in toner content in consequence of the above-described toner supply to the image carrier, a toner replenisher replenishes the developing device with the toner.
The above developing device of the two-component development system has the following problem. As the developer is used over a long period of time, the carrier in the developer is gradually deteriorated so as to become incapable of adequately charging the toner. As a result, the developing device becomes incapable of accomplishing proper image formation.
It has been a conventional practice to remove the developer suffering from the carrier deterioration from the developing device for replacement with a fresh developer or to replace the developing device per se with a new one.
However, in the case where the developer suffering from the carrier deterioration is removed from the developing device for replacement with a fresh one, or where the developing device per se is replaced with a new one, the developer actually contains a substantial amount of toner that is still usable. Namely, there is a problem that the usable toner remaining in the developer is wastefully discarded.
More recently, therefore, there has been proposed an apparatus wherein the above developing device is provided with separation means for separating the toner from the developer to be removed, as disclosed in Japanese Patent Publication No.3581720. The separation means includes a developer collection portion and a toner recovery portion. A charge of the opposite polarity to that of the toner is applied to a developer collection sleeve so as to separate the toner from the developer to be removed. The separated toner is returned to the developing device for recycling.
However, in the case where the developing device is provided with the developer collection portion and the toner recovery portion as the separation means for separating the toner from the developer to be removed, and the charge of the opposite polarity to that of the toner is applied to the developer collection sleeve for separating the toner from the developer to be removed, the developing device need be equipped with many devices. Thus, the developing device is increased in cost and in size.
SUMMARY OF THE INVENTION
According to the invention, an image forming apparatus comprises: a developing device that allows a developer including a toner and a carrier to be retained on a developer carrier having a magnet member equipped with a plurality of magnetic poles mounted on an inner periphery thereof and rotates the developer carrier to deliver the developer to an image carrier and that forms a toner image by supplying the toner of the developer to the image carrier by applying a developing bias voltage from a bias voltage source between the developer carrier and the image carrier; a transfer device for transferring the toner image formed on the image carrier to a transfer receiving material; a toner recovery device for recovering the toner remaining on the surface of the image carrier after the transfer of the toner image; and a toner return device for returning to the developing device the toner recovered by the toner recovery device, wherein the magnet member is rotated to reposition the magnetic poles thereof at the time of toner recovery operation in which the toner supplied from the developer carrier to the image carrier is prevented from being transferred to the transfer receiving material while the toner recovery device is operated to recover the toner from the developer in the developing device.
These and other objects, advantages and features of the invention will become apparent from the following description thereof taken in conjunction with the accompanying drawings which illustrate a specific embodiment of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram illustrating an image forming apparatus according to one embodiment of the invention wherein an image is formed by transferring a toner image formed on an image carrier to a transfer receiving material;
FIG. 2 is a schematic diagram illustrating the image forming apparatus of the above embodiment wherein a magnet member mounted on an inner periphery of a developer carrier is rotated to reposition magnetic poles thereof at the time of toner recovery operation in which the toner supplied to the image carrier is prevented from being transferred to the transfer receiving material while a toner recovery device is operated to recover the toner.
FIG. 3 is a fragmentary illustration of the image forming apparatus of the above embodiment wherein the magnet member mounted on the inner periphery of the developer carrier is rotated to reposition the magnetic poles thereof at the time of toner recovery operation in which the toner supplied to the image carrier is prevented from being transferred to the transfer receiving material while the toner recovery device is operated to recover the toner.
DESCRIPTION OF THE PREFERRED EMBODIMENT
An image forming apparatus according to an embodiment of the invention will hereinbelow be described in detail with reference to the accompanying drawings. It is to be noted that the image forming apparatus of the invention is not limited to the following embodiment but changes or modifications may be made thereto as needed so long as such changes or modifications do not depart from the scope of the invention.
As shown in FIG. 1 , the image forming apparatus of the embodiment operates as follows. A surface of an image carrier 1 comprising a rotary photosensitive drum is charged by a charger 2 . Subsequently, a latent image forming device 3 employing a laser or the like exposes the surface of the image carrier 1 to light according to image information, to thereby form an electrostatic latent image on the image carrier 1 .
A developing device 10 containing therein a developer D including a toner and a carrier supplies the toner of the developer D to the electrostatic latent image formed on the image carrier 1 . Thus, a toner image corresponding to the electrostatic latent image is formed on the image carrier 1 .
Subsequently, the toner image thus formed on the image carrier 1 is transported to be placed opposite a transfer device 4 in the form of a roller, while a transfer receiving material 5 such as a recording sheet or an intermediate transfer belt is brought into space between the image carrier 1 and the transfer device 4 . Thus, the toner image formed on the surface of the image carrier 1 is transferred to the transfer receiving material 5 by means of the transfer device 4 .
An edge of a cleaning member 21 provided at a toner recovery device 20 is pressed against the surface of the image carrier 1 after the image transfer. The toner remaining on the surface of the image carrier 1 is recovered by the cleaning member 21 and collected in the toner recovery device 20 .
Subsequently, the toner thus recovered from the surface of the image carrier 1 and collected in the toner recovery device 20 is returned to the developing device 10 by means of a return device.
In the above-described developing device 10 , a magnet member 11 a including a plurality of magnetic poles N, S, . . . is mounted on an inner periphery of a developer carrier 11 comprising a rotary development roller. This developer carrier 11 is disposed in opposed relation to the above image carrier 1 .
Within the developing device 10 , a partitioning wall 12 extends in an axial direction of the developer carrier 11 . This partitioning wall 12 divides the interior of the developing device 10 into a first developer transport portion 13 and a second developer transport portion 14 , which are provided with a first agitating/transporting member 13 a and a second agitating/transporting member 14 a , respectively. The agitating/transporting members transport the developer D while mixingly agitating the developer D.
The above first agitating/transporting member 13 a and second agitating/transporting member 14 a are brought into rotation. In the first developer transport portion 13 , the developer D is transported along the developer carrier 11 and supplied to the developer carrier 11 . In the second developer transport portion 14 , the developer D is transported in the opposite direction to the developer movement in the first developer transport portion 13 so that the developer D is circulated between the second and first developer transport portions through circulation ports (not shown) formed at opposite ends of the partitioning wall 12 .
As described above, the developing device 10 supplies the toner of the developer D to an area of the electrostatic latent image formed on the surface of the image carrier 1 so as to form thereon the toner image corresponding to the electrostatic latent image. In this process, the magnetic poles N, S, . . . of the magnet member 11 a are set to predetermined positions for development. Accordingly, a magnetic pole S 1 of the magnet member 11 a , that is located opposite the developer D in the developing device 10 , allows the developer carrier 11 to retain the developer D on an outer periphery thereof.
The developer carrier 11 is rotated to transport the retained developer D toward the image carrier 11 . Meanwhile the amount of developer D so carried on the developer carrier 11 to the image carrier 1 is regulated by a regulating member 15 which is opposed to and spaced a required distance away from the developer carrier 11 .
As regulated in this manner, the developer D is carried on the developer carrier 11 to be placed opposite the image carrier 1 . A controller 30 drives a bias voltage source 16 to apply a proper developing bias voltage Vb 1 between the developer carrier 11 and the image carrier 1 for adequately supplying the toner of the developer D to the area of the electrostatic latent image formed on the surface of the image carrier 1 . Thus, the toner image corresponding to the electrostatic latent image is formed on the surface of the image carrier 1 .
In the developing device 10 , the second developer transport portion 14 is provided with a toner density sensor 17 for detecting a toner content of the developer D. In the case of a significant decrease in the toner content of the developer D in consequence of supplying the toner of the developer D to the surface of the image carrier 1 as described above, the toner density sensor 17 detects such a toner decrease and outputs a detection result to the controller 30 .
In a case where the toner content of the developer D falls to a predetermined value or less, a toner shortage is detected by the toner density sensor 17 . In response to this, the controller 30 drives a toner replenisher 41 to supply the toner to a toner replenishment path 42 and also drives a rotating device 44 to rotate a toner transporting member 43 comprising a screw member disposed in the toner replenishment path 42 . The toner thus fed into the toner replenishment path 42 is transported by rotating the toner transporting member 43 so that the toner is delivered to a toner supply port 45 disposed between the toner replenishment path 42 and the second developer transport portion 14 . The toner is fed into the second developer transport portion 14 of the developing device 10 through this toner supply port 45 .
The toner recovered from the surface of the image carrier 1 by the toner recovery device 20 is returned to the developing device 10 by means of a toner return device. The toner recovery device 20 is provided with a recovered-toner advancing member 22 which is a rotating member. The toner recovered from the surface of the image carrier 1 by the cleaning member 21 is advanced into a recovered-toner transport path 23 by the recovered-toner advancing member 22 .
In the recovered-toner transport path 23 , a recovered-toner transporting member 24 is provided for transporting the toner recovered and delivered therein as described above. The toner recovered and delivered into the recovered-toner transport path 23 is transported by rotating the recovered-toner transporting member 24 . Thus, the recovered toner is delivered to a recovered-toner inlet port 25 disposed between the recovered-toner transport path 23 and the toner replenishment path 42 . Thus, the recovered toner is fed into the toner replenishment path 42 through the recovered-toner inlet port 25 .
The recovered toner fed into the toner replenishment path 42 is transported by rotating the toner transporting member 43 in the same way as in the above described toner replenishment. The recovered toner is delivered to the toner supply port 45 disposed between the toner replenishment path 42 and the second developer transport portion 14 and is returned into the second developer transport portion 14 of the developing device 10 through the toner supply port 45 .
In the image forming apparatus according to the embodiment, the above-described image development by the developing device 10 involves gradual deterioration of the carrier contained in the developer D. While the developing device 10 carries on the image development, the developer D is mixingly agitated by the first agitating/transporting member 13 a and the second agitating/transporting member 14 a , gradually deteriorating the carrier contained therein.
Before the developer D suffering from the carrier deterioration as described above is removed from the developing device 10 , the image forming apparatus of this embodiment performs a toner recovery operation wherein the toner recovery device 20 recovers the toner from the developer D loaded in the developing device 10 .
The image forming apparatus of the embodiment performs the toner recovery operation as follows to recover the toner from the developer D loaded in the developing device 10 . As described above, the electrostatic latent image is formed on the surface of the image carrier 1 by charging the surface of the image carrier 1 by means of the charger 2 , followed by exposing the image carrier surface 1 to light by means of the latent image forming device 3 .
Then, the developing device 10 supplies the toner of the developer D to the electrostatic latent image so formed on the image carrier 1 . According to the embodiment as shown in FIG. 2 and FIG. 3 , the magnet member 11 a is rotated a little to bring the magnetic pole S 1 of the magnet member 11 a , that is located opposite the developer D in the developing device 10 , closer to the developer D in the developing device 10 . In addition, the controller 30 controls the developing bias voltage of the bias voltage source 16 that is applied between the developer carrier 11 and the image carrier 1 . That is, the bias voltage source is controlled to apply a predetermined developing bias voltage Vb 2 more positive than the developing bias voltage Vb 1 for image formation, thereby causing more toner to be supplied to the image carrier 1 .
When the magnetic pole S 1 of the magnet member 11 a is brought closer to the developer D in the developing device 10 , the magnetic pole S 1 of the magnet member 11 a strongly attracts the developer D in the developing device 10 , allowing the developer carrier 11 to carry a sufficient amount of developer D thereon to the image carrier 1 .
The following effects are obtained if the developing bias voltage Vb 2 of the developing bias voltage source 16 applied between the developer carrier 11 and the image carrier 1 is raised from the developing bias voltage Vb 1 for image formation in a positive direction to supply the toner to the image carrier 1 . That is, less of the carrier of the developer D delivered to be placed opposite the image carrier 1 is supplied to the image carrier 1 , while more of the toner of the developer D is supplied to the image carrier 1 . It is therefore ensured that the toner of the developer D is adequately supplied to the image carrier 1 even if the magnetic pole S 2 , opposed to the image carrier 1 at the image development, of the magnet member 11 a is rotated to be displaced. To further increase the amount of toner supplied to the image carrier 1 , the above-described latent image forming device 3 may preferably form, on the surface of the image carrier 1 , an electrostatic latent image corresponding to a solid image.
When the toner recovery operation is performed by the toner recovery device 20 to recover the toner from the developer D in the developing device, the transfer receiving material 5 is inhibited from being introduced into space between the image carrier 1 supplied with the toner as described above and the transfer device 4 . Specifically, the image carrier 1 and the transfer device 4 are spaced apart while the toner supplied to the image carrier 1 is introduced into the toner recovery device 20 instead of being transferred to the transfer receiving material 5 .
In this toner recovery device 20 , the toner supplied to the image carrier 1 as described above is recovered therefrom by means of the cleaning member 21 and the recovered toner is introduced into the recovered-toner transport path 23 by means of the recovered-toner advancing member 22 which rotates. The toner thus introduced into the recovered-toner transport path 23 is transported by the recovered-toner transporting member 24 to the recovered-toner inlet port 25 disposed between the recovered-toner transport path 23 and the above-described toner replenishment path 42 . The recovered toner is introduced into the toner replenishment path 42 through the recovered-toner inlet port 25 .
The following operation is performed in the toner replenishment path 42 to which the toner is supplied. The controller 30 inhibits the rotating device 44 from rotating the toner transporting member 43 so as to disable the toner transporting member 43 to transport the toner fed into the toner replenishment path 42 . By doing so, the toner fed into the toner replenishment path 42 is prevented from being returned to the developing device 10 through the toner supply port 45 but is allowed to accumulate in the toner replenishment path 42 .
Thus, the toner of the developer D loaded in the developing device 10 is sequentially supplied to the image carrier 1 and allowed to accumulate in the toner replenishment path 42 . Accordingly, the developer D loaded in the developing device 10 is gradually decreased in the toner content.
The amount of toner remaining in the developer D is reduced in this manner. When the toner density of the developer D is reduced to a predetermined value or less, the developer D in the developing device 10 may be replaced with a fresh one or otherwise, the developing device 10 per se may be replaced with a new one. Thus, the amount of wastefully discarded toner is notably reduced.
After the developer D in the developing device 10 is replaced with a fresh developer or otherwise, the developing device 10 per se is replaced with a new one, as described above, the toner accumulated in the toner replenishment path 42 may be supplied to the developing device 10 through the above-described toner supply port 45 . This facilitates the effective use of the toner accumulated in the toner replenishment path 42 .
As described above, the toner recovered by the toner recovery device 20 is accumulated in the toner replenishment path 42 . In this regard, it is preferred to provide a shutter 46 adapted to open and close the toner supply port 45 in order to make sure that the toner fed into the toner replenishment path 42 is prevented from being returned to the developing device 10 . It is preferred that the shutter 46 closes the toner supply port 45 to allow the recovered toner to accumulate in the toner replenishment path 42 . Further, a toner storage portion for accumulation of the recovered toner may also be provided independently from the toner replenishment path 42 .
When the toner recovery operation according to the embodiment is performed to recover the toner from the developer D in the developing device 10 , the magnet member 11 a is rotated a little to bring the magnetic pole S 1 thereof closer to the developer D in the developing device 10 . In addition, the bias voltage source 16 applies, between the developer carrier 11 and the image carrier 1 , the predetermined developing bias voltage Vb 2 that is raised from the developing bias voltage Vb 1 for image formation in the positive direction to supply the toner to the image carrier 1 . However, the developing bias voltage applied between the developer carrier 11 and the image carrier 1 by the bias voltage source 16 may not be raised to the predetermined developing bias voltage Vb 2 at once. It is also possible to raise the developing bias voltage stepwise in the positive direction to supply the toner to the image carrier 1 .
It is also possible to take a procedure wherein the developing bias voltage of the bias voltage source 16 applied between the developer carrier 11 and the image carrier 1 is raised to the predetermined developing bias voltage Vb 2 at once or stepwise and then, the magnet member 11 a is rotated a little to bring the magnetic pole S 1 thereof closer to the developer D in the developing device 10 .
In a case where the developer in the developing device suffers from the carrier deterioration and hence, is replaced with a fresh developer, the image forming apparatus of the invention performs the toner recovery operation wherein the toner supplied to the image carrier by the developer carrier is prevented from being transferred to the transfer receiving material while the toner recovery device recovers the toner from the developer in the developing device. Therefore, the developer loaded in the developing device is gradually decreased in the toner content.
If the magnet member is rotated to reposition the magnetic poles thereof when the above toner recovery operation is performed, the magnetic pole of the magnet member that is located opposite the developer in the developing device is shifted, attracting the developer at different place in the developing device and allowing the attracted developer to be retained on the developer carrier. It is particularly effective to bring the magnetic pole of the magnet member close to the developer in the developing device because the developer in the developing device is strongly attracted by the nearby magnetic pole of the magnet member so as to be efficiently retained on the developer carrier.
Therefore, in the case where the developer in the developing device suffers from the carrier deterioration so as to be replaced with a fresh developer, the image forming apparatus of the invention can efficiently recover the toner from the developer to be replaced although a special recovery device is not provided. In this manner, the reduction of wastefully discarded toner can be achieved easily.
When the above-described toner recovery operation is carried out in this image forming apparatus, the above bias voltage source applies, between the developer carrier and the image carrier, the developing bias voltage that is raised in the positive direction to supply the toner from the developer carrier to the image carrier. Such a developing bias voltage allows less of the carrier of the developer to be supplied to the image carrier but allows more of the toner of the developer to be supplied to the image carrier. Particularly, it is ensured that the toner of the developer retained on the developer carrier is adequately supplied to the image carrier even if the magnetic poles of the magnet member are repositioned and the magnetic pole in the opposed relation to the image carrier is displaced as described above.
Although the present invention has been fully described by way of examples, it is to be noted that various changes and modifications will be apparent to those skilled in the art.
Therefore, unless otherwise such changes and modifications depart from the scope of the present invention, they should be construed as being included therein. | An image forming apparatus includes: a developing device that allows a developer to be retained on a developer carrier having a magnet member equipped with a plurality of magnetic poles mounted on an inner periphery thereof and rotates the developer carrier to deliver the developer to an image carrier and that forms a toner image by supplying the toner of the developer to the image carrier by applying a developing bias voltage from a bias voltage source between the developer carrier and the image carrier; a transfer device for transferring the toner image formed on the image carrier to a transfer receiving material; a toner recovery device for recovering the toner remaining on the surface of the image carrier after the transfer of the toner image; and a toner return device for returning to the developing device the toner recovered by the toner recovery device. | 6 |
[0001] This application is a National Stage completion of PCT/EP2007/060458 filed Oct. 2, 2007, which claims priority from German patent application serial no. 10 2006 049 276.5 filed Oct. 19, 2006.
FIELD OF THE INVENTION
[0002] The invention relates to a device for rotationally fixing a shaft to a component rotationally mounted on the shaft.
BACKGROUND OF THE INVENTION
[0003] In transmission technology, gearwheels designed as loose wheels of various gear stages of a transmission device are connected in a rotationally fixed manner to a transmission shaft on which the loose wheels are arranged by means of so-called synchronization mechanisms. This means that when shifting a gear of a transmission device, differences in rotational speed between a loose wheel, that is to be connected, and a transmission shaft, assigned to this loose wheel, are compensated for by means of a frictionally engaging synchronization mechanism. When the loose wheel and the transmission shaft have reached the same speed, there is no more dynamic frictional torque, and so-called locking teeth release a claw of a synchronization mechanism in order to engage the desired gear in a positive-locking manner.
[0004] These kinds of synchronization mechanisms disadvantageously require an undesirably large amount of installation space due to their design, which incorporates friction elements, blocking devices, and claws, and are characterized by high manufacturing costs.
[0005] In addition to the synchronization mechanisms described above, there are transmission devices known from practice in which frictionally-engaged shifting elements of simple constructive design, such as plate-type shifting elements, are used to connect loose wheels. In order to keep shifting elements of that kind in an engaged state, they should generally be acted on in each case with a holding force equivalent to the engaged state of the shifting element, which is preferably hydraulically produced. However, this holding force, which has to be permanently applied, impairs the overall efficiency of a transmission device.
[0006] From CA 2 451 899 A1 is known a frictionally-engaged shifting element designed with so-called self-energization, which remains in an engaged state without a separately applied holding force due to an applied torque.
[0007] However, this has the disadvantage that the connection between a component rotatably mounted on a shaft and the shaft itself is produced in a positive-locking manner, so that coupling the component to the shaft is not problematic regarding the driving comfort when there are low rotational speed differences between the component, or, as the case may be, a loose wheel, and a shaft. If a connection, or, as the case may be, a rotationally fixed connection of the component to the shaft is necessary at high rotational speed differences between the component and the shaft, the positive-locking connection between the shaft and the component to be established through self-energizing, can lead to an impulse exchange with high torque peaks due to very brief response times, which results in an impairment of the driving comfort and undesirably high component stress.
SUMMARY OF THE INVENTION
[0008] It is therefore an object of the invention to make available a device for connecting a shaft in a rotationally fixed manner to a component rotatably mounted on the shaft, which is characterized by a low installation space requirement, can be cost-efficiently manufactured, and by means of which a high degree of driving comfort and simultaneously low component stress can be achieved.
[0009] With the device according to the invention for rotationally fixing a shaft to a component that is rotatably mounted on the shaft, preferably for connecting a gearwheel designed as a loose wheel of a gear stage of a transmission device to a transmission shaft with an actuating element displaceable in axial direction and rotatably mounted on the shaft, which can be rotationally fixed to the shaft via an actuator and which makes possible bringing the actuating element in operative connection with the component in a frictionally engaging manner in the rotationally fixed state by actuating the corresponding actuator, and with which a rotational speed difference between the component and the shaft can be at least approximately compensated for by means of the actuating element that can be actuated on the actuator side, the actuating element for rotationally fixing the component to the shaft by means of the actuator can be transferred from a rotationally fixed state into a state in which it can be rotated relative to the shaft and is operatively connected to at least one support body in such a way that the component, in the state in which the actuating element can be rotated relative to the shaft, can be acted on by the actuating element with an actuating force that is dependent on a torque to be transmitted from the shaft to the component, and which is independent of the actuation of the actuator.
[0010] In this way, a component that is rotationally fixed on a shaft can be connected to the shaft in a rotationally fixed manner by means of a shifting element designed with a self-energizing mechanism, wherein the rotationally fixed connection is established in two phases. During a first phase, a rotational speed difference between the component and the shaft is compensated for in a frictionally engaged manner, or, as the case may be, the component and the shaft are synchronized. During this first phase, the self-energizing mechanism is inactive, and a shifting force produced by an actuator is used to produce frictional torque between the existing actuating element, that is fixed to the shaft, and the component, in order to produce a state of synchronization between the component and the shaft.
[0011] During a second phase that follows the first phase, the self-energizing mechanism is activated by transferring the actuating element from a rotationally fixed state into a state in which it can be rotated relative to the shaft and is acted on by a contact force that is dependent on the torque to be transmitted from the shaft to the component and is independent from the actuation by the actuator of the actuating element. In this way, the component is rotationally fixed to the shaft without having to supply a holding force by the actuator when a predefined threshold value of the contact force is exceeded.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] Advantageous further developments of the object of the invention can be seen in the patent claims and the exemplary embodiments, which are described in principle with reference to the drawing.
[0013] In the drawings:
[0014] FIG. 1 shows a highly schematized partial longitudinal sectional view of a device according to the invention;
[0015] FIG. 2 shows a development drawing of an actuating element of the device according to FIG. 1 in neutral position:
[0016] FIG. 3 shows the actuating element of the device according to FIG. 1 in a representation corresponding to FIG. 2 during a synchronization phase;
[0017] FIG. 4 shows the actuating element of the device 1 according to FIG. 1 in a representation corresponding to FIG. 2 in a state in which it can be rotated relative to a shaft; and
[0018] FIG. 5 shows the actuating element of the device according to the invention in a state in which it connects the component to the shaft in a rotationally fixed manner.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0019] FIG. 1 shows a device 1 for connecting a shaft 2 in a rotationally fixed manner to a component 3 rotatably mounted on the shaft 2 , wherein the shaft 2 is designed as a countershaft of a countershaft transmission, on which the component 3 is arranged as a loose wheel.
[0020] As a variation of this, the device 1 can also be used in other transmission devices, such as automatic transmissions, double clutch transmissions, or planetary transmissions, as a synchronizing and shifting element for automatic actuation of a transmission device during gear shifting and the like.
[0021] A transmission main shaft 4 , on which a plurality of gearwheels 5 , 6 designed as fixed gears are arranged, is provided parallel to the countershaft 2 , wherein the gearwheel 5 meshes with the loose wheel 3 and the toothed wheel 6 with an additional loose wheel 7 rotatably mounted on the countershaft 2 .
[0022] The two loose wheels 3 and 7 can be actuated alternately by the device 1 in such a way that the loose wheels 3 and 7 can be transferred from a state in which they can be rotated on the countershaft 2 into a state in which they are rotationally fixed relative to the countershaft 2 , or from a rotationally fixed state into a state in which they can be rotated relative to the countershaft 2 , in order to transmit torque acting on the countershaft 2 via the first loose wheel 3 or the second loose wheel 7 and via the toothed wheel 5 or the toothed wheel 6 , to the main transmission shaft 4 .
[0023] For this purpose, the device 1 is designed with two rotatably and displaceably arranged on the countershaft 2 in axial direction actuating elements 8 , 9 , which can be rotationally fixed, via an actuator 10 , to the countershaft 2 and can be brought into positive-locking interaction with the loose wheels 3 and 7 as a consequence of a corresponding actuation from the actuator side in the rotationally fixed state. Furthermore, a rotational difference between the loose wheels 3 and 7 and the countershaft 2 can be at least approximately compensated for by the actuating elements 8 and 9 respectively, which can be actuated by the actuator.
[0024] The actuator 10 is brought herein into operative interaction with the actuating elements 8 and 9 in the manner described below via an actuating rod 11 and via a plurality of holding elements 12 connected to the countershaft 2 and designed to be movable with respect to the countershaft 2 , of which only one is shown in FIG. 1 , in order to bring the actuating element 8 or the actuating element 9 into frictionally engaging contact with the loose wheel 3 , or, as the case may be, the loose wheel 7 .
[0025] In this case, the holding element 12 is designed so as to be axially movable in a long slot 13 in axial direction of the countershaft 2 from a middle switching position SM in direction of the first loose wheel 3 , or in direction of the second loose wheel 7 and rotates during operation of the countershaft transmission at the rotational speed of the countershaft. The actuating rod 11 is configured in a rotationally fixed manner with respect to a housing of the countershaft, so that a rotational speed uncoupler shown in FIG. 1 is provided in the connecting area 14 between the actuating rod 11 and the holding element 12 .
[0026] FIG. 2 to FIG. 5 show the actuating elements 8 and 9 of the device 1 according to FIG. 1 in the form of a development drawing during the various shifting phases of the device 1 , starting with a state shown in FIG. 2 , in which neither the first loose wheel 3 nor the second loose wheel 7 are connected in a rotationally fixed manner to the countershaft 2 , up to a shifting state of the device 1 shown in FIG. 5 , in which the first loose wheel 3 is rotationally fixed to the countershaft 2 .
[0027] The actuating elements 8 and 9 are configured with a plurality of flanks 8 A to 8 F, or, as the case may be, 9 A to 9 F, which enclose an angle together with a cross sectional plane positioned vertical with respect to the axis of symmetry 15 of the countershaft 2 , and interact with a support body 16 to 18 fixed to the countershaft 2 in the region of the mutually facing flanks 8 A and 8 B, 8 C and 8 D, as well as 8 E and 8 F, or, as the case may be, 9 A and 9 B, 9 C and 9 D, as well as 9 E and 9 F.
[0028] In this way, the actuating elements 8 and 9 are in operative connection with the support bodies 16 to 18 , which are fixed to the shafts, in such a way that the loose wheel 3 or the loose wheel 7 can be acted on by an actuating force subject to a torque that is transmitted from the countershaft 2 to the loose wheel 3 or the loose wheel 7 , and which is independent of the actuation of the actuator, in a state where the actuating element 8 or the actuating element 9 of the actuation can be rotated in relation to the shaft.
[0029] In the neutral shifting state SM of the device 1 shown in FIG. 1 and FIG. 2 , the holding element 12 is connected, via a region 12 A, in a positive-locking manner to the actuating element 8 , and connected with a region 12 B in a positive-locking manner to the actuating element 9 , so that both actuating elements 8 and 9 are rotationally fixed to the countershaft 2 . Furthermore, the holding element 12 is connected, via a retaining element 19 , to a sleeve-like ring element 20 in the region of its peripheral surface facing away from the axis of symmetry 15 . The sleeve-like ring element 20 is arranged between the actuating elements 8 and 9 and can be brought into engagement with the plane surfaces of the actuating elements 8 and 9 facing the ring element 20 in the neutral shifting position SM of the device 1 shown in FIG. 1 .
[0030] Starting from the neutral shifting position SM of the device 1 shown in FIG. 2 , the holding element 12 is axially displaced toward the loose wheel 3 along the countershaft 2 with a corresponding actuation by the actuator. As that happens, the ring element 20 connected to the holding element 12 via the retaining element 19 is also moved in direction of the loose wheel 3 , and comes to rest against the actuating element 8 after it overcomes a provided play, whereby the actuating element 8 arranged in axial direction of the countershaft 2 is likewise displaced thereon in the direction of the loose wheel 3 .
[0031] With increasing shifting travel of the holding element 12 , the actuation element 8 is displaced against a similarly conically designed friction surface 3 A of the loose wheel 3 with a conical peripheral surface 8 A. At the same time, the loose wheel 3 is axially moved along the countershaft 2 in the direction of a shaft collar 21 , which is rotationally fixed the countershaft 2 and made to engage with an additional, conically designed friction surface 3 B engaged with a conically designed friction surface 21 A of the shaft collar 21 .
[0032] The sleeve-like ring element 20 is designed herein with a predefined elasticity, whereby the retaining element 19 is arranged in the position shown in FIG. 1 between the ring element 20 and the holding element 12 by means of a predefined spring force. The predefined elasticity of the ring element 20 and the spring force that results therefrom and acts on the retaining element 19 correspond to an actuation force that acts on the actuating element 8 and is directed in the axial direction, with which a rotational speed difference between the countershaft 2 and the loose wheel 3 , or, as the case may be, the countershaft 2 and the loose wheel 7 , can be at least approximately compensated for in a frictionally engaging manner.
[0033] If an actuating force originating from the actuator 10 exceeds the spring force that holds the retaining element 19 in the position shown in FIG. 1 between the ring element 20 and the holding element 12 , the ring element 20 is reversibly deformed in the radial direction of the countershaft 2 , and the retaining element rolls out of the groove-shaped recess 20 A of the ring element 20 , thereby enabling relative movement between the actuation element 8 and the holding element 12 , or, as the case may be, the region 12 A of the of holding element 12 .
[0034] This means that during a first shifting phase of the device 1 , the actuation element 8 , together with the holding element 12 is guided in the direction of the position shown in FIG. 3 starting from the position shown in FIG. 2 due to the actuation by the actuator, during which the holding element 12 connects the actuating element 8 in the region 12 A in a rotationally fixed manner to the countershaft 2 .
[0035] Only after the spring force of the ring element 20 is exceeded is it possible to have relative movement between the actuating element 8 and the holding element 12 , or, as the case may be, the region 12 A of the holding element 12 , and for the region 12 A to be guided out of the engagement with the actuating element 8 in the manner shown in FIG. 4 , while the area 12 B remains connected in a positive-locking manner with the actuating element 9 .
[0036] This means that the actuating element 8 is rotatably and displaceably mounted in axial direction on the countershaft in the shifting state of the device 1 shown in FIG. 4 , while the actuation element 9 is rotationally fixed to the countershaft 2 in the area 12 B and is pressed by means of a first spring device 22 , arranged between the loose wheel 7 and the actuation element 9 , against the ring element 20 . Between the loose wheel 7 and an additional shaft collar 23 is furthermore provided a second spring device 24 , which guides the loose wheel 7 in non-actuated state out of engagement with the additional shaft collar 23 .
[0037] A third spring device 25 and a fourth spring device 26 , respectively, are provided, in addition, between the shaft collar 21 and the loose wheel 3 , as well as between the loose wheel 3 and the actuation element 8 , in order to guide the loose wheel 3 with the corresponding shifting position of the device 1 out of engagement with the shaft collar 21 and the actuation element 8 .
[0038] If the shifting state of the device 1 shown in FIG. 4 is present, in which the actuation element 8 is frictionally engaged with the friction surface 3 A of the loose wheel 3 with its friction surface 8 A, the actuation element 8 will be twisted in direction of the arrow A shown in FIG. 4 subject to a torque to be transmitted from the countershaft 2 to the loose wheel 3 . The actuating element 8 comes then to rest against the supporting bodies 16 to 18 in the region of its flanks 8 B, 8 D, and 8 F and experiences an additional axial displacement in the direction of the loose wheel 3 , or, as the case may be, the shaft collar 21 depending on its torsion, whereby an actuating force acting on the loose wheel 3 increases without additional actuation of the actuating element 8 by the actuator, and the loose wheel 3 is rotationally fixed to the countershaft 2 depending on the torque to be transmitted. This shifting state of the device 1 is shown in FIG. 5 .
[0039] The loose wheel 7 can be rotationally fixed to the countershaft 2 by means of the device 1 , analogously to the previously described manner, by means of actuation by the actuator of the holding element 12 , starting from the neutral shifting position SM in the direction of the loose wheel 7 when there is a demand to engage the gear stage corresponding to the gear pairing between the loose wheel 7 and the gearwheel 6 .
[0040] In the exemplary embodiment of the device according to the invention shown in the drawing, the actuation force required for the synchronization of the loose wheels 3 , 7 and the countershaft 2 and the release of the self-energization of the device 1 is realized by means of the actuator 10 , which makes available the actuation force electromechanically, pneumatically, or magnetically.
[0041] In order to detect a state of synchronization between the loose wheel 3 , or, as the case may be, the loose wheel 7 and the countershaft 2 , the device 1 is provided with a control device, which is not shown in more detail. Using this device, it is possible to determine in advance a point in time at which the state of synchronization is achieved by monitoring the current operating state of the loose wheels 3 and 7 as well as the countershaft.
[0042] As an alternative to the exemplary embodiment of the device 1 shown in FIG. 2 to FIG. 5 , in which the actuating force in the region between the support bodies 16 and 18 and the actuating elements 8 and 9 is transmitted in the form of a slide bearing, it is provided in an execution example of the device according to the invention which is not shown in more detail that the actuation force in this region is transmitted by antifriction bearings.
[0043] As an alternative to the axial displacement of the holding element 12 of the device 1 , it is provided in additional embodiments, which are not shown in more detail in the drawing, that the rotationally fixed connection of the actuating elements 8 and 9 to the countershaft 2 can be disconnected through radial movement or twisting of the regions 12 A and 12 B of the holding element 12 , and that the self-energization of the device 1 can be released to the desired extent.
[0044] Furthermore, it is provided in additional exemplary embodiments of the device according to the invention, which are also not shown in more detail in the drawing, that the friction surfaces between the loose wheels and the actuation elements, as well as between the loose wheels and the shaft collars, are designed as cylindrical or as planar surfaces as an alternative to the conical design, wherein the last-mentioned embodiment with planar surfaces is characterized by shorter adjustment paths in comparison with the conical design of the friction surfaces.
[0045] As a deviation from the actuation of the actuating elements of the device according to the invention from the inside of the shaft, or, as the case may be, the countershaft, the actuating elements can also be actuated in the previously described manner from the outside in relation to the surface of the shaft in additional advantageous embodiments of the device according to the invention, for example, by means of selector forks or the like, in order to adapt a rotational speed of the component to be connected in a rotationally fixed manner to the a shaft to the rotational speed of the shaft and to then connect the two elements in a rotationally fixed manner.
[0046] The device according to the invention is characterized in principle by a compact construction, and driving comfort is improved in a simple and cost-efficient manner due to the purely frictionally engaged design in comparison with the synchronization mechanisms configured with claws.
[0047] A loose wheel, which is only affected by significant tilt torques in an engaged state, that is, in a state where torque is transmitted, is supported in addition in an engaged state by an actuation element and a shaft collar and is configured with a more rigid mounting base than in a disengaged state. In this way, the development of noise during operation is reduced with less need for axial installation space in comparison with loose wheels configured in the conventional manner, and the lifetime of a gearwheel is increase due to the reduced tilting.
REFERENCE CHARACTERS
[0000]
1 Device
2 Shaft, countershaft
3 Component, loose wheel
3 A, B Friction surface
4 Main transmission shaft
5 , 6 Gearwheel
7 Loose wheel
8 Actuating element
8 A Friction surface
8 A to 8 F Flank
9 Actuating element
9 A to 9 F Flank
10 Actuator
11 Actuating rod
12 Holding element
12 A, B Region
13 Long slot
14 Connecting area
15 Axis of symmetry
16 , 17 , 18 Support bodies
19 Retaining element
20 Ring element
20 A Groove-shaped recess
21 Shaft collar
21 A Friction surface
22 Spring device
23 Shaft collar
24 , 25 , 26 Spring device | A device for rotationally fixing a shaft to a component that is rotatably arranged on the shaft. The actuating element positively engages the components to rotationally fix the components to the shaft. The difference in rotational speeds, between the component and the shaft, can be at least approximately compensated for by the actuating element. The actuating element, for rotationally fixing the component to the shaft by the actuator, is operatively connected to at least one support body, which is rotationally fixed with respect to the shaft in such a manner that the actuating element can act upon the component with an actuating force that depends on the torque to be transmitted from the shaft to the component and which is independent of the actuation of the actuator in the state in which the actuating element can be rotated relative to the shaft. | 5 |
FIELD OF THE INVENTION
The present invention relates to simultaneously printing multiple images on printing paper.
BACKGROUND OF THE INVENTION
Photographic cameras capture a series of images on strips of sensitized film. After exposure, the film strip is chemically processed to develop stable negative images on the film. These film strips are passed through a printer that serially focuses each image onto a matching area on a strip of photosensitive paper. Each image is pre-analyzed for density and color balance, and the exposure of the film image onto the paper is controlled to correct for errors in film density and film color balance.
U.S. Pat. No. 5,274,418, Kazami et al discloses an arrangement for printing a plurality of images from a film strip onto a roll of photosensitive paper. A series of single images on the film strip are printed to print paper. The paper is moved for each successive negative so that a series of images on the film strip are sequentially formed in various areas of a frame on the paper. U.S. Pat. No. 4,959,683 to Otaka et al operates on a unitary negative to create separate prints from various areas of the negative. Both patents do not increase print speed and require an exposure series of individual exposures. U.S. Pat. No. 4,095,892 discloses separable shuttering arrangement for an image receiving sheet. No method of advancing paper or image strips is disclosed.
It is, of course, highly advantageous to be able to simultaneously print multiple images, each of which has the correct density and color balance.
SUMMARY OF THE INVENTION
It is an object of the present invention to simultaneously print high quality multiple images on printing paper.
It is another object of the invention to simultaneously print multiple images on printing paper so as to increase printer throughput without degradation to image quality.
This object is achieved by apparatus for simultaneously illuminating a plurality of images from a film strip at an illumination gate onto different positions of printing paper, comprising:
a) means for transporting a film strip having a plurality of images to the image gate wherein a plurality of images are to be illuminated;
b) illumination means for illuminating images in the film gate;
c) an optics system for focusing the illuminated film images onto separable areas of the printing paper; and
d) separate exposure control means for each image to be formed on the printing paper which are separately operable to control the amount of illumination of the film images.
ADVANTAGES
This invention provides for an increase in printing speed by permitting two or more images on a film strip to be printed simultaneously. In one embodiment, common illumination source and common optic are used to illuminate and focus both images simultaneously. The simultaneous printing offers a substantial increase in throughput of a printer.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a front schematic view of the printer in accordance with the present invention;
FIG. 2 is a top sectional view over the exposure control arrangement for the printing paper in FIG. 1;
FIG. 3 is a schematic of the control electronics according to the present invention; and
FIG. 4 is a front sectional view of another printing apparatus in accordance with the present invention which uses a display device that projects a plurality of images.
DETAILED DESCRIPTION OF THE INVENTION
The invention is directed to a printer transferring images from a film strip 16 to a strip of print paper 17. Images are taken as a series of frames on a length of sensitized film. The strips are chemically processed to develop stable negative images of captured scenes. These film strips are fed into printer 10 which create positive image prints on print paper 17 such as photographic paper.
In prior art arrangements, the film strip 16 moves in a path through the printer. A pre-scanning station (not shown) measures the density and color balance of each image. The negatives are advanced into an exposure station. A single image is illuminated and projected onto an area of the paper strip. A series of shuttering filters are used to control the exposure of the negative image on the strip to create a positive, enlarged image on the paper. The exposure and filtering times for each negative is individually controlled according to the pre-measured values to create an acceptable print on the paper.
FIG. 1 shows an improved printer 10. Film strip 16 carries a plurality of images that have been analyzed for density and color balance. In this embodiment, two images, 18a and 18b are brought into an exposing gate 15. Lamp 12 provides illumination that passes through a diffuser 14 to evenly illuminate film images 18a and 18b. Focusing optic 20 is used to focus a plurality of images on the paper surface. In this disclosed embodiment, two images are simultaneously projected onto the paper.
FIG. 2 shows a top sectional view of the printer, particularly showing the exposure control system in the printer 10. In fact, there are two exposure control arrangements which are separably operable, one for each image to be formed on the print paper 17. Print paper 17 travels under a shutter support 22. Shutter support 22 has openings that frame print images 19a and 19b that correspond to film images 18a and 18b respectively. A series of shutters 24a and 24b carry filters for exposure control of image a and image b. Shutter drivers 24a and 24b are disposed to drive shutters 26 into either a covering or uncovering position over print images 19a and 19b respectively. Alternatively, two separate color liquid crystal shutters can be disposed over print images 19a and 19b. The use of two separate shuttering/filtering systems permits separate control of exposure of two images.
FIG. 3 is a schematic of the electronic system used to control the printer 10. A processor 30 receives data from a film scanner 32. Paper and film motion are controlled by paper drive 36 and film drive 34, respectively. When the film strip and paper are aligned, processor 30 operates on shutter drivers 24a and 24b separately to control exposure of images a and b.
In operation, film strip 16 is advanced two images per cycle. The images are pre-scanned to determine exposure and color balance values for each individual image. The set of images is advanced into the printing station while shutters 26 cover print paper 17. Shutter drivers 24a and 24b are then operated to individually expose print images 19a and 19b according to individual predetermined exposure schedules. In operation, the time required to print the darkest negative will determine the print time for both images. The print time saved is equal to the faster print time of the two images. In practice, most pairs of images have approximately equal exposure, thus the printing time is nearly halved.
After exposure, shutters 26 have covered print images 19a and 19b. The paper is advanced a distance equivalent to the length of print images 19a and 19b. Simultaneously film strip 16 is also advance to the next pair of negative images. Printing time is also decreased because motion of both negative and paper strips is controlled by acceleration and deceleration times. Because acceleration and deceleration occurs only once for every two images, further processing time is saved on advance of the negative and paper strips. The process is repeated for each set of two images. Parallel printing of two images results in a significant reduction in printing time. The summary of times needed for printing using prior art and new art is shown in Table 1.
TABLE 1______________________________________PRIOR ART NEW ART______________________________________accel. frame 1 accel.move frame 1 move frame 1decel. frame 1 move frame 2print frame 1 decel.accel. frame 2 print (longer(tp1, tp2))move frame 2decel. frame 2print frame 2______________________________________
More than two images can be printed simultaneously. In another embodiment, two strips of negatives are processed side-by side on double width paper to print four images simultaneously. Four separate exposure stations are used to expose each of the four images.
Reference has been made to an embodiment that uses a common optic and illuminator. It is also possible to provide a separate illuminator and optic for each image being processed. The printing of multiple negatives occurring at the same time with separate illumination and optics improves printer throughput.
FIG. 4 shows another embodiment where the film strip is replaced by a color liquid crystal display 38. The liquid crystal display has a plurality of selectively energizable pixels that change in transmission density. Using the new art, two or more images are simultaneously loaded into the display and the print paper is advanced an equivalent number of printed image distances. After print paper 17 advances, the shutters according to the present invention simultaneously expose separate frames on the paper according to separate exposure schedules. Alternatively, the liquid crystal display acts as the shutter itself, shutting off separate colors as each pixel on the paper is properly exposure. The liquid crystal printer according to this invention will achieve a higher printing speed due to the double image printing and double image paper advance. Separate image exposure is also provided to optimize print quality.
The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
PARTS LIST
10 printer
12 lamp
14 diffuser
16 film strip
17 print paper
18a film images
18b film images
19a print images
19b print images
20 focusing optic
22 shutter support
24a shutter drives
24b shutter drives
26 shutters
30 processor
32 film scanner
34 film drive
36 paper drive
38 liquid crystal displays | Printer throughput is increased in a printer that prints sequential images on a film strip onto a matching strip of photosensitive printing paper. A film gate supports two or more images on the film strip. An illuminator provides light to the images in the film gate. An optics system focuses the film images onto separable areas of the printing paper and a shutter over each printing area individually exposes the printing areas. | 6 |
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. Patent application Ser. No. 15/143,503 filed Apr. 29, 2016 entitled MODULAR BASIN APPARATUS of which is herein incorporated by reference in its entirety.
[0002] 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 reproduction of the patent document or the patent disclosure, as it appears in the U.S. Patent and Trademark Office patent file or records, but otherwise reserves all copyright rights whatsoever.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0003] Not Applicable
REFERENCE TO SEQUENCE LISTING OR COMPUTER PROGRAM LISTING APPENDIX
[0004] Not Applicable
BACKGROUND
[0005] The present disclosure relates generally to modular devices that can be assembled and disassembled by a user to form a useful article. More specifically, the present disclosure relates to an apparatus having a plurality of plates that can be assembled and disassembled by a user to form a device having a central concave basin that may be used to accommodate articles or to form a structural support for items.
[0006] In many applications, it may be desirable to provide a modular device that can be assembled and/or disassembled by a user to provide a useful article. In some applications, modular devices are desired because they may include a small form factor when disassembled, but may retain a much larger form factor when assembled into a useful article. A small form factor may be desirable when a user is travelling, transporting the device, storing the device, or generally isn't using the device. When the user desires to use the article for an application, the modular device may be unpacked and assembled to form the useful article.
[0007] Modular devices of this nature are used for a variety of applications, for example in gardening as flower pots or planters, as furniture for seating or storage, or for other applications such as a portable fire pit or grill for receiving items such as firewood.
[0008] Conventional modular devices for assembly and/or disassembly by a user are often bulky and are not easily assembled at a desired location. What is needed then are improvements in modular devices for allowing assembly and/or disassembly by a user for the purpose of forming useful article.
BRIEF SUMMARY
[0009] This Brief Summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.
[0010] One aspect of the disclosure is to provide a modular basin apparatus including a central cavity shaped to receive items. The modular basin apparatus includes a first panel, a second panel and a third panel. Each panel includes one or more slots shaped to receive a portion of another panel. A user may assemble the apparatus using the slots to receive portions of the other panels, forming a three dimensional standing apparatus with central cavity positioned to receive one or more items. The apparatus may be used as a fire pit or grill in some embodiments.
[0011] Another aspect of the present disclosure is to provide a modular basin apparatus having first, second and third panels each having the same planform profile such that the panels may be stacked for transport or storage.
[0012] A further aspect of the present disclosure is to provide a modular basin apparatus having an additional fourth panel to provide an upper surface supported by the first, second and third panels.
[0013] Yet another aspect of the present disclosure is to provide a modular basin apparatus having first, second and third panels with slots that may be collinearly aligned to allow a user to assemble the apparatus.
[0014] Another aspect of the present disclosure is to provide a modular basin apparatus that may be assembled to provide a three-dimensional structure, and disassembled by a user to provide a flat stack of two-dimensional panels.
[0015] In some embodiments, the present disclosure provides a modular fire pit apparatus, including a first panel, a second panel and a third panel. The first panel includes a first panel lower edge, a first panel primary edge, and a first panel secondary edge. The first panel is in the shape of an equilateral triangle with truncated corners, forming a six-sided polygon having a first planform profile. The second panel includes a second panel lower edge, a second panel primary edge, and a second panel secondary edge. The second panel is in the shape of an equilateral triangle with truncated corners, forming a six-sided polygon having a second planform profile. The third panel includes a third panel lower edge, a third panel primary edge, and a third panel secondary edge. The third panel is in the shape of an equilateral triangle with truncated corners, forming a six-sided polygon having a third planform profile. In some embodiments, the first, second and third planform profiles are substantially the same. The first, second and third panels may be modularly assembled by a user using one or more slots on each panel.
[0016] Numerous other objects, advantages and features of the present disclosure will be readily apparent to those of skill in the art upon a review of the following drawings and description of a preferred embodiment.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] FIG. 1 illustrates a perspective view of an embodiment of a modular basin in accordance with the present disclosure.
[0018] FIG. 2 illustrates a plan view of an embodiment of a first panel in accordance with the present disclosure.
[0019] FIG. 3 illustrates a plan view of an embodiment of a second panel in accordance with the present disclosure.
[0020] FIG. 4 illustrates a plan view of an embodiment of a third panel in accordance with the present disclosure.
[0021] FIG. 5 illustrates a plan view an embodiment of first, second and third panels arranged for assembly in accordance with the present disclosure.
[0022] FIG. 6 illustrates a plan view of an embodiment of a fourth panel in accordance with the present disclosure.
[0023] FIG. 7 illustrates an elevation view of an embodiment of a modular basin apparatus in accordance with the present disclosure.
[0024] FIG. 8 illustrates an elevation view of an embodiment of a modular basin in accordance with the present disclosure.
[0025] FIG. 9 illustrates a top view of an embodiment of a modular basin in accordance with the present disclosure.
[0026] FIG. 10 illustrates an elevation view of an alternative embodiment of a modular basin in accordance with the present disclosure.
DETAILED DESCRIPTION
[0027] While the making and using of various embodiments of the present invention are discussed in detail below, it should be appreciated that the present invention provides many applicable inventive concepts that are embodied in a wide variety of specific contexts. The specific embodiments discussed herein are merely illustrative of specific ways to make and use the invention and do not delimit the scope of the invention. Those of ordinary skill in the art will recognize numerous equivalents to the specific apparatus and methods described herein. Such equivalents are considered to be within the scope of this invention and are covered by the claims.
[0028] In the drawings, not all reference numbers are included in each drawing, for the sake of clarity. In addition, positional terms such as “upper,” “lower,” “side,” “top,” “bottom,” etc. refer to the apparatus when in the orientation shown in the drawing, or as otherwise described. A person of skill in the art will recognize that the apparatus can assume different orientations when in use.
[0029] Referring further to the drawings, FIG. 1 illustrates an embodiment of a modular basin 10 including a first panel 20 , a second panel 40 and a third panel 60 . First, second and third panels 20 , 40 , 60 are joined together via a series of interconnecting slots to form an upright structure in the form of modular basin 10 . Each slot extends entirely through the thickness of the panel on which the slot is defined. First, second and third panels 20 , 40 , 60 each includes a substantially flat plate in some embodiments. Each panel can include any suitable material, such as but not limited to metal, steel, aluminum, titanium, plastic, polymer, acrylic, plexi-glass, glass, composite, graphite, stone, wood, paper, cardboard or any other suitable material. Each panel generally includes a sufficient thickness to allow basin 10 to stand on a flat or uneven surface in a generally upright position, as shown in FIG. 1 .
[0030] When first, second and third panels 20 , 40 , 60 are joined together, a central cavity 12 is formed on the upper side of the panel assembly. Cavity 12 includes an open concave depression in the center of the assembly. Cavity 12 is generally shaped to allow one or more objects to be placed in the cavity 12 . For example, in some embodiments, modular basin 10 includes first, second and third panels 20 , 40 , 60 joined to form a central cavity 12 to be used as a modular fire pit for receiving and burning firewood or some other combustible fuel such as charcoal or wood chips received in cavity 12 . In such embodiments, a fourth plate 80 may be positioned above the central cavity 12 to provide a grilling or cooking surface, as shown in FIG. 1 .
[0031] Modular basin 10 generally includes a first panel 20 , as shown in FIG. 2 in the form of a substantially flat plate. First panel 20 includes a first panel lower edge 22 , and a first panel primary slot 24 is defined in first panel 20 beginning along first panel lower edge 22 and extending into the body of first panel 20 at a generally acute angle. A first panel secondary slot 26 is defined in first panel 20 intersecting the first panel primary slot 24 at a position along the length of first panel primary slot 24 . First panel secondary slot 26 is longer that first panel primary slot 24 in some embodiments. First panel primary slot 24 and first panel secondary slot 26 are oriented at an obtuse angle open to the upward direction, as shown in FIG. 2 in some embodiments. Each of first panel primary slot 24 and first panel secondary slot 26 include a slot width substantially equal to the thickness of second and third plates 40 , 60 in some embodiments.
[0032] Referring further to FIG. 2 , in some embodiments, first panel 20 includes the shape of an equilateral triangle with truncated corners, forming a clipped triangle. First panel 20 includes a first panel handle 38 in some embodiments that allows a user to lift first panel 20 in an upright orientation. A first panel handle opening 36 is formed adjacent first panel handle 38 to allow a user's hand to pass through the panel when grasping first panel handle 38 .
[0033] Second panel 40 includes a second panel lower edge 42 positioned at a lower edge of second panel 40 in some embodiments. Second panel lower edge 42 includes the edge of second panel 40 that is positioned to engage a surface upon which modular basin 10 rests, such as the ground. Second panel 40 also includes a second panel primary edge 48 and a second panel secondary edge 50 . A second panel primary slot 44 is defined in second panel 40 beginning along the second panel primary edge 48 , as shown in FIG. 3 in some embodiments. Second panel primary slot 44 includes a slot that extends from the second panel primary edge 48 inwardly toward the body of second panel 44 . Similarly, second panel 40 also includes a second panel secondary slot 46 defined in second panel 40 beginning along the second panel secondary edge 50 and extending inwardly toward the body of second panel 44 . Second panel primary slot 44 and second panel secondary slot 46 do not intersect. In some embodiments, second panel primary slot 44 and second panel secondary slot 46 are equal in length. In additional embodiments, second panel primary slot 44 and second panel secondary slot 46 are equal in both length and in angle relative to a vertical reference axis. In other embodiments, second panel primary slot 44 and second panel secondary slot 46 are unequal in length. Each of second panel primary slot 44 and second panel secondary slot 46 include a slot width that is substantially equal to the thickness of first panel 20 and third panel 60 .
[0034] Referring further to FIG. 3 , in some embodiments, second panel 40 includes the shape of an equilateral triangle with truncated corners, forming a clipped triangle. Second panel 40 includes a second panel handle 58 in some embodiments that allows a user to lift second panel 40 in an upright orientation. A second panel handle opening 56 is formed adjacent second panel handle 58 to allow a user's hand to pass through the panel when grasping second panel handle 58 .
[0035] Referring to FIG. 4 in some embodiments a third panel 60 includes a substantially flat plate having a third panel lower edge 62 defined along the lower edge of third panel 60 . Third panel lower edge 62 is positioned to engage the surface or structure upon which assembled modular basin 10 rests, such as a ground surface. Third panel 60 includes a third panel primary recess 68 defined along the third panel lower edge 62 , and a third panel primary slot 64 is defined in third panel 60 beginning along the lower edge 62 in the third panel primary recess 68 and extending into the body of third panel 60 , as shown in FIG. 4 . Third panel primary slot 64 is generally oriented at an obtuse angle relative to a horizontal reference axis open to the left side of the third panel 60 as shown in FIG. 4 . Third panel 60 includes a third panel primary edge 70 and a third panel secondary edge 72 opposite the third panel primary edge 70 . A third panel secondary recess 69 is defined along the third panel secondary edge 72 , and a third panel secondary slot 66 is defined in the third panel 60 beginning in the third panel secondary recess 69 and extending into the body of third panel 60 , as shown in FIG. 4 . Third panel secondary slot 66 is shorter in length than third panel primary slot 64 in some embodiments.
[0036] Referring further to FIG. 4 , in some embodiments, third panel 60 includes the shape of an equilateral triangle with truncated corners, forming a clipped triangle. Third panel 60 includes a third panel handle 78 in some embodiments that allows a user to lift third panel 60 in an upright orientation. A third panel handle opening 76 is formed adjacent third panel handle 78 to allow a user's hand to pass through the panel when grasping third panel handle 78 .
[0037] Referring further to FIG. 4 , a portion of third panel 60 at the intersection of third panel secondary edge 72 and third panel lower edge 62 includes an insert portion 96 forming a flange that is dimensioned to be inserted through first panel secondary slot 26 on first panel 20 , as shown in FIG. 5 . Referring further to FIG. 5 , each of the first, second and third panels 20 , 40 , 60 are configured to be interconnected to form modular basin 10 . The assembly of first, second and third panels 20 , 40 , 60 may be accomplished by a user who manually combines the panels to form modular basin 10 . Similarly, a user may manually disconnect first, second and third panels 20 , 40 , 60 from each other to disassemble modular basin 10 . As seen in FIG. 4 , first panel 20 is positioned relative to second panel 40 such that first panel primary slot 24 is collinearly aligned with and receives second panel primary slot 44 , as shown in line “a”. As the first panel primary slot 24 and second panel primary slot 44 pass each other in a collinear orientation, a portion of second panel 40 is received in first panel primary slot 24 , and a portion of first panel 20 is received in second panel primary slot 44 .
[0038] Next, as shown by line “b” in FIG. 5 , third panel 60 is positioned relative to first and second panels 20 , 40 such that third panel primary slot 64 is collinearly aligned with second panel secondary slot 46 . In this position, insert portion 96 of third panel 60 is also aligned for insertion into first panel secondary slot 26 . Once aligned, third panel 60 can be moved toward first and second panels 20 , 60 such that insert portion 96 is received in and passes through first panel secondary slot 96 while third panel primary slot 64 is collinearly passes second panel secondary slot 46 . As third panel 60 advances, a portion of second panel 40 is received in third panel primary slot 64 , and a portion of third panel 60 is received in second panel secondary slot 46 . Third panel 60 is advanced until third panel secondary slot 66 rests against the surface of first panel 20 , providing a translation stop for third panel 60 . Once the first, second and third panels 20 , 40 , 60 are combined in this manner, a central cavity 12 is formed, and the modular basin apparatus may stand upright, as shown in FIG. 1 .
[0039] Referring to FIG. 6 , in some embodiments, a fourth panel 80 is provided. Fourth panel 80 may be positioned above the central cavity 12 supported by first, second and third panels 20 , 40 , 60 as shown in FIG. 1 . Fourth panel 80 may provide a surface against which items may be rested, for example a sitting surface in embodiments where modular basin apparatus 10 is used to for a chair or stool. Alternatively, fourth panel 80 may be positioned above central cavity 12 to provide a cooking or grilling surface where modular basin apparatus 10 is used as a portable fire pit or portable cooking device such as a grill. As shown in FIG. 6 , fourth panel 80 includes a cooking surface 91 including a plurality of passages 90 to allow passage of flames and/or heat from below. Fourth panel 80 can have numerous different configurations including a substantially solid panel in some embodiments.
[0040] Referring further to FIG. 8 , in some embodiments, fourth panel 80 includes the shape of an equilateral triangle with truncated corners, forming a clipped triangle. Fourth panel 80 includes a support at each corner in some embodiments. Each support provides a contact location for fourth panel 80 to be supported by one of the first, second and third panels 20 , 40 , 60 . As shown in FIG. 6 , in some embodiments, fourth panel 80 includes a fourth panel first support 82 in a first corner of fourth panel 80 , a fourth panel second support 84 in a second corner of fourth panel 80 , and a fourth panel third support 86 in a third corner of fourth panel 80 . A fourth panel first opening 82 a is defined in fourth panel 80 adjacent fourth panel first support 82 . A fourth panel second opening 84 a is defined in fourth panel 80 adjacent fourth panel second support 84 . A fourth panel third opening 86 a is defined in fourth panel adjacent fourth panel third support 86 . Each of the fourth panel first, second and third supports 82 , 84 , 86 may be used as a handle to allow user to grasp fourth panel to be carried in an upright orientation.
[0041] In some embodiments, first panel 20 , second panel 40 , third panel 60 , and fourth panel 80 include substantially the same planform profile, each including an equilateral triangle with truncated corners. Each panel in some embodiments also includes substantially the same outer dimensions. As such, when first panel 20 , second panel 40 , third panel 60 , and fourth panel 80 are disassembled, each panel may be stacked against one another to form a single stack of four panels having substantially the same outer planform profile and outer dimensions. When stacked, first handle 38 , second handle 58 and third handle 78 are substantially aligned. Additionally, when stacked first panel handle opening 36 , second panel handle opening 56 , and third panel handle opening 76 are substantially aligned. This alignment allows a user to simultaneously grasp first, second and third handles 38 , 58 , and 78 while simultaneously passing the user's fingers through first panel handle opening 36 , second panel handle opening 56 , and third panel handle opening 76 . Fourth panel 80 may also be added to the stack by placing any one of the openings 82 a, 84 a, 86 a on fourth panel 80 in alignment with first panel handle opening 36 , second panel handle opening 56 , and third panel handle opening 76 .
[0042] In additional embodiments, first, second, third and fourth panels 20 , 40 , 60 , 80 may be formed using a raw material. In alterative embodiments, first, second, third and fourth panels 20 , 40 , 60 , 80 include a surface treatment such as an application of a polymer, ceramic, porcelain, enamel, glaze, paint or other surface coating or treatment.
[0043] Referring further to FIG. 2 , first panel 20 includes a first panel support tab 34 protruding from first panel 20 into first panel handle opening 36 . First panel support tab 34 includes a substantially rectangular protrusion extending partially into first panel handle opening 36 in some embodiments. Similarly, second panel 40 includes a second panel support tab 54 protruding from second panel 40 into second panel handle opening 56 in some embodiments. Second panel support tab 56 includes a substantially rectangular protrusion extending partially into second panel handle opening 56 in some embodiments. Third panel 60 also includes a third panel support tab 74 extending from third panel 60 into third panel handle opening 76 in some embodiments. Third panel support tab 74 includes a substantially rectangular protrusion extending partially into third panel handle support opening 76 in some embodiments.
[0044] Each support tab 34 , 54 , 75 provides an engagement with a corresponding location on fourth panel 80 in some embodiments to keep fourth panel 80 centered above central cavity 12 when fourth panel 80 is positioned on modular basin apparatus 10 . First panel support tab 34 is partially received in fourth panel first opening 82 a, second panel support tab 54 is partially received in fourth panel third opening 86 a, and third panel support tab 74 is partially received in fourth panel second opening 84 a in some embodiments, as seen in FIG. 9 . In other embodiments, different support tabs may be received in different openings on fourth panel 80 , as fourth panel 80 may be rotated relative to modular basin apparatus 10 .
[0045] In alternative embodiments, as seen in FIG. 10 , fourth panel 80 may rest against the top edge of each of first, second and third panels 20 , 40 , 60 . As such, fourth panel 80 may be dimensioned with a larger planform profile than first, second and third panels 20 , 40 , 60 in some embodiments.
[0046] In various applications, modular basin apparatus 10 including first panel 20 , second panel 40 and third panel 60 provides a modular structure that can be easily assembled and disassembled by a user. Modular basin apparatus 10 may be used for such purposes as for a fire pit, grill, fire bowl, stool, chair, table, decorative planter, display device, storage device, feeding trough, wash basin, bird bath, presentation device, or an apparatus for storing particulates, solids or liquids such as a bowl.
[0047] Thus, although there have been described particular embodiments of the present invention of a new and useful MODULAR BASIN APPARATUS is not intended that such references be construed as limitations upon the scope of this invention. | A modular basin apparatus includes a first panel, a second panel and a third panel. The panels include a plurality of slots that receive portions of the other panels. A user may assemble the panels to form a three-dimensional basin apparatus. A concave cavity is formed on the upper side of the apparatus when assembled, and the cavity may be receive materials depending on the application of the assembly. In some embodiments, the apparatus may be used as a modular fire pit, chair, table, or other device. A fourth panel may rest against the first, second and third panels to provide an upper surface. In some embodiments, all panels include the same planform profile and outer dimensions such that they may be stacked in an arrangement having a uniform outer profile for improved transport and storage. | 5 |
BACKGROUND OF THE INVENTION
The present invention relates to novel pigments, and in particular, pigments that have been treated with certain organo-acid phosphate compounds.
The incorporation of pigments into polymer matrices has been performed for many years, and over the years, pigments have been and continue to be incorporated into polymers matrices for many reasons. For example, pigments may be used as fillers. They may also be used to impart better physical and chemical attributes to polymer matrices, including improved thermal stability, especially lacing resistance in extruded polymer film applications, and decreased chemical activity. In order to obtain different benefits, pigments may be treated in different ways, including by adding surface treatments.
Commonly used pigments include titanium dioxide, kaolin and calcium carbonate. Commonly known surface treatments that have been applied to pigments include silanes, alkylphosphonic acids and phosphorylated polyenes. The precise attributes that one wants in a treated pigment will depend in part on the application in which it will be used. Often one wants to provide a hydrophobic pigment that is stable, easy to prepare, cost effective, can be dispersed to a high degree in polymers, and does not react in the presence of other additives such as lithopone.
However, despite the numerous known surface treatments, for various reasons, including cost and desired properties, no known surface treatments are ideal for all applications. Thus, there is always a need to develop new and better treatments for pigments.
One under-explored option for treating pigments is the use of esters of phosphoric acids. These compounds have been suggested to mix with pigments and to form suspensions in, for example, aqueous coatings applications. However, such a use produces a unique product that may be used in a unique application. Thus, the limited teachings for use of esters of phosphoric acids in aqueous coatings applications do not suggest the pigments treated with low levels of organo-acid phosphates of this invention or that the pigments treated with low levels of organo-acid phosphates of this invention would have utility in plastics.
The present invention proides economical and easily prepared novel pigments that possess resistance to lacing when incorporated into polymeric articles (such as films), do not produce objectionable side reactions when mixed with common plastics additives such as lithopone, which contains zinc sulfide, and are stable such that they possess low levels of extractable organics. Durable plastics products that incorporate the treated pigments of the present invention resist yellowing when phenolic-type antioxidants are used. In addition, a polymer matrix containing up to about 85% of organo-acid phosphate treated titanium dioxide pigment, based on the weight of the polymer may be produced. The polymer matrix may be an end-product in and of itself or a product that will be further processed such as in a masterbatch, which can be let down into a polymeric film.
SUMMARY OF THE INVENTION
The present invention provides novel treated pigments for use in polymer matrices. The treated pigments of the present invention are organo-acid phosphate treated compounds comprising a pigmentary base that may be treated with the reaction products of: (1) at least one organic alcohol; and (2) P 2 O 5 and/or phosphoric acid. The phrases “at least one organic alcohol” and “organic alcohols” mean one or more types of organic alcohols, for example, a solution of hexanol or octanol or a mixture of hexanol and octanol. The organic alcohols, P 2 O 5 and phosphoric acid are selected such that their reaction products include an organo-acid phosphate that may be represented by the formula:
(R—O) x PO(OH) y
wherein
x=1 or 2;
y=3−x; and
R is an organic group having from 2 to 22 carbon atoms.
Alternatively, one may start with the organo-acid phosphate directly if it is available, rather than produce it from the reactants described above.
The treated pigments of the present invention may be combined with and readily dispersed into polymers to form polymer matrices. These polymer matrices have improved physical properties such as impact strength, tensile strength and flexural characteristics.
The treated pigments of the present invention may also be used to prepare highly loaded polymer masterbatches. These highly loaded masterbatches are especially useful in applications in which dispersion and thermal stability, especially resistance to lacing, are critical.
Based on the foregoing, there is still a need for better treated pigments. The treated pigments of the present invention have the advantages of being hydrophobic pigments that are stable, easy to prepare, cost effective, can be dispersed to a high degree in polymers, and do not react in the presence of other additives such as lithopone. Such treated pigments may be useful in the manufacture of plastics and other products.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides novel pigments for use in connection with polymers and offers several benefits over currently used pigments. According to the present invention pigments are treated with the reaction products of: (1) at least one organic alcohol; and (2) P 2 O 5 and/or phosphoric acid. The resulting treated pigments may then be combined with polymers to form novel polymer matrices.
The present disclosure is not intended to be a treatise on either pigments or the production of polymers matrices and readers are referred to appropriate, available texts and other materials in the field for additional and detailed information on any aspect of practicing this invention.
Suitable pigmentary bases for use in the present invention include titanium dioxide, kaolin, talc, mica and calcium carbonate. The phrase “pigmentary base” as used herein refers to the pigment that has not been treated with an organo-acid phosphate compound. Preferably, titanium dioxide is the chosen pigmentary base. When the pigmentary base is titanium dioxide, the titanium dioxide may be either rutile or anatase, both of which may be produced by processes that are well known to those skilled in the art.
Organic alcohols, and P 2 O 5 and/or phosphoric acid may be reacted to form organo-acid phosphates. The organic alcohols useful in the present invention may have hydrocarbon groups from about 2 to about 22 carbon atoms. Some examples of the organic alcohols suitable for use in the present invention include, ethanol, propanol, butanol, isobutanol, tertiary butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, decanol, dodecanol and the like. Preferably the alcohol is a linear hexanol, a linear octanol or 2-ethylhexanol. They may be combined with either or both P 2 O 5 and phosphoric acid. The conditions under which to react these materials in order to form the organo-acid phosphate are generally known or knowable to those skilled in the art.
Rather than beginning with the organic alcohols and P 2 O 5 and/or phosphoric acid, one may start directly with the organo-acid phosphate of the below formula (Formula I):
(R—O) x PO(OH) y
wherein
x=1 or 2;
y=3−x; and
R is an organic group having from 2 to 22 carbon atoms.
Preferably R is a linear hexyl- or octyl-aliphatic group or a branched octyl-aliphatic group. For example, R may be an ethylhexyl-group. The use of hexyl-, octyl- or ethylhexyl-aliphatic groups will result in excellent pigmentary performance.
Organo-acid phosphates are available commercially through, for example, Albright & Wilson Americas of Glen Allen, Va. or may be prepared by procedures known or knowable to those skilled in the art such as those procedures disclosed in U.S. Pat. No. 4,350,645, issued on Sep. 21, 1982 to Kuroaki el al., the teachings of which are incorporated by reference.
The organo-acid phosphate, which is the surface treatment of the present invention will be used to treat the pigmentary base and to form a treated pigment. The phrase “treated pigment” refers to any pigmentary base that has been surface treated or modified. The phrase “organo-acid phosphate treated pigment” refers to a pigmentary base that has been treated with the organo-acid phosphate of the reaction products of organic alcohols and P 2 O 5 and/or phosphoric acid or an organo-acid phosphate that may be represented by the above Formula I. The level of organo-acid phosphate used to treat the pigmentary base may range from about 0.01 percent to about 5 percent by weight, based on the weight of the pigmentary base; more preferably from about 0.3 percent to about 2.0 percent; and most preferably from about 0.4 percent to about 1.2 percent.
In the organo-acid phosphate treated pigment, the organo-acid phosphate may interact with the pigment in a number of manners such as through hydrogen bonding and/or covalent attachments such that the surface treatment resists extraction from the treated pigment. The organo-acid phosphates that are the reaction products of the organic alcohols, and P 2 O 5 and/or phosphoric acid are generally mixtures of mono- and di-substituted esters in combination with orthophosphoric acid.
The process for making the organo-acid phosphate treated pigment is easily and flexibly incorporated into existing pigment production processes. Preferably the combining of the pigmentary base and the surface treatment of the invention will occur at a temperature of from about 10° C. to about 270° C. The temperature at which the pigmentary base and the surface treatment are combined is dependent on the step in the pigment production process in at which the surface treatment is added.
A by-product of the reaction between the organo-acid phosphate and the pigment is thought to be water. Because water is the by-product, the organo-acid phosphate may be added at any one of, or several of, the operations in the pigment production process. For example, the organo-acid phosphate may be added to a washed filter cake prior to spray drying, to a high intensity milling device or to a micronizer feed prior to or concurrent with micronization. It is not as effective to add the organo-acid phosphate to a pigment slurry prior to filtration and washing since a portion of the organo-acid phosphate will be lost upon washing of the pigment. The organo-acid phosphate can be added to a washed filter cake at normal process operating temperatures. If the organo-acid phosphate is a solid substance, it may be dissolved in an appropriate solvent, such as water, alcohol, tetrahydrofurn, etc., before being added to the pigmentary base. It is desirable to add the organo-acid phosphate to a fluidized, washed filter cake with agitation in order to assure uniform mixing of the organo-acid phosphate among the pigment particles. The pH of the fluidized filter cake prior to addition of the organo-acid phosphate is not critical, and normal operating pH values are acceptable. These values are known or readily knowable to those skilled in the art. If the organo-acid phosphate is added to a dry pigment such as a spray drier product or micronizer feed, care must be taken to ensure uniform mixing of the organo-acid phosphate with the pigment powder.
Devices such as a V-shell blender equipped with an intensifier bar for application of the liquid organic or other suitable mixing devices known to those in the art may be used. Alternatively, the organo-acid phosphate may be metered into the micronizer along with the pigment powder to be ground. Air or steam micronization techniques may be used at temperatures from room temperature up to 250° C. or higher as is known or easily knowable to those skilled in the art.
If one adds the organo-acid phosphates of the present invention to the filter cake or to the micronizer feed, one will minimize the loss of the organic portion of the surface treatment and thereby improve manufacturing efficiency. The treated pigment may be fluid energy milled using steam or air to produce finished pigments that retain high levels of the organo-acid phosphate compound, which would reduce the overall cost of producing the treated pigment.
When, for example, the pigment is titanium dioxide, the organo-acid phosphates may be added to the untreated titanium dioxide directly obtained directly from a production process such as the chloride or sulfate processes. Alternatively, the pigmentary base titanium dioxide may be further treated with additional metal oxides, such as aluminum oxide, silicon dioxide, zirconium oxide and the like, using any process known to those skilled in the art, prior to treatment with the organo-acid phosphates of the present invention. Additionally, the untreated pigmentary base or the treated pigment may be secondarily treated with polyalcohols such as trimethylolethane and trimethylolpropane or alkanolamines such as triethanolamine.
Once the organo-acid phosphate treated pigment is formed, it may then be combined with a polymer. The nature of the surface treatment of the present invention allows the treated pigments to be easily incorporated into a polymer matrix. The phrase “polymer matrix” refers to the substance comprising of the polymer and the treated pigment. Polymers that may be of use in the present invention include polymers of unsubstituted ethylene monomers, including polyethylene, polypropylene, polybutylene, and copolymers of ethylene with alpha-olefins containing 4 to 12 carbon atoms or vinyl acetate; vinyl homopolymers, acrylic homopolymers and copolymers, polyamides, polycarbonates, polystyrene, acrylonitrile-butadiene-styrenes and polyethers. Other suitable polymer types also include polyvinylchloride, polyurethanes, polysulfones, polyimides, polyesters and chlorinated polyesters, polyoxyethylenes, phenolics, alklyds, amino resins, epoxy resins, phenoxy resins and acetal resins.
The treated pigment may be combined with the polymer and have a loading of up to about 85% by weight, based on the weight of the polymer matrix. Preferably a loading of treated pigment of about 50% to about 85% by weight based on the weight of the polymer matrix is used. This loading may be used as a masterbatch. A “masterbatch” is meant to refer to a mixture of 2 or more substances that are blended together and then blended with one or more other ingredients that may be the same or different as either of the first two substances. The methods for creating a masterbatch with the treated pigment are known or easily known to those skilled in the art. For example, the masterbatch may be created by combining the treated pigment and the polymer using a BR Banbury Mixer.
It has been found, surprisingly and unexpectedly, that the treated pigments of this invention do not generate potentially hazardous or noxious gases when used in combination with the polymeric filler lithopone, which contains combinations of zinc sulfide and barium sulfate. By contrast, when one uses phosphorylated polyenes in combination with lithopone a potentially hazardous gas is emitted.
It has also been found, surprisingly and unexpectedly that the treated pigments of this invention impart greater lacing resistance to polymers into which they are incorporated. Lacing, which is a believed to be a measure of volatility at specific weight percent pigment loadings and processing temperatures, may manifest as a void or hole in a plastic film.
EXAMPLES
The following examples set forth preferred embodiments of the invention. These embodiments are merely illustrative and are not intended and should not be construed to limit the claimed invention in any way.
Example 1
Octyl Acid Phosphate Prepared in Accordance with U.S. Pat. No. 4,350,645
To 65.12 g of 1-octanol (0.5 mol) and 9.0 g of water (0.5 mol), phosphorous pentoxide (70.96 g 0.5 mol) was added gradually with vigorous stirring while maintaining the temperature below 80° C. The reaction mixture was stirred for 3 hours at 80° C. Subsequently, another 65.12 g of 1-octanol (0.5 mol) was added. The mixture continued to stir for another 10 hours at 80° C.
The resulting mixture was analyzed via titration methods, following the teachings of International Patent Application Serial Number PCT/JP95/01891 and found to yield 63-68% mono octyl acid phosphate, ˜21% dioctyl acid phosphate and ˜7% phosphoric acid.
Example 2
Hexyl Acid Phosphate
Example 1 was repeated using 1-hexanol in place of the 1-octanol. The final product contains the presence of 60% monohexyl acid phosphate, 18% dihexyl acid phosphate, and ˜12% phosphoric acid.
Example 3
Polymer Matrices From Octyl Acid Phosphate Treated TiO 2 (Chloride Process)
51.8 mls of a 386.4 grams Al 2 O 3 /liter solution of sodium aluminate were added to 5000 grams of the TiO 2 in a 350 grams/liter slurry with mixing at 70° C. The pH was adjusted to 7.0 using a 50% sodium hydroxide solution, and the slurry was allowed to age for 30 minutes.
The aged slurry was filtered and washed three times with 5000 ml aliquots of 80° C. deionized water, and then dried overnight at 115° C. in a drying oven.
The dried filter cake was forced through an 8-mesh sieve prior to treatment with octyl acid phosphate 8.4 grams of the reaction product of octanol, P 2 O 5 and phosphoric acid from Example 1 were added drop-wise to 1200 grams of the dry, 8 meshed, alumina coated TiO 2 , which was spread to a 1-cm thickness on polyethylene film. The pigment was mixed and transferred to a one gallon wide-mouthed plastic bottle and agitated for 10 minutes on a roller mill. The resulting material was steam micronized to produce the finished pigment.
The finished pigment as incorporated into a low-density polyethylene in 75%, and 50% masterbatches for dispersion and lacing evaluations. Results are given in Table 1 below.
Example 4
Polymer Matrices From Octyl Acid Phosphate Treated TiO 2 (Sulfate Process)
51.8 ml of a 386.4 grams Al 2 O 3 /liter solution of sodium aluminate were added to 5000 grams of fine particle sulfate process rutile TiO 2 in a 350 grams/liter slurry with mixing at 70° C. The slurry pH was adjusted to 7.0 using a 50% sodium hydroxide solution, and the slurry was allowed to age for 30 minutes. The aged slurry was filtered and washed three times with 5000 ml aliquots of 80° C. deionized water and dried overnight at 115° C.
The dried filter cake was forced through an 8-mesh sieve in preparation for treatment with octyl acid phosphate. 8.4 grams of the octyl acid phosphate product were added dropwise from a syringe to 1200 grams of the dry, 8 meshed, alumina coated TiO 2 spread to a 1 cm thickness on polyethylene film. The pigment was mixed and transferred to a one gallon wide-mouthed bottle and agitated for 10 minutes on a roller mill. The raw pigment was steam micronized to produce the finished pigment.
The finished pigment was incorporated into 75% and 50% TiO 2 based masterbatches containing low-density polyethylene for dispersion and lacing evaluations. Results are given in Table 1 below.
Comparative Example 1
Rutile TiO 2, prepared by the chloride process, coated with hydrous alumina as described in Example 3 was treated with 0.60% by weight triethanolamine based on the weight of dry pigment. The triethanolamine treated pigment was steam micronized to produce the finished pigment.
The finished pigment was incorporated into 75% and 50% TiO 2 containing low-density polyethylene masterbatches for dispersion and lacing evaluations. Results are given in Table 1 below.
Comparative Example 2
A sulfate process rutile TiO 2 base was coated with alumina as described in Example 4. The organic treatment applied to the dry, 8-meshed alumina coated, sulfate process TiO 2 was 0.60% by weight triethanolamine based upon the weight of the dry pigment. The triethanolamine treated pigment was steam micronized to produce the finished pigment. The finished pigment was incorporated into 75% and 50% TiO 2 masterbatches for dispersion and lacing evaluations. Results are given in Table 1 below.
TABLE 1
Dispersion
(Counts/Second)
Lacing
Example 3
1,750
1.7
Example 4
5,140
1.5
Comparative Example 1
13,700
1.4
Comparative Example 2
24,000
1.2
The data illustrate that dispersion performance of both chloride and sulfate process-based pigments, treated with the octyl acid phosphate reaction product (Examples 3 and 4), is dramatically improved over like pigmentary bases treated with a conventional, commercially used organic treatment, triethanolamine (comparative Examples 1 and 2). Further, the excellent dispersion performance is obtained with no significant decay in resistance to lacing. The standard error for the lacing measurement is about 0.1 to 0.2.
Examples 5-21
Dispersion and Lacing
In the following examples (Examples 5-21), the organo-acid phosphate was added to a dry, chloride process base rutile TiO 2 further treated with 0.20% by weight of alumina, prior to micronization. The organo-acid phosphate ester was added as a neat liquid or in solution if the organo-acid phosphate was a solid material. The general preparation method used for producing the organo-acid phosphate, alumina treated pigmentary base was as follows:
25.9 mls of a 386.4 grams Al 2 O 3 /liter solution of sodium aluminate were added with mixing to 5000 grams of the TiO 2 in a 350 grams/liter slurry at 70° C. The pH was adjusted to 7.0 using a 50% sodium hydroxide solution, and the slurry was allowed to age for 30 minutes.
The aged slurry was filtered and washed three times with 5000 ml aliquots of 80° C. deionized water, and then dried overnight at 115° C. in a drying oven. The dried filter cake was forced through an 8-mesh sieve prior to treatment with the organo-acid phosphate. The desired amount of organo-acid phosphate was added dropwise to 1200 grams of the dry, 8 meshed, alumina coated TiO 2 , which was spread to a 1-cm thickness on polyethylene film. If the organo-acid phosphate was a solid material, it was dissolved in tetrahydrofuran (THF) prior to application to the dry pigment, and the THF was allowed to evaporate. The pigment was mixed and transferred to a one gallon wide-mouthed plastic bottle and agitated for 10 minutes on a roller mill. The resulting material was steam micronized to produce the finished pigment.
Example 5—0.9% Octyl Acid Phosphate Treated TiO 2
The pigmentary base prepared according to the above-described method was treated with 0.9% octyl acid phosphate prepared according to Example 1 and steam micronized to produce the final product. The finished pigment was incorporated into low-density polyethylene in 75% and 50% masterbatches for dispersion and lacing evaluations. Dispersion results were 780 XRF counts of TiO 2 /sec and lacing was rated a 1.5.
Example 6—1.1% Octyl Acid Phosphate Treated TiO 2
The pigmentary base prepared according to the above-described method it was treated with 1.1% octyl acid phosphate prepared according to Example 1 and steam micronized to produce the final product. The finished pigment was incorporated into low-density polyethylene in 75% and 50% masterbatches for dispersion and lacing evaluations. Dispersion results were 1,080 XRF counts of TiO 2 /sec and lacing as rated 1.3.
Example 7—0.90% Hexyl Acid Phosphate Treated TiO 2
The pigmentary base prepared according to the above-described method was treated with 0.9% hexyl acid phosphate prepared according to the method of Example 2 and steam micronized to produce the final product. The finished pigment was incorporated into low-density polyethylene in 75% and 50% masterbatches for dispersion and lacing evaluations. Dispersion results were 1,260 XRF counts of TiO 2 /sec and lacing was rated 1.3.
Example 8—1.1% Hexyl Acid Phosphate Treated TiO 2
The pigmentary base prepared according to the above-described method was treated with 1.1% hexyl acid phosphate prepared according to the method of Example 2 and steam micronized to produce the final product. The finished pigment was incorporated into low-density polyethylene in 75% and 50% masterbatches for dispersion and lacing evaluations. Dispersion results were 1,310 XPF counts of TiO 2 /sec and lacing was rated 1.2.
Example 9—0.5% Butyl Acid Phosphate Treated TiO 2
The pigmentary base prepared according to the above-described method was treated with 0.5% butyl acid phosphate obtained from Albright and Wilson Americas and steam micronized to produce the final product. The finished pigment was incorporated into a 75% by weight low-density polyethylene masterbatch for dispersion evaluation. The dispersion result was 12,720 XRF counts of TiO 2 /sec.
Example 10—0.7% Butyl Acid Phosphate Treated TiO 2
The pigmentary base prepared according to the above-described method was treated with 0.7% butyl acid phosphate obtained from Albright and Wilson Americas and steam micronized to produce the final product. The finished pigment was incorporated into a 75% by weight low-density polyethylene masterbatch for dispersion evaluation. The dispersion result was 2,180 XRF counts of TiO 2 /sec.
Example 11—0.90% Butyl Acid Phosphate Treated TiO 2
The pigmentary base prepared according to the above-described method was treated with 0.9% butyl acid phosphate obtained from Albright and Wilson Americas and steam micronized to produce the final product. The finished pigment was incorporated into a 75% by weight low-density polyethylene masterbatch for dispersion evaluation. The dispersion result was 1,030 XRF counts of TiO 2 /sec.
Example 12—0.9% 2-Ethylhexyl Acid Phosphate Treated TiO 2
The pigmentary base prepared according to the above-described method was treated with 0.9% 2-ethylhexyl acid phosphate, which was commercially available from Specialty Industrial Products, Inc. under the tradename Sipophos 2EHP, and steam micronized to produce the final product. The finished pigment was incorporated into a 75% by weight low-density polyethylene masterbatch for dispersion evaluation. The dispersion result was 790 XRF counts of TiO 2 /sec.
Example 13 1.1% 2-Ethylhexyl Acid Phosphate Treated TiO 2
The pigmentary base prepared according to the above-described method was treated with 1.1% 2-ethylhexyl acid phosphate, which was commercially available from Specialty Industrial Products, Inc. under the tradename Sipophos 2EHP, and steam micronized to produce the final product. The finished pigment was incorporated into a 75% by weight low-density polyethylene masterbatch for dispersion evaluation. The dispersion result was 280 XRF counts of TiO 2 sec.
Example 14—0.9% Cetyl Acid Phosphate Treated TiO 2
The pigmentary base prepared according to the above-described method was treated with 0.9% cetyl acid phosphate, which was commercially available from Colonial Chemical Company under the tradename Colafax CPE, and steam micronized to produce the final product. The finished pigment was incorporated into a 75% by weight low-density polyethylene masterbatch for dispersion evaluation. The dispersion result was 15,140 XRF counts of TiO 2 /sec.
Example 15—1.1% Cetyl Acid Phosphate Treated TiO 2
The pigmentary base prepared according to the above-described method was treated with 1.1% cetyl acid phosphate, which was commercially available from Colonial Chemical Company under the tradename Colafax CPE, and steam micronized to produce the final product. The finished pigment was incorporated into a 75% by weight low-density polyethylene masterbatch for dispersion evaluation. The dispersion result was 2,970 XRF counts of TiO 2 /sec.
Example 16—0.7% Oleyl Acid Phosphate Treated TiO 2
The pigmentary base prepared according to the above-described method was treated with 0.7% oleyl acid phosphate, which was commercially available from Albright & Wilson Americas under the tradename DURAPHOS APO-128, and steam micronized to produce the final product. The finished pigment was incorporated into a 75% by weight low-density polyethylene masterbatch for dispersion evaluation. The dispersion result was 25,730 XRF counts of TiO 2 /sec.
Example 17—0.9% Oleyl Acid Phosphate Treated TiO 2
The pigmentary base prepared according to the above-described method was treated with 0.9% oleyl acid phosphate, which was commercially available from Albright & Wilson Americas under the tradename DURAPHOS APO-128, and steam micronized to produce the final product. The finished pigment was incorporated into a 75% by weight low-density polyethylene masterbatch for dispersion evaluation. The dispersion result was 20,720 XRF counts of TiO 2 /sec.
Example 18—0.5% Bis(2-ethylhexyl) Acid Phosphate Treated TiO 2
The pigmentary base prepared according to the above-described method was treated with 0.5% bis(2-ethylhexyl) acid phosphate, which was commercially available from Albright & Wilson Americas, and steam micronized to produce the final product. The finished pigment was incorporated into a 75% by weight low-density polyethylene masterbatch for dispersion evaluation. The dispersion result was 5,610 XRF counts of TiO 2 /sec.
Example 19—0.7% Bis(2-ethylhexyl) Acid Phosphate Treated TiO 2
The pigmentary base prepared according to the above-described method was treated with 0.7% bis(2-ethylhexyl) acid phosphate, which was commercially available from Albright & Wilson Americas, and steam micronized to produce the final product. The finished pigment was incorporated into a 75% by weight low-density polyethylene masterbatch for dispersion evaluation. The dispersion result was 1,120 XRF counts of TiO 2 /sec.
Example 20—0.9% Bis(2-ethylhexyl) Acid Phosphate Treated TiO 2
The pigmentary base prepared according to the above-described method was treated with 0.9% bis(2-ethylhexyl) acid phosphate, which was commercially available from Albright & Wilson Americas, and steam micronized to produce the final product. The finished pigment was incorporated into a 75% by weight low-density polyethylene masterbatch for dispersion evaluation. The dispersion result was 1,530 XRF counts of TiO 2 /sec.
Example 21—1.1% Bis(2-ethylhexyl) Acid Phosphate Treated TiO 2
The pigmentary base prepared according to the above-described method was treated with 1.1% bis(2-ethylhexyl) acid phosphate, which was commercially available from Albright & Wilson Americas, and steam micronized to produce the final product. The finished pigment was incorporated into a 75% by weight low-density polyethylene masterbatch for dispersion evaluation. The dispersion result was 1,070 XRF counts of TiO 2 /sec.
Lacing Evaluations
The high temperature stability of polymers containing pigments is an important property of commercial polymer films, especially polyethylene film applications. Voiding or “lacing” accompanies the failure of films. Lacing is believed to be a measure of volatility at specific weight percent pigment loadings and processing temperatures.
For the present invention, lacing tests were conducted on 50% TiO 2 concentrate samples prepared using a Haake Rheocord 9000 Computer Controlled Torque Rheometer. Thus, 125 g of TiO 2 and 125 g of LDPE 722 manufactured by Dow Chemical Company were dry blended and added to the 75° C. preheated chamber with rotors running at 50 rpm. One minute after addition of the TiO 2 /LDPE mixture, the chamber temperature was raised to 105° C. Frictional heat generated by the mixing process was allowed to drive the rate of incorporation of the TiO 2 into the LDPE until a steady state mixture was achieved. The concentrate was removed from the mixing chamber and placed into a Cumberland Crusher to obtain finely granulated 50% concentrate samples. The granulated concentrates were conditioned for 48 hours at 23° C. and 50% relative humidity. These concentrates were then let down into Dow Chemical 722 LDPE to achieve a 20% loading of TiO 2 in the final film.
Lacing evaluations were run on 1″ extruder equipped with a cast film slot die. A temperature profile of 625° F. die, 515° F. clamp ring, 415° F. zone 3, 350° F. zone 2, and 300° F. zone 1 was used. The screw speed was set at about 90 rpm. A 25.4 cm polished chrome chill roll, set in conjunction with the extruder was used to maintain a 75-μm-film thickness, and to cool and transport the films. The chill roll distance from the die lips was about 22 mm and the temperature was about 27° C.
After the TiO 2 /LDPE mix was placed in the hopper, the material was allowed to purge until the appearance of a white tint in the film was first noted. To ensure the concentration of TiO 2 in the film had stabilized, a time interval of two minutes was allowed before lacing observations were recorded and a film sample obtained. The extruder was then purged with LDPE until the film turned clear. Lacing performance was determined by counting the relative size and number of holes generated in a film sample laid out on a dark surface. A 1.0-3.0 rating system was used. A rating of 1 was given to films with no lacing, 2 was given to films showing the onset of lacing and 3 was given to films with extreme lacing. Increments of 0.1 were used to give an indication of the relative performance between the samples.
Dispersion Testing
Using a small-scale laboratory extrusion apparatus, a measure of pigment dispersion into organic polymers was obtained by measuring the relative amount of pigment trapped onto screens of extruder screen packs. Tests were made using 75% TiO 2 concentrates in low density polyethylene prepared using a Haake 3000 Rheomix mixer. The mixer was controlled and monitored with a Haake 9000 Rheocord Torque Rheometer. 337.7 grams of micronized TiO 2 and 112.6 grams of NA209 LDPE manufactured by Equistar were dry blended and added to the 75° C. mixing chamber with rotors operating at 50 rpm. The mixer temperature was programmed to increase to 120° C. one minute after the dry blend was introduced to the mixing chamber. After a steady state mixture was achieved, the compound was mixed for an additional 3 minutes. The compound was removed from the chamber and granulated using a Cumberland crusher.
Dispersion tests were conducted using a Killion single screw extruder, model KL-100 equipped with a 20:1 length to diameter screw. The extruder was preheated at 330, 350, 390 and 380° F. from zone 1 to the die, respectively, and operated at 70 rpm. A purge of 1000 grams of NA952 LDPE manufactured by Equistar was run through the system, and a new screen pack was installed. The screen pack consisted of 40/500/200/100 mesh screens from the die towards the extruder throat. After temperature stabilization, 133.33 grams of granulated 75% TiO 2 concentrate was fed into the extruder. This was followed with 1500 grams of NA952 purge as the feed hopper emptied. After the LDPE purge was extruded, the screens were removed, separated and tested using a relative count technique from the measurements from an X-ray fluorescence spectrometer. The number of TiO 2 counts per second was obtained for the 100, 200 and 500 mesh screens in the pack and totaled to obtain the dispersion result. A count result of less than 5000 is considered to represent excellent dispersion.
Reactivity with Zinc Sulfide (Reactive Component in Lithopone)
Lithopone, a composition containing zinc sulfide is used as a filler and extender in various polymer compositions. When a TiO 2 pigment treated with a phosphorlated polyene is contacted with zinc sulfide at temperatures greater than about 20 to 25° C., noxious odors are generated. In contrast, no odors are generated when pigments of the present invention are contacted with zinc sulfide under the same conditions.
Zinc Sulfide Reactivity
Example 22
5 grams of Millennium Chemicals RCL-4 (lot # 234C4DQ), a pigment product comprising titanium dioxide and a phosphorylated polyene, were placed in a sealed vial with 1 g of zinc sulfide. The vial was heated to 195° C. for 10 minutes. Noxious vapors emanating from the vial were injected in to a Hewlett-Packard GC-MS and dimethyl disulfide and dimethyl trisulfide were detected.
Example 23
5 grams of the pigment as prepared in Example 3 were placed in a sealed vial with 1 g of zinc sulfide. The vial was heated to 195° C. for 10 minutes. No noxious odors were detected nor were sulfur components detected via GC-MS.
Extraction of Finished Pigments
Samples of finished pigments from Examples 3 and 4 were extracted using Soxhlet extraction procedures with hexane, tetrahydrofuran and a 10%:90% ethanol:water (W/W) mixture as extraction solvents. The carbon contents of the dried pigments were determined both before and after extraction. Results are shown below in Table 2.
TABLE 2
Example 3
Example 4
% Carbon
theoretical
0.31
0.31
before extraction
0.28
0.28
after hexane extraction
0.28
0.27
after THF extraction
0.29
0.27
after EtOH: H 2 O extraction
0.28
0.25
Based on the extraction results, the organo-acid phosphate is apparently strongly bonded to the TiO 2 pigment since carbons levels of the treated pigment are not significantly affected by extraction. Further, the octyl-acid phosphate appears not to be appreciably hydrolyzed during the high temperature steam micronization process since over 90% of the added carbon remains attached to the pigment after micronization. It would be expected that hydrolysis of the acid phosphate would liberate octanol, which is volatile and would evaporate during micronization.
Having thus described and exemplified the invention with a certain degree of particularity, it should be appreciated that the following claims are not to be so limited but are to be afforded a scope commensurate with the wording of each element of the claim and equivalents thereof. | A unique treatment for pigments is provided. This treatment, which uses certain organo-acid phosphate molecules, imparts improved physical and chemical qualities including lacing resistance, improved dispersion and decreased chemical reactivity when these treated pigments are incorporated into polymeric matrices. | 8 |
BACKGROUND OF THE INVENTION
1. Technical Field
This invention relates to devices that provide a convenient means for storing and carrying relatively small items that may be frequently needed while moving about in a wheelchair, while simultaneously enhancing the comfort of a standard wheelchair arm rest. Specifically, the device enables a user to easily, conveniently and safely transport such frequently needed items as keys, medicine and makeup, as well as larger items such as sweaters and umbrellas, without the need for carrying the items in a bulky purse or awkward bags.
2. Background Information
For those temporarily or permanently restricted to a wheelchair, the difficulties involved in securely transporting and keeping track of small, frequently needed items such as keys, medicine, reading glasses and makeup can be great. People restricted to wheelchairs frequently reside in group residences such as hospitals or nursing homes. Although security may be of the highest caliber, the resident may nevertheless live in constant fear that their items are at risk of being stolen should they be distracted by nearby activities or temporarily doze off. Indeed, small personal items may be easily taken from such a person should they be sitting on their lap or resting on a tray or in a basket fastened to the wheelchair arms. Similarly, a person restricted to a wheelchair on a shopping trip away from their home is frequently considered an easy target by potential thieves because that person frequently lacks the ability to defend their belongings and usually lacks the ability to pursue the person who has taken their goods. If the use of an arm or hand is also restricted, this difficulty may be greatly compounded. Under these circumstances, if one wishes to travel even the slightest distance from one's home or hospital room, one must depend on the assistance of another, carry a bulky pouch or purse in one's lap, or wear a shirt or vest with blousy, cumbersome pockets.
If one carries a pouch or purse in their lap, any number of circumstances may arise that could cause the pouch or purse to be sent tumbling to the floor, resulting in great distress to the person who has dropped it. Likewise, if the user has only one hand or arm available to hold the pouch and simultaneously unzip or unsnap it, it may be only with great difficulty or the assistance of a passerby that access to the contents of the pouch is ultimately gained.
Prior attempts at providing a storage compartment attached to the wheelchair are represented by the device disclosed in U.S. Pat. No. 4,919,443 issued to Kehler Apr. 24, 1990. The Kehler device is a storage box mounted on one of the upright posts to which the back support is attached, and must be pivoted about the upright post to the side of the wheelchair from its normal storage position behind the back support to gain access to the contents stored therein. Wheelchair users, however, frequently lack the PG,4 mobility needed to reach an object fastened behind them to the rear of the wheelchair.
Another problem frequently faced by wheelchair users is that when moving about in the wheelchair on wet surfaces, the large rear wheels tend to splash both the user and the person who may be pushing the wheelchair. Prior art devices of the type discussed lack any provision for splash guards that help protect the wheelchair user and the person pushing the wheelchair and keep them dry.
Similarly, large pockets on shirts or vests are frequently used to carry relatively small items, but they have no closure device by which to keep the contents of the pocket from spilling out. Further, if the pocket is close to the body as with a shirt pocket, it may be that its contents are too close to the face of the wearer to be suitably inspected, and the item being sought may not be easily identified. As for larger items such as sweaters, umbrellas or small packages, there is no secure, easily accessible way of transporting these items short of resting them on the lap of the wheelchair user. This method has the obvious drawback of lacking security, and allowing these larger items easily to fall to the ground.
SUMMARY OF THE INVENTION
The present invention is intended to provide a convenient storage pouch for users of wheelchairs. The pouch hangs from one or both of the wheelchair arm rests, and includes a padded section positioned above the arm rest, providing added comfort for the wheelchair user. More importantly, the arm rest padding encourages the user to rest his arm on the arm rest, increasing the security of the items stored in the pouches by rendering the pouches more difficult to remove from the wheelchair. Using VELCRO® fasteners, snaps or other easily operated fastening means, the pouch may be conveniently attached to or detached from the arm rest portion of the wheelchair. Other easily operated fasteners, such as strips of VELCRO®, may be provided to secure the openings to the pouch sections.
The device may include pouch sections located on both sides of the wheelchair arm rest, and may be made of a soft fabric material. The pouch section located on the outside of the arm rest may be shaped to the contour of the wheel on that side of the wheelchair. One or more storage compartments may then be located within the pouch section, each storage compartment having its own VELCRO® or other closure device. These storage compartments should be large enough to contain relatively bulky items such as sweaters, purses and packages, and a compartment may be provided for storing an umbrella. The pouch section located on the inside of the arm rest may be used for transporting relatively small items such as medicine containers, glasses, a wallet, makeup, etc. This inner pouch section also may be divided into separate compartments.
An object of the invention is to provide a secure means for transporting small to medium size items by people who are restricted to wheelchairs.
Another object of the invention is to provide a portable means, easily attachable to a wheelchair arm rest, for transporting small items such as keys, makeup or medication for wheelchair-bound persons.
Another object of the invention is to provide a secure storage means, easily attachable to a wheelchair, that also provides a splash guard to protect the occupant of the wheelchair, as well as a person who might be pushing the wheelchair, when the wheelchair is used on wet surfaces.
These and further objects and advantages of the invention will be readily understood as the following description is read in conjunction with the accompanying drawings, in which like reference numerals have been used to designate like elements throughout the several views.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a wheelchair with an embodiment of the invention installed and in normal use;
FIG. 2 is an end view of the wheelchair taken along line 2--2 of FIG. 1;
FIG. 3 is a cutaway view of another embodiment of the invention shown mounted to an arm of the wheelchair; and
FIG. 4 is a cutaway view of yet another embodiment of the invention shown mounted to an arm of the wheelchair.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
With reference to the drawings, and in particular to FIG. 1, the wheelchair arm rest and pouch is generally indicated by reference numeral 10. The secure storage device 10 of the embodiment shown in FIGS. 1 and 2 is attached to a wheelchair generally indicated by reference numeral 12.
Secure storage device 10 as illustrated in FIGS. 1 and 2 includes a first transverse or spanning portion 14 having a first edge 16 and a second edge 18 opposing first edge 16. First transverse portion 14 is positioned above the first arm resting portion 20 of the wheelchair 12. First flap portion 22 is hingedly attached to and downwardly depending from first edge 16 of first transverse portion 14. Second flap portion 24 is hingedly attached to and downwardly depending from second edge 18 of first transverse portion 14. At least one storage compartment 26 is provided integral with first flap portion 22, and at least one storage compartment 28 is provided integral with second flap portion 24. Each storage compartment 26, 28 has an access opening 30, and each access opening 30 has an open position and a closed position. First releasable attachment means 32, such as VELCRO®, snaps or buttons, is provided for releasably attaching first flap portion 22 to second flap portion 24. As may be most clearly seen in FIG. 2, releasable attachment means 32 is positioned below first arm resting portion 20 of wheelchair 12.
As shown in FIGS. 1 and 2, secure storage device 10 also includes second transverse portion 34 having a first edge 36 and a second edge 38 opposing first edge 36. Second transverse portion 34 is positioned above the second arm resting portion 40 of the wheelchair 12. Third flap portion 42 is hingedly attached to and downwardly depending from first edge 36 of second transverse portion 34. Fourth flap portion 44 is hingedly attached to and downwardly depending from second edge 38 of second transverse portion 34. At least one storage compartment 46 is provided integral with third flap portion 42, and at least one storage compartment 48 is provided integral with fourth flap portion 44. Each storage compartment 46, 48 has an access opening 30, and each access opening 30 has an open position and a closed position. Second releasable attachment means 50, such as VELCRO®, snaps or buttons, is provided for releasably attaching third flap portion 42 to fourth flap portion 44. As may be most clearly seen in FIG. 2, second releasable attachment means 50 is positioned below second arm resting portion 40 of wheelchair 12.
Finally, the embodiment of secure storage device 10 illustrated in FIGS. 1 and 2 includes connecting means 52 extending across the wheelchair seat portion 54 for connecting first flap portion 22 with third flap portion 42, whereby when the wheelchair user rests on wheelchair seat portion 54, connecting means 52 is maintained in position by the weight of the wheelchair user, providing additional security for secure storage device 10. A fastening strap member, not shown, may also be provided to attach connecting means 52 to the tubular supports 53 of wheelchair 12 to which wheelchair seat portion 54 is attached. Connecting means 52 may also include a padded portion 56 therein, providing greater comfort for the wheelchair user. Likewise, transverse portions 14, 34 may also include a padded portion 58 therein, whereby the user of the wheelchair, upon resting their arm upon padded transverse portions 14, 34, will enhance the security of secure storage device 10 by making it more difficult to remove from arm resting portions 20, 40 of wheelchair 12.
As shown in FIGS. 1 and 2, first releasable restraining means 59 and second releasable restraining means 60, including straps and releasable fasteners such as VELCRO®, snaps or buttons, may extend from second flap portion 24 and fourth flap portion 44, respectively. These releasable restraining means 58, 60 wrap around tubular supports 62, and prevent second flap portion 24 and fourth flap portion 44 from flapping about or otherwise becoming dislodged or tangled in the wheelchair wheels. Releasable restraining means 58, 60 may be found on this or other embodiments of the invention.
As illustrated in the several views, pouches may be provided in any or all of the flap portions in any of several configurations. Pouches of various sizes may be provided by placing dividers between or within pouches. Such a divider may be provided simply as by stitching 61, as shown in FIG. 3. Items that may be carried in the pouches include but are not limited to magazines 63, sweaters 64, umbrellas 66 or purses 68. Other items such as pencils, eyeglasses, cosmetics and medicine may be carried in any of the several pouches. The pouches may be left in an open position as shown in FIG. 3, but to provide greater security for the items stored therein, it is preferred that each pouch include a closure means such as VELCRO® fastener 70. Other fasteners such as the zipper fastener shown in FIG. 2, or snaps or buttons may also be employed. As also shown in FIG. 3, the pouches may also include a protective flap 74.
As may best be seen in FIG. 1, outer flap portions 24, 44 may be contoured along their bottom edge portions 76 to conform to the shape of the large rear wheel 78 of wheelchair 12. Each bottom edge portion 76 may include a spanning segment 80, which is shown as an accordion pleated insert in FIG. 3. Spanning segment 80 spans the depth of rear wheel 78, providing additional storage space within the pouches. When spanning segment 80 is present, it is preferred that it comprise a waterproof material, whereby items stored in the storage pouches or compartments of the outer flap portions may be protected from moisture deposited on spanning segments 80 by rear wheel 78 of wheelchair 12.
With reference to FIG. 4, an alternate embodiment of secure storage device 10 includes a transverse portion 82 having a first edge 84 and a second edge 86. Transverse portion 82 is positioned above arm resting portion 88 of wheelchair 12. First or inner flap portion 90 is hingedly attached to and downwardly depending from first edge 84 of transverse portion 82. Second or outer flap portion 92 is hingedly attached to and downwardly depending from second edge 86 of transverse portion 82. First releasable attachment means 94, such as VELCRO®, snaps or buttons, is provided to allow storage device 10 to be releasably attached to arm resting portion 88 of wheelchair 12. At least one storage compartment 96 is provided integral with at least one of the flap portions 90, 92. Each storage compartment 96 includes an access opening 30, each access opening 30 having an open position and a closed position. This embodiment of the invention may be used on one or both of the arm resting portions 88 of wheelchair 12. Transverse portion 82 may also include a padded portion 58 therein, whereby the user of the wheelchair, upon resting his arm upon padded transverse portion 82, will enhance the security of secure storage device 10 by making it more difficult to remove from arm resting portions 88 of wheelchair 12.
In the preferred version of this embodiment, first releasable attachment means 94 is integral with first or inner flap portion 90. It is also preferred that a weight member 98 be contained within first flap portion 90, preferably sewn into a storage compartment 96 contained within first flap portion 90. The use of weight member 98 within inner flap portion 90 weighs down inner flap portion 90, helping inner flap portion 90 maintain a generally downward depending alignment from transverse portion 82, increasing the comfort of the wheelchair user.
As with the first embodiment discussed above, second flap portion 92 may also be contoured along its bottom edge portion 76 to conform to the shape of the large rear wheel 78 of wheelchair 12. It should be kept in mind, however, that each embodiment of the invention may be provided with either an inner flap portion 22, 42, 90, or an outer flap portion 24, 44, 92, or both. Therefore, it follows that releasable attachment means 32, 50 may also be provided with this embodiment should both flap portions 90, 92 be incorporated therein.
In operation, the wheelchair arm rest and pouch 10 would be positioned above an arm resting portion 88 of wheelchair 1 with padded transverse portion 82 positioned above and along arm resting portion 88. Releasable attachment means 94 should be positioned on the inside edge of arm resting portion 88. Items may then be placed in the pouches provided on the inner or outer flap portions 90, 92. If there is an inner flap portion 90 that does not extend down to connecting means 52, a weight member 98 would preferably be sewn into the lower edge of inner flap portion 90. Items may be placed in any of the pouches as needed by the user of wheelchair 12, and the pouches should be secured using closure means 70, although some items such as umbrella 66 may protrude from their pouches. It is preferred, however, that items such as purse 68 be placed into a large enough pouch to ensure that any handles or other protruding portions will be completely enclosed and secured within the pouch. As the user of wheelchair 12 moves about, the contents of the various pouches will not be apparent to passersby, thus diminishing the likelihood that anyone would attempt to steal or otherwise remove any valuable items from the possession of the wheelchair user. Further, since the padded transverse portion 82 makes the arm resting portion 88 more comfortable for the wheelchair user, the presence of the user's arm resting on the arm rest 10 makes it more difficult to remove from wheelchair 12. This is especially useful in the instant when the wheelchair user dozes while resting in the wheelchair. If the user's arms are resting on the arm rests 10, the arm rests 10 may not be removed without waking the wheelchair user.
To install wheelchair arm rest and pouch 10 including connecting means 52 one would similarly position the two transverse portions 14, 34 above arm resting portions 20, 40, respectively. Connecting means 52 may not be attached permanently to inner flap portions 22, 42, and connecting means 52 must then be fastened as by zipper, snaps, etc. Likewise, connecting means 52 may also be provided with straps, laces or other fasteners for attachment to tubular supports 53 of wheelchair 12. Finally, with either embodiment of the invention, releasable restraining means 59, 60 may be provided for fastening outer flap portions 24, 44 to tubular supports 62 of wheelchair 12. Once these are fastened, this embodiment of secure storage device 10 is fully installed and ready for use as above.
It is anticipated that various changes may be made in the size, shape, and construction of the wheelchair arm rest and pouch disclosed herein without departing from the spirit and scope of the invention as defined by the following claims. | A device for providing a secure storage area for the personal items of a wheelchair user. The device includes padded arm rests to encourage the user to rest their arms on the comfortable, padded surface, further enhancing the security of the storage device by making it more difficult to remove the storage device from the arm resting portions of the wheelchair witthout detection by the wheelchair user. | 0 |
FIELD OF THE INVENTION
[0001] This invention relates to improvements in a wall mountable bracket. More particularly, the present wall mountable bracket allows for placement of the bracket on a wall hanger in a top down motion. The bracket has a narrow rotational engage window where the bracket slides onto the wall hanger. Once engaged the bracket rotates into vertical orientation and locks the bracket onto the wall hanger preventing disengagement from vertical lifting of the bracket.
BACKGROUND OF THE INVENTION
[0002] There are many types of TV, board and shelf mounting patents that incorporate a variety of different attachment methods. Each patent approaches the problem based upon security of the device on the wall and the method of installation. To focus the background this disclosure limits the identified patents with inventions that secure to a back brace with a top to bottom securing motion and to brackets that provide some form of blocking to prevent disconnection with the back brace if the bracket is lifted vertically without the use of screws or additional hardware to secure the bracket onto the back brace. Exemplary examples of bracket mountings is found in the below identified patents.
[0003] U.S. Pat. No. 5,018,323 issued May 28, 1991 to Knud Clauson and U.S. Pat. No. 7,086,543 issued Aug. 8, 2006 to Lee E. Remmers both disclose a wall panel of shelving system made from sheet material where the shelf or panel is brought down into a back member and the shelf or panel is rotated into a cavity in the back member. Once the shelf or panel in installed a detail on the bracket or panel minimizes upward motion of the bracket or panel to prevent the bracket or panel from being dislodged. While both of these patents provide the blocking ability to prevent the shelf or panel from being removed from the back member they utilize an open cavity in the back member for capturing the bracket or panel that increases the cost of manufacturing and the bracket or panel must still be lifted slightly to engage it with the back member. In addition these patents do not disclose a stop on one or both ends of the back member to prevent the bracket or panel from being slid off the side of the back member.
[0004] U.S. Pat. No. 5,050,832 issued Sep. 24, 1991 to E. Desmond Lee et al., discloses a modular storage unit mounting system. The wall fastening components include a “C” bracket that is secured to the storage unit and a back member that has a raised lip on the tip. The installer hooks the top of the “C” bracket on the back member and then rotates the storage unit until the storage unit rests against the wall. The lower part of the “C ” bracket prevents vertical motion of the “C” bracket to prevent accidental dislodging of the storage unit from the wall. While this patent provides a bracket and back member that is vertically located on a back member and the engagement prevents accidental removal from vertical motion the “C” bracket engages on the back member from bends located both above and below the back member. The bracketing system also requires the storage unit to prevent rotation of the bracket. The patent does not provide an end stop to prevent the storage unit from being slid off the side of the back member.
[0005] U.S. Pat. No. 4,311,295 issued Jan. 19, 1982 and U.S. Pat. No. 4,403,761 issued Sep. 13, 1983 both to Walker Jamar disclose a wall mounting presentation system having a locking holder. The wall securing components are similar in construction with the previously identified Desmond Lee patent where a “C” bracket connects and secures to the back member. One major difference is the shape of the back member. In Desmond Lee the back member was formed from sheet metal while in these patents the back member is molded. The Jamar patents are most specifically intended for use on a presentation board to allow the presentation board to be easily secured and removed using the “C” bracket on the back member. In FIGS. 4-6 in patent '763 the mounting bracket uses a hinge to articulate the presentation board over and onto the back member. The addition of the hinge adds another level of complexity. The bracketing system relies upon a loose fit for the bracket to make the presentation board easy to erect and take down and the loose fit also makes it susceptible to accidental removal. In operation the presentation board sits at an angle and requires the “C” bracket to pivot to maintain engaged contact with the back member. These patents do not provide an end stop to prevent the presentation board from being slid off either side of the back member.
[0006] What is needed is a simple bracket and back member that is installed from a top to bottom motion that locks the bracket to prevent accidental removal from vertical motion. The pieces would provide their own walls rotation stops and include details that prevent the brackets from being slid of the sides of the back member. The proposed bracket a back member provides this solution in a simple two or three piece system that can be used to hang a variety of items from flat panel televisions to writing boards, display signs, wall panels, posters, pictures and more.
[0007] While the disclosed wall mounting components are ideally intended for use as a cost effective wall mounting method for a flat screen television the device is also well suited for securing writing boards, display signs, wall panels, posters, pictures and other planar and multi dimensional items.
BRIEF SUMMARY OF THE INVENTION
[0008] It is an object of the wall bracket with integrated vertical lock for the bracket to be configured with an angled slot that allows the bracket to only be removed from the back member when the slot is properly aligned. The alignment ensures that the bracket is not dislodged from the back member if it is bumped or lifted. In operation the removal of the bracket requires the user to rotate away the bottom of the bracket to align the slot before they begin to lift the bracket from the back member.
[0009] It is an object of the wall bracket with integrated vertical lock to engage the wall bracket with the back member using a motion from top downward. This is particularly important when installing a heavy item where gravity forces the item downward. The down facing slot allows an installer to start with the apparatus far above the back member and slide the bracket down the wall until the bracket makes contact with the back member where it hooks onto the back member. Gravity will the pivot and rotate the slot into engagement with the back member thereby securing the two pieces in together.
[0010] It is another object of the wall bracket with integrated vertical lock to have details to prevent the brackets from sliding off the ends of the back member. The details are bent ears on the ends of the back member that stop the bracket from sliding past the end of the back member. This is particularly important because a user may hang a television on the brackets and then want to re-position the television on the wall by sliding the television and brackets on the back member. Without the bent ears a user could slide the monitor until one bracket becomes dislodged from the back member that would result in the display falling.
[0011] It is still another object of the wall bracket with integrated vertical lock to provide brackets that prevent excessive rotation of the mounted object. This is important because a mounted object such as a television requires some air flow for cooling and because the television should be mounted to align the television in a vertical orientation and without the rotation prevention details the television could rotate the screen to an undesirable angle.
[0012] Various objects, features, aspects, and advantages of the present invention will become more apparent from the following detailed description of preferred embodiments of the invention, along with the accompanying drawings in which like numerals represent like components.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 shows an isometric view of the bracket and back member secured together.
[0014] FIG. 2A-2D shows the bracket being engaged on the back member
[0015] FIG. 3 shows the bracket and back member mounted with a flat panel monitor or television.
[0016] FIG. 4 shows the engagement angle of the bracket.
[0017] FIG. 5 is a detailed view of the engagement portion of the bracket and the back member.
[0018] FIG. 6 is a side view of the bracket on the back member.
DETAILED DESCRIPTION
[0019] FIG. 1 shows an isometric view of the bracket 20 and back member 50 secured together and further bolted 56 to a wall. This is the configuration how the two components would be engaged when they are installed on a wall. This view provides a visual of the majority of the parts to provide a basic understanding of the design. Starting with the back member 50 that is formed from a sheet metal or equivalent material. The back member 50 is formed in an elongated shape from 12 inches or less to eight feet or more depending upon the installation. In the preferred embodiment for holding a flat panel monitor or television the back member is about 26 inches in length. This length is determined based upon the size of what is being supported. In the preferred embodiment the length allows the back member 70 to be disposed entirely behind the object being supported.
[0020] The back member has two parallel sections including a wall mounting section 53 and an upper tab 51 . While these sections are identified as parallel it is contemplated that there could be some angular relationship between them based upon a desired engagement with the bracket 20 . A horizontal bend section 52 joins the wall mounting section 53 and an upper tab 51 . The wall mounting section 53 has a plurality of holes or elongated slots 55 for placement of screws or bolts 56 to mount the back member to a wall 49 . In the preferred embodiment these slots 55 are located and configured for placement of the bolt(s) 56 into wall studs in a home or building. On the outside ends of the upper tab a side stop 54 is deformed from the upper tab 51 to prevent the bracket 20 from being slid off the end of the back member 50 .
[0021] The bracket 20 is also an elongated member that is made from sheet metal or equivalent material. The bracket is essentially an L bracket with a foot formed to make a wall contact tab 25 that is connected to a bottom bend 24 that is bend from the monitor mounting side 21 of the bracket. The L bracket has a monitor mounting side 21 where a monitor television cabinet, board or other item would be secures and a angled slot side 22 for mounting the bracket 20 onto the back member 50 . The monitor mounting side 21 has one or more holes 23 for hardware such as screws bolt or the like that go through the hole(s) 23 and into the device that is being hung. The angled slot 27 secures the bracket 20 onto the back member. Detailed description and images of the interface between the angled hook and the back member are found in FIGS. 2A-2D , 4 , 5 and 6 . Vertical stop 26 on the bracket 20 makes contact with the horizontal bend 52 of the back member to block, or lock, vertical motion or lifting of the bracket from dislodging the bracket 20 from the back member 50 .
[0022] FIG. 2A-2D shows the bracket 20 being engaged on the back member 50 . These figures, starting from FIG. 2A and continuing through FIG. 2D , show the installation and locking of the bracket 20 onto the back member 50 using motion only from above the back member down. Note not all item numbers appear in each figure and some figures will have item numbers that are not identified and described with each figure.
[0023] In FIG. 2A the bracket 20 is located above the back member 50 . The head radius 28 is near or in contact with the wall 49 as the bracket is moved downward 70 . As the bracket 20 makes contact with the upper tab 51 of the back member 50 the bracket will ride over the top of the upper tab as shown in FIG. 2B .
[0024] From FIG. 2B the bracket 20 has moved down where the upper tab is being engaged into the angled slot 27 . The angled slot forms an angle of between 15 and 45 degrees and is preferably between 25 and 35 degrees. In the preferred embodiment the angle is 30 degrees. The nose radius 31 guides the angled slot 27 onto the upper tab 51 . There is a narrow angle of engagement of the upper tab and the angled slot to ensure proper engagement and locking to the bracket 20 and the back member 50 . The angle of engagement is shown and described in more detail in FIG. 4 . The downward motion 70 continues until the nose radius 31 makes contact with the back bar vertical stop 57 as shown in FIG. 2C .
[0025] In FIG. 2C the downward motion of the bracket 20 has essentially stopped because the nose radius 31 of the bracket 20 is in contact with the back bar vertical stop 57 . The bracket 20 is now rotated 71 in the vertical slot 29 until the bracket 20 is in a vertical orientation as shown in FIG. 2D .
[0026] In FIG. 2D the bracket is in vertical orientation with the upper tab 51 engaged in the vertical slot 29 . The wall contact tab 25 (not shown) prevents additional rotation 71 of the bracket 20 beyond vertical. A clearance notch 30 provides clearance for a bolt 56 (not shown) that secures the back member. The side stop 54 prevents the bracket 20 from being slid off the end of the back member 50 because the material at the angled slot 27 will make contact with the side stop 54 . Once the bracket 20 and the back member 50 are engaged as shown in FIG. 2D vertical motion 72 is prevented because the vertical stop 26 is essentially in contact with the back bar vertical stop 57 . The only way to remove the bracket 20 is to rotate the bracket to align the angled slot 27 with the upper tab 51 .
[0027] FIG. 3 shows the bracket 20 and back member 50 mounted with a flat panel monitor or television 80 . This is a typical installation where first the brackets 20 are screwed or bolted 81 into the back of a television or monitor 80 . While other clamping, bonding or securing methods are contemplated the result is essentially the same to secure a cabinet, board or other object to the bracket(s) 20 . The back member 80 is shown secured to a wall using screws bolts 56 or similar hardware. The wall contact tabs 25 on the brackets 20 maintain the flat panel monitor or television 80 a vertical orientation and further provide an air gap for cooling of the flat panel monitor or television.
[0028] FIG. 4 shows the engagement angle of the bracket 20 . The bracket 20 has a narrow opening 32 for engagement onto the back member 50 (not shown). The narrow opening allows for a limited angle 82 where the two parts engage. This limited angle 82 is fairly naturally found (as shown and described in FIG. 2A-2D ) as the bracket 20 is moved along a wall 49 since there is only a limited space 33 between the wall 49 and the angled slot 27 . The gap between the angled slot 27 and the horizontal stop 26 is typically less than three times the thickness of the vertically elongated upper lip or upper tab 51 on the back member 50 .
[0029] FIG. 5 is a detailed view of the engagement portion of the bracket 20 and the back member 50 . This detailed view shows the upper tab 51 seated in the vertical slot 29 . From this view it is clear that vertical lifting of the bracket 20 will prevent removal of the bracket 20 from the back member 50 because the vertical stop 26 on the bracket is essentially in contact with the back bar vertical stop 57 that essentially locks the bracket 20 in position from accidental disengagement. The side stop 54 is shown to provide clarity how it prevents the bracket 20 from being slid off the end of the back member 50 . The clearance notch 30 is shown to provide clearance to a screw or bolt that secures the back member onto a wall as shown in more detail in FIG. 6 .
[0030] FIG. 6 is a side view of the bracket 20 on the back member 50 . In this figure the back member 50 is bolted 58 to a wall 49 the head 56 of the bolt 58 is visible with clearance from the bracket that is provided from clearance notch 30 . Bolts or screws 81 pass through the bracket 20 and enter into the object being mounted (not shown). The wall contact tabs 25 on the brackets 20 prevents rotation of the bracket and maintains the bracket 20 in a vertical orientation and may further provide an air gap or path. The vertical stop 26 on the bracket is essentially in contact with the back bar vertical stop 57 that essentially locks the bracket 20 in position from accidental disengagement. Spacer(s) 83 can be used on the screws or bolts 81 to change the angular relationship of a mounted object.
[0031] Another contemplated embodiment would use only one bracket 20 on a back member 50 that utilizes one or more similar angled hook(s) to secure the object to a wall. Another contemplated embodiment uses an angled bracket or spacer to angle the flat panel monitor or television.
[0032] Thus, specific embodiments of a wall mounting bracket have been disclosed. It should be apparent, however, to those skilled in the art that many more modifications besides those described are possible without departing from the inventive concepts herein. The inventive subject matter, therefore, is not to be restricted except in the spirit of the appended claims. | Improvements in a wall mount bracket are disclosed. The bracket works with flat panel televisions, monitors, signs and boards. An elongated back member is secured to a wall. The back member has a single vertical tang. One or more brackets have an angled slot that engages onto the tang. Once engaged the bracket is rotated to a vertical orientation. In the vertical orientation a ledge on the angled slot prevents the bracket from being lifted off the back member unless the bracket is rotated to align the angled slot with the tang. The back member further has bent tabs to prevent the bracket from being slid horizontally off the back member. The entire placement and locking of the bracket and the back member is performed from a top to bottom motion. | 5 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of International Application No. PCT/ES03/000357, filed Jul. 11, 2003, and the disclosure of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] The invention is related to obtaining the R(−)- and S(+)-5-[2-[[2-(2-ethoxyphenoxy)ethyl]amino]propyl]-2-methoxybenzenesulfonamide enantiomers, with a high degree of optical purity, by means of the separation of the diastereoisomeric salts which are formed from a mixture containing said enantiomers with an optically active acid, as well as to the development of a method which allows determining the degree of optical purity of said enantiomers once they are separated.
[0003] European patent EP 34432 discloses sulfamoyl-substituted phenethylamine derivatives exhibiting α-adrenergic blocking activity, useful as antihypertensive agents suitable for the treatment of congestive heart failure. Among said compounds is 5-[2-[[2-(2-ethoxyphenoxy)ethyl]amino]propyl]-2-methoxybenzenesulfonamide (I),
one of the enantiomers of which, specifically the R(−)- enantiomer, known as Tamsulosin, is useful in the treatment of congestive heart failure and benign prostatic hypertrophy.
[0005] Prior studies have proven that the pharmacological action of the R(−)-5-[2-[[2-(2-ethoxyphenoxy)ethyl]amino]propyl]-2-methoxybenzenesulfonamide enantiomer, hereinafter R(−)-I, is up to 320 times greater than that of its S(+)-5-[2-[[2-(2-ethoxyphenoxy)ethyl]amino]propyl]-2-methoxybenzenesulfonamide enantiomer, hereinafter S(+)-I [Honda, K., Nakagawa, Ch., Terai, M., Naunyn - Schimiedeberg's Arch. Pharmacol. (1987), 336(3): 295-302; Honda, K., Nakagawa, Ch., Momose, N., J. Pharm. Pharmacol. (1987), 39(4): 316-18]. Therefore, it is necessary to obtain the optically pure R(−)-I enantiomer substantially free of the S(+)-I enantiomer. It is also necessary to have an industrial process for the production of the R(−)-I enantiomer.
[0006] European patent EP 34432 discloses a process for the preparation of said compound of formula (I) although it does not disclose the obtainment of its optical isomers.
[0007] U.S. Pat. No. 4,731,478 discloses in its examples a process for obtaining the R(−)-I and S(+)-I enantiomers from the condensation of R(−)- or S(+)-5-[(2-amino-2-methyl)ethyl]-2-methoxybenzenesulfonamide with 2-(o-ethoxyphenoxy)ethyl bromide.
[0008] European patents EP 257787 and EP 380144 disclose a process for obtaining the R(−)-I enantiomer from the synthesis of the R(−)-5-((2-amino-2-methyl)ethyl)-2-methoxybenzene-sulfonamide chiral amine, in its optically pure form, and later condensation reaction by reductive amination or by nucleophilic substitution.
[0009] Until now, however, no reference has been found in the literature regarding methods for the resolution of compound (I).
BRIEF SUMMARY OF THE INVENTION
[0010] The invention confronts the problem of providing an alternative process for obtaining the R(−)-I enantiomer, with high optical purity, useful for use as a drug, susceptible to being applied at an industrial level.
[0011] The solution provided by this invention is based on the fact that the inventors have observed that some optically active organic acids are capable of forming, with the R(−)-I and S(+)-I enantiomers, diastereoisomeric salts of different solubility in the reaction medium, which allows their separation by crystallization. By letting the mixture of said diastereoisomeric salts crystallize in the reaction medium or in a suitable solvent, because of their different solubility, the crystals formed will be enriched in one of the diastereoisomeric salts and, accordingly, in one of the enantiomers, preferably in the R(−)-I enantiomer. The separation of the diastereoisomeric salts and their subsequent release yields the R(−)-I enantiomer with a high degree of optical purity, susceptible to being used as a drug.
[0012] The invention also provides a solution to the problem of quantitatively determining the optical purity of said R(−)-I, S(+)-I enantiomers or of their mixtures, which is based on derivatizing said enantiomers with (−)-menthyl chloroformate and analyzing the corresponding diastereoisomeric carbamates obtained by means of high performance liquid chromatography (HPLC).
[0013] Therefore, in one aspect, the invention is related to a process for separating the R(−)-I enantiomer or the S(+)-I enantiomer from a mixture containing said enantiomers, comprising (i) placing said enantiomer mixture in contact, in a solvent, with an optically active organic acid to form diastereoisomeric salts with said enantiomers, wherein said diastereoisomeric salts have different solubility in said solvent and can be separated by crystallization, (ii) separating the diastereoisomeric salt mixture enriched in the diastereoisomeric salt of one of the enantiomers, and (iii) releasing the previously separated diastereoisomeric salt mixture to obtain the R(−)-I or S(+)-I enantiomer or a mixture enriched in one of them.
[0014] The process provided by this invention allows obtaining the R(−)-I enantiomer with an optical purity equal to or greater than 99% by means of successive recrystallizations or resuspensions of the mixtures of the diastereoisomeric salts to gradually enrich said mixtures in the diastereoisomeric salt of the R(−)-I enantiomer. The R(−)-I compound thus obtained can be used as an active ingredient in pharmaceutical preparations.
[0015] In another aspect, the invention is related to a diastereoisomeric salt formed by the R(−)-I enantiomer or the S(+)-I enantiomer and an enantiomer of an optically active organic acid.
[0016] In another aspect, the invention is related to a method for determining the degree of optical purity of the R(−)-I, S(+)-I enantiomers or of their mixtures, which comprises derivatizing said enantiomers with (−)-menthyl chloroformate and analyzing the diastereoisomeric carbamate derivatives obtained by means of HPLC. Said diastereoisomeric carbamate derivatives, as well as their obtainment process, constitute additional aspects of this invention.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0017] The foregoing summary, as well as the following detailed description of the invention, will be better understood when read in conjunction with the appended drawings. For the purpose of illustrating the invention, there are shown in the drawings embodiments which are presently preferred. It should be understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown.
[0018] In the drawings:
[0019] FIG. 1 is a reaction equation for separating R(−)-I and S(+)-I enantiomers from a mixture according to one embodiment of the invention;
[0020] FIG. 2 is a diagram of a process for separating enantiomers from a mixture according to an embodiment of Example 1 of the invention; and
[0021] FIG. 3 is a diagram of a process for separting enantiomers from a mixture according to an embodiment of Example 2 of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0022] In a first aspect, the invention is related to a process for separating the R(−)-I enantiomer or the S(+)-I enantiomer from a mixture containing said R(−)-I and S(+)-I enantiomers, comprising:
(a) placing a mixture containing the R(−)-I and S(+)-I enantiomers in contact, in a solvent, with an optically active organic acid to form diastereoisomeric salts with said R(−)-I and S(+)-I enantiomers, wherein said diastereoisomeric salts have different solubility in said solvent and can be separated by crystallization; (b) separating the diastereoisomeric salt mixture enriched in the R(−)-I or S(+)-I enantiomer diastereoisomeric salt formed in step (a); and (c) releasing the diastereoisomeric salt mixture separated in (b) to obtain the R(−)-I or S(+)-I enantiomer or a mixture enriched in one of them.
[0026] This process can be completely or partially repeated, a variable number of times, to obtain the desired enantiomer with greater optical purity. In this sense, the enriched diastereoisomeric salt mixture can be resuspended or recrystallized again, once or several times, in a solvent, which can be the same one used in the reaction or another suitable solvent, until reaching the desired degree of optical purity in the separated enantiomer.
[0027] The enantiomer mixture can contain said R(−)-I and S(+)-I enantiomers at any relative proportion to one another. In a particular embodiment, said enantiomer mixture is a racemic mixture. The compound of general formula (I), in its racemic form, can be obtained by means of any of the methods disclosed in the literature, for example, by means of the process disclosed in U.S. Pat. No. 4,373,106, comprising the reductive amination of 4-methoxy-3-sulfonamidephenylacetone with 2-(2-ethoxyphenoxy)ethylamine.
[0028] The process for separating the R(−)-I and S(+)-I enantiomers from a mixture containing them, by means of optical resolution, is shown in FIG. 1 .
[0029] The process for separating the R(−)-I and S(+)-I enantiomers provided by this invention begins by dissolving or suspending the mixture containing the R(−)-I and S(+)-I enantiomers in a suitable solvent. Examples of suitable solvents include water, alcohols, ketones, nitriles or mixtures thereof. In a particular embodiment, said solvent is a mixture of acetone and water.
[0030] A resolution agent is added to said solution or suspension, as shown in FIG. 1 . The resolution agent used when putting into practice the process provided by this invention is an optically active organic acid capable of forming diastereoisomeric salts with said R(−)-I and S(+)-I enantiomers, which have different solubility in a given solvent and can be separated by crystallization. For putting into practice the process provided by this invention, it is essential that the diastereoisomeric salts formed comply with the aforementioned conditions.
[0031] In a particular embodiment, said optically active organic acid is selected from the group formed by D-10-camphorsulfonic acid, L-10-camphorsulfonic acid, (−)-N-(3,5-dinitrobenzoyl)-α-phenylglycine acid and (+)-N-(3,5-dinitrobenzoyl)-α-phenylglycine acid. The preferred optically active organic acid is D-10-camphorsulfonic acid or L-10-camphorsulfonic acid.
[0032] The optically active organic acids forming diastereoisomeric salts with the R(−)-I and S(+)-I enantiomers, wherein said diastereoisomeric salts cannot be separated by crystallization (for example because they form an oil rather than crystals), such as (−)-di-p-toluyl tartaric acid, are not useful for putting into practice the process provided by the present invention [see Example 4].
[0033] The amount of optically active organic acid to be added can be from approximately 0.5 to approximately 1.5 equivalents, preferably from approximately 0.7 to 1.1 equivalents, based on the amount of R(−)-I or S(+)-I enantiomer contained in the enantiomer mixture.
[0034] For the formation of the diastereoisomeric salts between the optically active organic acid and the R(−)-I and S(+)-I enantiomers, in solution, temperatures are needed which are comprised between room temperature (generally between 15° C. and 20° C. approximately) and the reflux temperature of the solvent used. The diastereoisomeric salts formed can be separated due to their different solubility in the solvent present in the reaction medium, either by means of crystallization or resuspension. To selectively crystallize one of the diastereoisomeric salts, the temperature of the reaction medium can gradually be lowered until reaching the temperature at which the selective crystallization of one of the diastereoisomeric salts over the other salt is achieved. Alternatively, selective crystallization can be achieved by means of stirring the diastereoisomeric salt mixture for a suitable time period. Generally, the first crystals will be enriched in one of the diastereoisomeric salts, although they will contain a certain, lesser amount of the other diastereoisomeric salt. By means of successive recrystallizations or resuspensions, the diastereoisomeric salt mixture can become enriched in one of the R(−)-I or S(+)-I enantiomers up to an enantiomeric excess of 99.5%.
[0035] In a particular embodiment, the resuspension of the diastereoisomeric salts is carried out only for a suitable time period and only at a suitable temperature, without needing to recrystallize the diastereoisomeric salts by prior dissolution in the solvent used.
[0036] The separation of the diastereoisomeric salt mixture enriched in the R(−)-I or S(+)-I enantiomer can be carried out, based on their different solubility, by any conventional solid/liquid separation method, for example, by filtration. The effective separation of the diastereoisomeric salt mixture enriched in the R(−)-I or S(+)-I enantiomer in the desired degree of optical purity may require one or more recrystallizations or resuspensions of the diastereoisomeric salt mixture.
[0037] Once the diastereoisomeric salt mixture enriched in one of the R(−)-I or S(+)-I enantiomers has been separated, the corresponding product enriched in the R(−)-I enantiomer or in the S(+)-I enantiomer is released. This release can be carried out by conventional methods, for example, by means of reaction with a base, such as sodium bicarbonate, sodium hydroxide, sodium carbonate, etc.
[0038] In a particular embodiment [see Example 1], the R(−)-I enantiomer is separated by placing an R(−)-I and S(+)-I enantiomer mixture in contact with L-10-camphorsulfonic acid, as shown in FIG. 2 . The mixture of R(−)-I and S(+)-I enantiomers reacts with L-10-camphorsulfonic acid [C(−)], in a solvent (acetone/water), to form the I(+)C(−) and I(−)C(−) diastereoisomeric salts. The I(−)C(−) salt precipitates preferably over the I(+)C(−) salt, which mainly remains in the mother liquors. The precipitate obtained, mainly containing the R(−)-I enantiomer with an enantiomeric excess (ee) of up to 88%, can be resuspended in a solvent, which can be the same solvent or another suitable solvent, and is kept at a temperature comprised between room temperature and the reflux temperature, for a time period comprised between 20 and 24 hours, to give rise to a second precipitate. This new precipitate can optionally be neutralized to give rise mainly to the R(−)-I compound with an enantiomeric excess of up to 90%, or it can be resuspended again, once or several more times, in a solvent, which can be the same solvent used previously or another suitable solvent, until achieving the required optical purity, of an enantiomeric excess of up to 99%. The S(+)-I enantiomer can be similarly separated, but using D-10-camphorsulfonic acid in this case.
[0039] In another particular embodiment, the R(−)-I enantiomer is separated by reacting a racemic mixture of R(−)-I and S(+)-I with (−)-N-(3,5-dinitrobenzoyl)-α-phenylglycine acid in acetonitrile/water [see Example 3].
[0040] The process for separating the R(−)-I and S(+)-I enantiomers provided by this invention can also be carried out, if so desired, by means of the alternating and separate use of two different optically active organic acids capable of forming diastereoisomeric salts with said R(−)-I and S(+)-I enantiomers, wherein said salts have different solubility in a given solvent and can be separated by crystallization. Said particular embodiment comprises:
(a) placing an R(−)-I and S(+)-I enantiomer mixture in contact, in a solvent, with a first optically active organic acid to form diastereoisomeric salts with said R(−)-I and S(+)-I enantiomers, wherein said diastereoisomeric salts have different solubility in said solvent and can be separated by crystallization, under conditions allowing the formation of a first precipitate; (b) separating said first precipitate from the mother liquors, said mother liquors mainly containing one of said diastereoisomeric salts formed in step (a), either the R(−)-I enantiomer or the S(+)-I enantiomer, and isolating the diastereoisomeric salt mixture enriched in the R(−)-I or S(+)-I enantiomer contained in said mother liquors; (c) releasing the R(−)-I and S(+)-I enantiomers present in the diastereoisomeric salt mixture enriched in the R(−)-I or S(+)-I enantiomer, isolated from the mother liquors in step (b), by cleavage of said diastereoisomeric salts, generating a medium comprising a mixture of the R(−)-I or S(+)-I enantiomers enriched in one of said enantiomers, and said first optically active organic acid; (d) removing said first optically active organic acid from the reaction medium; (e) placing said enantiomer mixture enriched in R(−)-I or S(+)-I obtained in step (c), substantially free of said first optically active organic acid, in contact, in a solvent, with a second optically active organic acid, different from the optically active organic acid used in step (a), to form the corresponding diastereoisomeric salts of said R(−)-I or S(+)-I enantiomers with said second optically active acid, wherein said diastereoisomeric salts have different solubility in said solvent and can be separated by crystallization, under conditions allowing the formation of a second precipitate and where the salt corresponding to the majority R(−)-I or S(+)-I enantiomer preferably precipitates in the reaction medium; (f) separating said second precipitate formed in step (e) from the mother liquors, said second precipitate containing a mixture of the diastereoisomeric salts formed in step (e) enriched in the diastereoisomeric salt corresponding to the majority R(−)-I or S(+)-I enantiomer, and (g) releasing the precipitated diastereoisomeric salts, enriched in the R(−)-I or S(+)-I enantiomer, to obtain the enantiomer mixture enriched in the R(−)-I or S(+)-I enantiomer.
[0048] The two different optically active organic acids used in steps (a) and (e) are chosen such that the one used in step (a) forms a diastereoisomeric salt with one of the R(−)-I or S(+)-I enantiomers, for example, with the S(+)-I enantiomer, which is less soluble then that of the other enantiomer, such that mainly the diastereoisomeric salt of said enantiomer precipitates, and the optically active organic acid used in step (e) is chosen such that it forms a diastereoisomeric salt with the other one of the enantiomers, R(−)-I or S(+)-I, in this case with the less soluble R(−)-I enantiomer, such that mainly the diastereoisomeric salt of said second enantiomer precipitates. The person skilled in the art will understand that, in accordance with the invention, multiple combinations can be made with the objective of separating the desired enantiomer.
[0049] The optically active organic acids which can be used in steps (a) and (e) can be any of those acids forming diastereoisomeric salts complying with the different, previously mentioned solubility and separation by crystallization conditions. In a particular embodiment, the optically active organic acids used in steps (a) and (e) are the different enantiomers of an optically active organic acid, for example the D- and L- enantiomers of 10-camphorsulfonic acid, or the (+) or (−) enantiomers of N-(3,5-dinitrobenzoyl)-α-phenylglycine acid. In another particular embodiment, the optically active organic acids used in steps (a) and (e) are particular enantiomers of different optically active organic acids, for example, D-10-camphorsulfonic acid can be used in step (a) and (−)-N-(3,5-dinitrobenzoyl)-α-phenylglycine acid can be used in step (e).
[0050] By means of the cleavage of the diastereoisomeric salts [step (c)] by conventional methods, on one hand, a mixture enriched in the R(−)-I and S(+)-I enantiomers and, on the other hand, said first optically active organic acid used in step (a), which must be removed from the reaction medium so that it does not interfere in step (e) in the formation of diastereoisomeric salts with the second optically active organic acid, are released into the reaction medium. The removal of said first optically active organic acid can be carried out by conventional methods, for example by extraction and separation of phases, depending on the nature thereof.
[0051] If so desired, to obtain a greater optical purity, said second precipitate separated in step (f) can be resuspended, in a solvent, which can be the same solvent as the one used in step (e) or another, different solvent, once or several times, to give rise to a new precipitate comprising a diastereoisomeric salt mixture even more enriched in one of the R(−)-I or S(+)-I enantiomers, for its later release.
[0052] In a particular embodiment [see Example 2], briefly represented in FIG. 3 , said first optically active organic acid is D-10-camphorsulfonic acid [C(+)] and the second one is L-10-camphorsulfonic acid [C(−)]. The D-10-camphorsulfonic acid [C(+)] is reacted in an acetone/water mixture (solvent) with a racemic mixture of R(−)-I and S(+)-I, to form the I(+)C(+) and I(−)C(+) diastereoisomeric salts, the I(+)C(+) salt precipitating preferably over the I(−)C(+) salt. The resulting mother liquors, enriched in the I(−)C(+) salt, are concentrated to dryness and the residue obtained is dissolved in a non-miscible solvent/water mixture, it is neutralized with a suitable base, such as sodium bicarbonate, to yield an enantiomer mixture mainly containing the R(−)-I enantiomer [I(−) in FIG. 3 ]. The second optically active organic acid [C(−)] is added to the resulting product to form the I(−)C(−) and I(+)C(−) diastereoisomeric salts, the I(−)C(−) salt precipitating preferably over the I(+)C(−) salt. This second precipitate thus obtained can be neutralized again with a suitable base, such as sodium bicarbonate, to yield an enantiomer mixture mainly containing the R(−)-I enantiomer with an enantiomeric excess of 90%, or, alternatively, said second precipitate can be resuspended in a solvent (which can be the same solvent previously used or another suitable solvent) at a temperature comprised between room temperature and the reflux temperature of the solvent, for a time period comprised between 20 and 24 hours, to give rise to a new precipitate, which is either neutralized to mainly yield the R(−)-I enantiomer with a high degree of optical purity, for example with an enantiomeric excess of approximately 99%, or said new precipitate is resuspended again, one time or more, until obtaining the R(−)-I enantiomer with the desired purity. The R(−)-I enantiomer with a very high optical purity (an enantiomeric excess of 99%) can be obtained by operating in this manner.
[0053] The S(+)-I enantiomer can be similarly obtained. To do so, L-10-camphorsulfonic acid is firstly added to the enantiomer mixture and, after isolating and neutralizing the mother liquors, D-10-camphorsulfonic acid is added.
[0054] In another aspect, the invention is related to a diastereoisomeric salt formed by the R(−)-I enantiomer or S(+)-I enantiomer and an optically active organic acid, wherein said optically active acid is capable of forming diastereoisomeric salts with said R(−)- and S(+)-I enantiomers with different solubility in a given solvent, and said diastereoisomeric salts can be separated by crystallization. In a particular embodiment, said diastereoisomeric salt is selected from:
the diastereoisomeric salt of the R(−)-5-[2-[[2-(2-ethoxyphenoxy)ethyl]amino]propyl]-2-methoxybenzenesulfonamide enantiomer and D-10-camphorsulfonic acid; the diastereoisomeric salt of the R(−)-5-[2-[[2-(2-ethoxyphenoxy)ethyl]amino]propyl]-2-methoxybenzenesulfonamide enantiomer and L-10-camphorsulfonic acid; the diastereoisomeric salt of the S(+)-5-[2-[[2-(2-ethoxyphenoxy)ethyl]amino]propyl]-2-methoxybenzenesulfonamide enantiomer and D-10-camphorsulfonic acid; the diastereoisomeric salt of the S(+)-5-[2-[[2-(2-ethoxyphenoxy)ethyl]amino]propyl]-2-methoxybenzenesulfonamide enantiomer and L-10-camphorsulfonic acid; the diastereoisomeric salt of the R(−)-5-[2-[[2-(2-ethoxyphenoxy)ethyl]amino]propyl]-2-methoxybenzenesulfonamide enantiomer and (−)-N-(3,5-dinitrobenzoyl)-α-phenylglycine; the diastereoisomeric salt of the R(−)-5-[2-[[2-(2-ethoxyphenoxy)ethyl]amino]propyl]-2-methoxybenzenesulfonamide enantiomer and (+)-N-(3,5-dinitrobenzoyl)-α-phenylglycine; the diastereoisomeric salt of the S(+)-5-[2-[[2-(2-ethoxyphenoxy)ethyl]amino]propyl]-2-methoxybenzenesulfonamide enantiomer and (−)-N-(3,5-dinitrobenzoyl)-α-phenylglycine; and the diastereoisomeric salt of the S(+)-5-[2-[[2-(2-ethoxyphenoxy)ethyl]amino]propyl]-2-methoxybenzenesulfonamide enantiomer and (+)-N-(3,5-dinitrobenzoyl)-α-phenylglycine.
[0063] On the other hand, as is well known, the rotatory power described for the R(−)-I and S(+)-I enantiomers, in their hydrochloric form, is (−) or (+) 4, at a concentration of c=0.35, using methanol as a solvent [Merck Index, Edition XII, item number 9217]. This rotatory power value is too low to allow quantitatively establishing the optical purity of each one of the enantiomers in a reliable manner.
[0064] For this reason, a method has been developed which allows differentiating the R(−)-I or S(+)-I enantiomers by means of their derivatization using (−)-menthyl chloroformate to form the corresponding diastereoisomeric carbamates, which are susceptible to being analyzed by conventional analytical techniques, for example, by BPLC.
[0065] Therefore, in another aspect, the invention is related to a method for determining the degree of optical purity of a composition comprising the R(−)-I enantiomer or the S(+)-I enantiomer, or mixtures of both enantiomers, comprising:
reacting a sample of said composition to be analyzed with (−)-menthyl chloroformate to obtain the corresponding diastereoisomeric carbamate derivatives, and analyzing the diastereoisomeric carbamate derivates obtained in step a) by means of HPLC.
[0068] The reaction between the R(−)-I and/or S(+)-I enantiomers with (−)-menthyl chloroformate is carried out in a solvent, in the presence of a base, to obtain the corresponding diastereoisomeric carbamate derivatives. In a particular embodiment, the reaction between said R(−)-I and/or S(+)-I enantiomers with (−)-menthyl chloroformate is carried out in a halogenated solvent, for example dichloromethane, in the presence of diisopropylethylamine, at room temperature, to form the corresponding diastereoisomeric carbamate derivatives.
[0069] The diastereoisomeric carbamates obtained are isolated and analyzed by HPLC. In a particular embodiment, said derivatives are analyzed using a Novapack® C-18 column and an acetonitrile/water mixture as an eluent. The diastereoisomeric carbamate derivatives of the R(−)-I and/or S(+)-I enantiomers formed appear as 2 peaks at 210 nm in the chromatograph and their area ratio allows determining the proportion of each one of the enantiomers in the composition to be analyzed. In this manner, and according to the present invention, the optical purity of compositions comprising the R(−)-I and/or S(+)-I enantiomers can be determined.
[0070] In another aspect, the invention refers to the two carbamate derivatives, diastereoisomeric to one another, represented by formulas II and III:
[0071] Said diastereoisomeric carbamate derivatives of formulas II and III correspond to the compounds obtained when reacting each one of the R(−)-I or S(+)-I enantiomers with (−)-menthyl chloroformate to give the compounds of formulas II or III respectively.
[0072] In another aspect, the invention is related to a process for obtaining diastereoisomeric carbamate derivatives which comprises reacting the R(−)-I enantiomer or the S(+)-I enantiomer with (−)-menthyl chloroformate, in a solvent, in the presence of a base. The solvent and the base can be any suitable solvent and base. In a particular embodiment, said solvent is a halogenated solvent, such as dichloromethane, and said base is an amine, such as diisopropylamine. The reaction can be carried out in a wide interval of temperatures, preferably at room temperature.
[0073] The following examples serve to illustrate the present invention and should not be considered as limiting thereof.
EXAMPLE 1
Separation of the R(−)-5-[2-[[2-(2-ethoxyphenoxy)ethyl]amino]propyl]-2-methoxybenzenesulfonamide Enantiomer [R(−)I] by Means of the Use of L-10-camphorsulfonic Acid
[0074] 36.7 g of a racemic mixture containing the R(−)-I and S(+)-I enantiomers are resuspended with stirring in 200 ml of an acetone/water mixture (80/20). Then, 23 g (1.1 equivalents) of L-10-camphorsulfonic acid are added, and it is stirred until dissolution.
[0075] The solution is seeded with the (−)L-10-camphorsulfonic-R(−)-I salt [I(−)C(−)], by means of which the solution begins to become cloudy, it is maintained with stirring at room temperature for 20-24 hours and is filtered.
[0076] The solid obtained is resuspended again in 5 volumes of acetone/water (80/20), first under reflux and then at room temperature, for 20-24 hours, and is filtered again.
[0077] The product obtained is dried to give 20.1 g of the I(−)C(−) salt, with a 35% yield.
Example 1.1
Analysis of the R(−)-I Enantiomer Optical Purity
[0078] To analyze the obtained R(−)-I enantiomer optical purity, proceed as indicated below:
[0079] 1 ml of solution saturated with NaHCO 3 in water and 1 ml of dichloromethane are added to a sample of approximately 70 mg of the product obtained in Example 1, it is stirred for 5 minutes and the phases are separated. Then, 0.5 ml of the organic phase are transferred to a test tube and 1 ml of a 0.1 M solution of diisopropylethylamine in anhydrous dichloromethane and 1 ml of a 0.1 M solution of (−)-menthyl chloroformate in the same solvent are added. The mixture is stirred for several minutes and 1 ml of water is added. The reaction can be checked by thin layer chromatography (TLC) using tetrahydrofurane (THF)/heptane/methanol (25/25/1) as an eluent. 0.4 ml of the organic phase are extracted and the solvent is vacuum removed. 5 ml of mobile phase are added, and this is analyzed by HPLC using acetonitrile (ACN)/water (65/35) as an eluent, with a flow rate of 1.0 ml/minute; detection at λ=210 nm; and with a Novapack® C-18, 3.9×150 nm column.
[0080] The solid obtained, after having been thus analyzed, shows an R(−)-I/S(+)-I enantiomer ratio of 95/5, which indicates an enantiomeric excess of 90% for R(−)-I.
[0081] The precipitated and dried salt is resuspended with stirring in 780 ml of ethyl acetate and 300 ml of 7% NaHCO 3 solution, and is heated to 40-45° C. until obtaining a solution. The phases are separated and the organic phase is washed again two times with 200 ml of water, and then a concentrated hydrochloric acid solution is added, adjusting the pH between 5 and 5.5. Then, the solvent is partially distilled at reduced pressure, to half the volume, and it is left to cool, the product precipitating as R(−)-I.HCl. Once dried, the collected product weighs 12 g (0.025 moles), obtaining an overall yield equal to 30%.
EXAMPLE 2
Separation of the R(−)-5-[2-[[2-(2-ethoxyphenoxy)ethyl]amino]propyl]-2-methoxybenzenesulfonamide Enantiomer [R(−)I] by Means of the Use of D and L-10-camphorsulfonic Acids
[0082] 46.89 g of a racemic mixture of R(−)-I and S(+)-I resuspended in 705 ml of acetone with 5% water are heated to 40-45° C., and 18.6 g (0.7 equivalents) of D-10-camphorsulfonic acid are incorporated. Once it is all dissolved under heat, it is left to cool at room temperature, seeding with the (+) salt of D-10-camphorsulfonic-S(+)-I [I(+)C(+)] acid. The suspension obtained is left to stir at room temperature for 20-24 hours and is filtered. The residue obtained from the mother liquors is resuspended in 705 ml of dichloromethane and 705 ml of 7% NaHCO 3 , and is stirred until dissolution.
[0083] After separating the phases, the organic phase is taken to residue and is replaced by 235 ml of acetone containing 20% water, to which 29.33 g (1.1 equivalents) of L-10-camphorsulfonic acid are added, stirring until dissolution.
[0084] It is seeded with the L-10-camphorsulfonic-R(−)-I (−) salt [I(−)C(−)], by means of which the solution begins to become cloudy, it is maintained with stirring at room temperature for 20-24 hours and is filtered. The solid obtained is resuspended in 5 volumes of acetone containing 20% water, it is taken to reflux for 30 minutes, it is left stirring at 20-25° C. for 20 hours, is filtered and dried to give 17.65 g (0.027 moles, 24% yield) of a white solid.
[0085] The optical purity of the R(−)-I enantiomer contained in the I(−)C(−) salt is analyzed using the process described in Example 1.1. The solid obtained shows a 99.5/0.5 ratio of the R(−)-I/S(+)-I enantiomers, which indicates a 99% enantiomeric excess for R(−)-I.
[0086] The precipitated and dried salt is resuspended with stirring in 680 ml of ethyl acetate and 255 ml of 7% NaHCO 3 solution, and is heated to 40-45° C., until obtaining a solution. The phases are separated and the organic phase is washed again two times with 170 ml of water, and then, a concentrated hydrochloric acid solution is added, adjusting the pH between 5 and 5.5. The solvent is partially distilled under reduced pressure, to half the volume, and is left to cool, the product precipitating as R(−)-I.HCl. Once dried, the collected product weighs 11.5 g (0.025 moles), an overall yield of 22% being obtained.
EXAMPLE 3
Separation of the R(−)-5-[2-[[2-(2-ethoxyphenoxy)ethyl]amino]propyl]-2-methoxybenzenesulfonamide Enantiomer [R(−)I] by Means of the Use of(−)-N-(3,5-dinitrobenzoyl)-α-phenylglycine Acid
[0087] 10 g of a racemic mixture of the R(−)-I and S(+)-I enantiomers resuspended in 300 ml of acetonitrile with 20% water are heated until dissolution, and 4.2 g (0.5 equivalents) of (−)-N-(3,5-dinitrobenzoyl)-α-phenylglycine acid are incorporated. The solution formed is slowly cooled to room temperature and is left stirring for 20-25 hours.
[0088] The solid formed is isolated and is subjected to analysis, using (−)-menthyl chloroformate, using the method described in Example 1.1, giving rise to an R(−)-I/S(+)-I mixture (86/14). The yield obtained is 5.8 g of the salt formed.
EXAMPLE 4
Separation of Racemic Mixture of 5-[2-[[2-(2-ethoxyphenoxy)ethyl]amino]propyl]-2-methoxybenzenesulfonamide with (−)-di-p-toluyl Tartaric Acid
[0089] 10 g of a racemic mixture of the R(−)-I and S(+)-I enantiomers resuspended in 50 ml of a 5% mixture of n-propanol are heated until dissolution, and 9.46 g (1 equivalent) of (−)-di-p-toluyl tartaric acid are incorporated. The solution formed is slowly cooled to room temperature and is left stirring for 20-25 hours.
[0090] Well formed crystals precipitate, which are isolated by filtration. The salt obtained is neutralized in an ethyl acetate and sodium hydroxide mixture to isolate the resulting base.
[0091] The rotatory power of the product obtained is measured at a concentration of c=0.35 in methanol, obtaining a value of practically 0, which indicates that neither of the two [R(−)-I] or [S(+)-I] enantiomers has been selectively isolated.
[0092] Later recrystallizations or the use of other solvents: methanol, acetone, acetonitrile, ethyl acetate, butanol or isopropanol, or their mixtures with water, resulted in the precipitation of the diastereoisomeric salts, such as a gum, or such as a precipitate in which the diastereoisomeric salts obtained are at 50% [once released, the base has rotatory power of zero or practically zero].
[0093] It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but it is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims. | The process for separating the R(−)- and S(+)-5-[2-[[2-(2-ethoxyphenoxy)ethyl]amino]propyl]-2-methoxybenzene-sulfonamide enantiomers comprises (a) reacting a mixture of said enantiomers with an optically active organic acid to form diastereoisomeric salts with said enantiomers, where in said diastereoisomeric salts have different solubility and can be separated by crystallization; (b) separating the diastereoisomeric salt mixture enriched in the salt of one of the enantiomers; and (c) releasing said salts to obtain the R(−)or S(+) enantiomer. The R(−)-5-[2-[[2-(2-ethoxyphenoxy) ethyl]amino]propyl]-2-methoxybenzenesulfonamide enantiomer has α-adrenergic blocking activity and is useful as an antihypertensive agent suitable for the treatment of congestive heart failure and benign prostatic hypertrophy. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method of measuring a hematocrit value of the blood, and separately sampling the plasma (or serum) and the blood cells (or blood clots), after separating blood into plasma and blood cells.
2. Description of the Related Art
The hematocrit value (to be referred to as an Ht value hereinafter) means a volume ratio of a blood cell component in blood. In general, the Ht value is represented by a ratio of a height of a settled blood cell component with respect to a total height of blood in a glass tube in which blood added with an anticoagulant is separated into a plasma component and a blood cell component. This value is an effective scale for checking whether blood is normal. Therefore, the Ht value is not only effective data for checking a human health condition but also essential data for checking whether blood is transfusable to patients. For this reason. Ht value measurement of blood from a donor is always performed upon blood transfusion. Separated plasma and blood cell components are sampled from a blood sample subjected to the Ht value measurement and used in various pathologic and compatibility tests.
The Ht value must be measured to assure safety of both a blood donor and a blood acceptor. For example, if the Ht value of a donor's blood is lower than a predetermined level, blood collection may cause anemia. Therefore, if the Ht value is significantly low, blood collection must be avoided. On the other hand, if the Ht value is abnormally high or low, an influence on a blood acceptor cannot be also neglected. Therefore, any use of such blood must be made very carefully or avoided in some cases.
The following methods and apparatus for measuring an Ht value and separately sampling a plasma component have been conventionally known.
An Ht measuring method is disclosed in Japanese Patent Disclosure (Kokai) No. 60-93348. In this method, blood added with an anticoagulant is centrifugally separated in a glass capillary and irradiated with collimated light, and the amount of light transmitted through the capillary is measured by a plurality of light-receiving elements. A transmitted light amount at a plasma portion is naturally larger than that at a blood cell portion. Therefore, the lengths of the plasma and blood cell portions are determined in accordance with a transmitted light amount detected by each light-receiving element, and the Ht value is calculated on the basis of the determined lengths and output to a suitable display unit such as a printer.
An apparatus for sampling a serum component is disclosed in Japanese Patent Disclosure (Kokai) No. 62-269037. By using this apparatus, serum can be separately sampled in an efficient manner from blood having a known Ht value as follows. That is, blood is separated into serum and blood clots in a collection tube. A suction nozzle located at a predetermined height from the bottom surface cf the blood collection tube is gradually descended at a predetermined rate. When the distal end of the suction nozzle reaches the surface of the serum layer, the serum is sucked from the suction nozzle and flowed through a duct connected to the nozzle. The duct includes a detection electrode. When the electrode detects a flow of the serum, it is determined that the suction nozzle reaches the serum surface. Therefore, by calculating a descent distance in accordance with a descent rate of the nozzle and a time interval from a timing at which the suction nozzle starts descent to a timing at which a detection signal is obtained, the height of the serum surface can be obtained. By multiplying the height of the serum surface by the known Ht value, the bottom surface height of a serum layer can be obtained. As a result, a descent distance of the suction nozzle can be determined, and the serum can be separately sampled efficiently.
The above conventional techniques have the following drawbacks.
That is, in both of the above conventional techniques, only either Ht value measurement or serum sampling can be performed. Therefore, since Ht measurement and serum sampling must be independently performed, a considerably long time is required.
SUMMARY OF THE INVENTION
It is a first object of the present invention to provide a method capable of simultaneously performing Ht value measurement of a blood sample which is separated into two blood components in a predetermined vessel, and of sampling each blood component.
It is a second object of the present invention to provide a method capable of easily discriminating each blood component sampled from blood which has an abnormal Ht value.
Note that in this specification, the term "blood component" is taken to mean plasma (or serum) and blood cells (or blood clots) separated in a sample vessel by centrifugal separation or the like. In addition, a first component means the plasma (or serum) separated as a supernatant liquid of the two components, and a second component means the blood cells (or blood clots) settled downward.
The above first object of the present invention is achieved by a method of performing measurement of a hematocrit value and separate sampling of blood components, comprising the steps of:
lowering a probe from a predetermined initial height into a predetermined sample vessel containing a blood sample separated into a first component layer as an upper layer and a second component layer as a lower layer, the probe being integrally formed with a liquid surface detection electrode and a suction nozzle;
monitoring a descent distance upon descent of the probe;
generating a first liquid surface detection signal from the liquid surface detection electrode when a distal end of the probe reaches a liquid surface of the first component layer;
sampling a predetermined amount of the first component into separate sampling vessel means through the suction nozzle of the probe in response to the first liquid surface detection signal;
generating a second liquid surface detection signal from the liquid surface detection electrode when the distal end of the probe reaches a liquid surface of the second component layer;
sampling a predetermined amount of the second component into the separate sampling vessel means through the suction nozzle of the probe in response to the second liquid surface detection signal;
calculating liquid surface heights of the first and second component layers on the basis of the initial height of the probe, the monitored descent distance of the probe, and the first and second liquid surface detection signals; and
calculating a total volume of the blood sample and a volume of the second component on the basis of the liquid surface heights of the first and second component layers, and calculating a hematocrit value from the volumes.
Preferably, the method of the present invention further comprises the step of:
comparing the calculated hematocrit value with a normal hematocrit value to check whether the sample blood is normal.
More preferably, the method of the present invention further comprises the step of:
applying an identification mark on one of the separate sampling vessel means or the sample vessel when the blood sample is determined to be abnormal.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic view showing an overall arrangement of an apparatus for carrying out a method of the present invention;
FIG. 2 is a perspective view showing a detection electrode and a drive unit of a suction/discharging means of the apparatus shown in FIG. 1;
FIG. 3A is a enlarged view showing one probe of the apparatus shown in FIG. 1; and
FIG. 3B is a sectional view showing another probe and the detection electrode of the apparatus shown in FIG. 1.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 is a schematic view showing an overall apparatus used for carrying out a method of the present invention, and FIG. 2 is a perspective view showing a main part of the apparatus. Referring to FIG. 1, reference numeral 1 denotes a sample vessel having a predetermined size and shape. The sample vessel 1 contains a blood sample added with an anticoagulant. The blood sample is separated into plasma 2 and blood cells 3 by centrifugal separation. As shown in FIG. 2, the vessel 1 is housed in a cassette 13 and held at a predetermined height. The cassette 13 is conveyed by a conveyor means (not shown) in an arrow direction at a predetermined pitch.
Two probes 6a and 6b are arranged parallel to each other above the vessel 1. The probes 6a and 6b descend to enter into the vessel 1 and are fixed to a drive unit 8. The drive unit 8 can vertically move. Especially upon measurement, the unit 8 descends at a predetermined rate to move the probes 6a and 6b downward at a predetermined rate. Detection electrodes 4 extend from lower ends of the probes 6a and 6b, respectively. When the probes 6a and 6b descend, the electrodes 4 are brought into contact with the surfaces of the blood components 2 and 3 and detect the surfaces. An initial height of each probe is set at a level separated upward from a bottom surface level a of the vessel 1 by a distance b.
FIG. 2 shows an arrangement of the drive unit 8 in detail. That is, the unit 8 comprises an arm 14 for fixing the probes 6a and 6b, a guide 17 for supporting the arm 14 so that the arm 14 can vertically slide, and a motor 18 for vertically sliding the arm 14 along the guide 17. The motor 18 is connected to a control means (not shown) for controlling descent of the arm 14.
FIG. 3A shows an enlarged view of the probe 6a, and FIG. 3B shows an enlarged sectional view of the probe 6b. As is apparent from FIG. 3A and B, each of the probes 6a and 6b comprises an insulative cylindrical member having a path P therein. Each detection electrode 4 comprises a cylindrical member consisting of a conductive metal. The electrode 4 is embedded in the cylindrical probe 6a (6b) throughout its entire length and projects from its distal end by a predetermined length. When the probes 6a and 6b descend and the electrodes 4 are brought into contact with the liquid surface of the plasma layer 2 or the blood cell layer 3, an impedance or the like changes between the electrodes 4, thereby detecting the liquid surface.
As shown in FIG. 2, tubes 15 are connected to proximal end portions of the probes 6a and 6b, respectively. Each tube 15 is connected to a suction means (not shown). Predetermined amounts of the plasma 2 and the blood cells 3 in the sample vessel 1 are drawn by the suction means through the paths P in the probes 6a and 6b and injected in separate sampling vessels 7 as shown in FIG. 1. Lead wires 16a are connected to the electrodes 4 at the proximal end portions of the probes 6a and 6b, respectively. The lead wires 16a are connected to a signal processor 5. With this arrangement, liquid surface detection signals ar output from the detection electrodes 4 to the signal processor 5.
A distance detector 9 is disposed at the drive unit 8 (FIG. 1) and detects a moving distance of the unit 8 (i.e., a moving distance of the probes 6a and 6b). The detector 9 is connected to the processor 5 through lead wires 16b. FIG. 2 shows an arrangement of the detector 9 in detail. Referring to FIG. 2, the detector 9 includes a slit member 19 projecting from the side surface of the arm 14 and descending together with the arm 14. A large number of slits are formed in the slit member 19 at predetermined intervals. A photoelectric detector 20 is arranged to sandwich the slit member 19. The detector 20 is fixed to a housing and therefore does not move even when the arm 14 descends. A light source of the detector 20 is located at a portion extending above one side surface of the slit member 19. A light-receiving element for the light source is located at a portion extending above the other side surface of the slit member 19 so as to oppose the light source. Therefore, when the arm 14 descends, the slit member 19 descends between these portions of the detector 20, and the light-receiving element detects light from the light source each time a slit of the member 19 passes through a detection portion. Since the slits are formed at predetermined intervals, the number of detection times corresponds to a descent distance of the arm 14.
On the basis of a descent distance signal supplied from the distance detector 9 and liquid surface detection signals supplied from the detection electrodes 4, the signal processor 5 calculates descent distances x and y required for electrodes 4 to detect the liquid surfaces of the plasma 2 and the blood cells 3, respectively. The signals x and y are output from the processor 5 to an arithmetic unit 10.
The arithmetic unit 10 calculates liquid surface heights c=b-x and d=b-y of the plasma and blood cell layers 2 and 3, respectively, in accordance with the signals x and y and the initial height b of the electrodes 4. In addition, the unit 10 calculates a volume (V 1 ) of the sample vessel 1 corresponding to the liquid surface height c and a volume (V 2 ) thereof corresponding to the liquid surface height d, thereby calculating an Ht value from V 2 /V 1 .
The Ht value calculated as described above is output from the arithmetic unit 10 to a determination unit 11. The unit 11 stores normal Ht value ranges of male and female subjects. The unit 11 checks whether the Ht value supplied from the arithmetic unit 10 falls within the normal range. The unit 11 is connected to a marking unit 12 and outputs a determination result thereto.
The marking unit 12 comprises a marking means (not shown). In response to the signal from the determination unit 11, the marking means marks a predetermined number, symbol or the like on the separate sampling vessels 7 in which the blood component in the sample vessel 1 is injected.
An embodiment of the present invention using the above apparatus will be described below.
The cassette 13 is conveyed by the conveyor means (not shown) so that the sample vessel is stopped immediately below the probes 6a and 6b. Descent or lowering of the drive unit 8 is then started. That is, upon driving of the motor 18, the arm 14 descends along the guide 17.
At the same time, the distance detector 9 starts output of signals corresponding to descent distances of the drive unit 8. That is, since the slit member 19 descends together with the arm 14, the photoelectric detector 20 generates a distance signal pulse each time a slit of the member 19 passes through the detection portion. The signal pulses are supplied to the signal processor 5 through the lead wires 16b.
As the drive unit 8 descends as described above, the probes 6a and 6b descend at a rate equal to that of the unit 8 and enter into the sample vessel 1. When the distal ends of the probes 6a and 6b are brought into contact with the liquid surface of the plasma layer 2, the two detection electrodes 4 detect this. The descent of the drive unit 8 is stopped immediately after this liquid surface detection, and the distal ends of the probes 6a and 6b are held at a predetermined depth in the layer 2. The suction means (not shown) is activated by liquid surface detection signals. As a result, a predetermined amount of the plasma 2 is drawn by suction and injected into a corresponding one of the separate sampling vessels 7 through the probe 6a.
The liquid surface detection signals from the electrodes 4 are also supplied to the signal processor 5 through the lead wires 16a. As described above, processor 5 calculates the descent distance x required for the electrodes 4 to reach the liquid surface of the plasma layer 2. On the basis of the distance x, the arithmetic unit 10 calculates the liquid surface height c=b-x of the layer 2 as described above. In addition, the unit 10 calculates the total volume V 1 of the blood sample (a volume from the bottom surface level a to the liquid surface height c of the vessel 1).
The motor 18 is then reactivated, and the drive unit 8 restarts descent. As the probes 6a and 6b further descend, the electrodes 4 are brought into contact with the liquid surface of the blood cell layer 3 and generate liquid surface detection signals. Upon generation of these detection signals, a predetermined amount of the blood cells 3 are drawn by suction. At this time, however, the blood cells 3 are drawn by suction through the other probe 6b not used for suction of the plasma 2 and injected in the other one of the separate sampling vessels 7 which does contain not the plasma 2.
The signal processor 5 calculates the descent distance y required for the electrodes 4 to reach the liquid surface of the layer 3. On the basis of the distance y, the arithmetic unit 10 calculates the liquid surface height d=b-y of the layer 3. The unit 10 also calculates the volume V 2 of the blood cells 3 (a volume from the bottom surface level a to the liquid surface height d of the vessel 1).
The arithmetic unit 10 then calculates the Ht value of the blood sample on the basis of Ht=V 2 /V 1 . The determination unit 11 compares the calculated Ht value supplied from the unit 10 with the normal Ht value range. If the calculated value falls within the normal range, the next blood sample is measured. If the calculated value is determined to be abnormal, however, the marking unit 12 operates before measurement of the next sample. As a result, a predetermined symbol, number or the like is marked on the one of the separate sampling vessels 7 containing the blood component determined to be abnormal.
As is apparent from the above embodiment, according to the method of the present invention, upon one descent ration of the probes 6a and 6b into the sample vessel 1, separate sampling of plasma and blood cell components and measurement of an Ht value can be simultaneously performed. In addition, determination of normality of a blood sample can be performed on the basis of the measured Ht value. Also, in the above embodiment, when a blood sample is determined to be abnormal, marking means marks a symbol or the like on a separate sampling vessel in which a plasma or blood cells are injected from the sample. In this manner, normality of the separately sampled component can be easily checked. Furthermore, as is apparent from the above description, the method of the present invention can be carried out by using a relatively simple apparatus.
In the above embodiment, marking is performed for the separate sampling vessels 7 when the Ht value is abnormal. Marking, however, may be performed for the sample vessel 1.
In addition, each of the probes 6a and 6b may be obtained by coating an insulating film on a predetermined portion of the electrode 4 when formed into a probe-like shape. | A method of performing measurement of a hematocrit value and separate sampling of plasma and blood cells, simultaneously. A probe including a pair of detection electrodes each in the form of a suction nozzle, is lowered from a certain initial height into a sample vessel containing blood that has bveen separated into an upper plasma layer and a lower blood cell layer, while the probe travel distance is monitored. When the detection electrodes touch the surface of the plasma layer, the plasma is sampled into a corresponding sampling vessel through one of the electrode suction nozzles. The probe is then lowered further until the electrodes touch the surface of the blood cell layer, and the blood cells are sampled into a different sampling vessel through the other one of the suction nozzles. A total sample blood volume and the volume of the blood cells are calculated in accordance with the measured travel of the probe between the upper and lower layers, and a hematocrit value is determined from the calculated volumes. | 6 |
BACKGROUND OF THE INVENTION
The present invention relates generally to pre-hung doors and, in particular, to a kit for installing a pre-hung residential door assembly that allows for improved, easier installation of a pre-hung door assembly adjacent an opening in a residential wall.
A typical pre-hung residential door assembly includes a substantially rectangular door frame having a preferably wood door hingedly attached thereto. The door assembly is configured for attachment to walls of a rough opening formed in a residential wall, for example in a house, a garage, or the like. These pre-hung door assemblies are advantageous in that the frame and the door are pre-aligned, requiring only the frame to be attached and aligned to the rough opening and eliminating the step of aligning the orienting the door to the frame.
The following U.S. patents and published patent application are relevant to pre-hung door assemblies and/or installation of pre-hung doors, the U.S. Pat. Nos. 2,919,798, 3,301,820, 3,411,240, 3,473,265, 3,584,416, 3,599,373, 4,718,195, 4,739,561, 5,159,782, 5,365,697, 5,655,332, 6,170,198, 6,725,604, and the U.S. Patent Application No. 2004/0060241.
While pre-hung door assemblies are advantageous and eliminate the step of aligning and orienting the door to the frame, properly aligning and orienting the door assembly in the rough opening remains a difficult and often time-consuming task due in part to the weight of the door assembly and in part to the need to shim the assembly in the opening. Often, after the shims have been inserted, some or all of the shims move or fall out when the door is opened to test the fit.
It is desirable, therefore, to allow for easier and quicker installation of a pre-hung door assembly that maintains the alignment between the door frame and the door while installing the pre-hung door assembly.
SUMMARY OF THE INVENTION
The present invention concerns a kit for installing a pre-hung door assembly to a rough opening in a residential wall.
A kit for installing a door assembly including a plurality of door frame brackets adapted to be attached to a door frame and to a wall having an opening in which the door assembly is to be installed, a plurality of door brackets adapted to be attached to a door and the door frame, and a lockset bracket adapted to be attached to a lockset hole formed in an edge surface of the door and to the door frame, the door brackets and the lockset bracket being operable to fix the door in relation to the door frame and said door frame brackets being operable to fix the door assembly relative to the opening.
The kit in accordance with the present invention is adapted to engage with a pre-hung residential door assembly, which includes a substantially rectangular door frame having a preferably wood door hingedly attached thereto. The door assembly is configured for attachment to walls of a rough opening formed in a residential wall, for example in a house, a garage, or the like.
The kit in accordance with the present invention includes at least one and preferably a plurality of door frame brackets, at least one and preferably a plurality of door brackets and at least one lockset bracket. Each bracket is preferably adapted to be attached to a predetermined location on the pre-hung residential door assembly.
The kit in accordance with the present invention allows for improved, easier, and quicker installation of a door assembly and advantageously keeps the door frame and the door aligned during installation of the door assembly.
DESCRIPTION OF THE DRAWINGS
The above, as well as other advantages of the present invention will become readily apparent to those skilled in the art from the following detailed description of a preferred embodiment when considered in the light of the accompanying drawings in which:
FIG. 1 is a front elevation view of a kit in accordance with the present invention shown attached to a pre-hung door assembly;
FIG. 2 is a fragmentary perspective view of the lock area of the door shown in FIG. 1 ;
FIG. 3 is a perspective view of a door frame bracket of the kit in accordance with the present invention;
FIG. 4 is a top plan view of the door frame bracket of FIG. 3 ;
FIG. 5 is a perspective view of a door bracket of the kit in accordance with the resent invention;
FIG. 6 is a top plan view of the door bracket of FIG. 5 ; and
FIG. 7 is a perspective view of a lockset bracket of the kit in accordance with the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIG. 1 , a pre-hung door installation kit in accordance with the present invention is indicated generally at 10 . The kit 10 includes at least one and preferably a plurality of generally F-shaped door frame brackets 12 , at least one and preferably a plurality of door brackets 14 , and at least one lockset bracket 16 .
The brackets 12 , 14 , wad 16 of the kit 10 are adapted to be attached at various locations on a pre-hung door assembly 18 , best seen in FIG. 1 and discussed in more detail below. The door assembly 18 includes a substantially rectangular door frame 20 having a preferably wood door 22 hingedly attached thereto. The door assembly 18 is configured for attachment to surfaces 24 of a rough opening 26 formed in a residential building wall 28 , for example in a house, a garage, or the like. The wall 28 may be an interior wall or an exterior wall and the door assembly 18 may be configured as an interior door (with a typically wood door 22 ) or an exterior door (with a typically steel door), as will be appreciated by those skilled in the art. The door 22 includes a lockset hole 30 , best seen in FIG. 2 , formed in a side edge surface thereof Surrounding the lockset hole 30 is a generally rectangular latch plate recess 31 having a bottom surface 31 a positioned inwardly (recessed) from the side edge surface of the door 22 . The lockset hole 30 also includes a cylindrical portion 30 a that extends from the bottom surface 31 a to a door knob hole 32 formed through front and rear surfaces of the door 22 .
Referring now to FIGS. 3-4 , the kit 10 includes at least one and preferably a plurality of the generally F-shaped door frame brackets 12 . The door frame brackets 12 include a base 34 and a pair of arms 36 extending from the base 34 that are spaced apart by a predetermined distance, indicated by an arrow 38 . The predetermined distance 38 is preferably sized to provide a snug fit for the door frame bracket 12 against the frame 20 of the door assembly 18 , discussed in more detail below. The base 34 defines an elongated hole or slot 40 extending through upper and lower surfaces thereof. The hole 40 is sized to accept a fastener (not shown) or the like when the kit 10 is used to attach the door assembly 18 to the surfaces 24 of the rough opening 26 . The base 34 may also define an aperture 41 in a portion of the base 34 between the arms 36 for receiving a fastener or the like.
Referring now to FIGS. 5-6 , the kit 10 includes at least one and preferably a plurality of the door brackets 14 , which include a first generally C-shaped door-engaging portion 42 that is adapted to engage with the door 22 and a second generally L-shaped frame-engaging portion 44 extending from the first portion 42 that is adapted to engage with the door frame 20 . The first portion 42 includes a pair of arms 46 extending from a base 48 that are spaced apart by a predetermined distance, indicated by an arrow 50 . The predetermined distance 50 is preferably sized to provide a snug fit for the door bracket 14 against the peripheral surface of the door 22 of the door assembly 18 , discussed in more detail below. The second portion 44 includes an arm 52 having a first section 54 extending from the base 48 in a direction opposite the arms 46 and second bent over section 56 that defines a space, indicated by an arrow 58 , between the bent over section 56 and the base 48 . The predetermined distance 58 is preferably sized to provide a snug fit for the door bracket 14 against the frame 20 of the door assembly 18 , discussed in more detail below.
Referring now to FIG. 7 , the kit 10 includes at least one lockset bracket 16 which includes a generally U-shaped body having a pair of arms 60 extending from a base 62 that are spaced apart by a predetermined distance, indicated by an arrow 64 . The predetermined distance 64 is preferably sized to provide a snug fit for the lockset bracket 16 against the frame 20 of the door assembly 18 , discussed in more detail below. A projection 66 extends outwardly from an outer surface of one of the arms 60 . The projection 66 is adapted to engage with the walls 31 b that define the lockset hole 30 latch plate recess 31 formed in the peripheral surface of the door 22 . While illustrated as substantially U-shaped, the projection 66 may conform to the outer surface of the arm 60 wad is preferably sized to engage with the walls of the lockset hole 30 so as to prevent the door 22 from moving with respect to the door frame 20 during use of the kit 10 , discussed in more detail below.
The door frame brackets 12 , the door brackets 14 , and the at least one lockset bracket 16 are preferably formed from a plastic material by, for example, an injection molding process. A suitable plastic material for one-time use of the kit is ABS (acrylonitrile-butadiene-styrene). A suitable material for a reusable kit is glass filled nylon. Similar plastic materials also can be used. By forming the door frame brackets 12 , the door brackets 14 , and the at least one lockset bracket 16 from a plastic material, the kit 10 may be made advantageously light weight and easy to manipulate during the installation of the pre-hung door assembly 18 , discussed in more detail below. Alternatively, the door frame brackets 12 , the door brackets 14 , and the at least one lockset bracket 16 are formed from any material having suitable material strength characteristics for use in a pre-hung door installation kit 10 .
The predetermined distances 38 , 50 , and 64 may be any distance as determined by the type of door assembly 18 (such as an internal or external residential door assembly), as will be appreciated by those skilled in the art.
When ready to install the door assembly 18 , the door frame brackets 12 are engaged with the door frame 20 by placing the arms 36 of the bracket 12 on opposing sides of the frame 20 and placing the base 34 between the arms 36 into close proximity with the outer surface of the frame 20 . Preferably, the door frame brackets 12 are attached to the frame 20 of the door assembly 18 prior to placing the door assembly 18 adjacent the rough opening 26 . The door frame brackets 12 may be secured to the frame 20 by placing a fastener, such as a wood screw or the like, through the aperture 41 to ensure that the door frame brackets 12 remain in a fixed location with respect to the frame 20 during use of the kit 10 .
The door brackets 14 are engaged with the door 22 by placing the arms 46 of the first portion 42 of the bracket 12 on opposing sides of the door 22 and placing the base 48 between the arms 46 into close proximity to the peripheral surface of the door 22 . This is preferably done while the door 22 is in a position swung away from the door frame 20 . The door brackets 14 are then engaged with the door frame 22 by swinging the door 22 to a closed position and placing the second section 56 of the arm 52 and the base 48 on opposing sides of the frame 20 and placing the first section 54 of the arm 52 into close proximity with the outer surface of the frame 20 .
The lockset bracket 16 is engaged with the door 22 by placing the projection 66 of the bracket 16 into engagement with the surfaces defined by sides of the latch plate recess 31 at the lockset hole 30 on the peripheral surface of the door 22 . This is preferably done while the door 22 is in a position swung away from the door frame 20 . Preferably, the projection 66 engages with the surfaces in an interference or press-type fit. The lockset bracket 16 is then engaged with the door frame 20 by swinging the door 22 to the closed position and placing the arms 60 on opposing sides of the frame 20 and placing the base 62 into close proximity with the outer surface of the frame 20 . Preferably the door brackets 14 and the lockset bracket 16 are engaged with the door 22 and the recess 31 of the lockset hole 30 , respectively, in succession prior to swinging the door 22 to the closed position.
After the brackets 12 , 14 , and 16 are engaged with frame 20 and the door 22 of the assembly 18 , the assembly 18 is then placed adjacent the rough opening 26 . The door frame brackets 12 are then attached to the walls 28 adjacent the rough opening 26 , such as by placing a fastener such as a nail, a drywall screw, or the like (not shown) through the elongated holes 40 of the brackets 12 and extends into the walls 28 . Preferably, the fasteners are placed to allow for movement of the assembly 18 within the rough opening 26 . As seen in FIG. 1 , the brackets 12 are placed on the opposing sides (the left and right sides as seen in FIG. 1 ) of the frame 20 , which allows for horizontal adjustment of the assembly 18 with respect to the opening 26 and on the upper or top side of the frame 20 , which allows for vertical adjustment of the assembly 18 with respect to the rough opening 26 . When the fasteners are placed in the brackets 12 and extend into the walls 28 , the brackets 12 and fasteners support the weight of the assembly 18 , advantageously allowing the user of the kit 10 to more easily manipulate the assembly 18 into a desired orientation within the rough opening 26 .
While the user of the kit 10 aligns the assembly 18 with respect to the surfaces 24 and the walls 28 of the rough opening 26 , the door brackets 14 and the lockset bracket 16 maintain the relationship between the door 22 and the frame 20 while the user makes adjustments to the assembly 18 , such as leveling, aligning, and orienting the door assembly 18 with respect to the surfaces 24 and the wall 28 of the rough opening 26 including the use of shims and the like (not shown). Because the lockset hole 30 is formed in the door 22 at a predetermined location with respect to the frame 20 when the door 22 and the door frame 20 are manufactured to form the assembly 18 , the lockset bracket 16 of the kit 10 advantageously makes use of this relationship and maintains correct alignment between the door frame 20 and the door 22 during use of the kit 10 .
After the assembly 18 is aligned in a desired position, the frame 20 is fixedly attached to the surfaces 24 of the rough opening 26 such as by nailing or the like. After the assembly 18 is attached to the surfaces 24 , the kit 10 is removed, and the assembly 18 is typically framed with molding (not shown) or the like that attaches to the walls 28 and covers the exterior surface of the frame 20 of the door assembly 18 to provide a pleasing appearance as is known in the art.
In an embodiment of the kit 10 , there are seven of the door frame brackets 12 , two of the door brackets 14 and one lockset bracket 16 . Preferably during use of the kit 10 , three of the door frame brackets 12 are located on each of the sides of the frame 20 and one of the brackets is located on the top of the frame 20 . Preferably during use of the kit 10 , the door brackets 14 are located above and below the door knob hole 32 . and the lockset bracket 16 is located in the latch plate recess 31 of the lockset hole 30 .
The kit 10 in accordance with the present invention allows for improved, easier, and quicker installation of a pre-hung door assembly 18 and advantageously keeps the door frame 20 and the door 22 aligned during installation of the door assembly 18 . In addition, the kit 10 is advantageously reusable such that a plurality of pre-hung door assemblies 18 may be installed utilizing the same kit 10 , making the kit 10 particularly advantageous for finish carpenters and the like during new home construction or remodeling projects.
In accordance with the provisions of the patent statutes, the present invention has been described in what is considered to represent its preferred embodiment. However, it should be noted that the invention can be practiced otherwise than as specifically illustrated and described without departing from its spirit or scope. | An installation kit for a pre-hung door assembly having a door frame and a door. The kit comprising a plurality of door frame brackets for attaching the door frame to an opening in a wall in which the pre-hung door assembly is to be installed, a plurality of door brackets adapted to be attached to the door and to the door frame, and a lockset bracket adapted to be attached to the door and to the door frame. The door brackets and the lockset bracket being operable to fix the door in relation to the door frame and the door frame brackets being operable to fix the door assembly relative to the opening. | 4 |
FIELD OF THE INVENTION
The field of the invention relates to page table coherency in a multiprocessor computer system. More specifically, the invention relates to a method and apparatus for performing TLB shootdown operations in a multiprocessor system.
BACKGROUND OF THE INVENTION
Computer systems often employ several different memory devices that are accessible to the system microprocessor. As such, the system microprocessor typically includes one or more memory management functions for managing the various memory devices. One memory management function that is implemented within the Pentium AE Pro processor manufactured by Intel Corporation of Santa Clara, Calif., is known as paging. Paging provides a mechanism by which virtual memory addresses may be mapped into physical addresses corresponding to memory blocks, or "pages." A page of memory is set to be a fixed size, such as 4 kilobytes. Each of the pages may be stored in either a quick-access memory device, such as dynamic random access memory ("DRAM"), or on a slower-access mass storage device, such as a magnetic or optical disk.
FIG. 1 illustrates a block diagram of a prior art virtual-to-physical address translation. The virtual address 200 includes three fields that are used to translate the virtual address into a physical address within a page of memory. The directory field 202 is an index that points to an entry 211 within a page table directory 210. The page table directory entry 211 in turn points to a page table 220. Thus, there exists one page table for each entry within the page directory 210.
Once the appropriate page table 220 has been located, the table field 204 of the virtual address is used to index a particular entry 221 within the page table. This page table entry (PTE) 221 points to a page of physical memory 230. Thus, for every PTE within page table 220, there exists a page of physical memory. Using the PTE 221, the microprocessor checks to see if the page 230 is in system memory (e.g., DRAM). If not, the page is retrieved from the system disk and loaded into system memory.
Once the appropriate page of physical memory 230 has been loaded, the offset field 206 of the virtual address is used to index a particular address 231 within the page 230. Thus the physical memory address 231 is translated from the virtual address 200.
As can be appreciated from the above description, address translation may take a large number of bus cycles, degrading system performance. Thus, prior art computer systems improve performance by caching the most recently-accessed PTEs within a translation cache, or translation lookahead buffer (TLB).
FIG. 2 illustrates a block diagram of a virtual-to-physical address translation using a TLB 360. The directory field 302 of the virtual address 300 is used to look up a tag entry 311 within the TLB 360. The tag entry 311 is then compared with the table field 304 of the virtual address 300. If the tag entry 311 and the table field 304 match, the match signal 340 is asserted, indicating that the physical address translation may be performed using the TLB 360.
The physical address entry 321 and valid bit entry 331 are both associated with the tag entry 311 of the TLB 360. So long as the valid bit entry 331 indicates that the physical address 321 is valid, and there is a tag match, then the physical address 321 is used to point to a page of physical memory 350. Once the page 350 is loaded into system memory (if required), then the offset field 306 of the virtual address 300 is used to index the physical address 351 of the data within the page 350.
As was mentioned herein above, each entry of the TLB 360 includes a valid bit, e.g. valid bit 331. The valid bit 331 indicates whether or not the physical address 321 still points to the correct page of system memory 350. One situation in which the TLB entry would be invalid is where a PTE (e.g., entry 221 of FIG. 2) changes due to a modification by an operating system or software routine. In such a case, the physical address 321 within the TLB would no longer point to the correct page of memory.
One way in which an operating system or software routine may invalidate the TLB entry is by asserting the invalidate page (INVPLG) instruction, coupled with an argument that indicates the virtual address of the PTE that was changed. The INVPLG instruction is executed by first checking to see if a physical address stored in the TLB corresponds to the INVPLG argument. If found, the valid bit associated with the TLB entry is deasserted. Typically, the INVPLG instruction is a privileged instruction, such that only the most privileged software routines may assert this instruction.
For computer systems including more than one microprocessor, called "multiprocessor" systems, each microprocessor may include its own TLB. All of the microprocessors, however, may share the same physical memory. As such, the TLBs located within each of the microprocessors must be coherent with each other.
One prior art method of maintaining coherency among several caches is referred to as "snooping." Snooping is typically used to maintain coherency for data caches. Each microprocessor monitors the memory transactions performed by all of the other microprocessors, that is, it "snoops" on the other data caches to see if the memory transaction affected its cache data. While snooping is commonly used to maintain coherency in data caches, it is typically not employed for maintaining TLB coherency.
A common method of maintaining coherency among the TLBs is by performing a TLB "shootdown" operation whenever a page table entry is changed. The shootdown operation ensures that changes to a page table entry get propagated to the other microprocessors' TLBs.
One prior art way of performing a TLB shootdown operation starts with halting all microprocessors in the multiprocessor system. This maintains architectural consistency between all of the microprocessors during the shootdown operation. Once the microprocessors have been halted, a first microprocessor invalidates its own TLB by executing the INVPLG instruction. The first microprocessor then sends an interrupt to the other microprocessors. Upon receiving the interrupt, the other microprocessors invalidate their TLB entries using the INVPLG instruction. The first microprocessor waits for all of the microprocessors to complete the TLB invalidation before bringing them out of the halt state, such that they may continue executing programming instructions.
This prior art method of performing a TLB shootdown operation is time consuming, causing the microprocessors to halt operation for a relatively long time. For example, the software interrupt instruction ("INT"), accompanied with an interrupt vector ("n") is often used to communicate the shootdown to the other microprocessors. The INT instruction operates as a far call instruction. Upon receiving an interrupt instruction, the microprocessor uses the interrupt vector "n" to access a descriptor in an interrupt descriptor table (IDT). The descriptor is then used to access an interrupt gate. The interrupt gate then points to an interrupt handler routine that must be loaded into memory, and executed by the microprocessor. The use of descriptors, gates, and interrupt handlers is time consuming, and therefore degrades performance of the multiprocessor system.
It is therefore desirable to provide for a TLB shootdown operation that reduces an amount of time required to invalidate multiple TLBs. It is further desirable to provide a method of performing a TLB shootdown operation that maintains the consistency of an architectural state of the multiprocessor system while performing the shootdown operation in a reduced amount of time. Moreover, it is desirable to provide a method of performing a TLB shootdown operation without invoking interrupt handler routines.
SUMMARY OF THE INVENTION
A method and apparatus for performing a TLB flush in a multiprocessor system is described. A first and second microprocessor, each including a TLB, are coupled to a bus. The first microprocessor requests a TLB flush transaction by asserting a TLB flush request coupled with a page number on the bus. The second microprocessor detects the TLB flush transaction request and invalidates a TLB entry within its TLB corresponding to the page number.
While the second microprocessor is invalidating its TLB entry, it asserts a busy signal on the bus that is detected by the first microprocessor. The busy signal is deasserted when the second microprocessor has completed invalidating its TLB entry.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention is illustrated by way of example and not limitation in the accompanying figures.
FIG. 1 illustrates a block diagram of a prior art address translation from a virtual address to a physical address.
FIG. 2 illustrates a block diagram of a prior art TLB address translation from a virtual address to physical address.
FIG. 3 illustrates a block diagram of a multiprocessor computer system in accordance with one embodiment of the invention.
FIG. 4 illustrates a signal diagram of a TLB flush transaction in accordance with one embodiment of the present invention.
FIG. 5 illustrates a flow diagram of a TLB shootdown operation in accordance with one embodiment of the invention.
DETAILED DESCRIPTION
A method and apparatus for performing TLB shootdown operations in a multiprocessor computer system is described. In the following description, numerous specific details are set forth, such as specific components, bus protocols, and signal values, in order to provide a thorough understanding of the present invention. It will be apparent, however, to one skilled in the art that these specific details need not be employed to practice the present invention. In other instances, well known components or methods have not been described in detail in order to avoid obscuring the present invention.
FIG. 3 illustrates a multiprocessor computer system 100 wherein a TLB shootdown operation of the present invention may be implemented. The first microprocessor 110 is locally coupled to an external second level (L2) cache 113. The second microprocessor 114 is also locally coupled to an L2 cache 117. Each of the microprocessors 110 and 114 include an execution unit, 112 and 116, respectively. The execution unit 112 executes programming instructions received by the microprocessor 110, and the execution unit 116 executes programming instructions received by microprocessor 114. Each of the microprocessors 110 and 114 also includes an internal TLB. The TLB 111 corresponds to microprocessor 110, and TLB 115 corresponds to microprocessor 114. The host bus 120 is a conduit for communications between microprocessor 110, microprocessor 114, and the bridge and memory controller 130.
The bridge and memory controller 130 handles the communication between the microprocessors 110, 114 and the devices coupled to peripheral bus 150. Devices coupled to the peripheral bus 150, such as peripheral device 170, may comprise hard drive interface chips, graphics controller chips, or add-in boards.
The bridge and memory controller 130 handles data transfer requests between the microprocessors 110, 114 and the system main memory 140. For instance, one of the microprocessors 110 or 114 may issue a read or write request on the host bus 120 using standard microprocessor timings. The bridge and memory controller 130 detects the request, and asserts the appropriate signals to main memory 140.
Programming instructions are typically stored in a mass storage device, such as a magnetic or optical disk (not shown). The computer programming instructions are then loaded from the disk into main memory 140 prior to execution. Either microprocessor 110 or microprocessor 114 reads the programming instructions and executes them via the execution unit 112 or 116, respectively.
For one embodiment of the invention, each of the microprocessors 110 and 114 comprise an Intel architecture processor, such as the Pentium AE Pro processor, manufactured by Intel Corporation. For other embodiments of the invention, one or more of the microprocessors of computer system 100 may comprise any general microprocessor for executing programming instructions. Moreover, while the computer system 100 is illustrated as including only two microprocessors 110 and 114, the present invention may be implemented within a multiprocessor computer system including more than two microprocessors.
The TLB shootdown operation of the present invention includes a TLB flush transaction that is communicated between the microprocessors 110 and 114 via the host bus 120. Transactions over the host bus 120 are implemented according to a host bus protocol. While the present invention will be described herein below with reference to a specific host bus protocol, it should be appreciated that the specifics of the protocol are not meant to limit the scope of the invention.
For one embodiment of the TLB shootdown operation, a microprocessor invalidates its own TLB via the INVPLG instruction prior to requesting the TLB flush transaction. This TLB shootdown operation will be described in more detail herein below with reference to FIG. 5.
The TLB flush transaction is considered a processor-to-processor transaction because it is used in communicating between two or more microprocessors. For one embodiment, the host bus is capable of communicating between various types of agents, such as memory devices, I/O devices, and microcontrollers. The TLB flush transaction may also be implemented for communication between any of these agents that include a TLB.
FIG. 4 illustrates a timing diagram of one embodiment of the TLB flush transaction of the present invention. In the following description, signal line names are referred to in all capital letters. Names that are not followed by a "#" sign (e.g., CLK) are active-high signal lines, and therefore are considered to be "asserted" when carrying a signal equaling a logical one. Names followed by the "#" sign (e.g., ADS#) are active low signal lines, and are considered asserted when carrying a signal equal to a logical zero. It should be appreciated that the designation of a signal line as active low or active high is not meant to limit the scope of the present invention.
The TLB flush transaction begins with a requesting microprocessor initiating the transaction on the host bus. For one embodiment, the requesting microprocessor must first arbitrate for control of the bus. This is referred to as the "arbitration phase" of the transaction. The arbitration phase may employ a round-robin arbitration algorithm to determine priority among several arbitrators. Arbitration for control of buses is well known in the art, and is therefore not described in detail.
Once the requesting microprocessor has gained control of the host bus, the transaction enters the "request phase." During the request phase, the requesting microprocessor issues a request for a TLB flush transaction on the host bus. For one embodiment, this occurs in two clock cycles.
At clock cycle 51, the requesting microprocessor asserts a signal on the ADS# line 502, along with an encoded request on the five request lines REQ 4:0!#503. These are request lines which already exist in some current microprocessors. For an alternative embodiment, the TLB flush transaction uses dedicated request lines added within the microprocessor. The values of the signals asserted on the request lines REQ 4:0!#503 correspond to the first half of a request for a TLB flush transaction. Five more signals are asserted on the same request lines REQ 4:0!#503 in the second cycle 52 of the request phase which define the complete encoding of the request for TLB flush transaction. For one embodiment, signals corresponding to details of the requested transaction, such as data transfer rates and length of the data transfer requested, are asserted in the second cycle of the request phase.
The TLB flush transaction is known as a "broadcast" transaction on the host bus. This means that the requesting microprocessor broadcasts the TLB flush transaction to all other microprocessors coupled to the host bus. The non-requesting microprocessors coupled to the host bus ("receiving microprocessors") receive the request from the requesting microprocessor. For one embodiment, a "central agent," (e.g. the bridge and memory controller chip 130, FIG. 3) also detects the TLB flush request. The central agent then asserts a signal on the TRDY# line 505 (clock cycle 54) to indicate to the requesting microprocessor that it may begin data transmission for the TLB flush transaction. For an alternate embodiment of the invention, one or more of the receiving microprocessors asserts the transaction ready signal on the TRDY# line 505 to indicate that data transfer may begin.
As can be seen by the dotted line in clock cycles 55-57, the target ready signal on the TRDY# line 505 need not be deasserted within one clock cycle. For another embodiment, the target ready signal may stay asserted until clock cycle 57. The number of clock cycles that the target ready signal remains asserted is not meant to limit the scope of the present invention.
At clock cycle 55, the receiving microprocessors then assert the TLB flush not done, or "busy," signal on the TND# line 504 to indicate that they are busy invalidating their TLBs. For one embodiment, the TND# line 504 comprises a wired-or line such that more than one microprocessor may assert the busy signal at one time. The TND# line 504 will be asserted while any one of the microprocessors is asserting a busy signal on the TND# line 504. While any one busy signal is asserted on the TND# line 504, the requesting microprocessor is stalled, waiting for each of the receiving microprocessors to complete the TLB invalidation.
At clock cycle 56, the requesting microprocessor asserts data signals on the data D 63:0!# lines 508, along with the data ready signal on the DRDY# line 507. This begins the "data phase" of the TLB flush transaction. The data ready signal asserted on the DRDY# line 507 indicates that valid data has been asserted on the data D 63:0!# lines 508. For one embodiment, the data phase is two clock cycles long.
The data signals asserted in the first clock cycle 56 correspond to the TLB entry to be invalidated. For one embodiment, the data signals driven in clock cycle 56 comprise a 49-bit virtual page number (VPN) that indicates the virtual address of the PTE that has been changed. This VPN is used to index the TLB entry to be invalidated.
The second data phase of clock cycle 57 is used to transfer other information about the entry to be invalidated. For instance, the data signals driven in clock cycle 57 may comprise a region identification for identifying a region where the page of memory is located, and a page size identifier that indicates the size of the page to be invalidated.
The data busy signal is asserted by the requesting microprocessor on the DBSY# line 506 during the data phase of the transaction to indicate that the data bus is being used for a two-clock data transfer. For one embodiment, the data busy signal remains asserted on the DBSY# line 506 until one clock cycle after the data phase, clock cycle 59. Alternatively, the data busy signal is deasserted in clock cycle 58.
Once each of the receiving microprocessors has received the data signals driven on lines D 63:0!# 508 during clock cycles 56 and 57, each is responsible for invalidating its TLB entry. As described herein above, for one embodiment this includes executing the INVPLG instruction, using as an argument the VPN received during the data phase. The busy signal is asserted on the TND# line 504, four clocks after the assertion of ADS# 502, while each microprocessor performs the invalidate page instruction. The TND# line 504 is toggled every other cycle due to uncertainty of rising edge due to wired or glitches. The TND# line 504 is sampled once every two clock cycles until it is sampled deasserted. Recall that the TND# line 504 will be asserted as long as one or more microprocessors are asserting a signal on the TND# line 504. Once all microprocessors have completed invalidating their TLBs, and have deasserted the busy signal on the TND# line 504 (not shown in FIG. 4), the TLB flush transaction is completed. Therefore, the requesting microprocessor may commence executing programming instructions.
FIG. 5 illustrates a flow diagram of a TLB shootdown operation in accordance with one embodiment of the invention. Recall that the reason for performing a TLB shootdown operation is because a page table entry (PTE) is changed by a software routine or operating system. Once the PTE has been changed, any TLB entries corresponding to the PTE must be invalidated.
The first step of the TLB shootdown operation, step 610, involves a check by the operating system prior to changing the PTE. The operating system checks to make sure that none of the microprocessors within the system is currently using the PTE that is to be changed.
Once the operating system has ensured that no microprocessors are using a PTE needing to be changed, one microprocessor is chosen to be the requesting microprocessor. The requesting microprocessor at step 620 changes the PTE. The requesting microprocessor also invalidates its own TLB entry corresponding to the changed PTE. For one embodiment of the invention, the PTE is "frozen" once it has been changed at step 620. This means that the PTE may not be accessed or changed until after the TLB shootdown has completed, thus ensuring architectural consistency within the system. For one embodiment, the operating system is responsible for ensuring that the PTE remains frozen during the entire TLB shootdown operation.
At step 630, the requesting microprocessor issues a TLB flush transaction request on the host bus. The TLB flush transaction request includes two parts: (1) a TLB flush transaction request code, and (2) a data field indicating the page number of the PTE that has changed.
The receiving microprocessors on the host bus receive the TLB flush request at step 640, and first determines whether the page number of the changed PTE is contained in its TLB. If so, the receiving microprocessor invalidates its TLB entry via a TLB invalidate instruction or operation (e.g., INVPLG). While each of the receiving microprocessors is invalidating its TLB, it asserts a busy signal on the TND# signal line. Recall that if any one of the microprocessors is asserting the busy signal on the TND# signal line, the receiving microprocessor is halted from executing programming instructions.
Step 650 illustrates that each receiving microprocessor deasserts its busy signal on the TND# line upon completing the TLB invalidation. For one embodiment, the TND# line is a wired-or, such that if any one microprocessor is asserting a busy signal on the TND# line, the TND# line is asserted. In order to transition from step 650 to step 660, the TND# line must be observed deasserted, such that no microprocessors are asserting a busy signal on the TND# line.
For an embodiment of the TLB shootdown operation, steps 630-650 are performed as described in detail with reference to FIG. 4.
At step 660, the requesting microprocessor signals to the operating system that each of the receiving microprocessors has finished invalidating its TLB. At this point, the changed PTE is unfrozen by the operating system, since the TLB shootdown operation has completed. The requesting microprocessor may continue executing programming instructions because the TND# line is deasserted.
Thus a mechanism for performing TLB shootdown operations in a multiprocessor computer system has been described. As described herein above, the TLB shootdown operation employs a specific TLB invalidation instruction (INVPLG). It should be appreciated, however, that the specific instruction or method used by a microprocessor for invalidating TLB entries is not meant to limit the scope of the invention. Moreover, the particular TLB flush transaction protocol and signal timings may be modified without departing from the scope of the present invention.
In the foregoing detailed description a mechanism for performing TLB shootdown operations in a computer system has been described. The present invention has been described with reference to specific exemplary embodiments thereof. It will, however, be evident that various modifications and changes may be made thereto without departing from the broader spirit and scope of the invention. The specification and drawings are, accordingly, to be regarded in an illustrative rather than a restrictive sense. | Prior art methods of maintaining coherency among multiple TLBs in a multiprocessor system were time-consuming. One microprocessor halted all other microprocessors in the system, and sent an interrupt to each of the halted microprocessors. Rather than invoking an interrupt handler, the TLB shootdown operation of the present invention provides for a TLB flush transaction communicated between multiple processors on a host bus. One microprocessor issues a TLB flush request on the host bus. The TLB flush request includes a page number. The microprocessors receiving the request invalidate the TLB entry corresponding to the page number. | 6 |
[0001] The present invention relates in general to electrocardiographic (ECG) and oxygen saturation signal recording and more particularly concerns a novel technique for processing the ECG and oxygen saturation signals.
BACKGROUND OF THE INVENTION
[0002] For background on ECG and oxygen saturation signal recording reference is made to U.S. Pat. No. 6,125,296.
[0003] A typical prior art approach for measuring oxygen saturation uses either a large nonportable bedside unit or a portable unit with recording capability.
[0004] An object of this invention is to provide an automatic mechanism for identifying those portions of the recorded pulse oxymetry data signals that are invalid.
[0005] Another object of the invention is to use pulse oxymetry data signals, which this invention determines as valid, and identify those segments of the data signals that are valid desaturation signals.
BRIEF SUMMARY OF THE INVENTION
[0006] In one aspect, the invention is a method for processing pulse oxymetry data signals. The method includes recording pulse oxymetry data signals. The pulse oxymetry data signals have a plurality of oxymetry waveforms. The pulse oxymetry data signals correspond to oxygen saturation data signals. The method also includes determining a correlation coefficient between sequential oxymetry waveforms and identifying a valid pulse oxymetry waveform.
[0007] This aspect of the invention may have one or more of the following features. Determining the correlation coefficient includes storing a first pulse oxymetry waveform segment having a first length in a first buffer, copying the first pulse oxymetry waveform segment from the first buffer to a second buffer, copying a second pulse oxymetry waveform segment having a second length to the first buffer, comparing the first length, the second length and a predetermined value, and determining a correlation length related to the first and second lengths and the predetermined value. Determining a correlation length includes taking the minimum of the first length, the second length, and the predetermined value. Determining a correlation coefficient includes determining a correlation coefficient from the first pulse oxymetry waveform segment and the second pulse oxymetry waveform segment, comparing the correlation coefficient to a threshold value, and filtering out an invalid pulse oxymetry waveform segment that has a correlation coefficient below the threshold value. Filtering out the invalid pulse oxymetry waveform segment includes eliminating pulse oxymetry waveform segments if 75% of the correlation coefficients for the last 6 seconds are above the threshold value of 0.9. The method also includes determining valid oxygen desaturation data signals. Determining valid desaturation signals comprises labeling oxygen saturation signals below a threshold value for a predetermined time as valid desaturation data. The threshold value is 88% and the predetermined time is 300 seconds. Determining valid desaturation signals comprises eliminating artifacts. Determining valid desaturation signals comprises ignoring desaturation signals below the threshold value that do not reach a peak value.
[0008] In another aspect, the invention is an apparatus for processing pulse oxymetry data signals. The apparatus includes a memory that stores executable instruction data signals and a processor. The processor executes the instruction data signals to record the pulse oxymetry data. The pulse oxymetry data has a plurality of oxymetry waveforms. The pulse oxymetry data signals correspond to oxygen saturation data signals. The processor also executes the instruction data signals to determine a correlation coefficient between sequential oxymetry waveforms and to identify invalid pulse oxymetry waveforms.
[0009] This aspect of the invention may have one or more of the following features. Determining the correlation coefficient includes storing a first pulse oxymetry waveform segment having a first length in a first buffer, copying the first pulse oxymetry waveform segment from the first buffer to a second buffer, copying a second pulse oxymetry waveform segment having a second length to the first buffer, comparing the first length, the second length and a predetermined value, and determining a correlation length related to the first and second lengths and the predetermined value. Determining a correlation length includes taking the minimum of the first length, the second length, and the predetermined value. Determining a correlation coefficient includes determining a correlation coefficient from the first pulse oxymetry waveform segment and the second pulse oxymetry waveform segment, comparing the correlation coefficient to a threshold value, and filtering out an invalid pulse oxymetry waveform segment that has a correlation coefficient below the threshold value. Filtering out the invalid pulse oxymetry waveform segment includes eliminating pulse oxymetry waveform segments if 75% of the correlation coefficients for the last 6 seconds are above the threshold value of 0.9. The processor also executes the instruction data signals to determine valid oxygen desaturation data signals. Determining valid desaturation signals comprises labeling oxygen saturation signals below a threshold value for a predetermined time as valid desaturation data. The threshold value is 88% and the predetermined time is 300 seconds. Determining valid desaturation signals comprises eliminating artifacts. Determining valid desaturation signals comprises ignoring desaturation signals below the threshold value that do not reach a peak value.
[0010] In still another aspect, the invention is an article that includes a machine-readable medium that stores executable instruction signals for processing pulse oxymetry data signals. The instruction signals cause a machine to record the pulse oxymetry data signals. The pulse oxymetry data signals have a plurality of oxymetry waveforms. The pulse oxymetry data signals correspond to oxygen saturation data signals. The instructions also cause a machine to determine a correlation coefficient between sequential oxymetry waveforms and to identify invalid pulse oxymetry waveforms.
[0011] This aspect of the invention may have one or more of the following features. Determining the correlation coefficient includes storing a first pulse oxymetry waveform segment having a first length in a first buffer, copying the first pulse oxymetry waveform segment from the first buffer to a second buffer, copying a second pulse oxymetry waveform segment having a second length to the first buffer, comparing the first length, the second length and a predetermined value, and determining a correlation length related to the first and second lengths and the predetermined value. Determining a correlation length includes taking the minimum of the first length, the second length, and the predetermined value. Determining a correlation coefficient includes determining a correlation coefficient from the first pulse oxymetry waveform segment and the second pulse oxymetry waveform segment, comparing the correlation coefficient to a threshold value, and filtering out an invalid pulse oxymetry waveform segment that has a correlation coefficient below the threshold value. Filtering out the invalid pulse oxymetry waveform segment includes eliminating pulse oxymetry waveform segments if 75% of the correlation coefficients for the last 6 seconds are above the threshold value of 0.9. The instructions also cause a machine to determine valid oxygen desaturation data signals. Determining valid desaturation signals comprises labeling oxygen saturation signals below a threshold value for a predetermined time as valid desaturation data. The threshold value is 88% and the predetermined time is 300 seconds. Determining valid desaturation signals comprises eliminating artifacts. Determining valid desaturation signals comprises ignoring desaturation signals below the threshold value that do not reach a peak value.
[0012] Some or all of the aspects of the invention described above may have some or all of the following advantages. The invention makes it impossible to automatically differentiate valid oxymetry data signals from invalid oxymetry data signals. The invention also automatically determines true desaturation signals from invalid desaturation signals.
[0013] Other features, objects and advantages will become apparent from the following detailed description when read in connection with the accompanying drawing in which:
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
[0014] [0014]FIG. 1 is a flowchart of a process for processing pulse oxymetry data signals;
[0015] [0015]FIG. 2 is a graph of a pulse signal and a corresponding pulse oxymetry signal;
[0016] [0016]FIG. 3 is a graph showing normal recorded pulse oxymetry data signals;
[0017] [0017]FIG. 4 is a graph showing invalid recorded pulse oxymetry data signals;
[0018] [0018]FIG. 5 is a flowchart of a process of detecting invalid pulse oxymetry data signals;
[0019] [0019]FIG. 6 is a graph showing valid recorded desaturation data signals;
[0020] [0020]FIG. 7 is a graph showing invalid recorded desaturation data signals;
[0021] [0021]FIG. 8 is a flowchart of a process for detecting desaturation signals; and
[0022] [0022]FIG. 9 is a block diagram of a computer system on which the process of FIG. 1 may be implemented.
DETAILED DESCRIPTION
[0023] Typically, an oxygen sensor is used to record pulse oxymetry signals. The oxygen sensor provides a signal representative of oxygen saturation. The oxygen sensor is applied to a finger or ear lobe. However, pulse oxymetry measurements are sensitive to patient movement. Small movements of the sensor can produce invalid data signals, which is difficult and time consuming for a user to discern.
[0024] It is especially difficult for the user to identify periods of desaturation in the data from false desaturation data. Desaturation periods are marked by low values of blood oxygen saturation. Desaturation can be caused by emphysema, blockages of the airways (e.g., snoring), etc. In many cases, it is difficult or impossible to differentiate a true desaturation from the invalid data signals by looking at the oxygen saturation data signals alone.
[0025] Referring to FIGS. 1 and 2, a process 10 automatically (i.e., without user intervention) determines invalid oxymetry data signals recorded from an electrocardiographic and oxygen saturation signal. Process 10 determines a cross-correlation coefficient between two adjacent pulse oxymetry waveforms and compares it to a predetermined value. Every pulse oxymetry waveform corresponds to a pulse wave having a series of R-waves 24 (e.g., first R-wave 24 a and second R-wave 24 b ). R-waves 24 are a depolarization of the apex of the heart whereby most of the ventricle is activated. R-waves 24 are represented by an upward deflection on a pulse signal 26 . R-waves 24 are used to identify the beginning of a pulse oxymetry waveform 28 (e.g., first pulse oxymetry waveform 28 a and second pulse oxymetry waveform 28 b ) in the pulse oxymetry data signal 30 . For example, first R-wave 24 a corresponds to first pulse oxymetry waveform 28 a and second R-wave 24 b corresponds to second pulse oxymetry waveform 28 b . Process 10 keeps those successive oxymetry waveforms that have a cross-correlation coefficient above the predetermined value. The valid oxymetry data signals are further reviewed to determine if the oxygen desaturation signal values are also valid. By automatically filtering-out erroneous and invalid oxymetry data signal, a physician has a better understanding of the condition of a patient to make a better diagnosis faster than having the physician sift through the recorded oxymetry data signals looking for false recorded data signals.
[0026] Referring to FIGS. 3 - 4 , a pulse signal 32 (e.g., pulse signal 32 a and pulse signal 32 b ) corresponds to a pulse oxymetry signal 34 (e.g., pulse oxymetry signal 34 a and pulse oxymetry signal 34 b ). In box 36 , pulse oxymetry waveform 34 a is valid because successive oxymetry waveforms are correlated. In box 38 , successive oxymetry waveforms are not correlated.
[0027] Process 10 records ( 12 ) the ECG and saturation data signals. In this embodiment an apparatus to record the signals is described in U.S. Pat. No. 6,125,296 (“'296” patent) and incorporated herein. Process 10 stores ( 14 ) the data signals in a removable memory (see '296 patent). Process 10 reads ( 16 ) the stored data signals from the removable memory. In this embodiment, the removable memory is a memory card that is placed in a memory card reader and subsequently read.
[0028] Referring to FIG. 5, process 10 determines ( 18 ) a correlation between successive pulse oxymetry waveforms by using a process 40 . Process 40 uses a correlation coefficient to filter out invalid data signals. Process 40 receives the present R-wave, R n , and determines ( 42 ) if the last R-wave has been received. If the last R-wave has been received, process 40 returns ( 44 ) to process 10 for further processing to determine the valid oxygen desaturation data signals ( 20 ). If more R-waves are present, process 40 copies ( 46 ) a previous segment of a pulse oxymetry waveform corresponding to the previous R-wave, R n−1 , and the R-wave previous to R n−1 , R n−2 , and a correlation length, L n−1 , from a new buffer to an old buffer. For each R-wave that is detected and is associated with a normal beat of sinus origin, process 40 copies ( 48 ) a segment of pulse oxymetry waveform corresponding to the present R-wave, R n , and the previous R-wave, R n−1 , to the new buffer. Process 40 determines ( 50 ) a correlation length of the present segment, L n , by comparing the pulse oxymetry waveforms in the new buffer to the old buffer. L n is determined by taking the smallest of: the time between R n and R n−1 , R n−1 and R n−2 , and a constant equal to 0.4 times a sampling rate of 180 or a constant of 72. Process 40 stores L n in the new buffer. Process 40 determines ( 52 ) the cross correlation coefficient, C n , as:
C n =Σ(( BUFN m )( BUFO m ))/((Σ( BUFN m ) 2 )(Σ( BUFO m ) 2 )) 1/2
[0029] for m=0, . . . LEN n−1 where BUFN are the pulse oxymetry waveform segment values in the new buffer, BUFO are the pulse oxymetry waveform segment values in the old buffer, and LEN n−1 is the correlation length of the previous pulse oxymetry waveform segment. Process determines ( 54 ) the validity by comparing the cross correlation coefficient to the predetermined value. If more than a fraction of the correlation coefficients of normal beats, FRAC, in the last NS seconds of data have the C n less than a threshold value, C th , then oxymetry data signals from R n to R n−1 are invalid. In this embodiment, if more than 75% of the coefficients of normal beats in the last 6 seconds of data signals have the C n less than 0.9, then the oxymetry signals from R n to R n−1 are invalid. The values of FRAC, NS, and C th are determined by the user. Again, process 40 determines if the last R-wave has been received ( 42 ).
[0030] Referring to FIGS. 6 - 7 , an ECG pulse signal 52 (e.g., ECG pulse signal 52 a and ECG pulse signal 52 b ) is compared to an oxygen saturation signal 34 (i.e., oxygen saturation signal 54 a and oxygen saturation signal 54 b ). In box 56 , a valid oxygen saturation signal is shown because oxygen saturation signal 54 a is correlated with ECG pulse signal 52 a . In box 58 , an invalid oxygen saturation data signal is shown because oxygen saturation signal 54 a is not correlated with ECG pulse signal 52 b.
[0031] Referring to FIG. 8, process 80 determines from the valid data signals the true desaturation data signals. Process 80 finds those points in an oxygen saturation signals that are below a certain threshold, desat_max_value, for a minimum amount time, desat_min_length. However, process 80 allows for some values to be above desat_max_value. For example, a patient has desaturation signals for fifteen minutes but every minute there was an oxygen saturation signal above desat_max_value for a few seconds. The patient would still be considered physiologically in a desaturation mode for the entire 15 minutes. Process 80 uses a time artifact value, desat_max_artifact, to disregard these occurrences. Desat_max_artifact is the maximum amount of time that during desaturation process 80 will ignore values above desat_max_value. Process 80 also uses a desat_max_peak value to ignore values below desat_max_value that never reach desat_max_peak. Process 80 also uses a desat_min_separation value. The desat_min_separation value is the minimum time that is allowed between periods where the saturation value is above desat_max_value. Process 80 measures values from 0 to the last_saturation_value. In this embodiment, desat_max_value is 88%, desat_min_length is 300 seconds, desat_max_peak is 85%, desat_max_artifact is 30 seconds, and desat_min_separation is 120 seconds. In this embodiment, the values in process 80 can be set by a user.
[0032] One embodiment of the invention is realized in the following software code:
1. if(open_file(&oxy_handle,“oxymin”,OPEN_READ_NO_MESSAGE) && 2. filelength(oxy_handle) && 3. open_file(&oxy_pulse,“oxypulse.dat”,OPEN_RANDOM) && 4. filelength(oxy_pulse) && 5. open_file(&beatstream, “beatstr”,OPEN_READ) 6. ) 7. { 8. MEM_BEAT_STREAM_FILE_FORMAT bt{0,0,0},lbt; 9. #define MAX_OXY_BUF ((SAMP_RATE*4)/10) 10. #define OXY_BEATS_CHECKED (OXYMINUTE_5::SecPerOxy*5) 11. struct 12. { 13. long offset; 14. int artifact_detected; //!=0 if aftifact detected 15. }det_buf[OXY_BEATS_CHECKED]; 16. short mk[4]={80,80,−80,−80}; 17. short oxy_buf[MAX_OXY_BUF+4],last_oxy_buf [MAX_OXY_BUF+4]; 18. int sb,sc,coll_len; 19. int oxymin_records; 20. double sumx,sumy,sumxy,coll; 21. OXYMINUTE_5 *ox_min_buf; 22. int beat_cnt; 23. memset(oxy_buf,0,sizeof(oxy_buf)); 24. beat_cnt=0; 25. close(oxy_handle); 26.// Printf(“\n process oxy ”); 27. open_file(&oxy_handle, “oxymin”,OPEN_RANDOM); 28. oxymin_records=filelength(oxy_handle)/sizeof(OXYMINUTE_5); 29. ox_min_buf=new OXYMINUTE_5[oxymin_records]; 30. lseek(oxy_handle,0,SEEK_SET); 31. for (lb=0;lb<oxymin_records;lb++) 32. { 33.read(oxy_handle, (char*)&ox_min_buf [lb], sizeof(OXYMINUTE_5)); 34. ox_min _buf[lb].status&=˜ (0x200 | 0x100); 35. } 36. while (!eof(beatstream)) 37. { 38. lbt=bt; 39. read(beatstream,&bt,sizeof(bt)); 40.lseek(oxy_pulse, (lbt.offset+(SAMP_RATE/10)−4)*2,SEEK_SET); 41. read(oxy_pulse,oxy_buf,MAX_OXY_BUF*2+8); 42. coll_len=MIN(MAX_OXY_BUF,bt.offset-lbt.offset); 43. sumx=0.0; 44. sumy=0.0; 45. sumxy=0.0; 46. for (ia=4;ia<coll_len+4;ia++) 47. { 48. sb=oxy_buf[ia]-oxy_buf [4]; 49. sc=last_oxy_buf[ia]-last_oxy_buf[4]; 50. sumx+=sb*sb; 51. sumy+=sc*sc; 52. sumxy+=sb*sc; 53. last_oxy_buf[ia]=oxy_buf [ia]; 54. } 55. if (sumx * sumy >0.0) 56. coll=sumxy/sqrt(sumx*sumy); 57. else 58. coll=0; 59.det_buf[beat_cnt%OXY_BEATS_CHECKED].offset=lbt.offset; 60.det_buf[beat_cnt%OXY_BEATS_CHECKED].artifact_detected=(coll <0.9) && lbt.beat_label==BEAT_LABEL_NORMAL; 61. sb=0; 62. sc=0; 63. for (ia=0;ia<OXY_BEATS_CHECKED;ia++) 64. } 65. if (det_buf[ia].offset>lbt.offset- (SAMP_RATE*OXYMINUTE_5::SecPerOxy)) 66. { 67. sb++; //total count 68. sc+=det_buf[ia].artifact_detected; 69. } 70. } 71. ia=lbt.offset/(SAMP_RATE*OXYMINUTE_5::SecPerOxy); 72. lb=0; 73. if (sc*4>sb*3 && ia>=0 && ia<oxymin_records) 74. { 75. ox_min_buf[ia].status|=0x200; 76.// Printf(“ ARTIFACT %5d sc %2d sb %2d”,ia,sc,sb); 77. lb=1; 78. } 79.#if 0 80.lseek(oxy_pulse,(lbt.offset+(SAMP_RATE/10)−4)*2,SEEK_SET); 81. if (lb) 82. sb=oxy_buf[0]−100; 83. else 84. if (coll>0.9) 85. sb=oxy_buf[0]+100; 86. else 87. sb=oxy_buf[0]+50; 88. oxy_buf[1]=sb; 89. oxy_buf[2]=sb; 90. oxy_buf[3]=sb; 91. write(oxy_pulse,oxy_buf,8); 92. if (DEBUG_ART_DESAT) 93. if ((beat_cnt%100)==0) 94. for (ia=0;ia<coll_len;ia++) 95. Printf(“ %3d”,oxy_buf [ia]); 96. #endif 97. beat_cnt++; 98. } 99.if (DEBUG_ART_DESAT) 100. Printf(“\n look for desats for %d records thresh %d %d %d %d ”,oxymin_records, 101. c_i.desat_spo2_thresh, 102. c_i.artifact_desat_skip, 103. c_i.desat_spo2_min _thresh, 104. c_i.desat_min length); 105. for (ia=0;ia<oxymin_records;ia++) 106. { 107. if (DEBUG_ART_DESAT) 108. if (ia<400)Printf(“ %d”,ox_min _buf[ia].spo2_max); 109. if ((ia&15)==0) 110. StatusPrintf(“Oxy %s”,time_to string(ia*OXYMINUTE_5::SecPerOxy*SAMP_RATE)); 111. if (DEBUG_ART_DESAT) 112. Printf(“\n at %3d %s %2d %2d %d %d”, 113. ia, 114. time_to_string(ia*OXYMINUTE_5:: SecPerOxy*SAMP_RATE+c_i.base_time), 115. ox_min _buf[ia].spo2_min, 116. ox_min _buf[ia].spo2_max, 117. ox_min buf[ia].OxyArtifact(), 118. (ox_min _buf[ia].status&0x100) !=0) 119. if (ox_min_buf[ia].spo2_max<=c_i.desat_spo2_thresh) 120. { 121. if (DEBUG_ART_DESAT) 122. Printf(“ start desat ”); 123. int term_loop; 124. for (lb=ia, lc=0, ld=0, le=0,term_loop=0;lb<oxymin_records && (lc<(c_i.artifact_desat_skip/OXYMINUTE_5::SecPerOxy)) && !term_loop;lb++) 125. { 126. if (ox_min _buf[lb].OxyArtifact() | | ox_min_buf[lb].spo2_max>c_i.desat_spo2_thresh) 127. { 128. if (le<=c_i.artifact_desat_min separation/OXYMINUTE_5::SecFerOxy && !lc) 129. term_loop=1; 130. lc++; 131. le=0; 132. } 133. else 134. { 135. lc=0; 136. 137. le++; 138. if (ox_min_buf[lb].spo2_min<=c_i.desat_spo2_min thresh) 139. ld++; 140. } 141. lb−=lc; 142. if (DEBUG_ART_DESAT) 143. Printf(“ check lb-ia %d ld %d lc %d le %d term %d”,lb-ia,ld,lc,le,term_loop); 144. if (((ib- ia)>(c_i.desat_min _length/OXYMINUTE_5::SecPerOxy)) && ld) 145. { 146. if (DEBUG_ART_DESAT) 147. Printf(“ DESAT IT ”); 148. for (lc=ia; lc<lb; lc++) 149. ox_min_buf[lc].status|=0x100; } 150. } 151. } 152. lseek(oxy_handle,0,SEEK SET); 153. for (lb=0;lb<oxyminn_records;lb++) 154. write(oxy_handle, (char*)&ox_min _buf[lb], sizeof(OXYMINUTE_5)); 155. delete [ ](ox_min_buf); 156. close (beatstream); 157. close(oxy_pulse); 158. close(oxy_handle); 159. if (((la=(clock( )-start_clock)) >0) && start_clock) 160. Printf(“ time at end of oxy art %g”,la/CLK_TCK); 161. }
[0033] Referring to FIG. 9, a computer 70 includes a processor 72 for processing oxymetry data signals stored on a memory card (not shown) and read by memory card reader 73 . Computer 70 also includes a memory 74 , and a storage medium 56 (e.g., hard disk). Storage medium 76 stores operating system 81 , data signals 82 , and computer instruction signals 78 which are executed by processor 72 out of memory 74 to perform process 10 . In this embodiment, the memory card is a Personal Computer Memory Card (International Association) (PCMCIA) which is compatible with the Advanced Technology Attachment (ATA) interface standard, and memory reader 73 is manufactured by Sandisk of Sunnyvale, Calif. In one embodiment, computer instructions include executable instruction signals.
[0034] Process 10 is not limited to use with the hardware and software of FIG. 9; process 10 may find applicability in any computing or processing environment and with any type of machine that is capable of running a computer program. Process 10 may be implemented in hardware, firmware, software, or a combination of two or more. Process 10 may be implemented in computer programs executed on programmable computers/machines that each include a processor, a storage medium/article of manufacture readable by the processor (including volatile and non-volatile memory and/or storage elements), at least one input device, and one or more output devices. Program code may be applied to data entered using an input device to perform process 10 and to generate output information.
[0035] Each such program may be implemented in a high level procedural or objected-oriented programming language to communicate with a computer system. However, the programs can be implemented in assembly or machine language. The language may be a compiled or an interpreted language. Each computer program may be stored on a storage medium (article) or device (e.g., CD-ROM, hard disk, read only memory (ROM) integrated circuit, or magnetic diskette) that is readable by a general or special purpose programmable computer for configuring and operating the computer when the storage medium or device is read by the computer to perform process 10 . Process 10 may also be implemented as a machine-readable storage medium, configured with a computer program, where upon execution, instructions in the computer program cause the computer to operate in accordance with process 10 .
[0036] In other embodiments, process 10 can be performed using a processor located on a patient. In still other embodiments, the recorder can perform process 10 . The invention is not limited to a specific location. Process 10 can be performed by a device connected to the patent, at the recorder, or anywhere external to the patient.
[0037] The invention is not limited to the specific embodiments described herein. The invention is not limited to the specific processing order of FIGS. 1, 5, and 8 . Rather, the blocks of FIGS. 1, 5, and 8 may be re-ordered, as necessary, to achieve the results set forth above.
[0038] Other embodiments not described here are also within the scope of the following claims. | In one aspect, the invention is a method for processing pulse oxymetry data signals. The method includes recording pulse oxymetry data signals. The pulse oxymetry data signals have a plurality of oxymetry waveforms. The method also includes determining a correlation coefficient between sequential oxymetry waveforms and identifying a valid pulse oxymetry waveform. | 0 |
BACKGROUND OF THE INVENTION
[0001] The present invention relates in general to substrate manufacturing technologies and in particular to methods and arrangement for the reduction of byproduct deposition in a plasma processing system.
[0002] In the processing of a substrate, e.g., a semiconductor wafer or a glass panel such as one used in flat panel display manufacturing, plasma is often employed. As part of the processing of a substrate (chemical vapor deposition, plasma enhanced chemical vapor deposition, physical vapor deposition, etc.) for example, the substrate is divided into a plurality of dies, or rectangular areas, each of which will become an integrated circuit. The substrate is then processed in a series of steps in which materials are selectively removed (etching) and deposited (deposition) in order to form electrical components thereon.
[0003] Many plasma processes include some type of plasma bombardment. For example, pure ion etching, often called sputtering, is used to dislodge material from the substrate (e.g., oxide, etc.). Commonly an inert gas, such as Argon, is ionized in a plasma and subsequently accelerate toward a negatively charged substrate. Likewise, reactive ion etch (RIE), also called ion-enhanced etching, combines both chemical and ion processes in order to remove material from the substrate (e.g., photoresist, BARC, TiN, Oxide, etc.). Generally ions in the plasma enhance a chemical process by striking the surface of the substrate, and subsequently breaking the chemical bonds of the atoms on the surface in order to make them more susceptible to reacting with the molecules of the chemical process.
[0004] However, a plasma processing system may also produce pollutants. Generally comprised of organic and inorganic byproducts, pollutants are generated by the plasma process from materials in the etchant gases (e.g., carbon, fluorine, hydrogen, nitrogen, oxygen, argon, xenon, silicon, boron, chlorine, etc.), from materials in the substrate (e.g. photoresist, silicon, oxygen, nitrogen, aluminum, titanium, etc.), or from structural materials within the plasma processing chamber itself (e.g., aluminum, quartz, etc.).
[0005] Some pollutants are volatile, and may be substantially pumped away by a vacuum system, while other pollutants form non-volatile or low-volatile sputtered species that tend to be deposited on interior surfaces and plasma chamber walls that tend to be difficult to efficiently evacuate from the plasma chamber. The resulting pollutant deposits may eventually flake and hence increase susceptibility of substrate defects, reduce the mean time between cleaning (MTBC), reduce yield, etc. For example, depending on the plasma process, conductive film deposits may form on plasma chamber interior surfaces which may impact the FW coupling of the plasma source and bias. In addition, byproduct deposits may contribute to plasma density drift.
[0006] Non-volatile and low-volatile byproducts include direct line-of-sight deposition of sputtered material, direct ion enhance etch byproduct deposition, volatile byproduct condensation, high sticking coefficient plasma dissociated byproducts, ion assisted deposition of plasma species, etc. Examples include high-k dielectrics (HfOx, HfSixOy, etc) byproducts, metal electrode (Pt, Ir, IrOx, etc.) byproducts, memory material byproducts (PtMn, NiFe, CoFe, FeW, etc), interconnect byproducts (Cu, Ru, CoWP, Ta, etc.).
[0007] In general, the emission profile for the sputtered atoms is generally characterized by a cosine distribution. This means that the emission rate at some angle other than normal (perpendicular) is equal to the normal incidence emission rate times the cosine of the angle from the normal. This is usually drawn as a circle touching the impact point, in which the circle is the envelope of the magnitudes of the emission at other angles. Generally, since sputtered atoms tend to be neutral, it is not possible to redirect their trajectories in flight, and hence the sputtered atoms tend to travel in straight lines.
[0008] The degree of deposit adhesion to surfaces within the chamber, and hence the subsequent degree of potential contamination, is usually dependent on the specific plasma processing recipe (e.g., chemistry, power, and temperature) and the initial surface condition of chamber process kits. Since substantially removing deposits may be time consuming, a plasma processing system chamber is generally substantially cleaned only when particle contamination levels reach unacceptable levels, when the plasma processing system must be opened to replace a consumable structure (e.g., edge ring, etc.), or as part of scheduled preventive maintenance (PM).
[0009] Referring now to FIG. 1 , a simplified diagram of an inductively coupled plasma processing system, such as a Lam Research Transformer Coupled Plasma Processing System™, is shown. In a common configuration, the plasma chamber is comprised of a bottom piece 150 located in the lower chamber, and a detachable top piece 152 located in the upper chamber. Generally, an appropriate set of gases is flowed into chamber 102 from gas distribution system 122 and through dielectric coupling window 104 . These plasma processing gases may be subsequently ionized at injector 108 to form a plasma 110 in a plasma generating region, in order to process (e.g., etch or deposition) exposed areas of substrate 114 , such as a semiconductor substrate or a glass pane, positioned with edge ring 115 on an electrostatic chuck 116 .
[0010] A first RF generator 134 generates the plasma as well as controls the plasma density, while a second RF generator 138 generates bias RF, commonly used to control the DC bias and the ion bombardment energy. Further coupled to source RF generator 134 is matching network 136 a , and to bias RF generator 138 is matching network 136 b , that attempt to match the impedances of the RF power sources to that of plasma 110 . Furthermore, pump 111 is commonly used to evacuate the ambient atmosphere from plasma chamber 102 in order to achieve the required pressure to sustain plasma 110 .
[0011] While these are severe issues to tackle requiring complicated high temperature chamber designs, special materials etc, there is no commonality to the behavior of these different materials. For example, if plasma process conditions allow it, a clean or a self-cleaning plasma recipe can be developed, or the chamber surfaces can be designed with materials that have a reduced sticking coefficient to the problem byproduct, or if the byproducts are sufficiently adhered or “stuck” to the chamber surfaces, the plasma process can be run until flaking becomes problematic. However, since these solutions are very process sensitive, the possibility of a single robust reactor design and process approach which can handle most of these materials and potential chemistries is problematic.
[0012] In view of the foregoing, there are desired methods and arrangement for the reduction of byproduct deposition in a plasma processing system.
SUMMARY OF THE INVENTION
[0013] The invention relates, in one embodiment, in a plasma processing system, a method of reducing byproduct deposits on a set of plasma chamber surfaces of a plasma processing chamber. The method includes providing a deposition barrier in the plasma processing chamber, the deposition barrier is configured to be disposed in a plasma generating region of the plasma processing chamber, thereby permitting at least some process byproducts produced when a plasma is struck within the plasma processing chamber to adhere to the deposition barrier and reducing the byproduct deposits on the set of plasma processing chamber surfaces.
[0014] The invention relates, in another embodiment, to a method of reducing a set of byproduct deposits on a set of plasma chamber surfaces in a plasma reactor. The method includes positioning a substrate in a plasma processing chamber. The method further includes positioning a deposition barrier in the plasma processing chamber, wherein a first plasma is configured to surround the deposition barrier when struck, and whereby the deposition barrier is configured to make contact with a first subset of the set of byproduct deposits from the substrate. The method also includes re-positioning the deposition barrier in the plasma processing chamber, wherein a second plasma is configured to surround the deposition barrier when struck, and whereby the deposition barrier is configured to make contact with a second subset of the set of byproduct deposits from the substrate.
[0015] The invention relates, in another embodiment, in a plasma processing system, to an arrangement for reducing byproduct deposits on a set of plasma chamber surfaces of a plasma processing chamber. The arrangement includes barrier means disposed in the plasma processing chamber, the barrier means being configured to be disposed in a plasma generating region of the plasma processing chamber, thereby permitting at least some process byproducts produced when a plasma is struck within the plasma processing chamber to adhere to the deposition barrier and reducing the byproduct deposits on the set of plasma processing chamber surfaces. The arrangement also includes attachment means for attaching the barrier means to one of a top, bottom, and side of an interior of the plasma processing chamber.
[0016] The invention relates, in another embodiment, to a deposition barrier arrangement configured to reduce byproduct deposits on a set of plasma chamber surfaces of a plasma processing chamber. The arrangement includes a deposition barrier configured to be disposed in a plasma generating region of the plasma processing chamber, the deposition barrier being configured to enable at least some process byproducts produced when a plasma is struck within the plasma processing chamber to adhere to the deposition barrier and thereby reducing the byproduct deposits on the set of plasma chamber surfaces.
[0017] These and other features of the present invention will be described in more detail below in the detailed description of the invention and in conjunction with the following figures.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] The present invention is illustrated by way of example, and not by way of limitation, in the figures of the accompanying drawings and in which like reference numerals refer to similar elements and in which:
[0019] FIG. 1 shows a simplified diagram of a inductively coupled plasma processing system, such as a Lam Transformer Coupled Plasma Processing System;
[0020] FIG. 2 shows a simplified diagram of a inductively coupled plasma processing system with a deposition barrier, according to one embodiment of the invention;
[0021] FIG. 3 shows a simplified diagram of a inductively coupled plasma processing system in which a deposition barrier is supported with a structure that is attached to the bottom of the plasma chamber, according to one embodiment of the invention;
[0022] FIG. 4 shows a simplified diagram of a inductively coupled plasma processing system in which a deposition barrier is supported with a structure that is attached to the top of the plasma chamber, according to one embodiment of the invention;
[0023] FIG. 5 shows a simplified diagram of a inductively coupled plasma processing system in which a deposition barrier is supported with a structure that is attached to a side of the plasma chamber, according to one embodiment of the invention;
[0024] FIG. 6 shows a simplified diagram of a inductively coupled plasma processing system in which a deposition barrier is supported with a structure that is attached to a chuck, according to one embodiment of the invention; and,
[0025] FIG. 7 shows a simplified diagram of a method for the reduction of low volatility line-of-sight byproducts in a plasma processing system, according to one embodiment of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0026] The present invention will now be described in detail with reference to a few preferred embodiments thereof as illustrated in the accompanying drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. It will be apparent, however, to one skilled in the art, that the present invention may be practiced without some or all of these specific details. In other instances, well known process steps and/or structures have not been described in detail in order to not unnecessarily obscure the present invention.
[0027] While not wishing to be bound by theory, it is believed by the inventor herein that sputtering deposition can be reduced on a set of plasma chamber surfaces through the use of a deposition barrier that is substantially surrounded by a plasma. That is, a deposition barrier may be positioned such that if a particle is sputtered from the substrate toward a plasma chamber surface, the particle will first strike the deposition barrier.
[0028] In a non-obvious fashion, sputtered atoms that would normally collide with other surfaces in the chamber, as well as the pumping manifold including the turbo pump, can be intercepted with a deposition barrier that is substantially easy to remove. For example, the deposition barrier may be automatically transferred in and out of the plasma chamber to an ex-situ cleaning process. In one embodiment, the deposition barrier can also protect the electrostatic chuck during wafer-less auto clean WAC™ (or wafer less chamber conditioning), in which plasma chamber components are exposed to the plasma as part of the cleaning or conditioning/seasoning process.
[0029] Referring now to FIG. 2 , a simplified diagram of an inductive coupled plasma processing system is shown, according to one embodiment of the invention. In a common configuration, the plasma chamber is comprised of a bottom piece 250 located in the lower chamber, and a detachable top piece 252 located in the upper chamber. Generally, an appropriate set of gases is flowed into chamber 202 from gas distribution system 222 and through dielectric coupling window 204 . These plasma processing gases may be subsequently ionized at injector 209 to form a plasma 210 , in order to process (e.g., etch or deposition) exposed areas of substrate 214 , such as a semiconductor substrate or a glass pane, positioned with edge ring 215 on an electrostatic chuck 216 .
[0030] A first RF generator 234 generates the plasma as well as controls the plasma density, while a second RF generator 238 generates bias RF, commonly used to control the DC bias and the ion bombardment energy. Further coupled to source RF generator 234 is matching network 236 a , and to bias RF generator 238 is matching network 236 b , that attempt to match the impedances of the RF power sources to that of plasma 210 . Furthermore, pump 211 is commonly used to evacuate the ambient atmosphere from plasma chamber 202 in order to achieve the required pressure to sustain plasma 220 .
[0031] In addition, a deposition barrier 206 is positioned at a height above the bottom surface of said plasma reactor, such that if a particle is sputtered from the substrate toward a plasma chamber wall, the particle will first strike the deposition barrier.
[0032] Referring now to FIG. 3 , the simplified diagram of a inductive coupled plasma processing system of FIG. 2 is shown, in which a deposition barrier is supported with a structure 308 that is attached to the bottom of the plasma chamber (lower interior surface), according to one embodiment of the invention.
[0033] Referring now to FIG. 4 , the simplified diagram of a inductive coupled plasma processing system of FIG. 2 is shown, in which a deposition barrier is supported with a structure 408 that is attached to the top of the plasma chamber (upper interior surface), according to one embodiment of the invention.
[0034] Referring now to FIG. 5 the simplified diagram of a inductive coupled plasma processing system of FIG. 2 is shown, in which a deposition barrier is supported with a structure 508 that is attached to a side of the plasma chamber (side interior surface), according to one embodiment of the invention.
[0035] Referring now to FIG. 6 the simplified diagram of an inductive coupled plasma processing system of FIG. 2 is shown, in which a deposition barrier is supported with a structure 608 that is attached to chuck 216 , according to one embodiment of the invention.
[0036] In one embodiment, the height of the bottom surface of the deposition barrier can be repositioned relative to the bottom surface of said plasma reactor, in order to better optimize plasma processing conditions. In another embodiment, the deposition barrier is substantially transparent to a generated RF. In yet another embodiment, the deposition barrier comprises a material that is substantially resistant to plasma attack (i.e., quartz, Y 2 O 3 , yttrium, CeO 2 , cerium, ZrO 2 , zirconium, Teflon, Vespel, substantially pure plastic, ceramic, SiC, BN, BC, SiN, SiO, etc.). In yet another embodiment, the deposition barrier comprises a material that generates a set volatile etch products when exposed to said plasma.
[0037] In another embodiment, the deposition barrier is heated independently of the plasma. In yet another embodiment, a RF bias is applied to the deposition barrier. In yet another embodiment, deposition barrier can be removed in-situ, for example by a robotic arm. In yet another embodiment, deposition barrier can be replaced in-situ, for example by a robotic arm. In another embodiment, the deposition barrier may be removed from the plasma processing system by a vacuum robot under automatic control.
[0038] In yet another embodiment, deposition barrier includes a substantially continuous surface. In yet another embodiment, deposition barrier includes a set of holes. In yet another embodiment, deposition barrier can be removed prior to, simultaneously with, or after the removal of said substrate from said plasma chamber. In yet another embodiment, deposition barrier is a Faraday barrier.
[0039] In another embodiment, the deposition barrier can be cleaned and reused. In yet another embodiment, plasma processing system includes a source RF that is coupled from the top, side, or bottom of the plasma chamber. In yet another embodiment, a set of plasma chamber walls can be heated and/or cooled independently of the plasma.
[0040] In another embodiment, the deposition barrier may be heated to encourage adhesion of thicker films and to prevent incorporation of volatile species which may lead to premature flaking. In yet another embodiment, the deposition barrier may be cooled to increase the sticking probability of substantially volatile deposition by products and to enable thicker films before flaking. In yet another embodiment, the deposition barrier may be cleaned in-situ by a plasma cleaning process when the deposition barrier has cooled down from being hot. In yet another embodiment, the deposition barrier is cleaned in-situ by a plasma cleaning process when the deposition barrier has heated up from being cool.
[0041] In another embodiment, the deposition barrier is comprised of a metal that does not substantially generate a set of volatile etch products when exposed to the plasma (e.g. Ni, Pt, Ir, anodized Al, Cu, etc.).
[0042] In another embodiment, the deposition barrier may be cleaned in-situ by a plasma cleaning process. In yet another embodiment, the deposition barrier may be cleaned in-situ by a wet chemical flush process. In yet another embodiment, the deposition barrier comprises a material that is substantially resistant to a wet clean process. In yet another embodiment, the deposition barrier is coated by a material that is substantially resistant to a wet clean process. In another embodiment, the deposition barrier may be lowered onto the chuck, in order to protect the chuck, while running an in-situ plasma chamber clean. In another embodiment, the deposition barrier may be lowered onto the chuck, in order to protect the chuck, while the chamber is idle between substrate processing cycles.
[0043] In another embodiment the deposition barrier may protect a source RF. In yet another embodiment, the source RF comprises an inductive source. In yet another embodiment, the source RF comprises a capacitive source. In yet another embodiment the source RF comprises an ECR (electron-cyclotron resonance) source. In yet another embodiment, the source RF comprises a microwave source. In yet another embodiment, the source RF may be coupled from the top of the plasma chamber. In yet another embodiment, the source RF may be coupled from the side of the plasma chamber. In yet another embodiment, the source RF may be coupled from the bottom of the plasma chamber.
[0044] In another embodiment, the deposition barrier may protect a set of plasma gas injectors from erosion and deposition clogging. In another embodiment, the deposition barrier may protect a set of in-situ metrology sensors (such as optical emission, interferometry, etc.) or the transparent windows covering them from erosion and deposition clogging. In yet another embodiment, the deposition barrier surface has a pre-determined roughness which facilitates control of adhesion of the depositing material. In another embodiment, the deposition barrier surface has a pre-determined surface composition which facilitates control of adhesion of the depositing material.
[0045] Referring now to FIG. 7 , a simplified method for the reduction of low volatility products in a plasma processing system is shown, according to one embodiment of the invention. Initially, a substrate is positioned in a plasma processing chamber at step 702 . Next a deposition barrier is positioned in the plasma processing chamber, wherein a plasma can be struck that substantially surrounds the deposition barrier, at step 704 . A plasma is then struck within the plasma processing chamber, at step 706 . If a particle is sputtered from the substrate toward a plasma chamber surface from the set of plasma chamber surfaces, the particle will strike said deposition barrier, as step 708 .
[0046] The invention has been described in terms of several preferred embodiments, there are alterations, permutations, and equivalents which fall within the scope of this invention. For example, although the present invention has been described in connection with a Lam Research Transformer Coupled Plasma Processing System™, other plasma processing systems may be used (e.g., etching, deposition, ion sputter, electron beam, cluster ion beam. etc.) It should also be noted that there are many alternative ways of implementing the methods of the present invention.
[0047] Advantages of the invention include methods and arrangement for the reduction of byproduct deposition in a plasma processing system. Additional advantages include substantially improving productivity and device yield, the use of a common plasma chamber design across multiple plasma processing applications (i.e., FeRAM, MRAM, Cu, MEMS, metal gate high-k gate, etc.), process repeatability, low CoC, low COO, high MTBC, low MTTCR, and the extended lifetime of plasma chamber parts.
[0048] Having disclosed exemplary embodiments and the best mode, modifications and variations may be made to the disclosed embodiments while remaining within the subject and spirit of the invention as defined by the following claims. | In a plasma processing system, a method of reducing byproduct deposits on a set of plasma chamber surfaces of a plasma processing chamber is disclosed. The method includes providing a deposition barrier in the plasma processing chamber, the deposition barrier is configured to be disposed in a plasma generating region of the plasma processing chamber, thereby permitting at least some process byproducts produced when a plasma is struck within the plasma processing chamber to adhere to the deposition barrier and reducing the byproduct deposits on the set of plasma processing chamber surfaces. | 7 |
BACKGROUND OF THE INVENTION
The present invention relates to a high temperature oil containment boom which allows for the in-situ burning of spilled or leaked oil during offshore oil spill cleanup operations. In-situ burning represents one of the most effective means of eliminating large quantities of spilled oil. If conducted properly, with due consideration for the temporary reduction of air quality and the potential for exposure to fire, the in-situ burning of an oil spill can result in the least overall impact to the environment.
The remoteness of the sites of many oil production and transportation activities such as in Alaska, combined with the nature of the environment, provides ideal conditions for oil spill cleanup through in-situ burning. When considered in comparison to mechanical cleanup, chemical dispersants, and natural elimination processes, burning often provides an important option when some of the other techniques alone are impractical.
Research has revealed that oil can be ignited and combustion sustained when the oil layer on water is at least 1 to 2 mm thick. As thicknesses increase beyond this minimum value, there is less tendency for heat loss to the underlying water and, therefore, the chances are greater for efficient combustion. Thick oil layers have been consistently burned with efficiencies in excess of 95%, even under arctic conditions. To achieve such success through burning, it is important to concentrate any spilled oil as quickly as possible and to contain the burning oil so that winds and/or currents can help thicken the oil slick. During the burning process, temperatures in the order of 1100° C. are common.
Conventional oil containment booms are elongated cylinders having a generally circular cross-section. These booms float in water with approximately one-third of the boom submerged below the surface of the water forming a floating barrier to the spilled oil. The booms are typically stored in a roll on the deck of a ship and deployed downwind of a spill where it floats on the surface of the water and temporarily contains the spill.
Two fireproof oil containment booms for in-situ burning of oil spills were exhibited at the 1985 Oil Spill Conference held at Los Angeles, Calif., Feb. 25 to 27, 1985.
According to its brochure, the TTI Geotechnical Resources Ltd. Fireproof Oilspill Containment Boom consists of alternate rigid flotation units 1.668 m long, 1.78 m high weighing 108.8 kg and flexible (accordian folded) panels 0.906 m long, 1.70 m high weighing 102 kg connected together by connectors 0.07 m long, 1.67 m high weighing 10 kg. The boom is of stainless steel construction and the maximum exposure temperature is stated to be 980° C.
The available literature for the Globe International Inc. Pyroboom fireproof oil spill barrier states that it utilizes a unique blend of refractory and metallic materials in a woven fabric coated with a high temperature polymer coating (silicone rubber). Flotation is provided by a series of stainless steel hemispheres containing a high temperature resistant, closed cellular material. Two such hemispheres with the woven fabric enclosed between them are bolted together to form spheres 16 3/16 inches (41 cm) in diameter spaced 34 inches (86 cm) apart at their centerlines along the length of the woven fabric. The boom has an overall height of 30 inches (76 cm) with a draft of 20 inches (51 cm) and a freeboard of 10 inches (25 cm), and weighs 8 to 10 pounds per lineal foot (11.9 to 14.5 kg/m). The operating temperature range of the boom is stated to be -55° F. to +2400° F. (-48° C. to 1315° C.).
A fire resistant oil containment boom system designated as the SeaCurtain ReelPak FireGard Oil-Fire Containment Boom System is described in a brochure issued by Kepner Plastics Fabricators, Inc. That boom system appears to comprise compartmented circular sections containing a continuous stainless steel coil wire covered with a double walled foam-containing refractory fabric with an additional portion extending downwardly from the circular section, the bottom edge of the downwardly extending section having a chain ballast member attached thereto. The boom is stored on a reel from which it is deployed. The boom is stated to have an operating temperature range from -40° F. to over 2000° F. (-40° C. to 1093° C.) and, depending on model, weighs 2.2 lbs. to 4.2 lbs. per lineal foot (3.3 to 6.3 kg/m).
U.S. Pat. No. 4,537,528 is directed to a fireproof boom for containing a flammable pollutant on a water surface, the boom comprising a flotation member of foamed polypropylene and at least two layers of heat-resistant, water-sorbent material surrounding the flotation member and extending into the water in the form of a depending skirt. The skirt functions to draw water up into the layers of heat-resistant material forming steam in the presence of flaming pollutant thereby allowing only the outer layer of heat-resistant material to become slightly singed. It is understood that a bottom-tensioned, cylindrical-flotation fire containment boom is manufactured by Fire Control Inc. utilizing the teachings of said patent. The boom consists of multiple layers of fire-resistant, wicking fabric positioned over steel canisters for flotation. An additional sacrifical layer and a coarse wire-mesh barrier are used externally for abrasion resistance. The boom weighs 7 lbs. per lineal foot (10.5 kg/m).
An oil boom system utilizes a multilayered, fire-resistant blanket, provided by Minnesota Mining and Manufacturing Company (3M Company), the assignee of the present invention, for use as an add-on high temperature protective blanket to convert most conventional types of boom for the containment of burning oil. The blanket is placed about the periphery of the boom and is held in position by any number of fastening systems.
SUMMARY OF THE INVENTION
The present invention relates to a high temperature oil containment boom which allows for the in-situ burning of spilled or leaked oil and, in the event that the contained oil as not burned, the boom can be recovered, cleaned in the same manner as a conventional oil containment boom and stored for future deployment. The boom is capable of withstanding sustained exposure to temperatures on the order of 1200° C., thus allowing in-situ burning of the contained oil during offshore oil spill cleanup operations. The oil boom can also be employed as a precautionary measure during the more traditional oilspill cleanup operations to provide protection should accidental ignition of the spilled oil occur. In this situation, the boom would, of course, be recovered and processed for redeployment.
The oil boom of the present invention comprises an outer layer of polymer coated fabric, a first underlayer of high temperature resistant and moisture resistant refractory fabric and a second underlayer of a high or intermediate temperature resistant refractory fabric which constrains and assists in retaining the integrity of a low density, high temperature resistant core. The layers are unified by sewing with high temperature resistant ceramic thread or by mechanical fasteners.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view, partly in section, of the high temperature oil containment boom of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The invention can best be understood by reference to the drawing. The high temperature oil containment boom 10 comprises an outer layer 11 of polymer coated fabric, a first underlayer 12 of high temperature resistant and moisture resistant refractory fabric, a second underlayer 13 of high or intermediate temperature resistant refractory fabric which constrains and assists in retaining the integrity (shape) of low density, high temperature resistant flotation core 14. Water line 20 shows that the boom 10 floats on the water with approximately one-third of the boom submerged below the surface.
Polymer coated fabric outer layer 11 is preferably a nylon fabric coated with low alkali content polyvinylchloride (PVC), having a basis weight of 0.61 kg/m 2 and available as Style 145230 from VERSEID AG. Outer layer 11 allows the high temperature oil boom to be conveniently handled and function, if desired, as a conventional non-fire oil containment boom. Outer layer 11, during fire containment, melts to the water line causing the high temperature resistant refractory fabric first underlayer 12 to be exposed to the burning oil. Outer layer 11, may also, if desired, be provided with a ballast chain pocket 15.
First underlayer 12 of high temperature resistant and moisture resistant refractory fabric is preferably a 1.29 mm thick open mesh, plain weave, 3×3 picks/cm fabric woven from 1800 denier, 1.5/4 plied continuous polycrystalline metal oxide fiber yarn comprising, by weight, 62% aluminum oxide, 14% boron oxide and 24% silicon dioxide and commercially available as Nextel 312 fabric from 3M Company. This specific fabric has a basis weight of 0.89 kg/m 2 . A useful but heavier and also more expensive fabric for first underlayer 12 is a tightly woven 3.35 mm thick, closed mesh, plain weave, 8×3 picks/cm fabric woven from the same Nextel 312 yarn. This heavier fabric has a basis weight of 1.35 kg/m 2 . Other high temperature resistant and moisture resistant fabrics which can be used as first underlayer 12 include fabrics fabricated from Nextel 440 ceramic yarn comprising, by weight, 70% aluminum oxide, 28% silicon dioxide and 2% boron oxide (3M Company), Astroquartz ceramic fibers (J. P. Stevens) and leached fiberglass filaments (Hitco or Haveg).
The high temperature resistant and moisture resistant refractory fabric of first underlayer 12 may optionally be coated with a polymer coating such as a silicone rubber, a neoprene rubber, a fluorinated elastomer or an acrylic polymer. The polymer coating serves to hold the yarns of the fabric firmly in place during assembly and provides an abrasion resistant coating for the fabric. A particularly preferred coating is Neoprene GN (duPont), which is applied to the fabric at a coating weight of 0.16 kg/m 2 . The polymer coating is applied by dip coating, with the polymer solution coating the yarn while leaving the mesh interstices substantially open, allowed to dry and cured at a temperature of 160° C. It will be appreciated that the polymer coating, in those areas exposed to the heat of combustion of the contained oil, will be burned off but it will have served its processing and protection functions. The fabric of first underlayer 12 retains its high temperature and moisture resistant characteristics even without the polymer coating.
The second underlayer 13 preferably comprises a 0.63 mm thick, high tensile strength, woven fiberglass fabric, Style 1583, weighing 0.54 kg/m 2 (Clark Schwebel). Layer 13 allows the boom to be assembled into a unified structure by constraining the low density, high temperature resistant core 14 and helps retain the integrity (shape) of the core 14 after exposure to burning oil. It is also useful in preventing the passage of oil through the boom during use.
High temperature resistant flotation core 14 preferably comprises inert, low density ceramic macrospheres (3M Company) which, especially for convenience in assembling the boom, may be retained in a plastic containment bag 14a. 3M Ceramic Macrospheres are inert, low density ceramic macrospheres containing a multiplicity of minute independent closed air cells surrounded by a tough outer shell. The spheres are impermeable to water and other fluids and, being a true ceramic, are functional at extremely high temperatures. It will be appreciated in this instance also that the plastic containment bag 14a, in those areas exposed to the heat of combustion of the spilled oil may melt; however, it will have served its processing function. Furthermore, layers 12 and 13 will serve to contain the ceramic macrospheres before and after exposure to burning oil. Pyrofoam insulation particles, available from High Temperature Insulation Materials, have also been found to be satisfactory for flotation core 14. Pyrofoam insulation particles are small, inert, low density, air filled, closed cells of expanded obsidian and are functional at extremely high temperatures.
Boom 10 is fabricated by layerwise assembling a composite of outer layer 11, first underlayer 12 and second underlayer 13 in registration over flotation core 14. The thus formed composite structure is unified by sewing along lines 16 using a high temperature resistant ceramic thread such as Nextel AT 32 ceramic thread (3M Company). Instead of sewing with the ceramic thread, a stainless steel wire could be used to simiarly "sew" the structure or suitably spaced mechanical fasteners could be employed. If desired, the outer layer 11 could also be sewn together along lines 17 providing a ballast chain pocket 15. Since seam lines 17 are below water during boom use, they are preferably produced by using heavy duty nylon thread. Boom 10 is preferably fabricated into individual flotation compartments or sections by sewing along lines 18 with high temperature resistant ceramic thread, each section measuring about five feet (1.5 m) in length. A typical boom is 25 feet (7.6 m) in length and thus comprises five sections. Longer length booms are fabricated by joining such individual booms using conventional connector means. The sectional design assists in handleability and eases storage of the booms, especially long length booms, since the sections allow for accordian folding of the boom. Also, accidental tearing or rupturing of the boom would limit the amount of flotation media which would be released and require recovery.
Since each of the components of boom 10 is non-hygroscopic, very little water is retained in the boom and recovery of the boom is not hampered by the added weight of absorbed water. In fact, after a fire use, the boom is lighter in weight since outer layer 11 and the protective polymer coating on first underlayer 12 would have been substantially burned off by the fire.
Laboratory testing has shown that high temperature oil containment boom 10 can function as a conventional oil containment boom and then can be redeployed for use in a burning operation. To further evaluate the utility of oil boom 10 under simulated fire use conditions, a 9 foot (2.7 m) diameter ring of an 8 inch (20.3 cm) float diameter boom with a 12 inch (30.4 cm) skirt, weighing 5.8 pounds per lineal feet (8.7 kg per lineal meter), was fire tested for two hours with a continuous feed heptane fire. The boom was extremely effective as a high temperature fire containment product at burning temperatures up to 1325° F. (720° C.). Smaller lab tests have been run up to 1800° F. (980° C.) with all materials remaining strong and unchanged.
Although oil boom 10 has been illustrated and described herein with some specificity, various modifications may readily suggest themselves and are contemplated. As one example, outer layer 11 could be produced using a polymer coated high temperature resistant refractory fabric although that would increase the cost and reduce handleability somewhat. | A high temperature oil containment boom which allows for the in-situ burning of spilled or leaked oil during offshore oil spill cleanup operations is disclosed. The boom can be used for precautionary fire containment during non-burn oil spill cleanups and can be easily recovered and redeployed. | 4 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 2002-011312, filed Jan. 21, 2002, the entire contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a portable information apparatus with a liquid-crystal display device
2. Description of the Related Art
A portable information apparatus, such as a laptop or a notebook computer or a word processor, is roughly composed of two units as shown in perspective views of FIGS. 7A and 7B . FIG. 7A shows the opened state of the apparatus and FIG. 7B shows the closed state of the apparatus. Specifically, one unit is a body 131 which has the function of inputting, processing, and storing information. The other unit is a display section 133 which has a display screen 132 for displaying information. The body 131 and the display section 133 , which are connected electrically with an FPC (Flat Package Cable), electric wires, or the like, are capable of displaying the information from the body freely on the display section 133 .
The body 131 and the display section 133 are connected via hinge parts 134 in such a manner that they can be opened and closed freely. The hinge parts 134 , whose configuration is shown in FIG. 8 , are fixed to the body 131 . The display section 133 can therefore be opened and closed freely to the body 131 as needed. Giving suitable friction to the rotating sections of the hinge parts 134 makes it possible to keep the opening angle of the display section 133 . That is, the user of the portable information apparatus can do setting, with the display section 133 inclined at an easy-to-see, easy-to-use angle. When the user doesn't use the portable information apparatus, he or she can close the display section 133 in such a manner that the display screen 132 is housed inside the apparatus. As a result, the fragile display screen 132 can be protected.
FIG. 9 is an exploded view of the display section 133 . As shown in FIG. 9 , the display section 133 is generally composed of a liquid-crystal display device 135 from an energy-saving viewpoint. To protect the liquid-crystal display device 135 from external forces, such as push or drop impact, the display device 135 is contained in a housing 136 . The housing 136 is formed in a resin mold made of PC/ABS resin or carbon-fiber-added, glass-fiber-added, or inorganic filler-added PC/ABS resin. Alternatively, the housing 136 is made of magnesium alloy or aluminium alloy. The housing 136 is composed of a cover housing 137 for protecting the surfaces of the liquid-crystal display device 135 excluding the display screen 132 and a frame housing 138 for protecting the periphery of the display screen 132 . The liquid-crystal display device 135 is fixed to the cover housing 136 by means of hinge metal fittings 139 .
With the body 131 engaged with the display section 133 , when the display section 133 is opened, if the hinge metal fittings 139 are supported only by the hinge parts 134 , great resistance is produced at the supporting sections, because the supporting sections at which the hinge parts 134 support the display section 133 are short. Consequently, stress is concentrated at the roots of the cover housing 137 supported by the hinge parts 134 . Therefore, the repeated opening and closing of the display section 133 can do damage to the roots of the cover housing 137 . To avoid this problem, the hinge metal fittings 139 are used structurally so as to act as what is obtained by lengthening the supporting sections of the hinge parts 134 in the direction in which the display section 133 is supported. That is, the cover housing 137 is supported in such a manner that not only area A but also area B of the hinge metal fitting can receive the load imposed when the display section 133 is opened. The hinge metal fitting 139 is formed by cutting a metal plate and bending the resulting plate. In this case, area A screwed to the hinge part 134 provided on the body 131 side and area B mechanically connected to the cover housing 137 and liquid-crystal display device 135 are formed in such a manner that area A and area B are perpendicular to each other. Area B is located in the spacing between the cover housing 137 and the liquid-crystal display device 135 at right and left with respect to the display screen. Area B is screwed to the cover housing 137 and liquid-crystal display device 135 at a plurality of places or is fastened to the latter in a similar manner. The screwed section of area A also has the function of preventing damage.
FIG. 10 is a schematic diagram to help explain the fixing structure using the hinge metal fittings 139 . The liquid-crystal display device 135 has two fastening sections formed at symmetrical positions on the side faces. On one side-face side, the fastening section close to the hinge is screwed via the hinge metal fitting 139 to the cover housing 137 . On the other side-face side, the fastening section is screwed directly to the cover housing 137 without a hinge metal fitting 139 . On the other side-face side, a projecting spacer 140 (shown in FIGS. 11C and 11D explained later) formed at the side face of the liquid-crystal display device 135 is inserted into an engaging hole made in the cover housing 137 and hinge metal fitting 139 , thereby engaging with the hole.
FIGS. 11A to 11 D are plan views and side views to help explain fastening methods at the fastening sections. The fastening methods are roughly divided into the following three types: (1) a method of fastening the cover housing 137 , hinge metal fitting 139 , and the liquid-crystal display device 135 together, (2) a method of screwing the liquid-crystal display device 135 and the cover housing 137 , and the cover 137 together, and (3) a method of allowing the liquid-crystal display device 135 to move in a specific direction with respect to the hinge metal fitting 139 and cover housing 137 .
FIGS. 11A and 11B show the method in item (1). A hole whose diameter is larger than the thread's outside diameter of a screw 141 and smaller than the head of the screw 141 . The screw 141 is screwed into a female screw formed at the side face of the liquid-crystal display device 135 . At the cover housing 137 of the screw fastening section, a pedestal 143 is formed from an concave portion of a rib 142 so as to prevent the head of the screw from projecting from the cover housing.
FIGS. 12A and 12B show the method in item (2). Since the hinge metal fitting 139 extends only to half of the right and left side faces of the liquid-crystal display device 135 , the liquid-crystal display device 135 and the cover housing 137 are screwed together directly at a place to which the screwed section of area A does not reach.
FIGS. 13A , 13 B, 14 A, and 14 B show the method in item (3).
To absorb the variation of tolerance in the liquid-crystal display device 135 , the screwing of the liquid-crystal display device 135 and the cover housing 137 used in item (1) and item (2) is done only at either right or left with respect to the display screen 132 . On the other hand, on the opposite side, the liquid-crystal display device 135 is designed to be movable with respect to the hinge metal fitting 139 and cover housing 137 . That is, the spacer 140 provided on the liquid-crystal display device 135 is guided into the hole (or a long hole) made in the hinge metal fitting 139 and cover housing 137 , which enables as much displacement as the variation of tolerance between the hole and the spacer 140 .
In the above-described fastening methods, however, the methods in item (1) and item (2) require the pedestal 143 for the head of the screw 141 at the side face of the cover housing 137 as shown in FIGS. 11A , 11 B, 12 A, and 13 B. In the fastening method of allowing the liquid-crystal display device 135 to move as in item (3), since the hole for guiding the spacer 140 is needed where there is no hinge metal fitting 139 , the same structure as the pedestal 143 has to be provided. When a pedestal is provided on the right and left side faces of the inside of the cover housing 137 , the rib 142 (shown in FIGS. 11B , 12 B, and 14 B) connected to the pedestal from inside the cover housing 137 is required to secure the strength of the pedestal.
FIG. 15A shows a state of a product before collision. When the product drops in the right-to-left direction with respect to the display screen and the side face of the display section receives impact, the rib 142 fixed with the screw 141 is deformed due to the impact as shown in FIG. 15B showing a state of the product after the collision. Generally, the longer the distance the product moves from when it receives the impact load until its speed decreases to zero, that is, the longer the braking distance, the lower the produced acceleration. However, since the rib 142 stands in the direction in which the product drops, it serves to restrict the displacement of the liquid-crystal display device 135 . This gives a high acceleration to the liquid-crystal display device 135 , with the result that the liquid-crystal display device 135 can be broken.
BRIEF SUMMARY OF THE INVENTION
An object of the present invention is to provide not only a mounting structure of a liquid-crystal display device which prevents the housing of the display section fixing the hinges from being broken even when the display section is opened and closed repeatedly and improves the drop strength, but also a portable information apparatus using the mounting structure.
To solve the above problems and achieve the object, a portable information apparatus comprising: a first housing; and a second housing which is mounted to the first housing in such a manner that it can be rocked freely, with its main face facing the first housing, and which includes a panel-like display device with a display screen exposed at the main face and a hinge member to mount the display device in the second housing, wherein the hinge member includes a fixed member fixed to the second housing and an extended member mounted to the fixed member and intervening between the display device and the inner wall of the second housing, and the extended member includes a pressing section which presses against the side face of the display device and a flexible curved section which is provided so as to be continuous with the pressing section and which is formed convexly at the inner wall of the second housing.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
FIG. 1A is a perspective view of a portable information apparatus according to a first embodiment of the present invention;
FIG. 1B is a plan view of the main part of the portable information apparatus;
FIG. 1C is an exploded perspective view of the main part of the portable information apparatus;
FIG. 2 is a perspective view of a liquid-crystal display device mounted in a cover housing;
FIG. 3A is a graph for a history of acceleration in a conventional structure by drop impact analysis and FIG. 3B is a graph for a history of acceleration in a structure according to the present invention;
FIG. 4 schematically shows a hinge member according to a second embodiment of the present invention;
FIG. 5 schematically shows a hinge member according to a third embodiment of the present invention;
FIG. 6 schematically shows a hinge member according to a fourth embodiment of the present invention;
FIG. 7A is a perspective view of the portable information apparatus, with the display section opened, and FIG. 7B is a perspective view of the portable information apparatus, with the display section closed;
FIG. 8 shows the configuration of a hinge part;
FIG. 9 is an exploded view of a conventional display section;
FIG. 10 is a schematic explanatory diagram of a fixing structure using conventional hinge metal fittings;
FIGS. 11A and 11B are a side view and a plan view of a conventional fastening section, respectively;
FIGS. 12A and 12B are a side view and a plan view of another conventional fastening section, respectively;
FIGS. 13A and 13B are a side view and a plan view of still another conventional fastening section, respectively;
FIGS. 14A and 14B are a side view and a plan view of still another conventional fastening section, respectively; and
FIG. 15A is a schematic diagram of a state of a product before a collision and FIG. 15B is a schematic diagram of a state of the product after the collision.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1A shows a portable information apparatus 10 , such as a laptop or a notebook personal computer or a word processor. As shown in FIG. 1A , the portable information apparatus 10 includes a first body 20 and a second body 30 joined with each other in such a manner that they can be opened and closed. The first body 20 , which has a box-like body housing 21 , includes not only a keyboard 22 and an input device, such as a pointing device, but also a CPU-carrying motherboard 24 and a hard disk 25 .
The second body 30 has a display section housing 31 . The display section housing 31 is composed of a box-like cover housing 32 with its top opened and a frame housing 33 to be mounted in the opening of the cover housing 32 . Inside the display section housing 31 , a liquid-crystal display device 34 for displaying information is housed. In the figure, numeral 34 a indicates the display screen of the liquid-crystal display device, 34 b indicates the left side face, and 34 c indicates the right side face.
The body housing 21 and the display section housing 31 are joined with each other via hinge parts 26 shown in FIG. 1C in such a manner that they can be opened and closed. When the portable information apparatus is not used or is being carried, closing the body housing 21 and the display section housing 31 so as to stack them one on top of the other enables the display screen 34 a of the liquid-crystal display device 34 to be protected. Giving suitable friction to the rotating mechanisms 26 a of the hinge parts 26 makes it possible to keep the opening angle of the second body 30 .
The motherboard 24 and the liquid-crystal display device 34 are connected electrically by means of FPC (Flat Package Cable), electric wires, or the like.
FIG. 1B is a plan view of the liquid-crystal display device 34 mounted in the cover housing 32 . In FIG. 1B , cylindrical projecting sections 35 a , 35 b are formed close to the upper end and the lower end, respectively, at the right side face of the liquid-crystal display device 34 . A cylindrical projecting section 35 c is formed close to the upper end at the left side face 34 b . In addition, a female screw 36 is provided close to the lower end at the left side face 34 b of the liquid-crystal display device 34 in FIG. 1 B.
In FIG. 1B , numerals 40 , 50 indicate hinge members made of elastic metal material (e.g., SUS). The hinge member 40 includes a fixed member 41 screwed to the cover housing 32 by means of a male screw S and an extended member 42 which is formed integrally with the fixed member 41 and provided along the spacing between the side face of the liquid-crystal display device 34 and the inner wall P of the cover housing 32 .
The extended member 42 is composed of a first flat plate section 43 , a curved section 44 , a second flat plate section 45 . The first flat plate section 43 extend almost parallel to the left side 34 b of the liquid-crystal display device 34 and has at least one part contacting the left side 34 b of the device 34 . The curved section 44 is continuous with the first flat plate 43 . The second flat plate section 45 extends almost parallel to the left side 34 b of the device 34 and has at least one part contacting the left side 34 b of the device 34 . The first flat plate section 43 has a hole 43 a . A male screw S lies in the hole 43 a and set in screw engagement with the female screw 36 of the liquid-crystal display device 34 . The curved section 44 has a ridge section 44 a , a flat top section 44 b , and a ridge section 44 c . The ridge section 44 a extends the first flat plate section 43 , slantwise to the inner wall P. The flat top section 44 b is continuous with the ridge section 44 a and has at least one part contacting the inner wall P. The ridge section 44 c is continuous with the top section 44 b , extends slantwise to the inner wall P and is coupled to the second flat plate section 44 . At the top section 44 b , a concave section 44 d is formed. In addition, the second flat plate section 45 has a hole 45 a . The projecting section 35 c of the liquid-crystal display device 34 is inserted in the hole 45 a and can freely side in the hole. A rib 45 b is provided at the tip of the second flat plate section 45 .
The hinge member 50 includes a fixed member 51 screwed to the cover housing 32 by means of a male screw S and an extended member 52 which is formed integrally with the fixed member 51 and provided along the spacing between the side face of the liquid-crystal display device 34 and the inner wall Q of the cover housing 32 .
The extended member 52 is composed of a first flat plate section 53 , a curved section 54 , and a second flat plate section 55 . The flat plate section 53 extend almost parallel to the right side 34 c of the liquid-crystal display device 34 and has at least one part contacting the right side 34 c of the device 34 . The curved section 54 is continuous with the first flat plate 53 . The second flat plate section 55 extends almost parallel to the right side 34 c of the device 34 and has at least one part contacting the right side 34 c of the device 34 . The first flat plate section 53 has a hole 53 a . The projecting section 35 c of the liquid-crystal display device 34 is inserted in the hole 53 a and can freely slide in the hole 53 a . The curved section 54 has a ridge section 54 a , a flat top section 54 b , and a ridge section 54 c . The ridge section 54 a extends from the first flat plate section 53 , slantwise to the inner wall P. The flat top section 54 b is continuous with the ridge section 54 a and contacts the inner wall Q. The ridge section 54 c is continuous with the top section 54 b , extends slantwise to the inner wall P and is coupled to the second flat plate section 54 . At the top section 54 b , a concave section 54 d is formed. In addition, a hole 55 a is made in the second flat plate section 55 . The projecting section 35 c of the liquid-crystal display device 34 is inserted into the hole 55 a in such a manner that it slides freely into the hole. A rib 55 b is provided at the tip of the second flat plate section 55 .
The extended sections 42 , 52 enable both of the side faces 34 b , 34 c of the liquid-crystal display device 34 to be held elastically against the cover housing 32 .
The shape of the curved sections 44 , 54 of the hinge parts 40 , 50 has only to be capable of giving nearly uniform elasticity in both of the right and left directions in such a manner that both of the side faces 34 b , 34 c of the liquid-crystal display device 34 become parallel with the inner walls P, Q of the cover housing 32 . As described above, a trapezoid shape with no base in its side view has only to be formed at each of the inner walls in such a manner that the shape projects toward the inner wall. If this is the case, the top sections 44 b and 54 b contact the inner walls P and Q of the cover housing 32 . Although the ridge portions 44 a , 44 c , 54 a and 54 c may be curved, not straight, the top sections 44 b and 54 b should better be flat and straight, extending almost parallel to the inner walls P and Q. More than one top section may be provided for each inner wall.
The hinge parts 40 and 50 may be shaped such that the line connecting the point where either contacts a side of the display device 34 and the point where either contacts or lies nearest the inner surface of the device 34 inclines to the side of the device 43 , not perpendicular to the side of the device 43 .
The hinge parts 40 and 50 may have only one ridge portion. (The hinge part 40 , for example, may be cut at the concave section 44 d .)
The top sections 44 b and 54 b contact the inner walls P and Q. Instead, they may be coupled to the inner walls P and Q by spacers or the like. The present invention can be applied not only to liquid crystal displays, but also to all portable displays for use in portable information apparatus, such as EL (Electro Luminescent) displays, PDs (Plasma Displays) and FEDs (Field Emission Displays).
Projecting rib tongues 32 a for locking the top sections 44 b , 54 b of the hinge parts 40 , 50 are formed at the cover housing 32 . The tongues 32 a prevent the liquid-crystal display device 34 from coming off the cover housing 32 . The ribs 45 b , 55 b of the hinge members 40 , 50 function as stoppers when the liquid-crystal display device 34 is moved by external forces.
With the above configuration, when the display section of the liquid-crystal display device 34 drops in the right-to-left direction with respect to the display screen, with the liquid-crystal display device 34 mounted in the cover housing 32 , acceleration produced in the liquid-crystal display device 34 can be decreased, because the curved section 44 , 54 of the hinge members 40 , 50 are distorted toward the liquid-crystal display device 34 .
As shown in the perspective view of FIG. 2 , when the liquid-crystal display device 34 mounted in the cover housing 32 in each of the embodiment and the prior art was dropped from a height of 100 mm and the right side face 34 c collided with the display screen of the liquid-crystal display device 34 , drop impact analysis was made to find acceleration in the direction of drop produced in the liquid-crystal display device 34 . In FIG. 2 , ch 1 to ch 5 indicate the measuring positions of acceleration G.
FIG. 3A is a graph showing a history of acceleration in the prior art structure. FIG. 3B is a graph showing a history of acceleration in the above-described structure. The abscissa axis indicates time and the ordinate axis indicates acceleration. In both of the graphs, similar trends were measured at ch 1 to ch 5 . It is clear that acceleration is lower in the structure of the embodiment shown in FIG. 3 B.
The result of the comparison has shown that changing the conventional structure in FIG. 3A to the structure of the embodiment in FIG. 3B makes it possible to almost halve the maximum value of the acceleration and therefore alleviate the impact against the liquid-crystal display device 34 remarkably.
In the portable information apparatus 10 , of the left and right hinge members 40 , 50 , only the hinge member 40 is screwed to the liquid-crystal display device 34 and the projecting parts 35 a , 35 b provided on the liquid-crystal display device 34 are guided and inserted into the holes 53 a , 55 a in the hinge member 50 . Therefore, when the second body 30 is manufactured by combining the two types of hinge parts, the assembly tolerance of the parts can be absorbed.
The projecting tongue 32 a is provided on each of the right and left inner side faces of the cover housing 32 in such a manner that the tongue is formed as a part of the cover housing 32 . The tongues 32 a are designed to be covered by the concave sections 44 d , 54 d formed at the top of the trapezoid of the top sections 44 b , 54 b of the hinge members 40 , 50 . This prevents the hinge members 40 , 50 and liquid-crystal display device 34 from separating from and coming off the cover housing 32 .
Furthermore, the ribs provided on the cover housing 32 restrict the displacement of the free tips of the hinge members 40 , 50 in the longitudinal direction of the hinge members 40 , 50 . This enables both of the screwed places and the places locked by the ribs to receive impact, when the display section drops vertically toward the display screen. Consequently, the impact on the screwed places is alleviated, which prevents the screwed places from being damaged.
As described above, in the portable information apparatus 10 according to the first embodiment, the hinge members 40 , 50 enable the liquid-crystal display device 34 not only to be used as means for being mounted in the cover housing 32 but also to add the function of withstanding external vibration or impact.
FIG. 4 schematically shows a second embodiment of the present invention. In the second embodiment, a hinge member 60 is used in place of the hinge members 40 , 50 . The hinge member 60 includes a fixed member 61 screwed to the cover housing 32 by means of a male screw S and an extended member 62 which is formed integrally with the fixed member 61 and provided along the spacing between the side face of the liquid-crystal display device 34 and the inner wall Q of the cover housing 32 .
The extended member 62 is composed of a first flat plate section 63 provided so as to make close contact with the right side face 34 c of the liquid-crystal display device 34 , a first curved section 64 , a second flat plate section 65 , a second curved section 66 , and a third flat plate section 67 . Specifically, in the second embodiment, the spring force of the hinge member 60 is produced in such a manner that the force is distributed to the first and second curved sections 64 , 66 according to the number of the curved sections. That is, the larger the number of curved sections, the higher the rigidity of the hinge member 60 against drop impact, since more springs are arranged in parallel. When a dropping height is large, or when the mass of the liquid-crystal display device 34 is large, high rigidity is required. In contrast, when the dropping height is small, or when the mass of the liquid-crystal display device 34 is small, low rigidity is required, because too high rigidity does not provide a suitable spring characteristic. That is, when a uniform curve is given to the hinge member 60 , the number of curved sections has only to be determined according to the required rigidity.
FIG. 5 schematically shows a third embodiment of the present invention. In the third embodiment, a hinge member 70 is used in place of the hinge members 40 , 50 .
The hinge member 70 includes a fixed member 71 screwed to the cover housing 32 by means of a male screw S and an extended member 72 which is formed integrally with the fixed member 71 and provided along the spacing between the side face of the liquid-crystal display device 34 and the inner wall Q of the cover housing 32 .
The extended member 72 is composed of a first flat plate section 73 provided so as to make close contact with the right side face 34 c of the liquid-crystal display device 34 , a first curved section 74 , a second flat plate section 75 provided so as to make close contact with the right side face 34 c of the liquid-crystal display device 34 , a second curved section 76 , and a third flat plate section 77 provided so as to make close contact with the right side face 34 c of the liquid-crystal display device 34 .
In the third embodiment, it is assumed that, when the portable information apparatus 10 drops, there are two cases: one case where the apparatus 10 falls from a small height (that is, the hinge with a low rigidity is required) and the other case where the apparatus 10 falls from a large height (that is, the hinge with a high rigidity is required).
Under this assumption, a first and a second curved section 74 , 76 differing in size are formed in the hinge member 60 as shown in FIG. 5 . When the dropping height is small, the second curved section 76 functions as a spring. When the dropping height is large, the second curved section 76 , together with the first curved section 74 , functions as a spring. As a result, the rigidity of the hinge member 70 can be changed according to the dropping height. Of course, the number of types of curved sections the single hinge member 70 has is not limited to two and further the number of curved sections is not limited to two. In the ridge sections of the curved sections of the hinge member 70 , the steeper their slope, the higher the rigidity of the spring. For example, the slope of the second curved section 76 is made steeper than that of the first curved section 74 . This makes the rigidity of the spring of the second curved section 76 higher.
FIG. 6 schematically shows a fourth embodiment of the present invention. In the fourth embodiment, a hinge member 80 is used in place of the hinge members 40 , 50 .
While in the first to third embodiments, a trapezoid curved section has been formed, a trapezoid curved section is not formed in the hinge member 80 . Specifically, the hinge member 80 includes a fixed member 81 screwed to the cover housing 32 by means of a male screw S and an extended member 82 which is formed integrally with the fixed member 81 and provided along the spacing between the side face of the liquid-crystal display device 34 and the inner wall Q of the cover housing 32 .
The extended member 82 is so formed that first to fourth arc-like curved sections 83 to 86 describe a large arc. All of the convex side of the arc is on the inner wall Q side. In this case, the top section 84 a of the second curved section 84 and the top section 86 a of the fourth curved section 86 make contact with the cover housing 32 . With this structure, as the dropping height increases, the curved sections functioning as a spring also increases, both of a large dropping height and a small dropping height can be dealt with.
As described above, according to the above embodiments, since the side faces of the liquid-crystal display device 34 are supported elastically and fixed to the cover housing 32 , the cover housing 32 to which the hinges are fixed will not be broken, even when the display section is opened and closed repeatedly. Furthermore, with the above structure, the drop strength is improved.
Therefore, even when a portable information apparatus, such as a laptop or notebook personal computer or a word processor, undergoes vibration or impact from the outside world, it is possible to prevent the apparatus from being damaged heavily.
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. | A portable information apparatus comprises a first housing, and a second housing which is mounted to the first housing in such a manner that it can be rocked freely, with its main face facing the first housing, and which includes a panel-like display device with a display screen exposed at the main face and a hinge member to mount the display device in the second housing, wherein the hinge member includes a fixed member fixed to the second housing and an extended member mounted to the fixed member and intervening between the display device and the inner wall of the second housing, and the extended member includes a pressing section which presses against the side face of the display device and a flexible curved section which is provided so as to be continuous with the pressing section and which is formed convexly at the inner wall of the second housing. | 8 |
CROSS REFERENCES TO RELATED APPLICATIONS
[0001] This application claims benefit under 35 U.S.C. § 119(e) from U.S. Provisional Patent Application Serial No. 60/325,167 filed on Sep. 28, 2001, the entire contents of said application being expressly incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The invention relates to a method and apparatus for controlling audio speakers and, more particularly, to a method and apparatus for controlling a plurality of remote audio speakers from a central station via centralized amplifiers.
BACKGROUND OF THE INVENTION
[0003] Public address systems have been configured traditionally with multiple speakers that are connected together and driven with a common signal, or combined together as multiple networks or zones with a common signal per zone. The common signal originates from one or more sources of audio signal selected for transmission to all speakers, or to all speakers in a zone.
[0004] Typically, a public address system is configured as a system in which the amplifiers are colocated with the speakers, that is, the amplifiers are located in the same enclosure as the speakers. A user can adjust the volume of the speakers at the amplifier. The design is simple. A signal from the same source is transmitted to each amplifier. If the amplifiers are distributed throughout the building, different listeners can adjust the volume of the speakers to suit the environment they are in. For example, a listener in a noisy machine shop can adjust the volume to a higher level than a listener receiving the same signal in an office.
[0005] U.S. Pat. No. 4,922,536 discloses frequency division (FDM) and/or time division multiplexing (TDM) to digitally transmit audio signals from multiple microphones to a control booth, and to digitally transmit audio signals from the control booth to speakers. At each end of the digital transmission, the digital signals are converted to analog signals for processing. The control booth provides the control for all of the speakers. In another example, use of a microprocessor in a computing system to control routing of audio signals on a computer bus is shown in U.S. Pat. No. 4,862,159. In both of these audio systems, the speakers are dumb devices, that is, there is no digital audio processing at the speakers themselves.
[0006] Another example of a distributed speaker system is disclosed in U.K. Patent Application GB 2,123,193A which discloses a speaker system having a master station and remote speakers. Each of the remote speakers has a unique address, and the volume of each speaker can be individually adjusted. However, each speaker requires a respective amplifier that is integrated with the speaker. The amplifier also acts as a switching device to turn the speakers on and off
[0007] Thus, it is desirable to provide more flexibility in a speaker system network by using separate audio signals at each speaker in the network. For example, an operator at a central point may wish to transmit a message to only selected speakers in a network, or in multiple networks or zones, rather than to all speakers in a network or zone. Further, it is desirable to maintain amplifiers for each of the speakers in a speaker system network in a central location. Thus, the remote units are less expensive and simpler to maintain.
[0008] It is also desirable to provide separate volume control for each speaker, and to selectively broadcast the audio signal to selected speakers in the network system. For example, it is desirable for a public address system to remotely adjust the volume at selected speakers and selectively broadcast to the speakers.
SUMMARY OF THE INVENTION
[0009] In accordance with the present invention, a speaker system is provided having distributed speakers and amplifiers and centralized speaker monitoring and command control.
[0010] In accordance with an aspect of the present invention, an intelligent speaker unit is provided for use in the speaker system. In such a system, remote speakers can be selected. The volume for the selected speakers can be adjusted for its corresponding environment, and all of these tasks can be accomplished from a master station. In addition, the volume of the remote speakers can be adjusted locally or remotely using a field programmable device. A central amplifier is colocated with the master station and can serve a plurality of speakers.
[0011] In accordance with another aspect of the present invention, power is provided to the remote speaker units using an inaudible signal that is controlled from the master station via a tone generator.
[0012] In accordance with still another aspect of the present invention, the remote speakers can be addressed individually or as part of a group. Thus, each remote speaker and each group are capable of receiving unique content specific, respectively, to the individual remote speaker address and group address.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] The details of the present invention can be readily understood by considering the following detailed description in conjunction with the accompanying drawings, in which:
[0014] [0014]FIG. 1 is a block diagram of a public address (PA) speaker system constructed in accordance with an embodiment of the present invention;
[0015] [0015]FIG. 2 is a block diagram of a master unit for the speaker system of FIG. 1 that is constructed in accordance with an embodiment of the present invention;
[0016] [0016]FIG. 3 is a block diagram of a remote unit for the speaker system of FIG. 1 that is constructed in accordance with an embodiment of the present invention;
[0017] [0017]FIG. 4 is a flow chart depicting a sequence of operations for configuring a speaker in accordance with an embodiment of the present invention;
[0018] [0018]FIG. 5 is a flow chart depicting a sequence of operations for initiating a group page in accordance with an embodiment of the present invention;
[0019] [0019]FIG. 6 is a flow chart depicting a sequence of operations for overriding a group page with an all call page in accordance with an embodiment of the present invention; and
[0020] [0020]FIG. 7 is a flow chart depicting a sequence of operations for changing a group identifier (ID) and/or a tap setting from a computer in accordance with an embodiment of the present invention.
[0021] To facilitate understanding, identical reference numerals have been used to designate identical elements that are common to the figures.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0022] Although the present invention is described for use in an industrial environment, the present invention can also be used in other types of environments. For example, the present invention can also find application in a residential environment and a commercial environment. One such commercial environment can be a department store. For instance, sales announcements can be targeted to specific departments or floors.It will be appreciated by those skilled in the art that, although the present invention is described in the context of a public address system, the invention can be modified to be used in speaker systems in general.
[0023] [0023]FIG. 1 depicts a public address speaker system 100 in accordance with a first embodiment of the present invention. In the illustrated embodiment, four master control units 102 A, 102 B, 102 C and 102 D are used to monitor and control respective sets of speakers connected thereto. By way of an example, connected to master control unit 102 A are a Generator/Mixer 122 1 , a first amplifier 124 1 , second amplifier 124 2 , third amplifier 124 3 and fourth amplifier 124 4 hereinafter referred to plurality of amplifiers 124 ), a first RS-485 bus 126 , a second RS-485 bus 128 , a plurality of remote units 130 depicted as a first remote unit 130 1 , a second remote unit 130 2 , a third remote unit 130 3 , a fourth remote unit 130 4 , a fifth remote unit 130 5 and a sixth remote unit 130 6 , and a plurality of speakers 152 depicted as a first speaker 152 1 , a second speaker 152 2 , a third speaker 152 3 and a fourth speaker 152 4 , a fifth speaker 152 5 and sixth speaker 152 6 . The other master control units have similar configurations, that is, they are each connected to a tone generator/mixer 122 , a plurality of amplifiers 124 , remote units and corresponding speakers. Each master control unit 102 is connected to a computer 154 . The generator mixer 122 preferably supplies a 35 Hz or similar tone that is not audible as the power signal for the speakers 152 .
[0024] The operation of the speaker system 100 will now be described in general. Speaker system 100 provides the ability to address each of the plurality of speakers 152 individually or as a group. Depending on how the master control units 102 and remote units 130 are configured, a plurality of speakers can be organized into groups allowing the speakers to receive the same program material where the program material can be music and/or speech, for example. Alternatively, the plurality of speakers can be configured wherein each speaker is separate from the other speakers and must be addressed individually. Although each speaker 152 is connected to a particular master control unit 102 , speakers connected to respective ones of the master control units (e.g., master control unit 102 A and 102 D) can be assigned to the same group via the computer 154 .
[0025] Each of the plurality of speakers 152 preferably has a unique 16-bit address. Each of the plurality of speakers 152 can further be assigned up to four group identifiers (IDs), allowing as many as 255 possible group assignments for the plurality of speakers 152 for each of the four groups. The group identifier allows specific speakers to be assigned to a group and receive the same program signal. For example, with regard to the speakers connected to master control unit 102 A, first speaker 152 1 and second speaker 152 2 can be assigned to group A. Third speaker 152 3 and fourth speaker 152 4 can be assigned to group B. Fifth speaker 152 5 can be assigned to group C, and sixth speaker 152 6 can be assigned to group D. This allows each group to be assigned to a specific area and receive addressed program material with respect to other groups, if desired. As a further example, first speaker 152 , can be assigned to more than one group.
[0026] The master control unit 102 is preferably assigned a 4-bit address, allowing up to 16 master control units 102 to be used in the speaker system 100 . In a second embodiment of the invention, the computer 154 can be connected to the master control unit 102 via the first RS-485 bus 126 . In this manner, up to 16 master controls units 102 can be controlled individually and/or simultaneously via the computer 154 using the master control unit 102 addresses.
[0027] The master control unit 102 is also connected to the 35 Hz generator/mixer 122 via the second RS-485 bus 128 . The RS-485 interface standard, which is hereby incorporated by reference in its entirety, is used in multipoint applications where at least one master control unit 102 and/or computer 154 controls many different devices. Although the present invention is depicted as using the RS-485 interface, the invention may be modified to include other types of interfaces and still fall within the scope of the present invention. In accordance with a preffered embodiment of the present invention, 35 Hz generator/mixer 122 can be connected to as many as four amplifiers. In FIG. 1, the 35 Hz generator/mixer 122 is, illustratively, connected to first amplifier 124 1 , second amplifier 124 2 , third amplifier 124 3 and fourth amplifier 124 4 . Each amplifier 124 can be connected to as many as thirty remote units 130 , and each remote unit controls a respective speaker 152 . Specifically, with regard to master control unit 102 A, first amplifier 124 1 is connected to first remote unit 130 1 and to second remote unit 130 2 . First remote unit 130 1 is connected to first speaker 152 1 . Second remote unit 130 2 is connected to second speaker 152 2 . Second amplifier 124 2 is connected to third remote unit 130 3 and fourth remote unit 130 4 . Third remote unit 130 3 is connected to third speaker 152 3 , and fourth remote unit 130 4 is connected to fourth speaker 152 4 . Third amplifier 124 3 is connected to fifth remote unit 130 5 which is in turn connected to fifth speaker 152 5 . Fourth amplifier 124 4 is connected to sixth remote unit 130 6 which is in turn connected to sixth speaker 152 6 .
[0028] Referring to the operation of speaker system 100 , an Enter Command Mode command is communicated to a particular master control unit 102 via the computer 154 and/or a master console with a memory and input devices (not shown). This command causes the master control unit 102 to enable a corresponding 35 Hz generator/mixer 122 to generate a 35 Hz power signal. As stated previously, the 35 Hz signal is inaudible and powers the corresponding remote units 130 . Specifically, the 35 Hz signal powers each of the remote units 130 via the colocated amplifier 124 . The remote units 130 each monitor the incoming message from the master unit 102 to determine whether it is being addressed either as an individual unit or as part of a group. Remote units 130 that are not being addressed power themselves off. If any of the remote units 130 are being addressed, the units remain powered on and communicate an acknowledgement to the master control unit 102 .
[0029] More particularly, the master control unit 102 communicates a command, along with data, wherein the two signal components comprise a message. The data portion of the message can comprise an address field, group identifier (ID) field, speaker status field and/or a tap setting field, as described below. The commands can comprise a command such as, but not limited to, an Idle/All-Page, Group Page, Speaker Page, Speaker Poll, Speaker Group A configure, Speaker Group B configure, Speaker Group C configure, Speaker Group D configure, Idle/All Page Tap Configure, Retrieve Configuration, Acknowledge Response, Config Response 1 , and Config Response 2 .
[0030] The tap setting is a predetermined audio setting and can comprise the following settings: off, low, mid, high and full. Each audio setting has a specific volume setting. The present invention can be modified by those skilled in the art to utilize numerical or other incremental or graduated settings to achieve specific volume levels and still fall within the scope of the present invention.
[0031] The Idle/All Page Tap Configure command is communicated to all remote units 130 and resets all tap settings to a default value. The Group Page command is communicated to remote units 130 that are assigned to a selected group. Rather than determining whether the command is addressed to the remote unit's 130 individual address, the remote unit 130 determines whether it is assigned to the group that is contained in the incoming message.
[0032] The Speaker Page command is communicated from a master control unit 102 to a specific speaker. All of the remote units 130 compare the address of the incoming message to their own address to determine whether the message is addressed to them. If the message is addressed to them, the unit remains powered on, executes the command, and/or communicate a response message to the master control unit 102 .
[0033] Speaker system 100 also has an audio current monitoring system that monitors the current between the remote units 130 and the speakers 152 . A conventional current transformer is preferably provided in the tap control and speaker fault sense circuit 142 (FIG. 3) to detect a drop in current between each of the speakers 152 and their corresponding remote units 130 . Additionally, the remote units 130 are polled via the Speaker Poll command. Specifically, each remote unit 130 is requested by the master control unit 102 to provide its status. If a current drop or no current is detected between the remote unit 130 and respective speaker 152 , the remote unit 130 communicates this information to the master control unit 102 . A repairman can then be dispatched to the identified remote unit 130 and/or speaker 152 and make the necessary repairs. If no faults are detected by the remote unit 130 , a positive indication is communicated to the master control unit 102 .
[0034] As stated previously, remote units 130 and their respective speakers 152 can be assigned, for example, to groups A, B, C and/or D. The Speaker Group A configure, Speaker Group B configure, Speaker Group C configure, and Speaker Group D configure commands are used to configure the remote unit 130 . The Idle/All Page Tap configure command is communicated from the master station 102 to the remote units 130 . The command establishes the default value for the Idle/All page command.
[0035] The Retrieve configuration command is communicated from the master station 102 to the remote stations 130 to determine the configuration of the remote settings. The remote units 130 respond with a Config Response 1 acknowledgement containing their address, the ID of the group, if any, that they belong to, and their status. The remote units can also respond with a Config Response 2 response containing their idle tap setting, the ID of the group, if any, that they belong to and their present tap setting.
[0036] [0036]FIG. 2 depicts components of the master control unit 102 for the speaker system in accordance with an embodiment of the present invention. Specifically, the master control unit 102 comprises a master microcontroller 110 which is connected to an RF transceiver 112 , a modem 116 (e.g., a 9600 baud RF modem), a power supply 114 , a system RS485 port 118 , and a tone generator RS485 port 120 . The modem 116 is also connected to the RF transceiver 112 which is connected to the RF channel & control circuit 108 . A plurality of audio lines 104 illustratively depicted as 104 1 , 104 2 , 104 3 and 1044 are connected to the RF channel selection & control circuit 108 . The power supply 114 is preferably connected to a 24V DC power connection 106 .
[0037] The microcontroller 110 controls the speakers and associated devices connected thereto, as well as serving as an interface between the computer 154 and the remote units 130 . The computer 154 and microcontroller 110 preferably communicate via the system RS485 port 118 .
[0038] As stated previously, each master control unit 102 has a unique 4-bit address that the computer 154 can use to address it. Upon receiving an indication from computer 154 that a command will be sent to a speaker, the microcontroller 110 of the addressed master control unit(s) enables its 35 Hz generator/mixer 122 . Specifically, the master microcontroller 110 communicates an activation signal to the 35 Hz generator/mixer 122 via the tone generator RS485 port 120 . The 35 Hz generator/mixer 122 , in turn, communicates a 35 Hz signal to the amplifier 124 which powers the remote unit(s) 130 connected to the speaker being addressed for the time period that the 35 Hz signal is being communicated.
[0039] The microcontroller 110 then communicates the command received from the computer 154 to the remote unit(s) 130 . The command is communicated to the modem 116 in a digital format. The modem 116 converts the received signal to an analog signal. The analog signal is then communicated to the RF transceiver which modulates the analog signal to an appropriate frequency.
[0040] The modulated analog signal is then communicated to the RF channel selection & control circuit 108 . When the microcontroller 110 communicates a command to a remote unit 130 , the microcontroller 110 preferably operates without data concerning the audio line 104 to which the remote unit is connected. Therefore, all of the remote units 130 are preferably powered on and the command is communicated on all of the audio lines 104 . Each of the remote units then determines whether the received command is addressed to it.
[0041] [0041]FIG. 3 is a block diagram of a remote unit 130 for the speaker system of FIG. 1 that is constructed in accordance with an embodiment of the present invention. The remote unit 130 preferably comprises a microcontroller 140 connected to a field configuration port 150 , a modem 148 , a transceiver 144 , an audio buffer 138 , a tap control & speaker fault sense circuit 142 , and a power supply 132 . The power supply is also connected to the audio buffer 138 , an RF transformer 136 and speaker transformer 134 .
[0042] The audio line connection 104 interfaces with the speaker transformer 134 , the RF transformer 136 and audio buffer 138 . When a signal is received at the remote unit 130 , the signal is routed and processed according to its frequency. For example, when a 35 Hz signal is received at the remote unit 130 via the audio line 104 , the 35 Hz signal is routed to the audio buffer 138 which then communicates the signal to the microcontroller 140 . The remote unit 130 is then activated to receive commands from the master control unit 102 .
[0043] It is conventional to use human speech to power up the remote unit 130 ; however, human speech fluctuates and can cause a circuit board to repeatedly power on and off. By having a 35 Hz signal, that is, a continuous inaudible signal as a power signal, no interference will occur between an audible page and the 35 Hz signal.
[0044] The received signal can also be a command from a corresponding master control unit 102 . The command is routed to the RF transformer 136 and communicated to the RF transceiver 144 where it is then demodulated and communicated via the RF transceiver 144 to the modem 148 (e.g., a 9600 baud RF modem) for conversion to a digital signal. The microcontroller 140 receives the digital signal from the modem 148 and executes the command.
[0045] For example, if the command required that a tap setting be made, the microcontroller 140 communicates the settings to the tap control & speaker fault sense circuit 142 which adjusts relays (not shown) that changes the transformer settings on the speaker transformer 134 . The tap control & speaker fault sense circuit 142 also monitors the current between the speaker 152 and the remote unit 130 (e.g., via a current transformer (not shown)). If a drop in current or no current is detected, the remote unit 130 informs the master control station 102 when a command for its status is received.
[0046] The field configuration port 150 allows on-site programming of the remote unit 130 . When the remote unit is first installed, its address needs to be stored on the remote unit 130 so that it can respond to messages addressed to it from the master control unit 102 . Any type of computer-related device can be used to program the remote unit 130 .
[0047] [0047]FIG. 4 is a flow chart depicting a sequence of operations for configuring a speaker in accordance with an embodiment of the present invention. The method 400 proceeds to step 402 where a field programming device (not shown) is connected to the field configuration port 150 (e.g., serial port). The field programming device can be a computer, processor, terminal and the like.
[0048] At step 404 , the field programming device communicates a Speaker Address Configure command which allows the field programming device to assign a 16-bit address to the remote unit 130 .
[0049] At step 406 , the field programming device communicates the Speaker Group A configure command to the remote unit 130 . The remote unit's address, Group (ID), and tap settings are provided as inputs, for example, to the microcontroller 140 and associated memory. These settings apply to Group A. Additionally, each group can comprise subgroups numbered from 1 to 255 (i.e., each speaker can belong to any of the 255 subgroups).
[0050] At step 408 , the remote unit 130 communicates an acknowledgement message to the field programming device. This indicates that the remote unit accepted the inputted information and serves as a confirmation.
[0051] At step 410 , the field programming device communicates the Speaker Group B configure command to the remote unit 130 . The remote unit's address, Group ID, and tap settings are provided as inputs to the microcontroller 140 . These settings apply to Group B. Additionally, each group can be numbered from 1 to 255, allowing 255 subgroups to be assigned to Group B.
[0052] At step 412 , the remote unit 130 communicates an acknowledgement message to the field programming device. This indicates that the remote unit 130 accepted the Group B configuration information and serves as a confirmation.
[0053] At step 414 , the field programming device communicates the Speaker Group C configure command to the remote unit 130 . The remote unit's address, Group ID, and tap settings are provided as inputs to the microcontroller 140 . These settings apply to Group C. Additionally, each group can be numbered from 1 to 255 allowing 255 subgroups to be assigned to Group C.
[0054] At step 416 , the remote unit 130 communicates an acknowledgement message to the field programming device. This indicates that the remote unit accepted the Group C configuration information and serves as a confirmation.
[0055] At step 418 , the field programming device communicates the Speaker Group D configure command to the remote unit 130 . The remote unit's address, Group ID, and tap settings are provided as inputs to the microcontroller 140 . These settings apply to Group D. Additionally, each group can be numbered from 1 to 255, allowing 255 subgroups to be assigned to Group D.
[0056] At step 420 , the remote unit 130 communicates an acknowledgement message to the field programming device. This indicates that the remote unit accepted the Group D configuration information and serves as a confirmation.
[0057] Although the method 400 depicts all four groups being inputted to a speaker, it is possible to practice the invention with no groups, or more or less than the use of four groups.
[0058] At step 422 , the field programming device communicates a Speaker Page configure command to the remote unit 130 . The address of the remote unit(s) 130 is inputted, along with tap settings. The remote unit(s) 130 store the received tap settings which are the volume levels each corresponding speaker will output when it receives a page to its individual address and not to its group address. As discussed above, each group has its own tap settings.
[0059] At step 424 , the remote unit 130 communicates an acknowledgement to the field programming device indicting that the inputted information is accepted.
[0060] At step 426 , the field programming device communicates an Idle/All Page configure command to the remote unit 130 . Tap settings and the remote unit's address are also inputted. The tap setting inputted is the default tap setting. All of the speakers are preferably set at the same default volume.
[0061] At step 428 , the remote unit 130 communicates an acknowledgement to the field programming device indicating that the settings inputted were accepted.
[0062] Computer 154 stores tables of which speaker is connected to which master control unit 102 and the settings of groups and individual speakers 152 . A user options the speaker system 100 via the computer 154 and/or the field programming device.
[0063] [0063]FIG. 5 is a flow chart depicting a sequence of operations for initiating a group page in accordance with an embodiment of the present invention. The method 500 is initiated at step 502 where a user selects a particular group to page from a master control unit.
[0064] At step 504 , the computer 154 alerts the master control unit(s) 102 corresponding to the speakers in the selected group that a command will soon be issued. In response to this indication, each master control unit 102 , at step 506 , enables its corresponding 35 Hz generator/mixer 122 , which communicates a power signal to all of the remote units 130 associated with that master control unit to provide power to the remote units 130 .
[0065] At step 508 , each master control unit 102 associated with the selected group communicates to the computer 154 a confirmation that the remote units are powered.
[0066] At step 510 , the computer 154 communicates to the master control unit(s) 102 that a group page has been requested, along with the group Id.
[0067] At step 512 , the master control unit(s) 102 communicate a Group Page command to the remote units 130 , along with the group IDs. Each speaker loop receives the command.
[0068] At step 514 , the remote units 130 compare the received group IDs to the group IDs that they were assigned. If the group IDs do not match, the remote units set their tap settings to off. However, if the group IDs do match, then the remote units set their tap settings to the assigned group setting.
[0069] At step 516 , the master control unit(s) 102 communicate to the computer 154 that the Group Page command has been configured.
[0070] At step 518 , the master control unit(s) 102 communicate to their corresponding remote units that there are no more commands to be carried out.
[0071] At step 520 , the master control unit(s) 102 disable their corresponding 35 Hz generator/mixers 122 . Specifically, an End Command Mode command is communicated to the 35 Hz generator/mixers 122 . The master control unit(s) 102 also communicate a confirmation message to the computer 154 that the 35 Hz generator/mixer is no longer powering the remote units 130 .
[0072] At step 522 , an audio signal is broadcast by the speaker system 100 via respective speakers 152 in the selected group. The remote unit(s) 130 and respective speakers 152 that were not part of the group page previously sent, set their tap settings to zero. Therefore, audio will not be broadcast from those speakers but rather only from the speakers that were identified as being in the selected group.
[0073] At step 524 , the computer 154 communicates to the master control unit(s) 102 that a command will be issued. In response to this communication, the master control unit(s) 102 , at step 526 , enable their corresponding 35 Hz generator/mixers 122 to power the remote units 130 and place the remote units 130 into the idle/default state. The master control unit(s) 102 communicate to the computer 154 that their remote units 130 are powered.
[0074] At optional step 528 , the master control unit(s) 102 can communicate the Idle/All Page command to the remote units 130 and set the tap settings for the remote units to a default setting. As indicated at step 528 , the paging type can go from a group page to an idle/all page without having to turn the 35 Hz generator/mixer off and then back on again. That means that the remote unit(s) 130 that are in the selected group remain powered while the remote unit(s) 130 that are not in the selected group become powered at step 526 .
[0075] At step 530 , the computer 154 communicates to the master control unit(s) 102 that there are no more commands expected. In response to the communication, the master control unit(s) 102 disable their corresponding 35 Hz generator/mixers 122 and send a confirmation to the computer 154 .
[0076] [0076]FIG. 6 is a flow chart depicting a sequence of operations for overriding a group page with an all-call page in accordance with an embodiment of the present invention. The method 600 is initiated at step 602 where a user selects particular group(s) to page from a master control unit(s) 102 from the computer 154 .
[0077] At step 604 , the computer 154 alerts the master control unit(s) 102 corresponding to the speakers in the selected groups that a command will soon be issued. In response to this indication, the master control unit(s) 102 , at step 606 , enable their corresponding 35 Hz generator/mixers which provide s a power signal that powers the remote units 130 associated with the selected groups.
[0078] At step 608 , the master control unit(s) 102 associated with the selected groups communicate to the computer 154 a confirmation message that the remote units 130 are powered.
[0079] At step 610 , the computer 154 communicates to the master control unit(s) 102 that a group page has been requested, along with the group ID.
[0080] At step 612 , the master control unit(s) 102 communicate a Group Page command to their corresponding remote units 130 , along with the group IDs. Each speaker loop receives the command.
[0081] At step 614 , the remote units 130 compare the received group IDs to the group IDs that they were assigned. If the group IDs do not match, the remote units 130 set their tap settings to off. However, if the group ID's do match, then the remote units 130 set their tap settings to the assigned group setting. The method 600 then proceeds to step 616 .
[0082] At step 616 , the master control unit(s) 102 communicate to the computer 154 that the Group Page command has been configured.
[0083] At step 618 , the master control unit(s) 102 communicate to their corresponding remote units that there are no more commands to be carried out.
[0084] At step 620 , a user over-rides the group page with an emergency All Call page via the master console. In response to the emergency All Call page, the computer 154 , at step 622 , communicates to the master control unit(s) 102 that an All Call page has been requested by a user.
[0085] At step 624 , the master control unit(s) 102 communicate an Idle/All Page command to their respective remote units 130 . Upon receiving the Idle/All Page command, the remote units 130 apply their default tap settings at step 626 .
[0086] At step 628 , the master control unit(s) 102 communicate to the computer 154 that the All Page command has been executed by the remote units 130 .
[0087] At step 630 , the computer 154 communicates to the master control unit 102 that no more commands are expected. In response, the master control unit(s) 102 disable their 35 Hz generator/mixers 122 and communicate the disablement of the generator/mixers 122 to the computer 154 .
[0088] At step 632 , the page is placed and the announcement goes to all the speakers 152 .
[0089] [0089]FIG. 7 is a flow chart depicting a sequence of operations for changing a group ID and/or a tap setting from a computer (e.g., computer 154 or a field programming device) in accordance with an embodiment of the present invention. The method 700 is initiated at step 702 where a user requests the change of a group ID or tap setting for a specific speaker(s) 152 .
[0090] At step 704 , the computer 154 communicates to the master control unit(s) 102 that a speaker command is about to be communicated. In response, the master control unit(s) 102 enable their respective 35 Hz generator/mixers 122 to power the remote units 130 and sends a confirmation to the computer 154 that the remote units 130 associated with the master control unit(s) 102 are powered and ready to receive the next command.
[0091] At step 706 , the computer 154 communicates to the master control unit(s) 102 that a group configuration is required. For purposes of illustration, the Group A configuration is selected. The address of the remote units 130 , group ID and desired tap settings are also communicated to the master control unit(s) 102 .
[0092] At step 708 , the master control unit(s) 102 communicate a Group A Configure command, along with the remote unit's 130 addresses, group ID and tap setting to their respective remote units 130 .
[0093] At step 710 , the remote units 130 compare the received addresses to their assigned address. If there is a match, the received configuration will be saved and an acknowledgement message is communicated to their respective master control unit(s) 102 . If there is no match, the remote units 130 will ignore the command and power off.
[0094] At step 712 , the master control unit(s) 102 wait for an acknowledgement from their respective remote units 130 . If the waiting period expires, the master control unit(s) 102 resends the command as many as three times before a fault is declared.
[0095] At step 714 , when an acknowledgement message is received or has timed out after three attempts to communicate with the remote units 130 , their respective master control unit(s) inform the computer 154 of the success or failure of the requested configuration.
[0096] At step 716 , the computer 154 repeats steps 706 to 714 if necessary and communicates to the master control unit(s) 102 that no additional commands will be sent.
[0097] At step 718 , the master control unit(s) 102 disable their respective 35 Hz generator/mixers 122 and send a confirmation to the computer 154 .
[0098] Those skilled in the art can now appreciate from the foregoing description that the broad teachings of the present invention can be implemented in a variety of forms. Therefore, while this invention can be described in connection with particular examples thereof, the true scope of the invention should not be so limited since other modifications will become apparent to the skilled practitioner upon a study of the drawings, specification and the following claims. | An apparatus and method for providing a centralized speaker system that allows multiple speakers connected to a central amplifier speaker line to be monitored and controlled from a central location via a master/slave protocol. The centralized speaker system comprises a central station for selectively communicating at least one of a command and an information signal to a destination device. A tone generator is adapted to communicate an activation tone to the destination device. An amplifier, which is colocated with the central station, is adapted to amplify the signals to the destination device. | 7 |
BACKGROUND OF THE INVENTION
This invention relates to an apparatus for dividing a beam into segments to facilitate optimization of yarn utilization.
There are a number of collars that can be attached to a cylindrical beam. Some of them require the collar to be slidably mounted over one of the ends of the beam such as U.S. Pat. No. 2,027,749, U.S. Pat. No. 2,144,989, U.S. Pat. No. 4,937,926 and U.S. Pat. No. 2,188,086. This can prove to be a burdensome and time consuming operation. Other collars such as U.S. Pat. No. 2,578,018 and U.S. Pat. No. 2,658,699 allow for a major portion of the collar to be removed leaving only a small circular thimble portion. However, this thimble portion must also be slidably mounted over one end of the beam.
The present invention solves the above problems and others in a manner not disclosed in the known prior art.
SUMMARY OF THE INVENTION
A collar for partitioning a beam that includes a first c-shaped member and a second c-shaped member operatively attached to said first c-shaped member to form a first ring, and a third c-shaped member and a fourth c-shaped member operatively attached to said third c-shaped member to form a second ring, with said first ring and said second ring operatively attached to each other.
It is an advantage of this invention to be able to divide a beam into sections thereby accomplishing optimal warping.
It is another advantage of this invention that the collar does not have to be slidably attached over one of the ends of a beam.
Yet another advantage of this invention is that the collar can be attached to a yarn beam without damaging the beam in any way.
Still another advantage of this invention is that the collar can be readily attached and removed from a beam with a minimum of labor or expense.
Another advantage of this invention is that the warping cycle time is optimized for short sets.
Yet another advantage of this invention is that pattern warping is facilitated.
Another advantage of this invention is that the collar is removedly attached so that a beam does not have to be dedicated or permanently altered.
These and other advantages will be in part obvious and in part pointed out below.
BRIEF DESCRIPTION OF THE DRAWINGS
The above as well as other objects of the invention will become more apparent from the following detailed description of the preferred embodiments of the invention, which when taken together with the accompanying drawings, in which:
FIG. 1 is an exploded perspective view of the collar constructed according to the present invention;
FIG. 2 is a perspective view of the collar constructed according the present invention which is secured to a beam;
FIG. 3 is a sectional view taken along line 2-2 in FIG. 2.; and
FIG. 4 is a perspective view of the collar constructed according to the present invention which is attached to a beam that is secured in a warper and has yarns drawn through a reed comb.
Corresponding reference characters indicate corresponding parts throughout the several views of the drawings.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now by reference numerals to the drawings, and first to FIGS. 1-3, a collar to divide a section beam is generally indicated by numeral 10. Referring now to FIGS. 1 and 3, the collar 10 has two main components which are a friction hub 12 and a yarn divider 14 which are mounted on a beam 1 that has flanged ends.
The friction hub 12, in the form of a compression ring, includes substantially identical c-shaped members 16 and 18 that each have substantially flat end flanges 20, 22, 24 and 26 respectively. The two c-shaped members 16 and 18 are preferably constructed out of metal, but also may be made of plastic, ceramic and so forth. End flange 20 is attached to end flange 26 by means of bolts 28 and 30 and threaded openings in flange 26. End flange 22 is attached to end flange 24 by means of bolts 32 and 34 and threaded openings in flange 22. Any attachment means used in this application does not necessarily mean bolts, but any means of hardware, adhesives, and so forth will suffice or any combination thereof. There needs to be enough pressure to hold the friction hub 12 onto the beam 1 without damaging the beam 1 and yet still hold the friction hub 12 securely in place under the dynamic loadings of the warping operation.
The yarn divider 14 also has two substantially identical c-shaped sections 36 and 38 each having side walls 40, 41, 42, and 43 respectively, which all have an inner and outer radius. Side walls 40, 41, 42 and 43 are all machined smooth and flat so that they present a substantially smooth surface to the yarn with minimal surface interruption at the point of interconnection, which thereby eliminates any snagging of the yarn.
C-section 36 has rectangular support members 50, 51, 52, 53, 54, 55, 56, 57, and 58 while substantially identical c-section 38 has corresponding support members 60, 61, 62, 63, 64, 65, 66, 67, and 68 as shown in FIG. 3. There are holes 130 in support members 50 and 60 through which pin 110 (i.e., roll pin, taper pin, and so forth) is pressed as well as holes 140 in support members 57 and 67 through which pin 120 is pressed to line up side walls 40 and 42 as well as 41 and 43 when yarn divider 14 is assembled or disassembled, as shown in FIGS. 1 and 3. Support member 50 attaches to support member 60 by means of bolt 70 through a threaded opening, support member 51 attaches to support member 61 by means of bolt 71 through a threaded opening, support member 57 attaches to support member 67 by means of bolt 72 through a threaded opening, and support member 58 attaches to support member 68 by means of bolt 73 through a threaded opening. This results in the attachment of c-section 36 to c-section 38. C-section 36 has three support members 52, 54 and 56 equidistantly spaced along the outer radius with member 54 at the apex of the curve. This equidistant spacing is preferred, but not necessary. C-section 38 is identical with corresponding support members 62, 64 and 66. The primary function of the support members 52, 54, 56, 62, 64 and 66 is to serve as webs or spacers between plates 40, 41, 42 and 43 respectively.
Support members 53 and 55 are located relatively close to the inner radius of c-section 36. Bolt 80 goes through a threaded hole in support member 53 as well as bolt 81 going through a threaded hole in support member 55 to secure c-shaped section 36 to the first c-shape member 16 of friction hub 12. Bolt 82 goes through a threaded hole in support member 63 as well as bolt 83 going through a threaded hole in support member 65 to secure c-shaped section 38 to the second c-shape member 18 of friction hub 12. This results in the yarn divider 14 being fixedly attached to the friction hub 12. The friction hub 12 is in the form of a compression ring whose primary purpose is to prevent rotation and axial motion of yarn divider 14.
Collar 10 may be cast in two c-shaped components or in part utilizing welding, adhesives or other means of structural connection to interconnect components for the purpose of creating an economically viable product. The yarn divider 10 is provided with a relative axial location with reference to the beam 1 by having the side walls 40, 41, 42, and 43 fit over and enclose the friction hub 12. There is a slight amount of clearance between the side walls 40, 41, 42, and 43 and friction hub 12. A slight amount of clearance between side walls 40, 41, 42 and 43 and the beam 1 allows the divider 10 to rotate freely when not attached to the friction hub 12 by bolts 80, 81, 82 and 83.
There is a curved cover plate 90 that conforms to the outer radius of c-shaped member 36 and attaches by means of bolt 94 to support member 50, bolt 95 to support member 54 and bolt 96 to support member 57. There is a corresponding curved cover plate 91 for c-shaped member 38 and attaches by means of bolt 98 to support member 60, bolt 99 to support member 64 and bolt 100 to support member 67. This cover plate 90 provides primarily a safety function and can be made of virtually any material and attached by hardware, adhesives, and so forth. An assembled collar 10 is attached to a beam 1 as shown in FIG. 2.
For economic reasons, any piece or component in the present invention may be integrally formed with any other piece or component such as friction hub c-shaped member 16 formed with yarn divider c-shaped section 36 and friction hub c-shaped member 18 formed with yarn divider c-shaped section 38, and so forth.
As shown in FIG. 4, the beam 1 is secured in a standard warper with the collar 10 being utilized to divide the beam 1 into independent sections thereby allowing the yarn 78 to run onto each independent section. The yarn 78 can be brought through a reed comb 87 that would be preferably movable. More than one collar 10 can be mounted on a single beam 1.
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 defined by the appended claims and their equivalents. | A collar for partitioning a beam which includes a first c-shaped member and a second c-shaped member operatively attached to said first c-shaped member to form a first ring, and a third c-shaped member and a fourth c-shaped member operatively attached to said third c-shaped member to form a second ring, with said first ring and said second ring operatively attached to each other. | 3 |
This patent application claims priority to, and is a continuation of, U.S. patent application Ser. No. 13/888,281, filed on May 6, 2013, which claims priority to, and is a continuation of, U.S. Pat. No. 8,434,188 from U.S. patent application Ser. No. 12/212,809, filed on Sep. 18, 2008, which claims benefit of U.S. Provisional Patent Application No. 60/973,737, filed Sep. 19, 2007. These prior patent applications are hereby incorporated herein by reference for all purposes.
BACKGROUND
Field of the Invention
The present invention pertains to various building tools and methods related thereto. For example, the invention involves various methods and apparatuses for comfortably gripped and efficiently controlled building tools. Further, the invention involves various methods and apparatuses for high quality, durable and/or lightweight building tools.
Description of Related Art
Various tools have been known in the past for working with cements, concretes, mastics and/or muds to, for example, prepare, apply and/or finish a desired shape or smooth surface for various building surfaces. For example, some tools used for applying material to or preparing the surface of, for example, concrete, include trowels. These types of tools are typically hand tools that are used to apply materials for making and/or smoothing various building surfaces such as floors and walls and may be used to apply various materials to building surfaces. These tools may be used by skilled craftsman working on a number of surfaces for long periods of time during the work day. As such, a comfortable grip(s) may be particularly important in developing a most desirable building tool(s).
Referring to FIGS. 1A-1D , one typical prior art trowel including a trowel tang and blade is shown. A handle 110 for gripping is provided. The handle has a generally oval or round shape. In particular, referring to FIG. 1A , the trowel 100 includes a tang 150 that connects the trowel handle 110 to the trowel blade 105 . The tang 150 includes a handle connecting member 151 , a blade attachment member 152 , and a handle support member 153 (see FIG. 1D ) that all cooperate as a tang 150 in connecting the trowel handle 110 to the trowel blade 105 . In the view of FIG. 1A , the connecting member 151 has a slight curve to its upper half so as to reflect its shape on either side to somewhat follow the round sides of the handle 110 , but as shown below connecting member 151 has a side view that is substantially straight and vertical relative to the plane (horizontal when the trowel bottom surface of the blade is set on a horizontal surface) of the handle 110 and trowel blade 105 . In other words, when looking at the trowel handle from the top as shown in FIG. 1C , the front or forward surface of the connecting member 151 of the tang has some curve to the left and the right of the center line, but when looking at the side view shown in FIGS. 1B and 1D , that from top to bottom the connecting member 151 is substantially straight and vertical having only a very slight slant relative to perfect perpendicular. Further, the back surface of the connecting member 151 is substantially flat and also approximately perpendicular to blade 105 and main axis of the handle 110 . The very top, and a substantial portion of, the connecting member 151 , is also as wide as the handle 110 , so as to cover a forward face of the handle 110 , resulting in a very abrupt drop and bulky front end surface to the tang 150 .
Referring now to FIG. 1B , a side view of a prior art trowel and trowel tang is shown. As more clearly shown in FIG. 1B , the handle connecting member 151 is a substantially solid and straight member having a front surface 151 A and a back surface 151 B each with an approximately linear top-to-bottom and side-to-side slope. Further, the handle connecting member 151 has a narrow width measured from the front surface 151 A to the back surface 151 B. A typical trowel, for example, may have a handle connecting member 151 with a front-to-back width of approximately 1 cm (0.4 inches). The handle connecting member 151 is coupled at one end to the blade attachment member 152 at a connection point 154 slightly offset in a forward direction from the center of the blade attachment member 152 . This typical trowel has a connection point 154 so that the front surface 151 A meets the blade attachment member 152 at a point 154 A having a distance of approximately 9.5 cm (3.75 inches) from a front end 152 A of the blade attachment member 152 and the back surface 151 B meets the blade attachment member 152 at a point 154 B having a distance of approximately 11 cm (4.375 inches) from the front end 152 A of the blade attachment member 152 . Note that the front point 154 A has an abrupt angle that is approximately 90 degrees, and the back point 154 B has a slightly rounded connection point but is still approximately a 90 degree angle, with the vertical axis of the connecting member 151 being approximately perpendicular to the horizontal axis of the blade attachment member. As can be clearly seen from this side view in FIG. 2B , the handle connecting member 151 is also connected approximately perpendicular to the blade attachment member 152 . The typical trowel may have a handle connecting member 151 with an angle (denoted 165 ) relative to the blade attachment member 152 of approximately 85 to 95 degrees. The blade attachment member 152 is elongated laterally across the trowel blade 105 and has a short height and narrow width that is used for coupling the blade attachment member 152 to the trowel blade 105 . The typical trowel may have a blade attachment member 152 with a height and width both of approximately ⅔ to 1⅓ cm (0.25 to 0.5 inches). Substantially the entire top surface of the blade attachment member 152 is approximately parallel to the trowel blade 105 having no slope so as to be approximately the same height across its entire length, from its very forward most point at the end of section 152 A, adjacent the connection point 154 of the connecting member 151 and blade attachment member 152 of the tang 150 , and through the very rearward most end of section 152 B.
Referring to FIG. 1C , a top view of a typical trowel is shown. From this view it can be seen that the handle member 110 with front portion 150 is approximately ⅓ the width of blade 105 and oriented to the center of the blade width. The constant width of the blade attachment member 152 is also illustrated as width 1 F and 1 G at ends 152 A and 152 B of the blade attachment member 152 , respectively, and is the same in size. The blade attachment member 152 is mounted to the blade 105 at approximately the center of the blade width and extends across most of the blade 105 length. The handle 110 is held to the tang via a cap 115 and a nut or bolt 120 . Most notably in FIG. 1C , the handle connecting member 151 is very narrow along the length of the blade 105 . The top most portion 151 C of the handle connecting member 151 is also very narrow and abuts the handle front portion 150 , but is slightly narrow than the handle 110 and handle front portion 150 . In any case, there is little lateral top surface of the handle connecting member 151 available onto which a user may place their hand, palm or finger on comfortably.
As more clearly shown in FIG. 1D , showing the handle 110 and cap 115 in cross sectional taken along line 1 D and 1 E of the FIG. 1C top view, the handle connecting member 151 is connected at its other end to the handle support member 153 so as to be approximately perpendicular to the handle connecting member 151 and approximately parallel to the blade attachment member 152 and trowel blade 105 . As shown, the typical trowel may have the entire length of the handle support member 153 with an angle (annotated as 170 ) relative to the handle connecting member 151 angle of approximately 85 to 95 degrees, both relative to the plane of the blade attachment member 152 . As previously indicated, the typical trowel also has a handle connecting member 151 with an angle (annotated as 165 ) relative to the blade attachment member 152 of approximately 85 to 95 degrees. The handle support member 153 includes a forward portion 153 A and a rearward portion 153 B, both approximately parallel to each other and approximately perpendicular to the handle connecting member 151 . The rearward portion 153 B is substantially round in shape and thinner than the forward portion 153 A. The forward portion 153 A of the handle support member 153 is substantially square in shape and thicker than the rearward portion 153 B. The major lateral axis through hole of the handle 110 is substantially straight so that the substantially straight handle support member 153 may be assembled easily into the lateral through hole (from end to end of the handle 110 ) in the handle 110 . An inside forward portion of the trowel handle 110 is through hole is hollowed with a similar square shape of the handle support member forward portion 153 A such that the thickness and square shape of the forward portion 153 A of the handle support member 153 allows the trowel handle 110 to snugly fit onto the handle support member 153 and prevents side-to-side rotation about a center axis of the trowel handle 110 during use. An end cap 115 and end nut 120 , hollowed with a similar round shape, are attached to the end of the trowel handle 110 and handle support member 153 , respectively, so as to prevent front-to-back sliding of the trowel handle 110 during use.
The trowel handle 110 has a top surface 110 A and a bottom surface 110 B and side surfaces (not labeled), which together provide a user with a gripping area and have only slight curvature due to a gradually increasing width in the trowel handle 110 . The trowel handle 110 meets the handle connecting member 151 at a handle interface 145 (see FIG. 1A ) in such a way that both the top surface 110 A and the bottom surface 110 B of the trowel handle 110 are adjacent to a portion of the handle connecting member 151 and are approximately perpendicular therewith.
These types of tools, for example trowels, are typically designed to be held by the hand of a user in a single manner and orientation. For example, with the typical prior art trowel shown in FIGS. 1A-1D , the user would most comfortably grip the handle coming from a the direction of the back end of the trowel (end with the end cap 115 ) with their fingers, palm and thumb of one hand surrounding the central portion of trowel handle 110 . However, many users may find it more advantageous to shift, modify, and/or change the orientation of their method of holding the trowel or tool(s). Therefore, it is advantageous to build such trowel(s) or tool(s) to be comfortably gripped and efficiently controlled by the hand of a user in various manners and orientations so as to increase the comfort and control of such tools for various surfaces or for use during long periods of time.
In addition to being used on various surfaces and for long periods of time, these types of tools are exposed to various bumps, jolts and mechanical stresses, as well as corrosive substances in their use. Therefore, it is advantageous to build such tools to be cost effective, light in weight and durable against extensive use and stress as well as the corrosion from corrosive materials they are designed to work on (e.g., concrete, mastic, mud, etc.).
SUMMARY
The present invention is directed generally to building tools that have improved comfort in gripping and/or efficient control that may be easily used in various manners and orientations. Further, the present invention is directed generally to building tools that are high quality, durable, and lightweight so as to help reduce user fatigue that occurs from extended tool use. For example, various tools may connect a handle in approximately parallel orientation with and to a work object (e.g., tool blade) to be moved by means of the handle and manual hand motion. The handle and work object may be connected together by a connecting member (or connecting means) that is a sloped, angled, and/or substantially curved member, so that a user has increased hand orientation options and/or increased and improved control over the tool while gripping the handle and/or connecting member in various manners and orientations, now enabled, during use. In various embodiment(s), the connecting member (e.g., a tang for a trowel) may include at least one portion that is relatively gradually and/or notably sloped, angled, and/or curved structure that may reasonably provide a comfortable extension of the handle and not just connect the handle to the work object, but augment the gripping and control of the tool. Further, various tools may include a handle that is shaped to smoothly continue the slope, angle, and/or curvature of such handle connecting member so that a user may shift, modify, and/or change the orientation of his or her grip onto and/or along the handle connecting member so as to be closer to the work object to be moved, for increased control by comfortably overlapping his or her hand onto at least a portion of the handle connecting member. This may result in a handle connecting member that is an alternative and/or extension of the gripping locations that are available with the handle alone.
Still further, various tools may include a handle connecting member having construction whereby a portion of the sides of the handle connecting member are removed so as to reduce the weight of the tool and may be designed in such a way as to increasing the structural integrity of the handle connecting member. For example, the handle connecting member may be formed, at least in part, with an I-beam or ribbed structure or cross-section.
Yet further, various tool(s) may include a connecting member or means formed to connect the handle to the object to be moved (e.g., a blade) having additional means of an attachment member (e.g., blade attachment member) that is elongated laterally across the object to be moved, and may be at least partially gradually sloped downwardly (or built up or taller in various locations). For example, the attachment member may be at least partially gradually sloped downwardly from the point(s) where connected to the handle connecting member, so as to increase the strength of the connecting means and/or the connection point(s). Further, the at least partially gradually sloped downwardly attachment member may add little weight and maintaining most of the distance between the handle and itself and the object to be moved to ensure sufficiently large distance for comfortable gripping without obstructing a user's fingers or hand. Still further, the connecting member may have a narrower width closer to a connecting point to an attachment member (e.g., blade attachment member) than at a location that interfaces or abuts a handle portion. And still further, the connecting member may have, for example, a ¼ circle radius on both an upper surface and a lower surface such that the two surface (and the entire outer surfaces of the handle and connecting member) approximately follow one another in a relatively smooth circular radius or curvature that narrows the width of the connecting member from a location against which the handle rests and the connection point to the blade attachment member (e.g., following a reducing circumference along the front length of the handle that is the general design shape of the handle). Yet even further, various tools may be made, at least in part, using a material including, for example, magnesium for the connecting member and/or the attachment member (e.g., trowel tang) to help reduce the weight of the tool.
In various embodiment(s), a trowel may include(s) a tang that may connect(s) the trowel handle to the trowel blade. The trowel may be, for example, a concrete trowel including a cross-ground trowel, a flat back end finishing trowel, a round/round finishing trowel, etc. A handle connecting member may be included with the tang and may assist the tang in coupling the trowel handle to the trowel blade. A handle support member may also be included with the tang and may be attached to the handle connecting member in such a way that at least a portion of the handle support member is approximately parallel with the trowel blade. A blade attachment member may further be included with the tang and may be attached to the handle connecting member and elongated laterally across the trowel blade. The handle connecting member may be a sloped, angled, and/or substantially curved member having a cross section that is thicker in one area than another. In various embodiments, the handle connecting member may be a larger circular shape where it interfaces to the handle and taper to a smaller round or oval shape in an area close to where it connects to the blade attachment member. In the case where the handle connection member is substantially curved, the handle connecting member may have a curved top/front surface and a curved bottom/back surface that approximately follows the curvature of the top/front surface. In one variation, the top/front surface may be substantially convex (as viewed from the top surface perspective) and the bottom/back surface may be substantially concave (as viewed from the bottom surface perspective) so as to approximately follow the curvature of the top/front surface and curve toward a major axis of the trowel handle. In another variation, the handle outer surface may be curved and may be shaped so to follow the curvature of the top/front surface and the bottom/back surface of the handle connecting member until the handle is approximately parallel to the trowel blade. In this case, the smooth transition between the handle and the handle connecting member permits a user to shift his or her normal forward grip in a lateral direction toward and/or over or around the handle connecting member for increased control of the trowel blade while maintaining a comfortable lower forward grip. In addition, the sloped design and/or smooth transition between the handle and the handle connecting member may also facilitate a user reversing the orientation of his or her lower forward grip by 180 degrees for dealing with various surfaces or action with the trowel while maintaining a comfortable reverse grip. In this case, the user's palm may rest comfortably even though it is primarily on the connecting member. In still another variation, the handle connecting member may have an I-beam construction whereby a portion of the sides of the handle connecting member are removed so as to reduce the weight of the trowel without reducing the structural integrity of the handle connecting member. In yet another variation, the blade attachment member may be gradually sloped from approximately the point where connected to the handle connecting member, so as to increase the strength of such connection point between the handle connecting member and the blade connecting member. In yet another variation, the trowel may be made, at least in part, of a magnesium material so as to create a more light weight trowel. For example, the trowel tang may be made of a magnesium alloy or metal including magnesium.
Still further aspects included for various embodiments will be apparent to one skilled in the art based on the study of the following disclosure and the accompanying drawings thereto.
BRIEF DESCRIPTION OF THE DRAWINGS
The utility, objects, features and advantages of the invention will be readily appreciated and understood from consideration of the following detailed description of the embodiments of this invention, when taken with the accompanying drawings, in which same numbered elements are identical and:
FIGS. 1A-1D depict a prospective view, side view, top view and partial cross-sectional side view, respectively, of a traditional trowel;
FIG. 2 is a perspective view of an exemplary trowel, according to at least one embodiment of the invention;
FIG. 3 is a side view of an exemplary trowel, according to one embodiment of the invention;
FIG. 4 illustrates a typical gripping on the handle area of an exemplary trowel, according to at least one embodiment of the invention;
FIGS. 5A-5B illustrates two of the possible forward gripping orientations of an exemplary trowel, according to at least one embodiment(s) of the invention;
FIGS. 6A-6B illustrate two of the possible reverse gripping orientations of an exemplary trowel and the inclusion of removing some material along a connecting member, according to at least one embodiment of the invention;
FIG. 7 is a top view of an exemplary trowel, according to at least one embodiment of the invention;
FIG. 8 is a cross-sectional view of an exemplary trowel of FIG. 7 taken across the line A, according to at least one embodiment of the invention;
FIG. 9 is a front view of an exemplary trowel, according to at least one embodiment of the invention; and
FIG. 10A-10C are cross-sectional views of an exemplary trowel of FIG. 9 taken across the lines 920 A- 920 B, 925 A- 925 B, and 930 A- 930 B, respectively, according to at least one embodiment of the invention.
DETAILED DESCRIPTION
The present invention is directed generally to building tools that are comfortable to grip and efficient to control in various manners and orientations. The present invention is also generally directed to building tools that are high quality, durable and in some cases lightweight. As such, the present invention includes various embodiments showing various apparatuses and methods for working with, for example, concrete, masonry, mastic, mud(s), finishing drywall, etc. Various embodiment(s) are directed to a trowel that may typically be used for applying and/or smoothing various building surfaces such as floors, walls, etc.
Various embodiments of the present invention are directed to a new geometry of the tang and handle of hand tools, for example trowels, floats, etc., that may be used for working with concrete, masonry, mastics, muds, adhesives, etc. in the building trades. Historically, these types of hand tools have had tang and handle configurations that were connected to one another and to a blade at approximately right angles (as show by the prior art trowel show in FIGS. 1A-1D described above), leaving the only comfortable grip area to be on the handle portion. The present inventions “Grip Right” or “EZ Grip” has been designed with ergonomics so as to provide a feel good grip(s) that has multiple comfortable gripping areas and orientations so that the tool may be gripped high or low along a handle and handle connection member area (e.g., a full tang—handle length) so that a worker's hand feels comfortable and remains feeling good even after many hours of working with the tool. The present invention handle and handle connecting member may also be designed so that the handle and handle connecting member may be gripped comfortably closer to the tools working member (e.g., trowel blade) to increase directional control of the tool for precision performance. For example, the handle and handle connecting member may have a smooth transition, the handle-to-tool connecting member and handle may have a curved radius shape to fit into the palm or support the fingers of a worker's hand, and/or the handle-to-tool connecting member may be at an angle or slope to the handle and/or the working portion of the tool. The invention may also include various other unique aspects, like the use of an I-beam type construction to increase the strength of the handle connecting member while maintaining a light weight structure. The invention may also include various aspects relating to the tang to blade connecting feature where the tang has a non uniform geometry where it has a taller cross sectional height where the blade is attached. This further increases the strength of the tool while keeping the weight as a minimum. In any case, the present invention marks a significant advancement in hand tool handle and connecting member design that increase the ease, comfort and versatility of working with the hand tool(s). This is particularly true for the embodiments of trowels and/or floats described below, but as one skilled in the art would understand, the generalities of the present invention may be applied to various other handle and handle connection applications and be equally useful.
Referring now to FIG. 2 , an exemplary trowel 200 according to one embodiment of the invention will now be described. A trowel 200 includes a tang 250 that connects the trowel handle 210 to the trowel blade 205 . The tang 250 includes a handle connecting member 251 and a blade attachment member 252 that assist the tang 250 in coupling the trowel handle 210 to the trowel blade 205 . The blade attachment member 252 is elongated laterally across the trowel blade 205 and is coupled at one side to the trowel blade 205 . The handle connecting member 251 is coupled at one end to the blade attachment member 252 at a connection point 254 and at another end to the handle 210 . In this case, the handle connecting member 251 may be a substantially curved member having a curved top/front surface 251 A and/or a curved bottom/back surface 251 B, each with an approximately non-linear top-to-bottom slope. In one variation, the top/front surface 251 A may be substantially convex (as viewed from the top and front sides) and/or the bottom/back surface 251 B may be substantially concave (as viewed from the bottom and back sides) so as to curve toward a major axis of the trowel handle 210 . The bottom/back surface 251 B may approximately follow the curvature of the top/front surface 251 A so as to be approximately parallel thereto. In one variation, the handle connecting member 251 narrows from top-to-bottom when looking at it from the side and from the front. The substantially curved top/front surface 251 A may have a convex curvature from approximately the location where it meets the trowel handle 210 at the handle interface 245 , to the location where it meets the blade attachment member 252 at a point 254 A. In order to provide a smooth connection between the top/front surface 251 A and the blade attachment member 252 , the substantially convex curvature of the top/front surface 251 A may transition to being concave (as viewed from the top and front sides) at an inflection point 254 A shortly before reaching the blade attachment member 252 . This permits the top/front surface 251 A of the handle connecting member 251 to gradually become parallel with a top surface of the blade attachment member 252 , rather than having an abrupt angle formed at point 254 A. This curved transition may help to strengthen the connection point 254 A and provide a comfortable surface for resting a portion of a user's hand. The substantially curved bottom/back surface 251 B may have a concave curvature (as viewed from the bottom and back sides) from approximately the location where it meets the trowel handle 210 , at the handle interface 245 , to the location where it meets the blade attachment member 252 at a point 254 B. In order to provide a smooth connection between the bottom/back surface 251 B and the blade attachment member 252 , the substantially concave curvature of the bottom/back surface 251 B may remain concave past a point 254 B where the bottom/back surface is perpendicular to a top surface of the blade attachment member 252 . This permits the bottom/back surface 251 B of the handle connecting member 251 to gradually become parallel with a top surface of the blade attachment member 252 . These substantially curved surfaces ( 251 A and 251 B) of the handle connecting member 251 also provide a location sufficiently parallel to the trowel blade 205 so that a user may comfortably rest or surround his or her hand in order to apply a force in a direction perpendicular and/or parallel to the trowel blade 205 . This area of the connecting member 251 is thus designed to not only support the handle 210 , but also so that it may be used itself as a hand support and/or grip area (by itself or in conjunction with the handle 210 ) and may provide increased control over the trowel blade 205 during use because a user's hand may reside closer to the connection point 254 and trowel blade 205 . It is also noteworthy that the interface location 245 between the handle connecting member 251 and the handle 210 may be in a forward direction and angled toward the front of the trowel 200 at an angle that is not substantially perpendicular to the lateral axis of the handle 210 .
In another variation, the handle connecting member 251 may be a substantially rounded member having a rounded top/front surface 251 A and/or a rounded bottom/back surface 251 B, each with an approximately non-linear side-to-side slope. Of course, the top/front surface 251 A and the bottom/back surface 251 B may meet at a location on the side of the handle connecting member 251 so that the handle connecting member 251 has an approximately circular or oval shape. These substantially rounded surfaces ( 251 A and 251 B) of the handle connecting member 251 provide a smooth, comfortable, and ergonomic location that a user may rest or surround his or her hand during use. In various embodiments, the handle connecting member 251 and at least a portion of the handle 210 may share a radial centerline axis 260 that is a smooth arc from connection point 254 into approximately one fourth of the handle 210 that is closest to the handle connecting member/handle interface 245 . In one variation, the handle connecting member 251 may be both a substantially curved member from top-to-bottom and a substantially rounded member from side-to-side. In this case, the substantial curvature of the handle connecting member 251 permits a user's hand to rest on or surround the handle connecting member 251 in order to apply a force in a direction perpendicular and/or parallel to the trowel blade 205 , while the substantial roundness of the handle connecting member 251 increases the comfort of such action. Of course, in at least one variation, rather than being curved, the connecting member front/top surface and/or back/bottom surface, may be substantially straight and at an angle relative to the plane of the blade 205 and lengthwise axis of the handle 210 .
In still another variation, the handle connecting member 251 may have a widened width measured from the front surface 251 A to the back surface 251 B. For example, the handle connecting member 251 may have a front-to-back width of approximately 1.5 to 2.5 cm (0.6 to 1.0 inches) that may vary along the radial curved center axis of the handle connecting member 251 . At the lower location near the connection location 254 , the thicker width may provide an increase in the strength of the handle connecting member 251 with the blade attachment member 252 so that significant forces being applied by a user to the handle and/or handle connecting member 251 by a user during use of the trowel 200 does not break the tang. The thicker width may also provide a user with a more substantial support or grip structure so that a user may more comfortably and ergonomically rest or grasp the handle connecting member 251 .
In yet another variation, the trowel handle 210 may also be a somewhat curved member having a curved top/front surface 210 A and/or a curved bottom/back surface 210 B, each with an approximately non-linear or curved top-to-bottom slope. The top/front surface 210 A may be somewhat convex and/or the bottom/back surface 210 B may be somewhat concave so as to curve from the outer surfaces of the handle connecting member 251 toward a major axis of the trowel handle 210 . The curvature of the top/front surface 210 A and/or the bottom/back surface 210 B of the trowel handle 210 may continue or follow the curvature of the top/front surface 251 A and/or the bottom/back surface 251 B of the handle connecting member 251 . In one exemplary embodiment shown in FIG. 2 , the curvature of the trowel handle 210 , however, continues only until a major axis of the trowel handle 210 is approximately parallel with the blade attachment member 252 and trowel blade 205 . Further, a shallow circular or oval indentation where a user's thumb or index finger might be placed on the top/front surface 210 A of the handle 210 while gripping in a normal forward manner may provide a comfortable and ergonomic grip (see, for example, the top view in FIG. 7 , item 765 ). This shallow indentation may only be a slight aberration in the curvature of the top/front surface 210 A so that the top/front surface 210 A may still be said to continue the curvature of the top/front surface 251 A of the handle connecting member 251 . In order to provide a smooth transition between the handle connecting member 251 and the trowel handle 210 , the front-to-back width of the trowel handle 210 near the handle interface 245 also follows the front-to-back width of the handle connecting member 251 (and visa versa). In this case, the smooth transition between the trowel handle 210 and the handle connecting member 251 effectively adds length to the available hand support or grip area because a user's hand may comfortably, easily, and ergonomically overlap the handle interface 245 onto the top/front surface 251 A and bottom/back surface 251 B of the handle connecting member 251 . Although not shown clearly in FIG. 2 , the sides of the trowel handle 210 and the handle connecting member 251 may also be coincident, at least at the handle interface 245 . The hand support or grip area, therefore, may be enlarged to consist not only of the top/front surface 210 A, at least portions of the side surfaces, and the bottom/back surface 210 B of the trowel handle 210 but also the top/front surface 251 A, at least portions of the side surfaces, and the bottom/back surface 251 B of the handle connecting member 251 . As the tang 250 including the handle connecting member 251 may be made, at least in part, of metal, the enlarged hand support or grip area may include metal.
In still another variation, the tang 250 may be made completely, or at least in part, of a material including magnesium, aluminum, long fiber carbon or glass filled materials, etc., so as to create a more light weight trowel. The material including magnesium may be magnesium alloy. For example, a magnesium alloy such as AZ31C containing approximately the following approximate percentages of materials: Magnesium: Al: 2.5-3.5%; Cu: 0.05% max; Fe 0.005% max; Mn 0.20% min; Ni 0.005% max; Si 0.30% max; Zn 0.60-1.40%; Ca 0.30% max; OT 0.30% max; Mg the remainder %. This composition or alloy of Magnesium may be particularly useful for forming parts by extrusion. Further, the formulation may have variations from those above, for example, the composition of magnesium may vary within the above by +/−5% for Al and Mg, and +5% on Mn. Another useful magnesium compound or alloy, may include the following substances in the following amounts: Aluminum (Al) at 8.5% to 9.5%; Copper (Cu) at 0.25% maximum; Manganese (Mn) at 0.15% minimum; Nickel (Ni) at 0.01% maximum; Silicon (Si) at 0.20% maximum; Zinc (Zn) at 0.45% to 0.9%; other materials (OT) at 0.30% maximum; and Magnesium (Mg) is the % remainder. This composition of Magnesium may be particular good for forming parts by casting. Further, other formulations are possible, such as the formulation of the magnesium alloy may vary within the above by +/−5% for Al and Mg, and +5% on Mn. The trowel blade 205 may be made of high carbon steel covered with a clear coat or from Stainless Steel.
The blade attachment member 252 and handle connecting member 251 may be part of an integral tang 250 made of the same material or may be welded together and made of the same or different materials such as materials including, for example, aluminum and/or magnesium. Of course, one skilled in the art would appreciate that a connecting member or tang of lightweight magnesium alloy may be useful in coupling a blade and a handle for a variety of other hand tools or other applications not specifically described herein where desired ergonomics, weight, durability, gripping and strength may be similar to the trowel described herein as exemplary embodiments.
The present invention may be made using the following process. The trowel 200 may be assembled form various parts. The handle 210 may be typically molded from various types of plastic and may (but need not) have an over-molded soft surface such as a thermoplastic elastomer. The tang 250 described in detail above may be produced by a casting process which produces a nearly finished part directly out of the mold. Cleaning excess parting line material from the casting process and machining the tang attachment features may complete the process for these parts. The trowel blade 205 may be stamped from hard sheet metal. In this manner, the blade 205 blank may then have fastening studs, or posts welded in place along the center of the blade. These studs may match mating holes machined into the base of the tang. The posts and mating holes may be spaced approximately 1-2 inches apart. The tang 250 may then be pressed onto the posts permanently securing the tang to the blade. The handle 210 may then be assembled onto the tang 250 and secured with an end cap (similar to FIG. 1 ) or plug (not shown in FIG. 2, 315 in FIG. 3 ) and nut 220 or nut 220 alone.
Referring now to FIG. 3 , this embodiment shows a side view of a trowel 300 as viewed from the left side. Although not shown, the right side view may be a mirror image of the left side view. The trowel 300 of this embodiment is similar to the trowel in the embodiment shown in FIG. 2 , but includes an angled handle connecting member 351 that may be connected to the blade attachment member 352 at a forward position with increased strength due to an inclined upper surface of the blade attachment member 352 near the connection point 354 . In this case, the handle connecting member 351 may be connected to the blade attachment member 352 in such a way that a major axis of the handle connecting member 351 along the line from “ 3 A” to “ 3 B” has an angle or slope, C ( 360 ), relative to a major axis of the blade attachment member 352 along the line from “ 4 A” to “ 4 B” of approximately 30 to 60 degrees. In a preferred embodiment, the angle or slope, C ( 360 ), between the handle connecting member 351 and the blade attachment member 352 is, for example, approximately 45 degrees. The slope may vary between, for example, approximately 20 degrees and approximately 75 degrees. This angle or slope, C ( 360 ), of the handle connecting member 351 relative to the blade attachment member 352 may provide increased control over the trowel blade 305 while gripping the trowel handle 310 . As this angle or slope, C ( 360 ), may also contribute to determining the area or distance, D, in between the trowel handle 310 and the blade attachment member 352 , the angle or slope, C ( 360 ), may be sufficient to provide an area along the bottom/back surface 310 B of the handle 310 that may be gripped by a user's finger(s) or hand. For example, with the handle connecting member 351 at an angle of approximately 45 degrees relative to the blade attachment member 352 , the area between the bottom/back surface 310 B of the trowel handle 310 and the blade attachment member 352 may be approximately 2.5 to 3.5 cm (1 inch to 1.3 inches). Further, the angle or slope, C ( 360 ), may also be sufficient to provide an area along the bottom/back surface 351 B of the handle connecting member 351 that may be gripped by a user's finger(s) or hand. For example, with the handle connecting member 351 at an angle of approximately 45 degrees relative to the blade attachment member 352 , the area between the bottom/back surface 351 B of the handle connecting member 351 and the blade attachment member 352 may be approximately 1.5 to 2.5 cm (0.6 inches to 1 inch).
The handle connecting member 351 may also be connected laterally along the blade attachment member 352 at an approximately forward connection point 354 toward the front end of the blade attachment member 352 A. For example, the trowel 300 may have a connection point 354 so that the front surface 351 A meets the blade attachment member 352 at a point 354 A having a distance of, for example, approximately 6.5 to 7.5 cm (2.5 to 3.0 inches) from a front end 352 A of the blade attachment member 352 and the back surface 351 B meets the blade attachment member 352 at a point 354 B having a distance of, for example, approximately 10 to 11 cm (4 to 4.375 inches) from the front end 352 A of the blade attachment member 352 . This forward connection point 354 may provide increased control over the trowel blade 305 while gripping the trowel handle 310 , especially where the handle connecting member 351 is substantially curved and may thereby shift the position of the trowel handle 310 more towards the rear of the trowel 300 .
The connection point 354 between the handle connecting member 351 and the blade attachment member 352 may be strengthened by forming it to have included a gradually sloping top surface, for example, at least a portion of an upper surface of the blade attachment member 352 on either side, or both sides, of the connection point 354 . A forward sloping surface 352 C (shown as a dashed line) may gradually incline from the front end 352 A of the blade attachment member 352 to a point 354 A where the top/front surface 351 A of the handle connecting member 351 meets the blade attachment member 352 . Of course, the forward sloping surface 352 C may begin its gradual incline from any point along the entire length of the blade attachment member 352 between the front end 352 A and the point 354 A. Likewise, a rearward sloping surface 352 D (shown with dashed line) may gradually incline from any point along the rear of the blade attachment member 352 , for example, at a midpoint thereof or near end 352 B of the blade attachment member 352 , to a point 354 B where the bottom/back surface 351 B of the handle connecting member 351 meets the blade attachment member 352 . Of course, the rearward sloping surface 352 D (shown with dashed line) may also begin its gradual incline from any point along the entire length of the blade attachment member 352 between the rear end 352 B and the point 354 B. In one embodiment like shown in FIG. 2 , the rearward sloping surface 352 D may begin its gradual incline from approximately the center of the length of the blade attachment member 352 between the rear end 352 B and the point 354 B. These inclined surfaces ( 352 C and 352 D) may provide additional structural strength to the connection point 354 so that a user may apply additional force to the trowel handle 310 and handle connecting member 351 without fracturing or breaking the trowel tang at connection point 354 . This is particularly important when using lighter weight material(s), such as a magnesium alloy or compound as the tang material, that is less strong.
Referring now to FIGS. 4, 5A-5B, and 6A-6B , various embodiments of the present invention are shown that include exemplary manners and orientations in which a user may grip the exemplary trowel. FIG. 4 shows a side view of a trowel 400 having one exemplary unique tang design according to at least one embodiment of the present invention and illustrate it as being gripped in a fairly typical or normal forward manner. As shown, when gripping the trowel in a forward manner the user's hand 425 (in this example the user's left hand shown in dashed lines) is gripping the trowel handle 410 only with the fingers encircling the sides and lower handle area 410 B, while the palm of the user's hand and the thumb abut the upper handle surface 410 A. In this case, the hand gripping is achieved entirely on the handle 410 and does not touch, cover or encroach on the handle connecting member 451 . The user's arm in this grip is approximately parallel with the major lateral axis of the handle 410 and the major lateral axis of the blade attachment member 452 . This is a fairly typical user's grip as is used with typical trowel and trowel tang designs (e.g., FIGS. 1A-1D ). Further, with this particular tang design, having an approximately 45 degree slope of the handle connecting member 451 , and hand 425 with grip illustration shown in FIG. 4 , one can see that the distance D between the bottom surface 410 B and top of the blade attachment member 452 provides plenty of room for the user's fingers when gripping the handle 410 in the forward manner. In fact, the slope of the handle connecting member 451 may be change to approximately 30 degrees and still provide sufficient distance D, with or without the increased height 425 D of blade attachment member 452 .
Referring now to FIG. 5A , a side view of a trowel 500 is shown according to one embodiment of the present invention and includes further exemplary illustrations of how a user may grip the handle 510 and handle connection member 551 in a lower forward manner. In one exemplary manner, the hand 525 (shown in dashed lines) may be shifted forward and downward onto the tang ( 550 ) so as to cover a portion of the handle connecting member 551 and the handle 510 . As shown, in this gripping manner the index finger of the hand 525 may surround the back/underside surface 551 B and the thumb may abut a portion of the front/top surface 551 A of the handle connection member 551 . The thumb side of the palm of the hand 525 may cover the interface 545 between the handle 510 and the handle connection member 551 . In one variation, the thumb of the user's hand 525 may be advanced lower on the front/top surface 551 A of handle connection member 551 so as to the be adjacent to or abut the upper surface of the front portion 552 A (or surface 552 C) of the blade attachment member 552 . In any case, the index finger of hand 525 may comfortably rest against or abut the lower back concave area where the handle connection member 551 and the back part of blade attachment member 552 meet. Furthermore, if the tang includes strengthening slope 552 D on the back portion of blade attachment member 552 , the index finger may also abut or rest on this raised surface also, while the distance D is sufficient for the index finger to comfortably fit into this are of the tang. These forward gripping positions are facilitated by the angled and smooth transition handle connection member 551 and may provide more stable control of the trowel during various uses.
Referring now to FIG. 5B , a side view of a trowel 500 is shown according to one embodiment of the present invention and includes a grip similar to the grips shown in FIG. 5A in a lower forward manner. However these exemplary grips are modified so that the top/front surface 551 A of the handle connecting member 551 is used as primarily a hand grip support with much of the palm of the hand 526 resting on the handle connection member 551 . In these cases, the index finger of the hand extended so that the tip of the finger rests along the top/front surface 551 A of the handle connection member 551 . Alternatively, the index finger may be extended ( 526 A) so that the index finger tip rests on the front portion 552 A of the blade attachment member 552 while the rest of the index finger no longer rests on the top/front surface 551 A of the handle connection member 551 . In this case, the palm of the hand 526 (shown in dashed lines) may be shifted forward a bit so that most of the palm of the hand straddling interface 545 is forward of interface 545 . As such, the middle finger may then abut the curved surface in the rear of the connection area 554 between the handle connecting member 551 and the blade attachment member 552 . Once again, these forward gripping positions are facilitated by the angled and smooth transition handle connection member 551 and may provide more stable control of the trowel during various uses.
Referring now to FIG. 6A , a side view of a trowel 600 according to one embodiment of the present invention is shown that includes a cut out side area 651 C and another exemplary hand 625 (shown in dashed lines) grip orientation, a reverse grip. In this example, a lower reverse hand grip orientation is shown. In the lower reverse hand grip orientation, approximately one half of the palm of the hand 625 may rest comfortably on the forward/top surface 651 A of the handle connecting member 651 and may straddle interface 645 between handle connecting member 651 and the handle 610 with a large portion of the palm resting on the forward most portion 610 A of the handle 610 . The four fingers may surround the sides and the lower/back portion 651 B of the handle connecting member 651 and the sides and lower portion 610 B of the handle 610 , with the majority of the finger grip area being on the handle 610 . Although, the butt of the palm of the hand 625 rests squarely on the handle connecting member 651 and provides the primary force during working with the trowel 600 . Given the smooth radial curvature of the handle connecting member's 651 front/top surface 651 and bottom/back surface 651 B, a comfortable and controlled reverse hand grip is enabled and there are no abrupt angles or edges on the trowel tang that may cause discomfort or blisters from extended reverse hand grip use of the trowel. In this embodiment the pinky finger may fit comfortably in the rounded rear facing surface of the connection area of the handle connecting member 651 and the blade attachment member 652 at connection area 654 as a result of sufficient distance D. This embodiment also shows that the pinky finger may abut the bottom/back surface 651 B of the handle connecting member 651 and may abut the top of the blade attachment member 652 , particularly if a slope 652 D is provided.
Further, the exemplary trowel shown in FIG. 6A includes a cut-away, indent, or valley area 651 C in the side of the handle connecting member 651 . The opposite side of the handle connecting member 651 may be symmetrical to the side shown in FIG. 6A . This area may help to reduce the weight of the tang and trowel, with little or no loss of the strength of the handle connecting member 651 by forming an I-beam type cross section of the handle connecting member 651 . This variation will be described in more detail below with reference to FIGS. 8-10C .
Referring now to FIG. 6B , an exemplary side view of a trowel 600 according to one embodiment of the present invention is provided and includes a hand 626 (shown in dashed lines) exemplary gripping in a lower reverse manner, but the grip has been modified so as to rotate the grip, move it slightly further toward the back of the trowel and handle, and extend the index finger across the top surface 610 A of the handle 610 while moving the thumb (also shown in dashed lines) to the far side of the handle 610 . Although the hand 626 fingers and thumb orientation is moved further toward the back of the handle 610 , the primary pressure point of the hand 626 remains the palm area of the hand 626 and the butt of the palm of the hand 626 rests squarely on the handle connecting member 651 , particularly on the front/top surface 651 A of the handle connecting member 651 . Again, in this manner and orientation of gripping, the handle connecting member 651 may be the primarily hand support mechanism while the handle with the fingers and thumb orientation thereon may become a control arm for proper orientation and movement of the trowel 600 . Once again, in this embodiment the pinky finger may fit comfortably in the rounded rear facing surface of the connection area of the handle connecting member 651 and the blade attachment member 652 at connection area 654 . The pinky finger may also abut the bottom/back surface 651 B of the handle connecting member 651 and may abut the top of the blade attachment member 652 , particularly if a slope 652 D is provided.
Referring to FIG. 7 , a top view of an exemplary trowel 700 , according to at least one embodiment of the present invention is shown. In this embodiment a thumb indent 765 has been added to the handle 710 and the I-beam cut away 751 C has been indicated on the handle connection member 751 , but is not the primary embodiment shown. The top view illustrates the rectangular shape of the blade 705 having straight sides. One skilled in the art recognizes that the blade may be one of many other shapes or designs, for example rounded, notched, irregular, etc., depending on the intended use of the trowel 700 . The blade attachment member 752 of the tang is shown in this view as having ends 752 A and 752 B, and a width or thickness of 7 F which may be in the range of, for example, 0.8-1.2 cm (¼ to ½ inches). Although the width may be wider, this exemplary range has proven sufficient for the stresses that this trowel will typically experience, even when the tang is made of lighter and less strong materials such as a metal including magnesium. The handle connection member 751 may be tapered from a narrow width equal to the width of 7 F (e.g., 0.8-1.2 cm (¼ to ½ inches)) where it connects to the blade attachment member 752 up to a width of, for example, 2.5-3.5 cm (⅞ to 1⅜ inches) at the interface 745 of the handle connection member 751 and the handle 710 . In preferred embodiments the width of the handle 710 and the abutting portion of the handle connection member 751 are made to be the same size so that there is a smooth transition in dimension between the two members. The width of the handle 710 at its widest portion may be, for example, 3.5 to 4.5 cm (1⅜ to 1⅞ inches), but may be made to any width as long as it fits comfortably in a user's hand. The far end of the handle 710 may be rounded. As will be seen more clearly in FIGS. 9 and 10A-10C , the handle may also preferably have a rounded or oval cross-section so that a user's hand may fit comfortably around it. As noted above, the handle may include a thumb indent or detent 765 where a thumb may comfortably set when the handle 710 is gripped in a typical forward manner. Further, the handle 710 may be attached to the tang using a plug, spacer or washer 715 and a nut or bolt 720 . A cross-sectional line 6 D- 6 E is provided so that a cross-section of handle 710 may be provides and the handle support member may be clearly seen and explained relative to FIG. 8 below.
Referring now to FIG. 8 , a partial cross-sectional view (handle section 810 ) of an exemplary trowel of FIG. 7 taken across the line 7 F- 7 F in FIG. 7 is shown, according to at least one embodiment of the invention. In this Figure it is shown that the tang may also include a unique handle support member 853 . The handle support member may have three separate areas, handle orientation portion 853 A, handle attachment stud 853 B and handle rotation reduction mechanisms 835 C that operate to ensure proper handle 810 mounting, connection, and orientation. As can be seen, the handle support member 853 and the hollow center interior of the handle 810 have two different angles incorporated therein. Various angles 800 C, 800 G, and 800 E are shown for the various different slopes of the tang and handle support portions as illustrated with lines 800 A- 800 A, 800 B- 800 B, and 800 D- 800 D. These angles and slopes are different than traditional trowel tangs and handle support configurations, and enable manufacturability of the curved or angled hand grip to the tang and comfortable gripping of the tool. As such, the handle support member 853 and hallowed out center interior of handle 810 have at least one angle that is not parallel with the plane of the blade 805 or the blade connecting member 852 axis. In this embodiment, the main axis 800 A- 800 A of the handle orientation portion 835 A is at an angle 800 C, which may be, for example, approximately 10 to 20 degrees from the approximately horizontal axis 800 B- 800 B of the handle axis stud 853 B (which is approximately parallel with the lateral main axis 800 F 0 800 F of the blade attachment member 825 ). (Compare to FIG. 1D that shows a straight handle support member 153 .) As noted previously, angle G (formed by axis 800 D- 800 D and 800 F- 800 F) may be approximately 45 degrees and may be formed at a larger or smaller angle as desired. The rotation reduction mechanisms 853 C may be triangular shaped protrusions that are located approximately in the center of each side of a square shaped handle orientation portion 853 A. The square shape of the handle orientation portion 853 A may provide the primary proper orientation and rotation reduction for the handle 810 , and the rotation reduction mechanisms 853 C may provide secondary rotation reduction and may result in the hollow end (female) of the handle 810 appear in a pattern, for example an 8 pointed star shape, to match. Finally, the far hollow or hollowed out end of the handle 810 may be capped with a holed pug 815 through which a threaded end of the stud 853 B may slide through. A nut 820 may then be threaded onto the threaded end of the stud 853 B so that the plug and handle may be secured to the handle support member and pulled tight against the handle connecting member 851 at the interface 845 , so as to be securely attached to the tang.
Referring now to FIG. 9 , a front or forward perspective view of an exemplary trowel is shown, according to at least one embodiment of the invention. This view clearly shows the indented sides 951 C on the left and right sides forming an I-beam shape on the handle connecting member 951 . The handle 910 is shown to be at the top of the handle connecting member 951 . The blade 905 is coupled to the bottom of the blade attachment member 952 . The top of the blade attachment member 952 is attached to the bottom of the handle connecting member 951 . Further, the handle connection member 951 may have a thicker top portion G and thinner bottom portion F, so as to smoothly transition from the interface with the handle 910 and the width of the blade attachment member 952 to improve the comfort of gripping the handle 910 and handle connecting member 951 . Cross-section lines 920 A- 920 B, 925 A- 925 B, and 930 A 930 B, are provided to better indicate the removal of portions of the left and right side of the handle connecting member 951 , as will be shown in FIGS. 10A-10C .
Referring to FIG. 10A-10C , cross-sectional views of an exemplary trowel of FIG. 9 with exemplary portions of the handle connecting member 910 removed to reduce weight, as taken across the lines 920 A- 920 B, 925 A- 925 B, and 930 A- 930 B in FIG. 9 , respectively, are shown, according to at least one embodiment of the invention. These figures show the varying cross sections of the connecting member 951 . With respect to FIG. 10A , this is a cross-sectional view taken across line 930 A- 930 B as provided by this exemplary embodiment. In this case the cross-section is taken high on handle connecting member 951 close to the handle 910 interface in and area that does not have material removed and is solid 1010 . As shown, this area of the handle connecting member 951 is approximately an oval or egg shape 1005 . With respect to FIG. 10B , this is a cross-sectional view taken across line 925 A- 925 B as provided by this exemplary embodiment. In this case the cross-section is taken at approximately the middle section of the handle connecting member 951 and shows how material has been removed from the left side 1015 and right side 1020 of the handle connecting member 1051 . As shown, in this exemplary embodiment the removal of material on the left side 1015 and right side 1020 results in an approximately I-beam shaped cross-section. With respect to FIG. 10C , this is a cross-sectional view taken across line 920 A- 920 B as provided by this exemplary embodiment. In this case the cross-section is taken at the lower portion of the handle connecting member 951 and shows how material has been removed from the left side 1025 and right side 1030 of the handle connecting member 1051 . As shown, in this exemplary embodiment the removal of material on the left side 1015 and right side 1020 results in an approximately I-beam shaped cross-section, albeit somewhat large on one side. As shown, the I-beam construction may have one portion thicker than another, e.g., the back/rear area may be thicker than the front portion. Although the reduced weight and removal of material in this exemplary embodiment results in an approximately I-beam shape, one skilled in the art would appreciate that material may be removed in a number of different ways and resulting shapes, and still provide sufficient weight reduction and strength for the material used to construct the tang and/or handle connection member 951 .
Various processes may be used for forming the tang. One process includes injecting material into a mold having the desired geometry. If the material is metal such as Aluminum or magnesium a casting method may be used. If the material is a plastic, an injection molding process may be used. These processes may be used to create all or any part of the tang. In any case, once cast or injected, the mold may be opened and the part(s) may be removed. The part(s) may require minor finishing to complete, if there are some imperfections relative to the final desired shape(s). Another variation may be to insert mold a piece of stronger material imbedded inside a less strong lighter material.
Although a particular embodiment(s) of the present invention has been shown and described, it will be understood that it is not intended to limit the invention to the preferred embodiment(s) and it will be obvious to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the present invention. Thus, the invention is intended to cover alternatives, modifications, and equivalents, which may be included within the spirit and scope of the invention as defined by the claims. Accordingly, the scope of the present invention should be determined not by the embodiments illustrated above, but by the claims appended hereto and their legal equivalents. | The present invention is directed generally to building tools with improved comfort in gripping and/or efficient control that may be used in various manners and orientations. A handle and work object (e.g., trowel blade) may be connected together by a connecting member (or connecting means) that may be a sloped, angled, and/or substantially curved member, so that a user has increased hand orientation options and/or control over the tool while gripping the handle and/or connecting member in various manners and orientations. In various embodiment(s), the connecting member (e.g., a tang for a trowel) may be a relatively gradually and/or notably sloped, angled, and/or curved structure that may reasonably provide a comfortable extension of the handle and augment the gripping of the tool. The various tools may include a handle connecting member having construction whereby a portion of the sides of the handle connecting member are removed. Magnesium may be used. | 4 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a divisional of copending U.S. application Ser. No. 09/502,134, filed Feb. 11, 2000, now issued as U.S. Pat. No. 6,380,790.
GOVERNMENT SUPPORT
This invention was made with Government support under Contract No. N65236-98-1-5407, awarded by DARPA. The Government has certain rights in the invention.
BACKGROUND OF THE INVENTION
This invention relates to integrators.
Integrators have high linearity, wide bandwidth, and low noise characteristics. Integrators, however, require a reset interval to discharge the capacitor in the integrator's feedback loop which results in significant “dead” times in measurements and harmful transients on the integrator's input. Additionally, the rapid discharge interval aggravates the problem of dielectric absorption, thereby undermining the lower limit of instrument precision.
Referring to FIG. 1, an integrator 10 includes a feedback loop having a switch 12 in parallel with a feedback capacitor 14 . The switch 12 allows the feedback capacitor 14 to discharge when the switch 12 is closed. Placing one or more strings of series resistors and capacitors in parallel with the feedback capacitor 14 with or without the switch 12 reduces at least some of the harmful effects of this discharge. However, even in some arrangements having multiple capacitors, dielectric absorption is still a problem since the charge in the series capacitors is redistributed with the feedback capacitor 14 .
SUMMARY OF THE INVENTION
The invention overcomes these unwanted effects of integrator reset by providing integrator circuit topologies that enable continuous integration, without the need for reset of the integrator circuit. One such integrator circuit includes a first integrator and a second integrator, each of the two integrators having a non-inverting terminal. Each of the non-inverting terminals is connected to an input node to alternately receive an input current for continuous integrator circuit integration without integrator circuit reset.
In further configurations, the inverting terminal of the second integrator can be connected to an inverting terminal of the first integrator. The non-inverting terminal of the second integrator can be connected to an output of the first integrator through a first capacitor, and the output of the second integrator can be connected to the non-inverting terminal of the first integrator through a second capacitor. In operation, the first integrator and the second integrator have voltages on respective ones of the inverting and non-inverting terminals that are substantially equal, and the two integrators produce output voltages that are complementary.
In a further integrator circuit provided by the invention, at least one integrator is provided, having an input for receiving an input current. A plurality of integrator feedback capacitors are provided, with each capacitor being connected to alternately charge and discharge, based on the integrator input current. This cooperative charging and discharging enables continuous integrator circuit integration without integrator circuit reset.
These integrator circuit topologies can be employed in a wide variety of applications in which low signal level, precise measurements are required. For example, in one biological application, the first integrator and the second integrator can be operated to each introduce an output voltage into a chemical bath on either side of a biological membrane. In this application, the integrator circuit is configured to detect fluctuations of ion channels. In another application, e.g., the integrator circuit can be configured for charge detection.
These applications are particularly well-served by the integrator circuit of the invention in its elimination of a need for rapid discharging of feedback capacitors during operation. The integrator circuit of the invention can perpetually integrate incoming current signals, such as low-level transducer signals, to produce an output of a continuous flow of two complementary voltages. This perpetual integration eliminates “dead time” and input transients, compensates for charge injection at the integrator input, and reduces the harmful effects of dielectric absorption. At the same time, the integrator circuit maintains a high degree of operational linearity, produces a low level of noise, and can accommodate a wide bandwidth of input signals.
Other features and advantages of the invention are provided in the following detailed description and the accompanying drawings, and in the claims.
DESCRIPTION OF DRAWINGS
FIG. 1 is a schematic diagram of a conventional integrator.
FIG. 2 is a block diagram of a chopper stabilizing circuit.
FIG. 3 is a schematic diagram of the block diagram of FIG. 2 .
FIG. 4 is a graph showing the output of the integrator circuit of FIG. 3 .
FIGS. 5-6 are graphs showing the chopper stabilization of the integrator circuit of FIG. 3 .
FIG. 7 is an unfolded view of the integrator circuit of FIG. 3 .
FIGS. 8-9 are graphs showing the output of the integrator circuit of FIG. 3 .
FIGS. 10-11 are graphs showing the response of the integrator of FIG. 3 to input current.
FIGS. 12-13 are graphs showing the charge injection compensation of the integrator circuit of FIG. 3 .
FIG. 14 is a graph showing currents detectable by the integrator circuit of FIG. 3 .
FIG. 15 is a graph showing charge detection by a conventional integrator circuit.
FIG. 16 is a graph showing charge detection by the integrator circuit of FIG. 3 .
FIG. 17 is a schematic diagram of the differentiator circuit of FIG. 2 .
DETAILED DESCRIPTION
Referring to FIG. 2, a chopper stabilizing circuit 20 includes a switching circuit 22 , an integrator circuit 24 , a sensing circuit 26 , a control circuit 28 , and a differentiator circuit 30 . In general, the chopper stabilizing circuit 20 has a topology and is controlled in a manner that eliminates the need for rapid discharging of feedback capacitors in the integrator circuit 24 . In particular, and as will be discussed in greater detail below, this advantage is accomplished by alternating the signal current from the switching circuit 22 to the integrator circuit 24 . In this way, the integrator circuit 24 can perpetually integrate these incoming current signals (low-level transducer signals) and output a continuous flow of two complementary voltages. The sensing circuit 26 detects when one of the complementary voltages reaches a threshold value and notifies the control circuit 28 . The control circuit 28 responds by sending a signal to the switching circuit 22 . This signal changes the position of switches in the switching circuit 22 , thereby alternating the signal current to the integrator circuit 24 . The differentiator circuit 30 receives the complementary voltages output by the integrator circuit 24 and provides a demodulated differentiation bit stream representing the slope of the complementary voltages. As will be described in more detail below, this chopper stabilizing circuit 20 eliminates dead time and input transients, compensates for charge injection at the input, and reduces the harmful effects of dielectric absorption. At the same time, the chopper stabilizing circuit 20 maintains high linearity, low noise, and wide bandwidth.
In the layout of the chopper stabilizing circuit 20 , the switching circuit 22 has an input at a first node 32 for receiving an input signal. The input signal includes the driving current/voltage for the chopper stabilizing circuit 20 from a load, a current source, and/or a voltage source. The switching circuit 22 has an output at a second node 34 that is determined by the position of the switch(es) included in the switching circuit 22 . The integrator circuit 24 has an input at the second node 34 for receiving an input signal from the switching circuit 22 and an output at a third node 36 . The sensing circuit 26 has an input at the third node 36 for receiving an input signal from the integrator circuit 24 and an output at a fourth node 38 . The control circuit 28 has an input at the fourth node 38 for receiving an input signal from the sensing circuit 26 and output at a fifth node 40 and a sixth node 42 . The switching circuit 22 has an input for receiving an input signal from the control circuit 28 at the fifth node 40 . This input signal controls the position of the switch(es) in the switching circuit 22 .
The differentiator 30 is shown in FIG. 2, though its presence is not necessary to ensure proper functioning of the chopper stabilizing circuit 20 . If it is not present, the integrator circuit 24 and the control circuit 28 may not necessarily have outputs at the third node 36 and the sixth node 42 , respectively. The differentiator circuit 30 has an input at the third node 36 for receiving an input signal from the integrator circuit 24 and at the sixth node 42 for receiving an input signal from the control circuit 28 . The input signal at the sixth node 42 controls the switch(es) included in the differentiator circuit 30 . The differentiator also has an output at a seventh node 44 .
Referring to FIG. 3, one particular embodiment of a chopper stabilizing circuit 20 includes a switching circuit 22 , an integrator circuit 24 , a sensing circuit 26 , and a control circuit 28 . The chopper stabilizing circuit 20 eliminates the need for rapid discharging of feedback capacitors 60 a-b (preferably Teflon®) in the integrator circuit 24 by alternating the signal current from the switching circuit 22 to two integrators 62 a-b included in the integrator circuit 24 . In this way, one feedback capacitor discharges while the other charges, thereby providing two inversely related output voltages (Vout+, Vout−) at Vout nodes 36 a-b . Once either of the output voltages reaches a predetermined threshold value (Vth), a regenerative comparator 76 a-b included in the sensing circuit 26 and connected to this output voltage is tripped. Hysteresis prevents the sensing circuit 26 from causing false resets. The comparator 76 a-b triggers a D-type flip-flop 78 through a NAND gate 79 , both included in the control circuit 28 . As the flip-flop 78 changes state, the outputs Q and Q-bar connected to the switches 66 a-b , 68 a-b cause them to reverse position. This reversal preserves the same orientation with respect to the load 72 , maintaining a uniform bias, while alternating the signal current to the integrator circuit 24 .
More specifically, the switching circuit 22 includes two pairs of two symmetric switches 66 a-b , 68 a-b . The switches 66 a-b , 68 a-b may be any type of standard MOS (metal oxide semiconductor) switch, e.g., MAXIM 326. Only one set of switches 66 a-b , 68 a-b is closed at a time, each closed switch providing a path for a signal to the non-inverting input terminal of an operational amplifier (opamp) 70 a-b , e.g., Burr-Brown OP627, included in the integrators 62 a-b . When the phase one (>1) switches 66 a-b are closed, a load 72 provides the input current (Io) to the first opamp 70 a while a voltage source 74 provides the bias voltage (Vb) to the second opamp 70 b . When the phase two (>2) switches are closed, the load 72 and the voltage source 74 provide current/voltage to the other opamp 70 a-b . The values of Vout+ at the Vout node 36 a and Vout− at the Vout node 36 b depend on the position of these switches 66 a-b , 68 a-b.
FIG. 4 shows the inverse relationship between Vout+ (Vcf2) and Vout− (Vcf1). In this scenario, the >2 switches 68 a-b begin closed and the feedback capacitors 60 a-b initially are discharged, so Vout+ and Vout− begin at Vb. When Io flows through the load 72 , Vout+ and Vout− alternately and inversely ramp up and down in accordance with: V t = Io Cf .
When Io decreases at a time t 1 , this relationship ceases.
The integrator circuit 24 can effectively integrate forever (constantly flowing Io), with negligible glitching during phase switching. This lack of glitch is helped by the symmetry of input stage of the integrator circuit 24 . Every input stage node 80 a-c sees one switch 66 a-b , 68 a-b turn on and another turn off during a phase transition. The already low charge injection of the switches 66 a-b , 68 a-b is then effectively reduced to tens of femtoCoulombs (fC). Additionally, the symmetric pair requires no voltage drop across a switch 66 a-b , 68 a-b , aiding in keeping leakage currents below a picoAmp (pA). The voltages at the input stage nodes 80 a-c are substantially the same.
Referring to FIGS. 5 and 6, it is appreciated that offset may be a problem as in FIG. 5, but techniques exist to alleviate this problem, e.g., a stabilizing circuit. FIG. 5 shows the chop before stabilization, and FIG. 6 shows the chopper stabilization of the integrator circuit 24 .
Referring to FIG. 7, an unfolded view of the integrator circuit 24 helps demonstrate the manner in which the circuit functions. The compensation of the integrator circuit 24 may be broken down into two sections: minor and major loops. The minor loop concerns the stability of each opamp 70 a-b ; the major loop comprises the total feedback loop around the integrator. The major loop encompasses a unity gain inverter with a voltage divider formed by the first feedback capacitor 60 a reacting with the capacitance off the input stage of the first opamp 70 a . The input capacitance is dominated by the opamp input capacitance and the parasitics of the switches 66 a-b , 68 a-b . The ratio of the capacitive voltage divider in this embodiment is approximately ten, which will keep the major loop crossover well below that of the minor loops. The minor loops are stabilized with the addition of shunt capacitances 82 a-b , which help compensate for phase lag due to shunt resistors 84 a-b (preferably metal film) reacting with the input capacitance of the opamps 70 a-b . With the bandwidth of the opamps 70 a-b on the order of 10 MHz in this embodiment, the chopper stabilizing circuit 20 should be able to track currents with a bandwidth of approximately 1 MHz.
FIGS. 8-13 further demonstrate the functioning of the integrator circuit 24 . FIG. 8 shows Vout+ and Vout− with 50 μs per horizontal division, the typical reset duration in standard integrators, e.g., Axopatch 200 B and nuclear physics instrumentation. FIG. 9 shows a zoom in on the reset transient, with the switching occurring of the order of 500 ns, e.g., 700 ns. The 2 pF feedback capacitor 60 a-b and a residual voltage jump of 20 mV signifies under 40 fC of charge injection. FIG. 10 shows the response of the integrator circuit 24 (top trace) to input current (bottom trace), a 2 nA peak-to-peak triangle wave. Because of this response, the integrator circuit 24 could be used for direct digitization of input current via single-slope integration by measuring the period between resets. FIG. 11 shows the response of the integrator circuit 24 in FIG. 10 superimposed with a 100 kHz sinusoid supplied by a 2 pF capacitor at the input. FIG. 12 shows the charge injection before compensation, and FIG. 13 shows the charge injection after compensation by the integrator circuit 24 .
Now referring to FIG. 14, the integrator circuit 24 can be used to detect the fluctuations of ion channels important in cell signaling and biological transport. These currents range from 0.1 pA to 100 pA, with bandwidths of 10 kHz. The integrator circuit 24 allows for measuring these currents without glitches from resetting.
Now referring to FIGS. 15 and 16, the integrator circuit 24 can also be used for charge detection. For example, x-ray and particle detectors output charge pulses that are usually integrated. Whenever a conventional integrator hits a limit value as in FIG. 15, it must reset and data can be lost. Using the integrator circuit 24 , the dead-time (lost data) is greatly reduced by the absence of capacitor resets as shown in FIG. 16 .
A differentiator circuit 30 , shown in FIG. 17, may be part of a chopper stabilizing circuit. The differentiator circuit 30 includes two switches 92 a-b . The switches 92 a-b may be any type of standard MOS (metal oxide semiconductor) switch, e.g., MAXIM 326. Each switch 92 a-b is either in a horizontal (>1) position, e.g., switch 92 a from a top start node 94 a to a top end node 96 a , or a diagonal (>2) position, e.g., switch 92 a from the top start node 94 a to a bottom end node 96 b , at any given time. Each closed switch 92 a-b provides a path for a signal at entering nodes 36 a-b to travel to the inverting terminal or to the non-inverting terminal of an opamp 100 . Input from a control circuit (not shown) determines the position of the switches 92 a-b . If the differentiator circuit is connected to the chopper stabilizing circuit 20 (see FIG. 2 ), the output from the control circuit 78 provides the phase information for the switches 92 a-b.
A number of embodiments of the invention have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims. | Provided are integrator circuit topologies that enable continuous integration without reset of the integrator circuit. One such integrator circuit includes a first integrator and a second integrator, each of the two integrators having a non-inverting terminal. Each of the non-inverting terminals is connected to an input node to alternately receive an input current for continuous integrator circuit integration without integrator circuit reset. The inverting terminal of the second integrator can be connected to an inverting terminal of the first integrator. The non-inverting terminal of the second integrator can be connected to an output of the first integrator through a first capacitor, and an output of the second integrator can be connected to a non-inverting terminal of the first integrator through a second capacitor. With such a capacitor connection, the capacitors alternately charge and discharge, based on integrator input current that is alternately directed between the non-inverting terminals of the integrators. | 6 |
[0001] The present invention provides secondary 8-hydroxyquinoline-7-carboxamide derivatives and pharmaceutically acceptable salts thereof, for use as antifungal agents. Specifically, these compounds were tested against Tricophyton Rubrum, Tricophyton Mentagrophytes, Aspergillus Niger and Scopulariopsis Brevicaulis . These compounds are active against Candida species such as Candida Albicans and Candida Glabrata.
BACKGROUND OF THE INVENTION
[0002] Pathogenic fungi can be divided in two categories: fungi that are able to induce diseases in normal subjects and less invasive fungi that are able to produce diseases only in critically ill hosts. In the past two decades there was a significant increase in the incidence of invasive opportunistic fungal infections and associated morbidity and mortality. This is mainly due to the major advances in modern medicine that have increased the survival of critical patients such as those in intensive care units (ICU) with intravascular and urinary catheters, total parenteral nutrition and hemodialysis or connected to ventilatory systems. Candida species commonly cause nosocomial blood stream infections among patients in the ICU. The UK hospitalized incidence of candidemia is about 3 per 100,000 bed days, and 40% to 52% of all cases occur in ICU (Schelenz S., J. Antimicrob. Chemother. 2008; 61, Suppl 1, 31-34). This kind of mycoses is frequently associated with considerable morbidity and mortality.
[0003] The attributable mortality rate is about 38%, although it can vary between 5% and 71%. During recent years there was a rising incidence of invasive pulmonary aspergillosis in patients admitted to ICU. The disease incidence ranges from 0.3% to 5.8% with an overall mortality rate exceeding 80% (Trof R. J. et al, Intensive Care Med., 2007; 33, 1694-1703). Critically ill patients are at risk to develop disturbances in immunoregulation during their stay in the ICU, which render them more vulnerable to fungal infections. Risk factors such as chronic obstructive pulmonary disease, prolonged use of steroids, advanced liver disease, chronic renal replacement therapy, near-drowning and diabetes mellitus have been described.
[0004] There was a dramatic increase also in the number of immunocompromised patients especially in the fields of solid organ and bone marrow transplantation, autoimmune syndromes, acquired immune deficiency syndrome (AIDS) and oncology.
[0005] About 40% of bone marrow transplant population develops invasive fungal infection (Khan S. A., Wingard J. R., Natl. Cancer Inst. Monogr. 2001; 29, 31-36). Candida and Aspergillus species are the most common pathogens responsible for nosocomial superficial and invasive mycoses in hematologic malignancies and bone marrow transplanted patients. In these patients the mortality associated with the systemic candidosis is very high (50-90%). Regarding solid organs transplantation, infective complications are more frequent in lung-transplanted patients. In addition to the immunosuppressive regimen, the increased susceptibility is mainly due to the constant exposure to the external environment. Parallel to immunosuppressive treatment intensity, invasive fungal infection may occur during the first days after surgical operation, its frequency is highest in the first two months and decreases after 6 months but it can occur also years after transplantation (Hamacher J. et al, Eur. Respir. J., 1999; 13, 180-186).
[0006] Invasive fungal infections are also frequent in other kind of solid organ transplantation such as kidney and liver transplants for which incidence of 5 to 50% are reported (Dictar M. O. et al, Med Mycol., 2000; 38 Suppl. 1, 251-258).
[0007] Mycoses are one of the major causes of morbidity in patients with AIDS and the incidence and severity of these infections increase with disease progression and the consequent impairment of T-cell-mediated immunity. The incidence of the different mycoses is closely related to the endemic opportunistic fungi present in the area of residence. Generally speaking the most frequent mycoses that affect AIDS patients are histoplasmosis, blastomycosis, coccidioidomycosis and paracoccidiomycosis (Sarosi G. A., Davies S. F., West J. Med., 1996; 164, 335-340).
[0008] Mucosal Candida infections are also extremely common. In normal patients all these mycosis are usually self-limited but in immunodepressed patients become highly invasive resulting in progressive and widespread dissemination.
[0009] Moreover, the increase of mycosis caused by organism resistant to current therapies became evident over recent years. This phenomenon is particularly evident for fungal infections caused by Candida albicans and fluconazole and other azoles (Bastert J. et al, Int. J. Antimicrob. Agents, 2001; 17, 81-91).
[0010] The antimycotic drugs currently available are not fully satisfactory due to their limited activity spectrum and to the heavy side effects associated to their use. The polyene drug Amphotericin B, for example, is active against Aspergillus , Zygomycete and other molds anyway, and due to its toxicity the licensed dosage for treatment of invasive mycosis is 3-5 mg/kg per day. In highly immunocompromised patients with invasive aspergillosis, liposomal encapsulated Amphotericin B, daily administered at 3 mg/kg, gave a favorable response in 50% of patients and 12-week survival rate of 72% (Cornely O. A. et al, Clin. Infect. Dis., 2007; 44, 1289-1297). The drug induced nephrotoxicity and hypokalemia in 14-16% of the patients. When daily administered at 10 mg/kg, Amphotericin B did not give any additional benefit and caused higher rates of nephrotoxicity (31%).
[0011] Azoles, introduced in the second half of the 1970s, are blockers of ergosterol synthesis. The use of the drugs belonging to this family is limited by their narrow spectrum of activity. Voriconazole, for example, is more active than Amphotericin B for the treatment of invasive aspergillosis but has no activity against zygomycetes (Johnson L. B., Kauffman C. A., Clin. Infect. Dis., 2003, 36, 630-637). The azoles employment is also limited by the induction of several side effects. Azoles interact with mammalian p450 enzymes resulting in interference with the metabolism of other drugs and, in addition, some azoles such as ketoconazole are able to block the cardiac potassium channel Kv1.5 causing Q-T prolongation and ‘torsade de pointes’ (Dumaine R., Roy M. L., Brown A. M., J. Pharmacol. Exp. Ther., 1998; 286, 727-735).
[0012] Allylamines such as Terbinafine bind to and inhibit squalene epoxidase resulting in a block of ergosterol synthesis. These drugs are very potent against Dermatophytes while their activity against Candida species is very poor. In some cases treatment with allylamines is followed by severe cutaneous adverse reactions. A recent multinational case-control study (euroSCAR) (Sidoroff A. et al, Br. J. Dermatol., 2007; 15, 989-996) revealed that Terbinafine systemic treatment is strongly associated with the development of an acute generalized exanthematous pustolosis (AGEP). This disease is characterized by the rapid occurrence of many sterile, nonfollicular pustules, usually accompanied by leucocytosis and fever. AGEP is generally attributed to the patient treatment with particular drugs and seems to be related to an altered T cells activity. Terbinafine treatment might also induce dermatomyositis, a severe autoimmune connective tissue disease characterized by erythema, muscle weakness and interstitial pulmonary fibrosis (Magro C. M. et al, J. Cutan. Pathol., 2008; 35, 74-81). In addition, as a variety of antifungal medications, Terbinafine might cause severe liver injuries (Perveze Z. et al, Liver Transpl., 2007; 13, 162-164).
[0013] Griseofulvin is a benzofurane introduced in 1960 for the treatment of dermatophyte infections. The compound induces its fungistatic activity by interfering with microtubule production. Griseofulvin displays limited activity in the treatment of onychomycoses and frequently causes severe side effects such as nausea, diarrhea, headache, confusion and fatigue (Korting H. C. et al, Antimicrob. Agents Chemother., 1993; 37, 2064-2068) that can cause the treatment discontinuation.
[0014] The two N-Hydroxy pyridones, Ciclopirox olamine and Octopirox, seem to mainly act by chelating polyvalent cations, resulting in the inhibition of the metal-dependent enzymes. They are employed against different fungal infections but their use is limited to topical treatment.
[0015] The echinocandins (Caspofungin, Micafungin, Anidulafungin) are semi-synthetic lipo-peptides and are the most recently introduced antimycotic drugs. They act by non-competitively inhibiting β-(1-3)-Dglucan synthase, an enzyme essential for the maintenance of the cell wall and are mainly used for intravenous treatment of invasive candidiasis and aspergillosis. They are fungicidal against yeast but only fungistatic against filamentous fungi; in addition, they are quite inactive against dimorphic fungi such as Blastomyces and Histoplasma . Echinocandins are generally well tolerated but animal reproduction studies showed adverse effects on fetus. For this reason FDA lists echinocandins as a pregnancy-risk category (http://www.fda.gov/medwatch/SAFETY/2004/mar_PI/Cancidas_PI.pdf; http://www.fda.gov/medwatch/safety/2007/Aug_PI/Mycamine_PI.pdf). WO98/11073 (U.S. Pat. No. 6,310,211) discloses 8-hydroxy-7-substituted quinolines as anti-viral agents.
[0016] US2003/0055071 discloses a generic class of compounds having HIV integrase inhibitory activity. As a matter of fact, most of the specific compounds disclosed in this reference bear a naphthydrinyl residue.
[0017] EP1375486 discloses nitrogen-containing heteroaryl compounds having HIV integrase inhibitory activity. N-benzyl-8-hydroxyquinoline-7-carboxamide. WO2008/14602 discloses quinoline derivatives active as CLK-1 inhibitors. EP1669348 discloses antifungal agents defined by a very broad formula which includes certain secondary amides.
[0018] From what described above, it is evident that the clinical need for efficacious antifungal drugs has dramatically increased in the few last years. Unfortunately the drugs actually available are not satisfactory due to their narrow spectrum of action, pharmacokinetic properties and severe side effects.
DESCRIPTION OF THE INVENTION
[0019] The present invention particularly provides compounds of general formula (I), endowed with a potent antifungal activity
[0000]
[0020] wherein R 0 is:
—H, —F, —Cl, —Br, —NO 2 , —CF 3 , —CO 2 R 11 , —(C═O)—NR 14 R 15 , —C 1 -C 6 alkyl, —CN, —(CH 2 ) m —NR 14 R 15 , —(SO 2 )—NR 14 R 15 , —(N—C═O)—NR 14 R 15 , —W—R 10 , —(CH 2 ) m -aryl, optionally substituted by one, two or three R 4 , or —(CH 2 ) m -heterocycle, optionally substituted by one or two R 5 ;
[0037] wherein R 1 is:
—H, —C 1 -C 3 alkyl, —OH, or —CF 3 ;
[0042] wherein R 2 is:
—H, or —CH 2 -phenyl, optionally substituted by one R 6 ;
[0045] wherein R 3 is:
—H, —C 1 -C 3 alkyl, —OH, —CF 3 , —CH═CH-furanyl, —CH═CH-phenyl, optionally substituted by one R 4 , —CH═CH-pyridinyl, —(CH 2 ) m -phenyl optionally substituted by one R 4 , —NHV, —CH 2 NHV, or —CH 2 Z;
[0057] wherein R 4 is:
—F, —Cl, —Br, —I, —NO 2 , —CF 3 , —CN, —CH 2 OH —C 1 -C 6 alkyl, —W—R 10 —(CH 2 ) m -aryl, optionally substituted by one or two R 5 , —(CH 2 ) m -heterocycle, optionally substituted by one or two R 5 , —(CH 2 ) m —C 3 -C 8 cycloalkyl, optionally substituted by one R 8 , —SO 2 —NH-heterocycle, —(CH 2 ) m —NR 14 R 15 , —(SO 2 )—NR 14 R 15 , —(C═O)—NR 14 R 15 , or —(N—C═O)—NR 14 R 15 ;
[0076] wherein R 5 is:
—H, —F, —Cl, —Br, —CF 3 , —W—R 10 , —C 1 -C 6 alkyl, —(CH 2 ) m -aryl, optionally substituted by one or two R 6 , —(CH 2 ) m -heterocycle, optionally substituted by one or two R 7 , or —(CH 2 ) m —C 3 -C 8 cycloalkyl;
[0087] wherein R 6 is:
—F, —Cl, or —Br;
[0091] wherein R 7 is:
—H, —F, —Cl, —Br, —OH, or —O—C 1 -C 3 alkyl; wherein R 8 is: —C 1 -C 4 alkyl, —W—H, —CH 2 —W—H, —(CH 2 ) m -aryl, optionally substituted by one or two R 6 , or —(CH 2 ) m -heterocycle, optionally substituted by one or two R 7 ;
wherein R 9 is:
—C 1 -C 7 alkyl, —C 3 -C 8 cycloalkyl, —C(O)R 11 , —C(O)NHR 11 , —C(OH)R 11 , —CH 2 OH, —CO 2 R 11 , or -aryl optionally substituted by one or two R 4 ;
[0112] wherein R 10 is:
—H, —C 1 -C 6 alkyl, —(CH 2 ) m -aryl, optionally substituted by one or two R 4 , —(CH 2 ) m -heterocycle, optionally substituted by one or two R 5 , —(CH 2 ) m —C 3 -C 8 cycloalkyl, or —CH(R 12 )R 13 ;
[0119] wherein R 11 is:
—H, —C 1 -C 7 alkyl, —(CH 2 ) m X 1 , or —(CH 2 ) m —C 3 -C 8 cycloalkyl;
[0124] wherein R 12 is:
—H, —(CH 2 ) m CO 2 —C 1 -C 6 alkyl, —(CH 2 ) m -phenyl, optionally substituted by one or two R 7 , —(CH 2 ) m -heterocycle, optionally substituted by one or two R 5 , —C 1 -C 6 alkyl, optionally substituted by one R 6 , —C 1 -C 4 alkyl NH—COOCH 2 -benzyl, or —C 1 -C 4 alkyl-S—CH 3 ;
[0132] wherein R 13 is:
—NH—CO 2 C(CH 3 ) 3 , —CN, —COOH, or —CO 2 R 11 ;
[0137] wherein R 14 and R 15 , independently from each other, are selected from:
—H, —C 1 -C 6 alkyl, —(CH 2 ) m -aryl, optionally substituted by one, two or three R 4 , —(CH 2 ) m -cycloalkyl, optionally substituted by one R 8 , —(CH 2 ) m -heterocycle optionally substituted by one or two R 5 , —(CH 2 ) m —W—R 10 , —(CH 2 ) m —CN, taken together with the nitrogen atom to which they are bound to form an optionally substituted 5- to 8-membered heteromonocycle containing from one to three heteroatoms selected from the group consisting of nitrogen, oxygen and sulphur, or taken together with the nitrogen atom to which they are bound to form an optionally substituted 5- to 8-membered heteromonocycle which is fused to one or two optionally substituted saturated or unsaturated rings or to other optionally substituted heterocycles containing from one to three heteroatoms selected from the group consisting of nitrogen, oxygen and sulphur;
[0147] wherein A is:
—(CH 2 ) m —X 1 , —(CH 2 ) m —C 3 -C 8 cycloalkyl, optionally substituted by one R 8 , —(CH 2 ) m —W—X 2 , —(CH 2 ) m —W—CH 2 —X 1 , or —(CH 2 ) m —CHR 9 —(CH 2 ) m —X 1 ;
[0153] wherein X 1 is:
-aryl, optionally substituted by one, two or three R 4 , -heterocycle, optionally substituted by one or two R 5 , —C 1 -C 8 alkyl, —CH(OH)-phenyl, —S-phenyl, —NHSO 2 -phenyl, optionally substituted by one, two or three R 4 , —CN, —OH, —C 3 -C 8 cycloalkyl, optionally substituted by one or two R 8 , or -4-cyano-2,3,4,5-tetrafluoro-phenyl;
[0164] wherein X 2 is:
-aryl, optionally substituted by one, two or three R 4 , -heterocycle, optionally substituted by one or two R 5 , —C 1 -C 8 alkyl, —CH(OH)-phenyl, or —C 3 -C 8 cycloalkyl, optionally substituted by one or two R 8 ;
[0170] wherein W is:
—NH—, —O—, or —S—;
[0174] wherein V is:
—R 11 , —C(O)R 11 , —SO 2 R 11 , or —C(O)NHR 11 ;
[0179] wherein Z is:
—C 1 -C 7 alkyl, —C 3 -C 8 cycloalkyl, —C(O)R 11 , —C(O)NHR 11 , or —CO 2 R 11 ;
[0185] wherein aryl is:
phenyl, naphtyl, biphenyl, tetrahydro-naphthyl, or fluorenyl;
[0191] wherein heterocycle is a 5-, 6- or 7-membered saturated or unsaturated ring containing from one to three heteroatoms selected from the group consisting of nitrogen, oxygen and sulphur, and including any bicyclic group in which any of the above heterocyclic rings is fused to a benzene ring or another heterocyclic;
[0192] wherein cycloalkyl is a saturated or unsaturated hydrocarbon ring including any bicyclic group in which the above ring is connected to a benzene, heterocyclic or other hydrocarbon ring;
[0193] wherein m is an integer from 0 to 6;
[0194] or a pharmaceutically acceptable salt or derivative thereof.
[0195] Further preferably in formula I:
[0196] R 0 , R 1 , R 2 and R 3 are H;
[0197] A is —(CH 2 ) m —X 1 ;
[0198] m is an integer from 0 to 1;
[0199] X 1 is
-aryl, optionally substituted by one or two R 4 , -heterocycle, optionally substituted by one or two R 5 , or —C 3 -C 8 cycloalkyl optionally substituted by one or two R 8 ;
[0203] wherein R 5 and R 8 are as defined above;
[0204] R 4 is
—Cl, —Br, —CF 3 , —W—R 10 , or —(CH 2 ) m —NR 14 R 15 ;
[0210] W is oxygen;
[0211] R 10 is
—H, or —C 1 -C 6 alkyl; R 14 and R 15 , are —C 1 -C 6 alkyl, or taken together with the nitrogen atom to which they are bound to form an optionally substituted 5- to 8-membered heteromonocycle containing from one to three heteroatoms selected from the group consisting of nitrogen, oxygen and sulphur;
[0217] aryl is preferably phenyl;
[0218] and/or heterocycle is preferably 2,3-dihydrobenzo[b][1,4]dioxine, pyridine, thiophene, triazole, thiazole, isoxazole, benzothiazole, pyrazine, imidazole or furane.
[0219] “Pharmaceutically acceptable salts or derivatives” refers to those salts or derivatives which possess the biological effectiveness and properties of the parent compound and which are not biologically or otherwise undesirable. Such salts include those with inorganic or organic acids, as for instance, the hydrobromide, hydrochloride, sulfate, phosphate, sodium salt, magnesium salt; such derivatives include the esters, the ethers and the N-oxides.
[0220] The compounds of the present invention and their pharmaceutical acceptable salts or derivatives may have asymmetric centres and may occur, except when specifically noted, as mixtures of stereoisomers or as individual diastereomers, or enantiomers, with all isomeric forms being included in the present invention.
[0221] The phrase “pharmaceutically acceptable”, as used in connection with the formulations containing the compounds of the invention, refers to molecular entities and other ingredients of such formulations that are physiologically tolerable and do not typically produce untoward reactions when administered to an animal such as a mammal (e.g., a human). Preferably, as used herein, the term “pharmaceutically acceptable” means approved by a regulatory agency, such as the FDA or the EMEA, or listed in the U.S. or European Pharmacopeia or other generally recognized pharmacopeia for use in mammals, and more particularly in humans.
[0222] Preferred compounds of the invention include but are not limited to compounds selected from the group consisting of:
8-Hydroxy-N-(thiophen-2-ylmethyl)quinoline-7-carboxamide 8-Hydroxy-N-(cyclohexylmethyl)quinoline-7-carboxamide 8-Hydroxy-N-benzyl-quinoline-7-carboxamide 8-Hydroxy-N-(4-chlorobenzyl)quinoline-7-carboxamide 8-Hydroxy-N-(4-methoxyphenyl)quinoline-7-carboxamide 8-Hydroxy-N-(4-(trifluoromethyl)benzyl)quinoline-7-carboxamide 8-Hydroxy-N-phenyl-quinoline-7-carboxamide 8-Hydroxy-N-(2-hydroxybenzyl)quinoline-7-carboxamide 8-Hydroxy-N-(furan-2-ylmethyl)quinoline-7-carboxamide 8-Hydroxy-N-(pyridin-3-ylmethyl)quinoline-7-carboxamide 8-Hydroxy-N-(4-methoxybenzyl)quinoline-7-carboxamide 8-Hydroxy-N-(4-bromobenzyl)quinoline-7-carboxamide 8-Hydroxy-N-(1,1-dioxidotetrahydrothien-3-yl)quinoline-7-carboxamide 8-Hydroxy-N-(4-(dimethylamino)benzyl)quinoline-7-carboxamide 8-Hydroxy-N-(tetrahydro-2H-pyran-4-yl)quinoline-7-carboxamide 8-Hydroxy-N-(4-morpholinophenyl)quinoline-7-carboxamide 8-Hydroxy-N-(4-(1H-1,2,4-triazol-1-yl)phenyl)quinoline-7-carboxamide 8-Hydroxy-N-(thiazol-2-yl)quinoline-7-carboxamide 8-Hydroxy-N-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)quinoline-7-carboxamide 8-Hydroxy-N-(4-morpholinobenzyl)quinoline-7-carboxamide 8-Hydroxy-N-((5-methylisoxazol-3-yl)methyl)quinoline-7-carboxamide 8-Hydroxy-N-((4-methylthiazol-2-yl)methyl)quinoline-7-carboxamide 8-Hydroxy-N-(isoxazol-3-yl)quinoline-7-carboxamide 8-Hydroxy-N-(benzo[d]thiazol-2-ylmethyl)quinoline-7-carboxamide 8-Hydroxy-N-((5-methylpyrazin-2-yl)methyl)quinoline-7-carboxamide 8-Hydroxy-N-((1-methyl-1H-imidazol-2-yl)methyl)quinoline-7-carboxamide 8-Hydroxy-N-((4-phenylthiazol-2-yl)methyl)quinoline-7-carboxamide 8-Hydroxy-N-(pyridin-4-ylmethyl)quinoline-7-carboxamide 8-Hydroxy-N-(pyridin-2-ylmethyl)quinoline-7-carboxamide
[0252] The compounds of the present invention can be prepared by the coupling of suitable 8-hydroxyquinolin-7-carboxylic acids 1-1 (or acid derivatives such as acid halides or esters) with the appropriate amines 1-2, as represented by the following general Chart 1:
[0000]
[0253] Alternatively the hydroxyl group of the carboxylic acid can be protected (as described in Bioorg. Med. Chem., 14, 2006, 5742-5755 or Synthesis, 12, 1997, 1425-1428 or DE540842) before performing the coupling with the amine and deprotected in the final stage.
[0254] Methods for coupling carboxylic acids with amines to form carboxamides are well known in the art. Suitable methods are described, for example, in Jerry March, Advanced Organic Chemistry, 4 th edition, John Wiley & Sons, 1992, pp. 417-425.
[0255] Methods for protecting and deprotecting aromatic hydroxyl groups are well known in the art. Protecting groups are manipulated according to standard methods of organic synthesis (Green T. W. and Wuts P. G. M. (1991) Protecting Groups in Organic Synthesis , John Wiley et Sons).
[0256] It will be apparent to those skilled in the art that the described synthetic procedures are merely representative in nature and that alternative synthetic processes are known to one of ordinary skill in organic chemistry.
[0257] The following examples serve only to illustrate the invention and its practice. The examples are not to be constructed as limitation on the scope or spirit of the invention.
EXPERIMENTAL SECTION
[0258] 1. Chemical Synthesis
[0259] Unless otherwise indicated, all the starting reagents were found to be commercially available and were used without any prior purification. The compounds of the present invention can be readily prepared using conventional synthetic procedure. In these reactions, it is also possible to make use of variants which are themselves known to those of ordinary skill in this art, but are not mentioned in greater detail. Furthermore, other methods for preparing compounds of this invention will be readily apparent to the person of ordinary skill in the art in light of the following reaction schemes and examples. Unless otherwise indicated, all variables are as defined above. Where reference is made to the use of an “analogous” procedure, as will be appreciated by those skilled in the art, such a procedure may involve minor variation, for example reaction temperature, reagent/solvent amount, reaction time, work-up conditions or chromatographic purification conditions. Abbreviations used in the instant specification, particularly in the Tables and in the Examples, are summarized in Table 1.
[0000]
TABLE 1
LC-MS (Liquid Chromatography
ESI (Electro Spray Ionization)
Mass Spectrum)
R t (retention time in minutes)
UPLC (Ultra Performance Liquid
min (minutes)
Chromatography)
h (hours)
TFA (Trifluoroacetic acid)
RT (room temperature)
μm (micrometers)
CH 3 CN (Acetonitrile)
mmol (millimoles)
THF (Tetrahydrofuran)
μL (microlitres)
MeOH (Methanol)
DMSO (Dimethyl sulfoxide)
Na 2 SO 4 (Sodium sulphate)
DCM (Dichloromethane)
SPE-SI (Solid phase extraction with
Silica gel)
CFU (Colony Forming Unit)
[0260] Except where otherwise indicated, all temperatures are expressed in ° C. (degrees centigrade) or K (Kelvin).
[0261] Proton Nuclear Magnetic Resonance ( 1 H-NMR) spectra were recorded on a Brucker 300 MHz. Chemical shifts are expressed in parts of million (ppm, δ units). Splitting patterns describe apparent multiplicities and are designated as s (singlet), d (doublet), t (triplet), q (quartet), quint (quintet), sxt (sextet), m (multiplet), br. s (broad singlet).
[0262] LC-MS were recorded under the following conditions:
[0263] Method A-C HPLC with Sample Manager and 2996 PDA Detector (Waters) interfaced with a Mass Spectrometer Single Quadrupole ZQ (Waters). ZQ interface: ESI positive mode. Full scan from 102 to 900 amu. Capillary 3.2V, cone 25V, extractor 3V, RF 0.3V, source temperature 115° C., desolvation temperature 350° C., gas flow 800 Uh, cone 100 Uh.
Method A: Column Aquity HPLC-BEH C18 (50×2.1 mm, 1.7 μm). Flow rate 0.6 mL/min, column at 40° C., injection 2 μL. Mobile phases: A phase=water/CH 3 CN 95/5+0.1% TFA, B phase=water/CH 3 CN=5/95+0.1% TFA. Gradient: 0-0.25 min (A: 95%, B: 5%), 3.30 min (A: 0%, B: 100%), 3.30-4.00 (A: 0%, B: 100%), 4.10 min (A: 95%, B: 5%), 4.10-5.00 min (A: 95%, B: 5%). Method B: Column Atlantis dC18 (100×2.1 mm, 3.0 μm). Flow rate 0.3 mL/min, column at 40° C., injection 2 μL. Mobile phases: A phase=water/CH 3 CN 95/5+0.1% TFA, B phase=water/CH 3 CN=5/95+0.1% TFA. Gradient: 0-0.20 min (A: 95%, B: 5%), 5.00 min (A: 0%, B: 100%), 5.00-6.00 (A: 0%, B: 100%), 6.10 min (A: 95%, B: 5%), 6.10-7.00 min (A: 95%, B: 5%).
Example 1
[0266]
8-Hydroxy-N-(thiophen-2-ylmethyl)quinoline-7-carboxamide
[0267] A mixture of 8-hydroxyquinoline-7-carboxylic acid (100 mg, 0.53 mmol) and di(1H-imidazol-1-yl)methanone (86 mg, 0.53 mmol) in THF (8 mL) was heated to 45° C. overnight, under nitrogen. The reaction mixture was allowed to cool to RT and thiophene-2-ylmethanamine (30 mg, 0.26 mmol) was added. The resulting mixture was stirred at RT for 24 h. Additional thiophene-2-ylmethanamine (15 mg, 0.1.3 mmol) was added and the reaction mixture was stirred for 60 h at RT. The reaction mixture was quenched with H 2 O and THF was evaporated to dryness. Saturated solution of sodium hydrogen carbonate was added to the aqueous phase and extracted twice with DCM. The separated organics were dried over Na 2 SO 4 , filtered and concentrated under reduced pressure. The residue was purified by SPE-SI cartridge (2 g, DCM to DCM:MeOH 99:1) affording the title compound (40 mg, 0.14 mmol) as a yellow solid.
[0268] LC-MS m/z (ESI + ): 285.1 (MW), R t =1.41 min (Method A).
[0269] 1 H-NMR (DMSO-d 6 ) δ: 9.43 (br. s, 1H); 8.91 (dd, 1H); 8.35 (dd, 1H); 8.00 (d, 1H); 7.65 (dd, 1H); 7.31-7.48 (m, 2H); 7.09 (dd, 1H); 6.99 (dd, 1H); 4.40-4.92 (m, 2H)
[0270] Following the procedure described above, the additional compounds of the present invention were prepared (Table 2).
[0000]
TABLE 2
LC-MS
R t ;
Ex.
Chemical name
1 H-NMR (DMSO-d 6 )
method
[MH + ]
2
δ: 8.90 (dd, 1H); 8.86 (t, 1H); 8.34 (dd, 1H); 8.00 (d, 1H); 7.64 (dd, 1H); 7.41 (d, 1H); 3.14-3.31 (m, 2H); 1.38-1.96 (m, 6H); 0.72-1.36 (m, 5H)
A
1.81; 285.2
3
δ: 9.33 (t, 1H); 8.92 (dd, 1H); 8.36 (dd, 1H); 8.03 (d, 1H); 7.65 (dd, 1H); 7.44 (d, 1H); 7.20-7.41 (m, 5H); 4.60 (d, 2H)
A
1.50; 279.1
4
δ: 9.34 (t, 1H); 8.92 (dd, 1H); 8.36 (dd, 1H); 8.01 (d, 1H); 7.66 (dd, 1H); 7.44 (d, 1H); 7.41 (s, 4H); 4.42-4.73 (m, 2H)
A
1.77; 313.1
5
(353K) δ: 11.15 (br. s, 1H); 8.87 (d, 1H); 8.31 (dd, 1H); 8.06 (d, 1H); 7.62-7.68 (m, 2H); 7.60 (dd, 1H); 7.28 (d, 1H); 6.82-7.03 (m, 2H); 3.79 (s, 3H)
A
1.51; 295.1
6
δ: 9.46 (t, 1H); 8.92 (dd, 1H); 8.36 (dd, 1H); 8.01 (d, 1H); 7.72 (m, 2H); 7.66 (dd, 1H); 7.60 (m, 2H); 7.43 (d, 1H); 4.68 (d, 2H)
A
1.90; 347.1
7
δ: 11.06 (br. s, 1H); 8.93 (d, 1H); 8.47 (d, 1H); 8.06 (d, 1H); 7.63-7.88 (m, 3H); 7.28-7.53 (m, 3H); 6.99-7.19 (m, 1H)
A
1.43; 265.1
8
δ: 9.63 (br. s, 1H); 9.19 (t, 1H); 8.92 (dd, 1H); 8.36 (dd, 1H); 8.06 (d, 1H); 7.66 (dd, 1H); 7.43 (d, 1H); 7.21 (dd, 1H); 6.99-7.16 (m, 1H); 6.84 (dd, 1H); 6.77 (td, 1H); 4.54 (d, 2H)
A
1.26; 295.1
9
δ: 9.27 (t, 1H) 8.91 (dd, 1H) 8.35 (dd, 1H) 8.01 (d, 1H) 7.65 (dd, 1H) 7.61 (dd, 1H) 7.41 (d, 1H) 6.42 (dd, 1H) 6.30-6.39 (m, 1H) 4.59 (d, 2H)
A
1.23; 269.2
10
δ: 9.44 (t, 1H); 8.91 (dd, 1H); 8.61 (d, 1H); 8.48 (dd, 1H); 8.35 (dd, 1H); 7.99 (d, 1H); 7.75-7.82 (m, 1H); 7.65 (dd, 1H); 7.41 (d, 1H); 7.38 (ddd, 1H); 4.62 (d, 2H)
B
2.08; 280.14
11
δ: 9.24 (t, 1H); 8.91 (dd, 1H); 8.35 (dd, 1H); 8.02 (d, 1H); 7.65 (dd, 1H); 7.42 (d, 1H); 7.32 (m, 2H); 6.91 (m, 2H); 4.34-4.66 (m, 2H); 3.74 (s, 3H).
A
1.47; 309.1
12
δ: 9.35 (t, 1H); 8.92 (dd, 1H); 8.36 (dd, 1H); 8.00 (d, 1H); 7.66 (dd, 1H); 7.49-7.60 (m, 2H); 7.44 (d, 1H); 7.29-7.40 (m, 2H); 4.43-4.70 (m, 2H).
A
1.74; 357.0
13
δ: 9.09 (d, 1H); 8.92 (dd, 1H); 8.37 (dd, 1H); 7.97 (d, 1H); 7.66 (dd, 1H); 7.43 (d, 1H); 4.58-4.93 (m, 1H); 3.56 (dd, 1H); 3.37 (ddd, 1H); 3.09-3.30 (m, 2H); 2.55-2.61 (m, 1H); 2.14-2.40 (m, 1H).
A
0.77; 307.1
14
δ: 9.20 (t, 1H); 8.91 (dd, 1H); 8.34 (dd, 1H); 8.02 (d, 1H); 7.64 (dd, 1H); 7.41 (d, 1H); 7.21 (m, 2H); 6.71 (m, 2H); 4.46 (d, 2H); 2.86 (s, 6H).
A
0.79; 322.1
15
δ: 8.91 (dd, 1H); 8.70 (d, 1H); 8.35 (dd, 1H); 8.01 (d, 1H); 7.64 (dd, 1H); 7.42 (d, 1H); 4.01-4.28 (m, 1H); 3.78-4.01 (m, 2H); 3.44 (td, 2H); 1.76-2.01 (m, 2H); 1.53-1.72 (m, 2H).
A
0.92; 273.1
16
δ: 10.63 (br. s, 1H); 8.93 (dd, 1H); 8.43 (dd, 1H); 8.07 (d, 1H); 7.69 (dd, 1H); 7.52-7.65 (m, 2H); 7.44 (d, 1H); 6.86-7.11 (m, 2H); 3.61-3.89 (m, 4H); 2.95-3.27 (m, 4H).
A
1.05; 350.2
17
δ: 11.28 (br. s, 1H); 9.25 (s, 1H); 8.94 (dd, 1H); 8.50 (dd, 1H); 8.22 (s, 1H); 8.05 (d, 1H); 7.90 (m, 4H); 7.74 (dd, 1H); 7.42 (d, 1H).
A
1.16; 332.1
18
(353K) δ: 8.90 (dd, 1H); 8.50 (dd, 1H); 8.13 (d, 1H); 7.74 (dd, 1H); 7.51 (d, 1H); 7.31 (d, 1H); 7.19 (d, 1H).
A
1.11; 272.0
19
δ: 10.72 (br. s, 1H); 8.93 (dd, 1H); 8.45 (dd, 1H); 8.03 (d, 1H); 7.70 (dd, 1H); 7.43 (d, 1H); 7.40 (d, 1H); 7.11 (dd, 1H); 6.86 (d, 1H); 4.12-4.37 (m, 4H).
A
1.43; 323.2
20
δ: 9.22 (t, 1H); 8.91 (dd, 1H); 8.35 (dd, 1H); 8.02 (d, 1H); 7.64 (dd, 1H); 7.42 (d, 1H); 7.25 (m, 2H); 6.92 (m, 2H); 4.49 (d, 2H); 3.60-3.90 (m, 4H); 2.93-3.18 (m, 4H).
A
1.10; 364.1
21
δ: 9.38 (t, 1H); 8.92 (dd, 1H); 8.36 (dd, 1H); 7.99 (d, 1H); 7.66 (dd, 1H); 7.42 (d, 1H); 6.22 (s, 1H); 4.59 (d, 2H); 2.38 (s, 3H).
A
1.10; 284.2
22
δ: 9.59 (t, 1H), 8.93 (dd, 1H), 8.38 (dd, 1H), 8.01 (d, 1H), 7.67 (dd, 1H), 7.44 (d, 1H), 7.16 (q, 1H), 4.83 (d, 2H), 2.35 (s, 3H)
A
1.08; 300.2
23
δ: 12.50 (br. s, 1H); 8.91 (dd, 1H); 8.85 (d, 1H); 8.61 (dd, 1H); 8.09 (d, 1H); 7.81 (dd, 1H); 7.30 (d, 1H); 7.13 (d, 1H).
A
1.11; 256.1
24
δ: 9.73 (t, 1H); 8.95 (dd, 1H); 8.39 (dd, 1H); 8.03-8.11 (m, 1H); 8.04 (d, 1H); 7.91-8.01 (m, 1H); 7.69 (dd, 1H); 7.35-7.58 (m, 3H); 5.02 (d, 2H).
A
1.50; 336.1
25
δ: 9.46 (t, 1H); 8.93 (dd, 1H); 8.57 (d, 1H); 8.50 (d, 1H); 8.37 (dd, 1H); 8.02 (d, 1H); 7.66 (dd, 1H); 7.44 (d, 1H); 4.70 (d, 2H); 2.49 (br. s, 3H).
A
0.98; 295.2
26
δ: 9.28 (t, 1H); 8.92 (dd, 1H); 8.36 (d, 1H); 8.05 (d, 1H); 7.66 (dd, 1H); 7.43 (d, 1H); 7.11 (d, 1H); 6.83 (d, 1H); 4.64 (d, 2H); 3.69 (s, 3H).
B
2.39; 283.2
27
δ: 9.75 (t, 1H); 8.94 (dd, 1H); 8.38 (dd, 1H); 8.01-8.07 (m, 2H); 7.93-8.00 (m, 2H); 7.67 (dd, 1H); 7.40-7.52 (m, 3H); 7.27-7.39 (m, 1H); 4.94 (d, 2H).
A
1.74; 362.1
28
δ: 9.40 (t, 1H); 8.93 (dd, 1H); 8.44-8.61 (m, 2H); 8.37 (dd, 1H); 8.02 (d, 1H); 7.66 (dd, 1H); 7.45 (d, 1H); 7.28-7.41 (m, 2H); 4.63 (d, 2H).
B
2.04; 280.1
29
δ: 9.46 (t, 1H); 8.93 (dd, 1H); 8.54 (ddd, 1H); 8.37 (dd, 1H); 8.06 (d, 1H); 7.78 (td, 1H); 7.66 (dd, 1H); 7.45 (d, 1H); 7.41 (d, 1H); 7.29 (ddd, 1H); 4.70 (d, 2H)
A
0.57 280.1
[0271] 2. Activity Testing: Methods and Results
[0272] Organisms Used to Test Antifungal Activity
[0273] Trichophyton Rubrum (ATCC 28188, PBI International); Trichophyton Mentagrophytes (ATCC 9533, PBI International); Aspergillus Niger (ATCC 16404, PBI International); Scopulariopsis Brevicaulis (ATCC 36840, DSMZ); Candida Albicans (ATCC 90028, PBI International); Candida Glabrata (ATCC 90030, DSMZ).
[0274] Preparation and Conservation
[0275] Strains were prepared from freeze-dried ampoules or freeze-dried pellets. An isolation of the suspensions was made on Potato Dextrose Agar (PDA) to test the strains purity. A strains' massive growth was then made streaking microbial suspensions on PDA plates.
[0276] Incubation was at 30° C. for 48-72 Hours (Candida yeasts) and for 7-10 days (filamentous fungi).
[0277] The yeasts' colonies and the filamentous fungi's conidia were harvested with 3-5 mL of RPMI 1640+50% glycerol and the aliquots frozen at −80° C.
[0278] Antifungal Susceptibility Testing
[0279] Compounds' minimal inhibition concentration (MIC) was determined through broth micro-dilution susceptibility test using a method developed in agreement with the National Committee for Clinical Laboratory Standards (NCCLS) (National Committee for Clinical Laboratory Standards. Reference Method for Broth Dilution Antifungal Susceptibility Testing of Yeasts; Approved standard-Second Edition M27-A2. 2002; Vol. 22, No. 15) (National Committee for Clinical Laboratory Standards. Reference Method for Broth Dilution Antifungal Susceptibility Testing of Filamentous Fungi; Approved standard M38-A. 2002; Vol. 22, No. 16).
[0280] Assays were carried out in RPMI 1640 with L-glutamine medium buffered to pH 7 with 0.165M 3-(N-morpholino)propanesulfonic acid (MOPS) and 10M NaOH and supplemented with 18 g glucose/litre. The tests were performed using 96 well sterile plates (inoculum size of 1×10 5 CFU/mL). Compounds stock solutions were prepared at 12.8 mg/mL in 100% DMSO. A series of twofold dilutions were prepared in plate using RPMI 1640. Final concentrations ranged from 0.125 to 128 μg/mL at 1% DMSO.
[0281] MIC is defined as the lowest concentration of antifungal agent which prevents any visible growth and was determined after 48 h of incubation for yeasts (35° C.) and after five days of incubation for filamentous fungi (35° C.).
[0282] Results
[0283] The MIC values for the most preferable compounds, calculated as the geometric means of the values obtained in two single experiments, are reported in Table 3.
[0000]
TABLE 3
Trycophyton
Tricophyton
Aspergillus
Scopulariopsis
Candida
Candida
Rubrum
Mentagrophytes
Niger
Brevicaulis
Albicans
Glabrata
Ex
ATCC 28188
ATCC 9533
ATCC 16404
ATCC 36840
ATCC 90028
ATCC 90030
1
0.50
0.50
0.25
0.25
1.00
1.00
2
1.00
0.71
0.35
2.00
1.41
1.41
3
0.35
0.18
0.18
0.35
1.00
1.00
4
0.71
0.50
0.35
0.71
2.00
1.00
5
0.35
0.50
0.71
0.71
0.50
0.71
6
1.41
1.00
0.50
1.41
1.41
1.41
7
0.50
0.71
0.50
2.00
0.50
1.00
8
0.71
0.50
0.25
1.00
2.00
2.00
9
0.71
1.00
1.00
0.71
0.71
0.71
10
2.00
2.00
1.00
1.00
4.00
11.31
11
1.00
1.00
1.00
1.00
2.00
1.41
12
1.41
1.00
0.71
1.41
1.41
1.41
14
1.00
0.71
0.50
1.00
2.83
1.41
17
2.52
2.00
1.00
1.26
2.00
2.83
19
0.25
0.50
1.00
1.00
2.00
2.00
20
1.00
0.50
0.50
4.00
4.00
2.00
21
1.00
4.00
1.00
2.83
2.00
2.00
22
1.41
2.83
1.00
1.00
2.00
2.00
24
2.00
1.00
0.50
1.00
2.00
2.83
29
2.00
2.00
0.50
1.00
4.00
4.00
[0284] Furthermore, the compound codified as E8 in EP1669348A1 was synthesized together with a new compound (codified as NiK-29298), not included among those disclosed in EP1669348A1, nor in the present invention, that can be used as a link between the class of compound described in the present application and those described in EP1669348A1 (Table 4).
[0000]
TABLE 4
E8
NiK-29298
[0285] The MIC values for these compounds, tested on the same organisms used to assess the potency of the derivatives described in the present application are reported in Table 5.
[0000]
TABLE 5
Candida
Trycophyton
Tricophyton
Aspergillus
Scopulariopsis
Candida
Glabrata
Rubrum
Mentagrophytes
Niger
Brevicaulis
Albicans
ATCC
Ex
ATCC 28188
ATCC 9533
ATCC 16404
ATCC 36840
ATCC 90028
90030
E8
>128
75
2-128
>128
1.41
1.00
NiK-29298
>128
128
64-128
>128
2.00
5.65
[0286] As it can be appreciated, all the compounds listed in table 3 are active on all the 6 strains tested, including yeasts, dermatophytes and molds. This broad spectrum of the compounds of the present invention accounts for a predicted efficacy on all kinds of fungal infections in humans or in animals, including skin, scalp and nail infections, mostly caused by dermatophytes; vaginal, mouth and intestinal infections, mostly caused by yeasts; ear, pulmonary, eye, and other systemic infections, mostly caused by molds.
[0287] Conversely, the compound E8, disclosed in EP1669348A1, and the compound NiK-29298, characterized by the same quinoline scaffold described in EP1669348A1, are active only on yeasts and do not display any appreciable activity against the other strains, including dermatophytes and molds.
[0288] Mechanism of Action
[0289] It is known in the art that ciclopirox, one of the most potent and broad spectrum antifungal agents, kills the fungal cells by chelating Fe 3+ , i.e. by subtracting the iron ions from the fungal cells, and its in vitro action is inhibited only by adding an adequate quantity of Fe 3+ ions to the medium. Ciclopirox is also known in the art to be the only antifungal agent which, due to its peculiar mechanism of action, does not induce resistances in fungal strains.
[0290] Method for the Assessment of the Mechanism of Action
[0291] To verify if the compounds mechanism of action is the chelation of iron ions, the MIC determination with Candida glabrata (ATCC 90030) strain was performed by the addition of excessive iron ions (100 μM FeCl 3 ) in the test medium. The viability of cells exposed to drugs, with or without the metal ion Fe 3+ , was evaluated by the OD measure at 540 nm.
[0292] The potency of compounds described in Example 3, 4, 11 12, E8 and NiK-29298 were evaluated on Candida glabrata in presence and in absence of 100 μM (100 micromoles) Fe 3+ .
[0293] The results are reported in the following FIGS. 1 , 2 and 3 .
[0294] In all figures, the lines and dots represent the percent inhibition of the fungal growth (in ordinate) by adding different concentrations of antifungal agents (in abscissa). Blue lines and dots are the experiments performed without iron supplementation, while red lines and dots represent the results of the experiments performed in presence of 100 μM Fe 3+ . As known from the art, ciclopirox effect is completely inhibited by presence of Fe 3+ and Candida glabrata is able to grow normally ( FIG. 1 ). Conversely, Fe 3+ has no effect on amphotericin, an antifungal agent known in the art to have a mechanism of action different from that of ciclopirox.
[0295] All the compounds of the present invention have similar behavior to ciclopirox, i.e. their antifungal activity is completely inhibited by presence of Fe 3+ ( FIG. 2 ).
[0296] On the contrary, the compound E8, disclosed by EP1669348A1, and the compound NiK-29298, with the quinolone scaffold described in EP1669348A1, unlike ciclopirox and unlike the compounds of the present invention, where not inhibited by the presence of Fe 3+ ions in the medium culture.
[0297] In conclusion, the compounds disclosed in EP1669348A1 have a narrow spectrum of action, limited to yeasts, while they do not display antifungal activity against dermatophytes or molds. Moreover, their mechanism of action is independent on iron chelation.
[0298] On the contrary, the compounds of the present invention are superior to those disclosed in EP1669348A1, In that they have a potent antifungal activity with a wide spectrum of action, extended to yeasts, dermatophytes and molds. This characteristic makes their efficacy predictable in a variety of fungal infections, including skin, scalp, nail infections, moreover vaginal, mouth and intestinal infections, finally ear, pulmonary, eye, and other systemic infections. Furthermore, the compounds of the present invention are superior to those disclosed in EP1669348A1, in that their mechanism of action is iron chelation, a mechanism known in the art to avoid development of resistance in fungal cells. | The present invention provides secondary 8-hydroxyquinoline-7-carboxamide derivatives of general formula (I) and pharmaceutically acceptable salts thereof. These compounds are useful as antifungal agents. Specifically, these compounds were tested against Tricophyton Rubrum, Tricophyton Mentagrophytes, Aspergillus Niger and Scopulariopsis Brevicaulis . These compounds are active against Candida species such as Candida Albicans and Candida Glabrata . | 2 |
BACKGROUND OF THE INVENTION
This invention relates to a catalytic composite for the conversion of hydrocarbons. Additionally, the invention relates to a process for the use of the catalyst. The catalyst of the present invention is particularly useful in the catalytic reforming of hydrocarbons boiling in the gasoline range to produce in high yield a high octane reformate suitable for blending gasolines of improved anti-knock properties.
Catalytic reforming to upgrade naphtha or low-boiling range hydrocarbons to higher octane gasoline has been practiced for many years using catalysts comprising platinum on a refractory support, such as alumina. In the 1960's a major advance was made in this area when it was discovered that, in reforming a low-sulfur content hydrocarbon feedstock, the use of a catalyst comprising platinum and rhenium on alumina provided greatly improved yield stability and a much lower fouling rate. See U.S. Pat. No. 3,415,737 to Kluksdahl.
Since that time, a number of other patents have issued in the area of catalytic reforming using platinum-rhenium catalysts. Some of these patents have been particularly focused on use of relatively high rhenium to platinum ratio catalysts, including the following: U.S. Pat. No. 4,356,081 to Gallagher, which discloses the use of catalysts having rhenium to platinum ratios of from about 1.08 up to as high as 17, rhenium contents from 0.362 to 0.875 weight percent and platinum contents from 0.05 to 0.344 weight percent; U.S. Pat. No. 4,425,222 to Swan, which discloses multi-stage reforming using forward reactors having a catalyst with rhenium to platinum ratio less than 1.2 a rearward reactor having a catalyst with a rhenium to platinum ratio greater than 1.5, and a swing reactor having some catalyst of each ratio.
Platinum-alumina reforming catalysts are often made by impregnating alumina with a platinum compound. For example, U.S. Pat. No. 3,617,519 discloses the preparation of a platinum-rhenium-alumina reforming catalyst wherein the platinum is impregnated into an alumina support by commingling the alumina support with an aqueous solution of chloroplatinic acid. Following the platinum impregnation, the impregnated carrier is typically dried and subjected to a conventional high temperature calcination or oxidation treatment.
U.S. Pat. No. 3,617,519 discloses that in most cases it is advantageous to adjust the concentration of the halogen component in the platinum-rhenium-alumina catalyst during the calcination step by injecting, into the air stream used therein, an aqueous solution of a suitable halogen-containing compound. U.S. Pat. No. 3,617,519 discloses that the halogen component can be added to the catalyst in various ways including adding the halogen during the impregnation through the utilization of a mixture of chloroplatinic acid and hydrogen chloride.
Typical calcination temperatures used in the preparation of the alumina support for reforming catalysts cover a wide range from about 800° to 1300° F., and frequently are 1100° F. or lower.
"Rheniforming F" catalyst, containing about 0.3 weight percent Pt, and about 0.6 weight percent Rhenium on an extruded alumina carrier has been marketed by the assignee of the present invention.
Rheniforming F has been sold under license and successfully used commercially for many years. This catalyst is particularly described as the first stage catalyst of the catalyst system described in U.S. Pat. No. 4,764,267 to Chen et. al. Rheniforming F is an extruded catalyst, that is, it is substantially cylindrical in shape. The extruded Rheniforming F catalyst has a bulk density of about 0.6 cc/g and a particle density of about 1.00 cc/g. A typical tamped packed bulk density is about 0.65 cc/g.
It is typically believed the yield stability performance of Rheniforming type catalysts are due to the metals loading levels. However, in the notoriously unpredictable hydrocarbon catalysis art, a catalyst having improved yield stability and increased liquid volume yield is always much desired.
SUMMARY OF THE INVENTION
In a broad embodiment, the present invention comprises a catalyst composition comprising about 0.24 to about 0.26 weight percent platinum and about 0.48 to about 0.52 weight percent rhenium disposed on a spheroidal alumina carrier.
In an alternative embodiment, the present invention provides for a reforming process for using a catalyst composition comprising 0.24 to 0.26 weight percent platinum and 0.48 to 0.52 weight percent rhenium disposed on an spheroidal alumina carrier.
We have found catalyst performance, particularly yield stability, to be affected by sulfur content in the hydrocarbon feed to the reactor containing Pt-Re catalyst.
We believe that at reforming conditions, sulfur in the feed alters the metals/acidity balance, significantly affecting catalyst performance. The catalyst of our claimed invention performs surprisingly well in reforming of hydrocarbons, which we believe is due in part to the acheivement of a metals loading which better balances the metals/acidity characteristics of the catalyst.
Among other factors, we found that when a spheroidal alumina, particularly gamma-alumina, catalyst base particles were loaded with a level of Pt and Re equivalent to the reactor-loaded density of Rheniforming F, surprisingly advantageous results were achieved in catalyst yield stability. Run-life increased about 15%, compared to the extruded Rheniforming F catalyst with the same reactor loaded metals density. Alternatively expressed, the "fouling rate" for our new catalyst was about 87% of that of Rheniforming F, with the same reactor-loaded metals density. Surprisingly, we also found LV% yield to improve for a reforming process utilizing the catalyst of the present invention. Yields of C 3 's and C 4 compounds were also lower, indicating a surprisingly lower cracking activity, and thus resulting in an increased liquid volume yield.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a graphical representation of the catalytic activity over time for three catalysts: Rheniforming F, the catalyst composition of our present invention, and a third commercially available reforming catalyst.
FIG. 2 is a graphical representation of liquid yield for three catalysts: Rheniforming F, the catalyst of our present invention, and a third commercially available reforming catalyst.
DETAILED DESCRIPTION
The preferred refractory inorganic oxide for use in the present invention is alumina. Suitable alumina materials are the crystalline aluminas known as the gamma-, eta-, and theta-alumina, with gamma- or eta-alumina giving best results. The preferred refractory inorganic oxide will have an apparent bulk density of about 0.3 to about 1.0I g/cc and surface area characteristics such that the average pore diameter is about 20 to 300 Angstroms, the pore volume is about 0.1 to about i cc/g and the surface area is about 100 to about 500 m 2 /g. There are several commercial routes to pure alumina.
Although alumina is the preferred refractory inorganic oxide, a preferred alumina is that which has been characterized in U.S. Pat. Nos. 3,852,190 and 4,012,313 as a byproduct from a Ziegler higher alcohol syntheses reaction as described in Ziegler's U.S. Pat. No. 2,892,858. For purposes of simplification such an alumina will be hereinafter referred to as a "Ziegler alumina." Ziegler alumina is presently available from the Conoco Chemical Division of Continental Oil Company under the trademark Catapal. This material is an extremely high purity alpha-alumina monohydrate (boehmite) which after calcination at a high temperature has been shown to yield a high purity gamma-alumina. It is commercially available in three forms: (1) Catapal SB--a spray-dried powder having a typical surface area of about 250 m 2 /g; (2) Catapal MG--a rotary kiln dried alumina having a typical surface area of about 180 m 2 /g; and (3) Dispal, a product having a typical surface area of about 185 m 2 /g. For purposes of the present invention, a preferred starting material is the spray-dried powder, Catapal SB. This alpha-alumina monohydrate powder may be formed into a suitable catalyst material according to any of the techniques known to those skilled in the catalyst carrier material forming art. Spherical carrier material particles may be formed, for example, from this Ziegler alumina by: (I) converting the alpha-alumina monohydrate powder into an alumina sol by reaction with a suitable peptizing acid and water and thereafter dropping a mixture of the resulting sol and a gelling agent into an oil bath to form spherical particles of an alumina gel which are easily converted to a gamma-alumina carrier material by known methods.
Preferred carrier materials have an apparent bulk density of about 0.3 to about 0.8 g/cc and surface area characteristics such that the average pore diameter is about 20 to 300 Angstroms, the pore volume is about 0.1 to about 1 ml/g and the surface area is about 100 to about 500 m 2 /g. In general, best results are typically obtained with a gamma-alumina carrier material which is used in the form of spherical particles having: a relatively small diameter (i.e., typically about 1/16 inch), an apparent bulk density of about 0.75 g/cc, a pore volume of about 0.4 ml/g, and a surface area of about 175 m 2 /g.
The preferred alumina carrier material may be prepared in any suitable manner and may be synthetically prepared or natural occurring. Whatever type of alumina is employed it may be activated prior to use by one or more treatments including drying, calcination, steaming, etc., and it may be in a form known as activated alumina, activated alumina of commerce, porous alumina, alumina gel, etc. For example, the alumina carrier may be prepared by adding a suitable alkaline reagent, such as ammonium hydroxide, to a salt of aluminum such as aluminum chloride, aluminum nitrate, etc., in an amount to form an aluminum hydroxide gel which upon drying and calcining is converted to alumina. The alumina may be formed in any desired shape such as spheres, pills, cakes, extrudates, powders, granules, etc., and utilized in any desired size. For the purpose of the present invention, a particularly preferred form of alumina is the sphere; and alumina spheres may be continuously manufactured by the well known oil drop method which comprises: forming an alumina hydrosol by any of the techniques taught in the art and preferably by reacting aluminum metal with hydrochloric acid, combining the hydrosol with a suitable gelling agent and dropping the resultant mixture into an oil bath maintained at elevated temperatures. The droplets of the mixture remain in the oil bath until they set and form hydrogel spheres. The spheres are then continuously withdrawn from the oil bath and typically subjected to specific aging treatments in oil and an ammoniacal solution of further improve their physical characteristics. The resulting aged and gelled particles are then washed and dried at a relatively low temperature of about 300° F. to about 400° F. and subjected to a calcination procedure at a temperature of about 850° F. to about 1300° F. for a period of about 1 to about 20 hours. This treatment effects conversion of the alumina hydrogel to the corresponding crystalline gamma-alumina. Size of the sheres are determined primarily by fluid hydraulics and volume considerations in the loaded reactor. While not limiting our present invention in any way, we have found a particle size of about 1/16th inch diameter to be preferred. See U.S. Pat. No. 2,620,314, the teachings of which are fully incorporated by reference herein, for additional details. Other patents describing the oil-drop method of manufacturing spheroidal alumina carriers are U.S. Pat. Nos. 3,887,493 to Hayes, 3,919,117 to Michalko, and 3,979,334 to Lee et al., all of which are incorporated by reference herein for the teaching of the oil-drop method.
One of the advantages of a spheroidal alumina carrier is a high crush strength relative to extruded alumina carriers.
A particularly preferred alumina is that which has been produced by electrolysis. Production of alumina through electrolytic purification is well known in the art, and is described in Kirk Othmer, p. 152-154. The Encyclopedia of Chemical Processing and Design, Vol. 3, p.66-67 also describes electrolytic refining of aluminum. Electrolysis produced alumina is particularly free of impurities such as titanium compounds. While not limiting our invention in any way, or due to any particular theory of operation, we believe the absence of titanium in the alumina source gives a spheroidal catalyst, having our claimed metals loading, superior properties relative to other catalysts previously known. Additionally, electolytically produced alumina has fewer alkali metals (such as sodium and potassium) and fewer alkaline earth metals (such as calcium and magnesium), the presence of which have been found to be undesirable in catalyst carrier material.
The platinum and rhenium are disposed in intimate admixture with each other on the porous inorganic oxide catalyst support. The platinum and rhenium can be disposed by suitable techniques such as ion-exchange, coprecipitation, impregnation, etc. One of the metals can be associated with the carrier by one procedure, for example ion-exchange, and the other metal associated with the carrier by another procedure, e.g., impregnation. However, the metals are usually associated with the porous inorganic oxide support by impregnation. The catalyst can be prepared either by coimpregnation of the metals onto the porous inorganic oxide carrier or by sequential impregnation. In general, the carrier material is impregnated with an aqueous solution of a decomposable compound of the metal in sufficient concentration to provide the desired quantity of metal in the finished catalyst and the resulting mixture is then heated to remove volatiles. Chloroplatinic acid is an example of an acceptable source of platinum. Other feasible platinum-containing compounds, e.g., ammonium chloroplatinates and polyammineplatinum salts, can also be used. Rhenium compounds suitable for incorporation onto the carrier include, among others, perrhenic acid and ammonium perrhenates.
Incorporation of the metals with the carrier ca be accomplished at various stages of the catalyst preparation. For example, if the metals are to be incorporated in intimate admixture with the alumina support, the incorporation may take place while the alumina is in the sol or gel form followed by precipitation of the alumina. Alternatively, a previously prepared alumina carrier can be impregnated with a water solution of the metal compounds. Regardless of the method of preparation of the supported platinum-rhenium catalyst it is desired that the platinum and rhenium be in intimate admixture with each other on the support and furthermore that the platinum and rhenium be uniformly dispersed throughout the porous inorganic oxide catalyst support.
The reforming activity of the catalyst is promoted by the addition of halides, particularly fluoride or chloride. Chloride is preferred. The halides provide a limited amount of acidity to the catalyst which is beneficial to most reforming operations. The catalyst promoted with halide preferably contains from 0.1 to 2 weight percent total halide content and more preferably from 0.5 to 1.5 weight percent, and still more preferably about 1 wt.% total halide content. The halides can be incorporated onto the catalyst carrier at any suitable stage of catalyst manufacture, e.g., prior to or following incorporation of the platinum and rhenium. Some halide is often incorporated onto the carrier when impregnating with the metals; e.g., impregnation with chloroplatinic acid results in chloride addition to the carrier. Additional halide can be incorporated onto the support simultaneously with incorporation of the metal(s) if so desired. In general, halides are combined with the catalyst carrier by contacting suitable compounds such as hydrogen fluoride, ammonium fluoride, hydrogen chloride, or ammonium chloride, either in the gaseous form or in a water soluble form with the carrier. Preferably, the fluoride or chloride is incorporated onto the carrier from an aqueous solution containing the halide. Preferably, low levels of halide are added during the reforming operation. This can typically be accomplished by adding an organohalide, such as t-butyl chloride, to the feed at a rate of about 1 ppm based upon the feed rate to the reformer.
Following incorporation of platinum and rhenium with the porous inorganic oxide, the resulting composite is usually dried by heating at an elevated temperature usually no greater than about 500° F. and preferably at about 200° F. to 400° F. Thereafter the composite is usually calcined at an even higher temperature, e.g., from about 800° F. up to about 1300° F. Calcination at less than 1100° F. is preferred.
Subsequently, the carrier containing platinum and rhenium is heated at an elevated temperature in a reducing atmosphere to convert the platinum to the metallic state and reduce the valence state of the rhenium. Preferably the heating is performed in the presence of hydrogen, and more preferably in the presence of dry hydrogen. In particular, it is preferred that this reduction be accomplished at a temperature in the range of 500° F. to 1000° F.
The catalyst composite used in the present invention, i.e., platinum and rhenium supported on a porous inorganic oxide spheroidal carrier, should be sulfided for use in the naphtha reforming process. Presulfiding can be done in situ or ex situ by passing a sulfur-containing gas, e.g., H 2 S, through the catalyst bed. Other presulfiding techniques are known in the prior art. The exact form of the sulfur used in the sulfiding process is not critical. The sulfur can be introduced to the reaction zone in any convenient manner. It can be contained in the liquid hydrocarbon feed, the hydrogen rich gas, a recycle liquid stream or a recycle gas stream or any combination thereof. After operating the reforming process in the presence of sulfur for a period of time short in comparison to the over-all run length which can be obtained with the catalyst, the addition of sulfur is preferably discontinued. The purpose for presulfiding the catalyst prior to contact with the naphtha or sulfiding the catalyst during the initial contact with naphtha is to reduce excessive hydrocracking activity of the catalyst which results in the production of high yields of light hydrocarbon gases, for example, methane.
For the purposes of this invention, the end of the reforming run (EOR) is defined as the time when the liquid yield has dropped by I LV% from its maximum value and product octane is maintained constant or an average catalyst bed temperature of 1000° F. is reached.
The present invention will be more fully understood by reference to the following examples. They are intended to be purely exemplary and are not intended to limit the scope of the invention in any way.
EXAMPLES
Example 1
Preparation of Platinum/Rhenium Catalysts
A 2:1 rhenium to platinum spherical catalyst would be prepared by a pore-fill method by incipient wetness beginning with the following solution: a chloroplatinic acid solution which contains: 0.237 grams (g) of Pt as metal; a perrhenic acid solution which contain 0.474 g of Re as metal; and aqueous HC1 which contains 1.10 g of chloride. This solution of the three components is diluted to a total volume of 59 ml with deionized water. The solution is contacted, (i.e. sprayed or slowly dripped), in a manner to assure substantially even deposition of metals on alumina. The impregnated alumina is allowed to stand for 16 hrs and then dried for 2 hrs at 250° F. Next, it is calcined for 2 hrs at 950° F. in flowing dry air. Analysis of the catalyst would show 0.24 wt % Pt, 0.48 wt % Re, and 1.0 percent C1. The resulting catalyst has a bulk density of 0.77 g/cc, a pore volume of 0.55 cc/g, and a nitrogen surface area of 195 m 2 /g.
Example 2
Start-up Procedure
After the platinum and rhenium had been added to the solid support and after calcination, the catalyst was loaded in a reactor unit. The reactor was a one-inch tube with an internal diameter of 3/4 inch. A volume of 80 cc of catalyst were loaded.
Dry air was passed through the reactor unit and the temperature was raised to 400° F. and held for 0.5 hour. The temperature was then raised to 600° F., held for 0.5 hour; to 800° F. and held for 0.5 hour; and to 950° F. and held for at least 2.0 hours so that the water content of the effluent gas was 100 ppm or less. The reactor was then cooled to 800° F. with nitrogen.
The catalyst was reduced with hydrogen at 800° F., and then purged with nitrogen and cooled to 600° F. At 650° F., the feed of Example 3 was introduced at a rate of 120 cc per hour. The reactor temperature was increased to 825° F. at a rate of 25° F. per hour.
The catalyst was sulfided during feed start-up by injecting a 4.0 percent solution of di-methyl disulfide in the feed at 0.35 cc per hour. Injection continued for 5.5 hours or until sulfide break-through at about 3-5 ppm H 2 S was observed. The water level was maintained below 25 ppm using a recycle dryer.
EXAMPLE 3
Feed Properties and Reforming Conditions
The feed for all the reforming runs was an Arabian Naphtha having an API gravity of 60.6; 63.5% paraffins, 27.3% naphthenes and 9.2% aromatics. The D-86 distillation (%--° F.) showed start--168; 5--202; 10--210; 20--218; 30--226; 40--234; 50--241; 60--253; 70--269; 80--289; 90--316; 95--331 end--377.
Reaction conditions were 200 psig, 2.0 liquid hourly space velocity (LHSV), 3.5 hydrogen to fresh feed hydrocarbon mol ratio, and constant product octane of 100 RON. T-butyl chloride was injected (1 ppm) with the feed to maintain the chloride level on the catalyst at about 1 wt.%.
Example 4
Comparative Catalyst A
A 1:2 Pt/Re catalyst was prepared as in Examples 1 and 2, except that the catalyst base was an alumina extrudate, substantially cylindrical n shape, having the following properties: Surface Area was equal to about 190 M 2 /G, particle density was equal to about 0.98 measured on base before impregnation, Chloride wt.% was equal to about 1.4%. Metal loadings were 0.3 wt % Pt and 0.6 wt % Re.
Example 5
Comparative Catalyst B
A commercially available extruded and substantially cylindrical reforming catalyst, CAT B, having a metals loading of 0.22 wt % Pt and 0.44 wt % Re was purchased from a commercial catalyst supplier. The startup procedure of Example 2 was used.
Example 6
Reforming Comparisons
The three catalysts--the catalyst of this invention prepared by Examples 1 and 2, the catalyst of Example 4 and the Catalyst of Example 5 were compared at substantially identical reaction conditions with identical feeds, as described in Example 3. Metal loadings in the reactor were substantially identical at 0.12 lbs/ft 3 Pt, and 0.24 lbs/ft 3 Re for the catalyst of our invention and comparative catalyst A.
The results are shown in FIGS. 1 and 2. As can be seen, the catalyst of the present invention, labelled "CR-63", gives improved life (defined by end-of-run at 1000° F.) and improved liquid volume yields. | A catalyst composition and process for using said catalyst is disclosed wherein the catalyst comprises 0.24 to 0.26 weight percent platinum and 0.48 to 0.52 weight percent rhenium disposed on an alumina spheroidal carrier. | 2 |
BACKGROUND OF THE INVENTION
This invention relates to garage door actuation systems and particularly providing temporary access permission for some user or users while maintaining near-permanent access permission for other users.
In modern society, homeowners frequently have products delivered to their homes or admit workers to their homes to perform prearranged tasks. This usually involves the inconvenience of scheduling a time of arrival by the outsiders and the scheduling of homeowner time to meet and admit them. The some cases, the keys to the house may be given to the outsiders, however, given the ease of key copying, lending keys is not a situation undertaken lightly.
The garage door of many homes is controlled by a garage door opening apparatus which protects from unwanted uses by means of electronically transmitted and received access codes. The access codes and their use provide sufficient security that for many homeowners the garage door is one of the primary means of entering and exiting the house. Since the access codes of many garage door opening apparatuses are changeable, house access could be provided to outsiders by giving them an access code transmitter or access to a keypad type access code sender. After the outsiders no longer have a need to access the house, the garage door actuating apparatus could then be reprogrammed to new codes for continued high security. Although the reprogramming of existing garage door opening apparatus may provide a partial solution to the outside worker access problem, the reprogramming after the outsider use takes time and in some cases many never be done. Also, during a period of reprogrammed use it is possible that other regular users will be denied access and/or they may have to reprogram their access code transmitters.
A need exists for a door security system which provides access to outsiders for a limited period, does not limit access to regular users and which automatically removes the limited access by outsiders with little or no service inconvenience to regular users.
SUMMARY OF THE INVENTION
This need is met and an advance in the art is achieved with the present invention, in which a garage door actuating receiver stores both normal codes called semipermanent access codes for use by, for example, homeowners and temporary access codes for use by outsiders. The normal, semipermanent codes of the system remain unchanged and a temporary code can be programmed into the door opening system for use by outsiders. The receiver counts the passage of time and at some predetermined time after programming a temporary code, it is invalidated. The receiver responds to received access codes and activates the door only when a received code matches a stored valid code. Thus, the receiver never stops responding to proper semipermanent access codes so that regular users are not inconvenienced. On the other hand, the temporary codes are active for only a limited period, e.g. two hours. During that time the outside workers can enter the temporary access code and be admitted by the door opener. When two hours of our example expires, however, the temporary codes are automatically invalidated by the receiver, for example, by erasing them from memory. Accordingly, any attempt to use the temporary access code after two hours will be ignored.
Other arrangements for computing the duration of limited access might also be used, either alone or in conjunction with the elapsed time invalidation. For example, the temporary code might be stored in the receiver and invalidated after a predetermined number of uses to activate entry. After invalidation, re-use of the temporary code would be ignored.
According to an embodiment described below, a door jamb code transmitter called a keypad transmitter is used to enter temporary access codes during a temporary code learning and for outsider access. Before the outsiders arrive, the temporary access code is stored in the receiver along with the other specifics, such as number of entries or elapsed time. The temporary access code can then be given to the outsider who makes use of it by entering it into the keypad of the door jamb transmitter. The outsider can gain repeated access to the house via the key pad until the temporary access code is automatically invalidated when the elapsed time expires and/or the preset number of entries has occurred. The access of regular users of the door opener is not changed by the temporary code. Thus, all users have access to the house without difficult program changes and the temporary access automatically clears itself, also without reprogramming.
More specifically, the keypad transmitter permits activation of a barrier movement system by transmitting a rolling code including a fixed code portion. The fixed code portion includes an indication of which keypad keys were pressed by a user and which of three special keys, enter, * and #, have been used to initiate transmission. In ordinary usage of the keypad transmitter, the user enters four password digits and presses the enter button. A resulting rolling code is generated in which the fixed code portion conveys the password and enter button identity. The receiver interprets the rolling code and activates movement of a barrier or garage door. In accordance with a disclosed embodiment the operator can press the password and send it using the * key. When the receiver receives a password sent with the * key, it sets a temporary password learn mode.
When a four digit password and enter key indication is received from the keypad transmitter while the temporary password learn mode is active, the four digit password is entered as a temporary password and a learn duration mode is entered. The operator then sends a code to the receiver specifying either the amount of time for which the password is valid or the number of activations to be permitted using the temporary access code. The duration code is entered at the keypad by pressing keys to represent the numeric value and sending the code with the * key when time is represented, or the # key when activations are entered. The time or usage value is then stored in the receiver.
When time is the limiting factor for the temporary password, the receiver periodically decrements a timer and tests it for "0". When the timer is found to have "0" value, the temporary password is erased from receiver memory. When the number of activations is the limiting factor, the stored usage value is decremented each time the temporary password is used and when it becomes "0" the temporary password is erased.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a garage having mounted within it a garage door operator embodying the present invention;
FIG. 2 is a block diagram of a controller mounted within the head unit of the garage door operator employed in the garage door operator shown in FIG. 1;
FIGS. 3a-3b are a schematic diagram of the controller shown in block format in FIG. 2;
FIG. 4 shows a power supply for use with the apparatus; and
FIG. 5 is a detailed circuit description of the radio receiver used in the apparatus;
FIG. 6 is a circuit diagram of a wall switch used in the embodiment;
FIG. 7 is a circuit diagram of a rolling code transmitter;
FIG. 8 is a representation of codes transmitted by the rolling code transmitter of FIG. 7;
FIGS. 9a-9b are flow diagrams of the operation of the rolling code transmitter of FIG. 7;
FIG. 10 is a circuit diagram of a keypad transmitter;
FIG. 11 is a representation of the codes transmitted by the keypad transmitter of FIG. 10;
FIG. 12 is a circuit diagram of a fixed code transmitter;
FIG. 13 is a representation of the codes transmitted by the fixed code transmitter of FIG. 12;
FIG. 14 is a flow diagram of the interrogation of the wall switch of FIG. 6;
FIG. 15 is a flow diagram of a clear radio subroutine performed by a controller of the embodiment;
FIG. 16 is a flow diagram of a set number thresholds subroutine;
FIG. 17 is a flow diagram of the beginning of radio code reception by the controller;
FIGS. 18a-18c are flow diagrams of the reception of the code bites comprising full code words;
FIGS. 19a-19c are flow diagrams of a learning mode of the system;
FIGS. 20a-20b are flow diagrams regarding the interpretation of received codes;
FIGS. 21a-21b and 22 are flow diagrams of the interpretation of transmitted codes from keypad type transmitters;
FIG. 23 is a flow diagram of a test radio code subroutine used in the system of FIG. 3;
FIG. 24 is a flow diagram of a test rolling code counter subroutine;
FIG. 25 is a flow diagram of an erase radio memory subroutine;
FIG. 26 is a flow diagram of a timer interrupt subroutine;
FIG. 27 is a flow diagram of a protector pulse received routine;
FIG. 28 is a flow diagram of routines periodically performed in the main programmed loop; and
FIG. 29 is a flow diagram of portions of a travelling down routine.
The attached Appendix, consisting of pages A-1 through A-83, is a program listing for a microcontroller used in the disclosed embodiment.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawings and especially to FIG. 1, more specifically a movable barrier door operator or garage door operator is generally shown therein and referred to by numeral 10 includes a head unit 12 mounted within a garage 14. More specifically, the head unit 12 is mounted to the ceiling of the garage 14 and includes a rail 18 extending therefrom with a releasable trolley 20 attached having an arm 22 extending to a multiple paneled garage door 24 positioned for movement along a pair of door rails 26 and 28. The system includes a hand-held transmitter unit 30 adapted to send signals to an antenna 32 positioned on the head unit 12 and coupled to a receiver as will appear hereinafter. An external control pad 34 is positioned on the outside of the garage having a plurality of buttons thereon and communicate via radio frequency transmission with an antenna 32 of the head unit 12. A switch module 39 is mounted on a wall of the garage. The switch module 39 is connected to the head unit by a pair of wires 39a. The switch module 39 includes a light switch 39b, a lock switch 39c and a command switch 39d. An optical emitter 42 is connected via a power and signal line 44 to the head unit. An optical detector 46 is connected via a wire 48 to the head unit 12.
As shown in FIG. 2, the garage door operator 10, which includes the head unit 12 has a controller 70 which includes the antenna 32. The controller 70 includes a power supply 72 (FIG. 4) which receives alternating current from an alternating current source, such as 110 volt AC, and converts the alternating current to required levels of DC voltage. The controller 70 includes a super-regenerative receiver 80 (FIG. 5) coupled via a line 82 to supply demodulated digital signals to a microcontroller 84. The receiver 80 is energized by the power supply 72. The microcontroller is also coupled by a bus 86 to a non-volatile memory 88, which non-volatile memory stores user codes, and other digital data related to the operation of the control unit. An obstacle detector 90, which comprises the emitter 42 and infrared detector 46 is coupled via an obstacle detector bus 92 to the microcontroller. The obstacle detector bus 92 includes lines 44 and 48. The wall switch 39 (FIG. 6) is connected via the connecting wires 39a to the microcontroller 84. The microcontroller 84, in response to switch closures and received codes, will send signals over a relay logic line 102 to a relay logic module 104 connected to an alternating current motor 106 having a power take-off shaft 108 coupled to the transmission 18 of the garage door operator. A tachometer 110 is coupled to the shaft 108 and provides an RPM signal on a tachometer line 112 to the microcontroller 84; the tachometer signal being indicative of the speed of rotation of the motor. The apparatus also includes up limit switches 93a and down limit switches 93b which respectively sense when the door 24 is fully open of fully closed. The limit switches are shown in FIG. 2 as a functional box 93 connected to microcontroller 84 by leads 95.
FIG. 4 shows the power supply 72 for energizing the DC powered apparatus of FIG. 2. A transformer 130 receives alternating current on leads 132 and 134 from an external source of alternating current. The transformer steps down the voltage to 24 volts and the reduced feeds alternating current is rectified by a plurality of diodes 133. The resulting direct current is connected to a pair of capacitors 138 and 140 which provide a filtering function. A 28 volt filtered DC potential is supplied at a line 76. The DC potential is fed through a resistor 142 across a pair of filter capacitors 144 and 146, which are connected to a 5 volt voltage regulator 150, which supplies regulated 5 volt output voltage across a capacitor 152 and a Zener diode 154 to a line 74.
The controller 70 is capable of receiving and responding to a plurality of types of code transmitters such as the multibutton rolling code transmitter 30, single button fixed code transmitter 31 and keypad type door frame mount transmitter 34 (called keyless).
Referring now to FIG. 7, the transmitter 30 is shown therein and includes a battery 670 connected to three pushbutton switches 675, 676 and 677. When one of the pushbutton switches is pressed, a power supply at 674 is enabled which powers the remaining circuitry for the transmission of security codes. The primary control of the transmitter 30 is performed by a microcontroller 678 which is connected by a serial bus 679 to a non-volatile memory 680. An output bus 681 connects the microcontroller to a radio frequency oscillator 682. The microcontroller 678 produces coded signals when a button 675, 676 or 677 is pushed causing the output of the RF oscillator 682 to be amplitude modulated to supply a radio frequency signal at an antenna 683 connected thereto. When switch 675 is closed, power is supplied through a diode 600 to a capacitor 602 to supply a 7.1 volt voltage at a lead 603 connected thereto. A light emitting diode 604 indicates that a transmitter button has been pushed and provides a voltage to a lead 605 connected thereto. The voltage at conductor 605 is applied via a conductor 675 to power microcontroller 678 which is a Zilog 125CO113 8-bit in this embodiment. The signal from switch 675 is also sent via a resistor 610 through a lead 611 to a P32 pin of the microcontroller 678. Likewise, when a switch 676 is closed, current is fed through a diode 614 to the lead 603 also causing the crystal 608 to be energized, powering up the microcontroller at the same time that pin P33 of the microcontroller is pulled up. Similarly, when a switch 677 is closed, power is fed through a diode 619 to the crystal 608 as well as pull up voltage being provided through a resistor 620 to the pin P31.
The microcontroller 678 is coupled via the serial bus 679 to a chip select port, a clock port and a DI port to which and from which serial data may be written and read and to which addresses may be applied. As will be seen hereinafter in the operation of the microcontroller, the microcontroller 678 produces output signals at the lead 681, which are supplied to a resistor 625 which is coupled to a voltage dividing resistor 626 feeding signals to the lead 628. A 30-nanohenry inductor 628 is coupled to an NPN transistor 629 at its base 620. The transistor 629 has a collector 631 and an emitter 632. The collector 631 is connected to the antenna 683 which, in this case, comprises a printed circuit board, loop antenna having an inductance of 25-nanohenries, comprising a portion of the tank circuit with a capacitor 633, a variable capacitor 634 for tuning, a capacitor 635 and a capacitor 636. A 30-nanohenry inductor 638 is coupled via a capacitor 639 to ground. The capacitor has a resistor 640 connected in parallel with it to ground. When the output from lead 681 is driven high by the microcontroller, the capacitor Q1 is switched on causing the tank circuit to output a signal on the antenna 683. When the capacitor is switched off, the output to the drive the tank circuit is extinguished causing the radio frequency signal at the antenna 683 also to be extinguished.
Microcontroller 678 reads a counter value from nonvolatile memory 680 and generates therefrom a 20-bit (trinary) rolling code. The 20-bit rolling code is interleaved with a 20-bit fixed code stored in the nonvolatile memory 680 to form a 40-bit (trinary) code as shown in FIG. 8. The "fixed" code portion includes 3 bits 651, 652 and 653 (FIG. 8) which identify the type of transmitter sending the code and a function bit 654. Since bit 654 is a trinary bit, it is used to identify which of the three switches, 675, 676 or 677 was pushed.
Referring now to FIGS. 9a through 9b, the flow chart set forth therein describes the operation of the transmitter 30. A rolling code from nonvolatile memory is incremented by three in a step 500, followed by the rolling code being stored for the next transmission from the transmitter when a transmitter button is pushed. The order of the binary digits in the rolling code is inverted or mirrored in a step 504, following which in a step 506, the most significant digit is converted to zero effectively truncating the binary rolling code. The rolling code is then changed to a trinary code having values 0, 1 and 2 and the initial trinary rolling code is set to 0. It may be appreciated that it is trinary code which is actually used to modify the radio frequency oscillator signal and the trinary code is best seen in FIG. 8. It may be noted that the bit timing in FIG. 8 for a 0 is 1.5 milliseconds down time and 0.5 millisecond up time, for a 1, 1 millisecond down and 1 millisecond up and for a 2, 0.5 millisecond down and 1.5 milliseconds up. The up time is actually the active time when carrier is being generated. The down time is inactive when the carrier is cut off. The codes are assembled in two frames, each of 20 trinary bits, with the first frame being identified by a 0.5 millisecond sync bit and the second frame being identified by a 1.5 millisecond sync bit.
In a step 510, the next highest power of 3 is subtracted from the rolling code and a test is made in a step 512 to determine if the result is equal to zero. If it is, the next most significant digit of the binary rolling code is incremented in a step 514, following which flow is returned to the step 510. If the result is not greater than 0, the next highest power of 3 is added to the rolling code in the step 516. In the step 518, another highest power of 3 is incremented and in a step 520, a test is determined as to whether the rolling code is completed. If it is not, control is transferred back to step 510. If it has, control is transferred to step 522 to clear the bit counter. In a step 524, the blank timer is tested to determine whether it is active or not. If it is not, a test is made in a step 526 to determine whether the blank time has expired. If the blank time has not expired, control is transferred to a step 528 in which the bit counter is incremented, following which control is transferred back to the decision step 524. If the blank time has expired as measured in decision step 526, the blank timer is stopped in a step 530 and the bit counter is incremented in a step 532. The bit counter is then tested for odd or even in a step 534. If the bit counter is not even, control is transferred to a step 536 where the bit of the fixed code bit counter divided by 2 is output. If the bit counter is even, the rolling code bit counter divided by 2 is output in a step 538. By the operation of 534, 536 and 538, the rolling code bits and fixed code bits are alternately transmitted. The bit counter is tested to determine whether it is set to equal to 80 in a step 540. If it is, the blank timer is started in a step 542. If it is not, the bit counter is tested for whether it is equal to 40 in a step 544. If it is, the blank timer is tested and is started in a step 544. If the bit counter is not equal to 40, control is transferred back to step 522.
FIG. 10 shows a keypad type rolling code transmitter 34 which is sometimes referred to as a keyless transmitter because it replaces an old style entry in which a physical key was used. Transmitter 34 includes a microprocessor 715 and non-volatile memory 717 powered by a switched battery 719. Also included are 13 keys 710-713 connected in row and column format. The battery 719 is not normally supplying power to the transmitter. When a button, e.g. 701, is pressed, current flows through series connected resistors 714 and 716 and through the pressed switch to ground. Voltage division by resistors 714 and 716 causes the power supply 720 to be switched on, supplying power from battery 719 to microprocessor 715, memory 717 and an RF transmitter stage 721. Initially, microprocessor 715 enables a power on circuit 723 to cause a transistor 724 to conduct, thereby keeping the power supply 720 active. Microprocessor 715 includes a timer which disables power on circuit 723 a predetermined period of time, e.g. 10 seconds, after the last key 701-713 is pressed, to preserve battery life.
The row and column conductors are repeatedly sensed at input terminals L0-L7 of the microprocessor 715 so that microprocessor 715 can read each key pressed and store a representation thereof. A human operator presses a number of, for example, four keys followed by pressing the enter key 712, the * key 711 or the # key 713. When one of the keys 711-713 is pressed, microprocessor 715 generates a 40-bit (trinary) code which is sent via conductors 722 to transmitter stage 721 for transmission. The code is formed by microprocessor 715 from a fixed code portion and a rolling code portion in the manner previously described with regard to transmitter 30. The fixed code portion comprises, however, a serial number associated with the transmitter 34 and a key press portion identifying the four keys pressed and which of the three keys 711-713 initiated the transmission. FIG. 11 represents the code transmitted by keypad transmitter 34. As with prior rolling code transmission, the code consists of alternating fixed and rolling code bits (trinary). Bits 730-749 are the fixed code bits. Bits 730-739 represent the keys pressed and bits 740-748 represent the serial number of the unit in which bits 746-748 represent the type of transmitter. In some transmitters 34 no * and # keys are present. In this situation the * and # keys are respectively simulated by simultaneously pressing the 9 key and enter key or the 0 key and enter key.
FIG. 12 is a circuit description of a fixed code transmitter 31 which includes a controller 155, a pair of switches 113 and 115, a battery 114 and an RF transmitter stage 161 of the type discussed above. Controller 155 is a relatively simple device and may be a combination logic circuit. Controller 155 permanently stores 19 bits (trinary) of the 20 bit fixed code (FIG. 13) to be transmitted. When a switch, e.g., 113, is pressed, current from the battery 114 is applied via the switch 113 and a diode 117 to a 7.1 volt source 116 which powers RF transmitter stage 161. The 7.1 volt source is also connected to ground via a LED 120 and Zener diode 121 which produces a regulated 5.1 volt source 118. The 5.1 volt source is connected to power the controller 155.
Closing switch 113 also applies battery voltage to series connected resistors 123 and 127 so that upon switch 113 closing, a voltage on a conductor 122 rises from substantially ground to an amount representing a logic "1". Upon power up, controller 155 reads the logic 1 on conductor 122 and generates a 20 bit (trinary) code from the permanently stored 19 bits integral to the controller and the state of the switch 113. Controller 155 then transmits the 20 bit code to the RF stage 161 via a resistor 159 and conductor 157. The code is thus transmitted to receiver 80. Controller 155 includes an internal oscillator regulated by an RC circuit 124 to control the timing of controller operations.
FIG. 13 represents the code transmitted from a fixed code transmitter such as transmitter 30. The code comprises 20 bits in two 10 bit words with a blank period between the words. Each word is preceded by a sync bit which allows receiver synchronization and which identifies the type of code being sent. The sync bit for the first code word is active for approximately 1.0 milliseconds and the sync bit of the second word is active for approximate 3 milliseconds.
The wall switch 39 is shown in detail in FIG. 6 along with a portion of microcontroller 85 and the interrogate/sense circuitry interconnecting the two. Wall switch 39 comprises three switches 39b-39d. Switch 39d is the command switch which is connected directly between the conductors 39a. Switch 39b, the light switch, is connected between the conductors 39a via a 1 microfarad capacitor 386. Switch 39c, the vacation or lock switch, is connected between conductors 39a by a 22 microfarad capacitor 384. Wall switch 39 also includes a resistor 380 and diode 392 serially connected between conductors 39a. Microcontroller 85 interrogates the wall switch 39 approximately once every 10 milliseconds to determine whether a button 39b-d is being pressed. FIG. 14 is a flow diagram of the interrogation. At the beginning (step 802, FIG. 14) of each test, microcontroller 85 turns on transistor 368b by a signal applied from pin P35 to the base of transistor 368a and at the same time turns a transistor 369 off from pin P37. Pins P07 and P06 are connected to read the voltage level between conductors 39a by a conductor 385 and respective resistors 387 and 389. If pins P07 and P06 are low (step 804) the command switch 39d is closed (step 806) and a status bit is marked in RAM (step 830) to indicate such. Alternatively, if pins P07 and P06 are high, further tests (step 803) must be performed. First, microcontroller 85 turns transistor 368b off and transistor 369 on. Then, after a short pause (step 810) to allow stay capacitance to discharge, pins P07 and P06 are again sensed (step 812). If P07 and P06 are low, no switches have been closed (step 814) and their status in RAM is so set (step 830). However, if after the short pause the level of conductor 385 is high, microcontroller 85 waits approximately 2 milliseconds (step 816) and again tests (step 818) the voltage level of conductor 385. If the voltage is now low, the light switch 396 has been closed (step 820). This assessment can be made since 2 milliseconds is adequate time for the 1 microfarad capacitor 386 to discharge. If the input at pins P07 and P06 is still high at the 2 millisecond test, the controller retests (step 824) after an additional 16 millisecond delay (step 822). If the pins P07 and P06 are low after the 16 millisecond delay, the vacation switch 39c was closed (step 826) and, alternatively, if the voltage at pins P07 and P06 is high, no switches were closed (step 828). At the completion of the wall switch test the status bits of the three switches 39b, 39c and 39d are set to reflect their identified state (step 830).
The receiver 80 is shown in detail in FIG. 5. RF signals may be received by the controller 70 at the antenna 32 and fed to the receiver 80. The receiver 80 includes a pair of inductors 170 and 172 and a pair of capacitors 174 and 176 that provide impedance matching between the antenna 32 and other portions of the receiver. An NPN transistor 178 is connected in common base configuration as a buffer amplifier. The RF output signal is supplied on a line 200, coupled between the collector of the transistor 178 and a coupling capacitor 220. The buffered radio frequency signal is fed via the coupling capacitor 222 to a tuned circuit 224 comprising a variable inductor 226 connected in parallel with a capacitor 228. Signals from the tuned circuit 224 are fed on a line 230 to a coupling capacitor 232 which is connected to an NPN transistor 234 at its base. The collector 240 of transistor 234 is connected to a feedback capacitor 246 and a feedback resistor 248. The emitter is also coupled to the feedback capacitor 246 and to a capacitor 250. A choke inductor 256 provides ground potential to a pair of resistors 258 and 260 as well as a capacitor 262. The resistor 258 is connected to the base of the transistor 234. The resistor 260 is connected via an inductor 264 to the emitter of the transistor 234. The output signal from the transistor is fed outward on a line 212 to an electrolytic capacitor 270.
As shown in FIG. 5, the capacitor 270 couples the demodulated radio frequency signal from transistor 234 to a bandpass amplifier 280 to an average detector 282. An output of the bandpass amplifier 280 is coupled to pin P32 of a Z86233 microcontroller 85. Similarly, an output of average detector 282 is connected to pin P33 of the microcontroller. The microcontroller is energized by the power supply 72 and also controlled by the wall switch 39 coupled to the microcontroller by the lead 39a.
Pin P26 of microcontroller 85 is connected to a grounding program switch 151 which is located at the head end unit 12. Microcontroller 85 periodically reads switch 151 to determine whether it has been pressed. As discussed later herein, switch 151 is normally pressed by an operator who wants to enter a learn or programming mode to add a new transmitter to the accepted transmitters last stored in the receiver. When the operator continuously presses switch 151 for 6 seconds or more, all memory settings are overwritten and a complete relearning of transmitter codes and the type of codes to be received is then needed. Pressing switch 151 for a momentary time after a 6+ second press enters the apparatus into a mode for learning a new transmitter type which can be either rolling code type or fixed code type.
Pins P30 and P03 of microcontroller 85 are connected to obstacle detector 90 via conductor 92. Obstacle detector 90 transmits a pulse on conductor 92 every 10 milliseconds when the infrared beam between sender 42 and receiver has not been broken by an obstacle. When the infrared beam is blocked, one or more pulses will be skipped by the obstacle detector 46. Microcontroller scans the signal on conductor 92 every 1 millisecond to determine if a pulse has been received in the last 12 milliseconds. When a pulse has not been received, an obstacle is assumed and appropriate action, as discussed below, may be taken.
Microcontroller pin P31 is connected to tachometer 110 via conductor 112. When motor 106 is turning, pulses having a time separation proportional to motor speed are sent on conductor 112. The pulses on conductor 112 are repeatedly scanned by microcontroller 85 to identify if the motor 106 is rotating and, if so, how fast the rotation is occurring.
The apparatus includes an up limit switch 93a and a down limit switch 93b which detect the maximum upward travel of door 24 and the maximum downward travel of the door. The limit switches 93a and 93b may be connected to the garage structure and physically detect the door travel or, as in the present embodiment, they may be connected to a mechanical linkage inside head end 12, which arrangement moves a cog (not shown) in proportion to the actual door movement and the limit switches detect the position of the moved cog. The limit switches are normally open. When the door is at the maximum upward travel, up limit switch 93a is closed, which closure is sensed at port P20 of microcontroller 85. When the door is at its maximum down position, down limit switch 93b will close, which closure is sensed at port P21 of the microcontroller.
The microcontroller 85 responds to signals received from the wall switch 39, the transmitters 30 and 34, the up and down limit switches, the obstruction detector and the RPM signal to control the motor 106 and the light 81 by means of the light and motor control relays 104. The on or off state of light 81 is controlled by a relay 105b, which is energized by pin P01 of microcontroller 85 and a driver transistor 105a. The motor 106 up windings are energized by a relay 107b which responds to pin P00 of microcontroller 85 via driver transistor 107a and the down windings are energized by relay 109b which responds to pin P02 of microcontroller 85 via a driver transistor 109a.
Each of the pins P00, P01 and P02 is associated with a memory mapped bit, such as a flip/flop, which can be written and read. The light can thus be turned on by writing a logical "1" in the bit associated with pin P01 which will drive transistor 105a on energizing relay 105b, causing the lights to light via the contacts of relay 105b connecting a hot AC input 135 to the light output 136. The status of the light 81 can be determined by reading the bit associated with pin P01. Similar actions with regard to pins P00 and P02 are used to control the up and down rotation of motor 106. It should be mentioned, however, that energizing the light relay 105b provides hot AC to the up and down motor relays 107b and 109b so the light should be enabled each time a door movement is desired.
The radio decode and logic microcontroller 84 (FIG. 2) of the present embodiment can respond to both rolling codes as shown in FIG. 8 and fixed codes as shown in FIG. 13; however, after it has learned one type of code all permissible codes will be of the same type until the system memory is erased and the other type of code is entered and exclusively responded to. When the apparatus is first powered up or after memory control values have been erased in response to a greater than 6 second press of program button 151, the system does not know whether it will be trained to respond to fixed or rolling codes. Accordingly, the system enters a test mode to enable it to receive both types of access codes and determine which type of code is being received. In the test mode the apparatus periodically resets itself to receive one of rolling codes or alternatively, fixed codes, until a code of the expected type is received. A short press of switch 151 after the 6+ second press causes a learn mode to be entered. When a code is correctly received in the test mode, and the apparatus is in a learn mode, the type of expected code becomes the code type to be received and the received fixed code or fixed code portion of a received rolling code is stored in nonvolatile memory for use in matching later received codes. In the case of a received rolling code, the rolling code portion is also stored in association with the stored fixed code portion to be used in matching subsequently received rolling codes. After a rolling code has been learned by the system, only additional rolling codes can be learned until a reprogramming occurs. Similarly, after a fixed code is learned, only additional fixed codes can be received and learned until reprogramming occurs.
From time to time while receiving incoming codes, it is determined that a code being received is not proper and a clear radio subroutine (FIG. 15) is called by microcontroller 85. A decision step 50 is first performed to determine whether the apparatus is in a test mode or a regular mode. When not in a test mode, flow proceeds to a step 62 to clear radio codes and blank timer after which the subroutine is exited. When decision step 50 identifies the test mode, steps 52-60 are performed to arbitrarily select the fixed code or rolling code mode and set up necessary values to seek the selected mode. In step 52 the lowest bit of a continuous timer is selected as a randomizer. The value of the lowest bit is then analyzed in a decision step 54. When the lowest bit is a "1" the fixed test mode is selected in step 56 and the numeric thresholds needed for receiving fixed codes are stored in a step 60 before clearing the radio codes and exiting in step 62. When decision step 54 determines that the lowest bit is a "0", the rolling code mode is selected in step 58 followed by the storage of rolling code numeric threshold values in step 60. Flow proceeds to step 62 when radio codes are cleared and the clear radio subroutine is exited.
The set number thresholds subroutine (step 60 of FIG. 15) is shown in more detail in FIG. 16. Initially, a step 180 is performed to identify which mode is presently selected. When the mode is determined to be a fixed code mode, steps 182, 184 and 186 are next performed to set the sync threshold to 2 milliseconds, the number of bits per word to 10 and the decision threshold to 0.768 milliseconds. Alternatively, when step 180 determines that the rolling code mode is selected, steps 192, 194 and 196 are performed to set the sync threshold to 1 millisecond, the number of bits per word to 20 and the decision threshold to 0.450 milliseconds. After the performance of either step 186 or 196 the subroutine returns in step 188.
The primary received code analysis routine performed by microcontroller 85 begins at FIG. 17 in response to an interrupt generated by a rising or falling edge being received from the receiver 80 at pins P32 and P33. Given the pulse width format of coded signals, the microcontroller maintains active or inactive timers to measure the duration between rising and falling edges of the detected radio signal. Initially, a step 546 is performed when a transition of radio signal is detected and a step 548 follows to capture the inactive timer and perform the clear radio routine. Next, a determination is made in step 550 of whether the transition was a rising or falling edge. When a rising edge is detected, step 552 is next performed in which the captured timer is stored followed by a return in step 554. When a falling edge is detected in step 550, the timer value captured in step 548 is stored (step 556) in the active timer. A decision step 558 is next performed to determine if this is the first portion of a new word. When the bit counter equals "0" this is a first portion in which a sync pulse is expected and the flow proceeds to step 560 (FIG. 17).
In step 560, the inactive timer value is measured to see if it exceeds 20 milliseconds but is less than 100 milliseconds. When the inactive timer is not in the range, step 562 is performed to clear the bit counter, the rolling code register and the fixed code register. Subsequently, a return is performed. When the inactive timer is within the range of step 560, step 566 is performed to determine if the active timer is less than 4.5 milliseconds. When the active timer is too large, the values are cleared in step 568 followed by a return in step 582.
When the active timer is found to be less than 4.5 milliseconds in step 566, a sync pulse has been found, the bit counter is incremented in step 570 and a decision step 572 is performed. In decision step 572, the active timer is compared with the sync threshold established in the set number thresholds subroutine of FIG. 16. Accordingly, decision step 572 uses a value of 2 milliseconds when a fixed code is expected and a value of 1 millisecond when a rolling code is expected. When step 572 determines that the active timer exceeds the threshold, a frame 2 flag is set in step 574 and a fixed keyless code flag is cleared in step 576. Thereafter, a return is performed in step 582. When the active timer is found in step 572 to be less than the sync threshold, a decision step 578 is performed to determine if two successive sync pulses have been of the same length. If not, the keyless code flag is cleared in step 576 and a return is performed in step 582. Alternatively, when two equal successive sync pulses are detected in step 578, the fixed keyless code flag is set in step 580 and a return is implemented in step 582.
When the performance of step 558 identifies that the bit count is not "0", indicating a non-sync bit, the flow proceeds to step 302 (FIG. 18A). In the sequence of steps shown in FIGS. 18a-18c, microcontroller 85 identifies the individual code bits of a received code word. In step 302 the length of the active period is compared with 5.16 milliseconds and when the active period is not less, the registers and counters are cleared and a return is performed. When step 302 indicates that the active period was less than 5.16 milliseconds, a step 306 is performed to determine if the inactive period is less than 5.16 milliseconds. If it is less, the step 304 is performed to clear values and return. Alternatively, when step 306 is answered in the affirmative a bit has been received and the bit counter is incremented in a step 308. In the subsequent step 310 the value of the active and inactive timers are subtracted and the result is compared in step 312 with the complement of the decision threshold for the type of code expected. When the result is less than the complement of the decision threshold, a bit value of "0" has been received and flow continues through a step 314 to step 322 (FIG. 18B) where it is determined whether or not a rolling code is expected.
When step 312 determines that the time difference is not less than the complement of the decision threshold flow proceeds to decision block 316 (FIG. 18a) where the result is compared to the decision threshold. When the result exceeds the decision threshold, a bit having a value 2 has been received and the flow proceeds via step 318 to the decision step 322. When decision step 316 determines that the result does not exceed the decision threshold, a bit having a value of 1 has been received and flow continues via step 320 to decision step 322.
In step 322, microprocessor 85 identifies if rolling codes are expected. If not, flow proceeds to step 338 (FIG. 18b) where the bit value is stored as a fixed code bit. When rolling codes are expected, flow continues from block 322 to a decision step 324 where the bit count is checked to identify whether a fixed code bit or a rolling code bit is received. When step 324 identifies a rolling code bit, flow proceeds directly to a step 340 (FIG. 18b) to determine whether this is the last bit of a word. When a fixed bit is detected in step 324, its value is stored in a step 326 and a step 328 is performed to identify if the currently received bit is an ID bit. If the bit count identifies an ID bit, a step 330 is performed to store the ID bit and flow proceeds to the storage step 338 (FIG. 18b). When step 328 determines that the currently received bit is not an ID bit, flow continues to step 334 (FIG. 18b) to determine whether the currently received bit is a function bit. If it is a function bit, its value is stored as a function indicator in step 336 and flow continues to step 338 for storage as a fixed code bit. When step 334 indicates that the currently received bit is not a function bit, flow proceeds directly to step 338. After the storage step 338, flow for the fixed bit reception also proceeds to step 340 to determine whether a full word has been received. Such determination is made by comparing the bit counter with the threshold values established for the type of code expected. When less than a word has been received, flow proceeds to step 342 to await other bits.
When a full word has been received, flow proceeds to a step 344 where the blank timer is reset. Thereafter, flow continues to decision step 346 to determine if two full words (a complete code) have been received. When two full words have not been received, flow proceeds to block 348 to await the digits of a new word. When two full words are detected in step 346, flow proceeds to step 350 (FIG. 18c) to determine whether rolling codes are expected. When rolling codes are not expected, flow continues to step 358. When rolling codes are expected, flow proceeds from step 350 through restoration of the rolling code in a step 352 to a decision step 354 where it is identified if the ID bits indicate a keyless entry transmitter, e.g., transmitter 34. When a keyless entry transmitter code is detected, a flag is set in step 356 and flow proceeds to a decision step 362, discussed below. When step 354 indicates that the code is not from a keyless transmitter, flow continues to the decision step 358 to identify whether a vacation flag is set in memory. The vacation flag is set in response to a human activated vacation switch and when the vacation flag is set, no radio codes are allowed to activate the door open while codes from keypad (keyless) transmitters such as 34 are permitted to activate the system. Accordingly, if a vacation flag is detected in step 358, the code is rejected and a return is performed. When no vacation flag has been set, flow proceeds to a step 362 where it is determined if a learn mode is set. Learn modes can be set by several types of operator interaction. The program switch 151 can be pressed. Also, by preprogramming, microprocessor 85 is instructed to interpret the press and hold of the command and light buttons of the wall control 39 while energizing a code transmitter. Additionally, prior radio commands can place the system in a learn mode. The decision at step 362 is not dependent on how the learn mode is set, but merely on whether a learn mode is requested. At this point it is assumed that a learn mode has been set and flow continues to step 750 (FIG. 19A).
In step 750, a determination is made concerning the type of code expected. When a fixed code is expected, flow proceeds to step 756 where the present fixed code is compared with the prior fixed code. When step 756 does not detect a match, the present code is stored in a past code register and a return is executed. When step 750 identifies that rolling code is expected, a step 752 is performed to determine if the present rolling code matches the past rolling code. If no match is found, flow proceeds to step 754 where the present code is stored in a past code register and a return is executed. When step 752 determines that the rolling codes match, the fixed portion of the received rolling code is compared with the past fixed portions in step 756. When no match is detected, the code is stored in a past code register and a return is executed. When step 756 detects a match, flow proceeds to step 758 to identify if the learn was requested from the wall control 39. If not, flow proceeds to step 766 (FIG. 19B) where the transmitter function is set to be a standard command transmitter. When step 758 determines that the learn mode was commenced from wall control 39, flow proceeds to step 760 to determine whether fixed or rolling codes are expected. When fixed codes are expected, flow proceeds to step 766 (FIG. 19B) where the function is set to be that of standard command transmitter. When rolling codes are identified in step 760, flow proceeds to step 762 (FIG. 19a).
In step 762 it is determined if the light and vacation switches of the wall control 39 are being held. If so, the transmitter is set to be a light switch only in step 763 and flow proceeds to step 768. When step 762 is answered in the negative, flow proceeds to step 764 to determine if the vacation and command switches are being held. If they are, flow proceeds to step 765 to set the transmitter function as open/close/stop and flow proceeds to step 768. When step 764 determines that the vacation and command switches are not being held, flow proceeds to step 766 where the transmitter is marked as a standard command transmitter. After step 766, a step 768 is performed to identify if the received code is in the radio code memory. If the present code is in radio code memory, flow proceeds to step 794 (FIG. 19C). If the received code is not in radio code memory, flow proceeds from step 768 to 780 to determine whether the system is in a permanent or a test mode. When step 780 determines that the system is in a test mode, the current radio mode, either fixed or rolling, is set as a permanent mode in step 782 and flow proceeds to a step 784 to set the current thresholds by storing a pointer to the storage location in ROM into permanent memory.
After step 784, flow proceeds to step 786 (FIG. 19b) to determine if the present code is from the keypad transmitter and specifies an input code 0000. If so, the step 787 is executed where the received code is rejected and a return is executed while remaining in the learn mode. When the code 0000 is not present, flow continues to step 788 to find whether a non-enter key (* or #) was pressed. If so, flow proceeds to step 787. If not, flow continues to decision step 789 to identify if an open/close/stop transmitter is being learned. When the present learning does not involve an open/close/stop transmitter, flow proceeds to step 792 where the code is written into nonvolatile memory. When step 789 determines that an open/close/stop transmitter is being learned, flow proceeds to step 790 to determine if a key other than the open key is being pressed. If so, flow proceeds to block 789 and if not, flow proceeds to block 792 where the fixed code is stored in nonvolatile memory.
After step 792, step 794 is performed to determine if rolling code is the present mode. If not, flow proceeds to step 799 where the light is blinked to indicate the completion of a learn and a return is executed. When step 794 identifies the mode as rolling code, flow proceeds to step 795 where the received rolling code is written into nonvolatile memory in association with the fixed code written in step 792. After step 795, the current transmitter function bytes are read in step 796, modified in step 797 and stored in nonvolatile memory. Following such storage, the work light is blinked in step 799 and a return is executed.
The performance of step 799 concludes the learn function which began when step 362 (FIG. 18c) identified a learn mode. When step 362 does not identify a learn mode, flow proceeds from step 362 to step 402 (FIG. 20A). In step 402 the ID bits of the received code are interpreted to identify whether the code is from a rolling code keypad type transmitter, e.g. 34. If so, flow proceeds to step 450 (FIG. 21A). When the ID bits do not indicate a rolling code keypad entry, flow proceeds to a step 404 where a check is made to see if an 8 second window in which a learn mode may be set exists which was entered from a fixed code keypad transmitter. When the learn mode exists, flow proceeds to step 406 to determine if the operator has entered a special "0000" code. If the special code has been entered, flow proceeds from step 406 to step 410 where the learn mode is set and an exit performed. When step 406 does not detect the special "0000" code, flow proceeds to a step 408, which step is also entered when no 8 second learn mode was detected in step 404.
In step 408 the received code is compared with the codes previously stored in nonvolatile memory 88. When no match is detected, the radio code is cleared and an exit is performed in step 412. Alternatively, when step 408 detects a match, flow proceeds to step 414 (FIG. 20a) which identifies when rolling codes are expected. When step 414 determines that rolling codes are not expected, flow proceeds to step 428 where a radio command is executed and an exit performed. When step 414 determines that a rolling code is expected, flow proceeds to step 416 to determine if the rolling portion of the received code is within the accepted range. When the rolling portion is out of range, step 418 is performed to reject the code and exit. When the rolling code is within the range, step 420 is performed to store the received rolling code portion (rolling code counter) in nonvolatile memory and flow proceeds to a step 422, which identifies whether the function bits of the received code identify a light control signal. When a light control signal is identified, flow proceeds to step 424 where the status of the light is changed, the radio is cleared and an exit performed. When the presently received code is not identified in step 422 as a light control, flow proceeds to step 426 to identify if the present code is an open/close/stop command. When step 426 does not identify an open/close/stop command, flow proceeds to the step 428 where a radio command is set and an exit performed.
When step 426 identifies an open/close/stop command, flow proceeds to step 430 (FIG. 20b) to interpret the command. Step 430 identifies from the function bits of the received code which of the three buttons was pressed. When the open button was pressed, flow proceeds to a step 432 to identify what the present state of the door is. When the door is stopped or at a down limit, step 434 is entered where an up command is issued and exit performed. When step 432 identifies that the door is traveling down, a reverse door command is issued and an exit performed in step 436. In the third case, when step 432 detects the door to be open, step 440 is entered and no command is issued.
When step 430 identifies that the close transmitter button was pressed, flow proceeds to step 438 to identify what state the door is in. When step 436 determines that the door is traveling up or at a down limit, the step 440 is performed where no command is issued and an exit performed. Alternatively, when step 438 identifies that the door is stopped at other than the down limit, a down command is issued in a step 442. When step 430 determines that the stop button was pressed, flow proceeds to step 444 to identify the state of the door. When the door is already stopped, flow proceeds from step 444 to step 448 where no command is issued and an exit performed. When the door is identified in step 444 as traveling, a stop command is issued in step 446 and an exit performed.
It will be remembered that when step 402 (FIG. 20A) identifies that a rolling code keypad code is received, flow proceeds to step 450 (FIG. 21A). In step 450 the serial number portion of the received code is compared with the serial numbers of those codes stored in nonvolatile memory. When no match is detected, flow proceeds to step 452 where the code is rejected and an exit performed. When step 450 detects a match, flow proceeds to step 454 to identify if the rolling code portion is within the forward window. When the code is not within the forward window, flow proceeds to the step 452 where the received code is rejected and an exit is performed.
When the received rolling code portion is found to be within the forward window in step 454 a step 456 is performed where the received code is used to update the rolling code counter in memory. This storage keeps the rolling code transmitter and rolling code receiver in synchronism. After step 456, a step 458 is entered to identify which code reception mode has been set. When normal code reception is identified in step 458, a step 460 (FIG. 21B) is performed to identify if the user input portion of the received code matches a stored user password. When a match is detected in step 460, flow proceeds to step 470 to identify which of the keypad input keys, *, # or enter, was pressed. When step 470 identifies the enter key, a step 472 is performed in which a keyless entry command is issued and an exit initiated. When the * key is detected in step 470, flow proceeds to step 476 where the light is blinked and the learn temporary password flag is set to identify the learn temporary password mode. When step 470 identifies that the # key was pressed, flow proceeds to a step 474 to blink the light and to set a standard learn mode.
When the performance of step 460 determines that the received user input portion does not match one stored in memory, flow proceeds to step 462 where the received user input portion is compared to temporary user input codes. When step 462 does not discover a match, a step 464 is performed to reject the code and exit. When step 462 identifies a match between a received user input code and a stored temporary password, flow proceeds to step 466 to identify whether the door is at the down limit. If not, flow proceeds to step 472 for the issue of a keypad entry command. When step 466 identifies that the door is closed, a step 468 is performed to identify whether the previously set time or number of uses for the temporary password has expired. When step 468 identifies expiration, the step 464 is performed to reject the code and exit. When the temporary password has not expired, flow proceeds to step 478 (FIG. 21b) where the type of user temporary password, e.g., duration or number of activations, is checked. When step 478 identifies that the received temporary password is limited to a number of activations, a step 480 is executed to decrement the remaining activations and a step 472 is executed to issue an entry command. When step 478 identifies that the received keypad password is not based on the number of activations (but instead on the passage of time) flow proceeds from step 478 to the issuance of an entry command in step 472. No special up date is needed for timed temporary passwords since the microcontroller 85 continuously updates the elapsed time.
It will be remembered that a step 458 (FIG. 21A) was initiated to identify the reception mode presently enabled. When the learn temporary password mode is detected, flow proceeds from step 458 to step 482 (FIG. 22). In step 482 a query is performed to determine the enter key was used to transmit the received code. When the enter key was not used, a step 484 is performed to reject the code and exit. When the enter key was used, a step 486 is performed to determine whether the received user input code matches a user code already stored in memory. If so, a step 488 is performed to reject the code. When step 486 identifies no matching user input codes, the new user input code is stored as the temporary password in step 490 and flow proceeds to step 492 where the light is blinked and the learn temporary password duration learn mode is set for subsequent use. When the learn temporary password duration mode is later detected in step 458, flow proceeds to a step 481 where the user entered code is checked to see if it exceeds 255. This is an arbitrary limit to either 255 activations or 255 hours of temporary access. When the user entered code exceeds 255 it is rejected in step 483. When the user entered code is less than 255, a step 485 is performed to identify which key was used to transmit the keypad code. When the * key was used, the transmitted code is to indicate a time duration for the temporary password the time duration mode is set in step 487 and a time is started in step 491 using the code as the number of hours in the temporary code duration. When step 485 determines that the # key was used to transmit the code, a flag is set in step 489 indicating that the temporary mode is based on the number of activations and the number of activations is recorded in step 491. After step 491, the light is blinked and an exit is performed.
FIG. 23 is a flow diagram of a radio code match subroutine. The flow begins at a step 862 where it is determined whether a rolling code is expected or not. When a rolling code is not expected, flow proceeds to a step 866 where a pointer identifies the first radio code stored in nonvolatile memory. When step 866 determines that a rolling code is expected, all transmitter type codes are fetched in a step 864 before beginning the pointer step 866. After step 866, a decision step 868 is performed to determine whether an open/close/stop transmitter is being learned. If so, a step 870 is performed in which the memory code is subtracted from the received code and the flow proceeds to a step 878 to evaluate the result. From step 878 the flow proceeds to a step 878 to evaluate the result. From step 878, the flow proceeds to a step 880 to return the address of the match when the result of the subtraction is less than or equal to two. When the result of the subtraction is not less than or equal to two, the flow continues from step 878 to step 882 to determine if the last memory location is being compared. If the last memory was compared, step 884 is performed to return a "no match."
When step 868 indicates that the system is not learning an open/close/stop transmitter, flow continues to step 872 to determine if the memory code is an open/close/stop code. If it is, flow proceeds through steps to step 874 where the received code is subtracted from the memory code. Thereafter, flow proceeds through step 878 to either step 880 or 882 as above described. When step 872 determines that the current memory code is not an open/close/stop code, flow proceeds to step 876 (FIG. 23). In step 876 the received code is compared with the code from memory and, if they match, step 880 is performed to return the address of the matching code. When step 876 determines that the compared codes do not match, flow continues to step 882 to determine if the last memory location has been accessed. When the last memory location is not being accessed, the pointer is adjusted to identify the next memory location and the flow returns to step 868 using the contents of the new location. The process continues until a match is found or the last memory location is detected in step 882.
FIG. 24 is a flow diagram of a test rolling code counter subroutine which begins at a step 888 in which the stored rolling code counter is subtracted from the received rolling code and the result is analyzed in a step 890. When step 890 determines that the subtraction result is less than "0", flow continues to step 892 where the subroutine returns a backward window lockout. When step 890 determines that the subtraction result is greater than 0 and less than 1000, the subroutine returns a forward window indication in step 892.
FIG. 25 is a flow diagram of an erase radio memory routine which begins at a step 686 of clearing all radio codes, including keyless temporary codes. Next, a step 688 is performed to set the radio mode in nonvolatile memory as testing for rolling codes or testing for fixed codes. Step 690 is next performed in which the working radio mode is set as fixed code test and the fixed code number thresholds are set in a step 692. A return step 694 completes the subroutine.
FIG. 23 shows a timer interrupt subroutine which begins at a step 902 when all software times are updated. Next, flow proceeds to a step 904 to determine whether a 12 millisecond timer has expired. The 12 millisecond timer is used to assure that obstructions which block the light beam in protector 90 and cause the absence of a 10 millisecond obstructive pulse, are rapidly detected. When the 12 millisecond timer has not expired, flow proceeds to a step 914 discussed below. Alternatively, when the timer expires, a step 906 is performed to determine if a break flag, which is set at the first missed pulse, is set. If it is not set, flow proceeds to step 910 in which the break flag is set. If the break flag was detected in step 906, flow continues to step 908 in which an IR block flag, indicative of a plurality of missed 10 millisecond obstruction pulses, is set. Flow then proceeds through step 910 to step 912 where the 12 millisecond timer is reset. Decision step 914, which is performed after step 912, determines whether it has been more than 500 milliseconds since a valid radio code has been received. If more than 500 milliseconds has transpired, step 916 is performed to clear a radio currently on air flag and an exit is performed. When step 914 determines that 500 milliseconds has not expired, flow proceeds directly to exit step 918.
FIG. 27 is a flow diagram of an IR pulse received interrupt begun whenever a protection pulse is received by microcontroller 85. Initially, a step 920 is performed in which the IR break flag is reset and the flow proceeds to step 922 where the IR block flag is reset. This routine ends by resetting the 12 millisecond timer in step 924 and exiting in step 926.
The control structure of the present embodiment includes a main loop which is substantially continuously executed. FIG. 28 is a flow diagram showing portions of the loop. Every 15 seconds a step 928 is performed in which the local radio mode is loaded from nonvolatile memory and the number thresholds are set in a step 930. This activity ends with a return step 946. Every hour a step 932 is performed to determine if a keypad temporary timer is currently active. If so, flow proceeds to step 914 where the time is decremented and a return is executed at step 946.
Every 1 millisecond a step 936 is performed to determine if the IR break flag is set and the IR block flag is not set. This condition is indicative of the first missed protector pulse. If the determination in step 936 is negative, a return is performed. If step 936 detects only the IR break flag and not the IR block flag, a step 938 is performed to identify if the door is at the up limit. When the door is not at the up limit, a return is performed. When step 938 detects the door at the up limit, a step 940 is performed to identify if the light is on. If the light is on, it is blinked a predetermined number of times in step 942 and a return is executed. When step 940 determines that the light is off a step 944 is performed to turn the light on and set a 4.5 minute light keep on timer. A return is executed after step 944.
FIG. 29 is a flow diagram illustrating the use of the IR protection circuit in door control. At a step 948 a decision is made whether a memory matching keypad type transmitter is on the air. If so, flow proceeds to step 956 to determine if the down limit of door travel has occurred. If the down limit has been reached, a step 958 is performed to set a stopped at down limit state of the door. When step 956 determines that the down limit has not been reached, a step 960 is performed to continue the downward travel of the door. When step 948 is answered in the negative, a step 950 is performed to determine if the command switch is being held down. If it is, flow proceeds to step 956 and either step 958 or 960 as discussed above. When step 950 is answered in the negative, a step 952 is performed in which the IR break flag is checked. If the break flag is set, signalling an obstruction, a step 954 is performed to reverse the door, set the new state of the door and set an obstruction flag. When step 952 does not detect an IR break flag, flow proceeds to step 956 as above described. It should be mentioned that the conditions established in steps 948 and 950 are intended to allow the operator to override the obstruction detector.
While there has been illustrated and described a particular embodiment of the present invention, it will be appreciated that numerous changes and modifications will occur to those skilled in the art, and it is intended in the appended claims to cover all those changes and modifications which fall within the true spirit and scope of the present invention. By way of example, the transmitter and receivers of the disclosed embodiment are controlled by programmed microcontrollers. The controllers could be implemented as application specific integrated circuits within the scope of the present invention. ##SPC1## | A garage door opener system includes providing temporary access permission for some user or users while maintaining near permanent access permission for other users. The temporary access permission may be controlled by number of uses or a predetermined amount of time. | 4 |
FIELD OF THE INVENTION
The present invention pertains to a cylinder liner for an engine, the cylinder liner including a water jacket and being of unitary construction. More particularly the liner is a unitary, cast construction and includes a draftless water jacket. Such liner is created by use of a two piece core which allows the liner to be cast vertically, as one piece and without any drafts therein.
DESCRIPTION OF THE PRIOR ART
Heretofore the process for creating a cylinder liner incorporating a water jacket has been a very time consuming, imperfect process yielding a multiple piece unit having drafts in water passages thereof and requiring use of a core of many pieces to yield a liner to the outside of which bands must be welded to create an enclosed water jacket. Further, the casting of the liner has necessarily been horizontal, inherently yielding poor concentricity between the inside liner bore and the outside diameter.
As will be described in greater detail hereinafter, the disclosure herein provides a two piece core around which a one piece liner incorporating a draftless water jacket is vertically molded, creating a liner with an improved concentricity, larger airports and water paths which are straight, causing less water swirl and better cooling.
SUMMARY OF THE INVENTION
Accordingly it is a primary object of the invention to provide a one piece liner incorporating a water jacket.
It is a further object of the invention to provide a water jacket, the water paths of which are draftless.
It is still a further object of the invention to provide a simple two piece core about which the one piece liner may be cast.
It is yet a further object of the invention to provide a core which allows vertical casting of the one piece liner.
It is a further object of the invention to provide a liner having improved concentricity between the inner liner bore and the outer diameter.
It is a further object of the invention to provide a method of vertically casting a one piece liner incorporating a water jacket.
These and other objects are met by the two piece core, the method, and the one piece liner formed thereby, all of which will be described in greater detail hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a prior art liner;
FIG. 2 is a cross sectional view through the prior art liner of FIG. 1;
FIG. 3 is a perspective view of a one piece liner made in accordance with the teachings of the present invention;
FIG. 4 is a cross sectional view through the liner of FIG. 3;
FIG. 5 is a perspective view of a two piece water jacket passage forming cylinder liner core made in accordance with the teachings of the present invention;
FIG. 6 is an exploded perspective thereof;
FIG. 7 is a side elevational view thereof;
FIG. 8 is a front elevation thereof;
FIG. 9 is a rear elevational view thereof;
FIG. 10 is a top plan view thereof;
FIG. 11 is a bottom plan view thereof;
FIG. 12 is a top plan view of a mold section used to create air ports in the liner.
FIG. 13 is a cross sectional view through a mold having the core therein; and
FIG. 14 is a cross sectional view through the liner of FIG. 3 showing drafts which have been eliminated therefrom in phantom.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawings in greater detail, there is illustrated in FIGS. 1 and 2 a cylinder liner incorporating a water jacket made by present day horizontal casting methods using a core having many pieces. The first piece comprises a cast liner having an inner bore and water paths therethrough, the water paths lacking an exterior wall because of complex core design. The exterior surface of the liner is stepped so that a steel band may be slid over each of the upper and lower openings and welded thereover. Such construction leaves significant areas having a draft. These areas of draft inherently cause swirl of water passing thereacross, slowing water flow. Further, these areas cause a decrease in the size of the water path. Still further, if the bands are improperly welded into place, leakage can occur.
The cylinder liner 10 of the present invention shown in FIGS. 3 and 4 avoids all these shortcomings by being vertically cast as a unitary structure.
First, the poor concentricity produced by prior art horizontal pouring is eliminated as will be described in greater detail in connection with the description of FIG. 5, et seq.
Secondly, all previously existing drafts are eliminated, as best shown in FIG. 4. In this respect, it will first of all be seen that water passages 12 in the water jacket portion 14 of the liner 10 are created without any drafts therein. This allows water to travel through these passages 12 much more quickly, significantly increasing the level of cooling.
Further, because a center area 16 of the liner 10 does not need to be undercut, air ports 18 produced by the present method can be significantly larger than those previously obtainable. Such larger air ports 18 provide for improved combustion of fuel in the center bore 20 of the liner 10. Such improved combustion greatly increases fuel economy for any engine incorporating such a liner 10.
Further, labor in creating the liner 10 is significantly reduced because no welding is required. Also, the potential for leakage is virtually eliminated by eliminating the need for welding.
Still further, even though the air ports 18 have been increased in size, the water passages 12 extending therebetween have not been reduced in size, creating substantially straight passages 12 rather than passages which are reduced in diameter as they pass between the air ports 18.
All of the features are easily provided in the liner 10 of the present invention for two reasons. First, the liner 10 is vertically rather than horizontally cast. Second, such vertical casting is only possible because a simple two piece core 30 has been developed as shown in FIGS. 5-12.
It will first of all be understood that the two piece core 30 of the present invention is suspended within a mold 32 shown in FIG. 12, the core 30 being used to create the water passages 12 of the liner 10.
The two piece core 30 includes a substantially cylindrical bottom piece 34 which is suspended within the mold 32 at a predetermined position to form a lower section of the water passages 12. To be suspendable within the mold 32, a bottom piece 34 is provided with a plurality of radial fingers 36 which seat upon an upper surface 38 of an appropriate section of the mold 32.
It will be understood that the mold 32 is made up of several sections. The bottom or base section 40 includes a floor 41 into which a plurality of radial paths 42 extend outwardly from a center hollow 44 formed therein. Next follows a circular mold portion 46 which has undercut areas 48 in the surface 38 within which the core fingers 36 are accommodated, suspending the core bottom piece 34 a predetermined height above the floor 41 of the mold 32.
Such suspended positioning is necessary so that the molten material can flow below and around the core 30 to create a one piece liner 10 having a solid head portion 50. To create the smooth inner bore 20 for the liner 10, a thick walled hollow cylinder shaped mold section 52 is then seated within a center hollow 54 in the core bottom piece 40. It will be seen that this section 52 rests on the bottom 41 of the mold base 40, providing a clearance thereunder from the center bore 44 therein into communication with the radial paths 42 in the base 40. It will further be seen that a top surface 56 of the mold section 40 is stepped inwardly upwardly. A further mold section 58 which is nearly identical to mold section 46 is then seated upon mold section 46.
Next a mold section 60 is set in place. This mold section 60 is shown in FIG. 12 to be of a configuration which will form the throughbores 52 through the thickness of the cast liner 10. These throughbores 52 are synonymous with the air ports 18 in the finished liner 10.
As stated above, the water passages 12 in the liner 10 extend upwardly through the circle of air ports 18, in the areas between adjacent ports 18. To produce these interposed water path sections 65, a plurality of towers 68 extend upwardly from an upper end edge 70 of the core bottom piece 34 and are located relative to one another in a manner to each be between adjacent spokes 72 on the mold section 60. If desired, one of the towers 68 may be provided with a unique tip configuration (not shown) to serve as a positioner for an upper piece 82 of the core 30 to be positioned thereover. The spokes 72 are centrally engaged to a thick walled, cylindrical hub 74 having a throughbore 76 centered therein. The hub 74 is radially outwardly stepped and has an outer surface 75 having a diameter equal to that of the thick walled mold section 52. When the mold section 60 seats over the mold section the hub 74 engages an upper surface 78 of the mold section 52 in a manner to provide a smooth continuation of the outer surface 80 of the mold section 52.
It will be seen that in the disclosed embodiment the spokes 72 are not truly radial, being slightly pitched therefrom. Such angulation is proposed to provide a greater surface area for the air ports 18, which also act as a heat sink, the increased surface area increasing cooling capacity. If desired, alignment slots 83 may be provided in the hub 74 which will coact with alignment ribs (not shown) in contiguous surfaces of the cylindrical members 52 and 106.
Next, a mold section 84 having a plurality of slots 86 in a top end edge 88 thereof is next positioned over the mold section 60, prior to placement of the core upper piece 82.
The core upper piece 82 is also a cylindrical piece 82. A bottom end edge 90 of the piece 82 has a plurality of short slots 92 therein which engage to and upon the tower 68 extending upwardly from the bottom piece 34, through open areas 94 between the spokes 72 on the mold section 60. If one of the towers 68 has been created with a unique locating configuration, then one of the slots 86 must be provided with a cooperating configuration.
The core upper piece 82 is also provided with a plurality of radial fingers 96 which coact with the slots 86 in the mold section 84, the fingers 96 positioning the core upper piece 82 again in a suspended manner in an engaged configuration relative to the towers 68 on the core bottom piece 34 to create a complete water path through the liner 10 between an inner wall 98 and an outer wall 100 thereof.
A further mold section 102 is positioned over the mold section 84, extending the mold 32 above the level of a top edge 104 of the core upper piece 82.
Two identical mold sections 106 comprising a narrow thick walled hollow cylindrical member 106 are stacked within the core upper piece 82 and the mold piece 102. The mold sections 106 have a bottom wall 108 which is radially outwardly stepped, the bottom wall 108 of the lower section 106 nests within and against a coacting top surface 110 of the hub 74 of mold section 60. An exterior surface 112 of these mold section 106 forms the final continuation of the smooth cylindrical mold surface created by the cylindrical member 52 and the hub 60 which will define the center bore 20 in the liner 10.
Finally, a mold top section 114 having a center pour port 116 therein is positioned appropriately and a pour trough 118 having a bore 120 therein which aligns with the pour port 116 is engaged. The top section 114 has a plurality of vent ports 121 therein as well.
Molten metal is then poured into the trough 118, flows down through aligned center bores 116, 122, 123, 124, 126 and 128 of the mold sections 114, 106, 106, 60 and 52, respectively into the radial paths 42 and flows up and around the core 30, within the confines created by the plurality of mold sections.
Once the poured metal cools, the mold sections, being made of sand, are broken away revealing the one piece liner 10.
Ports 130 produced in the outer sidewall 100 of the liner 10 by the radial fingers 36 and 96 of the core pieces 34 and 82 serve as an outlet for the material of the core trapped within the casting. Once the core material has been eliminated from within the casting, the ports 130 may be plugged in any known, suitable manner to produce a smooth outer surface 100 to the one piece liner 10.
As described above, the liner 10, core 30 and method of the present invention provide a number of advantages, some of which have been described above and others of which are inherent in the invention. Also, modifications may be proposed to the liner 10, core 30 and method without departing from the teachings herein. Accordingly, the scope of the invention is only to be limited as necessitated by the accompanying claims. | The unitary cylinder liner incorporating a water jacket is vertically cast as a one piece unit. The water jacket is draftless, allowing water to circulate therethrough more efficiently, increasing cooling capabilities. Such vertical one piece casting is made possible by the novel two piece core which eliminates the need for welding of metal bands onto an outer surface of the liner to produce the water jacker thereof. A novel method of vertical casting is also provided by use of the two piece core. | 5 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is divisional application of U.S. patent application Ser. No. 13/029,955, filed Feb. 17, 2011now U.S. Pat. No. 8,150,534, for Electrode Array for Even Neural Pressure; which is a divisional application of Ser. No. 12/397,974, filed Mar. 4, 2009 now U.S. Pat. No. 7,912,556 for Electrode Array for Even Neural Pressure, which is a continuation-in-part of U.S. application Ser. No. 12/258,296, filed Oct. 24, 2008 now U.S. Pat. No. 8,014,868 for Electrode Array for Even Neural Pressure. This application further claims the benefit of U.S. Provisional Application No. 61/033,723, “Attachment Arrangement for a Neural Stimulation Electrode Array”, filed Mar. 4, 2008. This application is related to and incorporates by reference US patent applications 20030069603 for “Medical Tack with a Variable Effective Length”; 20080288037 for “Flexible Circuit Electrode Array’; and 20020111658, for “Implantable retinal electrode array configuration for minimal retinal damage and method of reducing retinal stress”
GOVERNMENT RIGHTS NOTICE
This invention was made with government support under grant No. R24EY12893-01, awarded by the National Institutes of Health. The government has certain rights in the invention.
FIELD OF THE INVENTION
The present invention is generally directed to neural stimulation and more specifically to an improved electrode array and means of attachment for a neural stimulation electrode array. The present invention is more specifically directed to a method of obtaining even pressure between an electrode array and a retina by attaching the electrode array at multiple points.
BACKGROUND OF THE INVENTION
In 1755 LeRoy passed the discharge of a Leyden jar through the orbit of a man who was blind from cataract and the patient saw “flames passing rapidly downwards.” Ever since, there has been a fascination with electrically elicited visual perception. The general concept of electrical stimulation of retinal cells to produce these flashes of light or phosphenes has been known for quite some time. Based on these general principles, some early attempts at devising prostheses for aiding the visually impaired have included attaching electrodes to the head or eyelids of patients. While some of these early attempts met with some limited success, these early prosthetic devices were large, bulky and could not produce adequate simulated vision to truly aid the visually impaired.
In the early 1930's, Foerster investigated the effect of electrically stimulating the exposed occipital pole of one cerebral hemisphere. He found that, when a point at the extreme occipital pole was stimulated, the patient perceived a small spot of light directly in front and motionless (a phosphene). Subsequently, Brindley and Lewin (1968) thoroughly studied electrical stimulation of the human occipital (visual) cortex. By varying the stimulation parameters, these investigators described in detail the location of the phosphenes produced relative to the specific region of the occipital cortex stimulated. These experiments demonstrated: (1) the consistent shape and position of phosphenes; (2) that increased stimulation pulse duration made phosphenes brighter; and (3) that there was no detectable interaction between neighboring electrodes which were as close as 2.4 mm apart.
As intraocular surgical techniques have advanced, it has become possible to apply stimulation on small groups and even on individual retinal cells to generate focused phosphenes through devices implanted within the eye itself. This has sparked renewed interest in developing methods and apparatus to aid the visually impaired. Specifically, great effort has been expended in the area of intraocular retinal prosthesis devices in an effort to restore vision in cases where blindness is caused by photoreceptor degenerative retinal diseases; such as retinitis pigmentosa and age related macular degeneration which affect millions of people worldwide.
Neural tissue can be artificially stimulated and activated by prosthetic devices that pass pulses of electrical current through electrodes on such a device. The passage of current causes changes in electrical potentials across visual neuronal membranes, which can initiate visual neuron action potentials, which are the means of information transfer in the nervous system.
Based on this mechanism, it is possible to input information into the nervous system by coding the sensory information as a sequence of electrical pulses which are relayed to the nervous system via the prosthetic device. In this way, it is possible to provide artificial sensations including vision.
One typical application of neural tissue stimulation is in the rehabilitation of the blind. Some forms of blindness involve selective loss of the light sensitive transducers of the retina. Other retinal neurons remain viable, however, and may be activated in the manner described above by placement of a prosthetic electrode device on the inner (toward the vitreous) retinal surface (epiretinal). This placement must be mechanically stable, minimize the distance between the device electrodes and the visual neurons, control the electronic field distribution and avoid undue compression of the visual neurons.
In 1986, Bullara (U.S. Pat. No. 4,573,481) patented an electrode assembly for surgical implantation on a nerve. The matrix was silicone with embedded iridium electrodes. The assembly fit around a nerve to stimulate it.
Dawson and Radtke stimulated cat's retina by direct electrical stimulation of the retinal ganglion cell layer. These experimenters placed nine and then fourteen electrodes upon the inner retinal layer (i.e., primarily the ganglion cell layer) of two cats. Their experiments suggested that electrical stimulation of the retina with 30 to 100 μA current resulted in visual cortical responses. These experiments were carried out with needle-shaped electrodes that penetrated the surface of the retina (see also U.S. Pat. No. 4,628,933 to Michelson).
The Michelson '933 apparatus includes an array of photosensitive devices on its surface that are connected to a plurality of electrodes positioned on the opposite surface of the device to stimulate the retina. These electrodes are disposed to form an array similar to a “bed of nails” having conductors which impinge directly on the retina to stimulate the retinal cells. U.S. Pat. No. 4,837,049 to Byers describes spike electrodes for neural stimulation. Each spike electrode pierces neural tissue for better electrical contact. U.S. Pat. No. 5,215,088 to Norman describes an array of spike electrodes for cortical stimulation. Each spike pierces cortical tissue for better electrical contact.
The art of implanting an intraocular prosthetic device to electrically stimulate the retina was advanced with the introduction of retinal tacks in retinal surgery. De Juan, et al. at Duke University Eye Center inserted retinal tacks into retinas in an effort to reattach retinas that had detached from the underlying choroid, which is the source of blood supply for the outer retina and thus the photoreceptors. See, e.g., E. de Juan, et al., 99 Am. J. Ophthalmol. 272 (1985). These retinal tacks have proved to be biocompatible and remain embedded in the retina, and choroid/sclera, effectively pinning the retina against the choroid and the posterior aspects of the globe. Retinal tacks are one way to attach a retinal electrode array to the retina. U.S. Pat. No. 5,109,844 to de Juan describes a flat electrode array placed against the retina for visual stimulation. U.S. Pat. No. 5,935,155 to Humayun describes a retinal prosthesis for use with the flat retinal array described in de Juan.
In U.S. Pat. No. 6,743,345 “Method of Metallizing a Substrate” to Christian Belouet et al. a process for metallizing a substrate is disclosed, comprising coating the part with a precursor composite material layer consisting of a polymer matrix doped with photoreducer material dielectric particles; irradiating the surface of the substrate with a light beam emitted by a laser; and immersing the irradiated part in an autocatalytic bath containing metal ions, with deposition of the metal ions in a layer on the irradiated surface, and wherein the dimension of the dielectric particles is less than or equal to 0.5 μm. The process includes three steps. The first step is to coat the substrate part with a precursor composite material layer consisting of a polymer matrix doped with photoreducer material dielectric particles. The second step is to irradiate the surface of the substrate with a light beam emitted by a laser. The third step is to immerse the irradiated part in an autocatalytic bath containing metal ions, with deposition of the metal ions in a layer on the irradiated surface, wherein the dimension of the dielectric particles is less than or equal to 0.5 μm.
In U.S. Pat. No. 5,599,592 “Process for the Metallization of Polymer Materials and Products Thereto Obtained” to Lucien D. Laude a positive metallization process for metallizing a polymer composite piece containing a polymer material and oxide particles is disclosed, the oxide particles being made of one or more oxides, comprising three successive steps. The first step consists of the irradiation of a surface area of a polymer piece to be metallized with a light beam emitted by an excimer laser. The polymer piece is made from a polymer material and oxide particles. The oxide particles are made from one or more oxides. The second step consists of immersing the irradiated polymer piece in at least one autocatalytic bath containing metal ions. The immersion induces the deposit of the metal ions onto the irradiated surface area to form a metal film on the surface area, resulting in the selective metallization of the surface area of the polymer piece. The third step consists of thermally processing the metallized polymer piece to induce diffusion of the deposited metal film into the polymer material of the polymer piece. The disclosure of U.S. Pat. No. 5,599,592 is incorporated herein by reference.
Lucien D. Laude et al. report that excimer lasers are effective tools in engraving ceramics and polymers, changing irreversibly the surface of the irradiated material, and restricting these effects to specific areas of interest. See L. D. Laude, K Kolev, C I. Dicara and C. Dupas-Bruzek “Laser Metallization for Microelectronics for Bio-applications”, Proc. of SPIE Vol. 4977 (2003), pp 578-586.
In U.S. Pat. No. 5,935,155 “Visual Prosthesis and Method of Using Same” to Mark S. Humayan et al. it is disclosed a visual prosthesis, comprising means for perceiving a visual image, said means producing a visual signal output in response thereto; retinal tissue stimulation means adapted to be operatively attached to a retina of a user; and wireless visual signal communication means for transmitting said visual signal output to said retinal tissue stimulation means.
In U.S. Pat. No. 6,878,643 “Electronic Unit integrated Into a Flexible Polymer Body” to Peter a. Krulevitch et al. it is disclosed a method of fabricating an electronic apparatus, comprising the steps of providing a silicone layer on a matrix, providing a metal layer on said silicone layer, providing a second layer of silicone on said silicone layer, providing at least one electronic unit connected to said metal layer, and removing said electronic apparatus from said matrix wherein said silicone layer and said second layer of a silicone provide a spherical silicone body.
J. Delbeke et al. demonstrate that silicone rubber biocompatibility is not altered by the metallization method. See V. Cince, M.-A. Thil, C. Veraart, I. M. Colin and J. Delbeke “Biocompatibility of platinum-metallized silicone rubber: in vivo and in vitro evaluation”, J. Biomater. Sci. Polymer Edn, Vol. 15, No. 2, pp. 173-188 (2004).
All of these soft polymer arrays approximate the shape of neural tissue, particularly the retina. However, there is a need for an improved means for attaching an electrode array to neural tissue and, thereby, improving the array's ability to conform to the neural tissue.
SUMMARY OF THE INVENTION
An electrode array attached to neural tissue, such as the retina, necessarily has graded pressure exerted on the tissue, with higher pressure near the attachment point. Pressure improves contact between the electrodes and neural tissue while too much pressure may damage neural tissue. Hence it is advantageous to obtain equal pressure across the array field. In the present invention multiple and selective attachment points are provided on an electrode array allowing a surgeon to select the attachment points providing the best electrode tissue contact.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the preferred electrode array with two attachment points.
FIG. 2 is a perspective view of the preferred electrode array with three attachment points.
FIG. 3 depicts the electrode array of the preferred embodiment.
FIG. 4 depicts an electrode array of an alternate two point attachment
FIG. 5 depicts an electrode array of an alternate three point attachment.
FIG. 6 depicts an electrode array with another alternate three point attachment.
FIG. 7 shows the whole flexible polymer array with the bond pad and the traces with holes at the edge of the electrode array.
FIG. 8 shows an enlarged view of the electrode array with holes at the edge of the polyimide to improve silicone adhesion.
FIG. 9 depicts the top view of the flexible circuit array being enveloped within an insulating material.
FIG. 10 depicts a cross-sectional view of the flexible circuit array being enveloped within an insulating material.
FIG. 11 depicts a cross-sectional view of the flexible circuit array being enveloped within an insulating material with open electrodes and the material between the electrodes.
FIG. 12 depicts a cross-sectional view of the flexible circuit array being enveloped within an insulating material with open electrodes.
FIG. 13 depicts a cross-sectional view of the flexible circuit array being enveloped within an insulating material with electrodes on the surface of the material.
FIG. 14 depicts a cross-sectional view of the flexible circuit array being enveloped within an insulating material with electrodes on the surface of the material insight the eye with an angle in the fold of the flexible circuit cable and a fold between the circuit electrode array and the flexible circuit cable.
FIG. 15 depicts a side view of the enlarged portion of the flexible circuit array being enveloped within an insulating material with electrodes on the surface of the material in the eye and contacting the retina.
FIG. 16 is a perspective view of the implanted portion of the preferred retinal prosthesis.
FIG. 17 is a side view of the implanted portion of the preferred retinal prosthesis showing the fan tail in more detail.
FIG. 18 is a view of the completed package attached to an electrode array.
FIG. 19 is a cross-section of the package.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following description is of the best mode presently contemplated for carrying out the invention. This description is not to be taken in a limiting sense, but is made merely for the purpose of describing the general principles of the invention. The scope of the invention should be determined with reference to the claims.
FIG. 1 shows the preferred electrode array. The array 10 is preferably made of metal traces sandwiched between polyimide layers. The array 10 and cable 12 are a single polyimide structure. A relatively hard polymer, such as polyimide, is needed to protect delicate metal traces from breaking. A molded array body 34 , preferably silicone, is molded over the polyimide structure. Perforations 58 in the polyimide promote adhesion of the molded array body 34 . A backbone structure 38 is molded in silicone across the back of the array 10 . Attachment points 54 are provided on either side of the array field to provide even pressure across the array surface. A strain relief 56 is provided around each attachment point 54 . The strain relief 56 may be thinner or softer polymer. The strain relief 56 may also include cut out portions. In the preferred embodiment the attachment point 54 is a hole suitable to accept a retinal tack (not shown).
FIG. 2 shows an alternate embodiment with three attachment points 54 . The additional attachment point is in the center of the electrode field. With either embodiment, a surgeon may decide at the time of surgery which attachment point to use. The ideal attachment may be determined through impedance. Electrodes with higher impedance have more intimate contact with neural tissue and result in lower a threshold of neural stimulation. Hence, a surgeon may place a tack in the attachment point 54 closest to the cable 12 and measure impedance across the electrode array. If acceptable impedance is found, no additional tacks are required. If not, tacks may be placed where additional force is needed to obtain good electrode contact.
A retinal array is pre-curved to match the approximate curvature of the retina. However, retinas vary considerably in their curvature. In a small eye, the array may not be curved enough. Using only the center attachment point 54 would achieve the best result. In a large eye, the array may be too curved. Using the outer attachment points 54 would achieve the best result.
FIG. 3 shows the flexible circuit electrode array 10 in another embodiment. A flexible circuit cable 12 connects to the flexible circuit electrode array 10 . Further, an attachment point 54 is provided near the heel of the flexible circuit electrode array 10 . A retina tack (not shown) is placed through the attachment point 54 to hold the flexible circuit electrode array 10 to the retina or other neural tissue. A stress relief 56 is provided surrounding the attachment point 54 . The stress relief 56 may be made of a softer polymer than the flexible circuit, or it may include cutouts or thinning of the polymer to reduce the stress transmitted from the retina tack to the flexible circuit electrode array 10 . A molded body 34 covers the flexible circuit electrode array 10 , and extends beyond its edges. It may be further advantageous to include wings 36 adjacent to the attachment point 54 to spread any stress of attachment over a larger area of the retina or other neural tissue. There are several ways of forming and bonding the molded body 34 . The molded body 34 may be directly bonded through surface activation or indirectly bonded using an adhesive. The molded body 34 may be a molded completely around the electrode array 10 and cable 12 .
Preferably the electrode array 10 is constructed from a hard polymer such as polyimide while the molded body 34 is constructed from a softer polymer such as silicone. Traces and electrodes can be laid out on a hard polymer by photolithography and the hard polymer protects the delicate traces. A soft polymer molded body 34 then protects the neural tissue from the hard polymer.
Further a strap 26 may be provided over the array 10 opposite the attachment point 54 near the heel attached at either end by attachment points 54 with retinal tacks. Retinal nerve fibers and blood vessels run orbitally out from the optic nerve. It may be advantageous not to tack between the electrode array 10 and the optic nerve as you may damage the nerve fibers which are stimulated by the electrode array 10 . The strap 26 allows the attachment points 54 to be out of the line of the stimulated nerve fibers. The optic nerve 30 is the central access point for both nerve fibers and blood vessels. 32 . A tack through either a nerve fiber or blood vessel may cause damage to the area to be stimulated by the electrode array 10 .
Alternatively, FIG. 4 show a central secondary attachment point 54 , with a stress relief 56 . If the array is not aligned with the nerve fibers a central secondary attachment point may be preferable. FIG. 4 varies from FIG. 2 in that the attachment point 54 near the toe is within the flexible body 34 but outside the array 10 . This provides additional stress relief from attachment.
FIG. 5 shows another alternate embodiment. It this case the array may be place in the preferred orientation or an opposite orientation, with the cable passing over the optic nerve. The attachment points 54 includes stress reliefs 56 . Attachment points 54 , with stress relief 56 , are included in the wings 62 . An additional advantage of this embodiment is that any rotational torque from the array cable is transmitted to the electrode field portion of the flexible body.
FIG. 6 shows another alternate embodiment similar to the embodiment shown in FIG. 3 , but with attachment points 54 integral to the array body rather than on a separate strap. As with the embodiment of FIG. 3 , the attachment points are outside of the area of the nerve fibers and blood vessels supplying the areas to be stimulated.
FIG. 7 shows the preferred electrode array for a visual prosthesis. The structure is a single polyimide sandwich with metal traces. The array 10 is at one end. Bond pads 92 are at the other end and the cable 12 is in the middle. One trace connects each electrode with a bond pad. The flexible circuit 1 is a made by the following process. First, a layer of polymer (such as polyimide, fluoro-polymers, silicone or other polymers) is applied to a support substrate (not part of the array) such as glass. Layers may be applied by spinning, meniscus coating, casting, sputtering or other physical or chemical vapor deposition, or similar process. Subsequently, a metal layer is applied to the polymer. The metal is patterned by photolithographic process. Preferably, a photo-resist is applied and patterned by photolithography followed by a wet etch of the unprotected metal. Alternatively, the metal can be patterned by lift-off technique, laser ablation or direct write techniques.
It is advantageous to make this metal thicker at the electrode to improve contact with neural tissue, and at the bond pad to improve contact with the package. This can be accomplished through any of the above methods or electroplating. Then, the top layer of polymer is applied over the metal. Openings in the top layer for electrical contact to the electronics package 14 and the electrodes may be accomplished by laser ablation or reactive ion etching (RIE) or photolithography and wet etch. Making the electrode openings in the top layer smaller than the electrodes promotes adhesion by avoiding delamination around the electrode edges.
FIG. 8 is an enlarged view of the electrode array 10 . Traces must be routed around the attachment point 54 and stress relief 56 . The electrode field 9 , shown by a dotted line, is that portion of the electrode array having electrodes and stimulating neural tissue.
FIG. 9 depicts the top view of the flexible circuit array 10 being enveloped within a molded body 34 . The electrode array 10 is encased within the oval-shaped molded body 34 , a plurality of electrodes 13 made of a conductive material, such as platinum or one of its alloys, but that can be made of any conductive biocompatible material such as iridium, iridium oxide or titanium nitride. The electrode array 10 is enveloped within a molded body 34 that is preferably silicone. “Oval-shaped” electrode array body means that the body may approximate either a square or a rectangle shape, but where the corners are rounded. This shape of an electrode array is described in the U.S. Patent Application No. 20020111658, entitled “Implantable retinal electrode array configuration for minimal retinal damage and method of reducing retinal stress” and No. 20020188282, entitled “Implantable drug delivery device” to Robert J. Greenberg et al., the disclosures of both are incorporated herein by reference.
The molded body 34 is made of a soft material that is compatible with the electrode array 10 . In a preferred embodiment the molded body 34 made of silicone having hardness of about 50 or less on the Shore A scale as measured with a durometer. In an alternate embodiment the hardness is about 25 or less on the Shore A scale as measured with a durometer.
FIG. 10 depicts a cross-sectional view of the flexible circuit array 10 being enveloped within the molded body 34 . It shows how the edges of the molded body 34 are lifted off due to the contracted radius at the edges. The electrode array 10 preferably also contains a fold A between the cable 12 and the electrode array 10 . The angle of the fold A secures a relief of the implanted material.
FIG. 11 depicts a cross-sectional view of the flexible circuit array 10 being enveloped within a molded body 34 with open electrodes 13 and the molded body 34 between the electrodes 13 .
FIG. 12 depicts a cross-sectional view of the flexible circuit array 10 being enveloped within the molded body 34 with open electrodes 13 . This is another embodiment wherein the electrodes 13 are not separated by the molded body 34 . This may allow closer contact with the neural tissue.
FIG. 13 depicts a cross-sectional view of the flexible circuit array 10 being enveloped within the molded body 34 with electrodes 13 on the surface of the molded body 34 . This is a further embodiment with the electrode 13 on the surface of the molded body, preferably silicone. The embodiments shown in
FIG. 14 depicts a cross-sectional view of the flexible circuit array 10 being enveloped within the molded body 34 with electrodes 13 on the surface of the molded body 34 insight the eye with an angle K in the fold of the flexible circuit cable 12 and a fold A between the circuit electrode array 10 and the flexible circuit cable 12 . The molded body 34 and electrode array body 10 are in intimate contact with retina R. The surface of electrode array body 10 in contact with retina R is a curved surface with a matched radius compared to the spherical curvature of retina R to minimize pressure concentrations therein. Further, the decreasing radius of spherical curvature of the molded body 34 near its edge forms edge relief that causes the edges of the molded body 34 to lift off the surface of retina R eliminating pressure concentrations at the edges. The edge of molded body 34 is rounded to reduce pressure and cutting of retina R.
FIG. 15 shows a part of the FIG. 14 enlarged showing the electrode array 10 and the electrodes 13 enveloped by the molded body 34 , preferably silicone in intimate contact with the retina R.
The electrode array 10 embedded in or enveloped by the molded body 34 can be preferably produced through curing the silicone in a mold around the polyimide array 10 . The molded body 34 has a shape with a decreasing radius at the edges so that the edges of the molded body 34 lift off from the retina R.
FIG. 16 shows a perspective view of the implanted portion of the preferred retinal prosthesis. A flexible circuit 1 includes a flexible circuit electrode array 10 which is mounted by a retinal tack (not shown) or similar means to the epiretinal surface. The flexible circuit electrode array 10 is electrically coupled by a flexible circuit cable 12 , which pierces the sclera and is electrically coupled to an electronics package 14 , external to the sclera.
The electronics package 14 is electrically coupled to a secondary inductive coil 16 . Preferably the secondary inductive coil 16 is made from wound wire. Alternatively, the secondary inductive coil 16 may be made from a flexible circuit polymer sandwich with wire traces deposited between layers of flexible circuit polymer. The secondary inductive coil receives power and data from a primary inductive coil 17 , which is external to the body. The electronics package 14 and secondary inductive coil 16 are held together by the molded body 18 . The molded body 18 holds the electronics package 14 and secondary inductive coil 16 end to end. The secondary inductive coil 16 is placed around the electronics package 14 in the molded body 18 . The molded body 18 holds the secondary inductive coil 16 and electronics package 14 in the end to end orientation and minimizes the thickness or height above the sclera of the entire device. The molded body 18 may also include suture tabs 20 . The molded body 18 narrows to form a strap 22 which surrounds the sclera and holds the molded body 18 , secondary inductive coil 16 , and electronics package 14 in place. The molded body 18 , suture tabs 20 and strap 22 are preferably an integrated unit made of silicone elastomer. Silicone elastomer can be formed in a pre-curved shape to match the curvature of a typical sclera. However, silicone remains flexible enough to accommodate implantation and to adapt to variations in the curvature of an individual sclera. The secondary inductive coil 16 and molded body 18 are preferably oval shaped. A strap 22 can better support an oval shaped coil. It should be noted that the entire implant is attached to and supported by the sclera. An eye moves constantly. The eye moves to scan a scene and also has a jitter motion to improve acuity. Even though such motion is useless in the blind, it often continues long after a person has lost their sight. By placing the device under the rectus muscles with the electronics package in an area of fatty tissue between the rectus muscles, eye motion does not cause any flexing which might fatigue, and eventually damage, the device.
FIG. 17 shows a side view of the implanted portion of the retinal prosthesis, in particular, emphasizing the fan tail 24 . When implanting the retinal prosthesis, it is necessary to pass the strap 22 under the eye muscles to surround the sclera. The secondary inductive coil 16 and molded body 18 must also follow the strap 22 under the lateral rectus muscle on the side of the sclera. The implanted portion of the retinal prosthesis is very delicate. It is easy to tear the molded body 18 or break wires in the secondary inductive coil 16 . In order to allow the molded body 18 to slide smoothly under the lateral rectus muscle, the molded body 18 is shaped in the form of a fan tail 24 on the end opposite the electronics package 14 . The strap 22 further includes a hook 28 the aids the surgeon in passing the strap under the rectus muscles.
Referring to FIG. 18 , the flexible circuit 1 , includes platinum conductors 94 insulated from each other and the external environment by a biocompatible dielectric polymer 96 , preferably polyimide. One end of the array contains exposed electrode sites that are placed in close proximity to the retinal surface 10 . The other end contains bond pads 92 that permit electrical connection to the electronics package 14 . The electronic package 14 is attached to the flexible circuit 1 using a flip-chip bumping process, and epoxy underfilled. In the flip-chip bumping process, bumps containing conductive adhesive placed on bond pads 92 and bumps containing conductive adhesive placed on the electronic package 14 are aligned and melted to build a conductive connection between the bond pads 92 and the electronic package 14 . Leads 76 for the secondary inductive coil 16 are attached to gold pads 78 on the ceramic substrate 60 using thermal compression bonding, and are then covered in epoxy. The electrode array cable 12 is laser welded to the assembly junction and underfilled with epoxy. The junction of the secondary inductive coil 16 , array 1 , and electronic package 14 are encapsulated with a silicone overmold 90 that connects them together mechanically. When assembled, the hermetic electronics package 14 sits about 3 mm away from the end of the secondary inductive coil.
Since the implant device is implanted just under the conjunctiva it is possible to irritate or even erode through the conjunctiva. Eroding through the conjunctiva leaves the body open to infection. We can do several things to lessen the likelihood of conjunctiva irritation or erosion. First, it is important to keep the over all thickness of the implant to a minimum. Even though it is advantageous to mount both the electronics package 14 and the secondary inductive coil 16 on the lateral side of the sclera, the electronics package 14 is mounted higher than, but not covering, the secondary inductive coil 16 . In other words the thickness of the secondary inductive coil 16 and electronics package should not be cumulative.
It is also advantageous to place protective material between the implant device and the conjunctiva. This is particularly important at the scleratomy, where the thin film electrode array cable 12 penetrates the sclera. The thin film electrode array cable 12 must penetrate the sclera through the pars plana, not the retina. The scleratomy is, therefore, the point where the device comes closest to the conjunctiva. The protective material can be provided as a flap attached to the implant device or a separate piece placed by the surgeon at the time of implantation. Further material over the scleratomy will promote healing and sealing of the scleratomy. Suitable materials include DACRON®, TEFLON®, GORETEX® (ePTFE), TUTOPLAST® (sterilized sclera), MERSILENE® (polyester) or silicone.
Referring to FIG. 19 , the package 14 contains a ceramic substrate 60 , with metalized vias 65 and thin-film metallization 66 . The package 14 contains a metal case wall 62 which is connected to the ceramic substrate 60 by braze joint 61 . On the ceramic substrate 60 an underfill 69 is applied. On the underfill 69 an integrated circuit chip 64 is positioned. On the integrated circuit chip 64 a ceramic hybrid substrate 68 is positioned. On the ceramic hybrid substrate 68 passives 70 are placed. Wirebonds 67 are leading from the ceramic substrate 60 to the ceramic hybrid substrate 68 . A metal lid 84 is connected to the metal case wall 62 by laser welded joint 63 whereby the package 14 is sealed.
Accordingly, what has been shown is an improved method making a neural electrode array and improved method of stimulating neural tissue. While the invention has been described by means of specific embodiments and applications thereof, it is understood that numerous modifications and variations could be made thereto by those skilled in the art without departing from the spirit and scope of the invention. It is therefore to be understood that within the scope of the claims, the invention may be practiced otherwise than as specifically described herein. | An electrode array attached to neural tissue, such as the retina, necessarily has graded pressure exerted on the tissue, with higher pressure near the attachment point. Greater pressure improves contact between the electrodes and neural tissue while too much pressure may damage neural tissue. Hence it is advantageous to obtain equal pressure across the array field. In the present invention a central attachment point in the electrode field applies the most even pressure. Further, multiple and selective attachment points may be additionally provided on an electrode array allowing a surgeon to select the attachment points providing the best electrode tissue contact. | 0 |
This is a divisional of application Ser. No. 08/398,465, filed on Mar. 3, 1995 U.S Pat. No 5,563,833.
RELATED APPLICATION
U.S. patent application Ser. No. 08/398,468, filed Mar. 3, 1995, entitled "BIST Tester for Multiple Memories"(Atty. Docket No. BU9-94-146).
FIELD OF THE INVENTION
This invention relates generally to testing of memory devices, and in one aspect to a built-in self-test for VLSI circuits which are contained on semiconductor chips. In a more particular aspect, this invention relates to a built-in test for memories on semiconductor chips wherein there are a plurality of memories on the chip and wherein one memory is associated with another; i.e., one memory provides at least part of the information required by one or more additional memories known as associated memories during conventional operation. Such a memory relationship can be, for example, on microprocessors wherein there are conventional memories which store data such as data cache unit (DCU) memories and which have associated therewith CAM memories, i.e., content addressable memories, which supply part of the address to the DCU memories during conventional operation, although other types of associated memories can be tested according to this invention.
BACKGROUND ART
Testing of associated memories of the type described above, formed on semiconductor substrates, has often been done by the provision of a built-in self-test (BIST). BISTs include a state machine formed on the silicon substrate which contains the associative memories and the other VLSI circuit components such as the logic components of a microprocessor chip. Such a BIST is shown in copending application Ser. No. 08/398,468, filed Mar. 3, 1995 and entitled "BIST Tester for Multiple Memories" (Atty. Docket No. BU9-94-146); and a state machine for testing a DCU type memory is shown in U.S. Pat. No. 5,173,906.
In testing multiple memories, conventional prior art practice has been to surround each of the memories with latches and multiplexors and to test each memory independently, from data supplied by the state machine of the BIST or through a scan-chain from an off-chip tester. Also, conventional prior art has employed a separate BIST for each memory. While in many cases this works quite well, it does have certain drawbacks, especially in the case of testing associated memories. One such drawback is the requirement of a significant amount of chip area or "real estate" needed for forming the latches and multiplexor which bound the various memories. Another drawback is the totally independent testing of an associated memory (i.e., one that in normal operation receives a portion of its information or data, such as a portion of the address, from another memory) is that the path between the two memories is not tested. This is because the test signals to this dependent memory are separately supplied from the BIST rather than being supplied through the source memory. Thus, totally independent testing does not test the performance of the associated memories using the critical path between one memory and the other. Any problems or improper functioning of the critical data path between the two memories in the transfer of data is not detected by this type of testing since each memory is tested separately and independently from data generated from the BIST machine which does not use one memory to supply data to another memory, i.e., with the signal timings and along the path which the data flows during functional operation. While the problem of testing associated memory is extant in BIST tests, it also exists in other types of tests of memories, e.g., signals from off-chip testers applied to test memory circuits and other dependent circuits.
SUMMARY OF THE INVENTION
According to the present invention, an associated memory structure comprised of a plurality of memories amenable for testing and a method of testing the memories is provided. First and second memories are formed (on a semiconductor substrate in the preferred embodiment) wherein the data in the first memory provides a basis for at least a portion of the input to the second memory during functional operation of the two memories. Means for inputting test signals into the first memory is provided, and preferably an output latch for receiving the output test data from the first memory is provided. Means are provided for loading the first memory with data which is utilized as a basis for providing at least a portion of the input to the second memory. An access path from the output port of the first memory to the input port of the second memory is provided to thereby allow use of the data in the first memory to generate at least a portion of the input of the second memory. The first memory is first tested independently of the second memory. Thereafter, the first memory is loaded with preconditioned algorithmic data that is used as a basis for inputs to the second memory during testing of the second memory. The second memory is then tested by generating inputs to the first memory during the test of the second memory, which will cause outputs of the first memory to be supplied to the second memory which constitutes at least a portion of test data inputted to the second memory. A latch is provided to capture the output of the test data from the second memory.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagrammatic view of the functioning of a content addressable memory (CAM) and its function to provide input to a data cache unit (DCU) memory in one embodiment of this invention;
FIG. 2 is a block diagram showing a typical prior art construction of a typical configuration for testing the functioning of a CAM memory associated with a DCU memory;
FIG. 3 is a block diagram showing the construction according to this invention of the interconnection for testing the functioning of a CAM memory and a DCU memory receiving some input data therefrom;
FIG. 4 is a block diagram of the invention showing specific architecture that provides for parallel processing of the CAM and RAM;
FIG. 5 is a block diagram of the invention showing the circuitry of a single CAM column and associated cascaded OR;
FIG. 6 is a circuit diagram of the invention showing a specific first cascaded OR circuit that is associated with every CAM address location;
FIG. 7 is a circuit diagram of the invention showing a specific second circuit in the cascaded OR that receives output signals from the first cascaded OR circuit shown in FIG. 6; and
FIGS. 8a and 8b illustrate a circuit diagram of the invention showing a third circuit in the cascaded OR that receives output signals from the second circuit of the cascaded OR shown in FIG. 7.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The embodiment described here utilizes a content addressable memory (CAM) and a random access memory (RAM) where the RAM obtains part of its addressing from the CAM. According to prior art techniques, each would need input and output latches and would be tested independently. As described herein, a method and structure has been provider test the two memories while maintaining their interdependent nature during test just as in functional operation. This method provides a reduction in area consumption by test-only circuitry and also enhances the test quality by eliminating timing differences between test operation and functional operation.
Referring now to FIG. 1, a representation of a typical content addressable memory (CAM) 10 and its functioning to provide a partial input to a data cache unit (DCU) memory 12 is shown. In this representation, eight column locations (Column 0-Column 7) are provided, and 64 rows of wordlines (WL0-WL63) are provided. Eight bits of binary data ("1"s, "0"s) are stored in each row/column location and form the basis of the data to which inputs are compared. Each row/column location has at least one additional data valid bit (not shown) that must be set true for the output compare to be functional.
The test inputs are from a built-in self-test (BIST) state machine such as that described in related application Ser. No. 08/398,468, filed Mar. 3, 1995, and entitled "BIST Tester for Multiple Memories"(Atty. Docket No. BU9-94-146) or from BISTs as described in U.S. Pat. No. 5,173,906 which is incorporated herein by reference.
In operation, the CAM 10 receives the necessary compare data CD as input to input port 14 of the CAM 10 wherein the compare data CD is compared to determine if that particular bit pattern is stored at a given word line. (In this embodiment, eight bit patterns are compared, but other patterns can be used.) This is shown diagrammatically in FIG. 1 wherein a series of bit patterns are stored in the CAM 10. In the illustrated embodiment, each wordline (row) contains eight 8-bit patterns. Each pattern is stored at a different column location (Column 0-Column 7) on the wordline. The CAM 10 works on the principle that eight data bits are stored in each column/row location, and that the input is supplied to input port 14 as compare data bits CD. If a match occurs at a column location on the selected wordline, then the column comparator asserts a "1". If columns happen to match the compare data CD, then all eight column comparators would assert "1"s and the CAM 10 output at output port 16 would be "11111111". If a mismatch is found in a column on the selected wordline, then the column comparator output is forced to a "0". The eight comparator outputs from output port 16 of CAM 10 are supplied as one part of the input to DCU 12 at input port 18 thereof. In the illustration as shown, if compare data bits 00010000 were supplied to input port 14, there would be a comparison in column 3 of the selected wordline causing the column 3 comparator to assert a "1" and the remaining seven column comparators to output "0"s which would result in the CAM 10 outputting via output port 16 the 8-bit address 00010000 to input port 18 of the DCU 12. The CAM output matches the 8-bit pattern in column 3 because the column locations were purposely written with the patterns shown in FIG. 1 and not because the CAM actually outputs the pattern store in column 3. This operation is well known in the art and need not be further described.
The input port 18 of the DCU 12 receives the output from the CAM 10 as a one of eight bit address. A word address, defined as WA, data, and Read/Write (R/W) control supplied by the BIST state machine is also received at port 18. The path from the CAM 10 to the DCU will be described presently. In any event, the output of the CAM is a function of the data stored therein and the compare data CD.
Referring now to FIG. 2, a typical prior art configuration or construction and interconnect of a CAM 10 and DCU 12 with the necessary latches and multiplexors used to both verify the integrity of and control the selection between the operational path and the test paths to and from memories 10 and 12 is shown. It is to be understood that this figure is representative of only one particular configuration involving two specific types of associated memories, which is but one of several possible connections of multiplexors and latches for functional operation and testing. Nevertheless, FIG. 2 represents a typical implementation of both operational and test paths for these types of associated memories.
As indicated above, in this embodiment, the CAM 10 is provided which in normal operation (i.e., not test mode) provides a part of the bit address to the DCU 12. The remainder of the bit address, as well as the wordline address for the DCU 12 is provided from a separate source, i.e., a source different from the CAM. Data and R/W control are also provided from a source separate from the CAM. Thus, in operation, when the memories are being utilized and there needs to be an access to the DCU memory 12, a portion of the address for such access is supplied by the CAM 10. Such type of associated memory operations is well known in the
Also as is well known in the art, it is necessary to test both the CAM and the DCU memories before chip functional operation. To this end, in the past, both the CAM 10 and the DCU 12 have been tested independently through all phases of BIST testing, even though there is an associative relationship between the DCU 12 and the CAM 10 during functional operation. The testing and operation of the memories 10 and 12 is typically carried out using a prior art structure similar to that in FIG. 2.
The operational path between memories 10 and 12 is comprised of CAM output 24 being supplied as input to multiplexor group 26 (which in structure is defined by eight multiplexors), and the output 28 of multiplexor group 26 provided as input to input port 18 on the DCU 12 as an 8-bit predecoded address. The test path into the DCU 12 is comprised of an 8-bit predecoded address provided as input 32 to multiplexor group 30 (which in structure is defined by eight multiplexors); the output 34 of multiplexor group 30 is supplied to latch group 36 (which in structure is defined by eight latches); the output 37 of latch group 36 is supplied as the other input to multiplexor 26; and the output 28 of multiplexor group 26 is provided to DCU's inputs port 18. A second test path for verifying CAM outputs is comprised of output 24 being supplied as input to multiplexor group 26, output 28 of multiplexor group 26 being routed along feedback path 42 to the other input of multiplexor group 30, output 34 of multiplexor group 30 being supplied to latch group 36, and output 37 of latch group 36 being supplied to CAM data compression 44. CAM data compression 44 can be actuated by load result signal LR1 from the BIST. Similarly, latch 46 receives an output from output port 48 of the DCU 12, and provides DCU data compression 52 with an output. DCU data compression can be actuated by lead result signal LR2.
Still referring to FIG. 2, when the CAM 10 is operating in a functional manner, i.e., supplying functional data, the output from the CAM 10 is supplied to the multiplexer 26, and the select signal 38 selects this input 24 as that passed to output 28 of multiplexer 26 which is delivered to the input port 18 of the DCU memory 12 to supply the eight pro-decoded address bits.
However, as indicated before, the CAM 10 and the DCU memory 12 must be tested before they are put into operation or made functional. To this end, both the CAM and the DCU memories are tested separately. To test the CAM 10, the necessary test patterns are supplied as inputs to the CAM and to compare with data in memory, and the compare results are outputted from output port 16 to the functional data line 24 to the multiplexer 26. Conventional test patterns can be applied as is well known in the art in this case, the signal select 38 is used to select the CAM out 24 to provide the output 28 from the multiplexer 26 which then feeds back signal 42 to provide the output from multiplexer 30 to the latch 36 which constitutes the test data being captured from the CAM 10. The output 37 from latch group 36 (which in structure is defined by eight latches) is delivered to the data compression 44, and the lead result signal is actuated during the testing of the CAM to lead the test results. Thus, the CAM 10 is tested independently of the DCU.
Turning now to the testing of the DCU memory 12 and still referring to FIG. 2, when the memory 12 is to be tested, the select signal 40 selects the BIST input signal 32 to be outputted as the output 34 from the multiplexor 30 to the latch 36. The latch 36 supplies as output 37 a signal to the multiplexor 26 where the select signal 38 selects the input 37 to the multiplexor 26 as the output 28 to the input port 18 of the memory 12. Thus, for testing the DCU memory 12, the 8-bit pre-decoded address which is provided to the input port 18 of the DCU 12 is not provided from the CAM 10 (from which it is provided during functional operation), but rather is provided from the BIST test machine and controlled by the signal patterns thereof. There are two undesirable results of this construction. First, a significant amount of area is required because of the utilization of two multiplexors and a latch. Moreover, and more significantly, the timings of signals on the functional path through the CAM memory 10 to the input port 18 of the DCU 12 for the eight bits of the address is not being tested, and the timing of these functional signals may vary from the timing of the test signals generated by the BIST machine. Thus, while the DCU 12 may perform well with all of the signals from the BIST machine in the test mode, in actual operation the DCU memory 12 may not properly function when it receives addresses at input port 18 from the CAM memory 10 based on the timing of the CAM memory 10 and the timing of the functional path.
Turning now to FIG. 3, construction of the interconnection between the CAM memory 10 and the DCU memory 12 according to the present invention is shown. According to this invention, the functional output 24 from the output port 16 of the CAM 10 is asserted directly on the input port 18 of the DCU 12 without the interposition of any multiplexors or latches in the path and is used both in the functional mode and the test mode of the DCU 12. A latch 36 is provided to receive the output from the output port 16 of the CAM memory 10 which is the same type of latch as shown in FIG. 2, and a data compression 44 also is provided which is the same as shown in FIG. 2. A latch 46 is connected to the output port 48 of the DCU memory 12 which in turn is provided with a data compression store 52 that is actuated by load result signal LR2.
In conventional operation of the embodiment as shown in FIG. 3, the output from the output port 16 of the CAM memory 10 is supplied directly to the input port 18 of the DCU memory 12 as eight pre-decoded address signals in the same way that the input signal is provided in the prior art from the multiplexor 26, although in this case it is supplied directly to the input port 18. During the normal operation and supplying of the data as the functional data on line 24 to the input port 18, data is being supplied to the latch 36, but signal LR1 to the data compression 44 is not actuated so that the outputted data is not captured with load result.
The testing of the CAM and the DCU memories in the embodiment as shown in FIG. 3 is as follows. For testing purposes, the CAM memory is first tested by supplying the necessary input patterns thereto as described with respect to FIG. 2 from a BIST. The output of the compare pattern is loaded into the latch 36 and the load result signal LR1 is actuated to enable the data compression 44 to test the CAM in the same way the CAM memory 10 has been tested in the prior art.
Once the CAM memory 10 has been tested, the DCU memory 12 can then be tested. The CAM memory 10 is loaded with the preconditioned decode addresses by BIST for the particular tests being performed on the DCU memory from the BIST. Then, the DCU memory 12 is tested, supplying the word address portion of addresses through the port 18 just as in FIG. 2. However, compare data CD is provided to the CAM input port 14 by the BIST which corresponds to the three-bit portion of address being tested in the DCU 12 and the output from the CAM 10 provides the 1 out of 8 select address as input to the DCU 12 during the test. The output from the DCU memory 12 is outputted from port 48 into latch 46, and the load result signal LR2 is actuated to capture the output and determine pass/fail result of the test in the data compression store 52. Thus, the testing of the DCU 12 is done utilizing input from the CAM memory 10 using its particular signal timings on the path 24 which will be the same as utilized during actual operation of the memory devices rather than a separate timing path from the testing machine as in the prior art.
The following FIGS. 4-7 describe parallel processing of the CAM and the RAM in a DCU. CAM designs have been classically used in the word dimension as fully associative elements. An address field is compared against a column of CAM cells organized N cells wide and R rows deep. If a match occurs, a wordline associated with the matched row is selected. The selected wordline drives across standard memory cells which contain the desired data. This prior art process creates a situation where the RAM is waiting for the CAM to process its row selection address. In current processor architectures, a key design goal is to design processors that operate at ever faster processing speeds. This design goal holds true for both testing and general operation of the microprocessor architecture.
In reference to FIG. 4, there is a block diagram showing an architecture that provides parallel processing of the CAM and RAM which does not require the RAM to wait for the CAM to process the row address for the RAM. In addition, there is a CAM design that performs associative or semi-associative decode bit addressing of a RAM. It is noted that RAM 300 and MUX 500 can be operated as a TAG, a data storage array architecture, or a DCU, generally indicated by element number 360. In operation, decoder 100 will select which one of 64 rows in the CAM 200 and RAM 300 will be selected when the decoder receives a row address signal 105. Concerning the operation of the RAM 300, the selected RAM row will download all data stored in the selected data locations onto the associated eight RAM columns, referred to as C1-C8. For example, data locations 320 through 340 would be downloaded to C1 through C8, respectively. The RAM data will thereby be routed to MUX 500, illustrated as an 8×1 MUX, where one of the eight inputs from the RAM will be enabled to immediately route one of the columns of RAM data to output line 510. Concerning the operation of the CAM 200, a row address 105 signal arrives at the decode 100, a compare address 400 is simultaneously routed, via lines 420, to every CAM location (i.e., locations 220 to 240) on every CAM row. If there is a match on the selected row, then a cascaded OR 260 (one per column C1 to C8) will pull the associated CAM column output line 110 high. The output lines 110, which form a bus 120, are each coupled to MUX 500. In operation, for example, CAM column C1 can output a signal to output line 110 that will program MUX 500 to allow data in RAM column C1 to be output to output line 510. In summary, by using a row decode circuit 100 to simultaneously select the row of the RAM and CAM, and by using bit addressing of the CAM, the MUX 500 can be enabled before the data in the selected row of the RAM arrives. Therefore, the RAM processing will not have to wait for the CAM processing to first be completed.
In reference to FIG. 5, there is shown a block diagram of the specific circuitry for a single CAM column and associated cascaded OR. The column of CAM locations and associated OR is divided into four equal blocks 600a-600d each having equal numbers of rows or address locations, i.e., location 220. In this example for illustration purposes, there are ten bit cells in each CAM location. When the location receives the compare address, the results will either cause match line 610 to be a high or low voltage level. For example, when the compare address 400 matches the location 220, the cascaded OR coupled to the first CAM column C1 will be activated to output a high signal on the matching column output line 110. More particularly, the sequence of events are as follows: match line 610 outputs a high voltage, wordline select (WLS) 630 strobes, first cascaded OR circuit 620 will pull line 650 low, the second cascaded OR circuit 640 outputs a high voltage on line 670a, and the third cascaded 0R circuit 660 will output a high voltage signal on the associated output line 110. It should be noted that WLS 630 is the input from the decode circuit 100. It should be further noted that the decode circuit 100 includes the wordline driving circuitry (not shown).
In reference to FIG. 6, there is a circuit diagram of the first cascaded OR circuit 620 that is coupled to every CAM address location. In operation, if a match occurs between the compare address and the CAM location, match line 610 will remain high, via PFET 614, and NFET 619 will remain activated. Output line 650 will then be brought low after WLS 630 strobes. If there is no match, the following sequence occurs: match line 610 is brought low, NFET 619 will be turned off, so that when WLS strobes, NFET 618 will be activated, and output line 650 is maintained high. Whether there is a match or not, circuit 620 needs to be reset to the starting conditions. The starting conditions are reset after WLS strobes, by strobing rest RST1, causing PFET 612 to pull line 610 high with the assistance of PFET 614 so that output line 650 will be maintained high. It is pointed out that PFET 616 operates to reduce noise and prevent NFET 619 from turning on when there is no match. It is also noted that when WLS 630 strobes, it strobes across the entire eight columns in the CAM.
Referring now to FIG. 7, there is a specific circuit diagram of a second circuit 640 in the cascaded OR. In operation, when output line 650 remains high, via PFET 656, PFET 652 remains deactivated; preventing output line 670a from being pulled high. When output line 650 is pulled low by activating NFETs 618 and 619, PFETs 656 and 654 are overpowered, and output line 670a is driven high turning off PFET 654. To rest circuit 650 to the initial conditions, reset signal RST2 strobes causing PFET 658 to pull output line 650 high with the assistance of PFET 656. It is noted that PFET 654 is used to reduce noise effects and prevents PFET 652 from accidentally turning on by assisting in pulling line 650 high.
Referring now to FIGS. 8a and 8b, there is a circuit diagram of a third circuit 660 in the cascaded OR in operation, when any of the output lines 670a-670d are brought high, a related NFET 720a-720d will drive node 722 low, which will drive output line 110 high via inverter 924. In contrast, when output lines 670a-670d all remain low, node 722 remains high, thus leaving output 110 low. It is noted that PFETs 710a-710d are used to reduce noise effects and prevent accidental turning on of the driving NFETs 720a-720d. To reset circuit 660, NAND gate 726 is activated by only strobing reset RST1, because SET is always maintained high after the initial start up of the integrated circuit. As a result, RST2 is driven low, and NFETs 700a-700d are activated to restore all output lines 670a-670d to a low voltage level. Additionally, PFET 920 will pull node 722 high, thus driving output line 110 low with the assistance of NFET 900 and inverter 924. It is noted that the SET signal is pulsed when the ship is powered up to initiate the cascaded OR for operation.
It is noted that there are many variations that one skilled in the art may employ in practicing the bit decoding of the RAM. In particular, the CAM columns may be divided into any number of parts and not just the four as illustrated. The re-partitioning of the CAM would then require a reconfiguration of the cascaded 0R circuitry to provide for more levels or stages. Similarly, one skilled in the art would easily conceive of other logic devices other than the cascaded OR as illustrated.
Accordingly, the preferred embodiment of the invention will provide for parallel processing of the CAM and the RAM. Since the CAM processing is faster, the RAM data is immediately output upon reaching the MUX circuitry. With the foregoing description in mind, however, it is understood that this description is made only by way of example. Additionally, the invention is not limited to the particular embodiments described herein. Moreover, it is noted that there are various rearrangements, modifications, and substitutions that may be implemented without departing from the true spirit of the invention as hereinafter claimed.
Thus, it can be seen that according to the present invention where there are associative memories, i.e., one memory dependent upon another for its input during normal operation, testing of the associative memory is performed during the test function by actually providing signals for test purposes from the memory associated therewith from which it will receive signals as during functional operation to thereby provide a more accurate and reliable test of the two memories and utilizing less chip area.
The particular invention as has been described in the preferred embodiment as it is utilized to test a CAM memory and an associated DCU memory. However, it is to be understood that the invention has equal applicability to the testing of many types of memory configurations wherein one memory is associated with another. One example of this is in certain TAG memories, i.e., memories which provide a tag of data which are added to data in another memory. These memory configurations can be tested in this manner. Moreover, the invention is not limited to BISTs, but is also applicable to other types of memory testing where one memory is dependent upon another during functional operation; e.g., memories where signals are received from off the chip for memory.
Accordingly, the preferred embodiment of the operation of a CAM decoder to supply addresses to associated memories during BIST testing has been described. With the foregoing description in mind, however, it is understood that this description is made only by way of example, that the invention is not limited to the particular embodiments described herein, and that various rearrangements, modifications, and substitutions may be implemented without departing from the true spirit of the invention as hereinafter claimed. | An associated memory structure having a plurality of memories amenable for testing and a method of testing the memories is provided. First and second memories are formed, wherein data in the first memory provides a basis for at least a portion of the input to the second memory during functional operation of two memories. Preferably, an output latch for receiving the output test data from the first memory is provided. Means are provided for loading the first memory with data which is utilized as a basis for providing at least a portion of the input to the second memory. An access path from the output port of the first memory to the input port of the second memory allows use of the data in the first memory to generate at least a portion of the input to the second memory. The first memory is first tested independently of the second memory. Thereafter, the first memory is loaded with preconditioned data that is used as a basis for inputs to the second memory during testing of the second memory. The second memory is then tested by generating inputs to the first memory during testing of the second memory. Thus, outputs of the first memory constitute at least a portion of test data inputted to the second memory. A latch is provided to capture the output of the test data from the second memory. | 6 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to Korean Patent Application No. 10-2013-0080361, filed on Jul. 9, 2013, and all the benefits accruing therefrom under 35 U.S.C. §119, the contents of which in its entirety are herein incorporated by reference.
BACKGROUND
[0002] 1. Field
[0003] The present disclosure relates to a multidirectional vibration generator using a single vibrator and its vibration generating method, and more particularly, to a single vibrator multidirectional vibration haptic feedback device giving a vibration effect with multidirectional frequencies according to a frequency of a driving source and a method for giving a haptic effect using a single vibrator.
[0004] 2. Description of the Related Art
[0005] Generally, haptic feedback allows a user to feel sense of touch, force, motion or the like by means of a keyboard, a mouse, a joystick, a touch screen or the like. In particular, the technique in relation to touch feedback using the sense of touch on the skin may be relatively easily implemented, and this is widely applied to touch control interfaces of portable devices such as cellular phones, PDA or the like. In addition, the touch feedback improves the feeling of manipulation to a device and also gives the sense of reality and immersion to a user, and thus various techniques capable of implementing various kinds of touches are being developed.
[0006] In this tendency, many attempts are being made to diversify vibration effects of a vibration generating device, and particularly it is needed to develop a multi-mode vibration generating device capable of giving vibrations having a plurality of frequencies to a vibration generating device.
[0007] FIG. 9 shows an example of a general haptic feedback device. The general haptic feedback device depicted in FIG. 9 uses four vibrators 201 , 202 , 203 , 204 . If a specific point 200 is touched by a user, a width 211 , 212 and a height 213 , 214 are measured and calculated based on the touched specific point 200 , so that the vibrators 201 , 202 , 203 , 204 have different values depending on a touched location.
[0008] However, this device uses a plurality of vibrators 201 , 202 , 203 , 204 , and thus it is difficult to design the entire device or system in a small size.
[0009] In addition, FIG. 10 shows another example of a general haptic feedback device. The haptic feedback device depicted in FIG. 10 includes an input unit 301 , a control unit 304 , a vibrator driving unit 305 , a first vibrator 302 , and a second vibrator 303 . The first vibrator 302 and the second vibrator 303 may vibrate to generate a vibration stimulus when a driving signal of the vibrator driving unit 305 varies.
[0010] Moreover, in this device, vibration stimuli generated at specific frequencies of first and second vibrators are synthetically exhibited as shown in FIG. 11 . In other words, the synthetic vibration of the first vibrator 302 and the second vibrator 303 are shown as the sum of vibrations of a vibration frequency having an absolute value (|f1-f2|) which is a difference between a first vibration frequency (f 1 ) and a second vibration frequency (f 2 ) and vibrations of a frequency having a mean value ((f1+f2)/2) of the first vibration frequency (f 1 ) and the second vibration frequency (f 2 ).
[0011] However, as shown in FIG. 11 , in this device, a vibration desired by a user may not be easily generated other than the vibrations of a vibration frequency having an absolute value (|f1-f2|) which is a difference between the first vibration frequency (f 1 ) and the second vibration frequency (f 2 ) and the vibrations of a frequency having a mean value ((f1+f2)/2) of the first vibration frequency (f 1 ) and the second vibration frequency (f 2 ), and even though vibrations are generated, their magnitudes are very small.
[0012] In addition, since two vibrators are used as described above, it is still difficult to design the entire device or system in a small size.
[0013] Next, FIG. 12 shows another example of a general haptic feedback device, which particularly includes a single vibration driving unit. In other words, this device includes an electromagnetic circuit 404 for receiving a driving power and generating an electromagnetic force, a driving unit 403 disposed at an upper portion of the electromagnetic circuit to vibrate in a plurality of vibration frequencies according to the frequency of the driving power, and a case unit 400 surrounding the electromagnetic circuit and the driving unit.
[0014] However, this device also includes two vibration modes (for example, an x-axis mode and a y-axis mode) having different inherent vibration frequencies f 1 and f 2 as shown in FIG. 13 so that a vibration effect is implemented with a waveform where f 1 and f 2 are synthesized. In addition, a vibration desired by a user may not be easily generated other than the inherent vibration frequencies, and even though vibrations are generated, their magnitudes are very small.
RELATED LITERATURES
Patent Literature
[0015] 1. Korean Unexamined Patent Publication No. 10-2010-0104975
[0016] 2. Korean Patent Registration No. 10-1097782
[0017] 3. Korean Unexamined Patent Publication No. 10-2013-0010591
SUMMARY
[0018] The present disclosure is directed to providing a multidirectional vibration generator using a single vibrator and its vibration generating method, which allows a small design and may generate a vibratory motion in a desired direction just by changing a frequency using the single vibrator.
[0019] The present disclosure is also directed to providing a multidirectional vibration generator using a single vibrator and its vibration generating method, which may generate a vibratory motion in a desired form not only at resonance points but also in a frequency band therebetween by directly designing a system having a desired resonance frequency and locating two or more resonance frequencies at desired locations, and also may generate a uniform amplitude even in a driving frequency band.
[0020] In one aspect, there is provided a vibration generating method, which includes: providing a vibration generating device which receives a driving power and generates a vibration; and controlling vibration of a vibrator of the vibration generating device, wherein the vibration of the vibrator is controlled by systematizing an inertia matrix and a stiffness matrix of the vibrator, and wherein the inertia matrix and the stiffness matrix simultaneously satisfy diagonalization.
[0021] In addition, the vibration generating device may be a 4-bar mechanism spring damper systems disposed at both sides of the vibrator in parallel in a vertical direction, vertical distances from a center of the vibrator to the upper spring damper system and the lower spring damper system may be identical, and a spring constant (k 1 ) of the upper spring damper system may be identical to a spring constant (k 2 ) of the lower spring damper system.
[0022] In addition, a vibration frequency (ω) of the vibrator may be determined, and a motion of the vibrator may be determined by designing spring constants and vertical distances of the upper and lower spring damper systems.
[0023] In addition, the vibrator of the vibration generating device may be a single vibrator.
[0024] In addition, a vertical spring damper system may be added to a lower portion of the center of the vibrator, and the 4-bar mechanism may be replaced with an eccentric motor or a piezoelectric vibration body.
[0025] In another aspect, there is provided a vibration generating device for receiving a driving power and generating a vibration by means of an electromagnetic force, which includes: a motor for generating a power with the received driving power; a vibrator connected to a vibration frame connected to the motor to vibrate according to a frequency of the motor; and a plurality of spring damper systems disposed at both sides of the vibrator, wherein the vibration generating device uses the vibration generating method defined in the claim 1 .
[0026] In the present disclosure, a vibration device or system capable of generating a vibratory motion in a desired direction just by changing a frequency using the single vibrator may be designed in a small size.
[0027] In addition, since the present disclosure is based on the analytical designing technique and does not use a resonance frequency obtained through interpretation, a system having a desired resonance frequency may be directly designed.
[0028] In addition, in the present disclosure, two or more resonance frequencies may be located at desired locations, so that a vibratory motion in a desired form may be generated not only at resonance points but also in a frequency band therebetween, and a uniform amplitude may be generated in a driving frequency band.
[0029] In addition, since the vibration generating device of the present disclosure may widen an available frequency band by obtaining a vibratory motion in a desired form with an uniform amplitude even in a frequency band between resonance points, linearity of the change of a motion direction according to the change of frequency greatly increases, easier control is ensured, and the performance of the vibration generating device may be improved.
[0030] In addition, since the vibration generating device of the present disclosure implements multidirectional vibrations by driving a single vibrator and just needs a simple speed control system, the present disclosure may be a great help in reducing a size of a haptic device of mobile terminals or game consoles which require the transfer of various touches.
BRIEF DESCRIPTION OF THE DRAWINGS
[0031] FIG. 1 is a perspective view schematically showing a vibration generating device according to an embodiment of the present disclosure.
[0032] FIG. 2 is a systemically modeled diagram schematically showing the vibration generating device depicted in FIG. 1 .
[0033] FIG. 3 is a diagram schematically showing a vibration direction according to each vibration frequency of the vibration generating device depicted in FIGS. 1 and 2 .
[0034] FIG. 4 is a diagram schematically showing a concept of the vibration generating device depicted in FIGS. 1 and 2 .
[0035] FIG. 5 is a graph showing a displacement motion according to the change of frequency of a vibrator in the vibration generating device depicted in FIGS. 1 and 2 .
[0036] FIG. 6 is a graph showing the change of a vibration center point according to the increase of a driving frequency of the vibration generating device depicted in FIGS. 1 and 2 .
[0037] FIG. 7 is a diagram schematically showing a vibration generating device according to another embodiment of the present disclosure.
[0038] FIG. 8 is a graph showing the change of a vibration center point according to the increase of a driving frequency of a vibrator in the vibration generating device another embodiment of the present disclosure depicted in FIG. 7 .
[0039] FIG. 9 is a diagram schematically showing an example of a general haptic feedback device.
[0040] FIG. 10 is a diagram schematically showing another example of a general haptic feedback device.
[0041] FIG. 11 is a graph showing that vibration stimuli of vibrators of the general haptic feedback device depicted in FIG. 10 are synthesized.
[0042] FIG. 12 is a perspective view showing a haptic feedback device including a single vibration driving unit according to another example of a general haptic feedback device.
[0043] FIG. 13 is a graph showing that a vibration stimulus according to each vibration frequency of the general haptic feedback device depicted in FIG. 12 .
DETAILED DESCRIPTION
[0044] Hereinafter, a multidirectional vibration generator using a single vibrator and its vibration generating method according to an embodiment of the present disclosure will be described through preferred embodiments.
[0045] Prior to description, in various embodiments, components having the same configuration is endowed with the same reference sign and representatively explained in one embodiment, and other components will be described in other embodiments.
[0046] FIG. 1 is a perspective view schematically showing a vibration generating device 1 according to an embodiment of the present disclosure. As shown in FIG. 1 , it may be understood that the vibration generating device 1 of the present disclosure receives a driving force of a motor 18 so that a vibrator 12 vibrates, and the vibration is output through an output unit 13 .
[0047] In more detail, a frequency in a desired vibration direction is determined by a controller (not shown), and a control signal is sent to the motor 18 through an amplifier (not shown). As shown in FIG. 1 , in the motor 18 , a crank 17 , a coupler 16 , and a rocker 19 are mechanically connected in order. If the motor 18 is driven through the control signal, the vibration of the motor vibrates the crank 17 , the coupler 16 , and the rocker 19 in order.
[0048] In addition, the rocker 19 is mechanically connected to a vibration frame 11 through a rocker fixing unit 191 , and as a result, the vibration initiated from the motor 18 vibrates the vibration frame 11 .
[0049] A vibrator 12 is disposed at a center of the vibration frame 11 , and the vibrator 12 is mechanically connected to the vibration frame 11 through a spring 14 and a damper 15 mechanically connected to both side ends of the vibrator. In an embodiment of the present disclosure, the spring and damper 14 , 15 use two springs and dampers at one side, respectively for upper and lower portions, namely four springs and dampers 14 , 15 in total. In addition, even though an embodiment of the present disclosure employs the motor 18 and the vibrator 12 connected to four springs and dampers 14 , 15 , a person skilled in the art may also use other kinds of vibration generating mechanisms, for example an eccentric motor or a piezoelectric vibrator.
[0050] As described above, the vibration of the vibration frame 11 is transferred to the vibrator 12 through the spring 14 and the damper 15 . Here, the spring 14 and the damper 15 may be made of elastic material capable of transferring the vibration of the vibration frame 11 to the vibrator 12 , without being limited thereto.
[0051] At this time, the vibration of the vibrator 12 is made by means of an external force transferred through the spring 14 and the damper 15 , and the vibration of the vibrator 12 is generated according to a frequency response characteristic with respect to a force component.
[0052] In addition, the vibration of the vibrator 12 is transferred to the output unit 13 through an output connection unit 131 , and a user finally feels the vibration through the output unit 13 .
[0053] FIG. 2 is a systemically modeled diagram schematically showing the vibration generating device depicted in FIG. 1 , and as essential components of the vibration generating device 1 of the present disclosure, only the vibration frame 11 , the vibrator 12 , the output unit 13 , the spring and damper 14 , 15 , and the motor 18 are depicted schematically.
[0054] In addition, FIG. 3 is a diagram schematically showing a vibration direction or the like according to each vibration frequency of the vibration generating device depicted in FIGS. 1 and 2 . As shown in FIG. 3 , in the vibration generating device according to an embodiment of the present disclosure, different vibration directions of the output unit 13 were observed when the frequency of the motor 18 was changed to 3.98 Hz, 4.93 Hz, 5.41 Hz, and 7.00 Hz, respectively.
[0055] FIG. 4 is a diagram schematically showing a mathematical concept of the vibration generating device depicted in FIGS. 1 and 2 . For easier explanation, among the entire components of the vibration generating device 1 , the motor 18 , the vibration frame 11 , and the vibrator 12 are depicted, and the spring and damper 14 , 15 are depicted as physical symbols used in the art.
[0056] Here, the vibration frequency of the motor 18 is marked as “ω”, elastic modulus of the upper and lower springs and dampers 14 , 15 are marked as “k 1 ”, “k 2 ”, respectively, and the mass and the moment of inertia of the vibrator 12 are marked as “m” and “j”, respectively. In addition, a vertical distance from the center of the vibrator 12 to the upper spring and damper is marked as “h 1 ”, and a vertical distance to the lower spring and damper is marked as “h 2 ”.
[0057] The inertia matrix and the stiffness matrix through this system may be expressed as follows.
[0000]
M
=
[
m
0
0
0
m
0
0
0
j
]
,
K
=
[
k
1
+
k
2
0
h
1
k
1
+
h
2
k
2
0
0
0
h
1
k
1
+
h
2
k
2
0
h
1
2
k
1
+
h
2
2
k
2
]
[
Equation
1
]
[0058] Here, assuming that “k 1 =k 2 ”, “h 2 =−h 1 ”, an inherent vibration frequency and a mode vector of this system may be obtained as follows.
[0000]
TABLE 1
Inherent frequency
Mode vector
Mode 1
ω
1
2
=
2
kh
2
j
{circumflex over (x)} 1 = [0 0 1] T
Mode 2
ω
2
2
=
2
k
m
{circumflex over (x)} 2 = [1 0 0] T
[0059] In addition, in [Table 1], the stiffness and installation locations of the spring and damper 14 , 15 may be determined by setting desired “1” and “2” and deciding “k” and “h” satisfying them.
[0060] The system designed in this way may be calculated using [Equation 2] below as the vibration frequency of the vibrator 12 varies.
[0000]
δ
X
^
=
∑
y
=
1
2
X
^
y
T
δ
ω
^
ext
(
k
~
y
-
m
~
y
Ω
2
)
+
(
c
~
y
Ω
)
X
^
y
=
[
2
kp
(
2
k
-
m
Ω
2
)
+
(
2
c
Ω
)
2
kh
2
(
2
kh
2
-
j
Ω
2
)
+
(
2
ch
2
Ω
)
]
[
Equation
2
]
[0061] Here, “p” means a y coordinate of the rocker fixing unit 191 .
[0062] In addition, FIG. 5 is a graph showing a displacement motion according to the change of frequency of a vibrator through [Equation 1], [Equation 2] and [Table 1] in the vibration generating device depicted in FIGS. 1 and 2 . As shown in FIG. 5 , a displacement “dx” along an x-axis and a displacement “dy” along a y-axis are synthesized to exhibit an entire displacement “d”. In addition, as shown in FIG. 5 , it may be found that a vibratory motion is exhibited not only at resonance points but also in a frequency band between them, and it may also be found that a uniform amplitude is observed in the entire driving frequency band.
[0063] Therefore, it may be understood that a band width of the vibration generating device according to an embodiment of the present disclosure is greatly improved.
[0064] In addition, FIG. 6 is a graph showing the change of a vibration center point according to the increase of a driving frequency of the vibration generating device depicted in FIGS. 1 and 2 . As shown in FIG. 6 , it may be found that as the driving frequency of the vibration generating device increases, a vibration center moves along a y-axis where x=0 in an up-down-up pattern.
[0065] FIG. 7 is a diagram schematically showing a vibration generating device according to another embodiment of the present disclosure. As shown in FIG. 7 , in another embodiment of the present disclosure, a spring is added to a lower portion of the vibrator 12 along a y-axis.
[0066] In addition, the stiffness “k 3 ” of the added spring may be determined to satisfy the following equation in consideration of a third frequency “ω 3 ” to be designed.
[0000]
ω
3
2
=
2
k
m
[
Equation
3
]
[0067] The change of a vibration center point according to another embodiment of the present disclosure is depicted in FIG. 8 . As shown in FIG. 8 , it may be understood that three vibration modes are used in another embodiment of the present disclosure, and more various vibration patterns are available with respect to a wide frequency band.
[0068] As described above, it will be understood by those skilled in the art that the present disclosure may be modified in various ways without changing its technical aspect or essential features.
[0069] Therefore, it should be understood that all the above embodiments are just for illustration only, not intended to limit the present disclosure, and the scope of the present disclosure is defined by the appended claims rather than the above detailed description. In addition, all changes or modifications derived from the meaning and range of the claims and their equivalents should be interpreted as falling within the scope of the present disclosure.
Reference Signs
[0000]
1 vibration generating device
11 vibration frame
12 vibrator
13 output unit
131 output connection unit
14 spring
15 damper
16 coupler
17 crank
18 motor
19 rocker
191 rocker fixing unit | Disclosed is a vibration generating method includes providing a vibration generating device which receives a driving power and generates a vibration, and controlling vibration of a vibrator of the vibration generating device, wherein the vibration of the vibrator is controlled by systematizing an inertia matrix and a stiffness matrix of the vibrator, and wherein the inertia matrix and the stiffness matrix simultaneously satisfy diagonalization. A vibration generating device using this method is also disclosed. | 1 |
BACKGROUND OF THE INVENTION
The present invention relates to a protective device and control board having a plurality of functions for protecting, monitoring, and controlling a refrigeration or freezer machine.
SUMMARY OF THE INVENTION
The present invention is a control board for an ice machine, refrigerator or other refrigeration machinery having a protective circuitry that continuously monitors a supply voltage for both over voltage and under voltage conditions. The protective circuitry comprises a delay that prevents it from disconnecting the refrigeration machinery from the supply voltage during startup or detected temporary abnormalities. The protective circuitry also comprises at least one low and high temperature sensor, a pressure sensor, a door position sensor, a dirty filter sensor, a thermistor sensor, a defrost sensor, a communication error sensor and a pump down error sensor which may provide a shutdown signal to turn the protected refrigeration machinery off. The protective circuitry further comprises a diagnostic menu which facilitates service personnel during troubleshooting operations by providing a history of detected irregularities in the refrigeration machine operation.
An object of the invention is to monitor and protect motor circuitry and other electronic components in a refrigeration machine from harmful environmental conditions such as over voltage, under voltage, high temperature, and high pressure conditions.
A further object of the invention is to provide a control board that continuously monitors various environmental conditions, shuts down a protected refrigeration machine after a dangerous condition exists for a predetermined period of time and/or a predetermined number of occurrences and stores information concerning the dangerous condition such as number of occurrences, date and time of occurrences or other information necessary for service technicians to troubleshoot and repair a faulty condition.
An additional object of the invention is to provide a control board which is controllable by an input device and contains an interface for communicating between input/output devices such as laptops or palm top computers or other similar devices. The control board may also receive or supply information remotely via a modem, or other transmission device including landline, cellular, satellite, or other communication mediums.
Another object of the invention is to provide a control board which has a delay that allows continuous use of a refrigeration machine without interruption due to ramping of motors, compressors, ect.
Another object of the invention is to provide a control board which is universal and can therefore be used in various refrigeration machines, thereby realizing cost savings. Input/Output (I/O) ports used in one configuration may be used for a different function in a different configuration or mode merely by changing software functions through various techniques such as calling up an already stored software module or routine or downloading/uploading additional software programs. The software functions may be loaded at the factory and may be changed at a retail store or in the field by a service technician.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A and 1B depict schematic views of the control board operating within a refrigeration machine.
FIG. 2 depicts a frontal view of an input control panel of the control board.
FIG. 3 depicts a two board operation within a refrigerator/freezer machine.
FIG. 4 depicts a flowchart of a software program for implementing an embodiment of the control board while in a freezer mode.
FIG. 5 depicts a low voltage alarm sequence.
DETAILED DESCRIPTION
The present invention is a control board comprising a temperature control output for regulating a temperature in a compartment of a refrigeration machine by energizing a compressor. A defrost control output controls a duration of a defrost cycle in the refrigeration machine by raising the temperature in the compartment of the refrigeration machine. An evaporator fan control relay controls an evaporator fan. A door position contact indicates whether a door to the compartment of the refrigeration machine is open, ajar or closed. A condenser fan/pump down relay controls a condenser fan. The control board further comprises outputs including audible and visual alarming devices. A high pressure input receives an input signal indicating excessive or high pressure in the cooling system. A communication device is for communicating between another control board and/or an interface device by importing or exporting information between one another. A temperature input receives a temperature signal indicating an environmental or compartmental temperature. A reset input resets the control board to default settings. A clean filter input receives a signal indicative of the cleanliness of a filter. A thermistor error input receives a signal indicative of whether a cabinet sensor and/or an evaporator sensor readings are out of predetermined range. A door ajar input receives a signal from the door open contact. A communications error input receives a signal indicative of a problem with communications between two boards or an interface between the control board and an external input/out put device. A pump down error input receives a signal indicating a problem with the pump down mode of operation described below. An onboard programmable memory stores a set of instructions or routines which control the refrigeration machine and alert a user of harmful conditions to protect the refrigeration machine. A DIP switch switches the functions or reconfigures the operations of the control board. A power loss memory stores the set of instructions or routines and information relating to harmful conditions which may be downloaded to facilitate troubleshooting by a service technician.
In a second embodiment the board further comprises a low pressure input device for terminating a pump down mode.
In a third embodiment the board is switchable between a freezer and a refrigerator board.
In a final embodiment two control boards are connected via a serial interface connection.
Throughout the disclosure the terms micro-controller and software program are used interchangeably and it should be realized and recognized that direct references to the various sequences, modules and/or routines could be implemented with various electronic circuitry, hardware, or software in combination or separately to implement the disclosed invention.
The control board comprises several outputs which may include a temperature control output that is a relay output to energize an external compressor control contactor that controls the operation of a compressor. A set point for temperature is programmed via up/down arrows on a display board. A switching function allows for toggling between Fahrenheit or Celsius temperature displays. The. control board also controls on/off time values for compressor cycles. The minimum on/off time values are stored in an EEPROM/EPROM or similar types of memory storage devices. When an alarm requests turn off of the compressor, the minimum on time will be disabled allowing the compressor to shut off immediately. At startup, by pressing the reset and enter buttons on the display board simultaneously while turning the power switch on, the cooling cycle can be immediately started. Nothing else can disable compressor minimum compressor off time which is at least 2.5 minutes.
A defrost control output is a defrost element control relay. In a freezer mode, defrost parameters are programmed via up/down arrows on a display board. Defrost cycle termination is determined by temperature. For example, when the control board is configured to be in a freezer mode, the freezer defrost cycle may be terminated when the compartment temperature reaches 100° F. or if configured in the refrigerator mode defrost termination may commence when the compartment reaches 40° F.
The software routine controlling the control board may also comprise a subroutine having a minimum or maximum time period between termination of a defrost cycle and initiation of the next cycle. A default setting for an initial defrost cycle commencement may be 6 hours from the time of power up. Refrigeration defrost may also commence when an evaporator temperature is 13° F. and may include no minimum time between defrost cycles. The defrost cycle during a freezer mode can be automatically terminated if the defrost termination temperature is not reached within one hour of commencement of a defrost operation. During a freezer mode “DEF” is displayed on the display board when a defrost relay is energized and the display on the display board may return to a cabinet temperature when a cabinet temperature sensor falls below a preset value such as 15° F. above a programmed set point. In the refrigerator mode, the display board always shows the compartment temperature. In freezer mode, the compressor start up may be delayed up to five minutes after termination of a defrost cycle. In the refrigerator mode, startup of the compressor is delayed 2.5 minutes.
An evaporator fan control relay is controlled by an output from the control board. There are two programmable options for the evaporator fan during a freezer mode. In one embodiment, the evaporator fan runs continuously or runs inverse to the state of the compressor. Namely, the evaporator fan is off while the compressor is running, and on when the compressor is off unless the fan is set to be running continuously. The evaporator fan is off during defrost and start up of the evaporator fan is delayed until the evaporator temperature is below 25° F. In another embodiment, the ambient temperature conditions in a refrigeration compartment are monitored and when the ambient temperature conditions exceed a predetermined threshold value, the evaporator fan motor is operated synchronously with a compressor motor. However, the evaporator fan is operated continuously when a monitored compressor percentage run time for a compressor in refrigeration machine reaches a threshold level. That is, when the compressor percentage run time reaches a certain low level, the evaporator motor will run continuously.
There are two programmable options for the evaporator fan during normal run operation (cooling) in a refrigerator mode. The evaporator fan operates the same as in the freezer mode. The board when operating in the refrigerator mode has two programmable options for the evaporator fan during defrost. The evaporator fan is on during defrost or is off during defrost and start up of the evaporator fan is delayed until the evaporator temperature is below 35° F.
The control board may comprise several inputs. A door open contact is activated by a signal from a door switch. However, if the refrigeration machine has a glass door, an output may be used to control a door heater. Additionally the control board may be constructed such that various types of contacts may be used for indicating whether a door is open or not. The control board may comprise a feature which is selectable between an open contact and a closed contact through a DIP switch. The control board therefore monitors the time the door is open and performs an alarm at after a predetermined period of time is exceeded. This function may be disabled if the refrigerator/freezer has a glass door on the compartment through a DIP switch. A reset operation of this alarm function is performed if the door is closed.
A high pressure input is provided to the control board by a pressure sensor reading exceeding a predetermined threshold value. Likewise, the low pressure input is provided by a pressure sensor which may be in common with the same source providing the high pressure input. If either input is triggered a predetermined number of times within a predetermined period of time, then a specific error code is displayed on the display board for a specified period of time. When the specific error code is displayed a predetermined period of time, the error message may be displayed continuously on the display board. The buzzer may also be triggered to sound a predetermined number of times within a specified period of time to indicate a high pressure condition and may be deactivated by a reset on the display or reset button the control board. The compressor may likewise assume an off condition when the error code is determined and displayed within a specific period of time. A visual alarm such as a LED may be triggered if the high pressure condition is determined to exist. The memory may record the error conditions every time they occur or after a predetermined number of error occurrences within a predetermined period of time.
A programming input may comprise up/down arrows, an enter button and a reset button. The display board update time is stored in a nonvolatile EEPROM.
A high voltage low voltage input is connected to the control board 1 or connected circuitry such that a sensor detects when a voltage exceeds a predetermined value. If a high voltage condition exists the display board will indicate as much. The low voltage alarm will indicate a low voltage, likewise. The occurrences of these harmful conditions may be recorded in a memory by a memory storage function. This memory storage function may apply to all harmful conditions.
A condenser fan/pump down relay output may be provided with the control board. In a freezer mode this relay 10 is energized any time the compressor relay 6 is energized and de-energized anytime the compressor relay 6 is de-energized. In a refrigerator mode during normal run (cool) cycle, this relay 10 is energized any time the compressor relay 6 is energized and de-energized anytime the compressor relay 6 is de-energized except during a defrost cycle when the condenser fan/pump down is energized 10 and the compressor relay 6 is not. Thus, the logic output in highs or lows of the control of the compressor is the same as the condenser fan/pump down relay 10 during a normal run cycle in the refrigerator mode and inverse during a defrost cycle. The condenser fan is off when the high-pressure switch indicates that a high pressure condition exists a predetermined number of times within a preset time period.
In the pump down mode, the control board relinquishes control of the condenser fan. Therefore, the condenser fan continues operating in the mode it was in before the control board relinquished its control of the condenser fan. For example, if the condenser fan was in an on state before the control board ceases control of it, then the condenser fan will continue to remain on. If however, the condenser fan was off before the control board relinquishes control, it will remain off. Additionally, in this mode the output on the board relay is used to drive a pump down solenoid. During a default operation the control board will not control condenser fan operation. When the compartment temperature reaches cutout temperature which equals a set point minus a differential value, the compressor continues to run while the pump down solenoid relay is de-energized. But, when the low pressure switch is energized the compressor relay is de-energized. If the compressor is running, and a defrost mode is initiated, a delay is implemented during which the solenoid valve relay de-energizes while the compressor continues to run. Further, when the compressor relay de-energizes, the low pressure switch assumes a position indicating that a low pressure condition exists and may remain in such position for some period of time after the compressor restarts for the next cycle. For a restart, when the temperature is at cut on temperature which equals a set point plus a differential value, both the pump down solenoid relay and the compressor relay are energized. If the set point is not reached, the low pressure switch is ignored. If a “cut out” or “turn off” temperature is reached which equals a set point minus a differential while the low pressure switch is de-energized within a predetermined period of time, then the compressor shuts off. If the compressor shuts off a predetermined number of times within a predetermined period of time then the pump down mode will be converted to the standard run mode and a specific error code will be displayed on the display board. This mode may be controllable through a DIP switch.
Inputs for the control board may also comprise the following. A clean condenser filter contact closure is sensed from a filter sensor which may be indicated by both buzzer and visual alarm outputs.
Temperature sensors include a compartment sensor displayed on the display board. The temperature reading display may be updated regularly over a predetermined period of time. A defrost termination/fan control sensor readings initiates defrost termination. For a non-heated refrigerator defrost, this sensor may initiate the defrost.
A control board reset switch 32 is a momentary push button switch located on the control board for resetting the alarms. A control board test switch 31 (shown in FIG. 1 A)is a momentary push button switch located on the control board for cycling all relays in sequence, one at a time.
A programming menu comprises adjustable parameters accessible through “guarded access” to prevent unauthorized changes. Display of the programming sequence will revert automatically to compartment temperature display after a predetermined period of time after the last button on the display board 7 is pressed. All parameters are programmable through an up/down arrows 26 , 27 on the display board 7 . Access will be granted only by pressing and holding the up/down arrows 26 , 27 together for a predetermined period of time. Once access has been obtained the display board will show parameter designators and current values. Adjustable parameters may include a temperature set point “t”; a defrost frequency “dF”; and a Fahrenheit/Celsius selection.
The control board may also comprise alarm outputs which may be controllable. For example, high and low temperature alarms are disabled during a defrost cycle. Audible alarms may be disabled through control of a DIP switch in desired modes.
The control board may also comprise preprogrammed default conditions upon sensor failure. For example, if a compartment temperature sensor fails, the compressor will operate on a fixed percentage on-time basis. For example, a control board in the refrigerator mode may be control a compressor to be five minutes on and five minutes off. In the freezer mode the compressor may be ten minutes on and three minutes off. If the defrost sensor fails, the control board may initiate a defrost cycle after a predetermined period of time.
The control board may also include various alarm messages displayed on the display board and/or stored in the memory. These alarm messages may include a clean filter error message. A service required error message. “DEF” may be displayed on the display board when the control board is in a defrost cycle. A thermistor error indicates when a cabinet sensor and/or evaporator sensor readings are out of range. A high compartment temperature alarm is disabled during the defrost cycle. However, after a predetermined period of time above a preset value, the temperature sensor in the cabinet will indicate an error code. Likewise, a low compartment temperature may be indicated through an alarm output.
A defrost error may cause termination of a defrost cycle and resume or default to a refrigeration cycle if a defrost cycle has not been completed within a predetermined period of time. A communications error will be indicated if a communications is not established with another board. A diagnostic menu may be provided by gaining access by pressing and holding the keypads displayed on the display board for predetermined periods of times in various sequences.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENT
FIG. 1A depicts a schematic of the control board 1 . For ease in understanding, only some of the inputs to the micro-controller unit 3 are shown in FIG. 1 B. Voltage detection sensor 2 , defrost temperature sensor 14 , and cabinet or compartment temperature sensor 16 have outputs fed into an analog-to-digital converter 20 which are then digitized and relayed to the micro-controller unit 3 for analysis. An EEPROM 4 is connected in parallel with the micro-controller unit 3 to the output of the analog-to-digital converter 20 . The EEPROM 4 stores information such as operational faults, number and time of occurrences which may be accessed by a service technician to help in troubleshooting a faulty condition. Several inputs corresponding to the input buttons on the display board including an enter button 28 for entering and selecting information displayed on LCD display screen 11 as shown in FIG. 2 . Reset button 17 resets the micro-controller unit 3 to factory installed default settings. Up arrow 26 and down arrow 27 are used to scroll between functions and inputs on LCD display screen 11 . The micro-controller unit 3 drives both the LCD display screen 11 and buzzer 12 .
FIG. 1B depicts schematic views of voltage detection sensor 2 , defrost temperature sensor 14 , cabinet or compartment temperature sensor 16 , low and high pressure sensors 24 , 13 , door open sensor 9 , clean filter sensor 18 , evaporator fan relay 9 , defrost heater relay 29 , compressor relay 6 , and condenser relay 10 .
FIG. 2 shows an arrangement of buttons on the display board 7 . Up arrow button 26 and down arrow button 27 are used to scroll between information items displayed on LCD 11 . Reset button 17 is used for resetting the control board 1 to default settings programmed at the factory. Enter button 28 allows entry of selected features such as defrost or temperature set points chosen by scrolling through a programmed menu with up arrow 26 and down arrow 27 .
FIG. 3 depicts a block diagram of two boards connected together via communication ports 15 on each board 1 . One of the boards is configured in a freezer mode while the other is configured in the refrigerator mode. The dual temperature unit mode may be enabled with a DIP switch 22 . Two boards will operate together where one board is configured as a freezer and the other is configured as a refrigerator. To prevent an overload condition from occurring and therefore a circuit breaker from tripping, the two compressors will not start at the same time. The two boards will communicate between each other to determine when a compressor has been turned on. When a board determines that its compressor should be turned on, the board 1 will check to see how long it has been since the other board 1 has turned on its compressor and will start its compressor depending on when the other compressor was started, if at all. If one board cannot establish communications with the other board, it will delay for a period of time and again try to establish communications with the other board. If after a predetermined number of unsuccessful attempts the board does not establish communications with the other board, it will turn its compressor on and initiate a communications error to be displayed on the display board. The display board may be toggled between displaying informational data of the first board and informational data of the second board.
FIG. 4 is a flowchart of a freezer operation for an ice making machine. In step S 1 , power is turned on to the control board 1 through a power up sequence or a reset sequence. In step S 2 , a drain counter is reset to zero. In step S 3 , a sump is filled with water for a predetermined period of time. For illustrative purposes the fill timer is set to equal 60 seconds in the present embodiment. In step S 4 , the micro-controller checks the status of a water valve that supplies water for the ice making process and insures that it is on. The status of the compressor, water pump and hot gas used for defrost are also confirmed to be in the appropriately shown conditions. In step S 5 , an output test switch position is determined. If the micro-controller 3 determines that the output test switch position is in an active position then an output test is performed in step S 6 A on the sensors and relays to ensure that the ice making machine is operating properly. However, if the output test switch is inactivated, then the micro-controller begins checking the on-board alarms in step S 6 B. In step S 7 , the supply voltage to the ice making machine is checked for over voltage, under voltage or other dangerous conditions. In step S 8 the fill timer is monitored to determine whether the predetermined period of time has expired. If the predetermined period of time has not expired the routine returns to step S 4 as shown in FIG. 4 . However, if the time period has expired then the routine moves to step S 9 and the micro-controller determines whether a float switch is closed. If the float switch is open then the ice making machine returns to step S 3 and continues to fill the sump. If the float switch is closed then a minimum defrost time is set to a default or programmed time value. In this embodiment the time value for the minimum defrost time is 2 minutes. Next, in step S 10 the micro-controller calls up a defrost routine and the freezing tube or molding compartment is defrosted. Upon completion of the defrost routine, a freeze routine is called in step S 11 and the water in the freezing tube or molding compartment is frozen. The ice is then dumped into a storage bin which is monitored to determine whether it is full in step S 12 . If the bin is not full, the micro-controller will again call the defrost routine in step S 10 . If the bin is full, then all controlling outputs from the micro-controller, such as compressor on, water on, etc., are set to an off position and the micro-controller returns to steps S 5 through S 7 . This sequence avoids an unnecessary shutting down of the compressor in the middle of a freezing cycle.
An ice making machine embodiment is next disclosed. A control board comprises several outputs. For example, a compressor is controlled by a relay output from the micro-controller and is off during an initial fill cycle. The compressor is on during an initial fill cycle and on during freeze and defrost cycles. A hot gas output is on during the defrost cycle and off during freeze, fill, and drain cycles. A water pump relay is energized during the drain cycle at the start of the defrost. A water valve output is on during a fill cycle and a predetermined period of time during the defrost cycle.
Alarm outputs may include an audible alarm and may also include LEDs, or LCD displayed error messages or other visual alarms.
The control board also includes various inputs. A frequency detect input detects zero cross inputs from an AC voltage for determining line frequency. Temperature sensor inputs may include an evaporator sensor and a bin control sensor. The evaporator sensor is used to begin a harvest timer and monitor an evaporator for high temperature. The bin control sensor is used to determine if the bin is full. A float switch input is monitored during a freeze cycle to determine when to end the freeze cycle and begin a defrost cycle. For example, when water in a water storage tank is used up, the float switch will open to end the freeze cycle.
Next the operation of the ice making machine will be disclosed. During a power up sequence the micro-controller will delay all outputs for a predetermined period of time while waiting for voltage and sensor readings to stabilize, thereby assuring accurate readings. In one embodiment the predetermined period of time is 5 seconds.
During a fill sequence the water valve output is on and all other outputs are off for a predetermined period of time. The float switch is then checked. If the float switch is energized then a defrost sequence is activated. If the float switch is deenergized then a second fill sequence will be conducted. The float switch is also checked each time the ice making machine begins a freeze cycle. If the float switch is de-energized at the start of a freeze sequence, the micro-controller will call up a fill sequence. An open float position of the float switch indicates no water in the water tank.
During a defrost sequence the compressor and hot gas outputs are on. If a drain counter equals zero, then a drain sequence is executed and the water valve is turned on. If the defrost cycle lasts longer than a predetermined period of time, which may be 6 minutes, then the water valve is turned off for the rest of the defrost sequence. While an evaporator temperature is less than a temperature set point, which may be 48° F. the defrost timer may be reset to a value based on a switch setting. When an evaporator temperature reaches or exceeds the temperature set point, the defrost timer will no longer be reset and will begin to count down. The defrost sequence will be terminated when the defrost timer equals zero. The defrost sequence is typically executed after fill and freeze sequences. The drain counter may be set to a value depending on a switch setting. After a defrost sequence one is subtracted from the drain counter. For example, a DIP switch controlling the drain count may be set for a drain counter of 5 cycles. The drain sequence will be executed only once every fifth defrost sequence. If the drain counter is set for every defrost cycle, the drain sequence will not be executed during the first defrost after power on. The defrost sequence may have a minimum and maximum run time based a switch setting.
During a drain sequence, a unit delay will be implemented after which a delay water pump output will turn on for a predetermined period of time based on a switch setting. Upon completion of a drain sequence, the micro-controller will return to a defrost sequence.
At the beginning of a freeze sequence, the position of the float switch is checked. If the float switch is de-energized, the freeze sequence is terminated and a fill sequence is initiated. If the float switch is energized indicating that the water tank is full, the freeze sequence will continue and the compressor will remain on while all other outputs will be off. After a minimum freeze time period, the float switch will be monitored. When the float switch indicates that the water supply in the water tank is exhausted, the freeze sequence is terminated and a defrost sequence commences. The freeze cycle may also have a maximum run time.
Alarm scenarios include high evaporator temperature, defrost backup timer, shorted ice bin thermistor, open ice bin thermistor, low and high voltage. | Electronic circuitry provides protection for refrigeration machines by continuously monitoring supply voltage conditions and various other conditions. Information regarding abnormalities detected in the refrigeration machines or supply voltage is stored in a memory. The stored information may then be downloaded from the memory by a service technician. The electronic circuitry is universal and can therefore be used with various refrigeration machines. Further, the efficiency of a low temperature storage cabinet is enhanced by cycling the evaporator motor in comparison to a compressor percentage run time. Other factors are also considered in the running of the reach-in cabinet evaporator fan. | 5 |
BACKGROUND OF THE INVENTION
The present invention relates to the field of medical devices for delivering acoustic shock waves, and in particular to a device for delivering acoustic shock waves having a removable, replaceable component with a data storage unit.
Medical devices frequently have items exposed to a great deal of wear or consumption. Therefore, it is desirable to place these high-wear items in separate removable and replaceable components connected with the basic device and replace them when necessary. In general, these components are identified by the manufacturer's embossed serial and/or lot numbers. This identification is documented at the manufacturing facility before delivery. Thus, while the component can be traced if it is returned to the manufacturer, no information is provided on the wear of the component during operation of the medical device.
To ensure the necessary safety when medical devices are in operation, it is necessary for the manufacturer and/or operator of the device to be continuously informed of the status of all the device components. This is particularly important for liability issues. It is especially important to replace parts that are consumable or exposed to wear promptly. Because wear and consumption are heavily dependent on the use of the device, for safety reasons replacement is usually done early and at fixed intervals regardless of actual use. This runs counter to economical use of the device components.
U.S. Pat. No. 6,036,661 assigned to the assignee of the present invention discloses a medical device for application of acoustic shock waves in which a replaceable treatment head connected with a basic device has a memory that can be read by the basic device so that the operating values of the basic device can be adjusted to the specific treatment head being used. In addition, usage data on the treatment head such as total operating time, number of shots, and number of shots remaining for the service life are stored, and are read, processed, and displayed by the basic device. However, data exchange to and from the treatment head memory is possible only through the basic device.
Therefore, there is a need for a replaceable component such as for example a treatment head that stores usage data of the component, and can download/transmit data from the component head.
SUMMARY OF THE INVENTION
Briefly, according to an aspect of the invention, a removable and replaceable component for use in a device for delivering acoustic shock waves includes a storage medium that stores component usage information.
According to another aspect of the invention, a removable and replaceable component for use in a device for delivering acoustic shock waves includes a storage medium that stores component identification information.
The information within the component storage medium can be read from the component, even while the component is removed from the device for delivering acoustic shock waves. The component may be for example a treatment head, and/or a power supply unit. A basic idea of the invention is to place the replaceable items of the device that are exposed to wear or consumption in separate components, and provide them with a storage medium that stores information relevant to the component and its use, which can be read from the removable and replaceable component independently of the basic device via for example a standardized interface. The interface may be associated with a wireline or wireless communication channel.
The relevant information can be read from the component (e.g., a treatment head) even when the component is not mounted on the basic device. As a result, removable and replaceable components can be easily inventoried to determine for example the use information for each of the treatment heads in inventory. It is thus possible to ensure that the components are available in the proper number, are procured on time, and are serviced or reprocessed promptly, with economically optimal use of the components.
The operationally relevant information can also be read by the manufacturer from the memory of the component returned for repair or reprocessing. This facilitates improved quality management by the manufacturer. This information can also be evaluated for manufacturing logistics to document, evaluate, and optimize manufacturing, storage, delivery, reprocessing, etc.
The relevant information can also be read by the user at the site where the device is used and forwarded to the manufacturer without the component having to be shipped. If such data transfers are done at regular intervals, the manufacturer can perform remote maintenance. The user can be promptly alerted about necessary servicing and reprocessing tasks, thus facilitating planning by the manufacturer and operator.
Reading the component memory externally also makes it possible to document device use continuously. While using the device, the physician can read and document the treatment measures performed by the device as they relate to the patient. It is also possible for leases of such devices to be based on actual use of the device, rather than time. For example, the use information can be read by the user and transmitted to the device owner for billing purposes via the Internet, e-mail, or a data carrier, for example.
These and other objects, features and advantages of the present invention will become more apparent in light of the following detailed description of preferred embodiments thereof, as illustrated in the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a pictorial illustration of a removable and replaceable treatment head having a storage medium for use in a device for delivering acoustic shock waves; and
FIG. 2 is a pictorial illustration of a removable and replaceable power supply unit having a storage medium for use in a device for delivering acoustic shock waves.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 is a pictorial illustration of a removable and replaceable treatment head 10 having a storage medium 16 for use in a device for generating acoustic shock waves for extracorporeal shock wave therapy. The treatment therapy head 10 includes electrodes, for example for electrohydraulic shock wave generation, between which there is an electrical spark discharge. This causes the electrodes to be consumed, such that after a certain number of spark discharges the treatment head 10 has to be reprocessed. The treatment head 10 is connected via a cable 14 and a plug 12 to a basic device, not shown. U.S. Pat. No. 6,036,661 incorporated herein by reference and assigned to the assignee of the present invention, illustrates a removable treatment head connected to a basic unit. The basic device contains the power supply and control for the treatment head 10 .
The storage medium 16 is mounted on the part of plug 12 connected to the treatment head 10 . The attachment of the storage medium 16 to the treatment head 10 (e.g., the plug of the therapy head) is fixed so that the storage medium 16 is continuously connected to the plug 12 of the treatment head. The storage medium 16 is preferably a read-write memory. An optical memory (CD-R, CD-R/W), an electric flash card, a magnetic storage card, or a smart card for example can be used as the storage medium. In one embodiment, the storage medium 16 is configured as a chip card attached to the plug 12 of the treatment head 10 .
Data can be read from the storage medium 16 , and data can be written from the basic device into the storage medium 16 . If the plug 12 is separate, the treatment head 10 can be connected via this interface to an independent reader or a data carrier. In this way, the data stored in the storage medium 16 can be read independently of the basic device. It is also possible to write data to the storage medium 16 independently of the basic device.
The removable and replaceable component shown in FIG. 2 is a removable and replaceable power supply 18 of a device for generating acoustic shock waves. The power supply 18 is configured as a replaceable cartridge that is inserted into the basic device, and supplies for example the treatment head 10 illustrated in FIG. 1 . The power supply 18 includes a charging capacitor and a spark gap serving as a high-voltage switch. The spark gap is subjected to heavy wear, and as a result the power supply 18 has to be reprocessed or replaced after a certain amount of use.
As shown in FIG. 2 , the storage medium 16 is permanently connected to the cartridge of the power supply 18 via a flexible connecting element 20 , such as for example a cord, a wire, or a cable. In one embodiment, the storage medium 16 is provided with a separate interface and can be inserted into a corresponding socket either of the basic device or of a separate reader or data transmitting device.
The storage medium 16 may include the serial number and batch number of the removable and replaceable component that it is associated with. For example, if the storage medium is associated with the treatment head as shown in FIG. 1 , then the storage medium may include the serial number and batch number of that treatment head.
The information may also include the serial number and batch number of the basic device into which the component is placed. In addition, any other information/parameters of the component (e.g., 10 or 18 ) that identify its properties and method of operation may also be stored in the storage medium. This information is preferably entered into the storage medium 16 by the manufacturer and continues unchanged.
The storage medium 16 may include information documenting the use of the removable and replaceable component. The stored information may also include for example the current model version, and information on any servicing or reprocessing. This information is preferably entered by the manufacturer or service organization. In addition, information indicative of the use of the removable and replaceable component, such as for example the number, duration, and operating parameters of use may also be stored in the storage medium. This information can be entered into the storage unit either by the component itself and/or by the basic unit. If the component is a treatment head 10 , this information can be used for documentation of the medical treatment and for billing use.
Although the present invention has been shown and described with respect to several preferred embodiments thereof, various changes, omissions and additions to the form and detail thereof, may be made therein, without departing from the spirit and scope of the invention. | A medical device is described, which comprises a basic device and at least one replaceable component connected therewith, said component having an item belonging to the device that is subjected to high wear or consumption. A storage medium is connected to the component, which stores component-specific data and can be read independently of the basic device. | 0 |
BACKGROUND OF THE INVENTION
The invention relates to lock systems, particularly heavy duty lock systems, useful for example in exit and entry control hardware for commercial and public structures.
Heavy duty door latching and locking hardware, because of its typically rugged construction and of the stresses to which it is subjected, is susceptible to binding particularly in the latchbolt which in most prior art designs is adapted to be slid in and out of its keeper in rectilinear or sliding movements. For example, the pressure of people against a door when attempting an emergency exit can so stress a dead latched latchbolt that severe binding can occur. Panic bars are typically designed to overcome such stresses by brute force, although the strains on the internal linkage can approach the breaking point.
In normal non-emergency use the relatively small torque generated by a hand key is often inadequate to withdraw a latchbolt in which binding has occurred as a result for example of a poor fit in the keeper.
The present invention has for its object to overcome these and other disadvantages of prior art designs by providing a dual direction swinging mount for the latchbolt which enables it to swing in one direction to release the door for opening and to swing in the other direction to permit re-latching when the door closes. Dual dead latches are also provided to secure the latchbolt from unauthorized release in either direction of swinging movement. The latchbolt is contoured to present camming surfaces to the keeper for both directions of door movement and is further contoured on an inner edge to clear the primary dead latch linkage after initial release occurs.
The primary dead latch opposes swinging movement of the latchbolt out of its keeper under the pressure of the camming surface of the latchbolt engaging the keeper when an attempt is made to open the door. When released from its dead latch the latchbolt is cammed out of its keeper by the movement of the opening door. Thus the latchbolt becomes a passive rather than active element in the door unlocking process. The primary dead latch includes a double-armed rock shaft carrying a roller between its arms which blocks the swinging movement. The dead latch assembly is normally backed against stops by a spring causing it to assume a position in which it is over-centered or toggled so that the force on the latchbolt serves only to seat the dead latch more firmly. Release of the primary dead latch can be effected for example through a key-operated linkage in which the key through linkage swings the double arm rocker through a sufficient angle to pass over the center point of the toggle at which time movement of the door causes the keeper to operate on the front cam surface of the latchbolt to swing the latchbolt out of its latching position. Once out of the keeper, the spring of the rocker arms pushes the latchbolt back to its outermost position. It will be understood that the primary dead latch can also be released by other mechanisms, such for example as a panic bar, which when moved causes the rocker arms to swing through a sufficient angle to clear the latchbolt from its dead latch position.
The secondary dead latch, which prevents swinging of the latchbolt in the opposite direction, includes a tiltable latch plate, spring biased to a position which normally engages the end of the latchbolt remote from that of the primary dead latch. Thus the latchbolt cannot be "picked" by inserting a tool into the space between the keeper and the latchbolt housing.
When a door is opened pursuant to authorized release, once past the keeper the latchbolt swings back out to its normal position. Concurrently with this outward swinging movement, a feeler arm which is normally held in the edge of the keeper, swings outwardly under a spring biasing carrying with it a camming surface which moves the latch plate of the secondary dead latch away from and clear of the latchbolt thereby freeing the latchbolt to swing inwardly as the door closes. A rearwardly facing camming surface on the latchbolt engages the edge of the keeper to force the latchbolt inwardly allowing it to relatch. The feeler finger is also cammed inwardly at the same time but does not enter the keeper aperture but rather remains in its inward position thereby permitting the dead latch plate to assume the latching position in the path of swinging movement of the latchbolt.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a top view, diagrammatic in nature, of a hinged door shown closed in its frame and to which is attached locking mechanism in accordance with the present invention;
FIG. 2 is a view in front elevation of a section of a door showing the lock mechanism of the present invention;
FIG. 3A is a view taken on the line 3A--3A of FIG. 2 looking in the direction of the arrows and showing the latchbolt seated in its keeper;
FIG. 3B is a view corresponding to FIG. 3A showing the position of the depressed latchbolt as it releases from its keeper;
FIG. 3C is a view corresponding to FIG 3A showing the door approaching its closed position and showing the latchbolt swung inwardly in order to clear the barrier of the keeper in the process of relatching;
FIG. 4 is a top view of the complete latching assembly and illustrating also panic bar mechanism for emergency release of the latchbolt;
FIG. 5 is a front view of the latch assembly of FIG. 4; and
FIG. 6 is an end view of the latchbolt assembly.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIGS. 1 and 2, the invention, which is concerned primarily with a latchbolt assembly, is illustrated as embodied in an exit and entry control system for doors, particularly those in public and commercial structures. The complete system includes a housing 10 secured on the inner surface of an outwardly swinging door 11. Contained within the housing 10 is a latchbolt assembly 12, as well as a multi-mode control unit and alarm system which are disclosed and claimed in co-pending application Ser. No. 545,922, filed Jan. 31, 1975 and having a common assignee herewith.
The latchbolt assembly 12 operates in conjunction with a keeper 13 which is secured to a door frame 14, typically on its door stop 14a. In the system as illustrated, it is intended that the door be opened by means of a panic bar 15 at one end on a swinging link 17 mounted in the latchbolt assembly 12 and at its other end, adjacent the door hinge 16, on a swinging link 17' with both links 17 and 17' being normally spring biased outwardly to present the panic bar 15 in a position spaced away from the face of the door. When pushed in the direction of opening of the door, the panic bar swings in a plane which is perpendicular to the surface of the door and moves slightly to the right as viewed in the drawings.
As best seen in FIGS. 4 and 5, the swinging link 17 takes the form of a bell crank having a first arm 17a which includes a pivotal coupling 17b with the panic bar 15. The bell crank link is pivotally secured by means of an arbor 19 to the frame 18 of the latch assembly 12. A second arm 17c of the bell crank is connected to the frame 18 by means of a coil spring 20 which urges it in a counterclockwise direction, as viewed in FIG. 4, against a stop 21. The stop 21 thus fixes the outer position of the panic bar 15. The arm 17c also engages a rocker plate 22 mounted on a pivot 22a in the frame 18. The rocker plate 22 engages a switch S (shown in broken lines) which controls an alarm system, the details of which are disclosed in the said co-pending application. The switch S is opened when the panic bar 15 is in its inactive or outer position causing the pivot plate 22 to press down against a switch spring S-1 and switch actuator S-2. When the panic bar 15 is pressed inwardly, the bell crank arm 17c rotates in a counter-clockwise direction, allowing the pivot plate 22 to swing in a clockwise direction under the force of the switch spring S-1, thereby actuating the alarm system. The bell link 17 includes a third arm 17d which actuates a dead latch release mechanism described at a later point.
The latch assembly 12 includes as its basic latching element a latchbolt 23 normally seated in the keeper 13 to secure the door in its locked condition. The latchbolt 23 is pivotally mounted in the frame 18 for swinging movement in both clockwise and counterclockwise directions. In the illustrated embodiment of the invention, two spaced apart pivot axes are utilized in the form of arbors 24 and 25. The arbor 25 is carried by the side walls 18a and 18b of the frame 18, as best seen in FIG. 6. A yoke assembly 26 including a pair of spaced apart arms 26a and 26b having a crosspiece 26c at one end is pivotally mounted on the arbor 25 to swing inwardly from right to left as viewed in FIG. 4. The outer or free ends of the arms 26a and 26b carry the arbor 24 on which the latchbolt is pivotally mounted so it can swing in a counterclockwise direction, as viewed in FIG. 4. A coil spring 27 around the arbor 24, best seen in FIG. 3A, biases the latchbolt in a clockwise direction, and a coil spring 28 around the arbor 25 biases the yoke 26 in a counterclockwise direction, both forcing the latchbolt to its outermost or latching position as shown. This outermost position is fixed by a stop 29 on the frame part 18b (FIG. 6) engaging a recess 30a in a stop plate 30 which is fixed to the yoke arm 26b to move as one therewith. The outermost position of the latchbolt 23 in its direct swinging movement on the arbor 24 is defined by the tail 23a of the latchbolt which rests on the coil spring 28 surrounding the arbor 25 (FIGS. 3A and 4).
Also pivotally mounted on the arbor 25 and able to swing free of the yoke 26 is a feeler finger 31 carrying a stop pin 31a (FIG. 4) received in a slot 32 in the frame wall 18a. The feeler finger is biased to its outer position by a spring 33 which engages an offset tail portion 31b of the feeler 31.
The latchbolt 23 is secured against rotation by a primary dead latch assembly comprising a rocker assembly 34 pivoted on an arbor 35 and comprising a pair of spaced apart arms 34a and 34b carrying a dead latch roller 36 on a cross shaft 37 joining the outer ends of the arms 34a and 34b. The dead latch rocker assembly 34 is urged by a spring 38 against a stop pin 39 which positions the dead latch roller 36 opposite the tail piece 23a of the latchbolt 23. As best seen in FIGS. 3A and 4, the dead latch rocker assembly is slightly overcentered with respect to the tail piece 23a so that a toggle lock is effected when the latchbolt 23 is stressed in a counterclockwise direction. The force generated by attempted rotation of the latchbolt in that direction presses the dead latch rocker assembly more tightly against its stop pin 39.
The dead latch rocker assembly 34 also includes tail extensions 40a and 40b which are engaged by the end of the third arm 17d of the bell crank linkage coupled to the panic bar 15. When the panic bar 15 is pressed inward, the arm 17d moves in a counterclockwise direction as viewed in the drawings, tilting the dead latch rocker assembly 34 in a clockwise direction to free the roller 36 from the tail piece 23a of the latchbolt. The latchbolt 23 is then free to rotate in a counterclockwise direction with the roller 36 riding on a contoured surface 23b on the inner face of the latchbolt, as best seen in FIG. 3B.
Actual rotation of the latchbolt 23 in the counterclockwise direction is effected by means of the contoured camming surface 23c engaging barrier wall 13a of the keeper 13. This force is generated by the person or persons who push the door open. In this fashion, the latchbolt withdrawal action is generated not by the control linkage but by the act of opening the door. Because the latchbolt swings, as opposed to sliding in more conventional rectilinear motion, binding of the latchbolt does not occur. The relatively small forces which are imposed on the dead latch rocker assembly when it is attempted to push the door open prior to release, are easily overcome by the panic bar actuated linkage because the slight overcentering or toggle action is precisely determined, with the roller 36 further reducing the frictional load. As soon as the latchbolt clears the barrier 13a of the keeper 13, it will swing to its initial position in a clockwise direction under the influence of the spring 27.
A secondary dead latch assembly is provided to prevent rotation of the latchbolt 23 in a clockwise direction about the arbor 25. Rotation in this direction is normally prevented by a pivotally supported dead-latch plate 41 urged about its pivots 41a by a leaf spring 42 in a counterclockwise direction to intercept a tail surface 23d on the latchbolt 23. The swinging feeler finger 31 includes a tail portion 31b which engages the dead latch plate 41 when the former is in its outer position as shown in FIG. 4, thus lifting the latch plate to release the latchbolt 23 to swing in a clockwise direction about its arbor 25. When the feeler finger is held in its innermost position, however, engaging an edge of the keeper 13, as seen in FIG. 2, the dead latch pivot plate 41 is spring-biased into its dead latching position. Thus, when the door is latched in its keeper, the latchbolt 23 cannot be rotated either in a clockwise or counterclockwise direction and thereby is resistant to picking. When the door is opened the feeler finger 31 swings outwardly to release the dead latch so that the latchbolt can be swung inwardly in clockwise direction about the arbor 25 by the camming action of its contoured trailing surface 23e against the barrier 13a of the keeper 13. The latchbolt is then able to relatch within the keeper when the door is fully seated against the door jamb.
As thus far described, the door cannot be opened without pressing the panic bar to release the dead latch rocker assembly 34 and free the latchbolt 23 to be cammed inwardly around the keeper as the door is pushed open by the exiting person. At such time and as more fully described in said co-pending application, an alarm system will sound through the action of the switch S indicating the door has been opened. The latch mechanism as described above can also be operated with a key. Key actuated entry or exit can be accomplished from the outside or from the inside by means of locks 43 and 44 on the inside and outside, respectively, of the door 11. As more fully described in said co-pending application, an actuating finger 45 (FIG. 4) is received in a slot 46 in the frame wall 18a next to an extension 47 on the dead latch rocker assembly 34. When the key is turned in the lock, the finger 45 engages the extension 47 to tilt the rocker assembly to free the dead latch roller from the tail piece 23a of the latchbolt 23.
It should be noted that the locking and latchbolt assembly is essentially symmetrical and can therefore be used on either the left hand side (as shown) or the right hand side of a door, it being required, however, that the assembly be inverted so that the housing side 18b is disposed upwardly.
While the invention has been described above referring to a preferred embodiment thereof, it will be understood that it can take various other forms and arrangements within the scope of the present invention. Thus, for example, a variety of configurations of the double swinging latchbolt can be made with compensating revisions in the specific nature of the dead latching mechanism. Also, a single pivot axis can be used for the double swinging latchbolt rather than two spaced apart pivot axes or arbors as shown in the drawing, sacrificing, however, certain ability to confine the apparatus within a relatively small space and further changing the moment arms of the mechanism. The invention should not, therefore, be regarded as limited except as defined in the following claims: | There is disclosed a latchbolt assembly which replaces conventional rectilinear latchbolt movement with dual direction swinging movement to reduce binding forces and which uses two independently operable dead latches in association with the dual swinging motions of the latchbolt. To facilitate release, as by key or panic bar actuation, the load of the latchbolt mass and friction is substantially eliminated by coupling the release system to one of the dead latches and thereafter utilizing camming action derived from the opening of the door to swing the latchbolt out of its keeper. Thus hard pressure against the door will not hamper the release. The second dead latch is operated by a latch feeler finger which frees the latchbolt only when the door is open thereby to facilitate relatching by swinging into the keeper as the door closes. | 4 |
This is a continuation of application Ser. No. 758,338, filed July 24, 1985.
BACKGROUND OF THE INVENTION
The present invention relates to a method and a system for maintaining tightness between two coaxial pipes transferring fluid under very high pressure and rotatable relative to each other around a common axis so as to enable, for example, a transfer of fluid under pressure between two parts of a machine which rotate relative to each other.
The method and system of the invention is particularly suitable for this function when the rotation between two parts of the machine is slow and alternating and has a small amplitude, with the fluid pressure being very high and the required service life being very long.
So-called swivel joints maintaining tightness between two coaxial pipes rotating alternately to each other are well known, with the swivel joints using a elastic material packings associated with cylindrical or flat and annular bearing surfaces against which they are applied, especially by the fluid pressure. Rotation of one of the two co-axial pipes relative to each other can only be obtained by the sliding of the packing and its bearing surface.
When the pressure of the fluid to be transferred is very high, the elastic material packings are strongly pressed against their bearing surface and sliding causes rapid wear of the elastic material packings. Additionally, when the fluid pressure is very high, the sealing lips of the elastic material are subjected to a severe shearing stress.
Currently, materials for the manufacturing of packings which have the necessary flexibility for perfect mating with cooperating bearing surfaces generally do not have a sufficient shear strength and the lips of the packing may be destroyed by tearing, especially upon reversing a direction of rotation of the system.
Therefore, the present invention proposes a system wherein the contacting components are not driven with any relative rotational motion and, without damage, may be pressed against each other as strongly as necessary, to form an efficient barrier regardless the pressure of the fluid.
Systems of the aforementioned type are disclosed in, for example, U.S. Pat. Nos. 3,944,263, 2,253,932 and 3,689,082 along with French patents A-2,227,784, A-1,572,520, A-1,585,213, and A-1,310,665, with these patents relating to static or non-rotating joints and swivel joints.
The aim underlying the present invention essentially resides in providing a system for maintaining tightness between co-axial pipes rotating relative to each other and which is capable of confining a fluid under very high pressure, with the system being sturdy and wear resistant so as to enable a long service life.
Advantageously, the present invention may be used as a substitute for the prior art swivel joints used on fluid transfer systems such as, for example, transfer systems between marine structures and a ship such as, for example, an oil tanker, especially when the two structures are connected by an arm and are free to rotate relative to each other.
According to advantageous features of the present invention, a system is proposed for maintaining tightness between two parts rotatable relative to each other, wherein at least two sealing units are provided, with each of these sealing units having at least two possible states, namely, one state ensuring tightness between the parts and the second state not ensuring tightness. Each of these sealing units is deformable and the drive means may be provided for intermittently actuating each of the sealing units.
In accordance with the present invention, at least one of the sealing units, not always the same sealing unit is permanently in the first state and sealing may be accomplished by rotating the pipes relatively to each other around a common axis.
At least one of the sealing units may comprise a sleeve adapted to be subjected to elastic torsional deformation along an axis thereof, tightly connected at one end to one of the pipes and including at the other end thereof a flange provided with temporary connection means to the other pipe.
According to the invention, the sleeve may comprise at least one rigid ferrule connected, over a portion of the length thereof, to one of the two pipes through a first ferrule made of elastically deformable material, with one of the two cylindrical lateral faces adhering to the pipe and the other to the rigid ferrule, and, over another portion of a length of the sleeve, to the flange provided with the temporary connection means through a second elastically deformable ferrule, with one of the two cylindrical lateral faces adhering to the flange and the other to the rigid ferrule.
It is possible in accordance with the present invention for the sleeve to include a stack of flat elastically deformable rings, with a flat ring located at one of the ends of the sleeve adhering to a flange integral with one of the two pressure fluid transfer pipes, and a flat ring located at the other end of the sleeve adhering to the flange provided with the temporary connection means and the other pressure fluid transfer pipe.
In accordance with further features of the present invention, the sleeve may be a flexible elastically deformable tube and, if necessary reinforced by a tensile resistant wire armor, with one of the ends of the tube including a flange integral with one of the two pressure fluid transfer pipes, and the other end of the tube including another flange provided with temporary connection means to the other pressure fluid transfer pipe.
According to the invention, the temporary connection means may comprise an elastically deformable ring placed around the pipe to be connected, with the ring being disposed in a groove provided in the end of the flange of the sleeve and one of the lateral walls of which is movable and actuated by an annular hydraulic jack.
The shape of the ring is changed from an initial shape when temporarily subjected to compression stress along its axis by the annular hydraulic jack, and transmits the compression stresses radially around the pipe to simultaneously insure tightness between the sleeve and the pipe and to provide a rotational driving of the end flange of the sleeve by the fluid transfer pipe.
In accordance with still further features of the invention, the temporary connection means may comprise a tight and elastic membrane integral with the end flange of the sleeve adapted to be subjected to elastic torsional deformation, with which it defines a variable geometry annular chamber concentric with the pressure fluid transfer pipe, the membrane being able to take, depending on whether the chamber which it defines is fed with pressure fluid or not, a first position where, inflated, it is strongly applied against the pipe and ensures tightness between the sleeve and the pipe and provides a rotational driving, by friction of the end flange of the sleeve by the aforementioned pipe and a second position where, deflated, it is returned by its own elastic stiffness against the flange in its initial shape at rest, and is no longer in contact with the aforementioned pipe.
Advantageously, this tight and elastic membrane may be an elastomeric tube fixed at both ends unto the end flange of the sleeve liable to elastic deformation, with which it defines a pressurizable annular chamber and whose compressive strength and elastic deformability are ensured by an internal armor made of braided wires, the wires forming between themselves a suitable angle, close to 20°, so that under the pressurization action of the chamber, the diameter of the tube may be increased by modification of the angle formed between themselves by the braided wires, and return to its initial size when the pressure fluid feed is stopped, by elastic return of the elastomer between the braided wires.
Additionally, according to further features of the invention, the temporary connection means may comprise a collar integral with the fluid transfer pipe to be connected and fixed in a groove provided in the end flange of the sleeve adapted to be subjected to elastic torsional deformation, with the side walls of the groove being composed of the body and the ram of an annular hydraulic jack. In this case, and with the forced fed fluid of the cylinder of the hydraulic jack causes the side walls to be brought closer to one another and to strongly nip the collar so as the ensure, tightness between the sleeve and the collar and the rotation by friction of the end flange of the sleeve through the aforementioned pipe.
Advantageously, the annular hydraulic jack which actuates the mobile side wall of the groove provided in the end flange of the elastic sleeve comprises a jack body and a ram which are co-axial and are interconnected on either side of the pressurizable annular chamber which they confine, by two ferrules of elastically deformable material. The side faces of the ferrules adhere to the jack body and the ram, so that the axial motion of the ram in one direction, under the effect of the pressure of the fluid contained in the annular chamber is tolerated by the shear deformation of the flexible material of the ferrules and the motion in the opposite direction can be obtained, when pressure rise in the annular chambers is interrupted, by the elastic stiffness of the flexible material of the ferrules which tends to recover to its initial shape.
According to the invention, the drive which intermittently actuates each of the two units providing tightness between the two pipes may be connected to the rotation of these two pipes in relation to each other through a cam integral with one of the two aforementioned pipes and in a position detector connected through the cam and fixed to the other pipe, the detector starting the operation of the connection means fitted on the sealing units.
Advantageously, the position detector may be a three position fluid slide valve to which the four pipes are connected and the cam with which is associated a slide operation feeler may have a three level contour. Two of the pipes connect each of the valves to each of the temporary connection means provided on the intermittently actuated sealing units. The third pipe connects the valve to a pressure fluid generator associated with a pressure accumulator, and the fourth pipe connects the valve to an atmospheric receiver tank out of which the aforementioned generator draws the fluid which it pressurizes. The three positions of the valve then correspond to the tripping sequences of the sealing units during which, successively, only one of the two aforementioned units is in operation, then both of them, then only the second etc., each of these sequences corresponding to one of the three levels of the cam.
As an alternative, with a view towards supplying the temporary connection means with pressure fluid, a pipe may connect the slide valve to the system comprising the two-coaxial fluid transfer pipes rotating in relation to each other so that the energy of the fluid to be confined can be used directly to operate the connection means.
To this end, a pressure booster comprising a staggered piston sliding in the tight body with two-coaxial bores mays be provided on the pressure fluid supply system of the temporary connection means.
The above and other objects, features, and advantages of the present invention will become more apparent when taken into connection with the accompanying drawings which show, for the purpose of illustration only, several embodiments in accordance with the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a longitudinal sectional view of a sealing system, according to the invention, wherein a sleeve adapted to be subjected to elastic torsional deformation includes flexible ferrules, and wherein the temporary connection means includes a collar integral with the pipe to be connected;
FIG. 2 is a longitudinal sectional view of a sealing system according to the invention, wherein the sleeve adapted to be subjected to elastic torsional deformation is a flexible tube, and wherein the temporary connection means includes a deformable ring;
FIG. 3 is a longitudinal sectional view of a sealing system according to the invention wherein the sleeve adapted to be subjected to elastic deformation includes a plurality of flexible flat rings, and wherein the connection means includes an inflatable and contractable joint;
FIG. 4 is a longitudinal sectional view of an inflatable expandable seal, represented in its initial position without pressure;
FIG. 5 is a longitudinal sectional view of the inflatable seal of FIG. 4 in an inflated and expanded position;
FIG. 6 is a schematic view representing in a simplified manner the connection means hydraulic drive system;
FIG. 7 is a schematic view of another embodiment of the connection means drive system of the present invention; and
FIG. 8 is a plan view illustrating a mode of setting of the slide valve position with respect to the cam.
DETAILED DESCRIPTION
Referring now to the drawings wherein like reference numerals are used throughout the various views to designate like parts, and more particularly, to FIG. 1, according to this figure, a device for maintaining tightness between two coaxial pressure fluid transfer pipes 1, 2 rotating relative to each other about a common axis is provided with a pressure fluid accommodated by the coaxial pipes 1, 2 flowing from one pipe to the other in, for example, the direction of the arrow 4.
The two pipes 1, 2 are rotatably guided by bearings 5, 6 with the pipe 2 including two collars 7, 7a which are retained in two grooves 8 and 8a, with the first groove 8 resulting from the assembly of the body of a hydraulic jack 9 with the ram 10 and the flange 11, and the second groove 8a resulting from the assembly of a jack 9a, preferably identical with the hydraulic jack 9, and with the ram 10a and the flange 11a, preferably identical with the ram 10 and flange 11, respectively. Each of the rams 10 (or 10a) is connected to the body of the hydraulic jack 9 (or 9a), through the ferrules 12 and 13 (or 12a and 13a) made of elastically deformable material, to define and annular chamber 14 (or 14a) described more fully hereinbelow, connected, through a port such as a part 15, to a hydraulic system supplied with pressure fluid.
The body of the hydraulic jack 9a and the ram 10a are shown in their initial relative position when the annular chamber 14a is not supplied with pressure fluid. In this position, the collar 7a of the pipe 2 has no contact with the sides of the groove 8a, formed by the flange 11a and the ram 10a, and pipe 2 can rotate freely relative to pipe 1. On the other hand, the body of jack 9 and ram 10 are shown in a position where, a pressure fluid admitted to the annular chamber 14, exercises an internal thrust. This thrust separates the ram 10 from the body of the jack 9 according to translatory movement in the direction of the longitudinal axis which causes groove 7 to shrink. The collar 8 is then strongly pressed between the flange 11 and the ram 10.
Each of the temporary connection means 16 and 16a including the jack 9 (or 9a), the ram 10 (or 10a), the two elastic ferrules 12, 13 (or 12a and 13a) and the flanges 11 and 11a, are connected to pipe 1 through a sleeve 17 (or 17a) adapted to be subjected to elastic torsional deformation around the axis 3. This sleeve comprises a rigid ferrule 18 (or 18a), adhering over a portion of its length with a ferrule 19 (or 19a) made of elastically deformable material and adhering over the other portion of its length with another ferrule 20 (or 20a) made of elastically deformable material.
Ferrules 19 and 19a also adhere with flanges 11 and 11a respectively, whereas, the ferrule 20 also adheres to the flange 21 in prolongation of the pipe 1, and the ferrule 20a, also adheres to the flange 22 in prolongation of the pipe 2 through the cylindrical casing 23. A series of passages 24, 25, 26 and 27 is provided through flange 21, ferrules 18-20 19, flange 11; body 9, elastic sleeve 17, and connecting device 16, so that the opening of the parts 15 into the annular chamber 14 is in communication with pipe 28 which is connected to the pressure fluid supply system described hereinafter.
Another series of pipes (not shown) also connects, through the elastic sleeve 17a and the temporary connection means 16a, the annular chamber 14 to the pressure fluid supply system described hereinafter.
The system further includes a hydraulic slide valve 29, rotatable with the pipe 2, through support 30, having a slide actuated by roller 31 which follows a contour of cam 32 rotatable with the pipe 1 through flanges 22 and 21 and casing 23.
FIG. 2 shows a second mode of implementation of the system for maintaining tightness, according to the invention, between two co-axial pipes 33 and 34 rotating in relation to each other around their common axis 35, the fluid under pressure which they transfer flowing from one to the other, for example, in the direction of arrow 36.
The two pipes 33, 34 are rotatably guided by bearings 37 and 38. The device includes two identical systems each including a sleeve 39 (or 39a) adapted to be subjected to elastic torsional deformation around the axis 35, and associated with a set of temporary connection means 40 (or 40a).
Each sleeve 39 (or 39a) includes a flexible pipe 41 (or 41a) made of elastically deformable material, to the best advantage reinforced by helically wound wire armour 42 (or 42a) which provides for a resistance to the pressure of the fluid conveyed from pipe 33 to pipe 34, which it temporarily confines as can be seen hereinafter. This flexible pipe 41 (or 41a) is fixed at one of its ends, for example, by means of a collar 43 (or 43a), to flange 44 which is integral with pipe 33 (or to flange 44a which is integral with pipe 33 through casing 45 and the flange 44). This flexible pipe 41 (or 41a) is fixed at its other end, for example, by means of a collar 46 (or 46a) to flange 47 (or 47a) supporting the set of temporary connection means 40 (or 40a).
This temporary connection means 40 (or 40a) includes, housed and sliding in a double bore 48 (or 48a) provided in flange 47 (or 47a), a staggered annular piston 49 (or 49a) equipped with seals 50 and 51 (or 50a and 51a) and an annular ring 52 (or 52a) made of elastically deformable material which is provided between this piston and an annular flange 53 (or 53a) blanking off the bore 48 (or 48a). The piston 49 (or 49a) defines with the flange 47 (47a) a variable geometry annular chamber 54 (or 54a) connected to the pressure fluid supply system described hereinafter, through the flexible pipe 55 (or 55a) and passage 56 (or 56a) provided in flange 44 (or 44a). As shown in FIG. 2, the two systems which include the sleeves 39 and 39a, and the temporary connection means 40 and 40a, which include the rings 52 and 52a, are provided around the pipe 34. The temporary connection means 40 are shown in a position where the ring 52, made of elastically deformable material, compressed between the flange 53 and the piston 49, the latter pushed by the pressure of the fluid admitted into the annular chamber 54, has changed shape and, behaving like an incompressible fluid, radially transmits the axial thrust it receives, and strongly surrounds the pipe 34. On the other hand, the connection means 40a is shown in the position where the pressure supply being stopped, the ring 52a has recovered, due to its elastic stiffness, to its initial shape by pushing back the piston 49a, and is no longer in contact with the pipe 34.
As is apparent from the following description, the device of FIG. 2 also includes a slide valve 57 which is rotatable with the pipe 34 through support 58. The slide valve 57 is actuated by the rollers 59 which follows the contour of the cam 30, rotatable with the pipe 33 through casings 61 and 45 and flanges 44 and 44a.
FIG. 3 provides an example of a device for maintaining tightness between two co-axial pipes 62 and 63, rotating relative to each other around their common axis 64, with the pressure fluid which they handle flowing, for example, in the direction of the arrow 65.
The two pipes 62, 63 are guided in rotation by bearings 66 and 67. The device includes two identical systems, each of which includes a sleeve 68 (or 68a) elastically deformable in torsion around the axis 64, associated to a set of temporary connection means 74 (or 74a). Each sleeve 68 (or 68a) including a stacking of flat rings 70 made of elastically deformable material, and rigid flat rings 71, each of the rigid flat rings being placed between two flat rings 70 made of elastically deformable material to which it adheres, for example, by sticking. The flat ring 70 made of elastically deformable material located at one of the ends of the sleeve 68 (or 68a) adheres to a flange 72 (or 72a) integral with the pipe 63, and the flat ring made of elastically deformable material located at the other end of this sleeve adheres to a flange 73 (or 73a) supporting the set of connection means 74 (or 74a). Each set of temporary connections means 74 (or 74a) includes as a companion a flange 75 (or 75a) which, by cooperating with the flange 73 (or 73a), defines an inner groove 76 (or 76a) and tightly presses the fastening rods 77 and 78 (or 77a and 78a) of the inflatable seal 79 (or 79a).
The inner groove 76 is associated with an outer groove 80 provided in the cylindrical casing 81 which prolongs co-axially the pipe 62 by surrounding the two temporary connection means 74 and 74a so as to create an annular housing 82 which totally encloses the mobile part 83 of the inflatable seal 79. In the same way, the inner groove 76a is associated with an outer groove 84, also provided in the casing 81, so as to create an annular housing 85 which totally encloses the mobile part 83a of the inflatable seal 79a. In FIG. 3, the seal 79 is shown in the position where the variable geometry inner chamber which it defines is supplied with pressure fluid through pipes 85, 86, 87 provided through the flange 73, through the stacking of flexible and rigid flat rings 70 and 71, through the flange 72 and through the wall of pipe 63 up to the union 153 connecting the pressure generation system described hereinunder. In this position, the mobile part 83 of seal 79 is expanded towards the outside and strongly pressed against the wall of groove 80. On the other hand, the seal 79a, whose inner chamber is also connected to the pressure generation system described hereinunder, namely through pipes 85a, 86a aand 87a, is shown in the position where, the pressure fluid supply being stopped, it is brought back, by its own elasticity, to its initial manufactured position, that is withdrawn. In this position, it is no longer in contact with the wall of groove 84.
As can be seen from FIG. 3, a slide valve 88 is rotatable with the pipe 63 through support 89. The slide of this valve is actuated by the roller 90 which follows the contour of cam 91 integral in rotation with the pipe 62 through the casing 81.
Any of the three types of torsionable sleeves as described can obviously be associated with any of the three connection means as described, without leaving departing from the scope of the invention.
FIGS. 4 and 5 show an alternative of the inflatable seal system used, as shown in FIG. 3 as part of the temporary connection means. This inflatable seal 92 comprises an expandable torsionally deformable cylindrical sleeve 93 made of elastically deformable material, reinforced by a low tensile braided wire armour 94 securely fixed onto two end flanges such as 95. The flanges are connected to the end flange 96 of the inflatable sleeve 93, which was identified for example in FIG. 3 by number 68 or 68a, so that it defines with the seal 92 an annular chamber 97, which can be supplied with pressure fluid through port 98. The reinforcing armour 94 of sleeve 93 including two layers of helical wound wires or cables made of low tensile material 99 and 99a forming an angle 100, for example, close to 20°, such that, when the chamber 97 is fed with pressure fluid, these cables are tensioned and take a more stable orientation and thus form a new angle 101, for example close to 55°, which causes an increase in the diameter of the expandable sleeve 93, as shown on FIG. 5, where said sleeve is thus strongly pressed against the inner wall of casing 102.
On the other hand, as shown on FIG. 4, when the pressure fluid supply is stopped, each diamond shaped element made of elastically deformable material, such as 103, imprisoned between the cables, which was deformed due to the change of orientation of these cables, tends, by elastic return, to recover its original shape. The elastic return of all the elements 103 causes the elastic return of the whole sleeve 93, which has recovered its initial cylindrical shape, and has no longer contacts with the casing 102. It can be noted that the increase in diameter of the sleeve 93 under the pressure effect is generally accompanied by a decrease of its length.
This is why, in the example of implementation shown in FIGS. 4 and 5, the end flanges such as 95 of said sleeve 93 could be connected to flange 96 which supports them through ferrules, such as 104, made of elastically deformable material, to which they adhere and whose shear deformability in the axial direction tolerates this length decrease.
Furthermore, it would be possible, according to the invention, to make an inflatable seal which, instead of expanding under the effect of an internal pressurization and coming into contact with the inner wall of a casing which surrounds it, would universally have the property of shrinking under the effect of an external pressurization and would come into contact with the outer wall of a transfer pipe.
FIG. 6 shows, in a schematic and simplified manner, an example of implementation of the pressure fluid system feeding the connection means described hereinabove, wherein the two pipes receiving the pressure fluid, jacks and inflatable seals, which actuate the connection means, are represented by two housings 105 and 105a.
In FIG. 6, the fluid is a hydraulic liquid which is withdrawn from a nonpressurized tank 106, and which, when pressurized by the pump 107, is stored in the oil and air accumulator 108. Two pipes 109 and 110 connect the two housings 105 and 105a to the pump 107 and the tank 106 through the hydraulic valve 111 provided with a slide 112 actuated by sensor 113 which follows the three level profile 119, 120 and 121 of the cam 114 with which it is maintained in contact by the thrust of spring 115. Slide 112 includes three sections 116, 117 and 118.
In FIG. 6, the slide is shown in its median position corresponding to the intermediate level 119 of the cam 114 profile, and in this position, both housings 105 and 105a are in communication with the pump 107 and fed with pressure fluid. One can easily imagine that, upon further rotation of the cam 114 relative to the slide valve 111, the sensor 113 will be brought into engagement with the level 120 of the cam profile closest to its rotation axis, whereby the slide 112 is displaced so that the inner ports of the section 116 communicate the housings 105, 105a through the pipes 109 and 110 with the non-pressurized tank 106.
In this position, the housing 105a is in communication with the pump 107 and pressurized, and the housing 105 is in communication with the atmospheric tank 106 and is depressurized. In the same manner, upon a further rotation of the cam 114 in the opposite direction relative to the slide valve 111, the sensor 113 will be brought into engagement with the level 121 of the cam profile furthest from its rotation axis, whereby the slide 112 is displaced in the opposite direction so that the inner ports of the section 116 communicate the pipes 109 and 110 with the non-pressurized tank 106. In this position, the housing 105 is in communication with the pump 107 and fed with pressure fluid, and the housing 105a is in communication with the atmospheric tank 106 and is depressurized.
The oil and air accumulator 108 is associated with the pump 107 so as to maintain pressure fluid feed for a certain time when, for any reason, the driving of said pump is stopped.
FIG. 7 shows, in a schematic and simplified way, an alternative of implementation of the connection means pressure fluid supply system, wherein the pressure fluid comes directly from pipe 139, which is to be confined, made up of two coaxial pipes 124 and 125 rotating relative to each other. The two pipes 124, 125 receiving this fluid, jacks and inflatable seals, which actuate these connection means, are represented by the two housings 122 and 123. The cam 126 is rotatably driven by the pipe 125 and the slide valve 127 by the pipe 124. The pressure fluid is drawn off pipe 124 through port 128. The pipe 129 connects this port to slide valve 127, the pipe 130 connects the slide valve to the non-pressurized tank 127. The pipes 132 and 133 connect the slide valve 127 to the two housings 122 and 123 respectively through two pressure boosters 134 and 134a.
Each pressure booster 134 or 134a includes a staggered piston 135 (or 135a) sliding in a tight body 136 (or 136a) provided with two co-axial bores 137 and 138 (or 137a and 138a) of different cross sections, so that the outlet pressure, on the side of the smaller diameter bore 138 (or 138a), is higher than the inlet pressure, on the side of the larger diameter bore 137 (or 137a), hence higher than the pressure in the system 139.
This supply system operates in the same way as the system described hereinabove in connection with FIG. 6, only the source of the pressure fluid is different with this alternative, the pressure fluid which came from the FIG. 6 system of the pump 107, comes directly from the pipe 139.
FIG. 8 shows a fixing mode for the slide valve 140 which, as in the examples of implementation described above, is associated with a cam 141, whose staggered profile includes three levels 1421, 143 and 144. Each of these three position of the slide valve corresponds to one of the cam levels. The slide valve 40 slides on a ring 145 integral in rotation with one of the fluid transfer pipes (not shown) with axis 146, rotating around this axis in relation to the other pipe 147 with same axis which bears the cam 141. For example, the valve 140 may slide on the ring 145 through guiding yokes 148 and 149, yoke 149 bearing the lock screws 150 and 150a.
As can be seen from the description hereinbelow, it may be of interest to be able to set, in this manner, the initial position of the slide valve 140 relative to profile of cam 141, especially when the rotation of the two fluid transfer pipes relative to each other around the axis 146 is limited to an angular motion of an angle smaller than the angle 151, corresponding to the perimeter of only one level of the cam such as for example 142 or 144.
The operation of the device thus described is easy to understand. For description purposes, this operation will be referred to the modes of implementation described on FIGS. 3 and 6, and then, as can be seen, the operation will be similar to the embodiments described in connection with FIGS. 1, 2, 4, 5 and 7.
During the rotation, relative to each other around axis 64, of the two fluid transfer pipes 62 and 63, tightness between these two pipes is maintained according to a multiple of three consecutive operating sequences, corresponding to three configurations of the device.
As shown in FIG. 6, the first sequence corresponds to a device configuration where the roller feeler 113 (90 on FIG. 3) moves along level 120 of cam 114 (91 in FIG. 3). The slide 112 of the valve is then in an extreme position, the spring 115 being released, where the inflatable seal 105 (79 in FIG. 3) is in communication with the atmospheric tank 106, and where the inflatable seal 105a (79a in FIG. 3) is in communication with the pressure fluid supply, for instance with pump 107.
FIG. 3 shows that, as a result, the depressurized seal 79 has no contact with the casing 81 integral with pipe 62, and that the flange 74 which supports the seal 79 can rotate freely with the pipe 63. On the other hand, the pressurized seal 79a is strongly applied onto the casing 81, so that it ensures tightness between this casing and the flange 74a which supports it and the rotational driving of this flange through the casing 81. The elastic sleeve 68a, whose ends are fixed on two flanges 72a and 74a which, driven by the pipes 62 and 63, rotate relative to each other, undergoes a torsional deformation which is necessarily limited angularly, for instance at 20° on both directions of rotation.
When the torsional deformation of sleeve 68a approaches the allowable limit, i.e., for instance after an 18° torsion, the roller sensor 113 reaches the level 119 of the cam 114 on which it then moves during for instance a 2° rotation. During this second operating sequence, the slide of the valve 111 is in a median position, and the two inflatable seals 105 and 105a (79 and 79a in FIG. 3) are pressurized simultaneously.
Tightness is ensured at the level of both the inflatable seal 79 and the inflatable seal 79a, and the fluid trapped between these two seals can be drained through the port 152, towards a leak recovery system (not shown).
The flange 75 which supports the seal 79, is driven into partial rotation through the casing 81 integral with the pipe 62, and the elastic sleeve 68 undergoes partial torsion, for instance, of 2°, whereas, the torsion of sleeve 68a reaches the maximum allowable angle considering the shear flexibility of elastomeric flat rings, such as 70, which make it up.
At that time, the roller sensor 113 reaches the level 121 of the cam 114 along which it moves during a rotation of for instance 18°. During this third operating sequence, the slide of valve 111 is in an extreme position, opposite to the position which it occupied during the first sequence, and in which the spring 115 is compressed.
In this configuration, the inflatable seal 105 (79 in FIG. 3) is still in communication with the pressure fluid supply, for example with pump 107. On the other hand, the inflatable seal 105a is put in communication with the atmospheric tank 106. As a result, the seal 105a (79 on FIG. 3) is depressurized and is no longer in contact with the casing 81 integral with the pipe 62. Owing to the elastic return of its elstomeric components, such as 70, the torsionally elastic sleeve 68a comes back to its initial position and is thus ready to take up the first sequence again. The three sequences described hereinabove may be repeated as many times as necessary to allow the rotation of pipes 62 and 63 in relation to one another, by maintaining tightness by a step-by-step operation of the device, confinement being interrupted only by one of the two similar components operating alternately, for instance 68, only when it is ensured by the other, for instance 68a.
It is easy enough to understand that the operation is similar if the inflatable seals are of the type of seal 92 shown on FIGS. 4 and 5.
Also, the operation is similar when the torsionally elastic sleeves are of the same type as the sleeves 17 and 17a of FIG. 1 or 39 and 39a of FIG. 2, and when the temporary tight connection is achieved in the same manner as that shown on FIG. 1 through the set of means 16 and 16a, or FIG. 2 through the elastic rings 40 and 40a.
The operation is also similar, if as in FIG. 7, the pressure fluid supply comes directly from the pipe 139 of the fluid to be confined, the pressure boosters 134 and 134a added to the system being only used to increase the pressure level of the inflatable seals to a value exceeding the pressure level in the pipe 139, to allow them to insure tightness. However, in that case, it is necessary to explain that the pistons 135 and 135a of these boosters can take two positions depending on whether the pipe 133 or 132 which connects them to slide valve 127 is in communication with the source of pressure fluid through pipe 129, or with atmospheric tank 131 through pipe 130. In the first case, the piston 135 (or 135a) under the effect of the fluid pressure exerted in bore 137 (or 137a) is pushed towards bore 138 (or 138a) whose content is pushed towards the temporary connection means actuator 122 (or 123). In this second case, the actuator 122 (or 123), by its own elastic return, return the fluid it contains towards the bore 138 (or 138a) to push the piston 135 (or 135a) towards the bore 137 (or 137a) whose vented content is pushed towards the tank 131.
The advantages of this invention mainly result from the possibility offered by the use of this device, to substitute means limited to the tightness between two fixed surfaces relative to each other for the means intended to obtain tightness between two surfaces rotating in relation to each other. Now, one knows that in the current state of the art, tightness between fixed surfaces is easily obtained for high pressures, even if the fluid is a gas.
On the other hand, the pressure level being reached, the reliability and life are limited if tightness is to be obtained between surfaces rotating in relation to each other, and above all if the rotation motions are alternating, and hence include many reversals of the direction of rotation.
The sealing system or device according to the invention can be used on all systems including high pressure pipes rotating slowly in relation to each other, and most motions of which are alternating oscillations of small amplitude, whereas rotations exceeding one turn are occasional. It is particularly suitable for swivel joints used in the development of subsea oil fields, for the transfer of production which may be oil or gas, between a marine structure with a fixed position relative to the sea bed and a floating structure which may be a processing vessel or a storage vessel and which under the action of wind, current and swell, weathervane about the marine structure. | A system for maintaining a tightness between two parts rotatable relative to each other. The system includes at least two sealing units, with each of the sealing units having at least two possible states or conditions, namely, a first state or condition for ensuring a tightness between the two parts and a second state or condition wherein it does not ensure a tightness. Each sealing unit is deformable and includes a drive arrangement for intermittently actuating each of the sealing units. | 8 |
BACKGROUND OF THE INVENTION
[0001] The present invention relates to metallo-organic cobalt compounds and their use in the prophylactic treatment of subjects to prevent chlamydia infections.
[0002] It has been discovered that certain conditions and diseases, e.g., inflammation, burns, wounds, and diseases caused by bacteria, fungi and viruses in mammalian species can be treated with certain complexes of cobalt having the structure:
[0003] wherein each A may be the same or different and is an alkyl group, a phenyl group or a substituted derivative of a phenyl group;
[0004] wherein each Y may be the same or different and is hydrogen, an unbranched alkyl group, a halide or a group having the structure
[0005] wherein R is hydrogen, an alkoxide group, and alkyl group, or OH;
[0006] wherein each B may be the same or different and each is hydrogen or an alkyl group;
[0007] wherein each X may be the same or different and each is a water soluble group having weak to intermediate ligand filed strength; and
[0008] Z — is a soluble, pharmaceutically acceptable negative ion.
[0009] Today, chlamydia infections are known to be significant causes of morbidity in human and veterinary medicine. Many of these infections present no noticable symptoms, yet can lead to sterility. New prophylactic treatments would decrease the incidence of these infections and improve overall health.
SUMMARY OF THE INVENTION
[0010] We have discovered a prophylactic use for the series of compounds having the structure:
[0011] wherein
[0012] each A may be the same or different and is an alkyl group, a phenyl group or a substituted derivative of a phenyl group;
[0013] each Y may be the same or different and is hydrogen, an unbranched alkyl group, a halide or a group having the structure
[0014] wherein R is hydrogen, an alkoxide group, an alkyl group, or OH;
[0015] each B may be the same or different and each is hydrogen or an alkyl group;
[0016] Z — is a soluble, pharmaceutically acceptable negative ion; and
[0017] each X may be the same or different and is an axial ligand selected from the group consisting of moieties having the formula:
[0018] wherein R 1 , R 2 , R 3 , and R 4 may be the same or different and maybe hydrogen or lower alkyl having from 1 to 4 carbon atoms; and
[0019] wherein R 5 , R 6 , R 7 , R 8 and R 9 may be the same or different and may be selected from the group consisting of electron donating groups and electron withdrawing groups;
[0020] with the proviso that R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are of a sufficiently small size so as not to prohibit the attachment of the axial ligand to the Co atom due to steric hindrance.
[0021] As used herein, the term “axial” when used in conjunction with the term “ligand” refers to the fact that the ligand is oriented outside the plane of the molecule and has the same meaning as described in connection with FIG. 1 of U.S. Pat. No. 5,049,557. As used herein, and unless otherwise indicated, an alkyl group means a linear, branched or cyclic alkyl group containing from one to six carbon atoms.
[0022] The compounds having the structure of Formula II exhibit prophylactic efficacy when applied as a topical composition to the contact site prior to contact with chlamydia and/or by inactivating chlamydia exposed to the composition. The compositions of the invention may further be used for antisepsis or disinfection of surfaces, such as, surgical tools or preparations such as, media or blood-derived products, which are contaminated with chlamydia.
DETAILED DESCRIPTION OF THE INVENTION
[0023] The compounds used in the present invention may be crystallized with numerous counter-anions. Counter-anions which are pharmaceutically acceptable and are water soluble, such as, halide ions, PF 6 — and BF 4 — , are preferred. The bromide and chloride salts of the present compounds are the most preferred because they are more water soluble than other salts of the compounds.
[0024] As discussed above, A may be an alkyl group, a phenyl group or a substituted derivative of a phenyl group. Preferably, the alkyl group is a C 1 -C 5 group with methyl, ethyl, and butyl groups being particularly preferred. Suitable substituted derivatives of the phenyl group are derivatives wherein each substituent is a halide, an alkyl group or a group having the structure
[0025] wherein R is hydrogen, an alkoxide group, an alkyl group or an OH group. To date, the most useful derivatives have proven to be those in which the substituents are halides, or alkyl groups.
[0026] Y may be hydrogen, an unbranched alkyl group, a halide or a group having the structure
[0027] wherein R is hydrogen, an alkoxide group, an alkyl group or an OH group. In certain embodiments, it is preferred that Y is chlorine, a hydrogen atom or a C 1 -C 3 alkyl group. In embodiments where Y has a structure
[0028] ,it is preferred that R is hydrogen, a methyl group or an OH group.
[0029] B may be hydrogen or an alkyl group, and preferably is a C 1 -C 3 alkyl group.
[0030] X may be imidazole or pyridinyl groups linked to the cobalt atom through a nitrogen of the ring. The imidazole or pyridinyl nuclei may have hydrogen atoms, or electron donating or withdrawing groups substituted thereon.
[0031] The electron withdrawing or donating groups which may constitute appendant groups R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are those known in the art to exert the specified electron withdrawing or donating effects on aromatic nuclei. Typical of electron donating groups are NO 2 — , Cl — , Br — , and the like. The identity of the particular group is not crucial so long as it does not impart properties to the molecules which are detrimental to the desired properties of the compound, e.g., decreased antiviral activity, increased toxicity, and the like. Additionally, the group must not be so large as to prevent the axial ligand to attach to the cobalt atom due to steric effects, e.g., steric hindrance.
[0032] Preferably, the groups attached to the imidazole nucleus are alkyl having from one to three carbon atoms. Of these, methyl and ethyl are most preferred. Preferred are the unsubstituted, 2-methyl, 4-methyl, and 2-ethyl imidazoles and the unsubstituted pyridinyl.
[0033] The following Table provides the structures of preferred compounds in accordance with the present invention. Compound 23, which is disclosed in U.S. Pat. No. 5,142,076 as exhibiting antiviral activity, is included as a comparison in the examples that follow.
[0034] In the following diagram, B is, in each case, methyl, and A, Y, X and Z — refer to those symbols as used in structure II.
COMPOUND Y X Z A 23 H —NH 3 Cl —CH 3 76 H Br —CH 3 82 H Cl CH 3 93 Cl Br —CH 3 96 H Br —CH 3 97 H Br —CH 3 98 H Br C 6 H 5 100 Cl Br —CH 3 101 Cl Br —CH 3 102 H Cl C 6 H 5 109 H Cl —CH 3
[0035] “Chlamydia” is used herein to mean any one or more of the bacteria in the genus chlamydia. The genus chlamydia includes the species C. pneumoniae, C. psittaci and C. trachomatis.
[0036] The compositions used in the instant invention include a pharmaceutically acceptable carrier and a compound as defined above in a chlamydia prophylactic effective amount. As used herein, the expressions chlamydia prophylactic effective amount, dosage or regimen mean that amount, dosage or regimen which results in a sufficient concentration of the particular compound at an appropriate site to reduce the risk of infection by chlamydia. By appropriate site, it is meant a site which potentially contains chlamydia or is an area of a subject of potential exposure to chlamydia or is an area of a subject that has been exposed to chlamydia but as a result of such exposure, the subject has not yet acquired chlamydia disease. As used herein, the expression acquired chlamydia disease means that the subject, in fact, has the disease and can no longer be treated prophylactically to reduce the risk of infection by chlamydia, but, rather, must be treated therapeutically to cure, ameliorate or reduce the effects of the disease.
[0037] For topical administration, the inventive composition may be placed in a pharmaceutically acceptable aqueous solution, ointment, salve, cream or the like. The compounds used in the present invention are water soluble, although the degree of solubility may vary from compound to compound, and may be dissolved in a number of conventional pharmaceutically acceptable carriers. Suitable carriers include polar, protic solvents, such as, water, or normal saline, or non-polar solvents, lipids and the like. The compounds may also be suspended in a suspension medium that is not miscible with water, for example, petrolatum, or may be formulated in an emulsion (water-in-oil or oil-in-water).
[0038] When the compounds of formula II are to be administered by the topical route for prevention of infection, i.e., prophylaxis or disinfection, their concentration in an aqueous solution, ointment, salve, creme, or the like can vary from about 0.00005% to about 5% by weight. A preferred concentration range lies between about 0.0005% and about 2% by weight. A particularly preferred concentration range is from about 0.5% to about 2%. Typically, the topical composition shows prophylactic effect when applied to the contact site from about 1 hour before contact with chlamydia to about 6 hours after contact with chlamydia. Preferably, the topical composition is applied within five minutes of contact with chlamydia. More particularly, the inventive compositions can be applied intravaginally for the prevention of sexually transmitted diseases. The topical composition containing the inventive compound could, for example, be applied with an applicator or an intravaginal device or the topical composition could be coated on a condom or other sexual barrier devices.
[0039] When the compounds of formula II are to be used for disinfecting liquid preparations, such as, media, blood-derived products or the like, their concentration in the liquid preparations is from about 0.005% to about 5% by weight. A preferred concentration range lies between about 0.05% and about 5% by weight. A most preferred concentration range lies between about 0.01% and about 2% by weight.
[0040] General methods for the synthesis of the compounds of the present invention are described in U.S. Pat. No. 5,049,557, referred to and incorporated by reference hereinabove. As noted therein, the reaction of Co(II) complexes with molar oxygen has been studied extensively (see, R. S. Drago and B. R. Corden, Acc. Chem. Res., 1980, 13, 353 & E. C. Niederhoffer, J. H. Timmons and A. E. Martell, Chem. Rev. 1984, 84, 137). Normally, cobalt (II) forms 2:1 peroxo bridged complexes in aqueous solutions (see E. C. Niederhoffer, J. H. Timmons and A. E. Martell, Chem. Rev. 1984, 84, 137). In recent years, a number of Co(II) complexes have been reported to give 1:1 cobalt-oxygen adducts at room temperature. These complexes usually contain ligands which when bound to Co(II) give rise to a low spin planar geometry. Addition of base and O 2 to these complexes leads to the formation of octahedral complexes where the base and the O 2 occupy axial positions (see, A. Summerville, R. D. Jones, B. M. Hoffman and F. Basolo, J.Chem. Educ., 1979, 56, 3, 157).
[0041] On the basis of measurements utilizing a variety of physical techniques, it is now a well-accepted fact that the most accurate electronic structure description of the CO:O 2 moiety is a Co(III) ion bound to O 2 — where the actual amount of Co→O 2 electron transfer depends on the nature of the ligand and the donor set (see, A. Summerville, R. D. Jones, B. M. Hoffman and F. Basolo, J. Chem. Educ. 1979, 56, 3 157, & D. Getz, E. Malmud, B. L. Silver and Z. Dori, J. Am Chem. Soc., 1975, 97, 3846). It has been shown that electron transfer increases with increase of the ligand field strength (see, R. S. Drago and B. R. Corden, Acc. Chem. Res., 1980, 13, 353). This can be easily understood from the molecular orbital diagram depicted in FIG. 1 of U.S. Pat. No. 5,049,557 and the description therein.
[0042] The following examples are provided to assist in further understanding the present invention. The particular materials and conditions employed are intended to be further illustrative of the invention and are not limiting upon the reasonable scope thereof.
EXAMPLE 1
[0043] Compounds for use with the present invention can be prepared by the following general procedure. In particular, a cobalt-II complex is prepared by mixing equimolar amounts of the N,N′-bisethylenediimine ligands, e.g., L23 and the like as disclosed in U.S. Pat. No. 5,049,557, with cobalt acetate in methanol under nitrogen. About 2.2 equivalents of the desired axial ligand is added followed by oxidation. The desired product may then be precipitated by the addition of a saturated aqueous solution of sodium chloride or sodium bromide followed by recrystallization from an ethanol-water solution.
[0044] Compound 96 (having bromide as the counterion) was synthesized as follows:
[0045] A 3-neck flask equipped with a nitrogen bubbler and a 2 liter dropping funnel was charged with 112 grams (0.5 moles) of the ligand (L23 or N,N′bis-(acetylacetone) ethylene-diimine) in 500 ml of absolute methanol. To the ligand solution is added 125 grams (0.5 moles) of cobalt acetate tetrahydrate dissolved in 1.5 liters of degassed methanol. The reaction mixture is stirred for 2 hours and then refluxed for 15 minutes on a hot water bath. An orange solution results to which 90 grams (1.1 moles) of 2-methyl imidazole dissolved in 100 ml of methanol are added. The reaction mixture is exposed to the open air while maintaining vigorous stirring. Ten grams of activated charcoal are added to the stirring mixture and the oxidation is continued overnight.
[0046] The mixture is then filtered and 50 grams of sodium bromide dissolved in a minimum amount of water is added to the filtered brown solution. The solution obtained is concentrated and allowed to crystallize. The crude product is recrystallized from hot ethanol-water solution by standing at room temperature or a lower temperature. The purity of the product is checked by elemental analysis, electronic spectra and NMR.
EXAMPLE 2
[0047] [0047] C. trachomatis elementary bodies were incubated for four hours on ice with different concentrations of Compound 96. At the end of that time, serial dilutions were performed on McCoy cell monolayers and the plates were incubated for two days, after which, C. trachomatis titers were enumerated.
[0048] When C. trachomatis was incubated with 5 mg/mL Compound 96, no inclusion bodies were detected. When the Compound 96 concentration was reduced to 0.5 mg/mL, there was a 93% reduction in the number of inclusion forming units. At 0.05 and 0.005 mg/mL Compound 96, the inhibitory effect was lost.
EXAMPLE 3
[0049] In a study of the mouse model, chlamydia infection was greatly reduced and hydrosalpingitis completely blocked by topical application of Compound 96 prior to challenge with chlamydia. Seventy-eight female Swiss Webster mice were pretreated with medroxyprogesterone acetate and were randomized into three groups to receive either saline (control) (24 mice), 0.5% Compound 96 (27 mice), or 2.0% Compound 96 (27 mice). The animals were anesthetized by intraperitoneal injection of sodium pentabarbital and then the vagina of each animal was swabbed with a moistened calcium alginate tipped swab. The animals were administered 15 μl of control or test compound intravaginally in one treatment. Twenty seconds later, they were challenged by intravaginal instillation with 15 μl of a suspension containing 5.0 log 10 infection forming units C. trachomatis mouse pneumonitis biovar (MoPn). Vaginal swabs were collected on days 3, 6 and 10 post-challenge to assess the effect of treatment on vaginal replication in the genital tract. In addition, on day 10, approximately half of the animals from each group were sacrificed, the upper genital tract harvested and the magnitude of chlamydia infection determined by quantitative culture. The remaining animals were sacrificed on day 35 post-challenge and the upper genital tract examined for evidence of hydrosalpingitis.
[0050] Outcome data for the study is presented in Table 1 below. All of the saline treated control animals developed lower tract infection which spread to the upper genital tract in all animals sacrificed on day 10 post-challenge. Treatment with 0.5% Compound 96 significantly reduced the number of animals which experienced lower genital tract replication but did not impact spread to the upper genital tract. In contrast, treatment with 2% Compound 96 significantly reduced the incidence of isolation of MoPn from both the lower and upper genital tract with the 3 animals that experienced lower tract replication being the only animals in which the organism was isolated from the upper genital tract. Quantitative culture data for Compound 96 treated animals from which the organism was isolated indicated that the titer of MoPn was not significantly reduced. Among animals that were sacrificed on day 35 post-challenge, 50% of controls had hydrosalpingitis in at least one of the oviducts. The incidence was not significantly reduced in animals that received 0.5% Compound 96, but again, 2% Compound 96 proved effective with none of the animals having hydrosalpingitis in either oviduct.
[0051] Table 1 below shows the effect of Compound 96 against genital chlamydia infection in a mouse model.
TABLE 1 Replication in Replication in Incidence Lower Tract Upper Tract of Group Having: Incidence a D3 Titer b Incidence c Titer d Hydrosalpingitis e Saline administered 24/24 2.9 ± 0.1 12/12 2.4 ± 0.1 6/12 0.5% Compound 96 21/27 f 2.8 ± 0.1 13/15 2.4 ± 0.1 5/12 administered 2.0% Compound 96 3/27 g 3.7 ± 0.1 3/16 g 2.7 ± 0.1 0/11 f administered
EXAMPLE 4
[0052] In another study of the mouse model, chlamydia infection was also greatly reduced by topical administration of Compound 96 prior to chlamydia challenge. Forty-eight Swiss Webster mice were pretreated with medroxyprogesterone acetate and were randomized into three groups to receive either saline (control) or 2.0% of Compound 96. In particular, sixteen mice received saline (control) twenty seconds prior to chlamydia challenge, sixteen mice received 2.0% Compound 96 five minutes prior to chlamydia challenge, and sixteen mice received 2.0% Compound 96 twenty seconds prior to chlamydia challenge.
[0053] The mice were anesthetized by intraperitoneal injection of sodium pentabarbital and then the vagina of each mouse was swabbed with a moistened calcium alginate tipped swab. The mice were then administered 15 μl of control or test compound intravaginally in one treatment. Either twenty seconds or five minutes later, they were challenged by intravaginal instillation with 15 μl of a suspension containing 5.0 log 10 infection forming units C. trachomatis mouse pneumonitis biovar (MoPn). Vaginal swabs were collected on days 3 and 6 post-challenge to assess the effect of treatment on vaginal replication in the genital tract. In addition, on day 10, the mice were sacrificed and the upper genital tract harvested and cultured to determine whether the mice had experienced ascending infection. The results are shown below in Table 2.
TABLE 2 Number Protected Number Protected Number Against in Against in Group Having: in group Lower Tract Upper Tract Saline administered 16 0 (0%) 0 (0%) 5 minutes prior to challenge 2% Compound 96 16 5 (31%) h 6 (38%) h administered 5 minutes prior to challenge 2% Compound 96 16 14 (88%) i 14 (88%) i administered 20 seconds prior to challenge
[0054] As in Example 3, all of the saline treated control mice developed lower and upper tract infection. Treatment with 2% Compound 96 twenty seconds prior to challenge provided good protection of both upper and lower genital tracts. The protection seen when Compound 96 was administrated five minutes before challenge was not as good as Compound 96 administrated twenty seconds prior to challenge. However, treatment with 2% Compound 96 five minutes before challenge significantly reduced the number of mice with lower and upper tract infection.
[0055] Thus, while there have been described what are presently believed to be the preferred embodiments of the present invention, those skilled in the art will realize that other and further embodiments can be made without departing from the spirit and scope of the invention, and it is intended to include all such further modifications and changes as come within the true scope of the invention. | The likelihood of chlamydia infection can be prevented by the topical application of metallo-organic cobalt compounds according to the following formula to the site of infection:
wherein each A may be the same or different and is an alkyl group, a phenyl group or a substituted derivative of a phenyl group; each Y may be the same or different and is hydrogen, an unbranched alkyl group, a halide or a group having the structure wherein R is hydrogen, an alkoxide group, and alkyl group, or OH; each B may be the same or different and each is hydrogen or an alkyl group; each X may be the same or different and each is a water soluble group having weak to intermediate ligand filed strength; and Z — is a soluble, pharmaceutically acceptable negative ion. Metallo-organic cobalt compounds may also be used to disinfect liquids which contain chlamydia. | 0 |
FIELD OF THE INVENTION
The invention relates generally to the field of communications, and more particularly to automated telephone and other telecommunications services.
BACKGROUND OF THE INVENTION
Telephone response systems, such as automated voice response units (VRUs) or others, raditionally rely on a human administrator to design the orderings of menus and information within the system. Thus, if the database and search logic are not properly installed, programmed or maintained, the familiar “Press 1 for billing inquiries, press 2 for order status . . . ” sequence may for instance require most callers to exhaust an entire list of options before reaching their desired selection. While techniques exist to make these systems easier to use by allowing voice rather than keypad entry of menu selections, there is no method to dynamically adjust the interface hierarchy based on caller usage.
As described in pending patents: Ser. No. 09/549,566 (entitled “Temporal Updates of Relevancy Rating of Retrieved Information in an Information Search System”); Ser. No. 09/549,669 (entitled “Implicit Rating of Retrieved Information in an Information Search System”); Ser. No. 09/549,568 (entitled “Usage Based Strength Between Related Information in an Information Retrieval System”); Ser. No. 09/751,934 (entitled “Automated Adaptive Classification System for Bayesian Knowledge Networks”); and provisional 60/314,796 (entitled “Method for Clustering Automation and Classification”), techniques exist where the information presented to users of a computer or Internet based question answering system changes dynamically, based on usage.
Such adaptive techniques have not however been incorporated into automated telephone systems, affecting the efficiency and user-friendliness of that type of support platform. Other problems exist.
SUMMARY OF THE INVENTION
The invention overcoming these and other problems in the art relates in one regard to a system and method for presenting a dynamic interactive interface to a user over a telecommunications network, for instance a wired or wireless telephone network. In an embodiment, the invention may be deployed, for instance, in a customer service department of a company that employs an automated phone system to provide answers to frequently asked questions. By incorporating the invention in such an automated phone or other system, callers can reach their desired information more quickly and with fewer inputs, without increasing administrative overhead. Historically telephone support systems may have caused customer dissatisfaction because of their lack of user-friendliness. However, the invention solves many of these problems while increasing system responsiveness.
In one aspect of the invention, the interactive selections made by callers in response to a voice or other menu may be captured and stored, for instance in a database. Data about those captured selections, such as their frequencies, times of day, duration and other parameters may be used to reconfigure the menu sequence, for instance so that menu selections which are historically made more frequently may be moved higher in the list for subsequent callers. Data may be captured from single callers, selected groups of callers or historical ensembles of all callers.
Thus, as each new caller selects an option, a usage counter on that menu item may for example increase. As each new caller bypasses that option to proceed to a subsequent peer level menu item the usage counter on the first item may in embodiments decrease. Over time, the menu items that have the highest visitation frequency may accumulate higher associated counts. The system may then present the menu options in revised order from the highest usage to the lowest usage, resulting in the most frequently selected options appearing earlier in the option listings.
In another aspect of the invention, the transitions between menu items may be captured and stored. These transitions may then be presented to subsequent callers as suggested options. In this regard, each transition from one menu option to another suggests that a caller finds those options related. As subsequent callers make the same transition, a usefulness counter may for instance be incremented on that transition to signify the strength of the relationship between the two options. In other embodiments, a directed graph connecting the two menu items may have an associated weight adjusted, such as in a Bayesian network. The system may then present a rank ordering of related menu options to callers who may otherwise have difficulty finding the desired option.
In another aspect of the invention, the usefulness rankings of each menu option and/or each menu option relationship, as described above, may be algorithmically decreased based on the last time the option was used. The invention in this regard may allow the menu options which have the most current interest to appear earlier in the list, while those options that were historically important but not currently useful may be moved further down the list.
In another aspect of the invention, when no caller usage data exists, such as in a recently initialized system, to allow the presentation of relationships between menu options, a method is available to automatically create relationships between similar items. In this embodiment the textual similarity between the contents of each menu item are analyzed and similar items may be related with a strength proportional to the relationship.
In another aspect of the invention, an automatic determination of the complete menu hierarchy may be generated. In this embodiment, the entire set of potential content to present in an automated telephone system may be analyzed for similarity and topic-subtopic relationships. The result is a dynamic creation of a complete menu system built by conceptual relationships. As new content is added to the system, options may be automatically added at the proper point within the menu hierarchy. Or, new content may be sufficiently distinct to cause a new hierarchy to be generated.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be described in detail below with reference to the attached drawing figures, in which like elements are referenced by like numbers, and in which:
FIG. 1 illustrates a telephone support environment in which an embodiment of the invention may operate.
FIG. 2 illustrates call processing in a dynamic telephone menu system according to an embodiment of the invention.
FIG. 3 illustrates call processing in a dynamic telephone menu system, according to an embodiment of the invention.
FIG. 4 illustrates generation of related menu choices by caller use, according to an embodiment of the invention.
FIG. 5 illustrates the use of relationships generated as in FIG. 4 , according to an embodiment of the invention.
FIG. 6 illustrates an automatic aging of usefulness information, according to an embodiment of the invention.
FIG. 7 illustrates call processing for automatic generation of relationships, according to an embodiment of the invention.
FIG. 8 illustrates processing for automatic generation of phone system menu groupings, according to an embodiment of the invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The invention in one regard relates to a system and method for presenting a dynamic interface over a telecommunications network, for instance a voice menu over a telephone system. For illustrative purposes, an embodiment of the invention is discussed below with reference to a customer support department that uses an automatic (self-service) phone answering system as a platform for customer communication and support. This is only an example of an operating environment, and is not intended to suggest any limitation in the scope of using or functionality of the invention. Neither should it be interpreted as implying any dependency or necessity of any one or combination of components illustrated in the exemplary operating environment.
FIG. 1 illustrates one such operating environment for an embodiment of the invention, in which one or more callers may use one or more transmission devices 102 a , 102 b . . . 102 n (n arbitrary) to communicate with a call center 104 , for instance to inquire about customer support, warranty, financial, billing or other information. The transmission devices 102 a , 102 b . . . 102 n may each be or include, for instance, conventional telephones communicating via plain old telephone service (POTS), wireless cellular phones or other mobile devices, voice over Internet Protocol (VoIP) clients, telephones connected via DSL or ISDN lines, or other communication devices. The call center 104 may include a voice response unit 106 , which may be capable of presenting callers with an automated voice menu. The voice menu may for instance be or include recorded human voices, or synthetic voices in different embodiments. Voice response unit 106 may for instance accept keypad inputs, voice or other inputs or responses from callers. The call center 104 may include an automatic call distributor 108 which may distribute incoming calls, selected calls or classes of calls from the one or more transmission devices 102 a , 102 b . . . 102 n to at least one of customer support stations 110 a , 110 b . . . 110 n (n arbitrary). Customer support stations 110 a , 110 b . . . 110 n may for example be or include computer workstations attended by human operators.
The call center 104 may also include a call server 112 , communicating with voice response unit 106 and automatic call distributor 108 . Call server 112 may likewise communicate with database 114 , for instance to access and store user account information, incoming or outgoing call time, duration, caller inputs and other parameters.
FIG. 2 illustrates interactive processing to present a voice menu interface according to an embodiment of the invention. Processing may begin at step 202 . In this embodiment, a call may be received in step 204 , for instance from a caller using one of transmission devices 102 a , 102 b . . . 102 n to connect with a dynamic phone menu, presented by voice response unit 106 or otherwise. The caller may be presented with an audible list of selectable items or options available on the system in step 206 . These might be, for example, “Support for my Widget” and “Support for my Gadget” with for example the first item representing the option which callers have historically chosen most frequently.
The audible menu sequence may in embodiments be interruptable, for instance by keypad or voice input, when a caller wants to supply a selection or other information while a menu item is playing. In embodiments, voice menu items may be simultaneously or alternatively presented via a text or graphical interface, for instance on the screen of a cellular phone having short message service (SMS) or other messaging capability, or otherwise.
The caller may select one of the two or more “Widget”, “Gadget” or other menu items in step 208 . When selected, a usefulness score stored in a usefulness counter 116 , for instance stored in database 114 , for that item may be increased after the selection, in step 210 . Should this selection cause a lower ranking menu item to receive a higher usefulness ranking than another item, that item may be elevated to an earlier point in the menu sequence for subsequent callers. In the illustrative case, the “Widget” item might for example have a usefulness score of 4 and “Gadget” might have a usefulness score of 3. The caller may accordingly be presented with “Widget” first, and “Gadget” second. Selecting “Gadget” may cause the “Gadget” item to increase to a usefulness score of, for example, 5, and the next caller may be presented with “Gadget” first and “Widget” second. Other scoring and ordering schemes may be used. In step 212 , processing ends.
FIG. 3 illustrates another call interaction, along the same general lines as that illustrated in FIG. 2 . Processing may begin in step 302 . A call may be received in step 304 , followed by option presentation in step 306 and the caller selecting an item, illustratively item “A”, in step 308 . In this embodiment, after the caller selects one item that was ordered on usefulness, the usefulness counter 116 for that item (“A”) may likewise be increased in step 310 . The caller may then return to the original menu as part of the same call, in step 312 . The menu list may be rank ordered based on all available usage information at the time. The caller may subsequently select a different item in step 314 , illustratively item “B”. In step 316 , the usefulness count of item “A” may be changed, for instance decreased to reflect the skipping over of that item, while the usefulness count of item “B” may increase. Selecting the new item may cause the prior selected item's usefulness score to decrease, and increase the current item's usefulness score. In embodiments, that action may cause some or all prior items in the same call to decrease in score as well. Processing may repeat through different menu items, and if not in step 318 processing may end.
In embodiments, the decrease in score or rank on a prior item or items generated for instance according to the process illustrated in FIG. 3 may cause the item to receive either a lower value than it had before the original interaction, a value equal to the value before the original interaction, or a value greater than the original value before the initial interaction, depending on implementation. In this case, the system may have a “Widget” item with for example a score of 4 and “Gadget” item with a score of 3. A caller initially selecting the “Gadget” item as an option may cause the “Gadget” score to increase to 5. Subsequently, the same caller may select the “Widget” item. “Widget” may then increase to a score of 6, while “Gadget” may then decrease to 4. Numbers used for increasing or decreasing a score may vary depending on implementation. For instance, values by which a score increases may be greater than or equal to that by which they decrease, or either may be made a function of the current item score, or of other parameters. Whole number, binary, decimal or other values may be used for scores, in different embodiments.
FIG. 4 illustrates an interactive process in which relationships between information items in a telephone response system are generated, according to an embodiment of the invention. In this embodiment, processing may begin in step 402 , and a call may be received in step 404 . For instance a caller may connect with a voice menu presented by voice response unit 106 or otherwise. Menu items may be presented as options in step 406 , and a user may select an item in step 408 , for instance by spoken input decoded by voice recognition or keypad input, and select an information item, such as a checking account balance. Subsequently, in step 410 the caller may return to the same or a different menu and select a different information item in step 412 , for instance a savings account balance. The system may detect that this caller has visited two information items in order, and build or strengthen an ordered or unordered relationship between these two items in step 414 . The relationship may be represented, for instance, by a normalized weighting score or otherwise. The system may similarly build relationships between any two or more items in immediate sequence, or between any two or more items in the history of the call or prior calls, of that caller or others.
FIG. 5 shows an embodiment illustrating how a caller may interact with menu item relationships generated according to the embodiment illustrated in FIG. 4 . Processing may begin in step 502 , and a call may be received in step 504 . A caller may for instance connect with a voice menu in step 506 , and in step 508 the caller may select an information item, for example the “Widget” item. After listening to the information item, in step 510 the caller may be presented with the option of listening to a related item, for instance the “Gadget” item as for instance discussed in the example related to FIG. 3 . In step 512 , the system may present an item determined to be related to the selected item, according to the process illustrated in FIG. 3 or otherwise. The caller may in embodiments be given a choice between all related items, or only the most related item, the three most closely related items, or items related in other ways. In embodiments, a caller's past set of menu selections may be stored in database 116 or otherwise, for selection, retrieval, modification or other purposes. Processing may repeat for different menu items. In step 514 , processing may end.
FIG. 6 illustrates a method for decreasing the visitation score on “old” items, as for instance shown in FIGS. 2 , 3 and 4 or otherwise. In this regard, “old” may refer to any item that has been visited prior to the current call. In step 602 , processing may begin. In step 604 , “old” items may be detected for a given caller or otherwise. The measure of what is “old” may be a configurable parameter, or may be statistically derived from the system information, for instance call data captured in database 114 . Visitation times may be kept associated with usefulness or relatedness scores previously described, or otherwise. In embodiments, once an item is detected to be older than a desired age, the usefulness score of that item may be decreased in a step 606 by multiplying by an adjustment factor, for instance between 0 and 1 (inclusive), or otherwise. Items so modified may also have their visitation time updated to the current time in step 608 , to signify that they have been recently manipulated. In step 610 , processing may end.
FIG. 7 illustrates how item relationships for instance generated according to the embodiment of FIG. 5 may be automatically generated to indicate a similarity relationship, without necessarily operating on historical call data. In step 702 , processing may begin. In step 704 , a similarity score may be detected indicating a similarity between a currently selected item and some or all other menu items. These automatically generated relationships may be used for example to start a newly initialized system, or applied to systems which are already operating. Similarly, systems whose set of information items change over time may in embodiments use this initializing feature to augment item relationships generated by human callers, for example because those new relationships may be sparse during the break-in period for new items. In embodiments, the relationship score between each item and every other item may be generated in pairwise fashion. These relationships may for instance be generated by matching the text from the content of each item, by correlating item types or hierarchical locations in a menu, or by other techniques. In step 706 , a relationship between a current item and some or all other items may be generated according to the strength of the similarity score.
The score associated with an item relationship may for instance be a function of the degree of relatedness between the item pair. If the pair is deemed sufficiently unrelated, no usefulness score, or a zero score, may be generated for that pair. Once the score for a pair relationship is generated, if the process illustrated in FIG. 6 is used, in step 708 the caller visitation time may be calculated appropriately. In step 710 processing may proceed to a next item in the menu. This process may be repeated until all potential relationships have been examined, testing for the final item in step 712 . This process may exhaustively evaluate all item pairs in the database, or in embodiments may include an optimization to eliminate some pairs from consideration, for instance those with no possible relation. Any clustering algorithm which allows pairwise consideration of information items may be employed in this process. In step 714 , processing may end.
FIG. 8 illustrates processing that may be used to generate a clustered menu structure based on examination of component information items, according to an embodiment of the invention. In step 802 , processing may begin. In step 804 , clusters of similar items in the menu space may be detected. Detection may be accomplished using a clustering algorithm to generate groups of similar items. In embodiments, the clustering algorithm may generate a hierarchical result, but this is not required in the general case. Upon completion of clustering, a set of classification rules to allow categorization of new information items may optionally be installed in step 806 . This may allow the system to change the number and content of information items, without changing the menu groupings generated by the clustering process. A label may be generated in step 808 , to associate with the item groupings to provide a descriptive label for each menu item generated in the clustering in step 804 .
In step 810 , menus may be made available for presentation to callers as in embodiments shown in FIGS. 2 , 3 , 4 , and 5 or otherwise. If desired, the system may support operations such as the addition of new items, deletion of existing items, or changing of existing items as shown in step 812 . Deletion of an item may remove it as a possible menu selection. On addition or change of an item, the previously learned classification rules may be applied to the new or modified items to determine the placement of the item in the menu hierarchy. These changes to the menu sequence or content may require a re-generation of labels for affected menu categories, and a return to labeling or other processing steps. Additionally, as an optional process, in step 814 the system may detect when a threshold of acceptable change in the information items in the menu system has been exceeded, in which case the process may automatically repeat from the clustering step. In step 816 , processing may end.
One step which may be included (not illustrated in FIG. 8 ) is to apply a heuristic or other optimization to the menu structure based on other desired parameters, such as total number of options presented at one time (for example, between 2 and 9 to allow single keystroke selection), total number of menu selections necessary to reach an item (for example, information items must be available within no more than 3 menu selection operations), or other hierarchical or other optimizations or rules. For instance, in an embodiment the call center 104 may detect the area code or telephone number of a call, as well as the time and date of a call, using for instance Caller ID or automatic number identification (ANI) or other protocols, and use that data as a selector into a menu type, plaint in a menu sequence, to adjust scores on usefulness, relatedness or other parameters, or for other purposes.
The foregoing description is illustrative, and variations in configuration and implementation may occur to persons skilled in the art. For instance, while the invention has been generally described in terms of a caller accessing a single menu sequence generated by a single voice response unit, in embodiments multiple menus may be presented, in serial or contingent fashion, which in embodiments may be generated by multiple voice response units or other platforms.
Likewise, while the invention has been described generally in terms of a telephone-type connection over which keypad or voice inputs may select items from a menu, in embodiments other inputs or selectors may be used, for instance keyboard inputs from a computer when communication takes place via VoIP or other protocols. Furthermore, while the menu has been generally described as being presented as a sequence of audible voice messages, in embodiments concurrent or separate graphical or textual presentation of some or all of a menu may be implemented, for instance via a teletype (TTY) interface to a telephone, or via a graphical presentation of menu items on a screen of a cellular phone, with or without simultaneous voice presentation.
For further example, while the invention has generally been described as involving an automated response to a caller using a voice response unit 106 and other resources, in embodiments a given call may be first handled by distribution to one of workstations 110 a , 110 b . . . 110 n for human intervention first, followed by automated handling, or the call may be transferred from automated processing by the voice response unit 106 to one of workstations 110 a , 111 b . . . 110 n alter a predetermined time, or based on user input. The scope of the invention is accordingly intended to be limited only by the following claims. | A system, method, and computer program product for dynamically adapting selections in an automatic phone support system is described. The invention may integrate a dynamic knowledge base of responses with the menu selections on an automated phone system or other response system to present the most frequently used items earlier in the option list, or otherwise order options and information. Call data may be captured from single callers or historical ensembles of callers. An automatically generated similarity relationship may be used to initialize the system without historical call data, based on textual similarity or other techniques. Prioritization of options provides a more enjoyable, efficient experience for callers without increasing administrative overhead. | 8 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a high-purity water producing apparatus suitable for use in the electronic industry and the like. For the purpose of the invention, "high-purity water" refers to highly pure water including so-called deionized water, ultrapure water and ultrahigh-purity water that can be produced by removing suspended solids, ions and non-ionic substances to an achievable extreme extent.
2. Prior Art
There has been a large demand for high-purity water in various industrial fields including the semiconductor device manufacturing industry, the pharmaceutical industry and the food processing industry, and a number of high-purity water producing apparatus have been proposed to meet this demand. Such apparatus include those comprising a pretreatment unit for removing suspended solids contained in raw water, a deionization unit for removing ions from pretreated water and a non-ionic substance removing unit for removing non-ionic substances from pretreated water.
However, currently available high-purity water producing apparatus have certain drawbacks. Firstly, there is a problem of high initial cost and high running cost that need to be reduced as much as possible, as is the case with other plants and equipment used in the industry. Secondly, there is a problem that the amount of waste water produced as a by-product of the process of producing high-purity water has to be reduced from the viewpoint of environmental protection. High-purity water producing apparatus that do not comprise any chemical-regeneration type ion exchange unit have been attracting attention in recent years as they can address the above problems. In those apparatus, the conventional chemical-regeneration type ion exchange unit is replaced by a reverse osmosis membrane unit, an electrodeionization unit (hereinafter referred to as an "EDI" unit) or a distillation unit that utilizes waste heat.
These new apparatus compare favorably with the conventional apparatus in that they do not require a regeneration unit and therefore do not produce waste water that normally contains salts to a considerably high concentration so that the plant having such an apparatus may do with a small facility for waste water treatment to consequently reduce the cost of waste water disposal and enhance the effect of environmental protection.
Apart from the above discussed problems, it has been found as a result of recent developments of analysis techniques that high-purity water produced from a high-purity water producing apparatus comprising a pretreatment unit, a deionization unit and a non-ionic substance removing unit is accompanied by a problem of containing boron at a significant concentration. This is considered to be a problem that must be seriously dealt with.
Boron contained in high-purity water attracted little attention in the past but, as it has become known that boron contained in high-purity water is a problem, currently there is a demand for means and measures for removing boron from high-purity water. Problems that have been pointed out for high-purity water with boron contained to a significant concentration include the following. The threshold voltage of an n-channel transistor formed on a substrate depends on the boron concentration of the substrate. Thus, the use of high-purity water containing boron to a high concentration level for cleaning wafers makes it difficult to control the boron concentration of the substrate and can result in the production of defective devices. Additionally, while minute n-channel MOS transistors have been designed and manufactured in response to a higher degree of integration for semiconductor devices, the manufacture of such minute devices requires the distribution pattern of boron concentration across the depth of the substrate to be accurately controlled in order to prevent a punch through effect from appearing. This in turn requires the use of high-purity water with a sufficiently low boron concentration in the course of manufacturing the devices. In the pharmaceutical industry, on the other hand, high-purity water to be used for manufacturing medicines is required to have a low concentration level for any impurities including boron. The boron contained in high-purity water has its origin in industrial water drawn from rivers and wells and containing boron to a concentration of several tens of ppb. While known apparatus for producing high-purity water is normally provided with a deionization unit, any existing deionization units cannot satisfactorily remove boron.
According to research carried out by the inventor of the present invention, while a high-purity water producing facility provided with a chemical-regeneration type ion exchange unit (for example a 2-bed type ion exchanger with a degasifier or a mixed-bed type ion exchanger) shows boron leakage in a relatively early stage of operation, the boron concentration of the high-purity water produced by such a facility can be reduced by increasing the frequency of the regenerating operation. On the other hand, the reverse osmosis membrane unit, the EDI unit and the distillation unit leak out boron respectively by about 60%, 25% and 65 on a constant basis so that it is practically impossible to satisfactorily remove boron from high-purity water by means of these units.
Thus, while known high-purity water producing apparatus comprising an EDI unit and some other deionization units have the advantages of not using any chemicals for regeneration, they are not suitable for producing boron-free high-purity water.
This problem will be discussed in greater detail by referring to FIG. 5 of the accompanying drawings which illustrates a known high-purity water producing apparatus comprising a non-chemical-regeneration type double pass RO unit. As shown in FIG. 5, the apparatus comprises a pretreatment unit 101 for removing suspended solids from feed water by coagulation/sedimentation/filtration or by suspended solids removal membrane, a decarbonator 102 for removing carbonic acid from the filtered water, where acid such as hydrochloric acid is added to the water and causes the latter to be exposed to air in an acidic atmosphere, although the water may be simply exposed to air without adding acid if it contains carbon dioxide to a large extent as in the case of underground water, and a double pass RO arrangement using a first reverse osmosis membrane unit 103 designed to eliminate ionic impurities and non-ionic organic substances and particles from the decarbonated water by adding alkali such as sodium hydroxide at the inlet port thereof to increase the pH of the water to a pH level of about 8.5 and turn the dissolved carbonic acid into bicarbonate ions and a second reverse osmosis membrane unit 104 for further treating the water after increasing the pH of the water to a pH level of about 9.5 by adding alkali at its inlet port.
The apparatus further comprises a vacuum degasifier 105 for expelling gases such as nitrogen, oxygen and carbon dioxide still contained in the water coming from the double pass RO unit and a non-regenerative type ion exchanger 106 containing a mixture of strongly acidic cation exchange resin and strongly basic anion exchange resin to produce primary deionized water having a specific resistivity of about 18 MΩ·cm.
While the primary deionized water produced by the apparatus as shown in FIG. 5 may be used as cooling water for manufacturing semiconductor devices, and water for washing quartz-made tools and other applications, it has to be forwarded to a secondary water deionizing system comprising a deionized water tank 107, an UV oxidizer 108, a cartridge polisher 109 and a membrane separation unit 110 to produce secondary deionized water to be sent to the points of use if high-purity water is to be used for washing silicon wafers. The series of units arranged upstream of the deionized water tank 107 is normally referred to as the primary water deionizing system. In the secondary water deionizing system, the UV oxidizer 108 decomposes organic substances into organic acids and carbonic acid and the cartridge polisher 109 removes organic acids and carbonic acid as well as other impurities contained to a small extent, whereas the membrane separation unit 110 removes fine particles from the water by means of an ultrafiltration membrane, micronic filtration membrane or reverse osmosis membrane. Note that the deionized water tank 107, the UV oxidizer 108, the cartridge polisher 109 and the membrane separation unit 110 are arranged to form a closed loop so that high-purity water may be constantly circulating there until drawn into any point of use in order to protect it against contamination by bacteria that occurs when water becomes stagnant.
While the known high-purity water producing apparatus of FIG. 5 which is a non-regenerative type apparatus having a configuration as described above and comprising a double pass RO unit as its principal deionization unit is advantageous in that it does not use any regenerating chemicals, it inevitably leaks out boron at a level of ppb from the initial stages of operation as shown in Table 1 below to make it inappropriate for producing boron-free deionized water. The boron concentrations listed in Table 1 are determined by means of an ICP-MS (inductively coupled plasma mass spectrometer).
TABLE 1__________________________________________________________________________ Non-regenerationPoint of EDI unit Distillation Double pass RO type ion Membraneanalysis Raw water outlet unit outlet unit outlet exchanger outlet separation__________________________________________________________________________No. 1 53 ppb -- -- 24 ppb 15 ppb 7 ppbconventionalapparatus(FIG. 5)No. 2 53 ppb 8 ppb -- -- 5 ppb 3 ppbconventionalapparatus(FIG. 6)No. 3 53 ppb -- 21 ppb -- 13 ppb 8 ppbconventionalapparatus(FIG. 7)__________________________________________________________________________
FIG. 6 illustrates another known high-purity water producing apparatus, which differs from the apparatus of FIG. 5 in that the decarbonator 102 of FIG. 5 is omitted and the first and second reverse osmosis membrane units 103 and 104 of the double pass RO arrangement are replaced by an RO unit 120 and an EDI unit 121, while the vacuum degasifier 105 is replaced by a membrane degasifier 122. Since the remaining components of this apparatus are identical with their respective counterparts of the apparatus of FIG. 5, they are denoted by the same reference numerals and will not be described any further. This non-chemical-regeneration type high-purity water producing apparatus comprising an EDI unit, again, leaks out boron of a ppb concentration level at the exit of the most downstream membrane separation unit 110 as shown in Table 2.
FIG. 7 illustrates still another known high-purity water producing apparatus realized by replacing the double pass RO arrangement of units 103 and 104 by an RO unit 130 and a distillation unit 131 and a membrane degasifier 132 is placed upstream of the UV oxidizer 108 in the secondary water deionizing system. Otherwise, the apparatus has a configuration the same as that of FIG. 5, and therefore the components are denoted by the same reference numerals and will not be described any further. This known deionized water producing apparatus comprising a distillation unit 131, again, leaks out boron of a ppb concentration level at the exit of the most downstream membrane separation unit 110 as shown in Table 1.
In view of the above observations, if can be seen that any non-regeneration type high-purity water producing apparatus comprising a reverse osmosis membrane unit, an EDI unit or a distillation unit as a principal deionization unit has little effect on removing boron, although such apparatus is effective for cost reduction and environmental protection.
SUMMARY OF THE INVENTION
It is therefore the object of the invention to provide a non-regeneration type high-purity water producing apparatus having a characteristic feature of known similar apparatus of being free from the problem of waste liquid disposal and hence having an excellent effect of environmental protection and also being capable of effectively removing boron which is a contaminant attracting particular attention in recent years.
According to the invention, the above object is achieved by providing a high-purity water producing apparatus comprising a pretreatment unit and a deionization unit respectively for removing suspended solids and ions contained in raw water, wherein said deionization unit includes at least a double pass RO unit, an electrodeionization type ion exchanger or a distillation unit or any combination thereof and the apparatus additionally comprises a boron removing unit placed downstream of the deionization unit for bringing the water treated by the deionization unit(s) into contact with a boron-selective ion exchange resin.
Any boron-selective ion exchange resin can be used for the purpose of the present invention so long as it selectively adsorbs boron. Specific examples of such boron-selective ion exchange resin include AMBERLITE (trade name: available from Rome and Haas Company), IRA-743T and DIAION CRB02 (trade names: available from Mitsubishi Chemical Industries Co., Ltd.) prepared by introducing polyvalent alcohol groups as functional groups. It is a prerequisite for a high-purity water producing apparatus according to the invention to use a boron-selective ion exchange resin. Since a known high-purity water producing apparatus using the standard strongly basic anion exchange resin can start leaking out boron at a high concentration very quickly, the ion exchange resin has to be replaced very frequently if the resin is of the non-regeneration type or it has to be chemically regenerated very frequently if it is of the regeneration type. Thus, in any case, such a known non-regeneration type high-purity water producing apparatus comprising a reverse osmosis membrane unit, an EDI unit or a distillation unit or a combination thereof as a principal deionizing component(s) may lose its advantages when the strongly basic anion exchange resin (regeneration type) is employed for the purpose of boron removal.
For the purpose of the present invention, "bring water into contact with" boron-selective ion exchange resin refers to feeding water to an ion exchanger column filled with boron-selective ion exchange resin. Such an ion exchanger column may also contain ion exchange resin of some other type in the form of a mixture or in different layers. While an apparatus according to the invention is not subject to any particular structural limitations, the use of a chemical-regeneration type boron removing unit undermines the merit of an otherwise non-regeneration type high-purity water producing apparatus. Thus, a boron removing unit is preferably placed downstream of the reverse osmosis membrane unit, the EDI unit or the distillation unit or a combination thereof. More specifically, it should better be placed at the downstream end of the primary water deionizing system (directly upstream of the deionized water tank) or in the secondary water deionizing system.
Preferably, a pretreatment unit should be arranged upstream of the deionization unit. It may be of any type such as in-line coagulation/coagulation/sedimentation, filtration, filtration, active carbon filtration or suspended solids removal membrane.
A high-purity water producing apparatus according to the invention comprises at least a double pass RO unit, an EDI unit or a distillation unit or a combination thereof for deionization and, additionally, it may comprise a non-regeneration type ion exchanger. If a non-regeneration type ion exchanger is used, it should preferably be placed downstream of the double pass RO unit, the electro-regeneration type deionization unit or the distillation unit or a combination thereof in order to minimize the frequency of replacement of the ion exchanger.
Since the boron-selective ion exchange resin in the above arrangement may leak out organic substances to a significant extent, a UV oxidizer designed to decompose organic substances and a membrane separation unit such as a reverse osmosis membrane unit designed to remove the decomposition products may preferably be placed downstream of the boron removing unit.
While certain arrangements for post-treatment are preferable to maximize the effect of installing a boron removing unit as described above, a high-purity water producing apparatus according to the invention may otherwise have any configuration as a non-regeneration type apparatus, such as the one illustrated in any of FIGS. 5 through 7, without limitations.
For the purpose of the invention, double pass RO is an arrangement where the water coming from a first RO unit (reverse osmosis membrane unit) is treated by a second RO unit to produce high-purity water. In addition to a simple two stage arrangement of RO units, an arrangement of regulating the pH level of the water coming from the first RO unit to improve the efficiency of removing free carbon dioxide from the water (as disclosed in Japanese Patent Application Laid-Open No. Hei 6-31272) may also be used for the purpose of the invention.
For the purpose of the invention, an EDI unit refers to any known deionized water producing unit having a configuration as described below. In an EDI unit, a mixture of anion exchange resin and cation exchange resin or a mixture of anion exchange fiber and cation exchange fiber is filled in the space between a cation exchange membrane and an anion exchange membrane in a deionization chamber and feed water is made to pass through the ion exchange layer, while a DC current is applied perpendicularly to the flowing water by way of the ion exchange membranes to electrically transfer ions contained in the flowing water into the concentrate brine flowing outside the ion exchange membranes in order to produce deionized water (as disclosed in Japanese Patent Application Laid-Open No. 4-71624).
For the purpose of the invention, a distillation unit is a unit for producing distilled water by means of a known ordinary distillation method. Known distillation units for producing highly pure distilled water include a distilled water producing unit using a multi-effect distillation technique (such as the one available from Organo Aqua) and MIRACLE PURE SERIES (trade name: Hitachi Shipbuilding and Engineering).
Thus, a high-purity water producing apparatus according to the invention can solve a serious problem which otherwise constrains the areas of application of any non-regeneration type apparatus by removing boron contained in raw water by means of a boron removing unit and, therefore, maximally exploit the advantage of a non-regeneration type apparatus comprising a reverse osmosis membrane unit, an EDI unit or a distillation unit or a combination thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a flow chart showing the configuration of an embodiment of high-purity water producing apparatus according to the invention and comprising a non-regeneration type double pass RO unit as a principal deionization unit.
FIG. 2 is also a flow chart showing the configuration of another embodiment of high-purity water producing apparatus according to the invention and comprising a non-regeneration type double pass RO unit as a principal deionization unit.
FIG. 3 is a flow chart showing the configuration of still another embodiment of high-purity water producing apparatus according to the invention and comprising a non-regeneration type EDI unit as a principal deionization unit.
FIG. 4 is a flow chart showing the configuration of still another embodiment of high-purity water producing apparatus according to the invention and comprising a non-regeneration type distillation unit as a principal deionization unit.
FIG. 5 is a flow chart showing the configuration of a conventional high-purity water producing apparatus comprising a non-regeneration type double pass RO unit as a principal deionization unit.
FIG. 6 is a flow chart showing the configuration of another conventional high-purity water producing apparatus comprising a non-regeneration type EDI unit as a principal deionization unit.
FIG. 7 is a flow chart showing the configuration of still another conventional high-purity water producing apparatus comprising a non-regeneration type distillation unit as a principal deionization unit.
DETAILED DESCRIPTION OF THE INVENTION
Now, the present invention will be described by referring to the accompanying drawings that illustrate preferred embodiments of the invention.
Embodiment 1
FIG. 1 is a flow chart showing the configuration of a first embodiment of high-purity water producing apparatus according to the invention and comprising a boron removing unit 1 that contains boron-selective resin (AMBERLITE IRA-743T: see above) and is placed between a vacuum degasifier 105 and a non-regeneration type ion exchanger 106.
This embodiment comprises a pretreatment unit 101 for removing suspended solids from raw water by coagulation/sedimentation/filtration or by suspended solids removal membrane, a decarbonator column 102 for removing carbonic acid from the filtered water, where acid such as hydrochloric acid is added to the water as necessary and causes the latter to be exposed to air in an acidic atmosphere, and a double pass RO arrangement using a first reverse osmosis membrane unit 103 designed to eliminate ionic impurities and non-ionic impurities such as organic substances and particles from the decarbonated water and a second reverse osmosis membrane unit 104 for further removing impurities. If necessary, the pH level of the water to be treated by RO may be regulated by adding an alkali agent such as sodium hydroxide as in the case of conventional apparatus mentioned earlier.
The embodiment further comprises a vacuum degasifier 105 for expelling gases such as nitrogen, oxygen and carbon dioxide still contained in the water coming from the double pass RO unit and a boron removing unit 1 containing boron-selective resin and placed downstream of the vacuum degasifier 105. Then, there is a non-regenerative type ion exchanger 106 containing a mixture of strongly acidic cation exchange resin and strongly basic anion exchange resin to produce primary deionized water having a resistivity of about 18 MΩ·cm and a reduced boron concentration of <10 ppt.
The produced primary deionized water is forwarded to a secondary water deionizing system comprising a deionized water tank 107, an UV oxidizer 108, a cartridge polisher 109 and a membrane separation unit 110 to produce secondary deionized water to be sent to the point of use.
For the purpose of the invention, a non-regeneration type ion exchanger 106 is preferably placed downstream of a boron removing unit 1, as in the above described embodiment, because the TOC (total organic carbon) leached from the AMBERLITE IRA-743T filled in the boron removing unit can be removed by the non-regeneration type ion exchanger.
Thus, the above embodiment that does not comprise any chemical-regeneration type deionization unit but comprises a double pass RO unit for deionization can effectively produce boron-free high-purity water continuously for a long time without generating any chemical regenerant wastes, thereby fully exploiting the advantages of a non-regeneration type apparatus.
Embodiment 2
FIG. 2 is a flow chart showing the configuration of a second embodiment of high-purity water producing apparatus according to the invention. This embodiment differs from the first embodiment of FIG. 1 in that the boron removing unit 1 (in FIG. 1) filled with AMBERLITE IRA-743T is moved to between the deionized water tank 107 and the UV oxidizer 108 and is denoted by reference numeral 2. Otherwise, this embodiment is exactly the same as the first embodiment.
This embodiment is advantageous over the first embodiment in that the anion concentration of the deionized water sent to the boron removing unit is even lower than that of the corresponding deionized water produced by the first embodiment, disregarding the negative boron ions, because the boron removing unit 2 is placed downstream of the deionized water tank 107 in the secondary water deionizing system. While the resistivity of the water flowing into the boron removing unit 1 of the first embodiment is about 5 MΩ·cm, that of the water flowing into the boron removing unit 2 of the second embodiment is greater than 18 MΩ·cm, meaning that the latter boron removing unit can be used for a prolonged period of time (about four times longer on the basis of the above resistivities) due to the reduced loading imposed on the boron-selective ion exchange resin contained in it.
Embodiment 3
FIG. 3 is a flow chart showing the configuration of a third embodiment of high-purity water producing apparatus according to the invention. This embodiment can be realized by arranging a boron removing unit 3 filled with AMBERLITE IRA-743T between the membrane degasifier 122 and the non-regeneration type ion exchanger 106 of the known primary water deionizing system of FIG. 6.
Since this embodiment comprises an EDI unit 121 as a principal deionization unit and does not have any chemical-regeneration type deionization unit, it can produce boron free high-purity water continuously for a prolonged period of time, while exploiting the advantages of a non-regeneration type apparatus.
The boron removing unit 3 may alternatively be placed between the deionized water tank 107 and the UV oxidizer 108 of the secondary water deionizing system. Such an arrangement can further prolong the service life of the boron removing unit 3 for the reason discussed above with reference to the second embodiment.
Embodiment 4
FIG. 4 is a flow chart showing the configuration of a fourth embodiment of high-purity water producing apparatus according to the invention. This embodiment can be realized by placing a boron removing unit 4 filled with AMBERLITE IRA-743T between the distillation unit 131 and the non-regeneration type ion exchanger 106 of the conventional primary water deionizing system of FIG. 7.
Since this embodiment comprises a distillation unit 131 as a principal deionization unit and does not have any chemical-regeneration type deionization unit, it can produce boron free high-purity water continuously for a prolonged period of time, while exploiting the advantages of a non-regeneration type apparatus.
The boron removing unit 4 may alternatively be placed between the deionized water tank 107 and the UV oxidizer 108 of the secondary water deionizing system. Such an arrangement can further prolong the service life of the boron removing unit 4 for the reason discussed above with reference to the second embodiment.
EXAMPLES!
Example 1
The arrangement of FIG. 1 and the following specific treatment units were used. The treated water at each of various sampling points was analyzed for boron concentration by means of an ICP-MS analyzer. Unit Arrangement:
pretreatment unit 101: coagulation/sedimentation/filtration unit
decarbonator 102: column packed with packing media and aerated up flow
double pass RO arrangement:
RO unit 103: NTR-759HR available from Nitto Denko
RO unit 104: NTR-759HR available from Nitto Denko
vacuum degasifier: column packed with packing media and vacuum suction from above
boron removing unit 1: AMBERLITE IRA-743T single bed type unit (water flow rate SV 50)
non-regeneration type ion exchanger 106: a mixed bed charged with a volume ratio of 1/1 of strongly acidic cation exchange resin and strongly basic anion exchange resin (water flow rate SV 30)
UV oxidizer 108: TFL-6; 0.35 KW-Hr/m3 available from Chiyoda Kohan
cartridge polisher 109: a mixed bed charged with a volume ratio of 1/1 of strongly acidic cation exchange resin and strongly basic anion exchange resin (water flow rate SV 50)
ultrafiltration membrane unit 110: OLT-3026 available from Asahi Chemical Industry
boron concentration of raw water: 53 ppb flow rate: 50m3/Hr, duration: 60 days
Table 2 below summarizes the results (at the end of 60-day service).
TABLE 2__________________________________________________________________________ Non-generation MembranePoint of EDI unit Distillation Double pass RO type ion separationanalysisRaw water outlet unit outlet unit outlet exchanger outlet unit outlet__________________________________________________________________________Example 153 ppb -- -- 24 ppb <10 ppt <10 pptExample 253 ppb -- -- 24 ppb .sup. 15 ppb <10 pptExample 353 ppb 8 ppb -- -- <10 ppt <10 pptExample 453 ppb -- 21 ppb -- <10 ppt <10 ppt__________________________________________________________________________
As seen from Table 2, a low boron concentration of <10 ppt was achieved at the exit of the non-regeneration type ion exchanger 106 of the primary water deionizing system.
Example 2
The arrangement of FIG. 2 and the specific treatment units as listed in Example 1 were used. The treated water was analyzed for boron concentration at various points by means of an ICP-MS analyzer. The results are summarized in Table 2.
As seen from Table 2, a low boron concentration of <10 ppt was achieved at the exit of the ultrafiltration membrane unit 110. With a continuous operation, the arrangement of this example proved to be effective for about four times as long as the counterpart of Example 1 for boron filtration.
Example 3
The arrangement of FIG. 3 and the specific treatment units as listed in Example 1 were used except that the RO unit 120, the EDI unit 121 and the membrane degasifier 122 were selected as follows. The treated water was analyzed for boron concentration at various points by means of an ICP-MS analyzer. The results are summarized in Table 2.
RO unit 120: NTR-759HR available from Nitto Denko
EDI unit 121: EDI-10 available from Organo Corporation
membrane degasifier 122: MJ-510P available from Organo Corporation
As seen from Table 2, a low boron concentration of <10 ppt was achieved at the exit of the non-regeneration type ion exchanger 106 of the primary water deionizing system.
Example 4
The arrangement of FIG. 4 and the specific treatment units as listed in Example 1 were used except that the RO unit 130, the distillation unit 131 and the membrane degasifier 132 were selected as follows. The treated water was analyzed for boron concentration at various points by means of an ICP-MS analyzer. The results are summarized in Table 2.
RO unit 130: NTR-759HR available from Nitto Denko
distillation unit 131: Multi-Effect Water Distiller available from Organo Aqua
membrane degasifier 132: MJ-510P available from Organo Corporation
As seen from Table 2, a low boron concentration of <10 ppt was achieved at the exit of the non-regeneration type ion exchanger 106 of the primary water deionizing system. | A high-purity water producing apparatus has an excellent effect of environmental protection and is also capable of effectively removing boron. It comprises a pretreatment unit, and a double pass RO unit an EDI unit or a distillation unit or any combination thereof as principal deionization unit(s) but does not comprise any chemical-regeneration type ion exchanger. It further comprises a boron removing unit and the water treated by the principal deionization unit(s) is brought into contact with a boron-selective ion exchange resin. | 8 |
FIELD OF INVENTION
This invention relates to tone generators and more particularly to push button tone generators utilized in conjunction with a telephone system.
DESCRIPTION OF THE PRIOR ART
With the advent of the touch tone telephone system, there has developed a need for transmitting devices which generate the required telephone tones. Such transmitting devices include dual tone generating multifrequency circuits, commonly referred to as the touch tone type of telephone. Another such device is the portable tone data transmitter which is the subject of U.S. Pat. No. 3,899,638 issued to James Hahn on Aug. 12, 1975. Both of the aforementioned devices suffer from two drawbacks. First of all, the tones generated are of low stability. Second of all, neither of the aforementioned transmitting devices is capable of remembering a telephone number.
In order to overcome these difficulties, systems have been developed which utilizes a crystal controlled tone generator which is capable of remembering a single seven-digit telephone number. Such a device is disclosed in the January, 1976 issue of Radio and Electronics. Even though this device does generate a tone with a more stable frequency and does have the capability of storing a single seven-digit number, programming of the seven-digit number into the memory means is very difficult and requires that the hard wire circuitry of the device be physically altered to achieve the programming. Furthermore, such device is only capable of remembering one seven-digit telephone number and has no capability to remember a second telephone number.
The desirability of being able to remember two sequences of numbers has increased with the advent of computer controlled telephone access systems. Such systems typically require that a user dial some telephone number to connect with the system and then to send some identification number to the computer via the telephone system. Accordingly, this typically requires that one first dial a seven-digit number and then dial a five-digit identification number. If one is only capable of automatically transmitting just the seven-digit telephone number, the user is presented with the problem of having to remember the five-digit identification number and dialing it into the system. Having the user remember the number presents another peculiar problem. This additional problem is that if a company leases a computer controlled access telephone system and must tell its employees the identification number, a certain percentage of the employees will tell their friends and the usage of the system leased by the company will be greatly increased thereby greatly increasing the cost of leasing. Accordingly, it is very desirable that any tone dialer to be utilized to access a computer controlled telephone system be capable of not only remembering the telephone number of the computer, but also the identification number of the leasee.
Accordingly, it is a general object of the present invention to provide a memory tone dialer which capable of remembering at least two sequences of numbers.
It is another object of the present invention to provide a memory tone dialer which is easily programmable without having to physically alter the basic hard wire circuitry of the device.
It is still another object of the present invention to provide a memory tone dialer which is capable of being made in an easily portable form.
It is still another object of the present invention to provide a memory tone dialer which is easy to manufacture and low in cost.
SUMMARY OF THE INVENTION
In keeping with the principles of the present invention, the objects are accomplished by a unique memory tone dialer which comprises a touch tone keyboard, a means for generating tones which correspond to the keys of the touch tone keyboard and a programmable means for remembering at least two sequences of numbers which may be telephone numbers or sets of numbers. In particular, the memory tone dialer utilizes solid state devices and therefore can be manufactured simply and in a small portable package. Furthermore, in the preferred embodiment, the means for generating tones is crystal controlled and the programmable memory means includes a miniature plug board upon which the sequences of numbers can be programmed. Furthermore, the remembered numbers can be accessed by depressing only a single key switch on the touch tone keyboard.
BRIEF DESCRIPTION OF THE DRAWINGS
The above mentioned and other features and objects of the present invention will become more apparent by reference to the following description taken in conjunction with the accompanying drawings, wherein like referenced numerals denote like elements, and in which:
FIG. 1 is a circuit diagram of a memory tone dialer in accordance with the teachings of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, shown therein is a schematic diagram of a memory tone dialer in accordance with the teachings of the present invention. The memory tone dialer is essentially made from CMOS and LPTTL devices and is broken down into three major devices. The devices are the tone generator 2, the sequencer 4 and the clock 6.
Electrically coupled to the R1 terminal of the tone generator 2 are the 1, 2 and 3 push-button switches of the touch pad keyboard 8. The 4, 5 and 6 switches of the touch pad keyboard 8 are connected to the R2 terminal of the tone generator 2. The 7, 8 and 9 push-button switches of the touch pad keyboard are connected to the R3 terminal of the tone generator 2. The zero key switch of the touch pad keyboard 8 is connected to the R4 terminal of the tone generator 2. The 1, 4 and 7 key switches of the touch pad keyboard 8 is connected to the C 1 terminal of the tone generator 2. The 2, 5, 8 and 10 key switches of the touch pad keyboard 8 are coupled to the C 2 terminal of the tone generator 2 and the 3, 6 and 9 key switches of the touch pad keyboard 8 are connected to the C 3 terminal of the tone generator 2. The switches are single pole double throw switches connected in a 2 × 7 matrix configuration.
A crystal X 1 in parallel with a resistor 10 is coupled to the tone generator 2. The collectors of transistors 12 and 14 are coupled to the positive terminal of battery 28. The LB terminal of tone generator 2 is coupled via resistor 16 to the base of transistor 12. The emitter of transistor 12 is coupled to the base of transistor 14. The HB terminal of tone generator 2 is coupled to the base of transistor 12 via resistor 18. The emitter of transistor 14 is coupled to one side of speaker 20. The other terminal of speaker 20 is coupled via resistor 22 to a terminal formed by the V SS terminal of tone generator 2, one side of capacitor 26, and the anodes of diodes 30, 32, 34 and 36. The other terminal of capacitor 26 is coupled to the V DD terminal of tone generator 2 and one terminal of resistor 24. The other terminal of resistor 24 is coupled to the positive terminal of battery 28. A zener diode 25 is coupled across capacitor 26.
The cathodes of diodes 32 through 36 are coupled respectively to the C 3 , C 2 and C 3 terminals of tone generator 2. Terminal C 1 of the tone generator 2 is also electrically coupled to the anodes of diodes 38, 40 and 42. The R 1 terminal of tone generator 2 is coupled to the anodes of diodes 44, 46 and 48. Terminal C 2 is coupled to the anodes of diodes 50, 52, 54 and 56. The R 2 terminal of tone generator 2 is coupled to the anodes of diodes 58, 60 and 62. The C 3 terminal of tone generator 2 is coupled to the anodes of diodes 64, 66 and 68. The R 3 terminals of tone generator 2 is coupled to the anodes of diodes 70, 72 and 74. The R 4 terminal of tone generator 2 is coupled to the anode of diode 76. The cathodes of diodes 38 and 44 are coupled together and connected to plug board terminal A while the cathodes of diodes 50 and 46 are coupled together and connected to plug board terminal B. The cathodes of diodes 64 and 48 are coupled together and coupled to plug board terminal C while the cathodes of diodes 40 and 58 are coupled together and coupled to plug board terminal D. The cathodes of diodes 52 and 60 are coupled together and coupled to plug board terminal E while the cathodes of diodes 66 and 62 are coupled together and coupled to plug board terminal F. The cathodes of diodes 42 and 70, 54 and 72, 68 and 74 and 56 and 76 are coupled together and each pair of cathodes is coupled respectively to plug board terminals G, H, I and J.
The negative terminal of battery 78 is coupled to ground. The junction formed by one terminal of capacitor 26 and one terminal of resistor 24 is coupled respectively to the collector and base of transistor 80 via diode 81 and then resistors 82 and 84. The cathode of diode 30 is coupled respectively to one side of the * switch 86, one side of the # switch 88, the ground input of clock 6 and the V S S terminal of sequencer 4 and the negative side of capacitor 90. The cathode of diode 30 is further connected to one input of nand gate 92 and one side of * switch 86 via a resistor 94, the V D D terminal of sequencer 4, the V c c and reset terminals of clock 6, one input of nand gate 92 and one terminal of # switch 88 via a resistor 96 and to terminals 98, 100, 102 and the positive terminal of capacitor 90 via resistors 104 and 106.
Capacitor 108 is coupled between the emitter and base of transistor 80 and the emitter of transistor 80 is coupled to the V SS terminal of sequencer 4. The collector of transistor 80 is coupled to terminal 110 of sequencer 4. The clock-out terminal of clock 6 is coupled to the clock-in terminal of sequencer 4. The other terminal of * switch 86 and # switch 88 are both coupled to ground.
The first sequential output terminal of sequencer 4 is coupled to one input of nand gate 110. The second sequential output of sequencer 4 is coupled to one input of nand gate 92. The third sequential output of sequencer 4 is coupled to one input of nand gate 112 and nand gate 114. The fourth sequential output of sequencer 4 is coupled to one input of nand gate 116 and nand gate 118. The fifth sequential output of sequencer 4 is coupled to one input of nand gate 120 and nand gate 94. The sixth sequential output of sequencer 4 is coupled to one input of nand gates 122 and 124. The seventh sequential output of sequencer 4 is coupled to one input of nand gates 126 and 128. The other inputs of nand gates 110, 112, 116, 120, 122, 92 and the cathode of diode 130 are coupled together. The other inputs of nand gate 114, 118, 94, 124 and 128 and the cathode of diode 132 are coupled together. The anodes of diodes 130 and 132 are coupled together and connected to the clock input terminal of sequencer 4.
The output of nand gates 110, 92, 112, 116, 120, 122 and 126 are coupled respectively to plugs a 1 , a 2 , a 3 , a 4 , a 5 , a 6 , and a 7 . The outputs of nand gates 114, 118, 94, 124 and 128 are coupled respectively to plugs b 1 , b 2 , b 3 , b 4 and b 5 .
It should be apparent that the * switch 86 and the # switch 88 are physically located as part of the touch pad keyboard 8. Furthermore, in practice, the tone generator 2 can be a MC14410P, the sequencer can be a
CD 4022, the clock 6, can be a NE555, and the nand gates can be SN74103. In addition, the crystal X 1 can be a 1MHz crystal and the touch pad keyboard 8 can be a chromerics ER21606.
In operation, the plugs a 1 through a 7 represent the first through seventh digits of a telephone number and the plugs b 1 through b 5 correspond to the five digits of the second memorized sequence of numbers. Furthermore, the plug board terminals A through J correspond to the numbers of the touch pad key board 8, 1 through zero. Accordingly, to program the memory tone dialer to dial a seven-digit phone number, the first digit of the phone number is programmed by connecting the plug a 1 to that terminal A through J which corresponds to the number of the first digit of the phone number. The second through seventh digit of the phone number are similarly programmed by connected plugs a 2 through a 7 to the appropriate plug board terminals A through J. For example, if the phone number was 457-3860, the plugs a 1 through a 7 would be coupled to plug board terminals D, E, G, C, H, F, J respectively. In a similar manner, the five digit sequence of numbers is programmed by connecting the plugs b 1 through b 5 to the appropriate plug board terminals A through J.
For the purposes of the following discussion, assume that a telephone number and a number sequence has been programmed into the memory tone dialer in the manner described above. If one desires to transmit the telephone number stored in the memory tone dialer, one first places the speaker 20 adjacent the microphone portion of a telephone coupled to a telephone system. Then one need only depress the * key switch 86. Closure of the * key 86 causes a ground to be applied to both the tone generator 2 and sequencer 4. Furthermore, the sequencer 4 is reset and clock 6 starts to run. The sequencer 4 then generates output pulses sequentially on the first through seventh sequential output terminal. The tone generator 2 is then driven by the nand gates 110, 92, 112, 116, 120, 122 and 126 via the plugs a 1 through a 7 and plug board terminals A through J. The tone generator 2 then generates the required tones which correspond to the telephone and applies them to the speaker 20. Speaker 20 couples the generated tones to the microphone of the telephone instrument, not shown. In a similar manner, the number sequence corresponding to the interconnection of plugs b 1 through b 5 to the required plug board terminals A through J is generated by depressing the # key 88.
The memory tone dialer can also be used to generate the required tones to dial an unmemorized telephone number by depressing the appropriate keys 1 through 0 on the touch pad keyboard 8.
It should be apparent to one skilled in the art that a power supply which converts standard 110 volt AC to a DC voltage suitable to operate the memory tone dialer can be substituted for the battery 78. Furthermore, a cable which directly interconnects with the telephone system may be substituted for the speaker 20. In addition, it should be apparent that by extending the circuitry described, that the five-digit sequence of numbers could be extended to seven and that the total memory capacity of the memory tone dialer could be increased to three or more sequences of numbers. Also, the keys could bear other legends and the memory tone dialer can be designed to generate the required number by depression of any one of the keys.
In all cases it is understood that the above described embodiment is merely illustrative of but one of the many possible specific embodiments which represent application of the principles of the present invention. Numerous and varied other arrangements can be readily devised by those skilled in the art without departing from the spirit and scope of the invention. | A memory tone dialer for touch-tone telephone lines. The tone dialer comprises a touch tone keyboard, a means for generating tones which correspond to the keys of the keyboard, and a programmable means for remembering at least two sequences of numbers which may be telephone numbers or sets of numbers. In the preferred embodiment, the tones generated by the tone dialer may be coupled to a telephone system by a speaker or a jack. | 7 |
The present invention relates to linear motor technology in general and active configuration electromagnetic thrust propulsion systems using pressurized fluid-film gap suspension and directional guiding in particular. The invention involves improvements in such technology as it relates particularly to compliant air-bearing support and transport of loads on curved profile guideway rails at high speeds. No mechanical moving parts are required to maintain the directional guideway guiding or the magnetic gap between the flexible primary active element and the guideway rail secondary passive element. The system includes inherent braking and locking provisions and fluid cooling for high power duty cycle advantages.
BACKGROUND OF THE INVENTION
Powered guided linear motion can be provided by many means. These include the use of rodless cylinder or cable cylinder actuators which offer a number of significant advantages over other mechanical alternatives such as belts or chains, lead screws or cam/crank drives. The process of converting rotary motion into linear motion often necessitates the use of complex mechanical linkages as well as wheels and sub-assemblies. As a result, the use of relatively simple rodless or cable cylinders has become quite common, although some moving and sliding parts having lubrication requirements are still present. Pneumatic rodless or cable cylinders do provide a degree of production ease with high acceleration and speed at low cost. Specialist skills are not required for operation or construction and installation is relatively easy and safe. Control and accuracy are now available with hydraulic power application; however, the advantages of self-guiding and structural strength with compactness are generally countered by a limitation to a maximum length of cylinder travel of only 42 feet.
The use of electromagnetic propelled systems for linear transit is an alternative of considerable merit and is used extensively for speedy movement. In many applications high thrust powers are used over long travel distances. The present state of the art of electromagnetic propulsion by linear motors is based on technology which exhibits low efficiencies due to mechanical positioning complications and other operating requirements which include low service factors due to heat build-up. Many of these drawbacks are overcome to a significant degree by the present invention as described herein which combines the simplicity of guided air-film suspension with active type electromagnetic propulsion.
Linear motor technology used with air-film suspension is not new. U.S. Pat. No. 5,128,569 suggests ways of using linear motors whose widely spaced passive primary units are incorporated directly into parallel extruded trough-like rails equipped with air nozzles. In this case the air-bearing suspension maintains a minimal magnetic air-gap and supports the compliant runners equipped with the linear motor secondaries. These secondary element runners are attached to the underside of carrier decks for low friction powered load transport. The runners basically include a polymer covered cellulose multiple web winding around a full length core of narrow width. This assembly exhibits some vertical flexibility with horizontal stiffness. A generally full length pocket cut into the bottom of the runner cellulose accommodates curved metallic plates which provide a secondary linear motor electromagnetic element. The entire runner assembly possesses the necessary cushioned compliancy for air-bearing suspension as well as the means for providing induced current magnetism for linear thrust in co-action with the widely spaced primary linear motor units of the guideway support rail(s). The foregoing description of the USA patent is related to electrically connected passive primary linear motor elements mounted in air suspension support rails and operating in conjunction with active secondary linear motor runner elements which support load carriers and have no external electrical connections. Passive primary linear motor elements are particularly suited to applications for simple transport of unit loads on air-film rails and tracks. No additional mechanical wheels are required to maintain magnetic air-gap nor are separate guiding or energy source collectors needed. Possible drawbacks of passive primary linear motor systems are the need for multiple linear motor units, and extensive compressed supply air routing over long distances. Also, the number of linear motor units and the length of air supply duct required can be very high with associated cost and pressure drop penalties. For example, in a transport system of a mile in length, some (528) motors would be required if employing a 10 foot (coast) interval between each rail motor primary unit. The passive system however has advantages of modular design and hard wired circuitry with short on-cycle energizing of the motors for highest thrust powers.
Operating experience with the air-film track passive type primary linear motor systems has shown that high currents for high thrust pulses can be attained during the extremely short on-time energizing of the primary units. The heat produced would be a severe limiting factor of operation were it not for the full-time cooling of all motors provided by the suspension compressed air flowing through the rail linear motor primaries--including motors in the off-cycle mode. The suspension air flow provides continuous forced-cooling of the secondary elements as well as the motor windings by high-density and high-velocity air allowing a high duty cycle and use of very high momentary overload currents for unique high thrust generation.
SUMMARY OF THE INVENTION
Whereas passive primary linear motor systems have advantages when a large number of unit loads are moved over a relatively short guideway--active or moving primary linear motor systems have distinct advantages associated with moving a small number of unit loads over relatively long distances. Active primary systems require only a single or a minimum number of linear motor primary units with localized suspension and therefore need only a very small air supply. In the active primary system it is the support rail which provides the secondary element for induced electrical magnetic thrust interaction. The few drawbacks of moving electric primary elements include a need for continuous or modulating energizing currents (with associated continuous heat generation) together with the need for essentially a full guideway length power collector device.
Present state of the art active type primary linear motors are used extensively for monorail load movement applications which include industrial overhead conveyor networks, mainly in automotive assembly plants. These typically require mechanical support and guide wheels and relatively complicated braking systems. Support wheel guiding devices are unsprung and were it not for wear adjustment provisions there could be damaging contact between the linear motor elements. Strict maintenance schedules are employed as described in various patents such as Canadian Patent No. 1,280,991 issued Mar. 5, 1991 to Daifuku Co., Ltd..
All active systems require power collector devices. Most of these are of the mechanical sliding shoe type with inherent safety, environmental, and high maintenance drawbacks. The rubbing and arcing of the electrical contacts greatly contribute to contact failure and environment ozone duress.
Linear motor primary active (and passive) units are long and narrow assemblies with wire conductor field coils wound around slotted steel lamination plates bolted together. These assemblies provide a longitudinal moving magnetic field when energized with polyphase electric currents. Generally, such motors are very rigid, except for that suggested in U.S. Pat. No. 3,547,041 which describes vertically hinged linear motors to accommodate trolley beam curves in a generally horizontal plane but for which a means of maintaining air gap is not defined.
Generally speaking the present invention may be broadly considered to provide an active linear inductions motor (LIM) propulsion system comprising: a passive secondary in the form of at least one elongated rail member having transversely arcuate operating surface means; an active primary member for interaction with the rail member; and means for providing pressurized fluid between the rail operating surface means and the primary member to support the primary member above the operating surface means and to maintain a magnetic air gap between the primary member and the operating surface means; wherein:
(a) the rail member includes electrically conductive and ferromagnetic means in close proximity to the operating surface means over the length thereof;
(b) the primary member includes: a plurality of laterally adjacent, longitudinally extending and articulated ferromagnetic laminations, the laminations having a longitudinally toothed surface that is transversely arcuate to be complementary to the rail operating surface means; electrical windings wound about selected groups of teeth of the laminations as a LIM primary; compliant means adjacent the laminations, capable of deformation under load and at least partial recovery after load removal; power means for obtaining electrical power continuously as the primary member moves along the rail and supplying polyphase electrical current to the electrical windings; and cooling means contained in the primary member for continuously providing cooling fluid to the laminations during operation of the primary member; and
(c) the means for providing pressurized fluid is adapted to inject pressurized fluid at high velocity into the space between the rail operating surface means and the compliant means to support the primary member above the operating surface means and to provide a minute pressurized magnetic and suspension gap between the primary and secondary members for efficient linear motor operation.
The advantages of operation of the present invention active linear motor in a fluid-film bearing suspension configuration are particularly enhanced when the primary assembly is the moving element on a simple passive concave or convex support guide rail made of an electrical conducting material. This guide rail could be a continuous aluminium pipe, an aluminium trough extrusion profile, or a conductively clad steel or iron pipe member. In any case a magnetic iron or steel backing can be used to increase the magnetism effect of the induced currents set up in the rail by the moving magnetic fields of the suspended primary element.
In the present invention the active linear motor primary elements are contingent to a fluid-film suspension mounting of a moving carrier platform which includes a relatively small pump or compressor with a fluid recirculation means through heat exchanger(s) and contaminant removal separator(s). An electrical power collector system for the linear motor is required for on-board powering. This system may typically involve a rectifier and inverter for current phasing with a control system of developed technology, along with a position sensing device such as an encoder. The present invention includes an optional means of using compliant fluid-film support for improved power collection.
The active primary linear motor of the present invention is particularly useful in those applications which require simplicity and efficiency of propulsion and braking operation for high speed travel over relatively long distance with minimal contact and maintenance. Applications could include multiple sequenced monorail air-film units as prevalent in overhead industrial assembly applications and in clean room or hygienic situations. The present invention suggests that such air-film suspended and tracked active primary linear motor systems are practical for extremely high speeds.
The present invention eliminates many of the existing mechanical and electrical limitations of mechanically suspended linear units by making use of externally fluid pressurized hydrodynamic compliant bearing principles for operating active type motors in a direct suspension arrangement. Flexibility of the primary linear motor assembly is a key requirement for operation in a compliant fluid bearing suspension. Described herein are many improvements by which the active primary element of a linear motor is incorporated into a fluid bearing suspension system by being made flexible while using a compliant pad layer and cover. An air-bearing and/or fluid bearing suspension system never herebefore achieved is provided.
At this point it should be mentioned that the specification hereinafter describes the present invention in terms of an air-bearing suspension or support system in which the active suspension or support medium is compressed air. It is also contemplated that in particular applications the system would work equally well using a pressurized liquid, such as water, as the active suspension or support medium. In its broadest form the present invention is thus presented as a system relying on pressurized fluid as the operating medium.
Improvements to electrical collector systems are also outlined herein. Such systems can enhance a non-contact inductive type electrical power pick-up system when applied to the air-film concept to eliminate the need for any mechanical positioning of the pick-up coil and virtually any physical contact in the entire system.
It should be noted that mechanical pick-up power contacts are prevalent at the present time but can be air-film guided and supported in a mini air-film system using a curved non-conducting support and guiding trough containing the power conductor strips for localized electrical power transfer as supported on a suitable loaded extension arm mounted on the active linear motor platform.
Induction coil means for power pick-up can also be employed to maintain the overall virtual absence of moving parts claim of the present invention. The exception to this claim will be the use of ancillary compressor and fan units. The present invention suggests several additional configuration improvements which allow the location and shielding of the induction pick-up coil primary conductors for proper containment of high frequency current radiation effects. As a result electrical powering of the system is carried out with environmental and safety advantages in a compact arrangement.
Also described are means of induced flow or forced flow primary motor lamination core cooling by the pressurized air or fluid supply as induced by inspirator or injector means in a closed-loop internal recirculation path and through internal heat exchangers. The induced injector flow should be directed onto extended motor core lamination cooling fin plates so as to take advantage of available thermal expansion cooling. Included in the fluid loop circuit is a means of removing contaminants and impurities such as water and oil vapours in compressed air by a separator/collector means. These removal devices are common to compressed air or fluid systems with discharge to a collector reservoir for periodic emptying or if appropriate to the atmosphere.
Recirculation of pressurized fluid is not restricted to active motors but can also be applied to passive linear motor systems. In the passive systems, the rail length(s) could serve effectively as the heat sink and could be combined with suitable radiator coolers at the recirculating fan or pump. The pressurized suspension fluid is recirculated through the multiplicity of rail profile ports by induced or mechanical means resulting in a rather lengthy system with continuous series internal cooling of the multiple linear motors. The heat sink provision of the rails would have the feature of rail heating for de-icing or drying as an inherent advantage.
The active linear motor system support incorporates a full length pad of cellulose web which allows interlocking motor core modules to flex a limited degree as required for the compliancy requirement of the suspension. A flexible air-bag mounting arrangement for the primary linear motor assembly is a preferred means which in combination with the cellulose support pad or alone provides the compliant support for the flexing motor modules while also providing a spring air-ride cushion and a fluid chamber for heat pick-up from the motor module lamination extension fins as well as a small reservoir supply for the suspension nozzles.
The air-bag or fluid-bag support can employ a separate pressure supply. The suspension nozzles in this case would be supplied through separate pipes or tubing or plenum mounting which piping or plenum would then also be exposed to the cooling of the recirculating air or fluid.
Linear motors are not limited to air cooling only but can also readily employ liquid coolant for even greater thrust power duty cycles and efficiencies. A variation of a means of liquid cooling of linear motors in the public domain is the relatively impractical use of copper tubing wound as the electrical core field winding of the linear motor poles. In this case the coolant flows within the conductor tube windings.
Nozzle mounting for the active linear motors can be exacting. Teflon® or other non-magnetic and heat resistant small tubing is run through each motor module for connection to individual stainless steel or similar hypodermic tubing nozzles of generally 0.020 inch internal diameter mounted and fixed to the cover and ground off flush with the cover at a narrow 29 degree or shallower inclination to the rail surface and directed also at approximately 45 degrees to the rail centerline as it passes through the outside module cover as described in U.S. Pat. Nos. 4,185,399 & 3,952,666 & 3,875,163 . In the present invention the nozzles are fixed to the cover and are free to move with the cover while offering very little limitation to cover movement freedom. Each nozzle is connected to the heat resistant flexible tubing or from a small diameter flexible header through the cellulose or like compliant layering or directed to an adjacent small clearance cavity of generally 0.5 inch diameter and 0.3 inches depth provided in the cellulose. This cavity provides a further degree of nozzle freedom and will contribute to desirable localized vibration or jackhammering and dither effects for assisting in the air-film propagation action.
The present invention embodies specific improvements to the primary element of an active linear motor system using a cooling system and power collector systems for operation in a compliant air-film bearing mode with high thrust capabilities without the use of any mechanical means to maintain a magnetic gap or guiding or cooling or even power collector operation. Active linear motor technology represents specific improvements to the application of air bearing support and powering of conveying systems and high speed transportation systems.
In particular there are described herein improvements to the carrier active electromagnetic element as well as to cooling of this element and further to electric power collection.
Location monitoring and speed control of the active linear motor primary assembly are generally provided through encoder comb markings along the guideway or laser doppler systems or satellite position locators for wireless communication to a base station for digital feedback computation in conjunction with an onboard microprocessor. This is important for control of headway clearance and for safety or trouble location in the overall transit system. A remotely controlled directed shutdown automatically stops any primary module and automatically applies inherent rail locking and holding brake features.
Rail for the active primary linear motor system is generally transversely convex as might be more common with pipe system guideways as described in U.S. Pat. No. 3,952,666 although it is possible to have the curved rail support surface transversely concave as described in U.S. Pat. No. 5,128,569. It follows that rail interaction can also take place on a top portion of the outside convex surface of a pipe, a longitudinal sector of a pipe, both the outside top and underside of a pipe, the internal concave bottom of a pipe, or both the internal concave upper and lower surfaces of a pipe sector.
Guiding is provided in all cases through the air-film suspension interface of the curved linear motor iron core laminations and compliant layer with polymer cover which mates and coacts generally with the curved underneath adjacent surface of the support rail(s).
Pressurized air from the small onboard compressor of generally 2 to 4 horsepower is cooled and is coursed through the core windings and laminations prior to entry at high velocity into the suspension air-film interface through the very small air nozzles in the polymer cover of the compliant cellulose layers. Passageways provided through or provided in the face of the core ferromagnetic laminations of the linear motor allow the threading of the flexible Teflon® or similar heat resistant tubing for direct connection of compressed air through the cellulose layers and thence through conjunctive holes, slits, pores or small bore hypodermic tube nozzles angularly fixed in the polymer covering. The air supply passing through the primary windings and laminations and compliant coverings effectively provides extra cooling for the continuously operating primary assembly. This embodiment alternatively makes use of a separate piping header or plenum supply dedicated to the suspension nozzles. In this case the separate header or plenum is independent of the linear motor cooling fluid flow. Since nozzle flow does not require any cooling of the heat of compression the resulting cooling load reduction allows increased availability for heat removal from the primary core for even more efficient operation.
LIM cooling may be enhanced through the provision of extended core lamination plates. Extended plates project proud of the top of every two or three standard (shorter) lamination plates of each LIM module. Transversely adjacent standard core plates are next to evenly spaced extended plates providing exposed finned air passage clearances for heat dissipation. Extended lamination plates are manufactured with the upper portion not less than a quarter depth more than standard lamination plates. The lamination plates otherwise include a plurality of longitudinally spaced generally rectangular teeth along the bottom operating portion which contain the magnetic electrical pole windings to coact with the secondary (support and guiding) element. A general mating profile of the lamination plates to the curved secondary element is achieved by a slight vertical displacement of the lamination plates relative to each other as described in U.S. Pat. No. 5,128,569. Alternately the lamination teeth can be of different depths so that the innermost teeth have a lesser depth than the outermost laminations (for a convex rail) or the final assembly of laminations may be machined to provide the required matching pole face curvature. The addition of the compliant filler material and cover completes the air bearing requirement for coaction with the curved secondary rail(s).
The side assembly surfaces of the core lamination plates can also be provided with vertical or near vertical top to bottom grooves on at least one side to allow compressed air flow between adjacent plates to the compliant padding and polymer cover and even to the air nozzles. This flow not only provides the necessary air for the suspension interface but provides efficient additional cooling of the linear motor core. The use of separate tube piping to each nozzle is preferred, however, as pressurization of the entire compliant layer system resulting from through-plate air flow requires some reinforcing or venting to reduce cover ballooning. This can be through additional nozzles in the compliant filler cover or through clearances along the sides of the LIM core, either of which could be wasteful of air.
Core lamination plates are assembled into separate modules which have mating end profile projections and recesses so as to provide interlocking and hinged sectionalizing of the linear motor core. Specific radial clearances at the end faces of the modules allow for slight relative flexing between adjacent modules for enhancing an overall assembly compliancy. A relatively thick cellulose ply pad, an air bladder, or a fluid bladder type spring loading system facilitates the necessary flexing movement. The interlocking extensions of the lamination plates assist in the magnetic flux between modules. Alignment, vertical plane rotation, and magnetic continuity are assured with the rounded pivotal projections of alternate plates fitting tightly into slightly larger radius rotational recesses of the next adjacent module. This pivoting contact allows some vertical flexing without having to resort to pinned hinges. The modules are held together in close contact by an encircling external tension member such as a rubber band or by a non-magnetic spring which does not hamper the flexing motion of the interlocking core modules. Alternatively, hinge pins can be used to eliminate the need for external tensioning and can be of ferromagnetic material or non-magnetic brass or Teflon® material.
Field windings of the active LIM are interconnected at the pivot areas so as to permit a degree of movement of adjacent core modules. One means of winding with flexing allowance is provided by looping of the windings and the use of flexible encapsulation which is available from those skilled in the art of manufacturing linear motors.
Suitable flexible seal strips or rod "spaghetti" or tubing of near plate thickness at each linear motor module interconnection reduce or prevent air leakage through the module flex joints.
The LIM cooling recirculation system comprises a jet injector-type venturi to induce and force the compressed air or fluid through the core fins and subsequent heat exchanger(s). The heat exchanger(s) remove both the heat of compression as well as the heat picked up from the top core fins of each linear motor module. In the air bladder springing system the injector recirculates the air while adding sufficient make-up air to sustain the suspension air-film nozzle flow. Of course it is recognized that electrically driven fan or pump devices can be utilized to recirculate this cooling compressed air or pressurized fluid. With an injector the endothermic expansion reaction is of additional cooling advantage especially if it takes place immediate to the LIM cooling fins. Suitable filtering and separator means well known to those skilled in the art of using compressed air or fluid flow are included in the recirculation loop preferably at the coolest and lowest velocity sections.
Removal of moisture and water and oil vapour from the recirculated air can be achieved immediately after injector cooling by a typical coalescent filtering separator bowl fixed below the injector and flow venturi. Rotational vanes in the filter impart a rotational spin to the flow to assist removal of the condensed moisture by centrifugal effects and gravity to a small bottom sump. A protruding "dry-pipe" air exit can preclude air droplet carryover. Water removal bleed from the sump to an automatic discharge commonly used in filters will allow for periodic visual inspection of the water removal operation process. Water removal takes place at the coolest part of the motor assembly, usually at the extreme lower front.
Ferromagnetic core lamination plates of the primary element are assembled to provide multiple teeth protrusions which are electrically conductor wound to create a plurality of magnetic poles which are energized in travelling field sequences usually by the application of polyphase electrical current. Motion of these magnetic poles relative to the electrical conductive metallic secondary surface induces electrical currents in this surface. In response to these current flows there are corresponding magnetic fields set up according to well known electrical and moving magnetic flux principles. Resulting strong attractive (or repulsive) reaction between the primary field flux and secondary surface flux provides powerful longitudinal thrust forces for load movement on the guiding suspension pressurized air-gap. Radial magnetic attractive forces are easily handled as a load surcharge by the suspension.
High power performance is dependent upon the capability of handling extremely high currents without undue heating of the primary element winding insulation. Heat deterioration of the insulation is accumulative and the so-called "Duty Cycle" is determined for each motor design to limit accelerated deterioration. The higher this rating--the higher the current rating and power capability of a motor. Winding insulation cooling means of the present invention is of paramount importance in the ability of the primary to handle the high currents and powers.
Wire for the LIM primary windings is wound over two longitudinal tubes which are withdrawn usually after encapsulation of the main core. The removal of these tubes provides cooling air flow ports right through the motor windings, as described in U.S. Pat. No. 5,128,569. Further cooling means for the present motors is provided by the finned extensions of the core lamination plates which release heat to the relatively cool recirculation air flow as previously described.
The extension fins and the intermodule pivotal interlocking means for core module articulation are kept free of epoxy encapsulation, when used, by the use of special slotted seal blocks fitted during the manufacturing process to cover those portions of the core lamination plates which must be kept free of encapsulation. All lamination projections which are to be free of epoxy are precoated with release agent to facilitate seal block removal.
Compliant air bearing operation requires a small pad of cellulose plies or like filler material between the linear motor pole faces and a continuous longitudinal enclosing cover. The configuration of the curved core face with the cover and filler plies is similar to that of the minimum cellulose runners of U.S. Pat. Nos. 4,838,169 & 5,090,330. The filler and cover are formed from materials that are capable of deformation under load and at least partial recovery after the load has been removed and have the capability of withstanding the high LIM operating temperatures and some suspension transient seal area friction.
The sectionalized and interlocking laminations for articulation of the linear motor core modules have a tendency to vibrate minutely in sympathy with the frequency of the energizing current. Vibration of this type can be desirable as it can lessen seal area friction of the compliant cover with the effects known as stiction or dither. Any audible noise present because of this effect will be muffled by the cover and compliancy layers so as not to be an intrusion to the normal very low audible levels of operation.
Means for ducting the compressed air through the core laminations of the linear motor by angled cut slots in the plates is described in U.S. Pat. No. 5,128,569 with general manufacturing methods being disclosed therein. Unencapsulated LIM cores can be employed for the LIM motors. The core laminations without epoxy encapsulation can use plates with one side thereof having vertical or near vertical grooving for through-core cooling air flow between adjacent laminations. Alternative use of thin Teflon® or the like washer spacers between lamination plates can allow through-flow of cooling air but this also reduces the core ferromagnetic density and may reduce the available thrust somewhat.
Active LIM units require that the guideway support contains or is the secondary element for the electromagnetic co-action propulsion. This guideway secondary member of curved profile is a usually a binary metal rail as supported on grade, on elevated steel or aluminum structures, or on other materials or structures such as formed concrete. In all cases the guideways include electrically conductive and magnetic sensitive materials. Some rails are clad on the exterior with copper or aluminium or like electrical conducting materials over ferromagnetic materials. The rail conductive cladding for induced current capability also provides protection from atmospheric oxidation of the suitable steel magnetic portion of the secondary element. Carried to an extreme, a rail could be the inside of a conductive pipe with ferromagnetic materials positioned on the outside at positions of most effectiveness. Claddings or support surfaces are selected with friction reducing properties in mind and can be augmented with low friction coatings, stainings or impregnations to further reduce seal area contact friction of the moving primary compliant covering. Friction reducing materials such as molybdenum disulphide powders or the use of motorized cleaning or application devices such as rotary brushes or wipers are options which can be included on the leading edge of the moving primary motor assembly.
Motor power collector devices of the non-contact type are preferred. With these, power supply conductors held in adjacent rail protective enclosures are used for the secondary power current supply. An air -film suspension arrangement for the collector device has been described previously and can also be employed in a similar assembly with the non-contact collector. A suspended coil(s) assembly is attached to and moves with the primary linear motor assembly. High frequency current is induced in the pick-up coils in close proximity to the power conductors (electromagnetic fields) somewhat similar to a reverse of LIM action but similar to transformer operation. Induced currents are rectified and inverted by onboard devices to the required polyphase cycle current for the LIM motor thrust generation. High frequency of the primary supply assures good coupling of the supply currents and the induced currents of the power coils.
Environmental concerns are very important and are accommodated in the general make-up of the collector portion of the present invention. Special attention is made to confine any electromagnetic wave influences generated. Aluminum grid plate or similar shielding of the linear motor end windings precludes inadvertent induced current problems with personnel or with motor coils in proximity to the power supply conductors. Various remote mountings of the collector coil arrangement reduce undesirable effects. Power conductors are enclosed and shielded so as to contain the electromagnetic fields. Use of extruded polymer supporting brackets for conductors in a continuous manner for the entire rail length is considered a safety provision. Electroplated or similar outside surface metallic coating is provided on the conductor brackets with multiple slot interruptions so that induced current continuity is blocked, yet this coating serves to shield any radiation as well as to inhibit and restrict any extraneous induced electric currents and associated heating which may be set up in any adjacent metal parts. Minor heating effects can be an advantage to heat the rails for cold or freezer or icing conditions.
Other features of the present invention will be described hereafter and with reference to the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a prior art passive LIM support and conveying system showing a track system incorporating several linear motor primary modules in accordance with present developments of the passive pressurized air-gap linear motor propulsion system.
FIG. 2 is a perspective view of the compliant runner support of the present air-film suspension system showing the wound cellulose web as wound around a central paperboard core and then covered by a polymer sheet.
FIG. 3 is a composite transverse sectional view of a runner such as in FIG. 2 but which has had a longitudinal pocket cut partially into the wound cellulose web for the inclusion of ferromagnetic and electroconductive plates to form the secondary of the passive LIM system.
FIG. 4a is a perspective view of the basic passive type air-film pressurized air-gap electromagnetic propulsion suspension system showing the air nozzles of a typical concave support rail which incorporates curved rail profile primary linear motors at intervals therealong to impart thrust to a compliant runner which incorporates the secondary coactive plates of the linear motor system.
FIG. 4b is a comparative perspective view of the basic active type air-film pressurized air-gap electromagnetic propulsion system of the present invention in which the primary element of the linear motor propels itself along the support using the conductive properties and guiding trough profile of the rail for both the secondary electromagnetic element and the suspension. Necessary electrical power pick-up for the suspended primary linear motor element is shown as an adjunct collector along the rail.
FIG. 5 is a sectional view of the active type pressurized air-gap flexible primary linear motor system of the present invention showing a compliant primary module mounting and a typical air-film support and guiding rail with air nozzle supply of compressed air to the rail secondary/runner primary interface and indicating the inclusion of internal ferromagnetic plates in rail ports and the adjunct power collector as attached to the rail. FIG. 5i shows an inductive type non-contact pick-up system and FIG. 5ii shows a spring-loaded sliding type pick-up more commonly used in present day applications.
FIG. 6 is a another sectional view of the active type pressurized air-gap flexible primary linear motor system of the present invention showing a compliant primary module mounting and a typical air-film support and guiding rail with air nozzle supply of compressed air to the rail secondary/runner primary interface and indicating the inclusion of internal ferromagnetic plates in rail ports and the adjunct power collector as attached to the side of the linear motor module in a more compact arrangement of a non-contact inductive type pick-up.
FIG. 7a is an illustration of a prior art material handling application in which an air-film suspension is used for the indexing movement of goods on multiple cylinder driven reciprocating air suspension platforms which co-act with air tube type lifts for raising and lowering loads to accumulate and convey such loads over distances of up to 200 feet. Multiple platforms (usually five load capacity) are used; they are automatically sequenced to transfer loads from platform to platform for high density storage and staging. FIG. 7b is an illustration of a prior art material handling application similar to that of FIG. 7a but with the use of passive type linear motor powered movement (instead of pneumatic cylinders) of only a single platform for essentially the same load capacity. The single platform is programmed to operate over the full 200 foot length of the conveying system for the accumulation and staging and high density storage of unit loads but more quickly and smoothly with virtually no moving parts.
FIG. 7c is an illustration of a prior art material handling application similar to that of FIG. 7a and FIG. 7b but with the use of active type LIM powered movement of the present invention (instead of multiple pneumatic cylinders or multiple passive linear motors) and using only one platform and one LIM system for reduced complication and increased travel distances. The single platform of the present invention is programmed to operate over the long distances of the conveying system for the accumulation and staging and high density storage of unit loads at each end of an extensive travel distance, but more quickly and smoothly than any prior art system and with virtually no moving parts.
FIG. 7d is a perspective view of an automated assembly line showing an actual proposal for automotive assembly and skid handling using pressurized air-gap passive linear motors. These could be replaced by fewer active LIM units according to this invention.
FIG. 8 is a perspective view of an application directly suited to the active pressurized air-gap linear motor propulsion system of the present invention. A single monorail type load handling system is shown as used extensively in large assembly plants such as automotive factories.
FIG. 9 is a side view of the entirely self-contained active linear motor prime mover showing the arrangement of the flexible primary cores in accordance with the present invention with an air bag mounting which incorporates a compressed air supply for both the air-film nozzles and recirculation cooling.
FIG. 10 is a cross-sectional view of the active linear motor prime mover showing a monorail assembly in co-action with a secondary pipe type support.
FIG. 10a is a cross-sectional view of an active linear prime mover showing a monorail assembly with a double, or upper and underside, positioning of linear motor units in co-action with the same secondary pipe type support rail. This arrangement in effect doubles the thrust available with essentially the same (one) pressurized air supply. The underside linear motor unit is positioned against the secondary via a supplementary loading system (in addition to the magnetic attraction usual with this motor) as shown by the use of a flexible air bag spring mounting very similar to that of the upper system.
FIG. 10b is a cross-sectional view of an active linear motor prime mover showing a monorail assembly with a double, or lower and upper positioning of linear motor units inside a pipe-like guideway and co-acting with the same secondary partial pipe type support. This arrangement in effect doubles the thrust available with the same (one) pressurized air supply. The upper linear motor unit is positioned against the upper inside concave surface of the pipe via a supplementary loading system (in addition to the magnetic attraction usual with this motor) as shown by the use of a flexible bag spring mounting very similar to that of the lower system. Ferromagnetic elements are attached to the outside of the electrically conductive pipe material in positions appropriate for the proper operation of the induced current thrust generation. The continuous slot along the pipe provides only sufficient clearance for the underslung "C"-shaped load support bracket so as to provide the maximum section for structural strength and to also provide maximum protection for the rail surfaces and power collector flexible power pick-up mounting as described previously, located at the backside inside surface.
FIG. 10c is a cross-sectional view looking from the front of dual self-contained air-film suspended active pressurized air-gap LIM propulsion units supported inside electrically conductive concave partial pipe system monorails arranged in a mirror image type track guideway with an extended carrier for load attachment outside and above. In this example the propulsion units are shown with bracket mountings to allow slightly canted LIM positioning for possible additional stability at high speeds and to show that LIM propulsion units need not always be mounted vertically. Each active LIM propulsion unit has a second LIM propulsion unit mounted on top of the pressurized air supply streamlined canopy and held to the upper inside (underside) of each concave pipe of the track system as described in FIG. 10b. The track guideway system comprises parallel electrically conductive pipes of aluminum, also as described previously in FIG. 10b. the use of interior pipe section guideway rails is of particular advantages with grade ballasting in that the support surfaces are almost fully protected from atmospheric contaminants and they offer a saving in the ferromagnetic elements. In addition, the power collector shown as an inductive non-contact coil type is mounted at the extreme opposite side to the pipe slot for maximum protection.
FIG. 11 is a perspective view of a self-contained monorail system showing the linear motor primary core elements and compressed air suspension and recirculation cooling of the interlocking LIM core module laminations with the pivoting protrusion noses and recesses of the laminations and the flexible core winding interconnections which allow limited articulation of each module.
FIG. 12 is a cross-sectional detail of a self-contained monorail active LIM system supported on a pipe rail assembly showing a concave LIM core lamination module with the ancillary compressor and recirculation cooling apparatus all mounted to one side opposite the load connection yoke to effectively counter-balance this yoke and to provide a flexible mounted power collector platform.
FIG. 13 is an artistic sketch of an elevated pipe tracked people and goods mover transportation system as might be used for rapid transit in an urban setting.
FIG. 14 is an artistic impression of an elevated high speed monorail vehicle module using active self-contained pressurized suspension and air-gap LIM propulsion with power collector or on-board gas turbine power source as might be employed for long distance transportation.
FIG. 15 is an artistic impression of an application of the active type linear motor propulsion as embodied in an elevator operation in which there are no cables.
FIGS. 16a-16d are drawings of the active LIM core lamination plate profiles which when assembled provide a curved face module while allowing a small degree of individual module flexing with complete overlapping for continuity of the magnetic flux flow and extension firming for heat dissipation to atmosphere of pressurized fluid coolant.
FIG. 17 is a side section showing the support platform with the air bladder spring air flowing over the LIM extension cooling fins with the compliant layer pad and polymer cover and the air jets exiting through the cover into the suspension air-film cavity interface with support surface.
FIG. 18 is a partial perspective view of a single nozzle with compressed air supply flexible tube attached. A clearance cavity is shown around the welded or screwed in place hypodermic or like nozzle.
FIG. 19 is a sectional view of a single nozzle cavity showing the nozzle hypodermic welded into the cover and that portion which has been removed by grinding or other process flush with the outside of the cover.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows the general arrangement of a typical SAILRAIL® air-film bearing suspension system 10 for conveying unit loads 12 on typical parallel air-film trough rails 14 and 16. Rail 16 is similar to rail 14 but is equipped with rail profile linear induction motor (LIM) primary elements 18 incorporated as part of and spaced along the rail 16. All rails and motors have a transversely concave upper working surface 20 and all have a plurality of longitudinally spaced angled nozzles 22 which extend through the surface 20 to pass pressurized air from longitudinally extending ducts 24 within the rails or from air plenums attached to the underside of the motors to the surface 20. The teachings of U.S. Pat. Nos. 3,875,163; 3,952,666; 4,185,399; and 5,128,569 relating to this technology are hereby expressly incorporated by reference.
The load 12 is shown resting on a deck 26 which in turn is supported by a pair of runners 28 and 30 which extend the length of the deck 26 and are received in the corresponding rails 14 and 16. As can be seen each of the runners 28 and 30 has a corresponding convex lower operating surface 32 that is complementary in curvature to the rail and motor working surfaces 20. The rail and motor upper working surfaces 20 are collinear to ensure a smooth transition of the runners 28 and 30 as the load travels along the rails and primaries.
The runner 28 as shown in FIG. 2 is typical of a long length compliant support air bearing runner with a continuous cellulose ply 34 tightly wound around a circular core 36 and then compressed flat by vertical loading onto a transversely concave form identical to the working surface 20 with the resulting shape then being covered with a polymer or similar cover sheet 38.
The runner 30 as shown in FIG. 3 is similar to runner having cellulose 34 wound on previously round core 36, with the same compressed shape and having a polymer sheet cover 38, but it differs from the runner 28 in that the cover is of high temperature capability such as Teflon® and a longitudinal pocket 40 is cut into the outside underside convex portion of the cellulose to closely accommodate thin ferromagnetic sheets 42 and thin electro conductive sheets 44 of copper or aluminum which have been curved to match the required radius to suit their juxtaposition in the runner. These plates serve as the secondary element of the passive linear motor in which the moving magnetic fields of the passive primary induce electric currents in the conductive plates to set up related magnetic fields in the ferromagnetic plates which co-act with the travelling magnetic fields of the primary to produce longitudinal thrust. The flexibility of these plates is important with the application to the compliant air bearing usage and to this end the ferromagnetic plates are slotted or segmented and taped together to increase their vertical flexibility (especially with curvature stiffening).
Also shown in FIG. 3 is a sectional view of a typical rail 14 or 16 showing the upper concave working surface 20 and internal longitudinal ports 24 which supply air to nozzles 22. The nozzles are angled in the rail working surface between LIM sections 18 but are oriented essentially vertically within the LIM core plates as shown within the superimposed LIM section 18. The LIM windings 46 and the blow-through cooling passages 48 for the compressed air supply to the rail nozzles are shown also.
A comparison of the passive and active types of the compliant bearing pressurized air-gap linear motors is illustrated diagrammatically in FIG. 4a and FIG. 4b. In FIG. 4a runner 30 is shown in air-film suspension with an extruded aluminum rail 16 and nozzles 22 while being moved forwardly by its internal secondary plates 42 and 44 in co-action with the stationary LIM primary elements 18 in the rail. FIG. 4b shows an active LIM system of the present invention in which the runner assembly 50 is air-film suspended by the nozzles 22 in an extruded aluminum rail 14. This runner contains flexibly hinged LIM primary modules 52 that generate longitudinally travelling magnetic fields and induce currents and corresponding magnetic fields in the extruded aluminum rail 14, which fields in turn co-act with the LIM runner travelling magnetic fields to produce a longitudinal thrust force. The active LIM runner 50 is suspended and guided on the pressurized air at the runner/rail interface as produced by air exiting the rail nozzles 22 and co-acting with the compliant covering 54 of the LIM modules 52. The power to the LIM runner is shown being supplied by an electrical collector 56 in a protective insulated semi-enclosure 58 attached to the side of the rail. Ferromagnetic plates or bars or the like 60 are inserted into the rail internal ports 24 to provide the necessary magnetic reinforcement of the LIM secondary which in this case is the continuous rail 14.
FIG. 5 is a cross section of an active LIM runner 50 of this invention as assembled with a typical deck plate 26 and suspended by pressurized air from nozzles 22 in aluminum rail 14. Alternative power collector semi-enclosures are shown, with the usual sliding spring loaded direct conductor contact type 62 or a newer inductive type non-contact collector 64 with rigid pick-up devices 66 or 68 attached to the deck plate 26 by a bracket extension 70. The flexibly hinged LIM modules 72 of the active runner 50 are supported by an upper compliant cellulose pad 74 which allows limited vertical intermodule movement of the hinged LIM modules 72. The mounting brackets 76 of the LIM modules 70 are such that the fastening bolts 78 of the LIM modules are free to move vertically in slotted means provided in the brackets 76. The convex working faces of the LIM modules are covered with a continuous pad 80 of a minimal number of cellulose web plies 82 and a polymer outer cover sheet 84. The ferromagnetic laminations 86 added inside the ports of the rail 14 include air and control wire passages 88 to allow air flow through the rails and to the nozzles.
FIG. 6 is an active LIM runner similar to that of FIG. 5 but with a more directly connected power pick-up assembly 90 bolted by a commonly used spline profile to match the side cavity of the rail 14. An inductive pick up 92 is connected to the runner by a bracket extension 94.
FIGS. 7a and 7b are perspective sketches showing examples of how LIM propulsion can be used to advantage in existing air-film material handling systems. The example application shown is a typical length of 100 feet and is usually installed on the floor of a warehouse. Multiples of loads 96 are loaded into the system and are moved and accumulated through the use of air-film suspended moving platforms 98 which shuttle back and forth in floor (or rack) mounted rails 14 and 16. Inflatable hose assemblies 100 lift the loads 96 clear of, or lower the loads 96 onto, the platforms 98 which, with reciprocating movement in a programmed sequence, intermittently move or accumulate these loads in an indexing manner for staging or storage or conveying with a minimum of moving parts.
FIG. 7a shows a present day pneumatic cylinder means 102 for moving the platform 98 one load position space equal to the full stroke of the cylinder. Movement is step-wise and relatively slow and requires the use of multiple platforms (four in the case of the 100 foot length shown) with overlap transfer and position indicating sensors all as operated from a central programmable control.
FIG. 7b shows a similar 100 foot length means for moving or accumulation or staging or conveying multiple loads 96 except in this case one of the support rails 16 for the single platform 104 contains ten (10) passive rail LIM primary units 18 as spaced 10 feet apart to co-act with at least one (1) platform runner 30 equipped with LIM secondary plates 42 and 44 as shown in FIG. 3. In operation the single platform 104 moves on air-film rails 14 and 16 over the full 100 foot length of the conveying or accumulating or staging system. Movement of a single platform is relatively fast and continuous without the incremental reciprocation movement of the FIG. 7a structure. Overall control is also achieved with the use of a central control and location sensors or encoder devices or doppler pulsed laser devices well known to those skilled in the art.
The examples of FIGS. 7a and 7b have been described so as to illustrate the advantages that can be gained by using passive LIM primary units 18 instead of pneumatic cylinder operation means 102. FIG. 7c illustrates the further advantages associated with using only a single active LIM primary system 50 of the present invention instead of ten (10) passive LIM 18 as shown in FIG. 7b.
FIG. 7c shows the rail 16 replaced by a rail 14 (without LIM units) which is augmented with internal ferromagnetic secondary plates 86 and an attached power collector 56. The single platform 104 is equipped with an active LIM unit 50 The use of only one active LIM unit 50 over the requirement of ten (10) passive LIM 18 units and all associated extra wiring and starters and sensors clearly indicates the advantages of the active units of the present invention in just this one example.
FIG. 7d is a perspective view of another example of an automated line application of a multiple passive LIM 18 driven sled supported assembly line with a return sled system indicated as proposed by an large automotive manufacturer. Here the replacement of the multiple passive LIM 18 rail units with only one active LIM 50 in each sled should be apparent.
FIG. 8 is a perspective view of a further application of in-process load handling in which a monorail adaption 106 of rail 14 supports active self-contained LIM air suspension and thrust units 108 which are analogous to active units 50. The unit 108 carries a hanger 110 which, in turn, supports the load 112. Active LIM units 50 have been described previously in FIGS. 3, 5 and 6 and thus operation in this monorail application is understood. However the self-contained active LIM assembly 108 requires further explanation.
FIG. 9 is a side section view of an active self-contained LIM air suspension and thrust unit 108 of the present invention. Here LIM core ferromagnetic lamination modules 114 are pivotally interlocked or mechanically linked to allow a limited amount of intermodule vertical flexing. These modules are shown to carry a load platform 116 through the use of a flexible air-bag member 118. This platform 116 serves as the load support means as well as the base plate for ancillary equipment which includes a small air compressor 120, drive motor 122, a high pressure air cooler 124, and additional serpentine cooling tubing 126 mounted in front of a compressed air heat exchanger 138. The LIM core modules 114 are similar to the pivotally assembled hinged modules 72 of compliant pad supported systems previously described in FIG. 5 except that the air-supported modules 114 include spaced apart laminations 128 each of which has a vertical extension 130 protruding as a fin into the air-bag member 18. The air provided by the compressor 120 is circulated through system high pressure air injector 132 into the air-bag member 118 for passage along the LIM core lamination extensions 130 and then subsequently to a first precooling heat exchanger 134. The air flows along passageway or conduit 136 to a second heat exchanger 138 which is equipped with a cooling air fan 140. All of this air equipment and control box 142 (for power conditioning and position response through an encoder pick-up mounted with the collector device and the rail) is contained within a streamlined cowling 144 equipped with louvred fore and aft openings 146 and an air inlet filter 148. An air intake muffler and filter 150 for the small system air compressor 120 supplies relatively cooler external ambient air to the compressor 120 which in turn supplies this air at 90 to 100 psig pressure as make-up air for the system as required to maintain approximately a 40 psig pressure for the air bearing suspension. The make-up air compensates for air lost through leakage and through operation of the nozzles of the air suspension system.
Compressed air required for the relatively few suspension nozzles 152 is fed through individual flexible supply tubes 154, core lamination air passages 156, or holes 158 drilled through the LIM core laminations 160 as shown in FIGS. 17, 18 & 19. The compliant element 162 of the self-contained active LIM runner at the support surface 164 of the concave rail 106 or convex (pipe) rail 166 is similar to that described in FIG. 5 in that a thin continuous compliant pad 170 extends over the working faces of the LIM modules over which a high temperature polymer sheet cover 172 is installed, the nozzles 152 extending through the cover 172.
Injector 132 contains an outside insulated venturi throat 174 for air velocity increase and corresponding pressure reduction according to Bernoulli principles which enhances the general pumping action of recirculation air as produced by the central high velocity jet 176 of the high pressure (100 psig) air supply. At this the already coolest part of the air recirculation system the rapid expansion of the air from the jet 176 to the lower (40 psig) air-bag pressure causes local expansion cooling according to Boyle's principles and the lowering of pressure combined with expansion cooling into a large expansion chamber 178 at this coolest part of the system causes any water contained in the compressed air to condense and drop out of the low velocity air stream in this chamber. A projecting sharp angled (entry) air outlet slot (commonly referred to as a so called "dry pipe" configuration) 180 physically reduces water droplet carryover. Further water droplet removal can be realized with the addition of small baffles and coalescent filtering media in the expansion chamber. Collected water is drained off from the bottom of the expansion chamber 178 by various automatic means readily known to those skilled in compressed air systems.
FIG. 10 is a cross-sectional view looking from the front of a self-contained air-film suspended active pressurized air-gap LIM propulsion unit 108 supported on a convex pipe system monorail 166. The extensions 130 of the LIM core laminations 128 are easily discernable with the high pressure air jet 176 and expansion chamber 178 and exit slot 182 shown. The monorail ferromagnetic pipe support 166 is shown with electric conductive cladding 184. The load support "C"-shaped carrier or bracket 110 centres the load forces symmetrically on the suspension system while allowing the offset rail supports 186 to be attached to the rail and to a main supporting structure (not shown).
FIG. 10a is a cross-sectional view looking from the front of a self-contained air-film suspended active pressurized air-gap LIM propulsion unit 108 supported on a convex pipe system monorail 166 with a second active pressurized air-gap LIM propulsion unit 109 mounted on an extended "C"-shaped carrier 111 and held to the underside of the convex pipe system monorail by an inverted second air-bag spring member 118 which applies the necessary loading and floating mounting for a second LIM core assembly 192 to the pipe system monorail. As only one module containing ancillary equipment is used to supply both the upper 190 and lower core assemblies 192 of the suspension and propulsion system, an electrical and air recirculation and make-up connection 113 is required to service the lower unit.
FIG. 10b is a cross-sectional view looking from the front of a self-contained air-film suspended active pressurized air-gap LIM propulsion unit 108 supported inside an electrically conductive concave partial pipe system monorail 185 with an extended "C"-shaped carrier 115 for central load attachment outside and below the monorail system and with a second active pressurized air-gap LIM propulsion unit unit 187 mounted on top of the propulsion unit 108 and held against the upper inside (underside) of the concave pipe system monorail by a second air-bag spring member 118 as inverted to apply the necessary loading and floating mounting of a second LIM core assembly 193 to the pipe. As only one module 190 containing ancillary equipment is used to supply both the upper and underneath laminations-containing portions 193,167 of the suspension and propulsion system an electrical and air recirculation and make-up connection 195 is required to service the upper unit. The monorail system comprises an electrically conductive pipe of, for example, aluminum of at least 18 inches in diameter, of which a full length longitudinal sector has been removed to define a slot 191 to clear the extended "C"-shaped load carrier system. Necessary ferromagnetic attachments 197 are affixed to the outside convex surface of the pipe monorail at positions and of suitable width as required to co-act with the active LIM units inside the monorail. The mounting bracket 186 is of full depth of the pipe so as to support the monorail on suitable column or wall support structures as well as to hold the pipe circular tolerance, as the pipe tends to open outwards with the section portion removal. The use of the interior of a pipe section as the guideway is of particular advantage in that the support surfaces are almost fully protected from atmospheric contaminants and they offer a saving in the ferromagnetic elements. In addition, the power collector is mounted at the extreme opposite side to the pipe slot and thus is protected to a considerable degree. It can be spring mounted, air-bag mounted, or even air-film suspension mounted (not shown).
FIG. 10c is a cross-sectional view looking from the front of dual self-contained air-film suspended active pressurized air-gap LIM propulsion units 108 supported inside electrically conductive concave partial pipe system monorails 199 arranged in a mirror image type track guideway with an extended carrier 117 for load attachment outside and above. In this example, the propulsion units are shown with bracket mountings 201 to allow slightly canted LIM positioning for possible additional stability at high speeds and to indicate that LIM propulsion units need not always be mounted vertically. Each active pressurized air-gap LIM propulsion unit has a second LIM propulsion unit mounted on top of it and held against the upper inside (underside) of each concave pipe of the track system as described in FIG. 1Ob. The track guideway system comprises parallel electrically conductive pipes of, for example, aluminum also as described previously. The use of interior pipe section guideway rails is of particular advantage with grade ballasting in that the support surfaces are almost fully protected from atmospheric contaminants and they offer a saving in the ferromagnetic elements. In addition, the power collector, shown as an inductive non-contact coil type 92 is mounted at the extreme opposite side to the pipe slot and is thus well protected.
FIG. 11 is a perspective view showing the assembly for further clarification of the present invention air-bag spring member 118 and the need for the LIM core windings 188 to exhibit a degree of flexibility between the LIM core modules.
FIG. 12 is a sectional view from the front showing an alternative construction wherein ancillary equipment is mounted in a separate module 190 to one side of the laminations-containing portion 192 to act as a counterbalance to the load support 194 as well as to lower the overall height of the assembly. The power collector system is shown as a module 196 mounted separately underneath the air supply and control module 190. A system for allowing limited float linkage for this collector pick-up is indicated.
FIG. 13 shows a two pipe track support system 198 with elevated supports 200. In this artistic rendering the active self-contained LIM propulsion units 202 are configured as "people movers" and as can be seen the present invention is clearly not restricted to interior (factory) applications. The present invention is capable of carrying loads of considerable weight.
FIG. 14 is an artistic perspective of a monorail-type self-contained pressurized air-gap LIM propulsion system 204. Various components of the system are shown in an exaggerated manner for ease of comprehension. These components include the air-bag spring 206, the flexible LIM module 208 and the compliant pad 210 having a high temperature flexible sheet cover 212. In this embodiment a small gas turbine engine (not shown) is mounted inside the streamlined cowling 214 and is capable of supplying additional thrust if desired. The compressor stage bleed acts as a source for compressed air and drives an on-board electrical alternator. This alternator is used for the energizing the LIM for variable thrust levels and speeds and provides power for a motor and an on-board compressor to effect the necessary extensive cooling of the flexible LIM primary system as operated on a long distance elevated monorail LIM secondary. The secondary in this application is provided by an elevated pipeline 216 having a ferromagnetic core 218 and an electrically conductive aluminum cladding 220.
FIG. 15 illustrates an artistic rendering of another application for the pressurized air-gap active LIM drive of this invention. In this case the application is an elevator system 222 in which air-bag mounted LIM units 224 operate on both sides of vertical pipe secondary elements 226 as shown or on a single central pipe secondary (not shown) to completely eliminate the need for heavy weights and speed limiting cables and headshaft drives, although a simple counterweight system may be employed if desired. The elevator cage is preferably streamlined in order to compensate for the high vertical speeds achievable.
FIGS. 16a-16d are detail drawings of the LIM lamination core plates used in this invention. Two types of core plates 230 and 232 are shown, both being formed of a ferromagnetic material of about 1.3 mm in thickness and being provided with longitudinally alternating generally rectangular teeth 234 and slots 236, the electrical windings being directed through the slots of the assembled plate modules as depicted earlier. In FIG. 16a the plates 230 are shown with the teeth 234 and slots 236 located along the lower portion thereof and with the upper portion having angled forward and rearward edges 238 and 240 respectively. The angled forward edge 238 has a generally semi-circular recess 242 formed therein while the angled rearward edge 240 has a generally semi-circular protrusion 244 formed thereon, each protrusion 244 being adapted for rotatable engagement with a corresponding recess 242 of a longitudinally adjacent plate 230. The fit between the protrusion 244 and the recess 242 is fairly tight, while limited clearance between adjacent angled edges 238 and 240 allows for a limited degree of vertically rotational movement between longitudinally connected plates 230.
FIG. 16b shows the other plates 232, which plates have rectangular teeth and slots 234 and 236, respectively, identical to those of the plates 230. The plates 232, however, are provided with vertical extensions 246 which form the fin extensions 130 mentioned above with respect to FIG. 9. The forward and rearward edges 248 and 250 of the plates 232 slope oppositely to the forward and rearward edges of the plates 230 and with these plates the forward edge 248 is provided with a semi-circular protrusion 252 while the rearward edge 250 is provided with a semi-circular recess 254, the protrusions 252 and the recesses 254 serving the same purpose as the protrusions 244 and the recesses 242 of the plates 230. The first-described plates 230 are shown in dotted lines in FIG. 16c in relation to the plates 232.
As seen in FIG. 16d the plates 232 are spaced apart so as to alternate laterally with the plates 230 across the width of a module 256, with the extensions 246 projecting upwardly so that they can reside within the confines of an air-bag in the overall assembly and thus be subjected to cooling air passing thereover as previously described. While every second plate is shown as having an extension 246 it is understood that more than one standard plate 230 could be positioned between spaced apart extended plates 232. The teeth and slots of adjacent laterally adjacent plates are aligned so that a plurality of slots extending the full width of a module are created, which slots receive the electrical windings as taught in U.S. Pat. No. 5,128,569. The windings that bridge the intermodule gaps should not be wound overly tightly so that the desired limited undulating movement of the modules relative to each other is not hindered. That undulating movement is available through the interengaging and alternating protrusion-in-recess pivotal connections provided at each end of the modules. If desired, the protrusions 244 and 252 can be provided with alignable central apertures 258 which in turn receive a hinge-pin 260 to connect (a) the laterally adjacent plates of one module together and (b) to pivotally connect each module to a longitudinally adjacent module.
As seen best in FIG. 16d the bottom surface of the teeth 262 defined by laterally adjacent plate teeth 234 are machined to have a convex profile, which profile is complementary to the concave trough or upper surface 20 of a rail 14 (for example). If the lamination module is to be used in a LIM primary that will be used on a convex rail (for example a pipeline-type monorail as in FIG. 14) the bottom profile of the module teeth 262 would be concave, rather than convex.
FIG. 17 is a side view section showing the support platform 116 with the air passing along the interior of the air-bag spring 118 flowing over the lamination extension cooling fins 130. The compliant layer pad 170 is shown, along with the polymer cover 172 and the air jets 264 exiting through the nozzles 152 provided in the cover 172 into the suspension air-film cavity interface with the appropriate rail support surface.
FIG. 18 is an enlarged partial perspective view of a single nozzle 152 with a flexible compressed air supply tube 154 attached thereto. A clearance cavity 266 is shown as surrounding the welded or screwed in place hypodermic or like nozzle 152. the flexible tube 154 is seen as passing downwardly from the interior of the air-bag 118 through a hole or gap 268 provided between an adjacent pair of laminations within a module.
FIG. 19 is an enlarged sectional view of a single nozzle cavity 266 showing the hypodermic or like nozzle 152 welded into the cover 172 and that portion of the nozzle which extended beyond the outer surface of the cover having been removed as by grinding or otherwise so that the nozzle is flush with the outer surface of the cover 172. Flexible tubing 154 as fed through the LIM module laminations 128 is attached to the nozzle 152 in such a manner so as to allow a degree of localized cover movement. The clearance pocket or cavity 266 of not more than an inch diameter is cut in the compliant pad 170 around the nozzle 152 to allow for additional localized flexing or vibration.
The foregoing has described an active LIM propulsion and suspension system which has numerous advantages and applications. It is understood that a competent engineer could readily devise alternative structures and applications without departing from the spirit of the present invention. Accordingly the protection to be afforded this invention is to be determined from the claims amended hereto. | The invention relates to an active linear induction motor system that has particular advantage with a SAILRAIL® air guided and supported air bearing system. In this case the secondary for the motor is the support rail, which rail can have a convex or a concave operating surface, is electrically conductive, and has ferromagnetic material in close proximity to the operating surface. The primary for the motor is found in a runner which cooperates with the rail and supports the load to be carried in the system. The primary includes a plurality of laterally adjacent, longitudinally extending and articulated ferromagnetic laminations having a longitudinally toothed surface that is transversely arcuate to be complementary to the rail operating surface. Electrical windings are wound about selected groups of teeth of the laminations as a LIM primary. A compliant pad adjacent the laminations is capable of deformation under load and at least partial recovery after load removal. Electrical power is continuously provided to the primary as it moves along the rail and polyphase electrical current is fed to the electrical windings. Cooling fluid is continuously provided to the laminations during operation of the primary. The system also provides pressurized fluid at high velocity into the space between the rail operating surface and the compliant pad, to support the primary member above the operating surface and to provide a minute pressurized magnetic and suspension gap between the primary and secondary members for efficient linear motor operation. | 5 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] The present application is a continuation of U.S. patent application Ser. No. 12/561,183 filed Sep. 16, 2009 and entitled “Float Rack,” which is incorporated herein by reference for all purposes.
TECHNICAL FIELD
[0002] The disclosure relates generally to storage systems, and in particular to storage of floatation devices.
BACKGROUND
[0003] A standard closed foam float design includes a pillow formed by a loop in the foam material. Such floats are often difficult to store and cause clutter near pools, in garages, or on boats.
SUMMARY
[0004] Embodiments of the present disclosure generally provide a rack for storing floats. A float rack may comprise a vertical support post, a plurality of slip-Ts and a plurality of float support arms. The vertical support post will typically have a top end and a bottom end. The slip-Ts are connected to the vertical support post to provide a rotating joint about the vertical support post. The float support arms are attached to the slip-Ts.
[0005] Other technical features may be readily apparent to one skilled in the art from the following figures, descriptions and claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] For a more complete understanding of this disclosure and its features, reference is now made to the following description, taken in conjunction with the accompanying drawings, in which:
[0007] FIG. 1 is a view of a float rack installed to a building near a swimming pool;
[0008] FIG. 2 is a close-up view of the float rack of FIG. 1 with a float;
[0009] FIG. 3 is a close-up view of a float rack with a float;
[0010] FIG. 4 is a close-up of a float rack with two floats;
[0011] FIG. 5 is a top view of the float rack of FIG. 4 ;
[0012] FIG. 6 is a view of a float rack;
[0013] FIG. 7 is a top view of the float rack in FIG. 6 ;
[0014] FIG. 8 is a view of a float rack;
[0015] FIG. 9 is a top view of float rack in FIG. 8 ; and
[0016] FIG. 10 is a sectional view of the float rack in FIG. 8 .
DETAILED DESCRIPTION
[0017] FIG. 1 is a view of a float, rack 10 with floats 12 installed on a building 14 near a swimming pool 16 . Float rack 10 has three arms 18 sized to support floats 12 as shown. Float rack 10 is mounted to an outside wall of building 14 in the figure shown, but may be mounted inside, as in a garage or storage area. Floats 12 are common closed cell foam floats with a loop forming a headrest 20 . Arms 18 are sized to fit within headrest 20 of float 12 .
[0018] FIG. 2 is a close-up view of the float rack 10 of FIG. 1 with a float 12 hanging by headrest 20 off of arm 18 . Arm 18 is shown to have ribbing 22 in its outer surface. Ribbing 22 provides an improved aesthetic and allows for easy sliding of headrest 20 over arm 18 . Arm 18 also has an end cap 24 to seal the arm 18 and provide for a smooth end. Arms 18 are attached to slip-Ts 26 which rotate about a vertical support post 28 . Vertical support post 28 has an upper end 30 and a lower end 32 , each having an end cap 24 .
[0019] Near the upper end 30 of vertical support post 28 is a fixed-T 34 attached to upper support 36 . A surface mount 38 is connected to the upper support 36 opposite the fixed-T 34 . Near the lower end 32 of vertical support post 28 is another fixed-T 34 attached to a lower support 40 . Another surface mount 38 is connected to the lower support 40 opposite the fixed-T 34 . Lower support 40 is slightly longer than upper support 36 to allow arms 18 to be aligned on one side of vertical support post 28 with multiple floats 12 .
[0020] Screws 42 are placed adjacent to slip-Ts 26 to prevent unwanted axial movement along vertical support post while allowing rotation of slip-Ts 26 about vertical support post 28 .
[0021] FIG. 3 is a close-up view of a float rack with a float 12 and twice as many arms 12 as in FIGS. 1 and 2 . Vertical support post 28 is elongated to allow for two slip-Ts 26 between the fixed-T 34 and the upper end 30 of vertical support post 28 . A single screw 42 is still sufficient to restrain unwanted axial movement as slip-Ts rotate against each other without interference. Likewise two slip-Ts 26 are positioned between the fixed-T and the lower end 32 of vertical support post 28 . Similarly two slip-Ts 26 are positioned near the middle of vertical support post 28 between fixed-Ts 34 .
[0022] Again, lower support 40 is slightly longer than upper support 36 to allow three arms 18 to be aligned on each side of vertical support post 28 with multiple floats 12 .
[0023] FIG. 4 is a close-up of a float, rack 10 with two floats 12 hanging by headrests 20 . In this embodiment the slip-Ts 26 are arranged along vertical support post 28 between fixed-Ts 34 . The uppermost arm 18 is similar to those discussed with regards to FIGS. 1 , 2 , and 3 . The three lower arms 18 each have an elbow 44 on arm 18 and a spacing member 46 , 48 , 50 between the elbows 44 and the slip-Ts 26 . The spacing element 46 is shorter than spacing element 48 which is in turn shorter than spacing element 50 . Thus spacing elements 46 , 48 , 50 act to stagger arms 18 and provide space for floats 12 . Thus upper support 36 and lower support 40 may be the same length.
[0024] FIG. 5 is a top view of the float rack 10 of FIG. 4 more clearly showing the different lengths of spacing elements 46 , 48 , 50 and the resultant spacing of arms 18 .
[0025] FIG. 6 is a view of a float rack 60 having a vertical support post 28 and three fixed-Ts 34 supporting pairs of arms 18 with end caps 24 . The fixed-Ts 34 are arranged to provide an even distribution of arms 18 as shown in FIG. 7 . Vertical support post 28 is secured in base 52 .
[0026] FIG. 7 is a top view of the float rack 60 in FIG. 6 showing the arrangement of arms 18 .
[0027] FIG. 8 is a view of a float rack 70 having a vertical support post 78 and a base 52 . Slip-Ts 26 support arms 18 with end caps 24 . Support post 78 may be a composite support post made of an outer support post 54 and an inner support post 56 , as shown in FIG. 10 . In the alternative, vertical support post 78 may be a single element with a screw below the slip-Ts 26 from unwanted axially movement.
[0028] FIG. 9 is a top view of the float rack 70 in FIG. 8 showing that arms 18 may rotate independently about vertical support post 78 .
[0029] FIG. 10 is a sectional view of the float rack 70 in FIG. 8 showing a composite version of vertical support post 78 . The composite version of vertical support post 78 has an outer support post 54 extending from base 52 to the bottom of slip-Ts 26 . Inner support post 56 extends from base 52 to the top of slip-Ts 26 . Slip-Ts 26 are sized to fit about inner post 56 but not slide over outer post 54 such that the terminus of outer post 54 forms a shoulder to support slip-Ts 26 . Inner post 56 runs the entire length of outer post 54 to provide additional rigidity to vertical support post 7
[0030] All of the above embodiments, or parts thereof, may be made with a thermoplastic polymer to prevent corrosion and rusting. Polyvinyl chloride (PVC) is a suitable material for these embodiments and furniture grade PVC is useful where a thicker wall is desired. It is possible to obtain furniture grade PVC with a colorant treatment throughout the material, to provide a more pleasant appearance and protection from fading, cracking, and brittleness. Where screws 40 are required they may be made of stainless steel to provide a non-corrosive alternative that has sufficient strength.
[0031] It may be advantageous to set forth definitions of certain words and phrases used in this patent document. The terms “include” and “comprise,” as well as derivatives thereof, mean inclusion without limitation. The term “or” is inclusive, meaning and/or. The phrases “associated with” and “associated therewith,” as well as derivatives thereof, may mean to include, be included within, interconnect with, contain, be contained within, connect to or with, couple to or with, be communicable with, cooperate with, interleave, juxtapose, be proximate to, be bound to or with, have, have a property of, or the like.
[0032] While this disclosure has described certain embodiments and generally associated methods, alterations and permutations of these embodiments and methods will be apparent to those skilled in the art. Accordingly, the above description of example embodiments does not define or constrain this disclosure. Other changes, substitutions, and alterations are also possible without departing from the spirit and scope of this disclosure, as defined by the following claims. | Embodiments of the present disclosure generally provide a rack for storing floats. A float rack may comprise a vertical support post, a plurality of slip-T joints and a plurality of float support arms. The vertical support post may have a top end and a bottom end. The slip-T joints are connected to the vertical support post to provide a rotating joint about the vertical support post. The float support arms are attached to the slip-T joints. | 4 |
CROSS REFERENCE TO RELATED APPLICATIONS IF ANY
NONE.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to the art of coverings for doors and windows and more particularly to the preparation of vanes which may be used for such door or window coverings. In its most preferred embodiment, the present invention relates to novel vane structures which include fabric coverings and foam cores. The present invention also relates to a method of making such foam core products.
2. Description of the Prior Art
A wide variety of coverings for doors and windows are known to the art. These include very old products such as roller shades and venetian-type blinds, as well as the newer types of “soft” window coverings including pleated and cellular blinds and shades, various light control products, and fabric covered vertical blinds. The latter typically include a track which extends across the opening to be covered, with trucks mounted in the track for movement by a wand device or by cords and pulleys. Vanes are attached to the truck and are pivotable about a longitudinal axis of the vanes to open them to a first position and thus permit light to enter a room and to pivot them to a second position in which the vanes overlie one another, in which case privacy is achieved.
Recently, a number of such vertical blind products have been proposed to include hollow fabric vanes, which can include stiffening compounds to insure that the bottom rotates the same amount as the top with no twist top to bottom to achieve an aesthetically pleasing product. Moreover, light weight fabrics have been attached to thin, rigid vanes to achieve a “blind with curtain” product, one of which is disclosed in U.S. Pat. No. 5,638,881 issued to Ruggles, et al. on Jun. 17, 1997 and entitled “BLIND WITH CURTAIN”.
It has also been proposed that vanes for door and window coverings can be prepared in a tubular configuration, the cross-section of such vanes simulating an air foil. They are preferably made from material having diagonal, dimensional stability or memory so that they resist stretching in the longitudinal direction. It is also known that with such vanes, a reinforcing strip can be applied to an open end of the vane to provide a positive and durable attachment for supporting the vane from an operating system. One patent describing such vanes is U.S. Pat. No. 5,797,442, issued Aug. 25, 1998 to Colson, et al., for “Vanes For Architectural Covering and Method of Making Same”.
The vanes used in the aforementioned Colson, et al. patent have a cross sectional configuration best illustrated in FIG. 6 d of the patent, i.e., one resembling an air foil. Various techniques are described for insuring that the shape is maintained, such as the use of stiffening compounds, or in the embodiment shown in FIG. 12, the use of a resilient rubber strip along the inside of the vane, i.e. at the blunt end. Various single and double thickness vanes and further vane structures are also disclosed in PCT International Application WO96/35881, to the same inventor, which application claims priority to the parent application of the aforementioned '442 Colson, et al. patent.
FIG. 1 of the Colson, et al. patent discloses a vertical arrangement in which a plurality of the vanes are suspended from a track 30 and are pulled across the opening to be covered using a wand. The vanes may also be rotated to an open, light-admitting position as shown in FIG. 1, or to a privacy position, shown in FIG. 3. If the vane is constructed from transparent or sheer materials, light can be admitted in a diffused pattern into the room when in the closed position, as illustrated in FIG. 4 of this patent.
While new window coverings are shown in the PCT application and the issued Colson, et al. patent, a variety of different and useful door and window coverings employing foil shaped vanes are not disclosed or contemplated. Furthermore, while some thermal insulation benefits may be obtained by using hollow vanes, the amount of insulation is relatively modest. Moreover, the hollow vanes employing fabric are delicate and will quickly become damaged in more severe end use applications. A door or window covering which overcomes these and other disadvantages of the prior art door and window coverings would be a significant advance in this art.
FEATURES AND SUMMARY OF THE INVENTION
A primary feature of the present invention is to provide a new foam core vane for door and window coverings.
Another feature of the present invention is to provide a method of manufacturing a new foam core vane for door and window coverings.
A different feature of the present invention is to provide an improved vane for door and window coverings which may be hung horizontally or vertically.
Another feature of the present invention is to provide a vane for door and window coverings which has high insulation characteristics when the vanes are in a position in which they overlap one another.
Yet another feature of the present invention is to provide a vane for door or window coverings which may be constructed from a wide variety of exterior covering materials.
How the foregoing and other features of the present invention are accomplished will be described in the following detailed description of the preferred embodiment, taken in conjunction with the FIGURES. Generally, however, the features are provided in a vane which, in cross-section, is generally in the shape of an air foil and which includes a fabric exterior and a foam core, preferably a core made of urethane or polyisocyanurate foam. The vanes are manufactured by folding a strip of material to form a receiving area for the deposit of foam-forming chemicals, continuing to fold the material and passing the material into a mold including upper and lower mold cavities which together define the desired final shape for the vane. Preferably, the mold is a traveling mold and the foam expands within the mold to fill the mold and press the fabric covering against the interior mold surface. An adhesive may optionally be applied to connect the two edges of the strip at what becomes the thin or rear of the foil. When the vane leaves the mold area, it is cut into desired lengths by a cutting means, such as a rotary knife. Other ways in which the above and other features of the invention are accomplished will become apparent to those skilled in the art after they have read the remainder of this specification, such other ways falling within the scope of the present invention if they fall within the scope of the claims that follow.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a door or window covering with which the vanes of the present invention may be employed;
FIG. 2 is a cross-sectional view taken along the line 2 — 2 of one of the vanes of FIG. 1;
FIG. 3 is a schematic view of the manufacturing method and apparatus used for preparing the foam core vanes of the most preferred form of the present invention;
FIG. 3A is a cross-sectional view taken through the line 4 — 4 of FIG. 3; and
FIG. 4 is a perspective view showing the vanes of the present invention in a horizontal orientation, only three of the vanes being shown, together with a head rail, bottom rail, lift cords and ladder cords.
In the various FIGURES, like reference numerals are used to indicate like components.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Before beginning the description of the preferred embodiment of the present invention and an alternative embodiment, several general comments should be made about the applicability and the scope of the present invention.
First, while the illustrated embodiment shows the vanes made with a foam core used in a vertical blind, the vanes could also be used in conjunction with other window covering designs known to the art, including the “blind with curtain” described in the aforementioned Ruggles, et al. patent or in various light control products in which one or two sheer fabrics are attached to the forward and rearward edges of the vanes.
Second, while the illustrated embodiment shows the vanes deployed in a vertical orientation, the vanes can be used in a horizontal system either with or without sheer fabric strips or sheets attached thereto. For example, the vanes could be manipulated and supported in the way typically practiced for venetian or mini-blind products in which a head rail and bottom rail are used together with lift cords for altering the distance between the bottom rail and the head rail, and tilting the vanes for light control.
Third, the cross-sectional shape of the vanes could also be widely varied without departing from the intended scope of the invention. The air foil shape of the illustrated embodiment is therefor for purposes of illustration, rather than limitation. The vanes could be prepared to have a symmetrical, oval, cross-sectional configuration, a configuration in which the vanes come to sharper points at both the forward and the rearward edges, vanes in which the cross-sectional shape is rectangular and, in connection with the latter, rectangles in which the foam core vanes are quite thin and resemble generally the types of slat vanes used with present day vertical blinds, or other cross-sectional shapes.
Fourth, the hardware used with the vanes of the present invention will not be described in detail because, in and of itself, the hardware does not form part of the present invention. Accordingly, such devices as the head rail, tracks, trucks, wands, pivot systems and the like can be selected from any of those currently known or developed subsequently as alternative for such present day products.
Fifth, polyurethane and isocyanurate foams are particularly preferred for use in the present invention because they are readily available and have been used for many years in furniture applications such as cushions for seating and for other insulation purposes for residential and commercial facilities. Other foams could also be used provided they have reaction times to allow them to fully inflate the fabric into the mold openings during the period the covering is captured within the mold cavities. Obviously, the time costs for manufacturing vane products will be lowest when the highest reactivity of the foam components is utilized. Furthermore, the foams may include well-known components for reducing flammability and/or smoke generation of the foams. The physical property of the foam itself can also be readily varied by those familiar with the foam art, so that the vanes could have a spongy feel when grasped or so that a more rigid foam is produced. Techniques for modifying the durometer, reaction speeds and physical properties of such foams are widely known and described in various texts dealing with foam chemistry and in product brochures of major manufacturers of the foam starting materials including polyols, isocyanates, catalysts and the like.
Sixth, the preferred and illustrated embodiment uses a single type of fabric for the entire outer covering of the vane. The material may be selected from woven and non-woven fabric materials of the type already known in the blind and door and window covering art including polyesters, polyolefins, rayons as well as natural materials such as cotton, linen, silk, wool or other fabric materials. Moreover, composite fabric starting strips can be used so that different sides of the vanes have different properties, such as color, light reflectancy, colorfastness and the like. Such composite fabric strips are known in the window covering art and are described, for example, in European Published Application No. EP 0 692 602 A1 (published 17.01.1996, Bulletin 1996/03) issued to the assignee of the present invention and describing the preparation of starting materials for cellular and light control products. The starting material is made by welding, such as by sonic welding, adjacent edges of fabric strips of two different types together. In that published application, the selection is generally made based on cost so that lower cost non-woven materials can be used for the exterior of a door or window covering and more expensive designer materials could be used for the portion of the product facing to the inside. Depending upon the final use of the foam core vanes of the present invention, the same considerations that govern the choice of materials in that published application could also be used for the selection of starting materials for foam core vanes.
Proceeding now to a description of the preferred embodiment of the invention, FIG. 1 illustrates a door or window covering 10 made from a plurality of elongate vanes 12 . In the illustration, a valance 14 extends across the top of the opening to be covered and the cut away portion of the valance shows a track 16 mounted behind the valance on the wall or ceiling. Trucks 18 , one for each of vanes 12 , are mounted for sliding movement along track 12 , the trucks 18 being interconnected with chains or other mechanisms (not shown) to maintain a preselected spacing between the trucks 18 when the door or window covering 10 is fully deployed across the opening as shown in the illustration. A clip 20 is provided at the top of each vane 12 for attaching the vanes 12 to the trucks 18 . A wand 22 is also shown in FIG. 1 for deploying door or window covering 10 to an open position (as illustrated) wherein the trucks 18 and vanes 12 are spaced apart from one another or a closed position (not shown) in which the truck 18 and vanes 12 are bunched together at one side of the opening. Wand 22 could also be used for causing the clips 20 to rotate causing a 90° movement of each of vanes 12 from the FIG. 1 position, typically when the door or window covering 10 is fully deployed over the opening. It should be appreciated then that in such rotated positions, the vanes 12 will overlap one another at least partially, providing light control and privacy. As mentioned previously, the rotation of the vanes can be accomplished in a variety of well-known ways, such as using beaded chains and pulley mechanisms.
The cross-sectional configuration of vanes 12 according to the preferred embodiment is illustrated in FIG. 2 . Vanes 12 are preferably shaped like an air foil having a blunt forward edge 24 , a pair of gently curving sides 26 and 28 and a tapered, pointed edge 30 . It will also be appreciated from this drawing that the vanes are comprised of a fabric outer covering 32 and a foam core 35 . The illustrated vane 12 has the same fabric covering 32 extending about the entire core 35 .
A preferred apparatus for preparing vanes 12 is schematically illustrated in the top view of FIG. 3. A strip 40 of starting fabric material is shown at the left side of the illustration and comes from a supply roll (not shown). Strip 40 progresses toward the right in FIG. 3 which will be the machine direction for purposes of the remaining description.
Strip 40 is folded using rollers 41 , folding boards or other devices which are well-known in the door and window covering art so that the beginning of the forward edge 24 is created. Downstream of the rollers 41 a pocket section 42 is formed in strip 40 , the section 42 being generally U-shaped in cross-section.
A pump 44 provides foam forming chemicals through a pipe 44 into the bottom of the pocket section 42 . The pump in turn is supplied from a plurality of sources with individual foam forming chemicals, such as polyols, isocyanates, water or other ingredients well-known in the foam art. The mixture of the chemicals to form the foam reaction can take place in the pump 43 , in pipe 44 or if separate conduits are provided in pipe 44 , upon deposit of the ingredients in pocket section 42 .
After the deposit of foam forming chemicals, the strip 40 enters a mold section 50 where right and left side mold halves 51 and 52 engage the strip and together define a cavity 57 having the desired final shape of the vane 12 . In the schematic illustration, the mold halves 51 and 52 are shown as short segments which travel on a continuous oval track and which together define a straight section 59 between an entry point 60 and an exit point 61 . Between points 60 and 61 the mold halves 51 and 52 form a continuous mold section having the desired final shape, i.e. a foil shape.
Other mold forming techniques could be used. For example, a pair of elastomeric mold halves could be employed and travel along a path similar to that depicted in FIG. 3 . Each half of such an elastomeric mold could have the configuration of one half of a foil shape. Moreover, the drives for the moving mold components are not illustrated in detail, but could include a pair of cog wheels 64 at each end of mold section 50 , one pair of which would be driven by a motor (not shown).
During movement of strip 40 between points 60 and 61 , a foam forming reaction takes place which forces the material of strip 40 outwardly toward the cavity 57 formed by mold halves 50 and 51 . The foam reactants are selected to insure that the foam has completely reacted by the time the strip 40 reaches point 61 . At such location, the foam will have completely pressed the fabric 32 against the interior of cavity 57 and formed a bond with the fabric 32 . The core 35 will be generally uniform in foam density. By reference to FIG. 3A it will be noted that the sides 26 and 28 come to a point at end 30 , and in some cases it may be advisable to add an adhesive or a sonic weld to this location to insure that the fabric covering 32 will not fray or unravel at the pointed edge. Such an adhesive could be applied upstream of point 60 from a hot melt adhesive bead applicator or could be provided as a sealant immediately upon the passage of vane 12 beyond point 61 .
The final component of the schematic apparatus shown in FIG. 3 is a rotary cut off knife 70 which cuts the completed vane precursor into the individual vanes 12 .
While the in situ formation of the foam core 35 within fabric coating 32 is preferred, the core 35 can also be prepared separately and the covering 32 can thereafter be wrapped about the core. Alternatively, the fabric covering 32 can be formed in the shape of a hollow tube and thereafter the formed foam core can be inserted therein. In either case, an adhesive may be applied to the inside of the fabric cover 32 or over the foam core 35 to form a bond between the fabric and foam or the foam core 35 can be frictionally held within the cover 32 .
A partial perspective view showing the vanes 10 of the present invention used in a horizontal orientation is shown in FIG. 4. A head rail 75 and a bottom rail 77 are illustrated in schematic form, with ladder cords 78 and lift cords 79 extending therebetween. Those skilled in the art will appreciate that mechanisms may be located in the head rail, bottom rail or both to raise and lower the bottom rail with respect to the head rail and to tilt the ladder cords to move the vanes 10 from a closed position in which they are generally parallel with one another to an open position in which they are substantially parallel. As mentioned previously, the hardware, lifting and tilting mechanisms are not, in and of themselves, part of the present invention and are hence not shown in detail.
While the present invention has been described in connection with a preferred embodiment and an alternate embodiment for the deployment of the vanes, it is not to be limited to the illustrated embodiment but is to be limited solely by the scope of the claims which follow. | Foam core vanes useful with door or window coverings and which may be hung vertically or horizontally include an outer fabric cover and an inner foam core. Preferably, the vanes are shaped to have a blunt forward edge, gently curving sides and a pointed rear edge, resembling an air foil. A method of preparing the vanes includes injecting foam producing chemicals into a fold of the outer fabric as the fabric enters a mold section comprised of upper and lower molds moving along tracks. The foam expands to press the fabric into the mold and cures during travel through the mold section. A rotary knife cuts the foam core vanes to the desired length. Preferred foams are urethane and polyisocyanurate foams. | 4 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method for preparing an aqueous dispersion of a developer and, in particular, to a method for preparing an aqueous dispersion of a developer which can provide recording paper substantially improved in the color developing density and color developing velocity of recorded images, and printability of the developing surface thereof; as well as a pressure-sensitive recording paper obtained by the use of a coating composition containing the aqueous dispersion of a developer.
2. Description of the Prior Art
Active clay has been called inorganic developer, while phenol resins of novolak type and metal salts of nuclear-substituted salicylic acid have been called organic developers and have widely been employed for making pressure-sensitive recording paper (see, for instance, Japanese Patent Publication for Opposition Purpose (hereinafter referred to as "J.P. KOKOKU") Nos. Sho 42-20144 and Sho 51-25174). Any organic developer of this type is finely divided or finely dispersed in a medium which is commonly water, mixed with an inorganic filler, an adhesive or the like and then applied onto the surface of a substrate such as paper (see, for instance, J.P. KOKOKU No. Sho 48-16341 and Japanese Patent Unexamined Publication (hereinafter referred to as "J.P. KOKAI") No. Sho 54-143322).
Incidentally, the metal salts of nuclear-substituted salicylic acids used as developers for pressure-sensitive recording paper (hereunder simply referred to as "developer(s)") are in general an amorphous solid having a specific softening point and is applied onto the surface of paper after dispersing in water. Therefore, it is quite desirable that developers be provided in the form of a water dispersion in which the developer has a desired particle size and which is thick and excellent in handling properties and safety.
However, when coarse particles of a developer is directly pulverized into fine grains in water containing a dispersing agent or the like with a ball mill or a sand grinder (sand mill), it is very difficult to obtain fine particles of a developer and the resulting dispersion becomes highly thixotpropic and has low fluidability which in turn makes the handling thereof difficult. On the other hand, an emulsified dispersion having good fluidability even at a high concentration can be obtained by adding an organic solvent or a plasticizer to a developer to form a liquid product and then emulsified and dispersed in water containing a dispersing agent with a strong dispersing means. However, the dispersed particles comprise, in this case, liquid drops containing an organic solvent or a plasticizer, therefore, the particles grow into large particles and the particles agglomerate in the vicinity of the wall of a container and deposit onto the wall during storage over a long time period. Thus, an emulsion having sufficient stability cannot be obtained.
Some solutions for these problems have been proposed in particular in J.F. KOKAI No. Sho 63-173680 or Sho 64-34782 which discloses a method for preparing an aqueous dispersion of a developer containing emulsion particles having a desired particle size, having good fluidability even at a high concentration and good in storage stability. The method comprises dissolving a developer in an organic solvent, emulsifying and dispersing the resulting organic solution in an aqueous solution containing a dispersing agent and then heating the resulting dispersion to distill off and remove the organic solvent.
In this way, to heat a dispersion per se for removing the organic solvent is desirable from the viewpoint of desired uses of the developers and the stability of the resulting dispersion, but strictly speaking, these proposed methods suffer from some problems.
More specifically, stable dispersed state of the emulsified dispersion of a developer containing an organic solvent must be held at a high temperature for a long time period for completely distilling off and removing the organic solvent from the dispersion per se. For this reason, the dispersion must be a system which is an excellent protective colloid. However, such an excellent protective colloid system is in general highly foamable and correspondingly the space in a distillation vessel is occupied by stable foams during the distillation of the organic solvent which prevents rapid removal of the organic solvent and in a worst case, the operation for removing it would often be interrupted. On the other hand, if a dispersion system having low foaming properties is selected, the system is in general a poor protective colloid, a part of the dispersion is broken during the operation for removing the organic solvent, in turn excessively large aggregates of a developer are formed and thus the resulting dispersion is often practically unacceptable.
These two tendencies reciprocal to one another become more conspicuous, as the size of the distillation vessel increases, the desired particle size of the developer is small, an external force such as the strength of stirring is high and the concentration of the developer is high. This is a major obstacle in production of stable aqueous dispersions of this kind in an industrial scale.
SUMMARY OF THE INVENTION
Accordingly, an object of the present invention is to provide a method for preparing an aqueous dispersion of a developer which can provide recording paper improved in the color developing density and color developing velocity of recorded images.
Another object of the present invention is to provide a method for preparing an aqueous dispersion of a developer which can provide recording paper substantially improved in printability of the developing surface thereof.
A further object of the present invention is to provide pressure-sensitive recording paper obtained using a coating composition containing the aqueous dispersion of the developer.
The aforementioned objects can effectively be achieved by providing, according to an aspect of the present invention, a method for preparing an aqueous dispersion of a developer which comprises dissolving a developer composition comprising a nuclear-substituted salicylic acid salt represented by the following general formula (I): ##STR2## (wherein R 1 , R 2 , R 3 and R 4 may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group having not more than 15 carbon atoms, a cycloalkyl group, a nuclear-substituted or unsubstituted phenyl group, or a nuclear-substituted or unsubstituted aralkyl group with the proviso that two adjacent groups selected from R 1 , R 2 , R 3 and R 4 may be bonded together to form a ring; n is an integer of not less than 1; and M represents magnesium, calcium, zinc, aluminum, iron, cobalt, nickel or a basic ion thereof); emulsifying and dispersing the resulting organic solution in an aqueous solution containing an acrylamide copolymer whose degree of polymerization is not less than 100 and which is obtained by copolymerizing 96 to 70 mole % of acrylamide and 4 to 30 mole % of an alkyl or alkoxyalkyl, having not more than 4 carbon atoms, ester of acrylic acid, methacrylic acid, itaconic acid or maleic acid; and then heating the resulting emulsified dispersion to remove the organic solvent by distillation.
According to another aspect of the present invention, there is provided a method for preparing an aqueous dispersion of a developer which comprises dissolving a developer composition comprising a nuclear-substituted salicylic acid salt represented by the following general formula (I): ##STR3## (wherein R 1 , R 2 , R 3 and R 4 may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group having not more than 15 carbon atoms, a cycloalkyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted aralkyl group with the proviso that two adjacent groups selected from R 1 , R 2 , R 3 and R 4 may be bonded to form a ring; n is an integer of not less than 1; and M represents magnesium, calcium, zinc, aluminum, iron, cobalt, nickel or a basic ion thereof); emulsifying and dispersing the resulting organic solution in an aqueous solution containing an acrylamide copolymer whose degree of polymerization is not less than 100 and which comprises 96 to 70 mole % of acrylamide and 4 to 30 mole % of an alkyl or alkoxyalkyl, having not more than 4 carbon atoms, ester of acrylic acid, methacrylic acid, itaconic acid or maleic acid; then heating the resulting emulsified dispersion to remove the organic solvent by distillation; and subjecting the resulting aqueous dispersion to a wet pulverization treatment so that the rate of reduction in the average particle size of the developer dispersed therein is not more than 10%.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The problems encountered when an organic solvent is completely removed from an emulsified dispersion containing the same have already been discussed above, but these problems can desirably be solved if a dispersion system which is a good protective colloid system and has very low foaming properties is developed.
In this respect, it has been found out that the acrylamide copolymer having a specific composition has high protective action in a colloidal system and can provide a dispersion system having low foaming properties and thus the foregoing problems can be eliminated. More specifically, it is confirmed that a dispersion system which is a good protective colloid system and has low foaming properties can be obtained when a specific acrylamide copolymer is employed, the degree of polymerization thereof being not less than 100 and the acrylamide copolymer being obtained by copolymerizing 96 to 70 mole % of acrylamide and 4 to 30 mole % of an alkyl or alkoxyalkyl, having not more than 4 carbon atoms, ester of acrylic acid, methacrylic acid, itaconic acid or maleic acid.
Specific examples of the alkyl or alkoxyalkyl, having not more than 4 carbon atoms, esters of acrylic acid, methacrylic acid, itaconic acid or maleic acid include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, sec-butyl acrylate, 2-methoxyetyl acrylate, 2-ethoxyethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethoxyethyl methacrylate, dimethyl itaconate, diethyl itaconate, dimethyl maleate, diethyl maleate or diisopropyl maleate. All these monomers are highly copolymerizable with acrylamide.
Acrylamide can be copolymerized with an alkyl or alkoxyalkyl, having not less than 5 carbon atoms, ester of acrylic acid, methacrylic acid, itaconic acid or maleic acid such as amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, decyl acrylate, isodecyl acrylate, lauryl acrylate, isododecyl acrylate, isotridecyl acrylate, 2-butoxyethyl acrylate, 2-isobutoxyethyl acrylate, amyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, 2-butoxyethyl methacrylate, dihexyl itaconate, dihexyl maleate or di-2-ethylhexyl maleate, but these monomers are beyond the scope of this invention. This is because, acrylamide copolymers obtained by copolymerizing a large amount of these esters have high protective action, but in general have high foaming properties. Further, if the degree of copolymerization and/or the content of these esters are reduced to minimize the foaming properties of the resulting copolymer, the protective action thereof is greatly impaired. Thus, the objects of the present invention cannot be attained by the use of these acrylamide copolymers. However, a small amount of these esters may be incorporated into the acrylamide copolymers used in the present invention as an optional component thereof so far as they do not adversely affect the intended effects of the present invention. In this case, the foregoing monomer ratio should be slightly changed in proportion to the amount of these esters used.
The acrylamide copolymers used in the present invention may further comprise other monomers copolymerizable with acrylamide so far as the intended effects of the present invention are not adversely affected. Specific examples of such monomers are acrylonitrile, acrylic acid, 2-hydroxyethyl acrylate, cyclohexyl acrylate, benzyl acrylate, 2-phenoxyethyl acrylate, 2-dimethylaminoethyl acrylate, tetrahydrofurfuryl acrylate, sodium acrylate, ethylene glycol diacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, methacrylic acid, 2-hydroxyethyl methacrylate, 2-dimethylaminoethyl methacrylate, tetrahydrofurfuryl methacrylate, sodium methacrylate, ethylene glycol dimethacrylate, itaconic acid, sodium itaconate, N-phenylmaleimide or vinyl pyridine.
The correlation between the protective action and the foaming properties of the acrylamide copolymer is further affected by the degree of copolymerization and the monomer ratio of repeating units constituting the copolymer. The polymers having very low degree of copolymerization exhibit very low protective action and, therefore, the degree of copolymerization of the acrylamide copolymer should be at least 100, preferably at least 200 to achieve the intended effects of the prsent invention. On the other hand, the upper limit of the degree of copolymerization is not critical, but if it exceeds 10,000, the viscosity of the aqueous solution of the resulting polymer becomes extremely high, hence the increase in the protective action thereof is not so conspicuous, but the foaming properties thereof are greatly increased. Thus, it is assumed that preferred degree of copolymerization is not more than 5,000, preferably not more than 3,000.
The correlation between the monomer ratio and the characteristics of the copolymer also depends on the kinds of the ester copolymerized with acrylamide and can be well appreciated as a balance between hydrophilicity and hydrophobicity judging from that the copolymer is considered to be a surfactant. In this case, acrylamide is considered to be a hydrophilic component and an ester a hydrophobic component. The extent of the hydrophobicity can be evaluated on the basis of the number of carbon atoms of the alkyl or alkoxyalkyl group constituting each ester. The higher the ester monomer ratio of the copolymer, the higher the hydrophobicity of the copolymer and the lower the solubility thereof in water. The monomer ratio favorable for the purpose of the present invention varies depending on the kinds of the esters used. Correspondingly, if only esters having low hydrophobicity are employed, a relatively high monomer ratio is preferred while if those having high hydrophobicity are employed, a relatively low monomer ratio is preferably selected. For instance, methyl acrylate having the lowest number of carbon atoms has the lowest hydrophobicity and the acrylamide copolymer preferably comprises 85 to 70 mole % of acrylamide and 15 to 30 mole % of methyl acrylate. And if butyl acrylate having relatively high lipophobicity is employed, the acrylamide copolymer preferably comprises 96 to 85 mole % of acrylamide and 4 to 15 mole % of butyl acrylate. Moreover, when ethyl acrylate having an intermediate hydrophobicity is used, the copolymer preferably comprises 92 to 75 mole % of acrylamide and 8 to 25 mole % of ethyl acrylate. Multi-component copolymers obtained by copolymerizing a plurality of esters with acrylamide may also be employed in the present invention. In such a case, the monomer ratio of the acrylamide copolymer can be determined if it is assumed that the hydrophobic component is composed of a plurality of esters. For instance, when ethyl acrylate and butyl acrylate are simultaneously used as the hydrophobic components, the acrylamide copolymer preferably comprises 95 to 77 mole % of acrylamide, 3 to 22 mole % of ethyl acrylate and 1 to 14 mole % of butyl acrylate.
Some of the methods for preparing the acrylamide copolymer of this type are detailed in, for instance, J.P. KOKAI No. Sho 62-241549. Most preferably, the polymerization reaction is performed in a medium mainly comprising water under the conditions at which a uniform reaction takes place from the viewpoint of smoothness of the polymerization reaction, uniformity of the composition of the resulting polymer and easiness of control of the degree of polymerization. Acrylamide is soluble in water, but the alkyl or alkoxyalkyl, having not more than 4 carbon atoms, ester of acrylic acid, methacrylic acid, itaconic acid or maleic acid are not soluble in water in a sufficient amount required for fulfilling the monomer ratio defined above. Thus, the polymerization reaction is preferably performed in a solvent comprising water and a small amount of a water-soluble organic solvent in order to uniformly dissolve these monomers and to hence perform the overall polymerization reaction.
Examples of such water-soluble organic solvents include methanol, ethanol, isopropanol, secondary butanol, tertiary butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 3-methoxybutanol, tetrahydrofuran, dioxane, dimethylformamide, dimethylacetamide, acetonitrile, dimethylsulfoxide, acetone or methyl ethyl ketone. The solution finally obtained after the copolymerization as such can be used for preparing the dispersion of the present invention, but the organic solvent is preferably removed from the solution.
The degree of polymerization of the copolymers is relatively easily be controlled. Among the foregoing water-soluble organic solvents, only isopropanol and secondary butanol have very high chain-transfer coefficients and have ability of controlling the degree of copolymerization. Other agents for controlling the degree of copolymerization may of course be employed. However, in the present invention, a mixture of acrylamide and esters in a desired monomer ratio is dissolved in a mixed solvent containing water and isopropanol or secondary butanol in an amount required for achieving a desired degree of copolymerization, then a polymerization initiator is added to the solution and the polymerization is thus initiated if the monomer mixture is sufficiently soluble in the mixed solvent. On the other hand, if monomer mixture is not sufficiently soluble and the solution is not uniform, an additional amount of a water-soluble organic solvent having a relatively low chain-transfer coefficient is added thereto till the solution becomes uniform and then the polymerization is initiated. Any polymerization initiators and conditions for the polymerization well-known in the art may arbitrarily be selected. All the acrylamide copolymers having a monomer ratio specified above are prepared according to the method discussed above.
The nuclear-substituted salicylic acid salts represented by the foregoing general formula (I) show high developing ability are effectively used for preparing pressure-sensitive recording paper and typical examples thereof are polyvalent metal salts of acids such as 3-methyl-5-(iso)nonyl salicylic acid, 3-methyl-5-(iso)dodecyl salicylic acid, 3-methyl-5-(iso)pentadecyl salicylic acid, 3-methyl-5-(α-methylbenzyl)salicylic acid, 3-methyl-5-(α,α-dimethylbenzyl)salicylic acid, 3,5-di-sec-butyl salicylic acid, 3,5-di-tert-butyl-6-methyl salicylic acid, 3-tert-butyl-5-phenyl salicylic acid, 3,5-di-tert-amyl salicylic acid, 3-cyclohexyl-5-(iso)nonyl salicylic acid, 3-phenyl-5-(iso)nonyl salicylic acid, 3-(α-methylbenzyl)-5-(iso)nonyl salicylic acid, 3-isopropyl-5-(iso)nonyl salicylic acid, 5-(iso)nonyl salicylic acid, 3-(iso)nonyl salicylic acid, 3-(iso)nonyl-5-methyl salicylic acid, 3-(iso)nonyl-5-cyclohexyl salicylic acid, 3-(iso)nonyl-5-phenyl salicylic acid, 3-(iso)nonyl-5-(α-methylbenzyl) salicylic acid, 3-(iso)nonyl-5-(4,α-dimethylbenzyl) salicylic acid, 3-(iso) nonyl-5-(α,α-dimethylbenzyl) salicylic acid, 3-(α,α-dimethylbenzyl)-5-(iso)nonyl salicylic acid, 3-tert-butyl-5-(iso)nonyl salicylic acid, 3,5-di(iso)nonyl salicylic acid, 3-(iso)nonyl-6-methyl salicylic acid, 3-(iso)dodecyl salicylic acid, 3-(iso)dodecyl-5-methyl salicylic acid, 3-(iso)dodecyl-6-methyl salicylic acid, 3-isopropyl-5-(iso) dodecyl salicylic acid, 3-(iso)dodecyl-5-ethyl salicylic acid, 5-(iso)dodecyl salicylic acid, 3-(iso)pentadecyl salicylic acid, 3-(iso)pentadecyl-5-methyl salicylic acid, 3-(iso)pentadecyl-6-methyl salicylic acid, 5-(iso)pentadecyl salicylic acid, 3,5-dicyclohexyl salicylic acid, 3-cyclohexyl-5-(α-methylbenzyl) salicylic acid, 3-phenyl-5-(α-methylbenzyl) salicylic acid, 3-phenyl-5-(α,α-dimethylbenzyl) salicylic acid, 3-(α-methylbenzyl) salicylic acid, 3-(α-methylbenzyl)-5-methyl salicylic acid, 3-(α-methylbenzyl)-6-methyl salicylic acid, 3-(α-methylbenzyl)-5-phenyl salicylic acid, 3,5-di-(α-methylbenzyl) salicylic acid, 3-(α-methylbenzyl)-5-(α,α-dimethylbenzyl) salicylic acid, 3-(α-methylbenzyl)-5-bromosalicylic acid, 3-(α,4-dimethylbenzyl)-5-methyl salicylic acid, 3,5-di-(α,4-dimethylbenzyl) salicylic acid, 3-(α,α-dimethylbenzyl)-5-methyl salicylic acid, 3-(α,α-dimethylbenzyl)-6-methyl salicylic acid, 3,5-di-(α,α-dimethylbenzyl) salicylic acid, 5-(4-mesitylmethylbenzyl) salicylic acid, benzylated-styryrated salicylic acid, 2-hydroxy-3-(α,α-dimethylbenzyl)-1-naphthoic acid or 3-hydroxy-7-(α,α-dimethylbenzyl)-2-naphthoic acid. Specific examples of the polyvalent metals are magnesium, calcium, zinc, aluminum, iron, cobalt and nickel, which may be in the form of basic ions.
These nuclear-substituted salicylic acid salts may be used alone or in any combination as the developers in the invention. In the foregoing exemplified compounds, the term "(iso)alkyl" herein means an isoalkyl or normal alkyl. In addition, the terms "isononyl group", "isododecyl group" and "isopentadecyl group" are defined to be substituents obtained through the addition of a propylene trimer; propylene tetramer or 1-butene trimer; and propylene pentamer, respectively. Moreover, these nuclear-substituted salicylic acid salts may be used in combination with a plasticizer, an ultraviolet absorber, an antioxidant, a photostabilizer and/or a resinous polymeric compound for further enhancement of the characteristic properties of the developer.
All of the developer compositions mainly comprising the foregoing nuclear-substituted salicylic acid salt are highly soluble in an organic solvent. Organic solvents are employed for the purpose of lowering the viscosity of the developer and of easily emulsifying and dispersing the same. The organic solvents to be used for such purposes are those which are relatively hardly dissolved in water, which have a low boiling point and which do not cause any chemical change or do not exert any influence on the developer during the preparation of the developer. Examples of such organic solvents are benzene, toluene, xylene, cyclohexane, methylcyclohexane, chloroform, carbon tetrachloride, trichloroethane, chlorobenzene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, butanol, amyl alcohol, methyl tert-butyl ether or diisopropyl ether.
The mixing ratio of the developer to the organic solvent is properly selected depending on the particle size of the desired developer particles dispersed in an aqueous solution. More specifically, the amount of the organic solvent used is adjusted to a large amount if the particle size of the desired developer particles is very small, while it is adjusted to a small amount if the the particle size of the desired particles is great. The preferred amount of the organic solvent to be used ranges from 20 to 500 parts by weight per 100 parts by weight of the developer.
The softening point of the developer determined in its dried state differs from that determined in the state having an equilibrium moisture content in water. The value obtained in the state having an equilibrium moisture content in water is lower than the former by about 50° C. and is defined as the softening point of the developer in the present invention. The developers having a softening point of less than 20° C. as determined based on this definition often provide dispersions having insufficient long-term storage stability and it is difficult to remove giant particles present in a very small amount in the dispersion, by a wet pulverization means. For this reason, the softening point of the developer is preferably controlled to 20° C. or higher.
The following method can be adopted for controlling the softening point of the developer:
1. To elevate a softening point which is too low, a developer having a high softening point or a resinous polymer compound having ability to increase the softing point is incorporated into a developer composition; or
2. To reduce a softening point which is too high, a developer having a low softening point or a plasticizer or further a metal salt of fatty acid is incorporated into a developer.
1. To elevate a softening point which is too low, a developer having a high softening point or a resinous polymer compound having ability to increase the softing point is incorporated into a developer composition; or
2. To reduce a softening point which is too high, a developer having a low softening point or a plasticizer or further a metal salt of fatty acid is incorporated into a developer.
The acrylamide copolymer comprising specific monomer units at a specific ratio of these repeating units as defined above is used as an aqueous solution in the present invention. The aqueous solution contains the acrylamide copolymer in the amount ranging from 0.2 to 20 parts by weight per 100 parts by weight of the developer.
Another dispersing agent is preferably simultaneously used for improving the dispersing properties of the acrylamide copolymer. Specific examples thereof are anionic surfactants represented by alkali metal salts of alkylsulfuric acid esters, alkylsufonic acids, alkylbenzenesulfonic acids, alkylnaphthalenesulfonic acid, N-methyltaurineoleic acid amide, dialkyl sulfosuccinates, sulfuric acid esters of alkylphenol-ethylene oxide adducts, high molecular weight anionic compounds represented by alkali metal salts of gum arabic, alginic acid, carboxymethyl cellulose, phosphated starches, lignin sulfonic acid, acrylic acid polymers, acrylic acid copolymers, vinylbenzenesulfonic acid polymers, vinylbenzenesulfonic acid copolymers or maleic anhydride copolymers, and water-soluble polymeric compounds such as polyvinyl alcohol, methyl cellulose or hydroxyethyl cellulose.
The size of the developer particles in the dispersion is determined by the emulsifying and dispersing process and thus the process is very important. In the emulsifying and dispersing process, a solution of the developer in an organic solvent is added to an aqueous solution containing an acrylamide copolymer and the resulting mixture is dispersed by a dispersion means such as ultrasonic dispersion mixer, a homogenizer or a homomixer to thus control the particle size to a desired value. In the dispersion, the disperse phase is the developer dissolved in the organic solvent and the continuous phase, i.e. disperse medium, comprises the aqueous solution, but according to the laboratory experiment, a water-in-oil type emulsion having reversed phase is rarely formed. Therefore, the dispersion operation should be performed with sufficient care. To prevent the reverse of phases, the pH of the dispersion system is preferably controlled to a higher alkaline level by the addition of, preferably an alkali hydroxide or alkali carbonate.
The size of the dispersed particles can be controlled by a variety of factors. Examples of such factors are 1. the kinds of dispersing means; 2. strength of the dispersing means (energy, rotational speed and the like thereof); 3. relative ratio of the disperse phase to the continuous phase; 4. viscosity of the disperse phase; 5. viscosity of the continuous phase; 6. temperature; and 7. the kind and the amount of a dispersant used. Thus, the emulsified dispersion is prepared so that the average particle size of the disperse phase determined after the removal of the organic solvent used preferably ranges from 0.3 to 5 μ and more preferably 0.5 to 3 μ.
Then the emulsified dispersion is transferred to an apparatus capable of removing the organic solvent by distillation. Most of organic solvent can form an azeotropic mixture with water and, therefore, they can be almost completely removed by azeotropically distilling the organic solvent together with water. The distillation apparatus is preferably equipped with a device capable of gently stirring to make the boiling of the dispersion smooth and to thus improve the efficiency of removing the organic solvent. More specifically, if the dispersion is vigorously stirred, it is liable to form aggregates of the developer and severe foaming makes the operations difficult. The most important aspect of the present invention is to use specific acrylamide copolymers as one of dispersants for suppressing the formation of aggregates of the developer as low as possible and for preventing the interruption of the operations due to foaming. In this case, if it is intended to rapidly complete the distillation process using a large scale distillation apparatus, foaming is sometimes observed at the end of the distillation. At this stage, an anti-foaming agent may be used so far as it does not adversely effect the developer, but it is not necessary in the usual operation.
The amount of the disperse phase in the dispersion of the developer from which the organic solvent has been removed ranges from 20 to 55% by weight on the basis of the total weight of the dispersion. The particle size thereof is approximately in Gaussian distribution and the rate of the particles which are outside the Gaussian distribution is not more than 0.2% in most of the cases. These particles are a kind of aggregate and the presence thereof sometimes limits the application thereof even though the rate is very small. Thus, these particles are preferably removed by screening or hydraulic classification.
Alternatively, these aggregates or coarse particles can effectively be converted into fine particles by the wet pulverization treatment of the dispersion and hence the liquid dispersion is preferably subjected to such a treatment. It is sufficient to achieve the reduction rate of the average particle size of the developer in the order of about 10% or less by this treatment. This is because, if the reduction rate is more than 10%, the liquid dispersion sometimes shows thixotropic properties and correspondingly the handling properties thereof are impaired. Moreover, it is found out that a developing sheet, in other word, pressure-sensitive recording paper in which such a wet-pulverized liquid dispersion of the developer is employed is improved, in particular, in printability and excellent in the initial developability (property which provides high developing density immediately after writing) as well as fastness to light (property which does not decrease developing density even if the developed image is exposed to light).
Examples of the wet-pulverization apparatuses used herein are a variety of sand mill type pulverizers in which a pulverization medium is used such as ball mill, pebble mill, sand mill (horizontal or vertical sand mill), cobol mill or attritor; and high-speed grainding apparatuses such as triple roll mill, high-speed impeller dispersion machine, high-speed stone mill or high-speed impact mill. Among these, preferred are sand mill type pulverizers and high-speed impeller dispersion machine and most preferably sand mill pulverizers, for example sand grinder, are used in the invention in the light of the easiness of the establishment of the processing conditions and high pulverization efficiency.
This wet-pulverization treatment is preferably carried out at a temperature of the aqueous dispersion in the order of not more than 30° C.
A coating solution for forming a developer layer can be prepared by adding, to the aqueous developer dispersion prepared according to the method of this invention, an adhesive such as a starch, casein, gum arabic, carboxymethyl cellulose, polyvinyl alcohol, styrene·butadiene copolymer latexes or vinyl acetate latexes; an inorganic pigment such as zinc oxide, magnesium oxide, titanium oxide, aluminum hydroxide, calcium carbonate, magnesium sulfate or calcium sulfate; and/or other additives.
Further, the developer coating composition thus prepared is applied onto a substrate such as wood-free paper, coated paper, synthetic paper and films using the usual coating devices such as an air knife coater, a blade coater, a roll coater, a size press coater, a curtain coater or a short dwell-time coater to thus give developing paper for pressure-sensitive recording.
EXAMPLE
The present invention will hereinafter be explained in more detail with reference to the following non-limitative working Examples and the practical effect attained by the present invention will also be discussed in comparison with Comparative Examples. In the following Preparation Examples, Examples and Comparative Examples, the terms "part" and "%" denote "% by weight" and "part by weight" respectively unless otherwise specified.
PREPARATION EXAMPLE 1
Preparation of Aqueous Solution of Acrylamide
To a four-necked 10,000 ml volume flask of hard glass equipped with a stirring machine, a thermometer, a dropping funnel and a reflux condenser, there were added 1,500 g of acrylamide, 300 g of butyl acrylate (molar ratio of acrylamide to butyl acrylate being about 90:10), 3,800 g of water and 1,400 g of isopropanol. The contents of the flask were uniformly dissolved by slowly operating the stirring machine. The resulting solution was heated and 4 g of a 2% isopropanol solution of azobisisobutyronitrile was dropwise added, through a dropping funnel, to the solution immediately after the solution started boiling. Immediately thereafter, the polymerization reaction was initiated and the reaction solution vigorously boiled due to the heat generated. Then 4 g of the same solution was dropwise added, through a drop funnel, to the reaction solution every one hour over four times. 3 Hours after the final addition of the solution, the conversion of the polymerization reaction exceeded 99%. At this stage, the reflux condenser was replaced with an apparatus capable of removing the isopropanol and about 1,000 g of a distillate mainly comprising isopropanol was removed. 1,500 g of water was added to the distillation residue and 1,000 g of a distillate mainly comprising isopropanol was again removed. Water added to the flask so that the total amount of the contents of the flask was 7,200 g, followed by cooling. The resulting aqueous solution comprised 25% non-volatile components and had a viscosity (determined at 25° C.) of about 700 cps and an average degree of polymerization ranging from 250 to 500.
PREPARATION EXAMPLE 2
To the same flask used in Preparation Example 1, there were added 1,375 g of acrylamide, 425 g of ethyl acrylate (molar ratio of acrylamide to ethyl acrylate being about 82:18), 4,000 g of water and 1,200 g of isopropanol. Thereafter, the same procedures used in Preparation Example 1 were repeated to give a viscous aqueous solution. The resulting aqueous solution comprised 25% non-volatile components and had a viscosity (determined at 25° C.) of about 900 cps and an average degree of polymerization ranging from 300 to 600.
PREPARATION EXAMPLE 3
To the same flask used in Preparation Example 1, there were added 1,420 g of acrylamide, 259 g of ethyl acrylate, 121 g of butyl acrylate (molar ratio: acrylamide/ethyl acrylate/butyl acrylate being about 85:11:4), 3,900 g of water and 1,300 g of isopropanol. Thereafter, the same procedures used in Preparation Example 1 were repeated to give a viscous aqueous solution. The resulting aqueous solution comprised 25% non-volatile components and had a viscosity (determined at 25° C.) of about 800 cps and an average degree of polymerization ranging from 250 to 600.
PREPARATION EXAMPLE 4
To the same flask used in Preparation Example 1, there were added 1,426 g of acrylamide, 331 g of ethyl acrylate, 43 g of 2-ethylhexyl acrylate (molar ratio: acrylamide/ethyl acrylate/2-ethylhexyl acrylate being about 85 : 14 : 1), 3,800 g of water and 1,400 g of isopropanol. Thereafter, the same procedures used in Preparation Example 1 were repeated to give a viscous aqueous solution. The resulting aqueous solution comprised 25% non-volatile components and had a viscosity (determined at 25° C.) of about 700 cps and an average degree of polymerization ranging from 250 to 500.
Preparation of Aqueous Developer Dispersion
EXAMPLE 1
500 g of zinc 3,5-di-(α-methylbenzyl)salicylate (softening point 72° C.) was mixed with and dissolved in 400 g of toluene to form a toluene solution. Separately, there were added, to a 3,000 ml volume beaker of stainless steel, 80 g of the aqueous acrylamide copolymer solution obtained in Preparation Example 1, 1.0 g of sodium carbonate and 760 g of water and the foregoing toluene solution was added to the beaker after uniformly mixing these components. The mixture was emulsified and dispersed at 45° C. for 15 minutes and at 11,000 rpm with T.K. Homomixer Model M (available from Nippon Tokushu Kika Kogyo K.K.). The emulsified liquid dispersion was transferred to a three-necked 5,000 ml volume flask of hard glass equipped with a stirring machine which was provided with a stirring blade of Teflon having a width of 8 cm, a thermometer and a distillation port, 300 g of water was further added thereto and the bottom of the flask was heated while operating the stirring machine at 120 rpm. The toluene was azeotropically distilled off together with water through the distillation port. The heating was controlled so that the distillation of the toluene was completed in about 2 hours and the distillation was continued for additional 3 hours to thus remove 800 g of distillate in all. After cooling the flask, the contents were filtered through a sieve having a pore size of 20 μ. The residue remaining on the sieve was weighed to be 0.3 g (on dry basis). The content of non-volatile components in the filtrate (the liquid developer dispersion) was 41.8% and the developer particles dispersed therein had an average particle size of 0.98 μ and were in the form of true spheres.
EXAMPLE 2
The same procedures used in Example 1 were repeated except that the aqueous acrylamide copolymer solution obtained in Preparation Example 2 was substituted for the aqueous acrylamide copolymer solution obtained in Preparation Example 1 to give a liquid developer dispersion having a content of non-volatile component in the order of 42.1%. In this case, the residue remaining on a sieve was weighed to be 0.7 g (on dry basis) and the developer particles dispersed therein had an average particle size of 1.03 μ and were in the form of true spheres.
EXAMPLE 3
The same procedures used in Example 1 were repeated except that the aqueous acrylamide copolymer solution obtained in Preparation Example 3 was substituted for the aqueous acrylamide copolymer solution obtained in Preparation Example 1 to give a liquid developer dispersion having a content of non-volatile component in the order of 41.7%. In this case, the residue remaining on a sieve was weighed to be 0.4 g (on dry basis) and the developer particles dispersed therein had an average particle size of 0.97 μ and were in the form of true spheres.
EXAMPLE 4
The same procedures used in Example 1 were repeated except that the aqueous acrylamide copolymer solution obtained in Preparation Example 4 was substituted for the aqueous acrylamide copolymer solution obtained in Preparation Example 1 to give a liquid developer dispersion having a content of non-volatile component in the order of 40.2%. In this case, the residue remaining on a sieve was weighed to be 0.6 g (on dry basis) and the developer particles dispersed therein had an average particle size of 1.01 μ and were in the form of true spheres.
EXAMPLE 5
350 g of the liquid developer dispersion obtained in Examples 1 which was not yet sieved to remove coarse particles and 500 g of glass beads having a diameter of 1.5 mm were added to a 1,000 ml volume pot of sand mill (Sandgrinder® Model TSG 4H; available from Igarashi Machinery Co., Ltd.) and were wet-pulverized at 1,800 rpm at 18° C. for 5 minutes. After removing the glass beads, the average particle size of the developer particles in the resulting dispersion was 0.95 μ. In this case, the amount of residues remaining on the sieve having a pore size of 20 μ was 0 g.
EXAMPLE 6
350 g of the liquid developer dispersion obtained in Examples 2 which was not yet sieved to remove coarse particles was treated in the same manner used in Example 5 to give a liquid developer dispersion having an average particle size of the developer particles dispersed therein in the order of 1.02 μ. In this case, the amount of residues remaining on the sieve having a pore size of 20 μ was 0 g.
EXAMPLE 7
350 g of the liquid developer dispersion obtained in Examples 3 which was not yet sieved to remove coarse particles was treated in the same manner used in Example 5 to give a liquid developer dispersion having an average particle size of the developer particles dispersed therein in the order of 0.94 μ. In this case, the amount of residues remaining on the sieve having a pore size of 20 μ was 0 g.
EXAMPLE 8
350 g of the liquid developer dispersion obtained in Examples 4 which was not yet sieved to remove coarse particles was treated in the same manner used in Example 5 to give a liquid developer dispersion having an average particle size of the developer particles dispersed therein in the order of 0.98 μ. In this case, the amount of residues remaining on the sieve having a pore size of 20 μ was 0 g.
EXAMPLE 9
425 g of zinc 3,5-di-(α-methylbenzyl)salicylate and 75 of an α-methylstyrene/styrene copolymer (copolymerization ratio=45:55 (mole %); average molecular weight=about 1,600) were mixed with and dissolved in 400 g of methyl isobutyl ketone to form a methyl isobutyl ketone solution. Separately, there were added, to a 3,000 volume beaker of stainless steel, 30 g of the aqueous acrylamide copolymer solution obtained in Preparation Example 1, 200 g of a 5% aqueous solution of polyvinyl alcohol having a degree of saponification of 98% and a degree of polymerization of 1,700, 0.5 g of sodium laurylsulfate, 1.0 g of sodium carbonate and 600 g of water and the foregoing methyl isobutyl ketone solution was added to the beaker after uniformly mixing these components. The mixture was emulsified and dispersed at 45° C. for 15 minutes and at 9,000 rpm with T.K. Homomixer Model M (available from Nippon Tokushu Kika Kogyo K.K.). The emulsified liquid dispersion was transferred to a three-necked 5,000 ml volume flask of hard glass equipped with a stirring machine which was provided with a stirring blade of Teflon having a width of 8 cm, a thermometer and a distillation port, 450 g of water was further added thereto and the bottom of the flask was heated while operating the stirring machine at 120 rpm. The methyl isobutyl ketone was azeotropically distilled off together with water through the distillation port. The heating was controlled so that the distillation of the methyl isobutyl ketone was completed in about 3 hours and the distillation was continued for additional 3 hours to thus remove 900 g of distillate in all. After cooling the flask, the contents were filtered through a sieve having a pore size of 20 μ. The residue remaining on the sieve was weighed to be 0.8 g (on dry basis). The content of non-volatile components in the filtrate (the liquid developer dispersion) was 39.6% and the developer particles dispersed therein had an average particle size of 1.13 μ and were in the form of true spheres. In addition, the softening point of the disperse phase was 75° C.
EXAMPLE 10
350 g of the liquid developer dispersion obtained in Examples 9 which was not yet sieved to remove coarse particles was treated in the same manner used in Example 5 to give a liquid developer dispersion having an average particle size of the developer particles dispersed therein in the order of 1.09 μ. In this case, the amount of residues remaining on the sieve having a pore size of 20 μ was 0 g.
EXAMPLE 11
495 g of zinc 3-isododecylsalicylate (softening point 43° C.) and 5 g of zinc salt of 2,6-di-tert-butyl-4-carboxyethylphenol (as an antioxidant) were mixed with and dissolved in 400 g of toluene at 50° C. to thus give a toluene solution. The toluene solution was treated according to the same manner used in Example 1 to obtain a liquid developer dispersion having a content of non-volatile components in the order of 42.1%. The residue remaining on a sieve was weighed to be 0.2 g (on dry basis). The developer particles dispersed therein had an average particle size of 0.92°.
EXAMPLE 12
350 g of the liquid developer dispersion obtained in Examples 11 which was not yet sieved to remove coarse particles was treated in the same manner used in Example 5 to give a liquid developer dispersion having an average particle size of the developer particles dispersed therein in the order of 0.90 μ. In this case, the amount of residues remaining on the sieve having a pore size of 20 μ was 0 g.
EXAMPLE 13
The same procedures used in Example 11 were repeated except that 200 g of zinc 3-isododecylsalicylate and 295 g of zinc 3,5-di-(α-methylbenzyl)salicylate (softening point 72° C.) were substituted for 495 g of the zinc 3-isododecylsalicylate (softening point 43° C. ) used in Example 11 to thus give a liquid developer dispersion having an average particle size of the developer particles dispersed therein was 0.98 μ.
EXAMPLE 14
350 g of the liquid developer dispersion obtained in Example 13 which had not yet sieved to remove coarse particles was treated in the same manner used in Example 5 to give a liquid developer dispersion having an average particle size of the developer dispersed therein was 0.93 μ. The dry weight of the residues remaining on a sieve having a pore size of 20 μ was determined to be 0 g.
COMPARATIVE EXAMPLE 1
The same procedures used in Example 1 were repeated using 20 g of sodium laurylsulfate and 60 g of water instead of 80 g of the aqueous acrylamide copolymer solution obtained in Preparation Example 1, but the operations could not be continued at the time when the amount of the distillate reached 420 g because of abrupt vigorous foaming. Thus, at this stage, the operations were interrupted and the contents of the flask was cooled and the dry weight of the residues remaining on a sieve having a pore size of 20 μ was determined to be 93 g. Moreover, the average particle size of the developer particles in the filtrate was 1.97 μ.
COMPARATIVE EXAMPLE 2
The same procedures used in Example 1 were repeated except that 80 g of an aqueous solution of a copolymer of acrylamide (94 mole %) and 2-ethylhexyl acrylate (6 mole %) which had been prepared in the same manner in Preparation Example 1 and which had a non-volatile content of 25%, an expected molecular weight ranging from 300 to 500 and a viscosity determined at 25° C. of 1,200 cps was substituted for 80 g of the aqueous acrylamide copolymer solution of Example 1, but the operations could not be continued as in Comparative Example 1. The dry weight of the residues remaining on a sieve having a pore size of 20 μ was determined to be 0.2 g. Moreover, the average particle size of the developer particles in the filtrate was 0.94 μ.
COMPARATIVE EXAMPLE 3
The same procedures used in Example 1 were repeated except that 80 g of an aqueous solution of a copolymer of acrylamide (98 mole %) and 2-ethylhexyl acrylate (2 mole %) which had been prepared in the same manner in Preparation Example 1 and which had a non-volatile content of 25%, an expected molecular weight ranging from 250 to 400 and a viscosity determined at 25° C. of 800 cps was substituted for 80 g of the aqueous acrylamide copolymer solution of Example 1 to give a liquid developer dispersion having a non-volatile content of 37.2%. The dry weight of the residues remaining on a sieve having a pore size of 20 μ was determined to be 76 g. Moreover, the average particle size of the developer particles in the filtrate was 1.39 μ.
COMPARATIVE EXAMPLE 4
2,000 g of Zinc 3,5-di(α-methylbenzyl)salicylate (softening point 72° C.) and 1,000 g of toluene were mixed and dissolved at 60° C. to prepare a toluene solution. Separately, 10 g of sodium laurylsulfate and 5,000 g of water containing 20 g of a copolymer of acrylamide (93% by mol) with 2-phenoxy-ethyl acrylate (7% by mol) having an average molecular weight of about 2,500 were placed in a 10,000 ml capacity stainless steel beaker and heated to 60° C. While this mixture was agitated at 8,000 r.p.m. by means of a homomixer (manufactured by Nippon Tokushu Kika Kogyo Kabushiki Kaisha, 200 watt), the toluene solution prepared above was added thereto over about 2 minutes, followed by further agitating and dispersing the mixture for about 20 minutes, transferring the resulting dispersion into a 10,000 ml capacity, hard glass, three-neck flask equipped with a stirrer, a thermometer and a distilling port, heating the flask while slowly rotating the stirrer to distil off toluene (1,000 g) and water (1,000 g) and obtain a dispersion containing almost no toluene. In this case, the heating of the flask was limited to prevent from foaming the content of the flask and overflowing the bubble through the distilling port, and the complete distillation of the toluene took 18 hours. This dispersion was cooled to obtain an aqueous dispersion containing about 33% of the developer. The resulting dispersed particles had an average particle diameter of just one micron, but also contained coarse particles of 20 microns or larger (12 g). When the dispersion was sieved with a sieve having opening parts of 20 microns, an aqueous dispersion of the developer capable of being used as it was, was obtained.
In the case where said operation is scaled up, it is evident from the experience that the operation for removing toluene take longer time than said 18 hours.
COMPARATIVE EXAMPLE 5
100 g of Zinc 3,5-di(α-methylbenzyl)salicylate (softening point 72° C.) and 100 g of toluene were mixed and dissolved at 70° C. Separately, 300 g of water containing 6 g of polyvinyl alcohol (polymerization degree 1,700; saponification degree 98%) was placed in a 500 ml capacity stainless steel beaker, and while it was agitated by means of T.K. homomixer (trademark, manufactured by Nippon Tokushu Kika Kogyo Kabushiki Kaisha) at 3,000 r.p.m., the above-mentioned toluene solution was added thereto, followed by raising the velocity up to 10,000 r.p.m. at the time of completion of the addition, agitating the mixture for 2 minutes, transferring the resulting dispersion into a 500 ml hard glass three-neck flask equipped with a stirrer, a thermometer and a distilling port, and heating the flask while slowly rotating the stirrer to distill off toluene and water from the distilling port. After this operation was continued at 100° C. for one hour, the dispersion contained almost no toluene. When it was cooled, the resulting dispersion contained about 33% of a developer. The average particle diameter of dispersed particles was 1.0 micron. This dispersion was placed in a 500 ml graduated cylinder and allowed to stand still for 48 hours and settled particles were then examined. Almost no settled particle was observed.
The dispersion was again placed in a flask and agitated by mean of stirrer at 1,000 r.p.m. at 40° C.. After 36 hours, the content of the flask changed to lose flowability. This phenomenon is not yet understood but suggest a risk of losing stability of the dispersion at high temperature. All of the dispersions prepared in the Examples 1 to 14 do not indicate that phenomenon.
Preparation of Coating Composition of Developer and Developing Paper for Pressure-sensitive Recording
EXAMPLES 1-1 TO 14-1
A coating solution of a developer was prepared by mixing and dispersing 15 parts (expressed in the amount of the developer) of each aqueous developer dispersion obtained in Example 1 to 14 (Developing Paper in Example 1-1, the dispersion obtained in Example 1 was used, in Example 2-1, the dispersion obtained in Example 2 was used, and so forth), 75 parts of calcium carbonate, 10 parts of zinc oxide and 100 parts of water and then adding and dispersing, in the resulting mixture, 100 parts of a 10% aqueous solution 0f polyvinyl alcohol (as a binder), 20 parts of a carboxyl-modified SBR latex (SN-307; solid content=50%; available from Sumitomo Norgatac Co., Ltd.) and 200 parts of water.
The resultant coating solution was applied onto the one side of base paper having a basis weight of 40 g/m 2 so that the basis weight of the paper increased by 5 g/m 2 (weighed after drying) and dried to give a developing paper for pressure-sensitive recording. Thus, the corresponding developing paper 1-1 to 14-1 were prepared. Any developing paper was not prepared from the liquid developer dispersions obtained in Comparative Examples 1 to 3 because the use thereof was not considered to be industrially acceptable.
Preparation of Coated Back Sheet
A microcapsule coating solution was prepared by dissolving Crystal Violet lactone in an alkylated naphthalene and then the resulting oily solution was formed into microcapsules. The resultant microcapsule coating solution was applied onto one side of base paper so that the basis weight of the paper increased by 4 g/m 2 (weighed after drying) and dried to give wood-free paper.
Preparation of Middle Sheet
The same microcapsule coating solution used for preparing the foregoing coated back sheet was applied onto the opposite side of each developing paper obtained in the foregoing Examples 1-1 to 14-1 so that the basis weight of the paper increased by 4 g/m 2 (weighed after drying) and dried to give middle sheet. The resulting sheets of the middle sheet were referred to as paper 1-2 to 14-2.
Test of Developing Paper
1. Test of Initial Developability
The developing paper obtained in Examples 1-1 to 14-1 and coated back sheet were allowed to stand at 0° C. for one hour, then each developing paper was put on the coated back sheet so as to face the coated sides thereof each other, the assembly was developed with a drop type color developing tester (weight: 150 g; height: 20 cm) and the color developing density was determined by Macbeth Reflection Densitometer 10 seconds and one day after applying a load.
2. Test of Fastness to Light
The developing paper was put on the coated back sheet so as to face the coated sides thereof each other, the assembly was developed under the action of a load in the order of 100 kg/cm 2 , the color developing density (D 0 ) of the color developed image was determined by Macbeth Reflection Densitometer. Then the developed image was irradiated with ultraviolet rays at a distance of 20 cm and thereafter the color developing density (D 1 ) was again determined. The fastness to light of the developing paper was evaluated on the basis of the value obtained according to the following relation:
Fastness to Light=(D.sub.1 /D.sub.0)×100
The closer the value to 100, the higher the fastness to light.
3. Test of Smudge of Printed Middle Sheet
Printing operation was performed using the middle sheet obtained in Examples 1-2 to 14-2 (on the developing layer surface) according to a wet offset printing system using Business Form Printing Press (17HB; available from Hikari Manufacturing Co., Ltd.) and 300 m of the printed middle sheet was rolled on a rolling core. The roll of the printed middle sheet was allowed to stand for 3 days at 50° C. and the extent of smudge in the region at a distance of 100 m from the core was visually evaluated according to the following evaluation criteria:
⊚: no smudge (no color development) was observed;
◯: the region was very slightly smudged (color developed);
Δ: the region was smudged (color developed) to some extent;
×: the region was severely smudged (color developed).
4. Test Results
The results thus obtained are summarized in the following Table 1. In this Table, the developing paper of Example 1-1 and middle sheet of Example 1-2 tested are both denoted as Example 1 and so forth.
TABLE 1______________________________________ Contamina- tionPaper Initial Developability Fastness of printedtested After 10 sec After 1 day to Light matter______________________________________Example 1 0.24 0.68 80 ◯Example 2 0.24 0.68 81 ◯Example 3 0.25 0.70 81 ◯Example 4 0.24 0.70 80 ◯Example 5 0.26 0.71 79 ⊚Example 6 0.26 0.70 80 ⊚Example 7 0.27 0.72 80 ⊚Example 8 0.26 0.72 79 ⊚Example 9 0.24 0.67 80 ◯Example 10 0.26 0.68 79 ⊚Example 11 0.26 0.71 82 ◯Example 12 0.28 0.73 81 ⊚Example 13 0.25 0.70 80 ◯Example 14 0.27 0.71 79 ⊚______________________________________
As has been explained above in detail, the present invention makes it possible to make the handling of the developer easier and to improve the quality of the pressure-sensitive recording paper obtained using the developer to thus enhance the commercial value thereof.
More specifically, according to the present invention, the resulting developer dispersion has good fluidability since the viscosity thereof is not more than 500 cps and hence it can easily be handled. Moreover, the dispersion never causes any increase in its viscosity and any increase in the particle size as well as the formation of aggregates (coarse particles) of developer are not observed even if it is stored at 25° C. for 200 days. | Herein disclosed are a method for preparing an aqueous developer dispersion which comprises the steps of dissolving, in an organic solvent, a developer which comprises a nuclear-substituted salicylic acid salt represented by the following general formula (I): ##STR1## wherein R 1 , R 2 , R 3 and R 4 may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group having not more than 15 carbon atoms, a cycloalkyl group, a phenyl group, a nuclear-substituted phenyl group, an aralkyl group or a nuclear-substituted aralkyl group, or two adjacent groups selected from R 1 to R 4 may be bonded together to form a ring; n is an integer of not less than 1; and M represents magnesium, calcium, zinc, aluminum, iron, cobalt, nickel or a basic ion thereof; emulsifying and dispersing the resulting solution in an aqueous solution of an acrylamide copolymer having a degree of polymerization of not less than 100 obtained by copolymerizing 96 to 70 mol % of acrylamide with 4 to 30 mol % of an alkyl or alkoxyalkyl, having not more than 4 carbon atoms, ester of acrylic acid, methacrylic acid, itaconic acid or maleic acid; then heating the emulsified dispersion to remove the organic solvent by distillation; and optionally finely wet-pulverizing the resulting aqueous dispersion to an extent that reduction in the average particle size of the developer dispersed in the dispersion does not exceed 10%. The recording paper is substantially improved in the developing density, developing velocity and printability. | 1 |
FIELD OF THE INVENTION
The present invention relates to a process for the preparation of improved cellulose pulps giving papers with improved tensile strength, tear strength, light-scattering, and low shive content, and to an apparatus for the preparation thereof.
DESCRIPTION OF THE PRIOR ART
In the preparation of cellulose pulps, such as thermomechanical pulp (TMP) and chemithermomechanical pulp (CTMP) the fibers are laid free from each other and from lignin. The defibration process must be carried out in such a way that fiber cutting is avoided as much as possible, since long fibers give high tearing resistance in the paper that is prepared from the pulp. Fibers that still cling together form so-called shives which can cause web breaks in the paper machine or a lowering of the quality of the paper produced. In order to obtain high tensile strength, and to avoid fiber rising in offset printing when the paper is subjected to wetting by water, strong bonds between the fibers are required. To ensure fibers with good bonding ability, the fibers must be developed, i. e. treated so that the fiber wall is softened, and the surface of the fibers treated so that most of the outer thin layer, the primary wall, is removed and fibrils are loosened from the secondary wall. Thereby better contact between the secondary walls is obtained, and any residues of the lignin-rich hydrophobic middle lamella are removed. Flexible fibers are a prerequisite for achieving a paper with a smooth surface, suitable for coating, in particular for light-weight coated paper.
The pulp coming from the screening department contains both fibers that are well suited for the manufacture of paper, and some material that must either be further treated, such as incompletely treated fibers and shives, or be removed from the system, such as sand and bark particles. There is also a certain amount of fines, consisting of small pieces of the middle lamella and the primary wall, parts of fibrils from the secondary wall, parenchyme cells, and short pieces of cut fibers. Most of the fines material increases the strength and the light-scattering ability of the paper. In order to separate out fibers with good bonding ability it has been suggested to use screens or hydrocyclones. Screens separate according to particle size and hydrocyclones according to specific surface area. Screen rejects, however, also contain long fibers, which should be recovered. Rejects refining increases the bonding ability of the fibers. Factors particularly affecting the fiber fractionation capability of a hydrocyclone are pressure drop, rejects ratio, hydrocyclone geometry, and pulp slurry feed consistency.
SUMMARY OF THE INVENTION
The present invention refers to a process for the preparation of improved cellulose pulps in which defibered cellulose pulps are screened for removal of shives, fibers with low bonding ability are removed in hydrocyclones, and rejects from the hydrocyclone treatment are treated in reject refiner, which is characterized in the combination of the following characteristics:
a) the base end outflow diameter (Db) of the hydrocyclones being less than 14 mm
b) the distance (Lu) between the inner base end outflow opening and the narrowest part of the apex opening being greater than 400 mm, and
c) the ratio between the volumetric flow through the apex opening (Qa) and the volumetric flow through the inlet opening (Qf) of the hydrocyclones being controlled to lie within the interval 0.10-0.60.
According to this process it is possible to obtain satisfactory fractionation according to fiber bonding ability in hydrocyclones and prepare a pulp which yields a paper with improved tensile strength, tear strength, light-scattering, and surface smoothness.
In a modified version of the process of the invention, in which an arrangement of a centrally and axially placed blocking device (B) of circular cross section in the base end outflow opening is substituted for the parameter a) above, it is possible to further improve the process, so that it yields a paper which, in addition to improved tensile strength, tear strength, light scattering, and surface smoothness, also has a very low shive content.
This modified process thus refers to a process for the preparation of improved cellulose pulps in which defibered cellulose pulps are screened for removal of shives, fibers with low bonding ability together with remaining shives are removed in hydrocyclones, and rejects from the hydrocyclone treatment are treated in refiner, said process being characterized by the combination of the following characteristics:
a) the distance (Lu) between the inner base outflow opening and the narrowest part of the apex opening of the hydrocyclone being kept greater than 400 mm
b) the ratio between the volumetric flow (Qa) through the apex opening and the volumetric flow (Qf) through the inlet openings of the hydrocyclones being regulated to lie within the interval of from 0.08 to 0.60 and
c) the base outflow channel of the hydrocyclones being provided with a centrally and axially arranged blocking device (B) of circular cross section, the ratio of the diameter (Dd) of this blocking device to the diameter of the base outflow opening (Db) being kept within the interval of from 0.1 to 1.2.
The invention also refers to an apparatus for application of the process in which cellulose pulps are screened comprising hydrocyclones C for separation of fibers with low bonding ability and device RR for refining rejects from the hydrocyclones C, characterized by the combination of the following characteristics:
a) the base end outflow diameter Db of the hydrocyclones being less than 14 mm
b) the distance Lu between the inner base end outflow opening and the narrowest part of the apex opening of the hydrocyclones being greater than 400 mm
c) means P,V for establishing a volumetric flow Qa through the apex opening of the hydrocyclones that relates to the volumetric flow Qf through the inlet opening of the hydrocyclones such that the ratio Qa/Qf is within the interval 0.10-0.60.
The invention includes a modified apparatus for application of the process of the invention which results in a very low shive content, in which the base outflow channel of the hydrocyclones are provided with a centrally and axially arranged blocking device B of circular cross section. This modified apparatus thus refers to an apparatus for application of the process of the invention in which cellulose pulps are screened comprising hydrocyclones C for separation of fibers with low bonding ability and device RR for refining rejects from the hydrocyclones C, which apparatus is characterized by the combination of the following characteristics:
a) the distance Lu between the inner base end outflow openings and the narrowest part of the apex openings of the hydrocyclones being greater than 400 mm,
b) means P,V for establishing a volumetric flow Qa through the apex openings of the hydrocyclones that relates to the volumetric flow Qf through the inlet openings of the hydrocyclones, such that the ratio Qa/Qf is within the interval of from 0.08 to 0.60, and
c) the base end outflow channel of the hydrocyclones being provided with a centrally and axially arranged blocking device B of circular cross section, the ratio of the diameter Dd of this blocking device to the diameter Db of the base outflow opening being within the interval of from 0.1 to 1.2.
The expression “hydrocyclones” above and in the following is intended to mean one or several in parallel interconnected hydrocyclones including so-called multihydrocyclone aggregates.
Although especially applicable to TMP and CTMP the process and the apparatus of the invention can also be used with other types of cellulose pulps when improved bonding ability is desired, such as beaten chemical pulp and pulp made from recycled fibers.
The ratio Qa/Qf that should be within the interval 0.10-0.60, can preferably be kept within specific limits, depending of the pulp treated. For chemical pulps the ratio Qa/Qf is preferably 0.10-0.25, whereas the corresponding preferred interval for TMP is 0.20-0.40, and for CTMP 0.10-0.30.
The process of separation of fibers with low bonding ability can be carried out in one or in several hydrocyclone stages with different Qa/Qf-ratios in each stage. If, for example, two hydrocyclone stages are used, the ratio Qa/Qf in the first stage can be kept within the interval 0.10-0.40, whereas the ratio in the second stage can be kept on a lower level, such as 0.05-0.25.
As for the dimensions of the hydrocyclones for separation of fibers with low bonding ability, when no blocking device is used, the preferred ratios between the length (Lc) and the greatest cone diameter (Dc) is kept within the interval 5.2-6.5, the ratio between the base outflow diameter (Db) and the greatest cone diameter (Dc) is kept within the interval 0.10-0.20, the ratio between the apex outflow diameter (Da) and the greatest cone diameter (Dc) is kept within the interval 0.18-0.30, and the ratio between the base outflow diameter Db and the apex outflow diameter (Da>) is kept less than 1.
When a blocking device is used, the dimensions of the hydrocyclones are the same as described above with the exception of the ratio between the base outflow diameter(Db) and the greatest cone diameter (Dc) which is kept within the interval 0.10-0.26.
The ratio of the diameter (Dd) of the blocking device at the end (E) to the diameter (Db) of the base outflow opening is preferably kept within the interval of from 0.1 to 0.9 when the blocking device is arranged within a central outlet tube (T) at the base end of the hydrocyclone and extending axially from the base outflow opening into the hydrocyclone chamber. Such extension can preferably be from 0 to 5 times the diameter (Db) of the base outflow opening. It is also possible to arrange the blocking device within the central tube (T) at the base end of the hydrocyclone, extending axially with its end (E) within this tube at a distance of from 0 to 5 times the diameter (Db) of the base outflow opening in the flow direction from the base outflow opening. In the latter case it is also possible to make the central tube (T) widening in the flow direction, and the diameter (Dd) of the end (E) of the blocking device greater than the diameter (Db) of the base outflow opening.
According to the invention it is also suitable to treat rejects from the hydrocyclones for separation of fibers with low bonding ability in one or more hydrocyclones designed for separation of sand, bark and heavy particles, and this treatment can be carried out in one or more hydrocyclone stages. In this case it is preferred that the ratio Qa/Qf is kept within the interval 0.05-0.10, and the ratio between the base outflow diameter (Db) and the apex outflow diameter (Da) is kept greater than 1.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates schematically a plant for application of the process and apparatus of the invention, in which shives, fibers with unsatisfactory bonding ability, and bark are separated from the pulp.
FIG. 2 shows schematically a side view of a hydrocyclone according to the invention.
FIG. 3 shows a view of the hydrocyclone in FIG. 2, seen from the base end.
FIG. 4 shows a blocking device arranged within a central tube with one end located within the central tube, the diameter of this end of the blocking device being greater than the diameter of the base outflow opening.
FIG. 5 shows schematically two hydrocyclone stages for separation of fibers with low bonding ability, connected to each other.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows a mill system for the fractionation of thermomechanical pulp (TMP) in which pulp emerging from the refiners is treated for the separation of shives, insufficiently developed fibers, sand, and bark. Screened, washed and preheated chips are fiberized in two refiner stages R 1 and R 2 (each stage inay contain several refiners in parallel). The pulp is diluted with water to a consistency of 3-4%, and led to a latency chest L 1 , where various forms of mechanical stress (latency) in the fibers, caused by the refining process, are released The pulp is then pumped, at a consistency of about 1.5% through the screen S, where the screen plates have either holes or slots, and where most of the shives are separated Undeveloped fibers together with sand, bark, and any short shives that may have been accepted by the screen S, are separated from the developed fibers by the special hydrocyclones C 1 and C 2 , forming a cyclone cascade and are withdrawn through the valve V 4 . Therefore, the material leaving through valve V 1 consists mostly of well developed fibers of good bonding potential and fines. The pulp suspension is pumped through the cyclones by the pumps P 1 and P 2 .
The fraction leaving C 2 through the valve V 4 contains undeveloped fibers, short shives, sand, and bark. It is passed to the cyclone cascade consisting of the stages D 1 , D 2 , and D 3 , fed by the pumps P 3 , P 4 , and P 5 . These cyclones are designed to give an efficient separation of sand and bark from the fiber material. The accepts from D 1 , leaving through the valve V 5 , join the shive-containing rejects from the screen S, and the combined stream is sent via the thickener U to a special rejects refiner RR.
Here, the fibers are given another treatment to enhance their bonding ability, and the fibers are fiberized. The pulp goes from the reject refiner to a latency chest L 2 , and from there back to the main stream, where it is again screened in S and fractionated in C 1 . The water withdrawn from the pulp in the thickener U can be used for dilution in the latency chest L 2 . Fibers and shives which were separated in the first pass, and which are still insufficiently developed or fiberized, are sent to the rejects refiner again. The final rejects from the cyclones in stage D 3 , leaving the system through the valve V 10 , contain sand and other heavy, non-fibrous material.
A system for chemimechanical pulp (CTMP) would be of essentially the same design—the main difference being in the treatment of the wood chips ahead of the main stream refiners, and in the way these refiners are run.
Cyclones for the Fractionation
The main stream hydrocyclones C 1 and C 2 separate primarily fibers of low bonding ability. In contrast to what takes place in screens, there is no fractionation according to fiber length in these cyclones. Also, sand and other types of heavy contaminants are separated, together with short shives. The combined process of fractionation according to bonding ability and separation of heavy contaminants is attained partly through the particular design of the cyclones, and partly by running the cyclones in a particular way.
As for the design of the cyclones, their size is quite different from what is common in forward hydrocyclones used for separating shives, sand, and bark from TMP. While the normal cyclones have a largest inner cone diameter Dc (See FIG. 2) of 150-300 mm and a length Lc of 1000-1200 mm, the corresponding dimensions of the fractionating hydrocyclones C 1 and C 2 are Dc=80 mm, and Lc=475 mm. Further, the diameters of both the inlet and the two outlets are of great importance. In the cyclones used in the mill and described in FIG. 1, the dimensions given in Table 1 and Table 2 below have proved to result in a satisfactory fractionation effect, while the heavy contaminants are also efficiently separated:
TABLE 1
Dc =
80.0 mm
(Lu/Dc =
5.94)
Di =
13.5 mm
(two inlets)
Db =
12.0 mm
(Db/Dc =
0.150)
Da =
18.0 mm
(Da/Dc =
0.225)
TABLE 2
Dc =
80.0 mm
(Lu/Dc =
5.94)
Di =
13.5 mm
(two inlets)
Db =
18.0 mm
(Db/Dc =
0.22)
Da =
18.0 mm
(Da/Dc =
0.22)
Dd =
12.0 mm
(Dd/Da =
0.67)
In hydrocyclones with dimensions in accordance with Table 1 and Table 2, and which are run at the conditions described in the following, most of the fibers with good bonding ability—i. e. flexible fibers of large specific surface—leave through the base opening, while undeveloped fibers pass mainly through the apex opening, along with sand and shives.
The ratio Db/Da is a very important design parameter. In conventional cyclones used for cleaning TMP and CTMP, this ratio is often close to 2, while it is less than 1 in the fractionating hydrocyclones used in the invention. In this respect, these cyclones resemble hydrocyclones used for separating light contaminants, e. g. plastics, from fibers, so-called reverse cyclones. However, when such hydrocyclones are run in the conventional way, the cleaned fibers (the accepts) leave through the apex outlet, and the contaminants (the rejects) leave through the base outlet together with a relatively small portion of the fibers. In the fractionating cyclones described here, the fibers follow a quite different flow pattern, as will be described in the following.
How much of the various fibers and contaminants that will leave through each of the two openings is determined by the distribution of the liquid in the cyclone. This distribution, also called the volume flow split, is given by the ratio Xq=Qa/Qf, where Qa is the volume flow rate through the apex opening, and Qf is the feed volume flow rate to the cyclone. Fibers with very strong bonding ability always go to the base opening, and fibers with very weak bonding ability always go to the apex opening in the cyclone designed according to the invention. However, the parameter Xq has a strong influence on how fibers with bonding ability between these two extremes are distributed. An increase in Xq, i. e. in the relative amount of the flow leaving through the apex, leads to a lower content of less developed fibers in the base fraction, while simultaneously more of the well developed fibers will leave in the apex fraction. With respect to the total result, it is normally advantageous to run the cyclones in stage C 1 in such a manner that a small portion of the well developed fibers is allowed to go with the apex fraction, whereby the content of not fully developed fibers in the base fraction becomes very low. This will also ensure that practically all sand and bark, and other heavy is passed on to the hydrocyclone D 1 through the valve V 4 in FIG. 1 . This amount depends of course on how one chooses to run the primary refiners R 1 and R 2 . The valves V 1 , V 2 , V 3 , and V 4 are used to regulate the flow distribution in the hydrocyclones C 1 and C 2 .
In conventional systems for cleaning TMP and CTMP, Xq for the cyclones in the C 1 position is normally around 0.10. For this reason the corresponding C 2 stage is considerably smaller than it is in the fractionation system of the invention, since a much smaller flow is coming from C 1 . It is therefore not practically possible to obtain any significant fractionation in a given conventional installation just by increasing the apex flow rate in C 1 , quite apart from the fact that the cyclones themselves would be unsuited for the purpose. Another important process operation parameter is the consistency of the feed to the cyclones in C 1 in the fractionation system of the invention. Generally, the fractionation efficiency is higher at lower than at higher consistencies. On the other hand, low consistencies also result in large flow volumes. The optimal feed consistency for the fractionating hydrocyclones will therefore usually lie in the range 0.3-1.2%.
With the cyclone dimensions and operating conditions given in the preceding paragraphs, the fiber fractionation occurs according to Table 3. This scheme shows by which cyclone opening the fibrous material will preferentially leave, according to their surface and flexibility. The more flexible the fibers are, and the larger their specific surface is, the stronger is their tendency to leave through the base outlet. Fibers which are flexible and also have a large surface (due to partially loosened fibrils in the fiber wall) have the best bonding ability.
Cyclones for the Separation of Contaminants of High Specific Weight
The stream leaving the hydrocyclone C 2 through valve V 4 in FIG. 1 consists for the most part of undeveloped fibers and shives, together with sand, bark, and other contaminants which have a specific weight above that of the fibers. This heavy matter is separated from the fibrous material by the hydrocyclones in the stages D 1 , D 2 , and D 3 . These cyclones are designed differently from those in C 1 and C 2 , and are run at other values of Xq, normally 0.05-0.10. Their main dimensions with reference to FIG. 2 are shown in Table 4.
TABLE 4
Dc =
80.0 mm
(Lu/Dc =
5.94)
Di =
13.5 mm
(two inlets)
Db =
26.5 mm
(Db/Dc =
0.331)
Da =
18.0 mm
(Da/Dc =
0.225)
The length of the cyclone chamber Lc is 475 mm. Thus, these cyclones are smaller than those usually applied for the separation of sand etc. in conventional systems, where e. g. Dc=150-300 mm and Lc=1000-1200 mm. In contrast to some of the fractionation hydrocyclones C 1 and C 2 , their base outlets are wider than their apex outlets, i. e. Db/Da is greater than 1. There is no blocking device in the base end outflow of these hydrocyclones.
The invention is illustrated by the following examples.
EXAMPLE 1
In a mill for producing newsprint TMP in accordance with FIG. 1, pulp samples were taken at two occasions with different sets of values for the volume flow split in the cyclones C 1 and C 2 . The sampling positions are shown in FIG. 5 . Each sample was tested for tensile index, tear index, and light scattering coefficient. The test results are given in Table 5 and Table 6, where
D=tensile index Nm/g
R=tear index Nm 2 /kg
L=light-scattering coefficient m 2 /kg
The volume flow splits Xq used in each test run are also shown in these tables
TABLE 5
Pos.
D
R
L
1
30.4
7.0
45.4
2
36.6
8.0
53.7
3
27.8
6.4
45.7
4
9.0
2.2
32.3
Xq in C1 = 0.24
Xq in C2 = 0.10
TABLE 6
Pos.
D
R
L
1
28.6
6.8
47.1
2
38.5
7.5
53.6
3
not observed
4
7.9
1.9
31.5
Xq in C1 = 0.20
Xq in C2 = 0.08
The data in the tables show clearly that at both the volume flow splits used, the pulp treated in accordance with the invention in the main line—position 2 —has considerably higher, i. e. better, values for all three quality parameters than the incoming pulp—position 1 —and that the pulp which is passed on for further treatment—position 4 —is much weaker and gives less light-scattering.
EXAMPLE 2
The large difference in strength between the base and apex fractions from the fractionating hydrocyclones has been suggested to be due to a much lower content of fines in the apex fraction, and also that the fines there probably have less strength-increasing increasing capacity than those in the base fraction. This hypothesis can, however, be rejected, which is shown in the following tests:
Samples were taken from the base and apex fractions in the cyclone stage C 1 in the same production line as that described above, and the tensile index was measured both in the whole sample and in samples partitioned according to fiber length in a Bauer-McNett fractionator. The 16-30 mesh fraction, i. e. fibers which have passed through the 16 mesh screen but are retained on the 30 mesh screen, contains neither shives nor fines (shives are retained by 16 mesh, while fines pass through 30 mesh). The tensile index of this fraction, which in the test comprised about 15% of the whole sample, is considered to be a good measure of how well developed the fibers are. The observed tensile index values, which are shown in Table 7 below, clearly show that the whole sample as well as the 16-30 and the 50-200 mesh fractions from the apex stream were of inferior quality, as compared to those of the base stream. It is therefore obvious, that the strength difference between the base and apex streams is not caused by differences in the amount or the quality of the fines.
TABLE 7
Tensile index of pulp from C1, Nm/g
Fraction
Base
Apex
Whole sample
38.6
21.5
16-30 mesh
9.0
4.8
50-200 mesh
54.4
20.5
EXAMPLE 3
TMP for newsprint was fractionated in a laboratory test in order to determine the amount of fibers with low bonding ability in the pulp and therewith the need of fractionation and size of subsequent refining equipment. The fractionation was carried out in three stages in accordance with FIG. 6 . The hydrocyclones used were of the same type as the hydrocyclones C, described in FIG. 1 . Samples were taken and tested for tensile index. For these trials, the fiber flow split Xm is also reported in addition to the volume flow split Xq. Xm is defined as the ratio between the apex pulp flow rate and the feed pulp flow rate of the cyclone. The results are shown in Table 8.
TABLE 8
Tensile index in TMP for newsprint, Nm/g
Cycl.
Feed
Base
Apex
1
32.7
47.4
21.4
2
40.2
14.0
3
39.9
8.5
Xm in 1 = 0.50
Xm in 2 = 0.64
Xm in 3 = 0.78
Xq = 0.28 in all stages
Table 8 shows that when newsprint pulp was fractionated, the base fractions from all three stages had a higher tensile index than the original pulp fed to cyclone 1 . The apex fraction from cyclone 3 contained 25% of the pulp flow to the system, and had a very low tensile index. This fraction could be assumed to consist mainly of fibers of very low bonding ability in need of further treatment in refiners.
EXAMPLE 4
TMP for LWC (light weight coated paper) was fractionated in a laboratory test in order to determine the amount of fibers with low bonding ability in the pulp and the need of fractionation and size of subsequent refining equipment. The fractionation was carried out in accordance with FIG. 6 . The hydrocyclones used were of the same types as the hydrocyclones C, described in FIG. 1 . Samples were taken and tested for tensile index and the fiber split Xm was reported. Pulp for LWC is normally defibrated at a much higher energy input to the main line refiners than is newsprint TMP, which results in a larger proportion of fully developed fibers. The effect of fractionation therefore could be expected to be lower. The result of the test is shown in Table 9.
TABLE 9
Tensile index in TMP for LWC, Nm/g
Cycl.
Feed
Base
Apex
1
46.6
55.3
39.5
2
49.9
30.5
3
44.1
19.4
Xm in 1 = 0.45
Xm in 2 = 0.56
Xm in 3 = 0.64
Xq = 0.32 in all stages
The results in Table 9 show surprisingly, that not only the base fraction of cyclone 1 , but also the base fraction of cyclone 2 , had a higher tensile index than did the pulp feed to the system. The rejects from cyclone 3 , which comprised 16% of the pulp feed to the system, showed a considerably lower tensile index than the original pulp. Consequently, fractionation according to the invention is advantageous even for TMP used for LWC.
In the above examples the invention is described using a separate refiner for the rejects from the hydrocyclones. According to the invention it is, however, also possible to return the rejects from the hydrocyclones to the refiners in the main line.
EXAMPLE 5
In a mill for producing newsprint TMP in accordance with FIG. 1, pulp samples were taken from the base outflow and from the apex outflow of the hydrocyclone C 1 without blocking device (A) and with a blocking device (B). The samples were tested for tensile index, light-scattering coefficient, and shive separation. Inlet consistency was 0.52% and Xq=0.25. In the test (A) the hydrocyclone had the measures given in Table 1, whereas in the test (B) the hydrocyclone with a blocking device had the dimension given in Table 2 and the end of the blocking device at the same level as the base outflow opening. The results are given in Table 10, in which D=tensile index Nm/g, L=light-scattering coefficient m 2 /kg, and S=shive separation efficiency in % for shives of length 2 and 4 mm, respectively:
TABLE 10
S
Cyclone
2 mm
4 mm
D
L
A
31
20
10.1
7.4
B
52
99
12.1
13.9
The data in the Table show clearly that the pulp treated according to the modification (B) has considerably improved shive separation efficiency when a blocking device as described above is used. There is also an improvement in tensile strength and light-scattering coefficient. | A process and apparatus for the preparation of improved cellulose pulps is provided, in which defibered pulp is screened for removal of shives, and fibers with low bonding ability are removed in hydrocyclones, and rejects from the hydrocyclones are treated in refiner. In the process a specific combination of characteristics for the hydrocyclones and the volumetric flow is used in order to prepare pulps which give products of improved qualities, such as higher tensile strength, tear strength, light-scattering, surface smoothness, and especially low shive content. | 3 |
RELATED APPLICATIONS
This application is a divisional application of U.S. Ser. No. 08/948,746, which was filed on Oct. 10, 1997, which application was a continuation-in-part application of U.S. Ser. No. 08/698,870 filed Aug. 16, 1996 now U.S. Pat. No. 5,782,594 which claims priority to German Application No. 19530466.7 filed Aug. 18, 1995. This application also claims priority to German Patent Application No. 197 10 246.8 filed Mar. 12, 1997.
FIELD OF THE INVENTION
The present invention relates to an element, for example a fastening element such as a hollow nut element or a bolt element in particular a nut element, for attachment to a plate-like component, wherein an annular or ring-shaped recess or groove is present at an end face of the element facing the component within a raised annular or ring-shaped contact surface, wherein at least one undercut is preferably provided in a side wall of the recess, and also features providing security against rotation are provided and wherein a cylindrical punch or pilot section concentric to the central longitudinal axis of the element projects at the said end face within the ring-shaped recess and the outer boundary wall of the cylindrical punch section has a preferably ring-shaped or annular undercut. In addition, the present invention relates to a method of attaching such an element to a plate-like component, to a component assembly and to a die button for use in the method for attaching the element to a plate-like component.
BACKGROUND OF THE INVENTION
An element of this type is known from U.S. Pat. No. 3,648,747, and also from the U.S. Pat. Nos. 5,340,251, 3,234,987 and 3,253,631.
Further elements of this type are known from the European patent application with the publication number EP-A-0 553 822 or the corresponding U.S. Pat. No. 5,340,251 and also from the European application with the publication number EP-A-0 669 473.
A similar element is also known from the European application with the publication number EP-A-0 663 247; however, this application is concerned with the manufacturing of an element of this kind rather than with the element itself.
Such elements are generally formed as elements with hollow bodies, or more precisely as nut elements, but could however also for example have a smooth cylindrical bore to receive a spigot. In addition, such elements could also be formed in the manner of bolt elements and in which case the head of the bolt element is secured to the sheet metal part or to the plate-like component and the head would have the above described design. Finally, the element can be regarded quite generally as a functional element, whereby it is possible to realize diverse functions. For example, the function of a nut through the provision of an element with a hollow body having an internal thread, or the function of a bolt by the provision of a shaft or spigot (tubular) part, or the function of for example a pin for the clamped attachment of other components, such as carpet eyes, or electrical terminals. Ultimately, it is not the function which is important, but rather the joint or attachment between the element and the plate-like component which normally consists of a sheet metal, but with other materials such as plastic panels is also possible.
The known elements in accordance with the above referenced patents and published applications are all elements having hollow bodies which are as a rule formed as nut elements. They all offer a certain degree of security against rotation (twist-out) so that on screwing-in a bolt element a rotation of the element having the hollow body is generally avoided. Moreover, the known elements have a certain press-out resistance. Nevertheless, improved security against rotation (twist-out) and higher press-out resistances are always desirable characteristics for such elements.
It has been shown with the known elements that the elements sometimes tear out of the plate-like component (normally a piece of sheet metal) in operation and under alternating loads. The manufacture of such elements having hollow bodies is also relatively complicated and a problem exists in as much as it is difficult to simultaneously keep the weight of the element small and to make the contact surface of sufficiently large dimensions.
The undercut in the side wall of the ring-shaped recess, which is necessary to produce the required press-out resistance of the hollow body is normally achieved by subjecting the element having a hollow body to a deformation or crushing process at the peripherally extending outer surface, whereby the side wall of the ring-shaped recess is brought from an initially axially parallel position into an inclined position. In this way, the opening to the ring-shaped recess between the pilot part and the now inclined side wall is reduced in comparison to the base surface of the recess and the undercut is produced. Through this crushing process, the element having the hollow body however also has an inclined flank at the outer jacket surface adjacent to the end face confronting the component. This can lead to a situation in which the contact surface at the end face of the element becomes too small, with the contact surface being so deformed during the attachment of the plate-like component that it acts in a knife-like cutting manner under load and a high surface pressure results between the component and the element having the hollow body.
As a result of this high surface pressure, the plate-like component yields or relaxes after a few hours of operation and the element is no longer as tightly attached to the component as desired. This leads eventually to settling or relaxation, so that the prestress of a bolt inserted into the element reduces to zero, whereby the bolted connection fails.
The inclined flank at the transition from the outer jacket surface into the end face of the element however also results in an unnecessary waste of material which is generally steel, because material which is present radially outside of the contact surface at the element does not provide any contribution to the strength of the connection or of the element. In other words, the elements are heavier than is absolutely necessary, which ultimately represents an economic disadvantage.
OBJECTS AND SUMMARY OF INVENTION
An object of the present invention is to further improve an element of the above describe kind in such a way that on the one hand the security against rotation and/or the press-out resistance are improved but, on the other hand, with the manufacture of the element being simplified, and with the further development preferably also being effected in such a way that a saving of material is possible. It should also be ensured that the characteristics of the element, i.e. the connection to the sheet metal part with respect to alternating loads is improved, i.e. the danger of settling of the element and reduction of the prestress force and eventual tearing of the element out of the sheet metal part should be substantially reduced.
In order to satisfy these objects, the element of the invention is characterized in that a material supply is formed at or adjacent to the free end face of the cylindrical punch section and is displaceable at least locally by means of a die button on insertion of the element into the annular or ring-shaped recess in order to capture or clamp material of the component which has previously been pressed by the die button into the ring-shaped recess between itself and the base surface of the ring recess.
A method for the insertion of an element of this kind is characterized in that the punch section of the element is indented locally at its end face using a die button which has teeth, for example from two to six teeth, which are arranged radially within its projecting cylindrical punch section, which project radially inwardly into the central passage of the die button and are set back from the end face of the projecting cylindrical section of the die button so that material is deformed and displaced from the punch section of the element into the ring recess in such a way that it projects from the inner side wall of the ring recess, at least substantially radially into the ring recess and there overlies material of the plate-like component which has previously been pressed into the ring recess by the end face of the projecting cylindrical section of the die button and preferably clamps this material between itself and the base surface or bottom wall of the ring recess.
The invention recognizes that in some elements of this type, it is difficult to ensure, in practical operation, that the sheet material is actually and always reliably deformed into the undercut in the cylindrical punch section. If this is, however, not ensured, then the security of the form-locked connection of the component to the undercut in the outer side wall of the ring-shaped recess is questionable. On the one hand, the security against rotation suffers, as does also the press-out resistance on the other hand. The stability in operation in the event of alternating loads is in many cases deficient.
With the previously known elements, a deformation of the cylindrical punch section is not intended and is also not possible, because otherwise the danger would exist that the inner thread of the nut element is deformed, whereby a bolt or screw cannot be threaded into the bore and the element would become unusable. One could indeed theoretically increase the radial dimensions of the cylindrical punch part, in order to reduce the danger of deformation of the thread cylinder. This would, however, lead to a situation in which the elements would become heavier and in which the contact surface would always be displaced further outwardly, so that one would always have to work with larger and thicker washers, in order to transfer the load from the bolt element to the nut element, whereby the connection as a whole become heavier and more expensive.
The invention here intentionally takes a different route in that the cylindrical punch section is not deformed in the sense of folding it over onto the sheet metal material in order to clamp the latter, but rather only a small portion of the cylindrical punch section is locally displaced downwardly relative to the remainder of the punch section by the die button, and thereby clamps the material of the component previously pressed into the peripherally extending recess between itself and the base surface of the ring recess. On the one hand, the form-locked connection between the element and the component is improved in the sense that at these locations the material of the component fully fills out the opening which is present, i.e. the undercut at the cylindrical punch section is fully filled out. On the other hand, the material displacement ensures that the end face of the die button permanently prestresses the material of the component in the region of the recess, whereby an even higher quality joint can be ensured.
Since the teeth of the die button, which are responsible for this material displacement, are only locally present within the through passage of the die button and have relatively small dimensions, it is possible to dispose of the punch slug which is punched out of the sheet metal part by the cylindrical punch section or pilot of the element through the through passage of the die button as desired, and indeed without having to provide a corresponding plunger at the setting head side with the task of pressing the punch slug through the through passage of the die button. A preceding hole punch is also not required. The element is preferably self-piercing.
Through this type of connection, a deformation of the thread is not longer a concern. It is only necessary to provide the cylindrical punch section of the element with a small supply of material which is suitable for this material displacement.
It is also particularly advantageous of the invention that one and the same element can be used with components of different thicknesses, so that it is for example entirely possible to cover with just one element the sheet metal thicknesses which are customary in the design of coachwork or car bodies. The invention is, however, particularly advantageously usable with thin and high-strength sheet metal because the problem of non-complete filling of the base region of the ring recess by the sheet metal material is particularly acute here.
Although a substantial improvement of security against rotation, of the press-out force and of the resistance to alternating loads is already provided by the above discussed features, it is also possible to achieve further improvements as disclosed in this application.
For example, the outer side wall of the recess may be so designed that it is of at least substantially polygonal shape in plan view in a manner known per se. In this way the security against rotation is improved relative to a round design of the ring recess.
The security against rotation can, however, be further increased if the recesses, which are mutually spaced from one another, are provided in the raised, peripherally extending contact surface, with these preferably being formed in such a way that they form radially inwardly projecting raised portions or noses at the outer side wall of the recess which form the undercuts.
It is also possible to provide noses which result in security against rotation in the region of the transition from the base surface of the ring shaped recess into the outer side wall and/or in the region of the transition between the base surface of the ring-shaped recess and the cylindrical punch section, and in both cases the noses providing security against rotation are preferably uniformly distributed around the element and are approximately triangular in plan view.
A particularly preferred embodiment of the element is characterized in that the cylindrical punch section which preferably has a ring-like undercut has a ring-like end face which is arranged at least substantially perpendicular to the central longitudinal axis of the element or of the punch section and merges via a ring shoulder into a ring region of the cylindrical punch section of larger diameter, with this ring region being set back from the free end face of the cylindrical punch section.
This embodiment leads, on the one hand, to the material which is displaced by the teeth of the die button originating from the ring shoulder region of the punch section, i.e. from a region radially outside of the annular or ring-like end face of the cylindrical punch section, whereby the danger of deformation of the thread is reduced. Moreover, it is easier to deform material from this region in such a way that the desired form-locked connection with the sheet material results.
Since the annular or ring-like end face of the cylindrical punch section or pilot lies radially within the ring shoulder, it leads to an easy deformation of the outer ring region of the punch slug, whereby the latter can be more easily disposed of past the teeth through the central passage of the die button without jamming having to be feared in this region.
Through the provision of noses or webs in the region of the ring shoulder of the cylindrical punch section, with the noses or webs preferably extending from the free end face of the cylindrical punch section up to the outer diameter of the ring-like region of the cylindrical punch section and being of approximately triangular shape in side view, this results in stiffening the element in this region on the one hand, but also in improving the piercing behavior on the other hand, because the plate-like component is ultimately pierced in the region of the ring shoulder, i.e. not at the free end face of the cylindrical punch section.
A particular advantage of the element in accordance with the present invention lies in the fact that it can be used with sheet metal parts of different thicknesses, i.e. one and the same element can be used for almost all the sheet metal thicknesses which are encountered in the construction of vehicle bodywork, i.e. sheet metal thicknesses from approximately 0.5 mm up to 3 mm or more. The die button simply has to be matched in each case to the prevailing sheet metal thickness.
Particularly preferred embodiments of the element and also of the method of inserting the same can be seen from the appended claims, the drawings and also from the subsequent description.
The invention will subsequently be explained in more detail with reference to embodiments and to the drawings.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a schematic longitudinal cross-sectional view through a nut element with piercing behavior and also through a die button, which cooperates with the nut element during formation of the connection to a sheet metal part;
FIG. 2 is a partial side cross-sectional representation of a part of a modified element having a hollow body similar to the element in FIG. 1, with only the region around the cylindrical punch section being shown and with only the left half of the element being illustrated, the right half being identical thereto;
FIG. 3 is a longitudinal cross-sectional view in accordance with FIG. 1, but of the preferred embodiment of the present invention;
FIG. 4 is a plan view of the element of FIG. 3 as seen in the direction of view arrow IV of FIG. 3, but prior to the insertion into a sheet metal part;
FIG. 5 is a plan view of the end face of the die button of FIG. 3 as seen in the direction of view arrow V, but without a sheet metal part;
FIG. 6 is a schematic part longitudinal cross-sectional view through the left half of the die button of FIG. 5 in the direction of the section plane VI--VI in FIG. 5;
FIG. 7 is a partial cross-sectional side view similar to FIG. 1, of the left half of the longitudinal cross-section and at an earlier stage of the insertion procedure with a further modified female fastener element, the section having been made at a different angular position than in FIG. 1; and
FIG. 8 is a part longitudinal cross-sectional through the left half of a further embodiment of a female fastener element in accordance with the invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
FIG. 1 first shows a longitudinal cross-section through an element 10 having a hollow body and through the die button 12 which cooperates with it immediately after carrying out an element installation procedure in which the sheet metal part 16 has been deformed into a ring recess 18 of the element 10, as a result of relative movement of the element 10 having the hollow body in the direction of the arrow 14 onto a sheet metal part 16 supported on the die button 12.
Generally, the arrangement is in the opposite direction to the illustrated arrangement, i.e. the element 10 is pressed from above by a setting head onto the sheet metal part and onto the die button lying beneath it. The element 10 is generally moved or fed by an installation or setting head (not shown) aligned coaxial to the central longitudinal axis 20 of the die button, i.e. the central longitudinal axis 22 of the element 10 should be aligned with the central longitudinal axis 20 of the die button.
The arrangement is normally arranged such that the setting head for the element 10 is attached to the upper tool of the press or to an intermediate plate of the press (not shown), whereas the die button 12 is associated with the lower tool of the press, or is arranged in or on the lower platen of the die press. However, the inverted arrangement of FIG. 1 is also possible. It is also not essential to use a press for the setting or installation process. For example a robot can be used to carry out the setting process.
At the right-hand side of FIG. 1 one can see a cross-section through the ring recess or annular groove 18 in the region of the end face of the hollow element 10 confronting the sheet metal part 16 or the die button 12, with this ring recess 18 being bounded at the radially outer side by an outer side wall 24, and at the radially inner side by an inner side wall 26 and at the bottom by a base surface or bottom wall 30 which preferably extends perpendicular to the central longitudinal axis.
In the cross-sectional illustration of the right-hand side of FIG. 1, the outer side wall 24 is inclined and thus forms an opening at the entry the ring recess 18 which is narrower in comparison to the radial dimension of the base surface 30, sometimes referred to as a re-entrant groove. The inner side wall 26 is formed by the radially outer surface of a cylindrical punch section or pilot 32 of the hollow element 10.
In plan view the ring recess can be circular, or it can also be of polygonal, for example octagonal shape at the outer side wall, with both variants are known in the prior art. The cylindrical pilot or punch section 32 appears may be circular in plan view (not shown) with an outer diameter D1 which corresponds at least substantially to the inner diameter of the die button 12 in the region of the sheet metal part, but which is functionally slightly smaller than the inner diameter of the die button opening. The cylindrical side wall 26 has an undercut in similar manner to the outer side wall of the ring recess 18, and axially beneath the ring-like piercing surface 34 at the free end face of the cylindrical punch section 32.
During the movement of the nut element 10 towards the sheet metal part or vice versa, the sheet metal 16 is pierced by the cooperation between the ring-shaped piercing surface 34 of the cylindrical punch section 32 and the corresponding ring-like piercing edge 36 of the cylindrical projection 38 of the die button 12, with the slug being disposed of through the central passage 40 of the die button 12 as shown. For easier disposal, the central passage 40 of the die button 12 is provided with a larger diameter above its end face. Since the end face 34 of the cylindrical punch section of the hollow element 10 lies a distance H above the contact surface 42 of the hollow element 10, it is the first to contact the sheet metal part 16 during the punch movement. The sheet metal part 16 is then deformed around the rounded shaping edge 44 of the hollow element 10 by the rounded forming edge 46 of the die button 12. The end face 48 of the projecting cylindrical part or pilot 32 of the die button 12 presses the sheet metal against the base surface 30 of the ring recess 18 and deforms the sheet material in a way that it can flow, into the undercut of the outer side wall 24, for example at 50, and can flow into the undercut 27 of the radially inner wall of the ring recess 18, as indicated at 52. If the hollow element has a polygonal shape in the region of the outer side wall of the ring shaped recess 18, then the die button 12 is of corresponding polygonal shape in the region of the shaping edge 46, as is for example evident from FIG. 5. When the outer side wall 24 is of polygonal shape, the outer jacket surface 11 of the hollow element is normally provided with a corresponding shape (for example, as shown in FIG. 4) which is, however, not essential.
One notes that the outer jacket surface of the hollow element 10 has an inclined flank 54 around it, with this inclination arising because the material at the outer side of the end of the hollow element 10 is generally deformed inwardly to produce the undercut at the outer side wall 24 of the ring recess 18.
Where the ring recess 18 is of polygonal shape in plan view, a security against rotation is formed by the hooked engagement of the sheet metal material into the undercut 25 of the outer ring wall 24. Through the form-locked, hooked engagement of the sheet material with this outer ring wall, a resistance against press-out is also produced.
One problem with the prior art pierce fasteners of this type is the fact that the deformation of the sheet metal material within the ring recess is not sufficient--particularly with thin and high-strength sheet metal such as carbon steel--to deform the sheet metal material fully into the undercut(s); particularly into the undercut 27 of the cylindrical punch section. This means that the sheet metal material is also not pressed firmly enough against the outer ring wall 24 of the ring recess 18, i.e. that press-out forces and torsional forces are more readily able to at least locally cancel the form-locked, hooked engagement of the sheet metal material with the hollow element 10 and to cause loosening or a loss of the hollow element 10.
Comparing the illustration of the female fastener at the right-hand half of FIG. 1 with a hollow element in accordance with the prior art, for example in accordance with EP-A-0 553 822, the distinction can be seen that a small supply of material is provided in the region of the cylindrical punch section which is indented at three uniformly distributed positions 55 and leads to an improved hooked engagement with the sheet material 16. One of the three positions 55 can be seen to the left-hand side of FIG. 1. The two other positions lie outside of the section plane of FIG. 1 and are thus not visible in FIG. 1.
At the left-hand side of FIG. 1, it can be seen that the die button 12 has a tooth extending in the longitudinal direction of the die button in the region 56, the tooth having locally deformed the material of the cylindrical punch section or pilot 32, in such a way that the material in the outer region of the cylindrical punch section 32 has been deformed downwardly and radially outwardly in FIG. 1, whereby a nose 58 is formed which lies in form-locked manner on the sheet metal material deformed in the ring recess 18. The material 58, which was displaced at this location and also at two further positions downwardly and radially outwardly, ensures that the material in the region 60, i.e. in the region of the undercut 27 is fully surrounded by the material of the hollow element 10, so that a loosening at these three positions is substantially more difficult than in the prior art. Moreover, this displacement of the material of the element leads to the sheet metal material being more firmly pressed into the undercut 25 of the outer side wall 24 of the hollow element, whereby the security against rotation of the connection, and also the press-out resistance are similarly improved.
It is important to note that this deformation of the small supply of material has taken place without damaging the thread cylinder 62 of the hollow element 10. The reference numeral 63 indicates the usual conical chamfers at the ends of the thread cylinder.
Reference 64 is a nose or a web which is preferably arranged in the transition between the base surface 30 of the ring recess 18 and the outer side wall 24. This nose or this web, which is of triangular shape in side view, can optionally be present. Several spaced noses or webs may be uniformly arranged around the central longitudinal axis 22 of the hollow element 10. These noses or webs promote the security of the connection against rotation between the hollow element 10 and the sheet metal part 16 in that the sheet metal part is deformed around the noses into the regions of the undercut 27 lying therebetween. The noses or webs preferably have exposed rounded edges in order to avoid cracks in the sheet material.
Thus, FIG. 1 illustrates an optional modification which can substantially improve the characteristics of the previously known pierce nuts of this kind. The embodiment of FIG. 1 can however be further improved as disclosed below.
A further possible improvement is shown in FIG. 2, and indeed by the provision of further webs or noses 166 in the transition region between the base surface 130 of the ring-shaped recess 118 and the undercut outer side wall 126 of the cylindrical punch section 132. The noses or webs 166 are formed and arranged in similar manner to the noses or webs 164 and can be provided in place of or in addition to the noses or webs 164.
Further improvements can also be effected.
In the first place, two lines 168 and 170 of FIG. 2 make it clear that the peripheral contact surface 142 of the element is smaller by an amount K, as a result of the inclined flank 154, than would be possible through the outer dimension of the jacket surface 111 of the hollow element 110. This signifies that the material of the hollow element 110 outside of the edge 172 has been largely wasted.
A waste of this kind is not present in the hollow element 210 of FIG. 3. In this embodiment, as in all further embodiments, reference numerals in the same sequence are used for common parts, so that it can be assumed that the previous description of the functional design of the parts also applies for parts with similar reference numerals, unless differences are specially described. For example, the female element 10 in FIG. 1 is numbered 110, in FIG. 2, 210 in FIGS. 3 and 4, 310 in FIG. 7, etc. That is to say, only the important deviations with respect to the previously described variants will now be described.
In the embodiments of FIGS. 3 and 4, wedge-like recesses 274 are provided at a total of eight positions around the peripherally extending contact surface 242 of the element and are produced by a cold heading process. These recesses 274 produce noses 276 which project radially into the ring recess 218 and form the undercuts 225 at the corresponding positions in the outer side wall 224 of the ring recess 218.
During the installation process, the material of the sheet metal part 216 is deformed both into the wedge-shaped recesses 274 and also into the regions 278 between the noses 276, whereby an enhanced security against rotation is produced relative to the previous embodiments.
The undercuts are fully sufficient in order to generate a comparable press-out resistance.
Since the undercuts are not formed by the production of an inclined flank (54 and 154 in the previous examples) the contact surface 242 is substantially greater in the examples of FIGS. 3 and 4 than in the previous examples. This improvement achieves lower surface pressures in operation, or permits the use of hollow elements with softer sheet metals. However, the outer dimensions of the hollow element 210 can also be reduced relative to the previous embodiments without concern regarding the loss of technical characteristics. That is to say, the elements are lighter and thus can be manufactured at less cost. The outer edge 243 of the contact surface 242 is simply provided with a small radius, for example 0.5 mm.
The FIGS. 3 and 4 however also illustrate a further improvement of the cylindrical punch section or pilot 232 of the hollow element 210. This embodiment has a ring-shaped end face 234 which however merges via a ring shoulder 280 into a ring region 282 of greater diameter. The material 258, which is displaced by the teeth 256 of the die button 212 over the material of the sheet metal part 216 into the undercut 227 of the cylindrical punch section of the element, originates from the region of the cylindrical punch section beneath the ring shoulder 280, whereby the danger of deformation of the thread cylinder 262 of the nut element is further reduced.
Noses 284, which are approximately triangular in side view, are provided in the region of the ring shoulder 280 and merge at their lower sides into the material of the ring shoulder 280 and in the region of their radially inner sides into the material of the cylindrical end face 234 of the cylindrical punch section. These noses 284, which can readily be seen in plan view in FIG. 4, on the one hand stiffen the cylindrical punch section of the hollow element 210 and, on the other hand, support the ring-like end face 234 of the cylindrical punch section, so that a collapse of the cylindrical punch section in this region is not a concern.
This embodiment leads, on the one hand, to the punch slug 288 being shaped so that it is somewhat rounded in its outer regions, as for example shown at 290, so that it can slide more easily through the central passage 240 of the die button.
The design of the cylindrical punch section in accordance with the embodiments of FIGS. 3 and 4 has, however, also the advantage that the undercut 227 in the region of the cylindrical punch section can be produced by a cold-heading process without the need to deform the cylindrical punch section radially outwardly by complicated rotations. Since this deformation of the cylindrical punch section, i.e. the provision of the ring shoulder 280, the formation of the undercut 227 and the formation of the noses 284, takes place prior to the cutting of the thread cylinder 262 through this deformation of the cylindrical punch section is not a concern. The manufacture of the element of the invention is possible by a cold-heading process and is relatively simple.
The FIGS. 5 and 6 show the die button 212 which can used with the element of FIGS. 3 and 4 in an end view and a cross-section respectively. It is evident from the end view of FIG. 5 that the projecting cylindrical section 238 of the die button 212 projects from a ring shoulder 239 extending generally parallel to the contact surface 242 of the corresponding nut element and perpendicular to the central axis 220. The projecting cylindrical section 238 of the die button 212 has a circular peripherally extending piercing edge 292, but a polygonal, here octagonal, radial outer shaping edge 294 which is slightly rounded as shown at 296 in FIG. 6.
The three teeth 256 can be seen in plan view in FIG. 5. It should be noted that these teeth extend over an angular amount of about 30°, in each case related to the central longitudinal axis 220 of the die button, and have a relatively small radial dimension r with respect to the radius R of the central passage of the die button 212 in the region of the end face. The angle of 30° is not critical and is simply given as a guide.
It is evident from FIG. 6 that the end faces 298 of the teeth 256 form step elements which are substantially set back from the free end face 248 of the die button and extend at least substantially radial to the axis 220. This signifies that they first come into use when the punch slug has already arisen through the cooperation between the cylindrical punch section of the hollow element 210 and the peripherally extending circular piercing edge 292 of the die button.
It is ensured through the octagonal shape of the section 238 of the die button 212 of FIG. 5, which is also used in FIG. 3, that the sheet metal material comes to lie in close engagement with the octagonal outer side wall 224 of the ring-shaped recess 218 including in its undercut 225.
Although three teeth 256, which can also be termed ribs or splines, already lead to reasonable results, the number of these teeth is not restricted to three. In principle, any desired number of teeth can be used. With more teeth their respective peripheral dimensions are preferably made smaller.
Finally, it is possible to replace the teeth 256 by a peripherally extending ring shoulder--or step--on the assumption that the punch slug 288 can be disposed of through the chamber 240 which could optionally be achieved by an ejection plunger if necessary, and assuming that the thread cylinder 262 is not damaged or deformed in undesired manner.
FIG. 7 shows an embodiment which falls between the embodiment of FIG. 1 and the embodiment of FIGS. 3 and 4. Here, wedge-shaped recesses 374 are likewise provided in the peripherally extending contact surface 342 of the hollow element 310. The cylindrical punch section 332 would, however, be essentially in accordance with the cylindrical punch section 332 of FIG. 1, i.e. approximately in accordance with the prior art, but with the provision of the required material supply for the deformation by the teeth 356 of the die button (not shown in FIG. 7).
Reference numerals 364 and 366 illustrate that in this embodiment noses or webs can also be provided in the region of the transition between the base surface 330 of the ring-like recess 318 and the outer side wall 324 and/or in the region of the undercut side wall 326.
Finally, FIG. 8 also illustrates a further embodiment of the embodiment of FIG. 3 in which additional noses 464 are provided in the region of the transition from the base surface 430 of the ring-like recess 418 into the outer side wall 424. This embodiment also illustrates that the ring shoulder 480 can optionally be placed somewhat deeper, which can be advantageous in some applications.
The external shape of the element, or of the head portion thereof if the element is a bolt element, can in principle have any desired form. For example, it can be circular, oval, polygonal, or can also have a grooved or pointed contour. In addition, the ring recess or annular groove 18. 118, 218 etc. can also be selected as desired and can therefore also have a circular polygonal, oval, grooved or ring-shaped contour, at least so far as the outer wall of the ring-like recess is concerned. Although the contour of the ring-like recess can in principle be selected independently of the outer contour of the element, or of the head of the element, it will generally be most convenient for the ring-like recess to have an outer contour which is at least substantially of the same shape as that of the outer contour of the element or of the head of the element. The reason for this is that a ring-like recess having a contour other than circular will involve the use of a die button having a projecting cylindrical projection 38, 138 etc. with a matching external contour and thus it is necessary for the die button and the element for which it is used to have the same angular alignment relative to the central longitudinal axis 20, 120 etc. If the ring-shaped recess has an outer contour other than round, then it can most conveniently be aligned if the outer contour of the element, or the head of the element, is of the same or related shape because this ensures that a clear orientation of the element can be specified in the setting head which will match the orientation of the die button in the respective tool.
It has already been pointed out that one element can be used with a variety of sheet metal thicknesses, for example from 0.5 mm to 3 mm. Elements in accordance with the present invention can be used also with a wide range of materials. They can in particular be used with any commercially available materials of draw quality, such as FPO steels 3, 4, 5 and higher. In additional, the elements can also be used for so-called ZSTE qualities of high-strength steels up to the highest strength levels, for example also including ZSTE 480. In addition, the elements can be used with aluminum and light alloy metal sheets.
The elements will predominantly be made in cold-forming steel materials in accordance with DIN 1654, although other steels could be used if the elements are formed by machining rather than by cold forming. For strengths above class 8, the cold forming steel materials selected will normally be heat treated in accordance with ISO 898 part 2. Elements made of such cold forming materials are able to satisfy all the normal requirements which arise in industry for the attachment of the elements to sheet metal panels and components.
As explained above, the die button used for the present invention will normally include teeth such as 256 which produce a linear displacement of the material of the element generally parallel to the central longitudinal axis 222, but could alternatively take the form of a complete ring shoulder which shifts a ring of material generally in the axial direction of the element. In each case, the die button required will have a special design, with the teeth or ring shoulder in the central passage of the die button being set back from the end face of the die button, i.e. the end face which confronts the sheet metal panel in use. This ensures that the end face of the die button presses the panel into the ring shaped recess before the teeth or ring shoulder shift material from the cylindrical punch part of the element to lock the panel material in the ring-shaped recess.
Although the base or bottom wall 30, 130, etc. of the ring-shaped recess is conveniently made generally flat and perpendicular to the central longitudinal axis 22, 122, etc. of the element, it can also have special profiles for special purposes such as are known in the prior art for shifting material beneath undercuts within the ring-shaped recess. | An element, for example an element with a hollow body or a bolt element, in particular a nut element, for attachment to a plate-like component, has a ring-shaped recess or annular groove present at an end face of the element facing the component within a raised ring-shaped contact surface. At least one undercut is preferably provided in a side wall of the recess, and also features radial recesses and noses which extend into the ring recess providing security against rotation. A cylindrical punch section or pilot concentric to the central longitudinal axis of the element projects at the said end face within the ring-shaped recess and the outer boundary wall of the cylindrical punch section preferably has ring-shaped undercut. A material supply is formed at or adjacent to the free end face of the cylindrical punch section and is displaceable at least locally by means of a die button on insertion of the element into the ring-shaped recess in order to capture or clamp material of the component which has previously been deformed by the die button into the ring-shaped recess between itself and the base surface of the ring recess. In this way an improved security against rotation, an increased press-out resistance and an improved behavior against alternating loads in operation is achieved. | 8 |
REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part of Ser. No. 09/859,559, filed on May 16, 2001, the entire contents of which is incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to a method useful in treating a condition related to the development of Alzheimer's disease (AD). The invention particularly relates to a process retarding or precluding Alzheimer's dementia by reducing or eliminating the concentration of at least one auto-antibody whose presence has been shown to initiate phagocytosis of astrocytic cells, thereby leading to Alzheimer's disease.
BACKGROUND OF THE INVENTION
[0003] Alzheimer's disease, also referred to as Alzheimer's dementia or AD is a progressive neurodegenerative disorder that causes memory loss and serious mental deterioration. Diagnosticians have long sought a means to definitively identify AD during the lifetime of demented patients, as opposed to histopathological examination of brain tissue, which is the only present means available for rendering an ultimate diagnosis of AD. AD is the most common form of dementia, accounting for more than half of all dementias and affecting as many as 4 million Americans and nearly 15 million people worldwide. Dementia may start with slight memory loss and confusion, but advances with time reaching severe impairment of intellectual and social abilities. At age 65, the community prevalence of AD is between 1-2%. By age 75, the figure rises to 7%, and by age 85 it is 18%. The prevalence of dementia in all individuals over age 65 is 8%. Of those residing in institutions, the prevalence is about 50%, at any age.
[0004] The social impact of this disease is enormous, caused by the burden placed on caregivers, particularly in the latter stages of the disease. The substantial economic costs are largely related to supportive care and institutional admission. The rapidly increasing proportion of elderly people in society means that the number of individuals affected with AD will grow dramatically, therefore finding an early accurate diagnosis and a cure for AD is becoming an issue of major importance world wide.
[0005] When an individual is suspected of AD, several recommended tests are performed:(1) Mini Mental State Examination (MMSE)—an office-based psychometric test in the form of a Functional Assessment Questionnaire (FAQ) to examine the scale for functional autonomy, (2) Laboratory tests—complete blood count, measurement of thyroid stimulating hormone, serum electrolytes, serum calcium and serum glucose levels, (3) Neuroimaging—most commonly used is computed tomography (CT) which has a role in detecting certain causes of dementia such as vascular dementia (VaD), tumor, normal pressure hydrocephalus or subdural hematoma. However, neuroimaging is less effective in distinguishing AD or other cortical dementias from normal aging. In primary care settings, some suggest that CT could be limited to atypical cases, but others recommend routine scanning. Magnetic resonance imaging (MRI) currently offers no advantage over CT in most cases of dementia.
[0006] While Alzheimer's is the most common form of dementia, accounting for at least 60% of cases, diagnostic procedures for determining the exact cause of dementia, among more than 80 different species, is difficult at best.
[0007] In comparison to other disease areas, the field of dementia raises questions concerning the value of diagnosis, since there is currently no cure or effective therapy available. In dementia, as in all other branches of medicine, the certainty of a diagnosis has an important impact on the management of the patient. While AD cannot be cured at present time, there is symptomatic treatment available and the first drugs (acetylcholinesterase inhibitors) for the temporary improvement of cognition and behavior are now licensed by the U.S. Food and Drug Administration. Other drugs are at different stages of clinical trials:(1) Drugs to prevent decline in AD—DESFERRIOXAMINE, ALCAR, anti-inflammatory drugs, antioxidants, estrogen, (2) Neurotrophic Factors:NGF, (3) Vaccine:the recent most exciting report by Schenk et al. (Nature 1999;400:173-7) raises the hope of a vaccine for AD. Unfortunately, a percentage of patients cannot tolerate the pharmaceutical agents currently made available due to allergic reactions, drug interactions, genetic inability to properly metabolize the agent, or the like, and therefore are unable to utilize the medicinal advantages of these agents. In addition, the pharmaceutical agents themselves have limited therapeutic value. After a length of time, the agent no longer is able to function as intended due to the body's tolerance, resulting in the buildup of autoantibodies. In this case, alternate therapy to control the level of autoantibodies circulating in the body by periodic removal may increase the length of time of an agent's medicinal value.
[0008] The specificity of the various therapies thus require sophisticated diagnostic methodologies, having a high degree of sensitivity for AD, in order to insure their success.
[0009] Currently there are a multitude of tests available which aid in the diagnosis of AD. However, the only true existing diagnosis is made by pathologic examination of postmortem brain tissue in conjunction with a clinical history of dementia. This diagnosis is based on the presence in brain tissue of neurofibrillary tangles and of neuritic (senile) plaques, which have been correlated with clinical dementia. Neuritic plaques are made up of a normally harmless protein called amyloid-beta. Before neurons begin to die and symptoms develop, plaque deposits form between neurons early on in the disease process. The neurofibrillary tangles are interneuronal aggregates composed of normal and paired helical filaments and presumably consist of several different proteins. The internal support structure for brain neurons depends on the normal functioning of a protein called tau. In Alzheimer's disease, threads of tau protein undergo alterations that cause them to become twisted. The neurohistopathologic identification and counting of neuritic plaques and neurofibrillary tangles requires staining and microscopic examination of several brain sections. However, the results of this methodology can widely vary and is time-consuming and labor-intensive.
[0010] Given the ability of both current and prospective pharmacological therapies to forestall and/or reverse the onset and/or progress of Alzheimer's dementia, it behooves us to promulgate interim methodologies to delay the seemingly irreversible loss of cognitive function.
[0011] Various biochemical markers for AD are known and analytical techniques for the determination of such markers have been described in the art. As used herein the term “marker” “biochemical marker” or “marker protein” refers to any enzyme, protein, polypeptide, peptide, isomeric form thereof, immunologically detectable fragments thereof, or other molecule that is released from the brain during the course of AD pathogenesis. Such markers may include, but are not limited to, any unique proteins or isoforms thereof that are particularly associated with the brain.
[0012] The markers particularly targeted according to the method of the invention are glial fibrillary acidic protein (GFAP) and glyceraldehyde-3-phosphate dehydrogenase (GAPDH).
[0013] Glial fibrillary acidic protein is an intermediate filament protein found almost exclusively in astrocytes which, in adults, control the level of GFAP expression. Astrocytes are a major type of glial cell which perform a variety of structural and metabolic functions, such as processing neurotransmitters, controlling extracellular ion levels, regulating the direction and amount of nerve growth, maintaining the blood-brain barrier, and participating in immune reactions. As astrocytes transform from a resting state into a process-bearing reactive state during events such as aging, GFAP expression is up-regulated. Since levels have been found to increase in the brain tissue and cerebrospinal fluid in patients suffering from AD, it has been suggested that reactive astrocytes may contribute to the neuropathology of AD (Wallin et al. Dementia, 7, 267 (1996)). In the AD brain, the loss of synapses is associated with an increase in the number of GFAP-positive astrocytes. In addition, this loss of synapses appears to be related to the extent of reactive astrogliosis (Brun et al., Neurodegeneration, 4, 171 (1995)). GFAP is a major component of the gliotic scars which result from gliosis, and which may interfere with subsequent reinnervation.
[0014] Glyceraldehyde-3-phosphate dehydrogenase is ubiquitous in the cell, with the major fraction in the cytoplasm associated with cytoskeletal proteins and membranes, and small amounts in the nucleus (van Tuinen et al., J. Histochem. Cytochem., 35 (1987)). Its size has been characterized in the prior art as between 35,000 to 38,000 Daltons. As a monomer, GAPDH promotes tubulin polymerization, the major constituent of microtubules (Durrieu et al., Arch. Biochem. Biophys., 252, 32 (1987)). GAPDH has many enzymatic and binding activities including forming complexes with the C-terminal region of the amyloid precursor protein (Schulze et al., J. Neurochem., 60 (1993)). The disruption in binding of GAPDH to cytoskeletal elements such as tubulin can result in the alteration of neuronal morphology, function, and survival. Its involvement in the neurodegeneration during the development of AD has been hypothesized due to its link to amyloid plaques (Sunaga et al., Neurosci. Lett., 200, 2 (1995)).
[0015] The present inventors have theorized that when autoantibodies to GFAP and/or GAPDH proliferate in the bloodstream and cross the blood-brain barrier, they couple with GFAP positive cells, particularly astrocytic cells. In the presence of these autoantibodies, e.g. anti-GFAP antibodies, the macrophages become clumped around the astrocytes, thereby initiating the phagocytosis process. If it could be demonstrated that the concentration of these autoantibodies are a controlling factor in the initiation of astrocytosis, then it would be possible to alter the course of disease progression by modifying anti-GFAP or the like autoantibodies associated with biochemical markers for AD in the circulating sera, thus providing physicians with an additional method for possibly circumventing or delaying loss of cognition at an early stage in the pathogenesis of this disease.
[0016] Certain types of treatment devices are known to be useful for the removal of biological markers. Removal of these markers is also known to be a valuable tool for reducing the manifestations of disease progression.
[0017] What is lacking in the art is a method effective for altering the course of disease initiation/progression in living Alzheimer's dementia patients alone, or in conjunction with, the use of pharmaceutical agents.
DESCRIPTION OF THE PRIOR ART
[0018] Generally, most scientific papers tend to focus on the peptide, β-amyloid, since it is postulated to be a major determinant of AD. This is supported by the observation that certain forms of familial AD mutations result in the over production of β-amyloid, particularly the longer form (1-42) which aggregates more readily than the shorter form. Hensley et al. (Proc. Natl. Acad. Sci., (1994), 91, pp3270-3274) examine the neurotoxicity based on free radical generation by the peptide β-amyloid in its aggregation state. Several synthetic fragments of the peptide are tested for resulting neurotoxicity. Based on the fact that oxygen seems to be a requirement for radical generation and glutamate synthetase and creatine kinase enzymes are oxidation-sensitive biomarkers, the inactivation of these enzymes are utilized as indicators of active attack on biological molecules by these fragmented β-amyloid aggregates.
[0019] In U.S. Pat. No. 5,004,697, Pardridge describes the use of modified antibodies for treatment and diagnosis of neurological diseases. A diagnostic composition is claimed involving an antibody capable of binding to antigens present in GFAP protein or an antibody to an Alzheimer's disease amyloid peptide. Delivery of these antibodies across the blood-brain barrier (BBB) is essential to the Pardridge invention in order to achieve diagnostic and/or therapeutic efficacy. Pardridge therefore requires modification of the antibodies by a process of cationization. There is no disclosure regarding the removal of circulating autoantibodies as a treatment method.
[0020] In U.S. Pat. No. 5,627,047, Brenner et al teaches astroctye-specific transcription of human genes. GFAP is acknowledged in the evaluation of AD, specifically the gene which encodes GFAP, however the patent is silent regarding autoantibodies to GFAP.
[0021] U.S. Pat. No. 6,187,756, a divisional of 6,043,224, issued to Lee et al. describes a method of alleviating the negative effects of a neurological disorder or neurodegenerative disease. The manner of alleviation is by administration of an antagonist of a β-adrenergic receptor coupled to cAMP or the administration of a protein kinase A or C signaling agent, for example. The importance of GFAP is only seen as it relates to cAMP; GFAP expression in astrocytes is increased by elevation in cAMP levels. Neither GFAP nor its autoantibody are recognized as having any significance in the treatment of AD.
[0022] U.S. Pat. No. 5,723,301 issued to Burke et al. teaches a method to screen compounds that affect GAPDH binding to polyglutamine. The role of GAPDH in neuronal death as a result of brain injury is described. Although a link of GAPDH to Alzheimer's disease is disclosed, the interest lies only in polyglutamine regions. Neither GAPDH nor its autoantibody are recognized as a target useful for direct intervention in the disease.
[0023] Many scientists have explored the significance of myelin basic protein, neuron specific enolase, and S100 autoantibodies in AD. As far as GFAP, there are conflicting results and opinions regarding the significance of serum autoantibodies against this protein. Although it has been suggested that the presence of anti-GFAP autoantibodies is related to Alzheimer's dementia, it is only as a secondary response. Generally, when GAPDH is utilized in Alzheimer's work, it is as a housekeeping gene or mRNA probe for other proteins of interest in the disease. Nothing in the prior art would suggest that a reduction in the amount of circulating autoantibodies to GFAP and GAPDH could have a beneficial effect in retarding the manifestations of Alzheimer's dementia. In addition, it has not been previously suggested to remove the circulating autoantibodies associated with these proteins to alleviate symptoms of the disease state.
SUMMARY OF THE INVENTION
[0024] The present invention is directed toward a process and a device which is useful for altering the progression of astrocyte phagocytosis, whereby the progression or development of Alzheimer's dementia may be altered or even eliminated. Although not wishing to be bound to any particular theory or hypothesis, the instant inventors have recognized what appears to be a causal relationship between the presence of certain autoantibodies, particularly those which bind to GAPDH and GFAP in circulating sera, and the progressive loss of cognitive ability associated with AD. it is theorized that reduction of these autoantibodies within the circulating sera, as a sole therapeutic modality or alternatively in conjunction with pharmacologic therapeutic agents, e.g. acetylcholinesterase inhibitors, may be effective in altering the development and/or progression of the disease, including but not limited to retardation of disease progression and/or increase of the period of efficacy of adjunct therapy. To this end, the instant inventors have demonstrated a causal relationship between the presence of autoantibodies to GFAP and the initiation of phagocytosis of astrocyte cells.
[0025] While it has not yet been conclusively demonstrated that a process for reduction of GFAP autoantibodies in circulating sera will modulate the development of Alzheimer's disease, it has nevertheless been shown that removal of such autoantibodies from circulating sera does, in fact, eliminate the initiation of phagocytosis of astrocytes.
[0026] While not wishing to be bound to a particular theory or mode of operation, it is believed that provision of a device to facilitate antigen-antibody interaction by creating an interfacial area containing a population of immobilized proteins which bind to the targeted autoantibodies, will result in a reduction in said phagocytosis, coupled with a concomitant reduction in the formation of plaques associated with Alzheimer's. These immobilized proteins, which function as a ligand, may be attached in various ways to a base, e.g. polystyrene, silicone, silica, or sepharose. The proteins may be oriented or non-oriented, fashioned in some orderly mode of attachment or alternatively by means of a single attachment or flexible attachment to improve the accessibility of the binding site. Illustrative, but non-limiting means of attachment may include the use of histidine residues for immobilization of proteins on various metal-chelate supports (Ho 1998); protein/autoantibody interaction (Kann 2000), and avidin-biotin mediated immobilization (Patel 2000).
[0027] Alternative forms of immobilized protein devices for blood treatment contemplated for use in the instant invention include functionalized hollow fiber cartridges containing the immobilized protein therein and capable of removal of autoantibodies by adsorption from blood which is allowed to flow through the cartridges (Legallais et al. 1999). Processes for extracorporeal immunoadsorption have been disclosed for treatment of diseases such as rapidly progressive glomerulonephritis, recurrent glomerular sclerosis, systemic lupus erythematosus, cancer, myasthenia gravis, Guillain-Barré Syndrome and hemophilia.
[0028] What has not heretofore been known in the art is that a disease process which occurs behind the blood-brain barrier, such as Alzheimer's dementia, could be effectively mediated by removal, from circulating body fluids, of those autoantibodies directly associated with reduction in cognitive ability associated with the disease.
[0029] The advantages which flow from the use of biological markers as treatment targets include strengthening the effectiveness of pharmaceutical agents, and assisting in slowing down the rate of disease progression.
[0030] Accordingly, it is an objective of the instant invention to provide a process effective for delaying, reducing and/or retarding the initiation of phagocytosis of astrocytic cells, which process has been linked to loss of cognitive ability associated with the progression of Alzheimer's disease.
[0031] It is a further objective of the invention to provide a method which includes analysis of at least one body fluid of a patient to determine the presence of at least one marker indicative of Alzheimer's dementia.
[0032] It is a still further objective of the instant invention to provide an immunoassay effective for the recognition of autoantibodies linked to the progression or manifestation of Alzheimer's dementia.
[0033] It is a still further objective of the invention to provide a test kit for gauging the progression or retardation of AD comprising a non-invasive point-of-care test which can be performed utilizing a sample comprising blood or any blood product.
[0034] It is yet a still further objective of the instant invention to provide a process and a related device effective for the selective removal of at least one antibody linked to the progression and/or manifestation of Alzheimer's dementia.
[0035] Other objects and advantages of this invention will become apparent from the following description taken in conjunction with the accompanying figures wherein are set forth, by way of illustration and example, certain embodiments of this invention. The figures constitute a part of this specification and include exemplary embodiments of the present invention and illustrate various objects and features thereof.
BRIEF DESCRIPTION OF THE FIGURES
[0036] [0036]FIG. 1 is of Western blots of brain tissue extracts comparing proteins found in AD brain to normal brain;
[0037] [0037]FIG. 2 is of 2D gels of brain extract from FIG. 1 highlighting the proteins of interest found in AD brain only;
[0038] [0038]FIG. 3 is a confocal micrograph of astrocytic cell interaction with macrophage dependent upon the presence of anti-GFAP antibodies.
DETAILED DESCRIPTION OF THE INVENTION
[0039] The markers which are targeted according to the method of the invention are those which are released into the circulation as a consequence of disease state and may be present in the blood or in any blood product, for example plasma, serum, cytolyzed blood, e.g. by treatment with hypotonic buffer or detergents and dilutions and preparations thereof, and other body fluids, e.g. CSF, saliva, urine, lymph, and the like.
[0040] For some markers, detectable levels of the marker are present normally in an individual. However, in response to a variety of physical, chemical, and etiologic insults such as brain injury, or disease, i.e. Alzheimer's, epilepsy, and multiple sclerosis, these levels become elevated due to a modification of stimulation, ultimately causing neuronal dysfunction and death.
Western Blotting
[0041] With reference to FIG. 1, tissue samples are obtained postmortem and are stored frozen until use. For experimental preparation, tissue samples are thawed and minced with a scalpel and subsequently transferred to glass tubes. A solution of phosphate buffered saline (PBS) containing a protease inhibitor cocktail, is added to the minced tissue, then homogenized using a polytron homogenizer. A detergent (Triton X100) is added to the homogenization buffer to enhance the extraction of proteins that are normally associated with cell membranes. The crude homogenate is centrifuged at 10,000 RPM in a refrigerated super-speed centrifuge to remove unbroken cells and cell debris which form a pellet. The pellet is extracted two more times by resuspending the pellet in the homogenization buffer and centrifugation as described above. The tissue extract containing the proteins is further subjected to electrophoresis on a polyacrylamide gel (12.5%) containing SDS and DTT to denature all the proteins. Following electrophoresis, the proteins are transferred onto a membrane (PVDF), blocked overnight with 5% Blotto/ 50 mM Tris Buffered Saline (TBS) pH7.4 at 4° C. and incubated with serum from patients diagnosed with Alzheimer's Disease for a period of 1 hour. After this incubation, the membrane is washed with TBS containing 0.05% Tween 20 (TTBS); and a solution containing the secondary antibody (goat anti-human IgG) conjugated to alkaline phosphate is added and incubated for an additional 2 hours. Following this incubation, the membrane is washed and the substrate (BioRad's alkaline phosphate substrate kit) is added which initiates the reaction for color development. Rinsing with ultra pure water terminates the reaction. The membrane is allowed to air dry, then is photographed. The photograph is then analyzed using specialized software to identify the protein bands that are present.
2D-gel Electrophoresis
[0042] With reference to FIG. 2, brain tissue extracts are separated by isoelectric focusing (IEF) using the Novex IEF gel system (pH gradient 3-10) for the first dimension. Proteins are further separated by SDS-PAGE (12.5% acrylamide) for the second dimension. Gels are then stained using Coomassie Blue stain and appropriately destained to remove background. Gels are imaged using a camera connected to a computer.
[0043] Protein ID
[0044] Spots of interest are physically cut out of the gel (see arrows—FIG. 2) using a scalpel and placed in individual tubes. Gel pieces are dehydrated to remove water, making it easier for the trypsin enzyme to penetrate the gel and digest the proteins. The gel pieces are incubated overnight (16 hours) at 37° C. with the trypsin. An aliquot of the trypsin digest fluid is removed and an initial separation step is conducted using Millipore's C18 zip tips. The filtrate is then spotted onto Ciphergen's NP1 chips and peptide sequencing is conducted. A trypsin blank is included on a blank piece of gel to enable a comparison of the peptide map of trypsin cleaving itself versus the protein of interest.
[0045] The sequences identified from the two spots cut out are GAPDH and GFAP; the upper band on the 2D gel (FIG. 2) corresponds to the sequence of GFAP and the lower band corresponds to GAPDH. It is apparent these bands do not appear on the normal brain extract 2D gel which would suggest these proteins play a role in the pathogenesis of AD.
[0046] The presence of antigen-presenting, HLA-DR-positive and other immunoregulatory cells, components of complement, inflammatory cytokines and acute phase reactants have been established in tissue of AD neuropathology. Although the data do not confirm the immune response as a primary cause of AD, they indicate involvement of immune processes at least as a secondary or tertiary reaction to the preexisting pathogen and point out its driving-force role in AD pathogenesis (Popovic et al., Int. J. Neurosci., 95, 3-4, (1998)).
[0047] In a further contemplated embodiment of the invention, a method of immune system modulation can be employed utilizing a patient's own immune system to specifically target autoantibodies of interest associated with AD to be attacked and eliminated. It has long been known in the prior art to incorporate an individual's own T-lymphocyte cells to kill tumor cells. Only recently has this type of therapy demonstrated success. By focusing on proteins particularly expressed by the biochemical markers of interest, antigen-presenting cells with this protein particularly expressed on its surface can bind to CD28 on the T-cell surface to then induce the cascade of events, ultimately eliminating cells expressing the protein particularly expressed. In current strategies, single chain antibodies are fused to the said protein particularly expressed by a cell type of interest assisting in the T-cell activation process.
Confocal Microscopy
[0048] Experiment #1
[0049] CCF-STTG1 cells (brain astrocytes that are GFAP +ve) are co-cultured with RAW cells (macrophage cell line) in the presence of, or without mouse anti-GFAP antibodies. Astrocytes are incubated with anti-GFAP Ab for 10 minutes and then the macrophages are added after and left to incubate for 30 min.
[0050] Results:
[0051] Without the Ab, the macrophages are not associated with the astrocytes, but in the presence of anti-GFAP antibodies the macrophages are clumped around the astrocytes. This initiates the phagocytosis process.
[0052] Experiment #2
[0053] CCF-STTG1 cells (brain astrocytes that are GFAP +ve) are co-cultured with RAW cells (macrophage cell line) in the presence of normal serum or AD serum. Astrocytes are incubated with serum for 10 minutes and then the macrophages are added after and left to incubate for 30 min.
[0054] With normal serum, the macrophages are not associated with the astrocytes, but with AD serum the macrophages are clumped around the astrocytes. This demonstrates the start of phagocytosis and attack of the brain cells.
[0055] As seen in FIG. 3, CCF-STTG1 astrocyte cells (arrowhead) and RAW macrophages (arrows) were co-cultured in the presence of a non-specific antibodies mixture (C-D) or anti-human GFAP antibody (E-F) or absence of antibodies (A-B). Binding of macrophages to astrocytes before wash is shown in A-C-E, and interactions remaining after wash in B-D-F. Specific binding occurs only in the presence of antibody specific to GFAP protein.
[0056] Thus, removal or reduction of the concentration of antibody specific to GFAP protein will retard or eliminate the initiation of phagocytosis, and concomitantly retard or eliminate the initiation of Alzheimer's related changes in the brain.
[0057] The level of any one or all of the specific markers of interest found in the patient's body fluid may be used for purposes of monitoring removal efficiency. Body fluid samples may be taken from a patient at one point in time or at different points in time for ongoing analysis. Typically, first sample is taken from a patient upon presentation with possible symptoms of AD and analyzed for presence of the particular markers. By “sample” is meant a body fluid such as blood. All the markers can be measured with one assay device or by using a separate assay device for each marker in which case aliquots of the same sample can be used. It is preferred to measure each of the markers in the same single sample, irrespective of whether the analyses are carried out in a single analytical device or in separate devices so that the level of each marker simultaneously present in a single sample can be used to provide meaningful data.
[0058] The presence of each marker is determined using antibodies specific for each of the markers and detecting specific binding of each antibody to its respective marker. Any suitable direct or indirect assay method may be used, including those which are commercially available to determine the level of each of the specific markers measured according to the invention. The assays may be competitive assays, sandwich assays, and the label may be selected from the group of well-known labels such as radioimmunoassay, fluorescent or chemiluminescence immunoassay, or immunoPCR technology. Extensive discussion of the known immunoassay techniques is not required here since these are known to those of skilled in the art. See Takahashi et al. (Clin Chem 1999;45(8) :1307) for S100B assay.
[0059] All patents and publications mentioned in this specification are indicative of the levels of those skilled in the art to which the invention pertains. All patents and publications are herein incorporated by reference to the same extent as if each individual publication was specifically and individually indicated to be incorporated by reference.
[0060] It is to be understood that while a certain form of the invention is illustrated, it is not to be limited to the specific form or arrangement of parts herein described and shown. It will be apparent to those skilled in the art that various changes may be made without departing from the scope of the invention and the invention is not to be considered limited to what is shown and described in the specification and drawings.
[0061] One skilled in the art will readily appreciate that the present invention is well adapted to carry out the objects and obtain the ends and advantages mentioned, as well as those inherent therein. The oligonucleotides, peptides, polypeptides, biologically related compounds, methods, procedures and techniques described herein are presently representative of the preferred embodiments, are intended to be exemplary and are not intended as limitations on the scope. Changes therein and other uses will occur to those skilled in the art which are encompassed within the spirit of the invention and are defined by the scope of the appended claims. Although the invention has been described in connection with specific preferred embodiments, it should be understood that the invention as claimed should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention which are obvious to those skilled in the art are intended to be within the scope of the following claims. | A method for treating a condition related to the development of Alzheimer's disease(AD) is disclosed. The method involves the removal of circulating autoantibodies of a biochemical marker or markers, specifically human glial fibrillary acidic protein (GFAP) and glyceraldehyde-3-phosphate dehydrogenase (GAPDH), from the sera of a patient in an amount effective to reduce or eliminate phagocytosis of astrocytic cells. The invention further includes a process of immune system modulation effective for autoantibody removal. | 0 |
The United States Government has rights in this invention pursuant to Contract No. W-31-109-ENG-38 between the United States Government and The University of Chicago and/or pursuant to Contract No. DE-AC02-06CH11357 between the United States Government and UChicago Argonne, LLC representing Argonne National Laboratory.
FIELD OF THE INVENTION
This invention relates to a computed radiography (CR) system, components and method relating to mammography.
BACKGROUND OF THE INVENTION
In recent years computed radiography (CR) systems have been successful in replacing analog screen/film (SF) in many clinical settings. Such CR systems use photostimulable x-ray storage phosphor plates (for example, BaFBr:Eu 2+ ), which are exposed in cassettes and then brought to an automated plate scanner, to read out the stored image information.
CR systems bring numerous advantages such as electronic transmission and storage, image processing, and computer-aided diagnosis to clinical departments, in a practical and highly affordable way. However, technical progress in the CR field has reached a plateau (perhaps in part because of economic developments at the chemical imaging companies who originally supported the development of the technology), and CR image quality performance has been surpassed by flat-panel based digital radiography (DR) systems.
DR systems, however, are much more expensive than CR, which has limited their clinical acceptance. A single CR reader can support multiple cassettes and replacing the SF cassettes with CR cassettes can retrofit an entire radiology department. Each individual detector in a room requires a separate DR detector. Furthermore, the replacement cost for a worn out or broken DR detector can be ten to one hundred times more expensive than replacing a CR cassette.
The image quality performance of CR has been limited in the past by three factors: (1) When the CR screen is made thick enough to achieve good x-ray absorption, the spatial resolution is disadvantaged compared to SF or DR, a particular problem for applications like mammography or bone radiography, (2) Because of limitations in screen conversion gain, collection efficiency, and detection efficiency, in a CR system that is not optimally designed, the number of detected electrons per absorbed x-ray (“gain”) can become low enough to become a secondary quantum sink, (3) CR systems have been observed to have rather high gain fluctuation noise, or “Swank noise”, compared to high quality SF or DR systems.
The proposed novel CR detector system is significant because it removes the above-mentioned image quality limitations at an affordable cost. A CR system based on novel transparent storage phosphor (TSP) materials and improved scanner apparatus provides image quality equal to or better than DR, in particular for the high-resolution application of mammography.
SUMMARY OF THE INVENTION
It is a principal object of the present invention to provide a computed radiography system, comprising a stimulating light source, a photostimulable glass imaging plate (PGIP) substantially transparent to the stimulating light positioned such that the stimulating light impinges the PGIP perpendicularly thereto producing photostimulated luminescence light (PLL) having a wave length different from the stimulating light source, a light collector having a light reflecting inner surface proximate the PGIP for collecting PLL emitted from the PGIP and having a hole or slot therein for admitting stimulating light into the light collector and onto the PGIP, an optical filter in communication with the light collector for blocking stimulating light waves and passing PLL therethrough, a light detector receiving PLL from the optical filter and the light collector, mechanism providing relative movement between the PGIP and the stimulating light source, and mechanism including an analog to digital converter for converting the collected and detected PLL to a diagnostic readout.
Another object of the present invention is to provide a computed radiography system, comprising a stimulating light source, a photostimulable glass imaging plate (PGIP) having nanocrystalline particles distributed therein substantially transparent to the stimulating light positioned such that the stimulating light impinges the PGIP perpendicularly thereto producing photostimulated luminescence light (PLL) having a wave length different from the stimulating light source, a hollow light collector having a light reflecting inner surface proximate the PGIP for collecting PLL emitted from the PGIP and having a hole or slot therein for admitting stimulating light into the hollow light collector and onto the PGIP, an optical filter in communication with the hollow light collector for blocking stimulating light waves and passing PLL therethrough, a light detector receiving PLL from the optical filter and the hollow light collector, mechanism providing relative movement between the PGIP and the stimulating light source, and mechanism including an analog to digital converter for converting the collected and detected PLL to a diagnostic readout.
A final object of the present invention is to provide a computed radiography system for reading exposed mammography plates, comprising a source of laser light having a wavelength in the range from about 500 nms to about 750 nms, a photostimulable glass imaging plate (PGIP) having nanocrystalline particles distributed therein previously exposed to x-ray radiation and substantially transparent to the laser light positioned such that the laser light impinges said PGIP perpendicularly thereto producing photostimulated luminescence light (PLL) having a wave length different from and less than the laser light, a hollow light collector having a light reflecting inner surface proximate the PGIP for collecting PLL emitted from the PGIP and having a hole or slot therein for admitting laser light into the hollow light collector and onto the PGIP, an optical filter in communication with the hollow light collector for blocking laser light and passing PLL therethrough, a light detector receiving PLL from the optical filter and the hollow light collector, mechanism providing relative movement between the PGIP and the laser light, and mechanism including an analog to digital converter for converting the collected and detected PLL to a diagnostic readout.
The first limitation described in the background section is overcome by the development of a storage phosphor material, which is transparent at the wavelength of the stimulating light. In a point scanned CR system using a transparent storage phosphor, the presampling Modulation Transfer Function (MTF) is determined by the size of the scanning laser beam, not the light scattering in the phosphor, and is thus decoupled from phosphor thickness. The imaging plate thickness can then be increased to maximize x-ray absorption for a given application, without suffering a resolution loss. This is a fundamental advantage of the novel TSP material.
The second limitation has been addressed on the materials side. ZBLAN storage glasses exhibit a useful dispersion in the behavior of optical turbidity (scattering) vs. wavelength, see U.S. patent application Ser. No. 11/267,056 filed Nov. 4, 2005 by Johnson et al., the entire disclosure of which is incorporated by reference. The optical scattering coefficient at the wavelength of the emitted (signal) light can be an order of magnitude higher than at the wavelength of the stimulating (scanning) light, due to scattering from the PSL-active BaCl 2 crystallites in the ZBLAN glasses. This is highly desirable in a scanned CR system, because the collection efficiency (gain) for the emitted light is then much improved. In addition, a novel design for the light collector apparatus in the scanner for these materials, which improves the efficiency (gain) by yet another factor of two (as well as reducing “flare” and image artifacts and improving dynamic range) is disclosed.
Finally, the third limitation of current CR systems due to gain fluctuation noise is reduced. At least part of this noise is due to the depth variation of the signal light collection efficiency and scanning light-stimulation efficiency brought about by light scattering from phosphor particles dispersed in a binder. These effects are absent in a transparent storage phosphor system.
The invention consists of certain novel features and a combination of parts hereinafter fully described, illustrated in the accompanying drawings, and particularly pointed out in the appended claims, it being understood that various changes in the details may be made without departing from the spirit, or sacrificing any of the advantages of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
For the purpose of facilitating an understanding of the invention, there is illustrated in the accompanying drawings a preferred embodiment thereof, from an inspection of which, when considered in connection with the following description, the invention, its construction and operation, and many of its advantages should be readily understood and appreciated.
FIG. 1 is a prior art experimental setup of the x-ray imaging system for testing the FCZ glass-ceramic plates;
FIG. 2( a ) is a photostiumulated luminescence (PSL) image of parallel gold bars (13 lp/mmm in spatial frequency) recorded on a 2% Eu-doped FCZ glass-ceramic plate annealed at 285° C. for 20 min., in which the horizontal stripes are caused by intensity variation of the x-ray beam having x-ray energy of 17 keV;
FIG. 2( b ) is a graphical representation of the modulation transfer function calculated from the photostimulated luminescence image of FIG. 1 ;
FIG. 3( a ) is a graphical representation of Eu L-III XANES spectra of FCZ glasses without ABF;
FIG. 3( b ) is a graphical representation of Eu L-III XANES spectra of FCZ glasses with 2-mol % ABF doping;
FIG. 4( a ) is a graphical representation of XRD patterns of an ABF undoped FCZ glass annealed at 280° C. for 20 min;
FIG. 4( b ) is a graphical representation of XRD patterns of an ABF doped FCZ glass annealed at 290° C. for 20 min;
FIG. 5 shows the setup for measuring the PSL decay curves shown in Figure and the optical line spread functions shown in FIG. 7 ;
FIG. 6 a is a graphical representation of an PSL signal decay for a FCZ glass-ceramic sample annealed a 290° C. for 20 mins;
FIG. 6 b is a graphical representation of PSL signal decay for comparison sample;
FIG. 7 a is a graphical representation of a line spread function for FCZ glass-ceramic sample annealed at 290° C. for 20 mins;
FIG. 7 b is a graphical representation of a line spread function for comparison sample;
FIG. 8 a is a graphical representation of ZBLAN attenuation and Mo anode x-ray spectrum;
FIG. 8 b is a graphical representation of ZBLAN attenuation and W anode x-ray spectrum;
FIG. 8 c is a graphical representation of ZBLAN x-ray spectrum absorption vs. thickness for Mo spectrum;
FIG. 8 d is a graphical representation of ZBLAN x-ray absorption vs. thickness for W spectrum;
FIG. 9 is a graphical representation of a projected DQE of proposed mammography system;
FIG. 10 is an SEM image of a 2% Eu 2+ -doped FCZ plate annealed at 285° C. for 20 min, revealing nanophase crystals (about 100 nm in average size) embedded in a glass matrix;
FIG. 11 is a graphical illustration of a first embodiment of the present invention shown in the form of a portable, self-contained device in a light-tight box
FIG. 12 is a graphical illustration of a second embodiment of the present invention shown in the form of a portable, self-contained device in a light-tight box;
FIG. 13( a ) is an enlarged view of the light collector of FIG. 11 ; and
FIG. 13( b ) is an enlarged view of the light collector of FIG. 12 .
DETAILED DESCRIPTION OF THE INVENTION
Storage phosphor materials of transparent glass ceramics were tested using collimated x-ray beams and high-resolution imaging to:
Characterize glass plates for particle composition and size by x-ray diffraction (XRD), Determine the charge state of the doped europium by x-ray absorption near edge structure (XANES), Measure the spatial resolution (modulation transfer function), and Identify the requirements to optimize glass properties for storage phosphor applications.
The invention includes novel glass materials that advance radiographic electronic imaging. The materials have superior resolution to existing polycrystalline x-ray imaging systems, and they provide high x-ray conversion efficiency.
The inventors fabricated ZBLAN glass-ceramic plates, co-doped with chlorine or bromine and heat-treated under a variety of conditions. These compositions were chosen because they show a significant room-temperature photostimulated luminescence (PSL) effect. To understand the structure-property relations with a view to optimizing these materials as high-efficiency and high-resolution storage phosphors, we performed x-ray imaging measurements and structural characterization. The transparent ZBLAN-based imaging plates have resolution superior to what is commercially available. Also, modifying the structure and controlling the thermal processing of the sample further improves their efficiency.
A significant PSL effect has been found in europium (II)-doped fluorozirconate glasses (ZBLAN), which were additionally doped with Br − ions. The PSL is attributed to the characteristic 5d-4f emission of Eu 2+ present in nanocrystals of BaBr 2 or BaCl 2 , which form in the glass upon annealing. Surprisingly, the metastable hexagonal form of BaX 2 (X═Br, Cl) is always formed first before it is converted into the stable orthorhombic form. The particle size increases upon annealing and so does the PSL efficiency of the glass ceramic. However, there is a saturation of the PSL efficiency, which is 9% for Br − -doping and 80% for Cl − doping of the Eu-doped BaFBr standard. There is a clear tendency for bigger but fewer particles for longer annealing. The particle size for the most efficient phosphor is about 100 nm. Comparing the PSL properties of the Eu-doped BaX 2 nanocrystals and those of bulk BaX 2 single crystals shows that most of the properties are quite similar. However, taking into account that the volume fraction of the nanocrystals is at most 20% of the glass ceramics, the PSL efficiency exceeds that of the bulk material by a factor of about five. An important issue for the readout process in glass-ceramic imaging plates is transparency, and in all systems there is a trade-off between PSL efficiency and transparency. The PSL increases and the transparency decreases with crystallite size.
Sample Preparation
The fluorobromozirconate (FBZ) glasses are derived from a modified fluorozirconate composition (ZBLAN20), which is known for its high stability against devitrification and is comprised of (53-x)ZrF 4 , 20BaF 2 , 5NaF, 15NaBr, 3AlF 3 , 1.5LaF 3 , 1.5YF 3 , 1InF 3 , and xEuF 2 (values are in mol %), where the nominal content of the substituted Br − ions is about 5% of the total number of anions.
For the fluorochlorozirconate (FCZ) glasses the nominal content of the substituted Cl − ions is close to 14% of the total number of anions with a nominal composition of (53-x)ZrF 4 , 10BaF 2 , 10BaCl 2 , 20NaCl, 3.5LaF 3 , 3AlF 3 , 0.5InF 3 , and xEuF 2 (in mole percent); the actual Cl − content could be lower due to chlorine evaporation during the heating cycle and thus the preferred chlorine ion content is in the range from about 10% to about 20% of the total number of anions. Two sets of FCZ glasses were fabricated: one set had the same composition as indicated above, and the other was doped with an extra 2-mol % of NH 4 HF 2 (ABF). The two sets of FCZ glasses were made from the same batch of raw metal fluorides. The first set was melted and quenched. The second set was melted, quenched, crushed, and doped with ABF, and then melted and quenched again.
The above constituent chemicals were melted in a glassy carbon crucible at 740° C. in an inert atmosphere of nitrogen and then poured into a brass mold, which was at a temperature below the glass transition temperature of 260° C. The as-made FBZ and FCZ glasses were subsequently annealed at temperatures between 200° C. and 295° C. for various times in an atmosphere of nitrogen, then slowly cooled to room temperature. The initial glasses were clear, but after annealing there was evidence of crystallization in all the glasses, from near-transparent materials to opaque and milky. The former behavior is consistent with Rayleigh scattering expected for a semi-transparent glass ceramic.
X-ray Imaging Performance at APS
X-ray imaging tests on FCZ imaging plates were performed at the 2-BM beamline of the Advanced Photon Source (Argonne National Laboratory, Argonne, Ill., USA). FIG. 1 shows the experimental setup. A 4 mm (horizontal)×2 mm (vertical) monochromatic x-ray beam was used as an imaging light source. A Huettner phantom or a GaAs knife-edge was used as an imaging object for measuring the modulation transfer function (MTF) of the imaging plates. (The MTF is a measure of the relative contrast of an imaging system as a function of spatial frequency.) The Huettner phantom has a series of parallel gold bars with spatial frequencies up to 20 line pairs per mm (25 micrometer per bar).
Although the high-resolution imaging system used in these experiments was not representative of the laser point scan system is used in the application of these materials to radiographic imaging or mammography, it is still useful to demonstrate the lack of geometrical blur in the materials, and directly illustrates the high potential for other imaging applications using the inventive plates.
An x-ray image of the phantom was projected on the sample (imaging plate), which was mounted on a rotation stage with X, Y, and Z motion control. The formed x-ray image on the sample was captured by a thermal-electrically cooled charge-coupled device (CCD) camera through 5× or 2.5× objective lenses. This setup was used for both storage phosphor and scintillation samples. In the case of scintillators, x-rays are continuously incident on the sample. An image of the phantom was formed instantly on the sample and taken by the CCD camera through the objective lens. In the case of storage phosphors, the exposure time of the incident x-rays (typically a few seconds) was controlled by an x-ray shutter. After exposure to x-rays, the sample was rotated by 180° and was illuminated by a laser beam (660 nm wavelength). The laser beam was larger than the x-ray beam so that the whole x-ray illuminated region on the sample was exposed by the laser beam. The “latent image” in the storage phosphor sample was then read out by the laser illumination, and the formed image was taken by the CCD camera through the objective lens. An optical filter was placed between the CCD camera and the objective lens to block scattered laser light but to let the stimulated luminescence light pass through. The laser beam was synchronized with the CCD camera so that the shutter of the camera was open while the laser was running.
The spatial resolution of the FCZ glass-ceramic storage phosphors was tested with a Huettner grid phantom as described above. FIG. 2 a shows the PSL image of the 13 lp/mm parallel bars recorded on a 2% Eu-doped FCZ glass-ceramic plate annealed at 285° C. for 20 min. The sample and the phantom were exposed to a monochromatic 17 keV x-ray beam for 5 sec, and then read out for 10 sec with a laser diode. The image clearly resolves the 13 lp/mm and should be able to resolve even finer features than that.
We used the data from FIG. 2 a to calculate the MTF of the sample. The resolution is defined as the value of the spatial resolution at a certain MTF value. The resolution of the 2% Eu-doped FCZ glass-ceramic plate was about 30 lp/mm at an MTF of 0.2. That means this imaging plate resolves features as small as 17 micrometer. This value is astonishing for a flash readout. Furthermore, point-by-point scanning of a 1% Eu-doped FCZ glass ceramic showed that an even higher resolution is possible.
We ran several tens of PSL tests on the best of the PSL-active samples and did not observe any degradation or decrease in the PSL efficiency. The results were completely reproducible. The stability of the PSL-active defects is comparable to that of commercially used Eu-doped BaFBr, i.e. storing an x-irradiated sample in the dark leads to a decrease in the PSL efficiency of 50% in the first 10 hours after exposure. In Eu-doped BaFBr the half time of the dark decay (“fading”) is about 24 hours.
Structural Characterization at APS
FIG. 3 shows the normalized Eu L-III XANES spectrum (solid curve) of an as-made 1% Eu-doped FCZ glass-ceramic. Two peaks can be clearly seen, at about 6.974 keV and 6.982 keV. They are caused by the 2p 3/2 →5d electronic transition, and they are characteristic white lines of Eu 2+ and Eu 3+ . The intensity ratio of these white lines indicates the Eu 2+ :Eu 3+ ratio. For the quantitative analysis, a pseudo-Voigt and an arctan function were used to fit each white line and the absorption edge, respectively. The quantitative analysis of the white lines yielded a Eu 2+ : Eu 3+ ratio of 1:1.
It was quite surprising that such a high fraction of Eu 3+ (50%) was found in the as-made FCZ sample, since Eu was added to the glass as Eu 2+ . One or more of the raw metal fluorides may contain a small amount of oxygen, which can oxidize Eu 2+ to Eu 3+ before and/or during glass melting. Atmospheric contamination of the EuF 2 raw material may also have converted a part of the EuF 2 to Eu 2 O 3 . Traditionally, in fluoride glass fabrication, when the quality of metal fluorides is not very high (i.e., contaminated by O 2− ), ammonium bifluoride (ABF) is used to fluorinate the oxides. Doping the FCZ samples with ABF reduces the O 2− concentration and converts directly and/or indirectly a part of the Eu 3+ back to Eu 2+ . The XANES spectrum of the as-made Eu-doped FCZ glass ceramic doped with ABF ( FIG. 3 b ) indicates that the Eu 2+ :Eu 3+ ratio changed significantly in favor of the Eu 2+ ; it increased to about 3:1.
ABF doping also has a critical effect on the phase transition induced by annealing of the as-made FCZ glasses. FIG. 4 a shows the XRD pattern of the ABF-undoped FCZ glass ceramic annealed at 280° C. for 20 min. The pattern for the orthorhombic BaCl 2 phase (Powder Diffraction File 24-0094) is shown for comparison at the bottom. The asterisks indicate an unidentified X phase with hexagonal symmetry. The estimated average crystal size is 140 nm for the orthorhombic BaCl 2 phase and 110 nm for the X phase (obtained from the XRD line-width analysis). The XRD patterns of the ABF-undoped samples in this study are consistent with those reported previously. A phase transition (from hexagonal to orthorhombic BaCl 2 ) occurs at and above 270° C., accompanied by the appearance of efficient storage-phosphor behavior.
The ABF-doped samples do not have the same XRD patterns as those of the undoped samples. The ABF-doped FCZ glass ceramics annealed at 270° C., 280° C., and 290° C. for 10-20 min do NOT show the orthorhombic BaCl 2 phase. FIG. 4 b shows the XRD pattern of the ABF-doped glass annealed at 290° C. for 20 min; the bottom pattern shows the data for the hexagonal BaCl 2 phase (PDF 45-1313) for comparison. Surprisingly, only the dominant hexagonal BaCl 2 phase and the minor unidentified X phase form during annealing of the ABF-doped glass at and above 270° C. In FIG. 4 b , the estimated average crystal size is 520 nm for the hexagonal BaCl 2 phase and 490 nm for the X phase. The ABF-doped glass ceramics are very poor storage phosphors (over two orders of magnitude lower in efficiency than their undoped counterparts), as confirmed by PSL measurements.
It is known that the PSL efficiency of the Eu-doped FBZ and FCZ glass ceramics is intimately related to the formation of orthorhombic BaCl 2 and BaBr 2 phases, respectively. The XANES and XRD analyses on undoped and ABF-doped FCZ glasses and glass ceramics showed that oxygen impurities might play a critical role in precipitating the orthorhombic BaCl 2 nanocrystals. The effect of oxygen could be twofold: First, oxygen results in many nucleation centers and causes rapid crystallization, which helps to form “imperfect” nanocrystals with vacancies and/or grain boundary segments. Such lattice defects are important for trapping electrons and holes that are created by the x-ray photons and important for the PSL process. Second, divalent oxygen impurities in the barium halide crystallites are probably charge-compensated by anion vacancies in the lattice, which can act as electron trap centers (F centers) and thus increase the PSL efficiency. This is well known from the commercial storage phosphor BaFBr:Eu.
A number of experiments were performed to measure materials and engineering parameters relevant to a point scanning readout system, and to allow projection of the Detective Quantum Efficiency (DQE) for the inventive detector system. These included measurement of the required stimulating exposure (laser power density×pixel dwell time), and integrated PSL signal (or “gain”, expressed as the number of detected electrons per absorbed x-ray). Measurements of optical light spreading of the stimulating laser light were also done, since this effect determines the MTF of the scanning system. Calculations of x-ray absorption vs. imaging plate composition and thickness, and x-ray beam spectrum, were also completed. Finally, the measured parameters were used to project DQE vs. spatial frequency for the inventive detector, and to compare with commercially available electronic mammography systems.
A PSL measurement system consisting of an integrating sphere, diode laser light source (656 nm), optical filters (BG3—blue, BG39—blue, FDIP—blue dichroic), and photomultiplier tube (PMT—Hamamatsu R6095), was assembled ( FIG. 5 ).
Samples were erased, given a known x-ray exposure, and placed on the entrance port of the integrating sphere, in the dark. After the laser was turned on, the resulting PSL signal, S, was observed to decay with stimulation time, t, and the data was recorded with a digital oscilloscope. The area under the PSL S vs. t curve is proportional to the number of detected electrons per absorbed x-ray, which we call g, see FIG. 6 . The source intensity at the sample port multiplied by the observed decay time gives the exposure required for stimulation, which we call 1/a. The PSL signal decay was also measured for a commercial BaFBr:Eu 2+ CR screen, for which the values of g and a are known under the same conditions. The gain g for ZBLAN samples of different thicknesses varied between 13% and 28% for the samples studied, corrected for differences in x-ray absorption. Since the net gain (after stimulation, collection, and detection) in a commercial scanner using the BaFBr imaging plate is about 5.5, the gain g for the second ZBLAN sample would be about 1.5, in a scanner of conventional design, and 3.0 in the proposed scanner system with improved light collector design.
Measurements of optical line spreading were done, using a (650 nm) laser source, to confirm the expectation of very high system MTF in the point-scanning mode, see FIG. 7 . The laser source was directed through a narrow optical slit in contact with the sample, and the line spread function (LSF) of the light emerging from the backside of the sample was recorded using a digital camera. (The experiments were also done using an edge source, with the same final results.) The measurement was done with a 1 mm thick ZBLAN sample, and also with a commercial mammography screen (LANEX Fine) sample, for which the x-ray LSF and MTF are known. The screen comparison LSF can be described by an exponential function exp(−bx), where b is 42 microns. The ZBLAN optical line spreading was observed to be smaller than the comparison, and b is estimated at 10 microns or less. Thus the LSF and MTF in a point scan system using a ZBLAN imaging plate will be determined mainly by the input scanning beam diameter, which can be adjusted to provide an optimal tradeoff between sharpness and (slow-scan) aliasing.
The mass attenuation coefficient for the ZBLAN material was calculated vs. x-ray energy, from its atomic composition, and is shown in FIGS. 8 a and b , along with x-ray spectra relevant to mammography (Mo anode, 40 kVp) and general radiography (W anode, 80 kVp).
For the mammography (Mo anode) case, ZBLAN plates of 300 microns or thicker give a quantum absorption efficiency of >90% ( FIG. 8 c ). For the higher kVp spectrum, thicker ZBLAN plates (500 microns or more) would be used ( FIG. 8 d ).
A simple SNR model was used to project the DQE vs. spatial frequency which could be obtained in a point scan system, using the measured properties of the ZBLAN imaging plates. The inputs are the x-ray absorption a, the excess noise factor A S , the gain g, and the MTF. Further electronic noise sources can be safely neglected, because of the large signal amplification supplied by the photomultiplier tube used for light detection. The LSF is characterized in the model by a parameter b in an exponential function, thus the MTF is a Lorentzian:
M
T
F
=
1
1
+
f
2
/
h
2
The absorption was calculated for a 300-micron plate and mammography spectrum, and was found to be 90%. The excess noise factor is conservatively estimated to be similar to that for a conventional BaFBr CR screen, and is taken as 0.7 (although one expects an improvement in excess noise in a transparent material because of the lack of optical depth effects.) The “baseline” gain is taken as 1.5, corresponding to a measured sample of a ZBLAN plate in a conventional (50 micron) point scanner. Two other cases are considered: g=3.0, corresponding to the improved efficiency light collector design, and g=6.0, corresponding to an anticipated 2× improvement in gain from materials optimization. The parameter, b, characterizing the MTF was taken as 70 microns (1/e 2 beam diameter), in order to minimize noise aliasing in the slow-scan direction, in a point scanner with 50 microns pitch. Temporal filtration via an electronic low-pass filter is used in the fast-scan direction, so that there is little or no noise aliasing in this direction. (We also note that the luminescence lifetime of the ZBLAN material in PSL mode was found to be 840 ns, so luminescence decay should be a negligible contributor to point scan MTF at the readout rates that are expected.) The results of the DQE projections are shown in FIG. 9 , and are compared with published DQE data for a commercial CR mammography system (MHRA 04094, “CR Systems for Mammography, Fuji FCR 5000MA, and FCR Profect CS”, UK Department of Health, 2004), and a commercial DR mammography system (Agfa DM1000 DR Mammography System, Agfa Health Care, 2006).
The “baseline” DQE of the ZBLAN point scan system, assuming a conventional scanner design, is projected to have better DQE than the commercial CR system at high spatial frequencies, but somewhat worse performance at low (2 cycles/mm or less) frequencies. The ZBLAN system with the improved scanner design surpasses the commercial CR at all frequencies, and approaches DR performance at high spatial frequencies. A further 2× improvement using the inventive materials results in a system with comparable or better performance than commercial DR (at lower cost) and improved signal-to-noise ratio at higher spatial frequencies. Previous studies have suggested that dose reduction compared to screen film mammography may be possible in commercial DR systems, but have indicated a concern about reduction in the visibility of microcalcifications because of increased noise. This problem is alleviated in the inventive system, which has improved signal-to-noise at higher spatial resolutions.
Scaled-Up Production of Glass Plates
The glass formulations are based on the strong glass network former zirconium fluoride (ZrF 4 ) that readily forms glass. So far, the glasses were produced on a small laboratory scale and the processing technology and optical quality of the products were not optimized for mammography applications. Samples made on a small scale typically contain flow lines, cords, and laps that can limit their optical performance.
Several optical quality glass plates approximately 2×2 cm 2 in size have been made. The plates made are ¼ the size of the ultimate target dimensions of 24×30 cm 2 that constitute the full size mammography plates.
Due to the potential for reaction and hydrolysis of the finely divided metal fluoride starting materials, the materials are handled in a controlled atmosphere glove box. High purity reagent grade materials (from Alfa-Aesar, Aldrich Chemical Company and Cerac, Incorporated) are used for the production of glasses. The precursor materials are weighed, blended, and melted in covered glassy carbon or platinum crucibles. The loaded crucibles are covered with a close fitting lid, placed in an electric furnace and heated to a temperature close to 740° C. to achieve complete melting of the mixture. The melts are held for periods of approximately 60 minutes. In some cases, the melt can be stirred by bubbling gas through a platinum capillary tube inserted through the crucible lid. In all cases, the melt will be fined to remove bubbles. The resulting liquid is cast into brass dies held at a temperature of ca. 200° C., slightly below the glass transition temperature of the glasses. The molds are heated either by equilibrating them with a surface contact heater or by cartridge heaters embedded in the die to enable introduction of controlled temperature gradients into the molds.
One problem in large scale production of ZBLAN based glass materials was identified and solved on a laboratory scale in the earlier work is the need to avoid reduction of zirconium tetrafluoride to lower fluorides. When reduction occurs, dark-colored precipitates can form in the glass. The principal mechanism of reduction of zirconium ions is: ZrF 4 +nEuF 2 =ZrF 4-n +nEuF 3 , the reaction also consumes the desirable divalent europium species (other highly reducing species can also reduce zirconium tetrafluoride). The reaction can be suppressed by operating in oxidizing conditions. Further, decreasing the duration of melt processing limits the degree of reaction since the kinetics are known to be fairly slow. The second issue in glass melting is reactive gasification of zirconium. This can occur by an exchange reaction: ZrF 4 +4Cl − =ZrCl 4 +4F − that leads to formation of volatile zirconium chloride. This reaction cannot be completely avoided when chlorides are present in the melt but its effect can be limited by using short melting times. Alternatively, the base glass can be melted before the addition of the chloride species. Working in a closed crucible helps to retard evaporation.
The cast glass plates were heat treated to develop the nano-phase species that provide the PSL response. Heat treatment was performed directly in the mold by increasing the power to the heaters or in a separate operation using a low temperature furnace. The heat treated plates were inspected for bulk and surface defects.
All glasses underwent Differential Scanning Calorimetry (DSC) to measure the glass transition temperature and crystallization temperatures of the materials and establish the “working range”, which is between the two. Thermal treatment schedules required to produce desirable microstructures in the materials were derived from these results.
The transmission spectrum of the glasses was measured in the wavelength range from 200-1200 nm using a Varian Cary 500 dual-beam spectrophotometer. The results were analyzed to determine the precise spectral band where maximum absorption occurs.
X-ray diffraction (XRD) was carried out on a bench-top system and at a synchrotron facility for better resolution. Increased stress comes about when the particles grow during thermal processing and undergo a phase change from hexagonal to orthorhombic. More stress creates more defects, and correspondingly the PSL increases. XRD is an important technique in the characterization of these materials.
X-ray Absorption Fine Structure (XAFS) experiments and EXAFS (Extended X-ray Absorption Fine Structure) were used to determine the structural distribution, for example inter-atomic distances, numbers of neighboring atoms (coordination number), degree of disorder, and identity of atoms in the immediate vicinity (approximately 5 Å). XANES (X-ray Absorption Near Edge Structure) is a subset of XAFS and is element specific; our experiments have focused on Eu, the optically active element in our inventive materials. Preliminary results have given the valence of the Eu, i.e. whether it is 2+ or 3+ and has given us an indication of the PSL efficiency. Eu 3+ is an indicator of the presence of oxygen impurities, which create defects. These defects enhance the PSL efficiency. Microscopy established size, shape and distribution of the nanocrystals in the glass matrix, see FIG. 10 , a SEM of a 2% Eu 2+ doped FCZ plate.
After making the first set of FCZ glass ceramics (starting with the standard composition) the samples were characterized in terms of glass transition temperature (DSC), nanoparticle size and phase (XRD, SEM, TEM), and optical properties (PL, transmission). The PSL efficiency and stimulating exposure requirement were measured using a PSL decay apparatus, while the transparency at the stimulating wavelength and optical scattering at the emitted wavelength were monitored by transmission spectrophotometry.
A bench top read-out system was used to measure the imaging properties of the plates in detail, including characteristic curve, MTF, and noise power spectrum, from which DQE was obtained. A Gioto screen film mammography system, with Mo tube target and Mo and Rh filtration was used to expose the plates. The exposures tested spanned a range corresponding to patient doses equivalent to and above and below the patient dose in screen film mammography. The measured DQE was compared with model predictions, and the correlation between measured PSL properties and imaging performance (DQE) was tested and refined.
As the optical and PSL properties and imaging performance were being measured, quantified, and modeled, the sample composition was varied. The base composition set to be studied was guided by the fundamental structural investigations of the glass materials. The relationships between composition, structure and processing and both measured PSL activity and imaging performance were established and quantified. Initially, the chlorine doping level was increased in order to increase the volume fraction of the PSL-active barium chloride nanoparticles in the glass. Secondly, the Eu (II) doping level was increased and anion vacancies introduced by co-doping the glass with monovalent cations like K + and/or divalent anions like O 2− .
Referring to FIG. 11 , a first embodiment of the inventive system is shown. It is in the form of a portable, self-contained device, in a light-tight box shown in dotted line. Exposed photostimulable plates ( 3 ) are read out using the light from source ( 6 ), which may be a laser source. The stimulating light passes through a beam expander ( 7 ) and reflects from a folding mirror ( 5 ). The stimulating light beam is focused to the desired beam size at the imaging plate surface by the objective lens ( 4 ). The stimulating beam enters the imaging plate ( 3 ) in a direction perpendicular to the plate surface.
The stimulating beam, upon entering the imaging plate, stimulated stored electrons and holes to recombine, producing photostimulated luminescence light, which has a wavelength different from that of the stimulating slight. This light is collected by the light collector ( 1 ) and is directed towards a light detector ( 2 ). Before entering the detector ( 2 ), the light passes through an optical filter, such as the band pass (colored glass) filters ( 15 ), which remove the stimulating light but allow the luminescent signal light to pass through. The detector ( 2 ) may conveniently be a vacuum photomultiplier tube or multiples thereof. The signal from the detector ( 2 ) is passed to signal processing element ( 1 ), which comprises a charge amplifier and A/D converter which is synchronized with scan control element ( 13 ), and which writes signal data to the image buffer element ( 12 ). The image plate ( 3 ) is moved in the x and y directions with respect to the stimulating beam by the translation stages ( 8 ) and ( 9 ), whose motion is controlled by the dual motor controller ( 10 ). The motor controller ( 10 ) is driven by software in scan control element ( 13 ), which in turn may reside in a personal computer ( 14 ). The entire apparatus is enclosed in a light-tight box with a door for placing and removing sample plates ( 3 ).
The light collector ( 1 ) design is a key element. It is important to maximize luminescent signal collection and gain in order to maximize the signal-to-noise ratio of the radiographic imaging system. In the particular design in FIG. 11 , the collector ( 1 ) is a cone with elliptical entrance port proximate the plate 3 , and a slot for the stimulating beam entrance. The clearance between the elliptical entrance port and the image plate surface, and the beam entrance slot size are minimized in order to collect as many emitted luminescent photons as possible. The emitted photons generally have a wavelength between about 350 to about 495 nms. Using a specular mirror surface finish for the inside surface of the collection cone, we find, from ray tracing simulations, a collection efficiency of 78%, more than twice that obtained in a conventional prior art CR scanner using a light guide and mirror arrangement. The collection cone or light collector may be made from any suitable material such as, but not limited to, aluminum or plastic. The interior mirror surface must be reflective to the photons emitted from the plate 3 having wavelengths in the range from about 350 nms to about 495 nms, but always shorter than the laser or stimulating light. In addition, the side of the plate 3 away from the stimulating light 6 may be reflective to the PLL or to light with wavelengths in range from about 395 nms to about 495 nms. A further benefit is that “flare”, which is stimulating light reflecting back to the plate from collector surfaces and causing image artifacts and reduced dynamic range, is minimized in the present system to be not greater than 1%. A HeNe laser from Coherent, Inc. producing 2 mW at 544 nm can be used as the light source 6 , for example, although light at between about 500 and 750 nm can be used, but light with wavelengths in the range from about 500 to about 650 are preferred. The blue BG3 and BG39 bandpass filters from Schott glass can be used for optical filtration. The R878 bialkali photocathode PMT from Hamamatsu, Inc. has a 5 cm diameter for good collection, and the quantum efficiency is about 25% at 400 nm. Translation stages in x-y configuration with stepping motors and dual motor controllers are available from Newmark Systems, Inc. with a travel of up to 30 cm and resolution of 1 micron, which is small compared to the expected scan pitch of 50 microns, for the application of digital mammography. The size of the stimulating beam at the imaging plate surface can conveniently be adjusted to be in the range 50-100 microns.
Referring to FIG. 12 , a second embodiment of the present invention is shown. It is in the form of a portable, self-contained device, in a light-tight box shown in dotted line. Exposed photostimulable plates ( 23 ) are read out using the light from source ( 27 ), which may be a laser source. The stimulating light passes through a beam expander ( 28 ) and reflects from galvanometer-driven rotating mirror ( 29 ), which comprises the light scanning element. The light beam reflected from the rotating mirror ( 29 ) then passes through the telecentric lens ( 24 ). The telecentric lens ( 24 ) must be equal or longer in length than the length of the scan line in the x direction. Lens ( 24 ) is telecentric in the image space, so that the principal rays emerge parallel to the optic axis, and thus enter the image plate ( 23 ) in a direction perpendicular to the plate surface. Lens ( 24 ) is further designed such that the stimulating beam is focused to a desired size at the plate surface, e.g. between 50 and 100 microns, for a 50 micron scan pitch.
The stimulating beam, upon entering the previously exposed to x-ray radiation imaging plate, stimulates stored electrons and holes to recombine, producing photostimulated luminescence light, which has a wavelength different from that of the stimulating light. This light is collected by reflecting mirror ( 25 ) and a trapezoidal light collector ( 21 ) and is directed towards a light detector ( 22 ). Before entering the detector ( 22 ), the light passes through the optical or band pass (colored glass) filters ( 26 ), which remove the stimulating light but allow the luminescent signal light to pass through. The detector ( 22 ) may conveniently be an array of photomultiplier tubes. The signals from the detector ( 22 ) are passed to signal processing element ( 31 ), which comprises a summing amplifier, a charge amplifier and A/D converter which is synchronized with scan control element ( 13 ), and which writes signal data to the image buffer element ( 32 ). The image plate ( 23 ) is moved in the y direction by the translation stage ( 26 ), whose motion is controlled by the motor controller ( 20 ). The scanning light beam is moved in the x direction by reflection from the galvanometer-driven rotating mirror ( 29 ), whose motion is controlled by the galvo control element ( 31 ). The motor controller ( 20 ) and the galvo controller ( 31 ) are driven by software in scan control element ( 33 ), which in turn may reside in a personal computer ( 34 ). The entire apparatus is enclosed in a light-tight box, shown in dotted line, with a door for placing and removing sample plates ( 33 ).
FIGS. 13( a ) and 13 ( b ) respectively, show the light collector 1 of FIG. 11 and light collector 21 of FIG. 12 in greater detail, both of which have interior mirror surfaces, as previously explained.
An air-cooled, laser-diode pumped, Nd:YVO4 laser from Showa Optronics Ltd., producing 3 W at 532 nm can be used as the light source ( 7 ), for example. The blue BG3 and BG39 bandpass filters from Schott glass can be used for optical filtration. The R6237-01 bialkali photocathode PMT's from Hamamatsu, Inc. are 75 mm square, and have a quantum efficiency about 30% at 400 nm, and can be used as the elements in the PMT array. A translation stage with stepping motor controller is available from Newmark Systems, Inc. with a travel of up to 30 cm and resolution of 1 micron, which is small compared to the expected scan pitch of 50 microns, for the application of digital mammography. The size of the stimulating beam at the imaging plate surface can conveniently be adjusted to be in the range 50-100 microns.
The light collector ( 1 ) and ( 21 ) design is a key element. It is important to maximize luminescent signal collection and gain in order to maximize the signal-to-noise ratio of the radiographic imaging system. In the particular design in FIG. 11 , the collector ( 1 ) is a cone while in FIG. 12 , it is a trapezoidal pyramid with slotted entrance port, and an opposing reflecting mirror to direct light into the entrance port of the collector ( 1 ). An entrance slot between the reflecting mirror and the top edge of the entrance port of the collector is provided, to allow entry of the scanning beam. The clearance between the entrance port/reflecting mirror and the image plate surface, and the beam entrance slot size are minimized in order to collect as many emitted luminescent photons as possible. Using a specular mirror surface finish for the inside surface of the collection device ( 21 ), we find, from ray tracing simulations, a collection efficiency of 64%, more than twice that obtained in a conventional CR scanner using a light guide and mirror arrangement ( 1 ), as in the prior art ( FIG. 1 ).
The glass-ceramic imaging plates are enclosed in light-tight cassettes, which may be similar to film-screen cassettes. The cassettes are carried to the x-ray tube (and patient), and exposures are made in the usual way. After exposure, the plates carry a stored latent image (which persists for several hours), and the cassettes are taken to the readout scanner. The scanner (which is inside a dark enclosure) transports the imaging plates beneath the scanning laser optics, and the image is read out and stored in the image buffer in the readout system. The computer which drives the readout system is connected on a network (which may be a LAN) which in turn can communicate with at least one other workstation with image processing and high-resolution display capability. Additionally, image archive storage, other display devices such as laser film printers, and other (possibly remote) workstations are useful and are optionally connected to the network.
A theoretical model for the imaging performance of a transparent storage phosphor (TSP) based CR system is set forth. The imaging performance of the FCZ-based glass-ceramic samples is evaluated using clinical mammography equipment (for exposure) and our laboratory readout system (for image readout). The measured imaging performance is compared to that predicted by the model so that the relevant imaging parameters of the glass-ceramic materials are determined. The model is used to guide further optimization of the material to achieve imaging performance comparable to flat-panel digital mammography systems.
DQE Model and Measurements for TSP System
In electronic radiography the image detection, processing, and display functions are separate; therefore, they optimized independently. The detective quantum efficiency (DQE), which is the (squared) ratio of output to input signal-to-noise ratio (SNR), is used as a fundamental metric for measuring and comparing the performance of detectors for electronic radiography. The DQE, or signal-to-noise per input quantum, is optimized in a TSP and readout system.
DQE Model
It is useful to develop a theoretical model for detector system DQE, which includes both phosphor materials and readout component parameters as inputs and which can be verified by supporting experiments. Such a model can be used to help design an optimal readout method, and also to co-optimize phosphor material and other parameters in such a way as to realize the best possible system performance. Here we present a simplified model. In the future the model will be improved to include such things as the effect of characteristic x-rays and incident x-ray obliquity on MTF, sampling and the effect on aliased NPS and DQE, and other physical phenomena that are found to be important for imaging performance.
Since the early work of Shaw and Van Metter on DQE of radiographic imaging systems, similar analyses have been done by other workers on various x-ray imaging systems. Based on previous work, a simple preliminary result for the DQE of a storage phosphor-based CR system, including both phosphor and readout is as follows:
D Q E ( f , Q ) = α 1 A s + 1 m · T 2 ( f ) · D Q E R ( Q )
where
α=x-ray absorption
A S =excess noise factor
m=number of stored charges/absorbed x-ray
T(f)=system MTF
DQE R (Q)=readout system DQE
f=spatial frequency
Q=x-ray exposure
This simplified model is suitable for initial research. The equation above resembles the corresponding result for the DQE of a screen/film system with the number of stored charges m replacing the number of promptly emitted photons, and the detective quantum efficiency of the readout system DQE R replacing the DQE of the film. The x-ray exposure dependence of the detector efficiency in CR arises from the readout system DQE R , and is physically due to noise sources such as photo multiplier tube (PMT) dark noise and laser noise, as opposed to fog and density saturation in the screen film system. As a result, the storage phosphor system has much wider exposure latitude, 10,000:1 vs. 40:1.
The readout system has three fundamental components corresponding to photostimulation, collection and detection of signal-carrying photons. A simple model for the SNR performance of the readout system may be written as:
D
Q
E
R
=
s
N
s
c
N
c
n
N
d
where
s=stimulation efficiency c=collection efficiency h=detector quantum efficiency N s =excess noise factor for stimulation N c =excess noise factor for collection N d =excess noise factor for detection
Factors Influencing DQE
The DQE model can be used to identify important factors to measure and to calculate their effect on the signal-to-noise performance of the CR system. We assume a scanning laser spot readout.
1. X-Ray Absorption Coefficient, a
This sets the upper limit on detection efficiency, and depends on the incoming x-ray spectrum and phosphor thickness. An advantage of TSP is that thickness may be increased without increasing image blur.
2. Storage Efficiency, m
This factor depends on phosphor composition and synthesis and has been extensively studied in previous research.
3. Exposure Constant, a
An extremely simple model of photostimulation gives:
s= 1−exp(− aCE )
where s is the stimulation efficiency, E is the stimulating light exposure, and a is the exposure constant, which is a characteristic of the storage phosphor material. This factor is related to the cross section for optical absorption of the storage states (e.g., F centers) in the material and determines the characteristics (intensity, exposure time) of the readout light source.
4. Luminescent Decay Time or “Afterglow”.
In a scanning spot system, this factor must be shorter than the pixel dwell time.
5. Modulation Transfer Function, T(f)
In a TSP system with spot scan, this factor will depend on residual stimulating light scatter (expected to be small), and on the size and shape of the stimulating spot. It is expected to be extremely high. It is also expected to depend on the magnitude of the stimulating exposure E, and care must be taken in readout to deal with this effect.
6. Noise Aliasing
This factor can be controlled or eliminated in a TSP system with spot scan, even though the MTF of the primary x-ray detector component is extremely high. For example, aliasing in the transport direction can be controlled by proper selection of the beam size along this axis. Aliasing in the fast-scan direction can be controlled by a combination of beam shape and electronic filtering. This is an advantage over flat-panel x-ray detector systems with high-resolution primary detectors where noise aliasing can be a problem in applications requiring high resolution, like mammography.
7. Gain, g
An important factor in any CR system is the overall gain, which is the final number of detected electrons produced, per absorbed x-ray. This plays a direct role in the model for DQE, as can be seen by combining equations FOR DQE and s:
g=m·s·c·η.
A rule of thumb is that for “good” (SNR limited by x-ray quantum noise, and not detector noise) performance in an x-ray detector system, the gain should approach 10.
8. Excess Noise in Phosphor, A S
The statistical efficiency of detection (in a charge integrating system) is limited by the fact that the optical pulses produced by individual absorbed x-rays have a wide distribution in size. In a CR system, the width of this distribution arises from charge storage fluctuations, characteristic K fluorescence escape, and optical effects, including the variation of stimulation probability and escape probability with absorbed x-ray depth. Excess noise effects in previous turbid CR phosphor screens have been observed to be larger than in conventional phosphors, at least partly due to the variation in stimulation efficiency, which is absent in the conventional system. TSPs, however, are expected to show little or no optical depth effects, which if proven true will be advantageous over previous systems.
9. Excess Noise in Readout, N s , N c , and N d
Excess noise in the readout components reduces their DQE below that for simple binomial processes, described by the quantum efficiencies for stimulation, collection, and detection. In stimulation, an example of an excess noise process would be laser noise. Another important effect in CR systems is excess noise due to “flare”. Flare results in noise in the signal from a low-exposure area, due to spillover of the stimulating light onto possibly adjacent high-exposure areas, and is a limiting factor in system dynamic range. An example of excess noise in the detection component would be noise from dynode chain statistics, if a photomultiplier tube were used.
Measurements
Each important factor in the model for DQE performance can be calculated, and the results compared with experiments. The various parameters of interest and the supporting measurements and methods are listed in the Table.
TABLE DQE model- related measurements. Factor Symbol Method Vary X-ray absorption Ionization chamber Thickness, x-ray spectrum Excess noise (prompt) A s Pulse Height Spectrum X-ray energy Exposure const a Bench top sensitometer Phosphor material Storage efficiency m Bench top sensitometer Phosphor material MTF T Offline scanner Phosphor, read exposure Flare F Offline scanner Target, collector Stimulation efficiency & noise s Component measurement Collection efficiency & noise c Component measurement Detector efficiency & noise Component measurement Stimulation spectrum Offline optical Phosphor material Emission spectrum Offline optical Phosphor material Afterglow time Offline optical Phosphor material
Imaging Performance Evaluation
Noise power spectrum (NPS) characterizes the amount of noise and its texture, will be measured using standard techniques. The shape of the NPS is important in determining the presence of secondary quantum noise. Secondary quantum noise is caused by having too few optical quanta detected per interacting x ray. If secondary quantum noise exists, then there will be a plateau in the NPS at high spatial frequencies. It differs from NPS due to the detector readout, because the plateau level will depend on the x-ray exposure, whereas detector noise is independent of x-ray exposure. Detective quantum efficiency (DQE), is a measure of the dose efficiency of the detector. It can be calculated using the equation:
D Q E ( f ) = K 2 M T F 2 ( f ) N P S ( f ) Q
where f is the spatial frequency, K is the slope of the characteristic curve, and Q is the x-ray photon fluence incident on the detector.
Noise equivalent quanta (NEQ), which characterizes the signal-to-noise properties of the detector. It can be calculated using the equation:
D
Q
E
(
f
)
=
K
2
M
T
F
2
(
f
)
N
P
S
(
f
)
The NPS will be measured as a function of x-ray exposure to the detector covering a range of exposures from 1 mR to 1 R. This will allow us to compute DQE and NEQ as a function of spatial frequency and x-ray exposure.
The Swank noise, A S , will be measured indirectly from measurements of image noise, input exposure, and quantum detection efficiency, A Q , as a function of energy, as follows. Uniform exposures over a small area of the glass phosphor can be made and read out. For a given exposure, the mean pixel value in the small area will be computed. Correcting for small changes in exposure, the standard deviation in the measured mean pixel values is the DC noise component of the detector. It is equal to the square root of the product of the x-ray fluence, A Q , and A S . Thus, A S can be estimated by converting the exposure to fluence.
The Lubberts effect can in principle be determined by comparing the MTF squared with the shape of the NPS due to x-ray quantum noise (the NPS normalized to 1 at zero spatial frequency). The x-ray quantum NPS can be determined from the total NPS and the NPS due to electronic noise and secondary quantum noise, both of which can be measured in separate experiments.
The secondary quantum noise can be measured following the method of Maidment and Yaffe. During readout the light collection efficiency of the lens system will be modified using neutral density filters placed between two low f-number lenses. By measuring the total NPS over a uniformly exposed region in the image as a function of the relative light collection efficiency, we can estimate the secondary quantum noise power at high spatial frequencies. This enables us to determine the required light collection efficiency to avoid degradation in DQE due to secondary quantum noise.
Contrast Detail Detectability
The CDMAM 3.4 phantom was specifically designed for digital mammography and contains rows and columns of gold disks with varying diameter and thickness. Disk diameter ranges from 0.6 to 2 mm (16 in total) and disk thickness ranges from 0.3 to 2 mm (16 in total). Each square (location) within the phantom contains two disks with one centrally located and the other in a randomly chosen corner.
The Aufrichtig method is based on the original work of Ohara, Burgess and Xue. A signal detection model is assumed in which a continuous decision variable internal to the observer with Gaussian probability density functions for the choice of “disk present” or “no disk present”. Then the percent correct is the distance between the means of these two distributions and is equal to the product of the disk contrast and a parameter u. Basically, for a given diameter size, the number of correct choices as a function of the aperture contrast is computed. From the fraction of correctly detected disks we obtained the maximum-likelihood estimate of u. One can then calculate its standard error based on assuming that there were K trials defined by N repetitions at L contrasts, based on the probability of a correct choice of k th trial, the disk contrast in k th trial, and the cumulative Gaussian distribution, as given by Aufrichtig.
While the invention has been particularly shown and described with reference to a preferred embodiment hereof, it will be understood by those skilled in the art that several changes in form and detail may be made without departing from the spirit and scope of the invention. | A computed radiography system including a stimulating light source such as a laser, a photostimulable glass imaging plate (PGIP) substantially transparent to the stimulating light positioned such that the stimulating light impinges the PGIP perpendicularly thereto producing photostimulated luminescence light (PLL), a light collector having a light reflecting inner surface proximate the PGIP for collecting PLL emitted from the PGIP and having a hole or slot therein for admitting stimulating light into the light collector and onto the PGIP. An optical filter in communication with the light collector for blocking stimulating light waves and passing PLL therethrough. A light detector receives PLL from the optical filter and the light collector, mechanism providing relative movement between the PGIP and the stimulating light source, and mechanism including an analog to digital converter for converting the collected and detected PLL to a diagnostic readout. The system is particularly useful in mammography. | 6 |
BACKGROUND OF THE INVENTION
The present invention relates to a turn signal switching device to actuate the turn signal lamps of an automobile, and more specifically, to a turn signal switching device for an automobile comprising a turn signal switch which actuates a directional turn signal lamp when moved in a desired direction and a self-cancel mechanism which restores the turn signal switch automatically to a neutral position in response to a return-rotating operation of a steering wheel. The switch and the self-cancel mechanism are constructed in a respectively separated form and connected by mechanically engaging them with each other when they are fitted to a steering column.
In the conventional turn signal for automobile, as shown by an embodiment of the prior art shown in FIGS. 1 and 2, for example, a self-cancel mechanism consisting of a cancel cam 1, a spring-fitted member 2, a moving member 3 and a cancel rotor 4 rotated together with a steering wheel 7 and a turn signal switch 28 actuated by the operation of a control lever 5 attached to the aforesaid moving member 3 have been mounted on a predetermined position at the upper face portion and the lower face portion of a supporting member 6 and installed integrally on the central lower face portion of the steering wheel 7. However, such traditional turn signal for automobile has incurred some shortcomings, i.e., the form and the operating method of the control lever 5 are limited by its relation with the self-cancel mechanism and, for example, it becomes an incoherent specific element even in combination with other various control switches. Moreover, the construction of the turn signal switch 28 is also restricted, making it difficult to simplify the mechanism. In order to overcome such disadvantages, e.g., as shown in FIG. 3, a turn signal for an automobile is known wherein a cancel detector 40 and a turn signal switch 38 having an automatic return mechanism have been composed separately and so arranged to return automatically a control lever 8 of the turn signal switch 38 by connecting to a flasher unit 39 with a so-called electrical means. This turn signal for an automobile has also had such drawback that the number of component parts including a semiconductor element 9, capacitor 10, resistor 11 and solenoid 12 increases and results in a cost increase.
In FIG. 3, an ignition switch 31 is fitted between a d-c power supply 32 and the turn signal switch 38. A diode 33 to absorb surge is fitted between the transistor 9 and the ignition switch 31. Resistors 34 and 35 are respectively connected in series to the base of the transistor 9. A left-side turn signal lamp 36 and a right-side turn signal lamp 37 are connected to the output side of the flasher unit 39.
The present invention has been made to atone for the abovediscussed shortcomings. Namely, the feature thereof is to provide a turn signal for an automobile wherein a sefl-cancel mechanism and a turn signal switch are separated and composed independently of each other. When attaching them to the steering column of automobile, for example, by connecting the control lever of the self-cancel mechanism and the turn signal switch mechanically with a simple engaging means by a boss and a hollow, they can be operated in conjunction with each other. The turn signal switch can be mounted in a relatively free, isolated and desired position. For example, the switch can be fitted combined with other various control switches and a greater latitude is allowed in the form and operating method of the control lever as a result of the restrictions having largely been relaxed, thus enabling to make the combination simpler and at a lower cost.
SUMMARY OF THE INVENTION
The present invention is an improvement of a turn signal for an automobile. It is an object of the present invention to provide a novel turn signal for an automobile wherein a turn signal switch connected to a circuit which flashes a left-side or a right-side turn signal lamp when a turn signal lever is operated to the right or left is isolated from a self-cancel mechanism which has a function to restore a cancel cam when the steering wheel is returned to the original position thereof upon completion of the left turn or right turn of an automobile and to stop the flashing action of the turn signal lamp, both being constructed independently of each other but joined with a control lever with each other to enable the mounting position of each component element to be selected as desired.
It is another object of the present invention to provide a simple and compact turn signal for an automobile wherein the operating method and configuration of a switch can be designed more freely.
It is a further object of the present invention to provide a turn signal for automobile which is applicable to place with relative ease by merely changing the length of the control lever and the fulcrum position and further to allow easy installment of the click joint of a lane change mechanism. The above-described other objects and novel features of the present invention will be more fully understood by reference to the following detailed description thereof, when read referring to the attached drawings. What is to be understood in particular is that the attached drawings are for the purpose of explaining the present invention, and not for limiting this invention to what is shown in the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plan view showing one embodiment of the prior art turn signal for an automobile.
FIG. 2 is a a front elevational view partially in phantom of the embodiment in FIG. 1.
FIG. 3 is an explanatory drawing showing another embodiment of a prior art turn signal for an automobile.
FIG. 4 is a plan view showing one embodiment of the turn signal for an automobile of the present invention.
FIG. 5 is a sectional view of the major part taken on line Y--Y in FIG. 4.
FIG. 6 is an exploded perspective view of the component parts of the one embodiment of a turn signal for automobile of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIG. 4, FIG. 5 and FIG. 6, a detailed description of the preferred embodiment of a turn signal for an automobile of the present invention is given hereunder.
Reference numeral 13 denotes a supporting member. The supporting member 13 is secured to the periphery of a steering shaft (not shown) at the lower portion of a steering wheel (not shown) and works as a base for attaching various parts to comprise a self-cancel mechanism 28. At the central portion of the supporting member 13, a cylindrical column 13a with a specified height is formed through which the steering shaft is inserted in a freely rotatable condition and further a cancel rotor 15 is spring-fitted. Also at the center of one end portion of the upper surface of the supporting member 13, a supporting shaft 13b is formed which bears a control lever 21 in a freely swingable state in a horizontal direction. On the line linking the centers of the cylindrical column 13a and the supporting shaft 13b, a circular arc-shaped opening 13c is made to receive a moving member 16 which holds a cancel cam 20 and swings together with the control lever 21. Furthermore, a hollow 13d is formed in the supporting member 13 to provide a clicking touch for a lane change which allows the central lever 21 to sense the positioning in relation to the moving member 16 when it is swung to the left or to the right from the center position to reach a nearly intermediate position of a predetermined travelling stroke, i.e., when the electric circuit is formed by operating a control knob 29a of the turn signal switch 29.
In addition, in the vicinity of the upper surface end portion at the opposite side of the supporting member 13, a cylindrical column 13e is formed which is used to spring-insert a horn contact 24 by fitting slidingly to the lower face of the steering wheel, for example, to constitute the electric circuit of a horn.
What is more, at a predetermined position at the lower side of the supporting member 13, there are columns 13f to secure the supporting member 13 to a specified position on the steering column. A spring 14 works to energize a cancel rotor 15 inserted in the cylindrical column 13a of the foregoing supporting member 13 to allow the rotor to move freely in the axial direction of the steering shaft in a predetermined range.
The cancel rotor 15 is virtually cylindrical and spring-fitted onto the outer circumference of the cylindrical column 13a of the supporting member 13 in a freely rotatable state through the spring 14. At the end of the upper face of the cancel rotor 15, a boss 15a is provided to enable the rotor to be rotated together with the steering wheel by engaging the boss with the lower face of the wheel. On the cylindrical outer periphery of the cancel rotor 15, a protuberance 15b is fitted at an axially specified position.
The moving member 16 is fitted with the cancel cam 20 and at the same time held by the control lever 21 to move on the upper surface of the base 13 together as the control lever 21 is actuated. At the right and left ends, a wall 16a is installed erectly to keep the cancel cam 20 at a predetermined position and in order to fit the cancel cam 20 to the control lever 21 after housing the cam within the wall 16a. For example, a square hole 16b is provided at both upwardly-extending sides of the wall 16a. Also at the lower side of the moving member 16 at the front end adjacent to the cylindrical column 13a of the supporting member 13, a projection 16c is formed. Furthermore, at the tip of the projection 16c, a hooked portion 16d is formed integral with the projection 16c. The portion 16d is fitted loosely into the circular arc-shaped opening 13c of the supporting member 13 to work as a slip-out preventive. And further, at the back-side end faces, opposing to each other, an upwardly-extending guide wall 16e is installed in parallel at both sides to enable the attachment of a spring 19 to push the back of the cancel cam with a specified pressure. A spring 17 and a steel ball 18 are fitted into a hole 16f made in the bottom of the moving member 16 and work to provide a clicking touch for positioning when the moving member 16 transfers to a predetermined position corresponding to the hollow 13 d of the supporting member 13.
The spring 19 is fitted into the guide wall 16e of the moving member 16 to push the cancel cam 20 toward the steering shaft from the back of the cancel cam 20.
The cancel cam 20 has a given thickness and at the front ends of an almost rectangular flat plate, a pawl 20a is formed by symmetrically-extending projections spaced at a predetermined distance. The pawl 20a is attached to the moving member 16 to face the cancel rotor 15 to be spring-inserted to the cylindrical column 13a of the supporting member 13. The central end at the back is pressed by the spring 19. The control lever 21 is, for example, made by bending a flat plate like a batten plate and at the one end, a cut groove 21a is formed which engages with the turn signal switch 29 and at the other end, for example, a generally T-shaped holder part 21b is formed as shown in FIG. 6 to fix the moving member 16 by holding the upper face of the cancel cam 20 fitted to the moving member 16. A mounting hole 21c acting as a fulcrum is made at a nearly intermediate portion between both ends to swing the moving member 16 in a predetermined direction through the control lever 21 following the operation of the control knob 29a of the turn signal switch 29, and the control lever 21 is fitted onto the supporting shaft 13b of the supporting member 13 in a freely swingable status. A plain washer 22 and a tightening element 23, for example, are adapted to fit the abovementioned control lever 21 to the supporting member 13. A horn contact 24 and a spring 25 are inserted together into the cylindrical column 13e of the supporting member 13 to be slide-fitted to the lower face of the steering wheel to constitute the electric circuit of the horn 42. A terminal 26 and a tightening element 27 are also provided to complete the construction of the self-cancel mechanism 28. The turn signal switch 29 is put on the steering column at the outer circumference of the steering wheel which is relatively separate from the said self-cancel mechanism 28, for example, as shown by a fictitious outline in FIG. 4, on a mounting base 30 in combination with other various switches. In other words, the switch 29 can be attached as a component part of the combination switch unit. The turn signal switch 29 has a control knob 29a and by the transfer of a moving board 29b of the turn signal switch 29 which is swung together with the swing operation of the control knob 29a to the left L or to the right R from the neutral position N as shown in FIG. 4, the electric circuit of the turn signal lamp is constituted. At the same time, a drive shaft 29c of the moving board 29b protruding from the front side wall is engaged with the cut groove 21a of the control lever 21 to swing the control lever 21 of the self-cancel mechanism 28 in a horizontal direction. Also, a switch mechanism is included which provides the alternate changeover of the main light and dimmer light of a head lamp (not shown) and passing operation by moving the control knob 29a from a position N to a position H upward as shown in FIG. 5.
Next, a description is given on the construction of the turn signal switch 29.
A control bar 29d is secured to the lower end of the control knob 29a. The control bar 29d sways back and forth as the control knob 29a is operated vertically from the position N to the position H and accordingly, a moving element 29e accommodated in a case 29m of a base 29l fixed to the back of the turn signal switch 29 is pressed or released. A spring 29g is wound around this moving element 29e. At the center of the moving element 29e, an elastic projection 29i is provided and the moving element moves a rotary cam 29h as the control lever 29d is pressed. By the action of the rotary cam 29h, a push pin 29f is moved and a moving contact 29j seesaws to contact alternatively either of a pair of fixed contacts 29k. Thus, the lighting condition of the head lamp is changed alternately from the main light to the dimmer light and vice versa and a passing operation is also acccomplished. The abovementioned rotary cam 29h, push pin 29f, moving contact 29j and fixed contacts 29k are all fitted on the back of the base 29l. Further, the control bar 29d turns to the left or to the right as the control knob 29a is turned to the left or to the right. Also, the moving board 29b moves slidingly and a ball 29s contacting the inner face of an outer case 29n also makes a sliding action. Further, a moving contact 29o slides to contact with a left or right fixed contact 29p. Thus, a left-side turn signal lamp 36 or a right side turn signal lamp 37 can be flashed.
Hereunder a description is given on the action of the present invention.
In FIG. 4, when the control knob 29a of the turn signal switch 29 is operated, for example, from the neutral position N shown in the drawing to the right position R to signal a change in the running direction of an automobile, the moving board 29b engaged with the turn signal switch 29 sways together to constitute the electric circuit actuating the turn signal lamps and at the same time, the drive shaft 29c of the moving board 29b protruding from the front side wall is transferred in the opposite direction. Consequently, the control lever 21 of the self-cancel mechanism 28 engaging with the drive shaft 29c moves horizontally pivoting about the mounting hole 21c fitted onto the supporting shaft 13b of the supporting member 13. The cancel cam 20 is moved together with the moving member 16 in the same direction as the operating direction of the control knob 29a as shown by the fictitious outline in FIG. 4 and results in the status that one of the pawls 20a of the cancel cam 20 is put in the rotary track of the protuberant element 15b fitted to the cancel rotor 15.
When the steering wheel is operated to the right in the above condition, the protuberant element 15b of the cancel rotor 15 comes against a slanted face 20b at the tip of the pawl 20a of the cancel cam 20 to work to turn the moving member 16 to the right through the cancel cam 20. Then, since the moving member 16 retaining the cancel cam 20 is left stopped at a predetermined position by a stopper (not shown) or the like, the cancel cam 20 itself is pushed in toward the back against the pressure of the spring 19, allowing the protuberant element 15b to pass through easily. When the directional change of the automobile to the right is finished and then the steering wheel is operated in the opposite direction, to the left, to change the automobile running direction, the protuberant element 15b of the cancel rotor 15 comes against an inside face 20c of the pawl 20a of the cancel cam 20 which is left put in the rotary track and is pressed. Therefore, the moving member 16 and the control lever 21 are moved to return automatically to their original neutral positions N. Thus, the control lever 29a is also returned automatically to the neutral position N together through the drive shaft 29c of the turn signal switch 29 which is kept engaged with the cut groove 21a at the one end of the control lever 21.
When the control knob 29a of the turn signal switch 29 is operated to the left position L, an action occurs as in the above operation of turning the control knob to the right position R, but in opposite directions.
As described hereinabove, the self-cancel mechanism 28 and the turn signal switch 29 are joined to each other by a very simple means through the control lever 21 supported by pivoting at an almost intermediate point to enable the mechanism and the switch to be moved at both ends toward the sides opposite to each other. Thereby, a given switch function actuating a given turn signal lamp as well as a required self-cancel function are composed. The embodiment of the present invention has the above-described construction and actions and secures the following specific effects, namely:
(a) since the self-cancel mechanism and the turn signal switch are composed separate from each other, the turn signal switch can be installed by selecting a relatively free, desired position and at the same time, the operating method and form of the switch can be designed more freely, making it possible to provide a simple and compact turn signal device for automobile, and
(b) the construction dividing the self-cancel mechanism from the turn signal makes application relatively easy, for example, only by changing the control lever length and the fulcrum position for a vehicle, and further makes the installation of a click joint for a lane change easier, providing turn signals for automobiles with a high general availability. | A turn signal for an automobile having a turn signal switch controlling the high beam and low beam of a head lamp by operating a control lever up and down and at the same time flashing right and left turn signal lamps by turning the control lever to the right and to the left, and a cancel mechanism stopping the flashing action of the turn signal lamps forcibly on completion of right turn or left turn of automobile, ensuring an organized operation by connecting the turn signal switch and the cancel mechanism placed spatially with a control lever and further, allowing the turn signal switch latitude of the mounting position thereof. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to impermeable liner structures for use in containment and control of the underground movement of gases, liquids, solutions, and solids in the mining, waste disposal, environmental remediation, and renewable energy industries.
2. Description of Related Art
Two types of in situ lining have been proposed by others. In one type, plastic lined coal shearer longwall undercuts in residual soils have been proposed as underliner for near surface waste storage basins. This proposal involves placement of sheets of plastic on freshly broken underground rock surfaces, which involves difficulties of joining, placement and maintenance of the liner.
In a second type of in situ lining, a leachate impermeable sand backfill liner placed in a coal shearer longwall undercut in residual soils has been proposed as a leachate cut off or collection layer between landfills.
Both of these proposals involve only liner construction in residual soils or soft, sedimentary rocks and the liner is oriented only in the near horizontal condition.
Curtain grouting is another in situ liquid and gas control technique. In curtain grouting liner materials are injected into a rock mass and fill the rock mass fracture system. The injection of liner materials cannot be directly observed, and the integrity of the grout curtain must be inferred. In reality, the fracture filling is erratic and a well placed grout curtain may be capable only of about 90-95% liquid containment.
Naturally occurring or artificially injected interstitial water may be frozen with the formation of liners capable of barricading liquid flows from ingress into localized underground zones. Such liners are effective although expensive to install and maintain against melting.
None of the prior art in situ liners solve the need for permanent, inexpensive, effective liners in hard-rock environments.
SUMMARY OF THE INVENTION
Recent research in the area of mechanical excavation mining systems has identified drillhole-excavation techniques with significant potential for environment application. The drillhole-excavation of narrow, wall-like channels, and the excavation of near horizontal channels, are the key excavations required for the creation of impermeable, in situ lined underground volumes. In situ liner segments can be shaped and joined to create solution control structures to barricade, divert, channel, vat retain, and encapsulate contaminated ground waters. Rock zone encapsulations can also be excavated and backfilled with solid wastes, or backfilled to optimize the pore space for the storage of liquids or compressed gas.
Drillhole-excavation tools useful in cutting suitable channels include a plasma based cutter, a penetrating cone mechanical tool, and a radial-axial drill-split mechanical excavator. These tools are used to cut channels approximately two ft. wide (0.6 m) through hard rock. Such tools may be used to create channels in hard-rock which are vertical through horizontal in orientation.
In all applications the selection of channel backfill material suited to the fluid, solution, gas, and toxic leachate control function is a key technology.
The backfill material may be a single layer filling of the channels with an impermeable material. In a second embodiment, the backfill material is formed by multiple layers of different materials. In a multiple-layer backfill, the channel wall or walls may be sprayed with a sealant, a impermeable material is used to coat the sealant, and a permeable monitoring or collecting material is used to fill the channel. The permeable monitoring material may be monitored for the presence and movement of solutions.
Liners may be used to create a variety of underground structures. These include an encapsulated volume of 6 impermeable lined walls which form an interior space, the interior of which may or may not be excavated or backfilled or otherwise altered. A catchment structure of 5 impermeable lined walls may be used as a retention basin or cofferdam. An open ended flow channel may be formed of 4 impermeable lined walls and packed with backfill. Finally, a flow diverter may be formed of three or fewer impermeable lined walls and used as a aquifer shunt or meteoric flow umbrella.
The underground structures created by this invention may be used for the storage of solid wastes in sealed containments, the control of ground water flows, and the storage of liquids and gases in the pore spaces of backfilled containments.
These structures provide cost effective earth based storage of solid wastes, flammable liquids and chemicals, compressed gases, fresh water, and heat and cold. They also allow a wide variety of environmentally attractive civil improvements for communities such as stored heat and cold for district heating and cooling, the safe storage of solar generated hydrogen, methane and acetylene gases, vertical landfilling, arid lands greening, and agriculture and silviculture through the creation of shallow, artificial aquifers. Liners containing foam, such as sand-polyurethane foam, may be used to cut off seismic waves due to blasting.
Further specific applications include liner-encapsulated deep underground rock quarries which are backfilled with municipal solid waste and hermetically sealed. Similarly, toxic wastes or despoiled ground waters may be stored in in situ lined vats. In situ lined ion exchange columns and filter beds may be used for the treatment of despoiled ground waters. In situ caps, seals, and diversion and drainage structures may be used to preclude mixing of ground water systems of unlike qualities. Contaminated ground water cut-off structures may be used to prevent the connection to surface water resources through springs, drainage tunnels, etc. Void space maximized underground containments may be used for the storage of flammable explosive fuels and for the storage of compressed gases such as methane, hydrogen, and acetylene. Impermeable lined structures may be used for the creation of near surface, open topped water impoundments to nonevaporatively store agricultural water in arid, deep aquifer terrains. Such structures allow creation of artificial wetlands and root irrigation agriculture and silviculture systems.
The underground structures created by this invention may be used to encapsulate broken or unbroken ores precedent to the injection of oxidation and or leach and or wash-water solution, of gases, and of thermal commodities, to abet the extraction of values from the aforesaid enclosed ores. These ore treatments are called solution controlled stope leaching and solution controlled stope autoclaving systems. In autoclave systems ores are batch processed underground using low-temperature, low-pressure, long residence time chemistries, as opposed to surface autoclave ore treatment chemistries which require high temperatures and pressures and short residence times. Stope leach and stope autoclave mining can also be pursued in separate, orebody adjacent, underground structures. The invention is also expected to inspire the mining industry development of bio-lixiviants, i.e., aqueous bacteria laden solutions that effect the leaching of values from ores or oxidize the ore precedent to other, chemical, values stripping steps; in this event, in situ liners compatible with the bio-reagents will need to be used.
The objective of this invention is to provide impermeable walls for underground structures in hard-rock.
Another objective is to provide methods for constructing impermeable walls for underground structures in hard-rock.
Another objective is to provide an impermeable single layer backfilling liner for channels thus forming underground structure walls in hard-rock.
Another objective is to provide an impermeable multiple layer backfilling liner for channels thus forming underground structure walls in hard-rock.
Another objective is to provide underground structures which may be used to store solid wastes in sealed containments, control ground water flows, and storage of liquids and gases in the pore spaces of backfilled containments.
A final objective is to provide simple, inexpensive, environmentally benign impermeable walls for underground structures.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagrammatic depiction of a cross section of a liner with a single-layer backfill.
FIG. 2 is a diagrammatic depiction of a cross section of a liner with a multiple-layer backfill.
FIG. 3 is a diagrammatic depiction of an underground isolation cell.
FIG. 4 is a diagrammatic depiction of an underground catchment basin.
FIG. 5 is a diagrammatic depiction of an underground open ended flow channel.
FIG. 6 is a diagrammatic depiction of an underground flow diverter.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Forming the Channels.
Narrow, preferably approximately two feet wide, excavations are cut into hard rock with vertical or horizontal orientation forming wall, roof, or floor-like channels. Suitable channel widths range from 6 inches to 4 feet. Such channels may be formed by drillhole-excavation.
At least three drillhole-excavation tool types have been identified as suitable for use in cutting the channels. 1. The "plasma blaster" plasma cutting tool, Noranda Minerals, Inc., was described in J. A. Lombardi, Mechanical Excavation Mining Systems. 2d International Symposium on Mine Mechanization and Automation, ed. G. Almgren, N. Kumer, N. Vagenas, Lulea, Sweden, June 7-10, Balkema, 1993, pp. 33-44. 2. The "Penetrating cone" excavator, was developed is by Sunburst Corp. and was described in C. Young, R. D. Dick, and W. L. Fourney, Small-Charge Cone-Fracture Technique for Rapid Excavation. Paper in Fragblast '90, Brisbane, Australia, Aug. 26-31, 1990, pp. 129-135. 3. The U.S. Bureau of Mines radial-axial drill-split mechanical excavator (drill-split tool) was described in J. J. Anderson, and D. E. Swanson, Laboratory Testing of a Radial-Axial Loading Splitting Tool. BuMines RI 8722, 1982, 26 pp.
A preferred process for cutting the channels uses the drill-split tool.
The drill-split tool consists of two separate parts: the drill, and the splitter. Both parts may be integrated in a single tool, which drills a hole, indexes the splitter to the drilled hole, splits, then rotates back to the drill. In this process, a radial-axial pressure is applied to the base of a drilled borehole and a cone of rock is spalled from the face of the rock. The volume of rock spalled from a drillhole at a free face is roughly proportional to the hole depth cubed.
V=1/3π(3.5).sup.2 D.sup.3
V is volume. D is depth of the hole. Local fracture patterns and extreme confinement, such as mining of a blind heading, reduce the volume of rock dislodged from that in the equation.
The drill-split tool may be operated using remotely operated drillhole-excavation tools mounted on a stope wall-walking jumbo or other cutting systems for narrow vein mining and wall construction. Although the channel cutting has been described using drillhole-excavation, other methods may be used to cut the narrow channels used in this invention.
Lining the Channels.
Single-Layer Backfill. A single-layer backfill consists of a liquid and gas impermeable material used to fill the channels. FIG. 1 is a cross-section of a channel with a single-layer backfill. A channel 20 is cut in the hard-rock mass 10. The channel is filled with sand-sodium silicate compound backfill 31. A sand-sodium silicate compound is suitable as single-layer backfill. Sand backfills in either vertical or horizontal channels may be redrilled and inundated with water activated polyurethane foam compounds. These sand-polyurethane foam backfills are cellular and water impermeable. Ground movements do not create fill traversing cracks when sand-polyurethane foam backfill is used. Hot mix asphalt-sand mixtures also may be used as single-layer backfill. Sand-flue-gas-desulferization cement is also a suitable single-layer backfill.
Autogenously healing substances flow and refill cracks which appear due to ground settlement. Crack self-healing preserves liner integrity. The above single-layer backfill materials exhibit autogenous healing.
Multiple-Layer Backfill. A multiple-layer backfill consists of several layers of materials, of which at least one layer is impermeable. A typical multiple-layer backfill comprises an impermeable material coating or sealant on one or both channel walls, an impermeable material coating the sealant, and a permeable material filling the remaining void of the channel. FIG. 2 is a cross section of a channel with a multiple-layer backfill liner. A channel 22 is cut in hard-rock mass 12. In this embodiment, both channel walls 14 are sprayed with impermeable bitumen sealant 32. The sealant on one wall is coated with impermeable sand-polyurethane foam 34. The remaining void of the channel is filled with permeable sand 36. The permeable layer is drained by monitoring or collecting drains and is used to channel and monitor the movement of fluids through the liner. The permeable layer can be used for in situ liner leak detection and collection of leaked fluids, for geohydrologic flow interception and diversion, and for stored fluid, solution, or gas interception and drainage.
Other multiple-layer backfills may be used. The materials used in the single-layer backfill may be used with multiple-layer backfills. In both single and multiple-layer backfills, the chemical and physical compositions of backfill materials and the engineered layering of materials is dictated by the nature of the chemical compositions, pressures, temperatures, viscosities, and flow rates of the substances interfacing with the in situ liner and the designed storage or processing function of the in situ liner construct.
The liners described above are adequate for the control of various materials such as fresh water, organo-chemical contaminated waters, brines, most gases, acid and base chemicals, gaseous or liquid energy fuels, trash and trash leachates, and dry chemical solids, at temperatures from below ambient to 200° C. and pressures to 200 psi.
Underground Structures.
The drillhole-excavation narrow-vein mining system proposed for use in the construction of wall-like in situ liner segments is limited to dips greater than 55°. This limitation is based on the need for the excavated rock to flow by gravity to the bottom of the excavation, to the mucking drift level. The drillhole-excavation longwall technique proposed for the creation of roof-and floor-like in situ liner segments is limited to less than 15% grades and 30° shield line slopes (dip), where dip is defined as the angle measured between the horizontal and the axis of the channel cut in the hard rock. Within these limits, channel topcuts, bottomcuts, and wall-like sidecuts can be connected in any fashion to form top and bottom fully closed six-sides, zonal isolations or isolation cells; bottom closed, top surface exposed, five-sided vats, catchments, or retention basins or cofferdams; bottom and top open four sided flow channels or funnels; and three or fewer sided ground water diversion surfaces or flow diverters. Of course, adequate provision for support must be made when bottomcuts are made.
FIGS. 3-6 show some examples of underground structures which may be formed by the impermeable linings of this invention.
FIG. 3 depicts an isolation cell 40 containing an encapsulated volume and constructed of 6 impermeable walls, 41, 42, 43, 44, 45, and 46. The interior of the isolation cell may be excavated if care is taken to leave rock material for the formation of two sided channels around the periphery of the cell. An evacuated cell may be filled with a wide variety of materials including municipal solid wastes, flammable liquids and chemicals, compressed gases, fresh water, toxic wastes, acidic and basic chemicals, and may be held at temperatures from below ambient to 200° C., and pressures from atmospheric to 200 psi. The isolation call may be excavated and filled with porous mineral material for storage of liquids and gases.
FIG. 4 depicts a catchment basin, retention basin, or cofferdam 50 constructed of four impermeable walls 51, 52, 53, and 54 and an impermeable floor 55. The level of the natural water table is indicated by arrows 56. A catchment basin may be used to provide near surface, open-topped water impoundments to nonevaporatively store agricultural water in arid, deep aquifer terrains. Such impoundments aid in creation of artificial wetlands and root irrigation agriculture and silviculture systems.
FIG. 5 depicts an open ended flow channel 60 constructed of four impermeable walls 61, 62, 63, and 64. An underground flow of fluid or gas may be directed through the channel and is indicated by arrows 65. In addition, the flow channel may be filled with packed bed ion-exchange media or materials for treatment of flows directed through the channel.
FIG. 6 depicts a flow diverter constructed of a single curved wall 71. A flow diverter may be constructed of three or fewer walls and is used as an aquifer shunt or meteoric flow umbrella. The diverter may be used to prevent the connection of contaminated ground water with surface water resources through springs, drainage tunnels, etc.
It will be apparent to those skilled in the art that the examples and embodiments described herein are by way of illustration and not of limitation, and that other examples may be utilized without departing from the spirit and scope of the present invention, as set forth in the appended claims. | In situ liners are impermeable compound backfilled underground rock channels which are artificially cut and laterally and vertically extensive. The backfilled channel cuts may be joined to form six-sided enclosures, five-sided basins, four-sided conduits, and three-sided (or less) diversion surfaces. The channel are backfilled by bulk materials (e.g. sand, untreated or pre-or post-placement treated), or the bulk material can be layered between spray-on liner materials on the channel hanging wall and floorwall. This in situ liner allows containment and control of solutions, liquids, gases, or solids, which may be permanently or temporarily stored, processed, or diverted. | 4 |
BACKGROUND OF THE INVENTION
The present invention relates generally to a guide rail or tensioner arm for guiding or tensioning a drive chain and more particularly to a sheet metal bracket with tabs formed on one edge which are bent in alternate directions for engagement with a plastic shoe or wear face. The guide rails or tensioner arms of the preferred embodiment of the present invention are designed for use as chain guides or tensioner arms in power transmission systems and engine timing systems using chain to drivingly connect the elements of the system.
Conventional engine timing systems include a crankshaft and a corresponding sprocket system which operates an engine with either a single or dual overhead camshafts. The operation of the system is based upon a chain which extends from the crankshaft to the camshaft (or camshafts) and returns to the crankshaft in an endless loop. Rotation of the crankshaft and the chain causes the camshaft to rotate.
Examples of engine timing systems are shown in U.S. Pat. No. 5,427,580, which is incorporated herein by reference. As the chain extends in an endless loop between the driving and the driven sprockets, such as those located on a crankshaft (driving) and camshaft (driven), the chain forms a “tight” side and a “slack” side. The tight side is formed by the tension in the span of chain between the links entering the driving sprocket and the links leaving the driven sprocket. A slack side is formed on the other span of chain between the links leaving the driving sprocket and entering the driven sprocket.
The performance and action of the chain can differ dramatically between the tight and slack sides. A chain tensioner is conventionally used on the slack side of the chain. The tensioner acts to take up or eliminate the slack in the chain. As the engine accelerates or decelerates, the tensioner arm may move closer to the chain to maintain the tension, i.e., reduce the slack in the chain. The tensioner arm typically includes a convex surface to match the path of the chain.
In contrast, a chain guide is conventionally used on the tight side of the chain. Such a guide does not include a tensioner piece, as the chain portion remains tight between the two sprockets. Typically, the guide is fixed to a mounting surface, such as a side of the engine block. The guide serves to maintain the desired path of the chain between the sprockets.
Conventional guide rails of the prior art may be formed as a single piece but more typically include two components, a bracket or carrier and a plastic shoe or wear face, that are produced independently of one another and interconnected by some form of locking device. The bracket may be made of metal or plastic and the wear face or shoe is typically made of plastic.
U.S. Pat. No. 4,832,664 discloses a guide rail that includes a carrier formed of a first plastic material and a slideway lining body made of a second different plastic material. Each of these two components is formed in a mold. The carrier and slideway lining body are interconnected to one another by dovetail connections, and secured by bent end sections. In the chain guide shown in U.S. Pat. No. 4,832,664, the carrier and sliding guideway body are formed on complementary dovetail cross-sections, and interlocked by the bent end section, or a similar meshing arrangement, that prevent relative movement between the two portions.
U.S. Pat. No. 5,813,935 discloses a guide rail where the wear face is produced by an extrusion molding process. The extrusion molding process is used in place of injection molding to permit the use of dovetail connections and provide interlocking components. The carrier portion is substantially an I-shape in cross-section with an extending dovetail section. The dovetail section on the carrier fits a complementary dovetail cross-section formed in the wear face. The carrier portion may be manufactured of die cast aluminum or magnesium; injection molded nylon; steel stamping; steel casting; or, steel or aluminum weldment.
Prior art brackets for chain guides, when made of metal, have often been formed with the bracket mounted to the engine at a location away from the chain centerline. FIG. 1 shows such a chain guide. The bracket is L-shaped in cross-section One side of the bracket 12 is mounted to an engine block 14 and the other side of the bracket 12 includes an attached shoe 16 with a channel shaped wear face 18 . The chain 20 passes along the channel shaped wear face 18 . The load applied to the bracket 12 by the chain 20 acts through distance “X” applying a stress to the bracket. To prevent the bracket 12 from bending or failing due to the stress, a bracket of thick material is used or an expensive stronger material is used.
The guide or tensioner arm of the present invention includes a carrier or bracket made from a formed sheet metal stamping. On a longitudinal edge of the bracket a series of extending tabs are formed. The tabs are bent perpendicular to the main body of the bracket in an alternating fashion. This forms a bracket which has a T-shape providing a base for mounting a plastic shoe with a wear face for guiding a chain.
SUMMARY OF THE INVENTION
The present invention is primarily concerned with a bracket or carrier for a tensioner shoe. The carrier and shoe is used as a chain guide or pivoting tensioner arm and may be applied to a power transmission system or engine timing system using a chain to drivingly interconnect driving and driven members.
In accordance with one embodiment of this invention, a chain guide is formed of two main interlocking parts. A first part includes a bracket. The bracket is formed of an initially flat, elongated stamped metal plate. The bracket has a pair of spaced holes.
Along one longitudinal edge of the bracket are formed a row of extending tabs. The tabs are defined by a series of slots formed in the edge of the bracket. The slots may originate from a row of holes formed in the bracket and extend to the longitudinal edge of the bracket. After the plate is stamped, the tabs are bent to a position perpendicular to the plane of the main body of the bracket. The tabs are bent in an alternate manner to each side of the bracket to form a T-shaped carrier member. The present invention contemplates the formation of 20-40 tabs, i.e., 10-20 tabs on each side of the bracket centerline.
The second part includes a plastic shoe having a wear face. The wear face has a channel formed therein to engage an associated chain. Opposite the wear face is a side which is adapted to engage the bracket. A series of hook-shaped tabs engage the tabs on the bracket. A retaining hook engages an end tab on the bracket to keep the shoe fixed to the bracket.
The assembly of the carrier and the shoe forms a chain guide which is typically applied to the tight strand of a power transmission chain.
Similar to the chain guide described above, a second embodiment of the present invention includes a chain tensioner arm having two main interlocking parts. A first part is a bracket as described in the first embodiment which further includes a hole optionally fitted with a bushing which is rotatably attached to a fixed pivot pin. The pivot pin is attached to the engine. A plastic shoe or the like is attached to the bracket. A chain tensioner is positioned to bear upon the bracket to cause the tensioner arm to tension a slack strand of the chain.
For a further understanding of the present invention and the objects thereof, attention is directed to the drawing and the following brief description thereof, to the detailed description of the preferred embodiment of the invention and to the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view of a prior art guide bracket and wear face illustrating the position of the chain and shape of the bracket.
FIG. 2 is a side view of the tensioner arm embodiment and the chain guide embodiment of the present invention in an engine between the crankshaft and one camshaft.
FIG. 3 is a sectional view of the guide bracket and wear face of the present invention illustrating the shape of the bracket and wear face along line 3 — 3 in FIG. 2 .
FIG. 4 is a side view of the bracket of the present invention.
FIG. 5 is a bottom view of the bracket of FIG. 4 .
FIG. 6 is a cross sectional view of the bracket of FIG. 4 along line 6 — 6 showing the tab.
FIG. 7 is a side view of another embodiment of the bracket of the present invention.
FIG. 8 is a side view of a shoe shown oriented to fit to the bracket of FIG. 7 .
FIG. 9 is a bottom view of the wear face of the shoe of FIG. 8 .
FIG. 10 is a top view of the shoe of FIG. 8 showing the bracket engaging tabs.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Turning now to the drawings, FIG. 2 depicts two embodiments of the present invention as used in a representation of an engine timing system. The illustration shows only a single bank of an engine timing system.
The engine timing system includes chain 30 , chain tensioner system 32 and chain guide 34 . The engine chain 30 extends from the sprocket 36 mounted on the crankshaft 38 to the sprocket 40 mounted on the camshaft 42 in an endless loop. The movement of the crankshaft 38 causes the camshaft 42 to rotate.
The crankshaft sprocket 36 is the driving sprocket and thus the tight side 44 of the chain 30 is formed between the links entering the crankshaft sprocket 36 and leaving camshaft sprocket 40 . The slack side 46 is the opposite side of the chain 30 between the two sprockets 36 , 40 .
The slack side 46 has a chain tensioner arm 32 and an actuator 50 , which may be a hydraulic tensioner or the like, to apply a force to the chain tensioner arm 32 . The tensioning arm and actuator are designed to act together to maintain the tension on the slack side 46 of the chain. The tight side 44 of the chain 30 has a chain guide 34 to keep the chain in position. The chain guide 34 is positioned so that its bottom side 48 is against the underside of the chain 30 . The chain 30 is forced into motion by the sprockets, resulting in its movement across the bottom of the chain guide. The chain tensioner arm 32 used in the chain tensioner system and chain guide 34 will be discussed in more detail below.
FIG. 3 depicts a cross section view of the chain guide 34 of the present invention having alternating tabs 60 A, 60 B for engaging a tensioner shoe 62 in use with a power transmission chain 30 . The chain guide 34 is mounted to the engine block 64 by a guide bracket 66 . The bracket has tabs 60 A, 60 B which are bent in an alternating manner perpendicular to the main body 68 of the bracket 66 . The plastic tensioner shoe 62 has a top side 72 with tabs 74 A, 74 B for engaging tabs 60 A, 60 B of the bracket 66 . Essentially, the tabs 74 A, 74 B on the tensioner shoe 62 form a channel into which the bottom portion of the bracket including the tabs may be inserted. Thus, the shoe 62 is retained in position on the bracket 66 .
The bottom side of the shoe 62 has a wear face 76 located thereon. The chain is positioned so that it runs across the wear face and is engaged and guided thereby. The wear face includes side rails 70 A, 70 B which are raised to help the chain maintain its position on the guide. The side rails are also shown in FIGS. 8 and 9. The bracket and tabs are shown in more detail in FIGS. 4-6.
As shown in FIG. 3, the bracket of the present invention is mounted to the engine block so that the chain is essentially centered over the main body of the bracket. The use of alternating tabs permits the centering of the chain over the main body of the bracket. By centering the chain, the torque or moment about the bracket main body is reduced, which permits use of a thinner main body formed of sheet metal.
FIG. 4 depicts the bracket 66 or carrier of the present invention. The main body 68 of the bracket 66 has a generally flat, elongated shape. A pair of spaced apart holes 80 , 82 are formed in the bracket. When the bracket is being used as part of a chain guide, both holes may be used to rigidly mount the bracket to the engine or a similar mounting element.
The bottom edge 88 of the bracket 66 has a slight camber to match a curved length of chain. Extending along the entire length of the bottom edge 88 of the main body 68 is a row or series of tabs 90 . When the bracket 66 is first formed, by stamping for example, the tabs 90 are coplanar with the main body 68 . A subsequent manufacturing step causes the tabs 90 to be bent perpendicular to the plane of the main body portion 68 of the bracket 66 in an alternating manner. In other words, a first tab 90 A formed at one end of the bracket edge may be bent to a first side of the bracket perpendicular to the main body portion of the bracket. The following, or next tab 90 B would be bent to the opposite side or second side. A third tab 90 C would be bent to the first side, and so on.
The alternate pattern of the orientation of the tabs 90 is shown in FIG. 5 . FIG. 5 depicts the tabs 90 on the bottom edge of the bracket 66 . The tabs 90 are bent perpendicular to the main body of the bracket and form a flat surface for mounting a plastic tensioner or guide shoe.
FIG. 6 is a cross sectional view of the bracket 66 of FIG. 4 . In this view the main body portion 68 of the bracket 6 has a left-facing tab 90 B. Adjacent tabs (not shown) would be right facing. Thus, a flat surface is formed along the bottom edge of the bracket to fit a plastic shoe thereto.
FIG. 7 depicts an alternate embodiment of the present invention. The bracket 166 may have a pair of spaced holes as in the previous embodiment. However, only a single hole is required. The hole 180 is provided with a bushing 184 . The bracket 166 is pivotally mounted to a pivot pin 186 by way of the bushing 184 . Thus, the bracket 166 , when combined with a plastic shoe, may be used as a tensioner arm as shown in FIG. 2 . As described in FIGS. 4 and 5, the bracket has a row of tabs 190 along the bottom edge 188 of the main body portion 168 of the bracket 166 . The bottom edge 188 of the bracket 166 has a slight camber to match a curved length of chain. The tabs 190 are bent perpendicular to the plane of the bracket body in an alternating manner to form a flat shoe mounting surface 188 which is the same surface as the edge. As in the above embodiment, the shoe mounting surface 188 is centered with respect to the body portion 168 of the bracket 166 .
FIG. 8 depicts a plastic guide shoe or tensioner shoe 200 adapted for use with the bracket 166 shown in FIGS. 4 and 7. The shoe has an elongated flat shape which has a slight camber to match that of the bottom surface of the bracket 166 . The top side 202 of the shoe has a plurality of tabs 204 which, in effect, form a C-shaped groove into which the tabs 190 of the bracket 166 are inserted. The tabs 204 of the shoe 200 hold the shoe onto the bracket 166 . At one end of the shoe 200 an end wall 206 is formed which prevents the shoe 200 from sliding off of the bracket. A retaining hook 208 acts to prevent the shoe from sliding off of the bracket in the reverse direction by hooking one of the bracket tabs 190 .
The bottom surface 210 of the shoe 200 contains a wear face 212 described in more detail in FIG. 9 . The wear face 212 includes a sliding surface 214 and a pair of side walls 216 A, 216 B. The chain moves across the sliding surface 214 of the wear face 212 and is retained in place by the side walls 216 A, 216 B.
FIG. 10 depicts the top surface 202 of the shoe 200 . The plurality of shoe tabs 204 extend inwardly from the outside edges of the shoe 200 . The end wall 206 is positioned at one end of the top surface 202 . The retaining hook 208 extends from the end wall 206 and is positioned to clip a tab of the bracket and prevent movement in the reverse direction or disengaging of the shoe from the bracket.
While several embodiments of the invention are illustrated, it will be understood that the invention is not limited to these embodiments. Those skilled in the art to which the invention pertains may make modifications and other embodiments employing the principles of this invention, particularly upon considering the foregoing teachings. | A guide or tensioner arm including a bracket made from a formed sheet metal stamping. The bracket is formed of a body portion with a series of tabs formed along a bottom edge. The tabs are bent perpendicular to the body portion of the bracket in an alternating fashion. This forms a bracket having a T-shape providing a flat base for mounting a plastic shoe. Since the body portion is centered with respect to the alternating tabs a strong bracket for holding the plastic shoe is provided to guide or tension an associated strand of chain in a power transmission system. | 5 |
This is a divisional of application Ser. No. 7/938,807 filed on Sep. 1, 1992, now U.S. Pat. No. 5,393,914.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention is related to gasoline engine cleaners and detergents, and more particularly to gasoline intake valve deposit (IVD) inhibitor additives, i.e., agents which assist in preventing and removing deposits from intake valves and related parts of a gasoline combustion engine. This invention also relates to combustion chamber deposit inhibitors, which reduce combustion chamber deposits, resulting in lower octane requirement increase and lower NO x emissions.
2. Description of Related Information
Combustion of a hydrocarbon motor fuel in an internal combustion engine generally results in the formation and accumulation of deposits on various parts of the combustion chamber as well as in the fuel intake and on the exhaust systems of the engine. The presence of deposits in the combustion chamber seriously reduces the operating efficiency of the engine. First, deposit accumulation within the combustion chamber inhibits heat transfer between the chamber and the engine cooling system. This leads to higher temperatures within the combustion chamber, resulting in increases in the end gas temperature of the incoming charge. Consequently, end gas auto-ignition occurs causing engine knock. In addition, the accumulation of deposits within the combustion chamber reduces the volume of the combustion zone, causing a higher than design compression ratio in the engine. This, in turn, can also lead to engine knocking. A knocking engine does not effectively utilize the energy of combustion. Moreover, a prolonged period of engine knocking can cause stress fatigue and wear in pistons, connecting rods, bearings and cam rods of the engine. The phenomenon noted is characteristic of gasoline powered internal combustion engines. It may be overcome by employing a higher octane gasoline which resists knocking for powering the engine. This need for a higher octane gasoline as mileage accumulates has become known as the engine octane requirement increase (ORI) phenomenon. It is particularly advantageous if engine ORI can be substantially reduced or eliminated by preventing or modifying deposit formation in the combustion chambers of the engine.
Another problem common to internal combustion engines is the formation of intake valve deposits, which is an especially serious problem. Intake valve deposits interfere with valve closing and eventually result in poor fuel economy. Such deposits interfere with valve motion and valve sealing, cause valve sticking, and, in addition, reduce volumetric efficiency of the engine and limit maximum power. Valve deposits are produced from the combustion of thermally and oxidatively unstable fuel or lubricating oil oxidation products. The hard carbonaceous deposits produced collect in the tubes and runners that are part of the exhaust gas recirculation (EGR) flow. These deposits are believed to be formed from exhaust particles which are subjected to rapid cooling while mixing with the air-fuel mixture. Reduced EGR flow can result in engine knock and in increased NO x emissions. It would therefore be desirable to provide a motor fuel composition which minimizes or overcomes the formation of intake valve deposits and subsequent valve sticking problems.
There are additives on the market which assist in the removal of deposits, particularly on the intake valves, such as OGA-472™, a product of the Oronite Co. of Wilmington, Del. These additives lack sufficient deposit cleanup activity, however, and their efficacy can be improved upon. In addition, polyisobutylene (PIB) based detergents tend to cause octane requirement increase.
Thus, it is an object of the present invention to provide a gasoline additive which will effectively remove deposits from, and prevent the formation of deposits on, the intake valves of a gasoline spark ignition engine. It is another object of the present invention to provide a gasoline additive which will perform this function without contributing to the buildup of combustion chamber deposits and, therefore, without causing octane requirement increase.
SUMMARY OF THE INVENTION
The present invention provides a novel class of compounds, useful as gasoline detergent additives, comprising hydrocarbyloxypolyether allophonate esters of 2-hydroxy ethane. These novel allophonate esters can be represented by the formula: ##STR1## where R is a C 9 -C 25 alkyl group, R 2 is a C 2 to C 4 oxyalkylene group, m is 0 or 1, and n is a number between about 5 and about 30.
The present invention also provides a motor fuel composition comprising:
(a) a major portion of a hydrocarbon fuel boiling in the range between 90° F. and 370° F.; and
(b) a minor amount, sufficient to reduce the formation of deposits on intake valves, of the hydrocarbyloxypolyether allophonate ester of 2-hydroxy ethane of FIG. 1.
A method of synthesizing the allophonate esters of the present invention is also provided.
DETAILED DESCRIPTION OF THE INVENTION
Applicant's have discovered a new class of allophonate esters which are useful as detergents in motor fuel compositions. These allophonate ester detergents are more efficacious in removing and preventing the build up of deposits on intake valves than some commercially available detergent packages. In addition, the allophonate ester motor fuel additives of the present invention will not contribute significantly, if at all, to octane requirement increase, a problem which confronts all gasoline spark ignition engines.
The allophonate esters of the present invention are represented by the formula: ##STR2## where R is a C 9 -C 25 alkyl group, R 2 is a C 2 to C 4 oxyalkylene group, m is 0 or 1, and n is a number between about 5 and about 30. In FIG. II, the R group is shown located in the para position. It is probable that the R group will sometimes be located in the ortho position, and the allophonate esters of the present invention therefore include mixtures of both the para and ortho isomers. The formula of FIG. II is hereinafter intended to represent both the para and ortho isomers and mixtures thereof.
Preferably, R is a C 9 to C 21 alkyl group, R 2 is an oxypropylene group, m=1, and n is a number between about 9 and about 15. In another preferred embodiment, R is a C 2 to C 21 alkyl group, R 2 is an oxypropylene group, m=0, and n is a number between about 9 and about 15.
More preferably, R is a nonyl group, R 2 is an oxypropylene group, m=1, and n is about 12. This more preferred allophonate ester can be represented by the formula: ##STR3## It should be noted that the phenyl ring can contain a second nonyl substituent. In such cases the first nonyl group would be in the para position and the second nonyl group would be in the ortho position to the remainder of the molecule.
SYNTHESIS OF ALLOPHONATE ESTERS
The allophonate esters of the present invention are the product of the reaction of a hydrocarbyloxypolyoxyalkylene amine with urea and ethylene carbonate: ##STR4## where R is a C 9 -C 25 alkyl group, R 2 is a C 2 to C 4 oxyalkylene group, m is 0 or 1, and n is a number between about 5 and about 30.
The polyetheramine reactants useful in the present invention can be represented by the formula: ##STR5## where R is a C 9 -C 25 alkyl group, R 2 is a C 2 to C 4 oxyalkylene group, m is 0 or 1, and n is a number between about 5 and about 30. The R group can be located in the para or ortho position.
Preferably, R is a C 9 to C 21 alkyl group, R 2 is an oxypropylene group, m=1, and n is a number between about 9 and about 15. In another preferred embodiment, R is a C 12 to C 21 alkyl group, R 2 is an oxypropylene group, m=0, and n is a number between about 9 and about 15.
The most preferred polyetheramine, nonylphenoxypolyoxypropyleneamine, can be represented by the formula: ##STR6## Nonylphenoxypolyoxypropyleneamine is available from Texaco Chemical Company. It should be noted that the polyetheramines useful in the present invention can have two nonyl groups substituted onto the phenyl ring. In fact, it is likely that commercially available nonylphenoxypolyoxypropyleneamine contains at least some of the di-nonyl substituted phenyl ring versions of this compound. In such cases, the second nonyl group is located in the ortho position relative to the bulk of the molecule.
Ethylene carbonate is commercially available from the Texaco Chemical Company.
The allophonate esters of the present invention can be prepared via the following reaction. In step one a polyetheramine is heated with urea at a temperature of about 130° C. for about 6-15 (preferably about 6) hours with stirring, under a nitrogen sparge to remove the evolved ammonia. After cooling, the mixture is filtered free of unreacted urea. The cooling and filtering steps are optional.
In step two, the polyether urea product of step one is reacted with ethylene carbonate at a temperature of about 130° C. for about 1-15 (preferably about 3) hours with stirring. The reaction mixture is filtered free of unreacted reactants, and stripped under vacuum at about 80° C. for about an hour. The product is an allophonate ester of the present invention.
The synthesis can also be performed in reverse order, i.e., the ethylene carbonate can be reacted with urea in the first step and the product of this first reaction can then be reacted with the polyether amine in the second step.
All of the reactions described above can be conducted in solution in hydrocarbon type heavy oils (e.g., SNO-600, SNO-850, etc.) Preferably, the reactants are employed in the stoichiometric amount, i.e., 1:1:1.
THE MOTOR FUEL COMPOSITION
The motor fuel composition of the present invention comprises a major portion of a hydrocarbon fuel boiling in the gasoline range between 90° F. and about 370° F., and a minor portion of the allophonate ester additive of the present invention sufficient to reduce the formation of deposits on intake valves.
Preferred base motor fuel compositions are those intended for use in spark ignition internal combustion engines. Such motor fuel compositions, generally referred to as gasoline base stocks, preferably comprise a mixture of hydrocarbons boiling in the gasoline boiling range, preferably from about 90° F. to about 370° F. This base fuel may consist of straight chain or branched chain paraffins, cycloparaffins, olefins, aromatic hydrocarbons, or mixtures thereof. The base fuel can be derived from, among others, straight run naphtha, polymer gasoline, natural gasoline, or from catalytically cracked or thermally cracked hydrocarbons and catalytically reformed stock. The composition and octane level of the base fuel are not critical and any conventional motor fuel base can be employed in the practice of this invention. In addition, the motor fuel composition may contain any of the additives generally employed in gasoline. Thus, the fuel composition can contain anti-knock compounds such as tetraethyl lead compounds, anti-icing additives, and the like.
In a broad embodiment of the fuel composition of the present invention, the concentration of the additive is about 25 to about 125 PTB (pounds per thousand barrels of gasoline base stock). In a preferred embodiment, the concentration of the additive composition is about 50 to about 125 PTB. In a more preferred embodiment, the concentration of the additive composition is about 80-100 PTB.
The additive of the present invention can also be used effectively with heavy oils such as SNO-600, SNO-850, etc., or with synthetics such as polypropylene glycol (1000 m.w.), at concentrations of 30-100 PTB, and 65 PTB in particular.
The additive of the present invention is effective in very small concentrations and, therefore, for consumer end use it is desirable to package it in dilute form. Thus, a dilute form of the additive composition of the present invention can be provided comprising a diluent e.g., xylene and about 1 to about 50 wt. % of the additive.
The preparation and advantages of the allophonate esters of the present invention are further illustrated by the following examples.
EXAMPLE 1
Preparation of N-nonylphenoxypolypropoxy Allophonate Ester of 2-Hydroxy Ethane
200 g (0.2 mole) of polyetheramine with molecular weight of about 1000 was reacted with 19.8 g (0.33 mole) urea at 130° C. for 2 hours. After 2 hours, 26.4 g (0.3 mole) of ethylene carbonate was introduced at 130° C. and reacted at this temperature an additional 6 hours. The reaction product was filtered hot and then vacuum stripped at 80° C. for 2 hours. The final clear product weighed 204.7 grams. It had the following analysis:
______________________________________Nitrogen 3.50 wt %TBN 12.78Molecular weight (by Gel Phase Chromatography) 990______________________________________
The structure, see FIG. I, was confirmed by infrared spectroscopy and nuclear magnetic resonance.
EXAMPLE 2
Intake Valve Keep Clean Test
The motor fuel composition of the present invention is advantageous in that it reduces intake valve deposit formation. The advantage of the instant invention in controlling intake valve deposit formation has been shown by the comparison of the performance of motor fuel compositions of the present invention and a motor fuel containing a commercially available detergent package.
The following fuel compositions were subjected to Honda Generator - IVD "Keep Clean" testing. Fuel A contained 100 PTB of the product of Example 1 as a detergent additive and Fuel B contained 60 PTB of a commercially available gasoline additive package. The base fuel used in each fuel composition was a commercial unleaded fuel with 45% aromatics, 6% olefins, and the remainder paraffins. The octane rating, calculated as the average of research and motor octane ratings was 87. Base fuel boiling point data is listed in Table I as follows:
TABLE I______________________________________Base Fuel______________________________________initial boiling point 99° F.50% point 253° F.90% point 410° F.end point 415° F.______________________________________
The Honda Generator Test employed a Honda ES6500 generator with the following specifications:
TABLE II______________________________________Honda ES6500 Generator______________________________________Type: 4-stroke, overhead cam, 2-cylinderCooling system: Liquid-cooledDisplacement: 369 cubic cm. (21.9 cu. in)Bore × stroke: 56 × 68 mm (2.3 × 2.7 in)Maximum Horsepower: 12.2 HP/3600 rpmMaximum Torque: 240 kg-cm (17.3 ft-lb)/3000 rpm______________________________________
Each generator was equipped with an auto-throttle controller to maintain the rated speed when load was applied. Load was applied to each generator by plugging in a water heater. Various loads were simulated by changing the size of the water heaters connected to the generator.
The procedure for the Honda Generator Test is as follows. The test was started with a new or clean engine (clean valve, manifold, cylinder head, combustion chamber) and a new charge of lubricant. The generator was operated for 80 hours on the fuel to be tested following the test cycle of 2 hours at 1500 Watt load and 2 hours at 2500 Watt load, both at 3600 r.p.m. The engine was thereafter disassembled and the cylinder head stored, with valve spring and seal removed, in a freezer overnight at 0° F.
IV Stickiness Test
A trained rater quantified the effort to push open the intake valves by hand. The amount of effort was correlated to valve sticking problems in vehicles: i,e., valves that could not be pushed open by hand generally correlated with cold starting problems in vehicles.
CRC IV Test
The intake system components (valve, manifold, cylinder head) and combustion chamber were rated visually according to standard Coordinating Research Council (CRC) procedures (scale from 1-10: 1=dirty; 10=clean). The performance of the test fuel was measured in part by the cleanliness of the intake system components.
Fuels A and B were subjected to the Honda Generator intake valve keep clean test procedure. The results are summarized in Table III:
TABLE III______________________________________ IVFUEL CRC IV Wt., mg., IV Stickiness______________________________________A 9.6 0.013 NoB 6.03 0.269 No______________________________________
The additive gasoline of the present invention, Fuel A, demonstrated excellent CRC valve ratings, virtually no deposits on the intake valves (13 mg or less) and exhibited no stickiness. The fuel containing the commercially available additive package showed a poor CRC rating and gave 269 mg intake valve deposits. Therefore the allophonate ester of the present invention demonstrates excellent detergency and intake valve detergency keep clean properties.
EXAMPLE 6
Thermal Gravimetric Analysis (TGA)
A sample of the allophonate ester of Example 1 was analyzed for rate of thermal decomposition using TGA analysis, in order to determine whether they will increase combustion chamber deposits. The procedure used was the Chevron test method, which involves heating the additive compound in air at a rapid rate and measuring its volatility at 200° C. and 295° C. The test method is more specifically described as follows:
The sample is heated to 200° C., kept at this temperature for 30 minutes, and then heated to 295° C., where it is kept for an additional 30 minutes. The weight of the sample, (initially about 20 mg) is recorded at the start, after the first heating period and after the final heating period. The difference in weights from the start to 200° C., and from 200° C. to 295° C. is recorded and the percent loss, i.e., volatility, is calculated. (The final weight at 295° C. is also considered residue.) The heating is done under a flow of air at 60 cc/min.
The following results were obtained:
TABLE IV______________________________________ % Volatilized Residue (in Air) (wt. %)Run Additive 200° C. 295° C. 295° C.______________________________________1 Product of Example 1-N- 15 90 10nonylphenoxypolyisopropoxyallophonate ester of 2-hydroxyethane2 OGA-472 ™ 34.5 62.8 37.2______________________________________
The test results for runs 1 and 2 show that at 295° C., 90% of the additive of the present invention had thermally decomposed and volatilized, compared to only 62.8% for a PIB containing derivative such as OGA-472™. These results indicate that the additives of the present invention should leave only small amounts of combustion chamber deposits during the actual engine operation, and therefore will not contribute to octane requirement increase. | The present invention provides a novel class of compounds, useful as gasoline detergent additives, comprising hydrocarbyloxypolyether allophonate esters of 2-hydroxy ethane. The present invention also provides a motor fuel composition containing the novel allophonate esters and further provides a method of synthesizing the allophonate esters of the present invention. | 2 |
CROSS REFERENCE TO RELATED APPLICATION
This application is a division of my prior application Ser. No. 900,983 filed Apr. 28, 1978, now U.S. Pat. No. 4,217,175 dated Aug. 12, 1980.
SUMMARY OF THE INVENTION
This invention relates to improvements in systems for the pyrolysis of shredded solid municipal waste in a pyrolysis retort which is indirectly heated by combustion of the char and gas pyrolysis components. The pyrolysis is effected in the absence of oxygen at a temperature producing a relatively high yield of pyrolysis oil in the vapor state, which is condensed in the system and recovered as a commercial oil product. The system includes a furnace for combustion of the char and gas at a temperature which melts the ash to liquid slag and from which the flue gas is recycled through the heating jacket of said retort.
One object of this invention is to substantially eliminate air pollution; this is accomplished (a) by provision of means for sealing the retort inlet from the shredded-waste feed hopper, (b) by the provision of an air-tight, insulated gravity char-and-fluid separator at the discharge end of the retort including means for transferring char from said separator to said furnace in sealed relation, and (c) by air-tight conduits for all flue-gas and vapors from the retort, furnace, and vapor condenser and the vent from the system to the atmosphere.
Another object is to conserve the limited heat available by combustion of the solid char and the gas pyrolysis products. This object is effected by providing refractory lining, insulation, and air-tight enclosure for said retort, said gravity-char-and-fluid-separator, and said furnace including the flue-gas recirculation elements of the system, and further by provision of means for pre-heating the combustion air supplied to said furnace by heat exchange with the flue-gas vented from the system, and simultaneously cooling the vented flue-gas substantially below the recirculating gas temperature. In addition, the combustion air intake is adjustably regulated to substantially eliminate excess oxygen over that needed for complete combustion, avoiding the presence of oxygen to any substantial amount in the recirculating gas.
Referring more specifically to the preferred means for sealing the retort at the shredded-waste inlet end and sealing the char-and-fluid-separator from the furnace, these are comprised of variable stroke rams injecting adjustable plugs of shredded waste (in the case of the retort) or char (in the case of the furnace) through a nozzle, said plugs forming and maintaining a seal of compressed solids substantially eliminating the flow of gas and vapor from the retort inlet or the furnace fuel inlet.
Referring more specifically to the preferred construction of the pyrolysis retort per se, the embodiment disclosed herein is comprised of a tubular jacket casing anchored at the discharge end of the retort and, at the feed end, overlapping the feed injection nozzle a short distance which axially supports the casing and permits it to slip thereon longitudinally sufficiently to compensate for the difference in the metal casing length and the overall length of the refractory-lined jacket due to thermal expansion and contraction from temperature variation. Inside said casing is a rotatable conveyor screw, also anchored at the retort discharge end by radial and thrust bearings and a packing gland shaft seal, and terminating shortly ahead of said nozzle at the feed end, at which the casing wall constitutes the screw support bearing. The spiral flights of said screw break up the sealing plugs of shredded waste leaving the nozzle, wipe the casing wall clear of an insulating layer of shredded waste and redistribute the solids in the retort as they are conveyed to the discharge end. Ending in advance of the feed nozzle, the screw is free for thermal expansion and contraction lengthwise without imposing stresses on the retort structure.
Referring more specifically to the preferred embodiment for adding furnace flue-gas to the recycling heating gas stream, this disclosure illustrates and describes a jet ejector motivated by an adjustable jet of recycling gas and connected, at the suction zone thereof, to the furnace flue. To regulate the pressure drop across the jet ejector and thereby adjust the rate of flue-gas removal from the furnace, a by-pass for a portion of the recycling gas is provided, said by-pass having therein an adjustable damper.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of the pyrolysis retort and furnace in the system;
FIG. 2 is a vertical cross-section through the jet condenser and gravity separator for the gas, vapor and sludge components;
FIG. 3 is a longitudinal vertical cross-section through the municipal waste inlet of the retort;
FIG. 4 is an isometric sketch of the structure supporting the ram and cylinder shown in FIG. 3;
FIG. 5 is a longitudinal vertical cross-section through the pyrolysis product discharge end of the retort, the gravity separator for the char and fluid components of said products and the char-combustion furnace;
FIG. 6 is section VI--VI in FIG. 5 and
FIG. 7 is a section VII--VII in FIG. 5;
FIG. 8 is a vertical cross-section through the furnace flue, the jet-ejector connected thereto, and the conduit between said jet-ejector and the pyrolysis retort;
FIG. 9 is a plan view of the instrumentation for operating the ram for injecting municipal waste into the retort and FIG. 10 is a sketch illustrating a component thereof;
FIG. 11 illustrates partly in section an alternate ram driving arrangement;
FIG. 12 is a sketch in section showing the sleeve connecting the ram and drive, and
FIG. 13 is section XIII--XIII in FIG. 11.
DETAILED DESCRIPTION
Pyrolysis of municipal refuse occurs through a substantial temperature range, and the relative proportions of oil and gas vary with the temperature. In systems which may be epitomized as refuse-fueled power plants embodying gas-fired steam boilers, a pyrolysis temperature of the order of 1400° F. may be selected, yielding a high ratio of gas to oil. In systems designed primarily to produce oil, which is the object of this invention, the pyrolysis temperature on the order of 1100° F. is desirable, yielding a high ratio of oil to gas. This point is noted first, before disclosure of the apparatus structure and process steps of my improved system, so that the purpose of the temperatures at various points in the system is clear.
Typically pyrolysis systems for oil production include a dryer for the shredded municipal waste, prior to delivery to a pyrolysis retort, the dryer and conveyor of hot pre-dried shredded waste being open to the atmosphere. This involves odor emission and also fire risks. With the system disclosed herein, pre-drying is eliminated and both drying and pyrolysis are accomplished in a single stage retort in the absence of oxygen.
Referring to FIG. 1, an indirectly heated retort 10 is shown, comprised of a tubular casing 11 within which is a spiral screw 13 for conveying the raw refuse therethrough. This casing and screw are constructed of stainless steel suitable to withstand corrosion at the temperatures necessary for pyrolysis of the refuse. The raw material feed enters the left hand end of the retort in FIG. 1 and is discharged therefrom at the right hand end. The casing 11 is surrounded by a heating jacket 12 through which hot gas is circulated as will be subsequently explained. The screw 13 is driven from beyond the delivery end by a motor 15 through a connecting shaft 14. For simplicity in this diagram, the driving transmission between the motor 15 and the shaft 14 and the journals, thrust bearings, etc. for the shaft 14 are not illustrated in FIG. 1, but it is here noted that the screw 13 is under tension, and has no shaft bearing at the feed end. The screw flights of 13 are therefore made slightly less in diameter than the casing 11, within which the screw floats.
Adjacent the feed end of the retort is shown a raw material feed hopper 16, through which, at its base, a reciprocating ram 17 passes concentric with the retort. This ram is reciprocated by a suitable driving means, the particular type illustrated in FIG. 1 being a piston rod 18 and cylinder 19 constructed to provide a variable ram stroke similar to that of the feeder disclosed in Reilly and Guy U.S. Pat. No. 3,563,398. The ram 17 thus intermittently forces a compacted plug of refuse material into the feed end of the retort 10, thus simultaneously sealing the entrance end of the retort against escape of hot vapors therefrom, and forcing the material against the flights of the screw 13. This screw 13 is driven at a rotation speed independent of the refuse feed rate by the ram 17, which speed exceeds that necessary to convey the maximum feed rate with the casing 11 full of solid particles. The screw thus breaks up the compacted refuse into loose particles and sweeps them into heating contact with the casing 11, and stirs and redistributes the particles in transit, thus preventing formation of an insulating layer thereof at the casing wall.
The retort terminates at the right hand end, in FIG. 1, at the top of char chute 20 having a gas and vapor discharge duct 21 entering the top thereof. The char, consisting typically of fixed carbon and ash, falls to the bottom of the chute 20 at which is provided a ram 17(a) similar to the ram 17 at the bottom of the feed hopper 16, and driven by piston rod 18(a) and cylinder 19(a) having a variable stroke as previously mentioned. This char chute 20 is adjacent a furnace 22, and the ram 17(a) forces the char into the furnace while simultaneously sealing the furnace entry port with compact char to prevent leakage of furnace gas therethrough. Thus the char is fed directly into the furnace 22 while it is still hot from the retort 10 without exposure to the atmosphere, avoiding smoke nuisance and conserving heat within the system. Combustion air is blown through a duct 23 to enter the furnace at the char entry port, and the char, which is above ignition temperature of its carbon content, burns as it falls towards the furnace bottom. The air is supplied through duct 23 at a rate sufficient to completely burn the char, and to maintain a temperature to melt the ash components of the char in the furnace combustion zone. The molten ash collects as slag at the furnace bottom below the char entry port, from which it is withdrawn through molten slag disposal duct 25.
For start up purposes, and to supply any additional heat necessary in case the char has insufficient heating value to maintain the furnace temperature high enough to melt the ash components of the char, a gas burner 26 may be provided, supplied combustion air through a branch of duct 23 and pyrolysis gas through pipe 43. Refractory baffles 27 and 28 are provided in the furnace to precipitate fly ash contained in the flue gas leaving the char combustion zone and collect such ash as molten slag which flows to the duct 25, through which the molten slag is tapped periodically, as well known in the art.
The hot gas circulation illustrated in FIG. 1 will next be briefly described. As previously noted, in the retort 10 the waste is heated to a pyrolysis temperature in the order of 1100° F. This is effected by a flow of heating gas which enters the retort jacket 12 at a temperature in the order of 1300° F. at the char and fluid discharge end of the retort 10 and leaves the jacket 12 at the retort feed end at approximately the 1100° F. pyrolysis temperature. This gas is recycled by fan 29 and ducts 30 and 30(a) to the nozzle 31 enclosed within jet ejector casing 32, into which, through flue port 24, flue gas at furnace temperature (e.g. 2500° F.) is drawn from the furnace and is blended with the recycled gas at the jet ejector, to produce the desired 1300° F. temperature. The jet ejector discharges this gas through jacket 35 (surrounding the duct 21) to the retort jacket. A by-pass 33 with a pressure-drop regulating damper 34 is provided to adjust the pressure drop across the jet ejector. Thus the jet ejector and the by-pass regulator function to regulate the rate of heat removal from the furnace without varying the furnace temperature. Thus the furnace can be operated at a temperature sufficiently high to melt the ash residue to a liquid slag for removal, while temperature of gas recycled is independently regulated at the lower temperature selected for indirectly heating in the pyrolysis retort.
A portion of the hot gas is withdrawn from duct 30(a) through an exhaust vent duct 36 and passes to the atmosphere through a stack pipe 37. In this transit the vent gas passes through a heat exchanger 38 having a jacket 39 in which the incoming fresh combustion air is pumped through a duct 40 and in which it is pre-heated and delivered to the duct 23 previously referred to. Suitable means is provided for balancing the pressure drop of the vent gases; for simplicity of illustration, a baffle 37(a) at the base of the stack pipe 37 is shown in FIG. 1.
Combustion air is supplied to the system by a gas pump 41 which receives air from the atmosphere through a filter 42 and delivers it to the heat exchanger 38 through the duct 40. The gas pump 41 is illustrated in FIG. 1 as a rotary positive displacement gas pump to deliver combustion air at a predetermined rate which is variable by adjusting the speed of the impellers.
It is to be understood that to prevent heat loss the components illustrated diagrammatically in FIG. 1 are all provided with insulation from the atmosphere. This insulation typically is constructed of cast refractory block sections against the hot components illustrated, surrounded by a layer of mineral fiber and an outside sheet metal casing, as well known to the art.
FIG. 2 illustrates diagrammatically the apparatus for separation and recovery of the gas and vapor components delivered by the duct 21 shown in FIG. 1. The duct 21 terminates at the top of a jet condenser 44 which extends downwardly into a cavity separating vessel 45. Preferably the vessel 45 has a relatively small horizontal cross-section and has substantial length providing substantial depths for the separated layers therein. The composition of the material delivered by the duct 21 consists mainly of water, pyrolysis oil, and gas, plus some solid residues from the char chute and furnace fly ash. A nozzle 46 at the top of the jet condenser 44 provides a shower of cold water supplied by pipe 47, which shower simultaneously washes the inlet gas and vapor and condenses the vapor components. These separate by gravity in the vessel 45, the gas fraction rising to the top thereof, the pyrolysis oil fraction forming a liquid layer below the gas and the water, and solid sludge settling below the oil. A liquid overflow duct 48 sets the uppermost liquid level 49, i.e. that of the separated oil. A capacitance type level controller 50 is provided to set the water-oil interface level, having a capacitance sensor 51 at the bottom thereof connected by rod 52 to the capacitance regulator at the top. This establishes an oil-water interface 53 at the sensor level, by a connecting line 54, to the motor 55(a) of a motorized valve 55 at the base of the vessel 45, opening or closing that valve to remove sludge consisting of water and solids, to a collecting vessel 56. This sludge has been substantially de-watered by gravity separation and is recycled to the feed hopper 16 for reprocessing in the retort.
At a substantially higher level where the vessel contains water and settling solids, a water outlet pipe 57 is provided shielded by an inclined baffle 58 to deflect solids away from the outlet. This water is pumped by a pump 59 through a heat exchanger 60 comprised of an inner tube 61 through which cooling water is circulated from pipe 63 at the top to pipe 64 at the bottom. The cooled water thence goes to the nozzle 46 through pipe 47 as previously noted.
The gas fraction is removed from the top of the vessel 45 through a pipe 65 and a filter 66 by means of a pump 67, and is thence returned through pipe 43 to the gas burner 26 shown in FIG. 1. The pyrolysis oil fraction overflowing through pipe 48 to a surge tank 68, from which it is periodically removed by opening valve 69.
Briefly summarizing the process results of the system as illustrated in FIGS. 1 and 2, the input consists of raw, shredded municipal waste plus the sludge recycled from the vessel 45, supplied at the feed hopper 16, and further the input consists of combustion air taken from the atmosphere by the blower 41. The net output from the system consists of (1) pyrolysis oil recovered in vessel 68, (2) the gas vented to the atmosphere through the duct 37, and (3) molten slag tapped from the furnace through duct 25. The char and gas pyrolysis components are consumed in the furnace 22 to generate th heat required for pyrolysis in retort 10 and condensation-prevention in jacket 35 of the duct 21 for gas and vapor transmission to jet condenser 44.
From the standpoint of achieving an economic heat balance, this result is effected by recycling the heating gas from the retort 10 through the jackets mentioned above, combined with the sealing of the retort and furnace by the inlet-plugging action of the rams 17 and 17(a), and with the pre-heating of combustion air by heat exchange with the vented gas in the heat exchanger 38, 39. Thus the heating value retained by the 1100° F. gas leaving the retort jacket 12 is conserved, and the relatively low B.T.U. content of the char and pyrolysis gas produced in the retort is adequate for the process except during the start-up step thereof. In some cases there may be an excess of pyrolysis gas over the amount consumed in the furnace. This excess may be used to power auxiliary operations such as the shredding of municipal waste for pyrolysis, or supplied to a gas distributing facility.
FIGS. 3 and 4 illustrate a preferred construction of the apparatus at the retort feed end of the embodiment of my invention generally shown in FIG. 1. FIG. 3 is a vertical cross-section at the center line of the retort 10 and feed hopper 16. Adjacent the rear of hopper 16 and slightly above the bottom thereof, 16(a) is attached to sleeve 16(b) through which the ram 17 slides in its forward and reverse movement. At the forward end of the feed hopper bottom 16(a) a tubular nozzle 70 extends between a pair of horizontal channels 71 and 72 through the end closure of the retort, into the end of the retort tube 11. The outside of the nozzle 70 constitutes the inlet end support for the tube 11 which does not extend all the way to the end of the jacket 12, but has a sliding fit on the outer end of the nozzle 70, to compensate for variation in the length of the tube 11 and jacket 12 due to thermal expansion and contraction of these components. The ends of the nozzle 70 taper inwardly to an inside diameter somewhat greater than the outside diameter of the ram 17, and the nozzle is retained in its position between the channels 71, 72 by bolts 70(a) through the channel webs and screwed into threaded holes in the nozzle 70 on opposite sides thereof.
The cylinder 19 is anchored at its end to the center of a horizontal H-beam 73, to which the flange of the cylinder 19 is bolted. This beam 73 is parallel to the channels 71, 72 and the beam and channels are shown in FIG. 3 supported by four posts 74, illustrated as structural steel angles. The thrust of the piston 17 forcing a slug of material into and through the nozzle 70 is countered by reaction at the center of the beam 73 and the channels 71, 72 (which together form a beam), which is transmitted to the tension members 75 connected between the ends of the beams by the top ends of the angles 74.
The details of the supporting structure illustrated particularly in FIG. 3 are disclosed only by way of example and may be varied to suit other designs; the important point is that the maximum live load produced by the feed operation is the force produced by the operation of the ram 17 in forward movement. Retraction of the ram is resisted by friction only and results in an opposite reaction at the ends of 71, 72 and 73, for which a pair of struts (not shown in FIG. 3) between the posts 74 on opposite sides, may be provided.
FIG. 3 shows the applicant's preferred construction of the retort jacket 12. The inside wall 76, spaced from the tube 11, is made of pre-cast refractory material. Around this is a layer of mineral fiber insulation 77, and the outside consists of sections of metal casing 78, which terminates at the feed end in a closure end plate 79 fastened to the adjacent flanges of channels 71 and 72 and having a central opening for the nozzle 70. At the feed end the duct 30 connects to the jacket, the inner wall being refractory blocks 76(a) surrounded by mineral fiber insulation 77(a) and encased in a metal wall 78(a).
FIG. 5 illustrates in greater detail the discharge end of the retort 10, the char chute 20, and the transfer of char from the bottom of the chute 20 into the furnace 22. The spiral flights of the retort screw 13 terminate at the entrance side wall 20(a) of the char chute but the screw shaft extends through the end plate 79(a) and a packing nut 80 to one side of a shaft coupling 81. Drive shaft 82, which corresponds in function to shaft 14 in FIG. 1, connects to the opposite side of the coupling 81. This shaft 82 is rotatably mounted on a pair of bearing blocks 83 between which a sprocket 84 is mounted. The sprocket 84 is driven by a roller chain 85 from sprocket 86 on a countershaft 87. Also mounted on the countershaft 87 is a V-belt pulley 88 driven by belt 89 from a V-belt pulley 90 on a gear motor 15. The bearings and supports for the countershaft 87 are not illustrated in FIG. 5, such structure being well known in the art.
Vapor and gas duct 21 enters the top housing of the char chute 20 and the retort jacket 12 connects to the jacket 35 surrounding the duct in that top housing, the refractory wall 76 and mineral fiber insulation 77 extending into the housing for this purpose. As illustrated in FIG. 5, this refractory and insulating material further extends adjacent the outside metal casing of the top housing of the chute, thus isolating the interior from radiation to the outside atmosphere.
The separated char at the bottom of the chute 20 is injected in slugs into the furnace 22 through a nozzle 70(a) by the intermittent thrusts of the ram 17(a) substantially as described in connection with feeding raw material to the retort. The nozzle 70(a), however, does not enter furnace like the nozzle 70 enters the retort, but abuts against the outside furnace wall at the tapered furnace inlet-opening block 91. This is a cast refractory block having a tapered opening 92 therethrough, the diameter of which at the inlet side corresponds to the inside diameter of the nozzle 70(a). On the outside furnace wall, and centered about the axis of the tapered opening 92, is mounted a circular hot air distributing duct 93, from which a plurality of air injection pipes 94 extend (generally radially inward as viewed in FIG. 6) and project through the block 91 to the face of the tapered opening 92. The orientation of the pipes 94 through the block 91 directs jets of air towards the point P in FIG. 5, at the inside furnace wall and on the axis of the tapered opening 92. These jets strike and mix with the entering hot char, facilitating the prompt burning thereof. Hot air is supplied under pressure to the circular duct 93 by pipe 23, as described previously with reference to FIG. 1.
In FIG. 1, the auxiliary gas burner 26 is shown on the same side of the furnace 22 as the char combustion inlet. This was partly for simplicity of illustration diagrammatically, but it may be noted that this arrangement is optional, and does not appear in FIG. 5. In that embodiment of this invention the auxiliary gas burner is mounted on an adjacent side of the furnace 22, at approximately the center of the combustion zone, as illustrated in FIG. 7 which is a vertical cross-section taken at the combustion zone center. The molten slag duct 25 in this embodiment is provided on the opposite side of the furnace and the gas burner is directed downwardly towards the entrance of the duct 25 to insure that the ash is melted to liquid slag for tapping through the duct 25.
FIG. 7 is viewed in a direction facing the furnace baffle 27 there illustrated as constructed of refractory brick. An opening 27(a) adjacent the furnace floor is shown in FIGS. 5 and 7 for flow of slag from the furnace behind the baffle 27, the furnace floor being downwardly inclined towards the center of the combustion zone as illustrated in FIG. 5 to facilitate flow towards the duct 25. In FIG. 7, this duct is shown as formed in a pre-cast refractory tap-out block 25(a), the gas burner 26 is similarly formed of a pre-cast refractory block with a gas nozzle within a combustion air casing mounted thereon, and supplied respectively, with pyrolysis gas and combustion air by the ducts 43 and 23 as explained heretofore.
FIG. 8 illustrates a preferred construction of the apparatus provided for hot gas circulation from the furnace 22 to jacket 12 of the retort 10, as generally disclosed with reference to FIG. 1. Hot gas from the furnace through the duct 24 enters the ejector 32 near the bottom of the lower cylindrical section of the nozzle housing 95. Above the cylindrical section of 95 is a frustro-conical top section. Nozzle pipe 96 extends axially through the cylindrical section of housing 95, terminated by a nozzle 31 within the frustro-conical section, and ejects therein a jet of hot air delivered from the retort jacket 12 by the fan 29 (see FIG. 1) through duct 30(a), which duct connects to the nozzle pipe 96. Above the bottom housing 95 is shown an expansion section 97, tapering from the small diameter bottom inlet to a larger diameter top outlet. This ejector construction, as well known in the art, sucks hot gas from the furnace and delivers that hot gas through duct 98 to the entrance opening 99 of the housing section 100 enclosing the gas-vapor duct 21 at the end of the jacket 35, thus delivering the heated gas to that jacket 35. As previously explained, this jacket 35 delivers that heated gas to jacket 12 of the retort 10. To regulate the pressure drop between the ejector nozzle 31 and the outlet of the expansion section 87, a by-pass 33 is provided, having a damper 34 therein to throttle the flow through 33.
The ejector housing 96 and the expansion nozzle 97 are constructed of pre-cast refractory blocks and have mineral fiber insulation adjacent the metal outside sheet metal casing, as heretofore mentioned with reference to FIG. 1.
Instrumentation for controlling the variable stroke of a ram 17 reciprocated by a cylinder 19 is diagrammatically illustrated in FIG. 9. An arm 101 extends laterally from the piston rod 18, which arm terminates in a collar 102. This collar 102 loosely surrounds a shift-shaft 103, which is shiftably supported by slide guides 104 mounted on the support framework. To one end of the shift-shaft 103 is attached a tapered collar 105, the tapered rim of which is in registry with the yoke of the reversing arm of a rotary pilot valve 106. Between the slide guides 104 a pair of spaced-apart collars 107(a) and 107(b) are adjustably secured; the former, 107(a) being shifted directly by the collar 102 of the arm 101 on the reverse stroke of the ram, and the latter, 107(b), being shifted by one end of a spacer 108 on the forward ram stroke when the collar 102 engages the opposite end.
The spacer 108 may be yoke shaped in cross-section as shown in FIG. 10 and a supply of several of these of different length are stocked for selection to place on the shift-shaft 103 between the collars 102 and 107(b). It is apparent from FIG. 9 that, since the result of shifting shaft 103 by collar 107(b) reverses the pilot valve 106 on the forward stroke of the ram 17, that the difference between the spacing of the collars 107(a) and 107(b) and the length of the selected spacer 108 determines the forward thrust distance of the ram 17. For the maximum ram stroke, no spacer 108 is placed on the shift-shaft, and the collar 102 contacts the collar 107(b) directly at the end of the stroke.
Reversal of pilot valve 106 effects reversal of a pilot-operated valve 109, the pilot operating cylinders 109(a) and 109(b) of which are connected to the rotary pilot valve as diagrammatically illustrated in FIG. 9. These valves are commercial items and it is unnecessary here to describe their internal structures, it being sufficient to note that shifting of the collar 105 to the right as seen in FIG. 9 operates the valve 109 at the end of the forward stroke, terminating oil flow under pressure through pipe 110 to rear end of the cylinder 19 and delivering it through pipe 111 to the forward end thereof to initiate retraction of the ram 17. A flow control valve 112 is shown in the pipe 111 to meter the rate of ram retraction to a desired, predetermined, speed. Hydraulic oil supplied from reservoir 113 is delivered to the valve 109 by pump 114 and conduit 115, and returned to the reservoir by conduit 116. Similar means, not illustrated in FIG. 9, supply oil at suitable pressure to the rotary pilot valve 106. In lieu of hydraulic piloting, as well known in the art, other controls may be substituted such as electrically operated pilot and reversing valves, and a reversing electrical limit switch reversed by the collar 105.
This invention is not limited to hydraulic cylinder operation of the ram, however; suitable mechanical drives, such as rack-and-pinion, eccentric cam, worm-screw, etc., may be alternately used. The applicant has designed and tested a worm-screw ram drive and one such arrangement is schematically illustrated in FIGS. 11, 12 and 13, which will next be described.
FIG. 11 is a plan view of this device, in which the sleeve 16(b) and adjacent hopper side wall and the ram driving worm-screw and nut structure are shown in cross-section. The ram, item 117 in FIG. 10, connects to the forward end of a driving worm-screw 118 by a coupling sleeve 128 (see FIG. 12) from which a stabilizing bar 128(a) extends laterally. The end of the bar 128(a) glides between the flanges of a channel bar 129 supported parallel to the ram and screw on the supporting frame member 130 (see FIG. 13). The worm-screw 118, thus held from rotating, is propelled by a nut and sprocket structure 119, rotatably supported by a pair of rotary and thrust bearings 120 and further by a thrust bearing 121 which carries the burden of thrust on the forward ram stroke. The outer races of these bearings are mounted in a fixed position on the supporting framework, a detail not shown in the drawings for simplicity of illustration. The nut 119 is threaded axially to engage the threads of the worm-screw 118 and has a sprocket portion 119(a) driven from an adjacent sprocket 112 through a chain 123. In FIG. 11 the sprocket 122 is shown mounted at the center of a shaft rotatably supported on bearings 124 and terminating at each end in clutches 125. Hydraulic motors 126 and 127, rotating in opposite directions, are selectably connected by operation of the clutches 125, disconnecting one motor and connecting the other simultaneously. The hydraulic motor 126 turns the nut 119 in the direction to propel the ram 117 forward; 127 turns it in the direction to retract the ram. Since less power is required to retract the ram than to propel it forwardly, the motor 127 need not be as powerful as motor 126, and 127 is preferably instrumented to rotate at a constant, predetermined speed, not illustrated in the drawings as such instrumentation is well known in the art.
Also, for simplicity of illustration, mechanism for shifting the clutches 125 is not included in FIG. 11. It is deemed obvious to the reader that, for example, the arm 128(a) may be provided with a collar similar to item 102 in FIG. 8, slideable on a shaft similar to item 103, and that a valve similar to item 106 may be connected to opposite ends of an auxiliary hydraulic cylinder the piston of which throws the clutches 125 simultaneously by suitable mechanical connections thereto.
In the foregoing specifications and the following claims, the word "screw" (item 13) is to be construed in the broad connotation as used in the material conveying art, comprehending screw conveyors having a variety of flight constructions such as helicoid, cut flights, paddles, ribbon flights, etc., which may be varied if desired in different zones of the pyrolysis retort. Also, the word "furnace" (item 22) comprehends a variety of well known constructions, such as, for example, cyclone furnaces, without limitation to the rectangular structure specifically described and illustrated. | This disclosure is directed to an economical system for the pyrolysis of municipal solid waste to recover valuable by-products while reducing the putrefaction and bulk of the residue requiring disposal. Prior to this treatment, the solid waste has been processed to remove most of the metallic components, and shredded, which steps are not part of the invention disclosed. The pyrolysis and by-product recovery technology is complicated by (a) the inherent variability of the chemical and physical characteristics of the shredded solid waste as received at the pyrolysis plant and (b) the relatively low heat value of said waste as thus received. This pyrolysis and product recovery system includes an improved pyrolysis retort indirectly heated principally by combustion of the least desirable by-product, the solid char, in combination with a furnace for the char combustion, a condenser for the pyrolysis vapor including means for gravity separation of the gas, liquid and solid residues entrained therein, and improved means for conveying the materials through the system including intermittently driven rams for delivering solids into the retort and furnace. | 2 |
CROSS REFERENCE TO RELATED APPLICATION
This application is a division of U.S. patent application Ser. No. 10/346,783, filed Jan. 17, 2003, now U.S. Pat. No. 7,413,703, and entitled “METHODS FOR PRODUCING AGGLOMERATES OF METAL POWDERS AND ARTICLES INCORPORATING THE AGGLOMERATES.” The aforementioned related application is hereby incorporated herein by reference.
BACKGROUND OF THE INVENTION
This invention generally relates to a process for producing agglomerates of metal powders. More particularly, this invention is directed to a process for producing rigid, porous, binder free agglomerates of metal powders. This invention is also directed to devices that include the rigid, binder free agglomerates.
Fine metal powders are used in a wide variety of devices to enable desirable chemical reactions. For example, catalysts are incorporated in the catalytic converts of vehicles powered by combustion engines. The catalyst facilitates the conversion of potentially harmful fumes to environmentally acceptable gases or liquids. In another example, metal powders are used to store gases, such as hydrogen, in a solid matrix to minimize the hazards associated with the storage and transport of hydrogen as a compressed gas. Fine metal powders are also used in batteries and fuel cells. Commercially available batteries, including both rechargeable and non-rechargeable batteries, are used to power portable devices such as flashlights, cameras and tape recorders. One chemical system used to produce rechargeable batteries incorporates a finely divided metal hydride in one of the electrodes. Another chemical system, typically used to manufacture non-rechargeable batteries, also known as primary batteries, uses an alkaline electrolyte, manganese dioxide as the active cathode material and zinc as the active anode material. The zinc is usually disposed within the central region of the battery as part of a gel. Prior to incorporating the zinc into the battery, the zinc is comminuted so that a quantity of zinc powder with a majority of particles ranging from 25 microns to 500 microns is obtained. The individual particles are suspended in the anode gel which prevents settling of the zinc particles within the battery.
One of the long-standing objectives of battery manufacturers is to produce batteries with the ability to power a device for longer and longer periods of time. The need to improve the battery's performance is especially acute in devices that require large currents. As disclosed in JP Kokai 57[1982]-182972, the high discharge characteristic of a battery can be improved by incorporating 5-30 weight percent of the zinc as particles with a particle size of 25 microns or smaller. Unfortunately, as the percentage of particles that are 25 microns or smaller increases, the viscosity of the anode may become too high to process in high speed manufacturing machines. One way to overcome this problem is to process all of the zinc particles into a single porous body. For example, U.S. Pat. No. 2,480,839 discloses an anode made of zinc powder or particles that have been compressed under sufficient pressure to agglomerate the particles into a coherent body shaped as a hollow cylinder. In another example, U.S. Pat. No. 3,645,793 describes cleaning the zinc powder with a mild acid and then pressing the zinc to form a porous structure. These patents are directed to the production of coherent structures that are suitable for use as an electrode in an electrochemical cell. All of the particles are included in the compaction process and form a part of the compacted electrode. Thus, these processes are not well suited for the production of electrodes that incorporate both agglomerated electrochemically active particles and non-agglomerated electrochemically active particles in the same electrode.
Other methods of handling the finely divided metal powders include the step of utilizing an agglomerant to form the agglomerates. The agglomerant may be a binder that acts as an adhesive to secure particles to one another thereby enabling the formation of the agglomerates. Alternatively, the agglomerant may be a pore former which facilitates the formation of the agglomerate but is then removed from the agglomerate thereby forming pores within the agglomerate. Unfortunately, the use of an agglomerant may have a negative impact on the performance of the agglomerated powder. For example, if a battery includes an electrode that uses agglomerates of electrochemically active material that incorporate an organic binder, such as polyvinyl alcohol (PVA), then the particles are inherently coated with the electrically nonconductive PVA. The coating increases the internal resistance of the electrode that includes the coated, agglomerated particles. As the electrode's internal resistance increases, the battery's run time decreases. Furthermore, there are potential problems associated with the cost of the binder as well as the volume of space occupied by the binder. As the volume of space dedicated to the binder increases, the quantity of electrochemically active material must be decreased to make room for the binder. As the quantity of active material is decreased, the cell's run time is reduced.
Therefore, there exists a need for a process that produces small, rigid, binder free agglomerates that do not compromise the performance of the agglomerated particles. The process should not require the use of an additive, such as a binder or pore former, to enable production of the agglomerates.
BRIEF SUMMARY OF THE INVENTION
The process of the present invention produces rigid, binder free agglomerates that are appropriately sized for mixing with non-agglomerated particles to produce a flowable mixture.
In one embodiment, this invention is a process that includes the steps of providing an electrochemically active material in comminuted form and then forming rigid, binder free agglomerates that consist essentially of the electrochemically active material.
In another embodiment, this invention is an electrochemical cell that includes an electrode that incorporates the rigid, binder free agglomerates that consist essentially of the electrochemically active material.
In another embodiment, this invention is a hydrogen storage vessel that incorporates the rigid, binder free agglomerates.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows steps in one embodiment of a process of this invention;
FIG. 2 is a cross section of an electrochemical cell of this invention that includes rigid, binder free agglomerates made by the process shown in FIG. 1 ;
FIG. 3 is a schematic drawing of a roll compactor and granulation process;
FIG. 4 shows a line chart of internal resistance data;
FIG. 5 shows a line chart of internal resistance data;
FIG. 6 shows a bar chart of cell service data;
FIG. 7 is a scanning electron micrograph of zinc powder agglomerates;
FIG. 8 is a scanning electron micrograph of zinc powder agglomerates; and
FIG. 9 is a scanning electron micrograph of zinc powder agglomerates.
DETAILED DESCRIPTION OF THE INVENTION
The following terms and phrases are defined for use herein.
The phrase “rigid, binder free agglomerate,” means an assemblage of particles which are rigidly joined together without the use of a binder. Therefore, each particle is physically secured to at least one other particle in the rigid, binder free agglomerate. Particles that are in close proximity to one another but are not associated via a physical connection are not considered to form a rigid, binder free agglomerate.
The term “agglomerated particles” means two or more particles that form an agglomerate.
The term “non-agglomerated particles” means two or more particles that are not physically associated with each other.
Referring now to the drawings and more particularly to FIG. 1 , there is shown a chart of process steps including both required and optional steps. Step 10 involves providing a quantity of electrochemically active material in comminuted form. In a preferred embodiment, the active material is zinc powder that has been produced by air atomization or centrifugal atomization of molten zinc. The majority of the zinc particles typically range in size from 25 microns to 500 microns. In step 12 , the particles may be sorted based on size, shape or some other characteristic before continuing with the processing of the comminuted powder. In step 14 , the comminuted powder is formed into porous, rigid, binder free agglomerates that consist essentially of the electrochemically active material. Preferably the electrochemically active material accounts for one hundred percent, by weight, of the binder free, rigid agglomerates. However, due the existence of impurities in commercial manufacturing processes, minute amounts of foreign material may unintentionally become incorporated into some of the rigid, binder free agglomerates during the manufacturing process. Preferably the contaminants would account for less than one percent, by weight, of the rigid agglomerates. More preferably, the contaminants would account for less than one-tenth of one percent, by weight, of the rigid agglomerates. Most preferably, the contaminants would account for less than one-hundredth of one percent, by weight, of the rigid agglomerates.
The rigid, binder free agglomerates formed in step 14 may be manufactured to the desired density and size by adjusting process parameters in a manufacturing process, such as, a compaction process, a direct fusing process or an induction heating process. However, if the rigid agglomerates are larger than desired, they may be granulated, as represented by step 16 , to reduce the size of the rigid agglomerates. Granulation may be accomplished, for example, in a machine that incorporates blades and/or beater bars to fragment the original rigid agglomerates into smaller rigid agglomerates. If desired, the fractured rigid agglomerates may then be sorted, as represented by step 18 , to generate rigid agglomerates having the desired size. The sorting may be accomplished by sieving the agglomerates. The agglomerates may also be annealed as represented by step 20 .
An electrochemically active material that is useful in a process of this invention is zinc or a zinc alloy that incorporates one or more of the following elements: indium, bismuth, aluminum, magnesium or lead. A suitable zinc alloy contains 100 ppm of bismuth, 200 ppm of indium and 100 ppm of aluminum. Comminuted zinc alloys that are suitable for use in electrochemical cells may be purchased from Umicore (Belgium), Noranda (Canada), Big River Zinc (United States) and Mitsui (Japan). The particles may be shaped as: flakes, as disclosed in U.S. Pat. No. 6,022,639; spherical particles, as disclosed in U.S. Pat. No. 4,606,869; various other shapes as disclosed in WO 98/50,969; or irregularly shaped.
As represented by step 12 in FIG. 1 , prior to forming the porous, rigid, binder free agglomerates, the comminuted active material may be processed to isolate particles within a desirable size range. A screening process that uses a single mesh screen, such as a 200 mesh screen, is a suitable means for sorting the particles. Alternately, a two mesh screen screening process may be used. For example, the comminuted active material may be processed by selecting only those particles that will flow through a 40 mesh screen but will not flow through a 325 mesh screen. The porosity of the rigid agglomerate can be influenced by selecting particles within a specified range. A preferred range of particle sizes is 25 microns to 70 microns. A more preferred range of particle sizes is 25 microns to 50 microns.
The step of forming rigid, binder free agglomerates from the comminuted electrochemically active material can be accomplished using a variety of manufacturing processes. In a preferred embodiment, the step of forming the agglomerates utilizes a compaction process. Suitable means for forming the comminuted material into rigid, binder free agglomerates includes a roll compactor or a high pressure extruder. In addition to relying upon pressure to form the particles into agglomerates, various forms of energy may also be used with the pressure to cause the particles to become agglomerated. For example, in addition to the use of pressure, the particles may be made to directly fuse with one another by contacting some of the particles with an ultrasonic welder thereby causing some of the particles to vibrate against adjoining particles. The vibration results in the generation of sufficient heat to cause localized welding of particles to one another. Induction heating may be used instead of an ultrasonic welder to effect direct fusing of the particles.
As represented by step 20 in FIG. 1 , the agglomerates of electrochemically active material may be annealed. The annealing is accomplished by heating the agglomerates to a temperature sufficient to release the stress created in the agglomerate during the process used to generate the agglomerates. For many comminuted metal powders, such as zinc, the agglomerated zinc must be heated to a temperature above 100° C. but well below the melting point of zinc. Preferably, the temperature of the agglomerate would not exceed 200° C.
Referring to FIG. 3 , forming of the agglomerates by compaction of the particles can be accomplished by feeding a quantity of comminuted particles into the gap between opposing rolls in roll compactor 30 . Compactor 30 includes a powder storage hopper 32 , a first screw conveyor 34 which is a horizontal screw, a second screw conveyor 36 which is a vertical screw, a first roller 38 and a second roller 40 . First roller 38 rotates in a clockwise direction, as indicated by arrow A, while second roller 40 rotates in a counterclockwise direction, as indicated by arrow B. Rollers 38 and 40 may be made of hardened steel. The gap (not shown) between rollers 38 and 40 is one of the variables that may be adjusted to form agglomerates with the desired porosity. The surface of rollers 38 and 40 may be modified to increase the coefficient of friction between the roller and the comminuted material. In a preferred embodiment, the surface of both rollers is coated with a ceramic layer to improve the coefficient of friction between the rollers and the zinc particles. Alternatively, the surface of the rollers may be sand blasted to improve their ability to grip the comminuted material and force it through the gap between the rollers.
Located beneath roll compactor 30 is granulator 42 which includes screen 46 . As the comminuted powder 48 in hopper 32 is fed to and through the gap between rollers 38 and 40 , the powder is formed into thin agglomerated strips 50 that are too long for use in an electrode of a cylindrical AA alkaline electrochemical cell that measures approximately 50 mm high and 14 mm in diameter. Strips 50 are made to collide with beater bar assembly 44 which fragments the pellets into smaller rigid agglomerates 52 . The openings in sieving screen 46 allow a portion of the fragmented rigid agglomerates to pass through the screen and accumulate in catch basin 54 . If desired, the accumulated agglomerates may be processed through additional granulation and screening machinery until rigid, binder free agglomerates within a desired size range are obtained. Preferably, the rigid, binder free agglomerates will pass through a 40 mesh screen. If desired, the agglomerates that pass through a 325 mesh screen may be eliminated.
In addition to the size of the agglomerate, the tap density of the rigid, binder free agglomerates is one of the characteristics that can be used to identify agglomerates that are suitable for use in electrochemical cells. Preferably, the tap density of the agglomerates is less than 2.95 g/cc. More preferably, the tap density is less than 2.85 g/cc. Even more preferably, the tap density is less than 2.60 g/cc. Most preferably, the tap density is less than 2.40 g/cc. Tap density is measured using the following procedure. First, dispense fifty grams of the binder free zinc agglomerates into a fifty milliliter graduated cylinder. Second, secure the graduated cylinder containing the zinc agglomerates onto a tap density analyzer such as a model AT-2 “Auto Tap” tap density analyzer made by Quanta Chrome Corp. of Boynton Beach, Fla., U.S.A. Third, set the tap density analyzer to tap five hundred and twenty times. Fourth, allow the tap density analyzer to run thereby tapping the graduated cylinder by rapidly displacing the graduated cylinder in the vertical direction five hundred and twenty times. Fifth, read the final volume of agglomerated zinc in the graduated cylinder. Sixth, determine the tap density of the agglomerates by dividing the weight of the agglomerates by the volume occupied by the agglomerates after tapping.
Compaction of comminuted electrochemically active material to form rigid, binder free agglomerates is a preferred manufacturing process because a large quantity of agglomerates can be generated quickly and inexpensively. Shown in FIG. 7 is a scanning electron micrograph (SEM) of agglomerated zinc particles. The agglomerates were produced using a roll compaction process that did not utilize additional energy input during the production process. Despite the compaction, the individual particles of zinc are readily distinguishable components of the agglomerates. The agglomerates are highly porous structures that are capable of storing a liquid, such as the electrolyte in an electrochemical cell, within the agglomerate. The agglomerates were formed without using a binder or pore former. Consequently, the surfaces of the particles are not coated and the voids between particles are not plugged with a binder that could inhibit the electrochemical performance of the zinc particles.
Other processes, referred to herein as direct fusing processes, can also be used to produce rigid, binder free agglomerates. One fusing process uses ultrasonic energy to fuse particles of the electrochemically active material to one another until binder free, rigid agglomerates with the desired tap density and size are obtained. Shown in FIG. 8 is an SEM of zinc agglomerates formed using ultrasonic energy. The agglomerates were formed without the use of a binder or other agglomerant. The size and shape of the individual particles are not distorted by the use of ultrasonic energy to fuse individual particles to one another. The agglomerates are highly porous structures capable of trapping and retaining liquid within the pores of the agglomerate.
Shown in FIG. 9 is an SEM of zinc particles formed using both compaction and ultrasonic energy. The individual particles of zinc were compressed during the compaction process thereby eliminating many of the voids between the particles.
Referring now to FIG. 2 , there is shown a cross-sectional view of an electrochemical cell. Beginning with the exterior of the cell, the cell's components are the container 60 , first electrode 62 positioned adjacent the interior surface of container 60 , separator 64 contacting the interior surface 66 of first electrode 62 , second electrode 68 disposed within the cavity defined by separator 64 and closure member 70 which is secured to container 60 . Container 60 has an open end 72 , a closed end 74 and a sidewall 76 therebetween. The closed end 74 , sidewall 76 and closure member 70 define a volume in which the cell's electrodes and electrolyte are housed. A quantity of electrolyte, such as a thirty-seven percent by weight aqueous solution of potassium hydroxide, is placed in contact with the first electrode 62 , second electrode 68 and separator 64 .
First electrode 62 includes manganese dioxide as the electrochemically active material and an electrically conductive component, such as graphite. Additives, such as Teflon® and polyethylene, may be added to the flowable dry mixture of manganese dioxide and graphite. The mixture is molded against the interior surface 78 of container 60 thereby forming a cylinder. Separator 64 is inserted into the cylinder defined by first electrode 62 thereby providing an electrically nonconductive, ionically permeable layer on the interior surface of first electrode 62 .
Second electrode 68 includes an electrochemically active component, such as zinc particles, a gelling agent and an aqueous based alkaline electrolyte. A suitable gelling agent is a crosslinked polyacrylic acid, such as Carbopol 940®, which is available from Noveon of Cleveland, Ohio, U.S.A. Carboxymethylcellulose, polyacrylanide and sodium polyacrylate are examples of other gelling agents that are suitable for use in an alkaline electrolyte solution. The aqueous based alkaline electrolyte includes thirty-six percent, by weight, potassium hydroxide, three percent, by weight, zinc oxide, and three-tenths of one percent, by weight, sodium silicate. The remainder of the solution is water. An aqueous based alkaline solution of 0.1 N potassium hydroxide is incorporated into the second electrode's manufacturing process. Other additives, such as organic and/or inorganic corrosion inhibitors, may also be included in the second electrode. Indium hydroxide is an example of a suitable inorganic corrosion inhibitor. The second electrode's components are blended to form a flowable gel. The zinc particles typically account for 63% to 72% by weight of the second electrode which may also be referred to herein as the anode.
Closure member 70 is secured to the open end of container 60 thereby sealing the electrochemically active ingredients within the cell. The closure member includes a seal member 80 and a current collector 82 . In other embodiments, the seal body could be a ring shaped gasket. The seal member includes a vent that will allow the seal member to rupture if the cell's internal pressure becomes excessive. The seal member may be made from Nylon 6,6 or another material, such as a metal, provided the current collector is electrically insulated from the container which serves as the current collector for the first electrode. Current collector 82 is an elongated nail shaped component made of brass. The collector is inserted through a centrally located hole in the seal member.
To demonstrate the advantages made possible by the process of this invention, conventional zinc powder was processed according to the following description and then used to manufacture electrochemical cells. The cells were then characterized by discharging them on a service test to determine the cells' run time. The internal resistance of representative cells was also measured. The data shown in FIG. 4 and FIG. 5 provide evidence that the cells made with rigid, binder free agglomerates of zinc in the cell's anode had a lower internal resistance during the discharge of the cells than did the comparable control cells which had an equivalent quantity of electrochemically active material that did not include any rigid, binder free agglomerates of zinc. Furthermore, as shown in FIG. 6 , the cells comprising the rigid, binder free, zinc agglomerates had significantly longer run times than did the cells with an equivalent quantity of electrochemically active material that did not include any rigid, binder free agglomerates of zinc.
In one trial, anodes for cells of the present invention were prepared as follows. First, a quantity of zinc alloy, in particulate form, was provided. The zinc alloy included 100 ppm of bismuth, 200 ppm of indium and 100 ppm of aluminum. The zinc powder was sieved by disposing the particles on a mesh screen with multiple openings and then vibrating the particles across the screen so that particles smaller than the openings would pass through the screen and particles larger than openings would not pass through the screen. The screen was constructed so that each opening had the same dimensions as every other opening in the screen. The zinc powder was sieved so that the particles smaller than 70 microns and larger than 25 microns were collected in a first portion of powder. Particles larger than 70 microns were collected in a second portion of powder. Only the first portion of powder was then fed through a roll mill compactor and granulator as depicted in FIG. 3 . A suitable roll compactor and granulator may be purchased from the Fitzpatrick Company of Elmhurst, Ill., U.S.A. In this trial, the compactor's rollers were made from 316 stainless steel and had a roll surface finish, prior to the application of a ceramic coating, of 32-62 RA. The ceramic coating had a thickness of 0.13 mm to 0.18 mm and a hardness of 72 Rockwell C. The roller's speed was three revolutions per minute. The roll pressure was 2,260 pounds per linear inch. The speed of the horizontal screw was 16 RPM, and the speed of the vertical screw was 175 RPM. The gap between the rollers was set at 0.254 mm.
After passing through the roll compactor, the comminuted particles were formed into strips of agglomerated particles that were fed into a granulator that fractured the strip into smaller granules of agglomerated particles. The speed of the granulator's rotor was 1000 RPM. The opening in the granulator's screen was 1.27 mm. The agglomerates that passed through the granulator's screen were then sorted using a 40 mesh, US standard, screen. The openings in a 40 mesh screen allow only agglomerates smaller than 420 microns to flow through the screen. The screening process generated a first distribution of agglomerates that flowed through the 40 mesh screen and a second distribution of agglomerates that did not flow through the 40 mesh screen. The rigid, binder free agglomerates in the first distribution had a tap density of 2.83 g/cc and the size of the agglomerates was between 150 microns and 300 microns. The following anode mixes were then prepared with only the first distribution of agglomerates. The quantities of the anode components are in percent by weight.
Lot Number
Anode Component
1
2
3
4
5
Zinc
Agglomerated
—
68.00
34.00
17.00
8.50
Non-agglomerated
68.00
—
34.00
51.00
59.50
Gelling Agent
0.44
0.44
0.44
0.44
0.44
36% KOH Electrolyte
30.20
30.20
30.20
30.20
30.20
w/ZnO and sodium
silicate
0.1 N KOH
1.36
1.36
1.36
1.36
1.36
TOTAL
100.00
100.00
100.00
100.00
100.00
AA size batteries were then made with each of the anode mixes. Within all five lots, all of the cell components except for the anode mixes were identical.
FIG. 6 shows the run times for cells from all five lots that were discharged per the following test regime. Each cell was “pulse” tested by individually discharging the cell at a rate of one amp for sixty seconds and then allowing the cell to rest for five seconds before the next pulse was begun. Each “sixty seconds on/five seconds off” cycle was counted as one pulse. The test was continued until the cell's closed circuit voltage fell below a 0.9 volt cutoff. The number of pulses that each cell provided before the cell's closed circuit voltage fell below the voltage cutoff was recorded. Shown in FIG. 6 , in bar chart format, is the data collected from the pulse testings. Lot number one is the “control” lot that incorporated only non-agglomerated zinc particles in the anode. The average number of pulses provided by the cells in lot one was defined as 100% for the purpose of creating a numerical performance standard against which the other lots could be normalized. The cells in lot number two contained only agglomerated zinc particles. In lot number three, one-half of the zinc, by weight, had been agglomerated and the other half had not been agglomerated. In lot number four, one-fourth of the zinc in each cell had been agglomerated and three-fourths was non-agglomerated. In lot number five, one-eighth of the zinc in each cell had been agglomerated and seven-eighths of the zinc had not been agglomerated. The data in FIG. 6 demonstrates that the electrochemical cells, in which at least a portion of the zinc was agglomerated into rigid, binder free agglomerates, provided approximately 12% to 23% more run time than comparable cells that contained only non-agglomerated zinc. Furthermore, the cells that contained no more than one-half of their zinc in the form of rigid, binder free agglomerates provided more service than cells that contained all of their zinc in the form of rigid, binder free agglomerates. Thus, the advantage of incorporating rigid, binder free agglomerates of zinc into the anode of alkaline electrochemical cells has been demonstrated.
In another trial, a quantity of comminuted zinc particles was agglomerated in a process similar to the previously described process used to produce agglomerates for lots two through five, except that the size of the agglomerates was limited to less than 825 microns but more than 250 microns for lot six and less than 250 microns but more than 100 microns for lot seven. Three lots of AA size cells were made in order to characterize the impact that incorporating rigid, binder free agglomerates of zinc into the anode would have on the cell's internal resistance during discharge on the previously described sixty seconds on/five seconds off, one amp constant current test. The anode formulas used to make the three lots of cells are shown below. The quantities of the anode components are in percent by weight.
Lot Number
Anode Component
6
7
8
Zinc
Agglomerated
70.00
35.00
—
Agglomerate size
250-825 microns-
100-250 microns
—
Non-agglomerated
—
35.00
70.00
Gelling Agent
0.42
0.42
0.42
36% KOH Electrolyte
28.39
28.39
28.39
with zinc oxide and
sodium silicate
Indium Hydroxide
0.02
0.02
0.02
0.1 N KOH
1.17
1.17
1.17
TOTAL
100.00
100.00
100.00
Within all three lots, all of the cells' components except for the anode mixes were identical.
Shown in FIG. 4 are two line graphs which show the changes in internal resistance when cells from lot 6 , represented by line 90 , and lot 8 , represented by line 92 , were discharged on the pulse test. The data clearly shows that the cells in lot six, which incorporated only rigid, binder free agglomerates, had lower voltage drops during discharge than did the comparable cells in lot eight that utilized only non-agglomerated zinc. The lower voltage drop is indicative of a lower internal resistance. As the cell's internal resistance decreases, the cell's run time will increase.
Shown in FIG. 5 are two line graphs which show the changes in internal resistance when cells from lot 7 , represented by line 94 , and lot 8 , represented by line 96 , were discharged on the pulse test. This data clearly shows that cells in lot 7 , which incorporated 50% by weight rigid, binder free zinc agglomerates and 50% by weight non-agglomerated zinc, had lower voltage drops during discharge on the pulse test than did the comparable cells in lot 8 that utilized only non-agglomerated zinc.
The data in FIGS. 4 , 5 and 6 demonstrate that including rigid, binder free agglomerates of zinc in the anode of electrochemical cells improves cell performance by reducing the anode's internal resistance during the discharge of the cell thereby allowing the cell's run time to be increased.
The above description is considered that of the preferred embodiments only. Modifications of the invention will occur to those skilled in the art and to those who make or use the invention. Therefore, it is understood that the embodiments shown in the drawings and described above are merely for illustrative purposes and are not intended to limit the scope of the invention, which is defined by the following claims as interpreted according to the principles of patent law, including the Doctrine of Equivalents. | Processes for making rigid, binder free agglomerates of powdered metal are disclosed. The agglomerates have a low tap density. Articles that contain binder free agglomerates made from electrochemically active powder are also disclosed. | 7 |
TECHNICAL FIELD
[0001] This invention is a kind of dust removal method of gas, which is especially involved in a dry dust removal method in organic chlorosilane production and is used in the methyl chlorosilane synthesis process that uses chloromethane and silicon powder as raw material.
BACKGROUND
[0002] Organic silicon compound is generated when silicon powder reacts with chloromethane with the action of catalyst. Organic silicon is not only a kind of new-style material itself, but also provides a new material base and technical guarantee for the development of relevant industry fields. High development speed is always kept in organic silicon industry, the yield of organic silicon (converting into siloxane) in China was up to 200 kt/a in 2006.
[0003] The gas mixture generated from the reaction of silicon powder and chloromethane with the action of catalyst is a kind of mixture that contains several kinds of silane gas and dusty raw material. It needs to remove dust from gas mixture during the production of organic silicon.
[0004] Currently, dry and wet dust removal equipment is mainly used in organic silicon plant, namely, several sets of serial cyclone separator dust-removal systems and venturi dust-removing system are used to effectively separate solid dust from the gas-phase products in a fluidized bed reactor. The concrete process flow is as follows: gaseous solid-phase reaction occurs between chloromethane and silicon powder in a fluidized bed reactor to generate mixed monomer methyl chlorosilane; the gas phase product generated from the reaction is removed of dust by means of cyclone; the separated solid is discharged into a dust box after being sent into a dust collector; After being separated with cyclone separator, the reaction gas that contains a small amount of dust enters the venture scrubber, where mixed methyl chlorosilane monomer is used as cleaning solution for wet dust removal; the gas that has been removed of dust enters the fractional condenser after passing through a gas evaporator and buffer tank; the cooled product enters degassing column, and finally methyl chlorosilane is obtained.
[0005] Some companies also use the combination of dry bag-type dust collector and water washing to remove the solid-phase dust from gas mixture. However, traditional cyclone dust collector and bag-type dust collector cannot completely remove the small-sized dust from gas mixture, and so it needs to use washing method to further remove dust from gas mixture. As a result, the entire process is complicated, and dust removal by water washing will consume a great amount of industrial water, and wastewater release will impact the environment.
[0006] An organic chlorosilane wet dust removal process has been announced in China's patent number CN1438226A. This process replaces the traditional dry dust removal process with a continuous wet dust removal method that uses organic chlorosilane as a cleaning solution; there are no dust removal steps of cyclone separator or bag-type collector during an entire process. However, the slurry of this dust removal method contains about 60% of organochlorosilane; in this case, it is difficult to extract the solid matter from the scullery, and the consumption of organic chlorosilane is high.
[0007] A kind of dry dust removal method and unit for organic chlorosilane gas is introduced in China's patent number CN101148453A. In this method, the DIA-SCHUMALITH 10-20 porcelain filter element produced by PALL Company is used to remove dust from dust-containing gas mixture, and the purified organosilane gas mixture gets into the next working procedure. DIA-SCHUMALITH 10-20 filter element is formed by way of binding porcelain and carborundum. Large-pored carborundum crystal lattice is used as a rigid and stable structure to support film; the film is the part that really plays filtering role, and is consisted of multi-aluminum andalusite, with thick of 100-200 μm and bore diameter of about 10 μm. However, this method is of terminal-type filtering method, and filter cake tends to accumulate on film surface, this would cause flow to rapidly decrease, and filtration resistance to increase, the frequent backwash for maintaining flow brings very high stress on the strength of film.
SUMMARY
[0008] The purpose for this invention is to provide a kind of dry dust removal method in organic chlorosilane production that has a simple process, high dust-removal efficiency and low environment pollution. In this method, inorganic film cross-flow filter is used to accomplish the separation of solid and gas and to simplify existing process so as to overcome the disadvantages of wet dust removal method such as complicated process and environmental pollution due to wastewater produced in water washing process.
[0009] Technical proposal of this invention: a kind of dry dust removal method in organic chlorosilane production; the concrete steps are as follows:
[0010] A) The high-temperature flue gas generated in a fluidized bed reactor is first delivered to inorganic film cross-flow filter with air compressor to remove dust for the first time.
[0011] B) The concentrated dust gas trapped by inorganic film cross-flow filter in the above-mentioned steps enters the bag filter to remove dust for the second time; the gas mixture purified with the bag filter returns to the inorganic film cross-flow filter via a fan.
[0012] C) The clean gas mixture passing through the inorganic film cross-flow filter enters the condenser for condensation, and then enters rectifying column to separate chloromethane and methyl chlorosilane; chloromethane returns to the fluidized bed reactor to participle in reaction.
[0013] D) The dust trapped by the inorganic film cross-flow filter and bag filter returns to the fluidized bed reactor to participate in reaction.
[0014] The foregoing inorganic film cross-flow filter is consisted of casing, film filtering element, upper figured plate and lower figured plate, of which the upper and lower figured plates are placed in the middle of the casing, and film filtering element is placed between the upper figured plate and lower figured plate; high-temperature flue gas inlet is provided at the top of inorganic film cross-flow filter, and concentrated dust flue gas outlet is provided at the bottom of the filter; clean gas outlet and blowback gas inlet are provided between the upper figured plate and lower figured plate; high-temperature flue gas enters the inorganic film filter for cross-flow filtration via the high-temperature flue gas inlet; the clean gas passing through the inorganic film cross-flow filter is drained out via the clean gas outlet; the concentrated dust gas trapped by the inorganic film filter enters the bag filter via the concentrated dust gas outlet.
[0015] The above-mentioned inorganic film cross-flow filter is provided with the connection of the blowback device; the blowback gas (d) is the clean gas passing through the inorganic film filter and compressed with the clean gas compressor, and enters the inorganic film filter for blowback cleaning via the blowback gas inlet. When film flux is decreased to 40-60% of initial flux, the clean gas at the outlet of the inorganic film filter is automatically used to intermittently blow back the film separator; in this way, the filter cake attached on the film surface falls off and sinks down to the bottom of the separator, thus effectively preventing film pollution.
[0016] The high-temperature flue gas in step A is preferred to flow into the inorganic film cross-flow filter in parallel with film surface; when the gas enters the inorganic film cross-flow filter, the film-crossing pressure is controlled at 0.01 MPa-1 Mpa, and the flow rate on the film surface is 1 m/s-100 m/s.
[0017] The film filtering element as described in the inorganic film cross-flow filter section is preferred to be tubular film made of ceramics and metal material; the mean pore diameter of the film is 0.02 μm˜50 μm, and the diameter of film channel is 3-100 mm.
[0018] The above-mentioned ceramic material is preferred to be aluminum oxide, zirconium oxide or silicon carbide; the forgoing metallic material is of stainless steel, FeAl alloy or FeCrAl alloy, etc.
[0019] The separation process of this invention is that, the high-temperature flue gas leaving the fluidized bed reactor is sent to the inorganic film cross-flow filter with air compressor to remove dust for the first time; the concentrated dust gas trapped by inorganic film cross-flow filter enters the bag filter to remove dust for the second time; the clean leaving the inorganic film cross-flow filter is used as blowback gas for intermittently blowing back the inorganic film cross-flow filter after being compressed with compressor; the remaining purified gas is condensed and rectified, and then is used to separate chloromethane gas and methyl chlorosilane, and the obtained product methyl chlorosilane and chloromethane gas return to the fluidized bed reactor to participate in the reaction; the dust trapped by the inorganic film cross-flow filter and bag filter return to the fluidized bed reactor to participate in the reaction.
[0020] The inorganic film in the invention has high mechanical strength, good stability, and is high-temperature resistant, thus effectively removing the dust of gas mixture.
Favorable Effect:
[0021] (1) On the base of producing methyl chlorosilane with a direct method, this invention process does not change the original reaction condition, and inorganic film is used to separate the small-sized dust of organic gas mixture so as to complete the separation of gas and solid in continuous production.
[0022] (2) The process of this invention is simple, and blowback gas needs not to be additionally heated.
[0023] (3) There is no dust-removing step by way of wet washing in this invention, and so the consumption of industrial water is little, and there is no wastewater drain, thus minimizing environmental pollution.
[0024] (4) The dust-removing rate in this invention is high, and separation efficiency exceeds 99.8%.
DESCRIPTION OF THE DRAWINGS
[0025] FIG. 1 shows the dust separation flow chart during the synthesis of methyl chlorosilane using direct method in this invention, where I—fluidized bed reactor; I—inorganic film cross-flow filter; III—bag filter; IV—fan; V—compressor; A—condenser; B—rectifying column.
[0026] FIG. 2 shows the structural schematic diagram of the inorganic film cross-flow filter in this invention.
[0027] Where, 1 —concentrated dust gas outlet; 2 —shell; 3 —film filter element; 4 —high-temperature flue gas inlet; 5 —upper figured plate; 6 —clean gas outlet; 7 —connection of blowback device; 8 —lower figured plate; 9 —dust charge port;
DESCRIPTION OF EMBODIMENTS
Example 1
[0028] The following is the detailed description of the invention in combination with the attached diagrams:
[0029] A) The high-temperature flue gas (a) leaving the outlet of reactor (I) is sent to the inorganic film cross-flow filter (II) for separation with the effect of a centrifugal fan (IV). The inorganic film cross-flow filter (II) is the product of Nanjing Jiusi High-tech Co., ltd, and the film filter element ( 3 ) is of 4 pieces of zirconia film with the pore diameter being 0.2 μm, channel quantity 19 , inner diameter of channel 6 mm, cross-flow velocity 30 m/s, film-crossing pressure differential 0.1 MPa; the dust content of the gas at the feed side is 0.9308 g/m 3 ; the flux of the film tube at the beginning of filtering is 51.5 m 3 /m 2 ·h; the dust content of the gas at the penetration side of the film tube is 1.1 mg/m 3 . Concentrated dust gas (c) trapped by the inorganic film filter (II) flows into the bag filter (III).
[0030] In this invention method as shown in FIG. 2 , the high-temperature flue gas (a) that contains solid particle of silicon powder and catalyst copper powder enters the inorganic film cross-flow filter (II) via high-temperature gas inlet ( 4 ), and then it enters the film filter element ( 3 ). The penetrating gas vertical to the flow direction of the former gas mixture is drained through the clean gas outlet ( 6 ). The trapped dust-rich gas (c) is drained out of the filter (II) via the outlet ( 1 ) at the concentrated dust side, and enters the bag filter (III). When flux in the inorganic film cross-flow filter (II) is obviously decreased to the setpoint 20.6 m 3 /m 2 ·h, the blowback system is automatically started up. The blowback gas (d) is the clean gas (b) that penetrates inorganic film filter (II) and is compressed with the compressor (V), and this stream of gas enters the inorganic film filter (II) for back washing via the blowback gas inlet ( 7 ); as a result, filter cake falls off and sinks down to the bottom of the separator; and then, the filter residue is automatically discharged through dust charge port ( 9 ).
[0031] C) After the clean gas (b) leaving the inorganic film cross-flow filter is condensed and rectified, the clean gas separates chloromethane gas (g) and methyl chlorosilane (h) so as to obtain product methyl chlorosilane (h) with purity of 99.99%; chloromethane gas (g) returns to the fluidized bed reactor to participate in the reaction.
[0032] D) The dust (e) trapped by the inorganic film filter (II) and bag filter (III) returns to the fluidized bed reactor (I) to participate in the reaction.
[0033] When blowback is performed, the blowback duration is 3 s and pressure is 0.2 MPa. The dust removal rate of gas mixture is up to 99.89% in this example.
Example 2
[0034] Dust and chloromethane enter a fluidized bed reactor, where reaction occurs to generate methyl chlorosilane gas mixture with the effect of catalyst copper powder; during the normal operation, the high-temperature flue gas is sent into the inorganic film cross-flow filter for separation with a centrifugal fan. The film filter element is of two pieces of single-tube alumina film with the pore diameter being 0.05 μm, inner diameter 8 mm, cross-flow velocity 25 m/s and film-crossing pressure differential 0.2 MPa. The dust content of the gas at the feed side is 2.9357 g/m 3 ; the dust content of the gas at the film penetration side is 2.6 mg/m 3 . Partial gas mixture containing large-sized dust is sent into the bag filter with a fan; the purified gas leaving the inorganic film cross-flow filter separates chloromethane gas and methyl chlorosilane after passing through the condensation and rectification steps, and the obtained product methyl chlorosilane and chloromethane gases return to the fluidized bed reactor to participate in the reaction; the dust trapped by the inorganic film filter and bag filter returns to the fluidized bed reactor to participate in the reaction. The experiment is carried out for 20 hours and the film needs not to be blown back; the dust removal rate of gas mixture is up to 99.91% in this example.
Example 3
[0035] Silicon powder and chloromethane enter a fluidized bed reactor, where reaction occurs to generate methyl chlorosilane gas mixture with the effect of catalyst copper powder; the gas mixture containing silicon powder and copper powder is sent into the inorganic film cross-flow filter with centrifugal fan. A piece of a single prorus 316L tube is used, with the pore diameter being 5 μm, inner diameter 60 mm, cross-flow velocity 20 m/s, film-crossing pressure differential 0.08 MPa. The dust content of the gas at the feed side is 4.6293 g/m 3 ; the dust content of the gas at the film penetration side is 4.0 mg/m 3 . Partial gas mixture containing large-sized dust is sent into the bag filter with a fan; the purified gas leaving the inorganic film cross-flow filter separates chloromethane gas and methyl chlorosilane after passing through the condensation and rectification steps, and the obtained product methyl chlorosilane and chloromethane gases return to the fluidized bed reactor to participate in the reaction; the dust trapped by the inorganic film filter and bag filter returns to the fluidized bed reactor to participate in the reaction. The experiment is carried out for 30 hours and the film needs not to be blown back; the dust removal rate of gas mixture is up to 99.91% in this example.
Example 4
[0036] Silicon powder and chloromethane enter a fluidized bed reactor, where reaction occurs to generate methyl chlorosilane gas mixture with the effect of catalyst copper powder; the high-temperature flue gas containing silicon powder and copper powder is sent into the inorganic film cross-flow filter with centrifugal fan. Film filter element is of a piece of a single prorus silicon carbide filter tube with the pore diameter being 10 μm, inner diameter 40 mm, outer diameter 60 mm, cross-flow velocity 15 m/s and film-crossing pressure differential 0.06 MPa. The dust content of the gas at feed side is 4.3684 g/m 3 ; the dust content of the gas at the film penetration side is 4.2 mg/m 3 . Partial gas mixture containing large-sized dust is sent into the bag filter with a fan; the purified gas leaving the inorganic film cross-flow filter separates chloromethane gas and methyl chlorosilane after passing through the condensation and rectification steps, and the obtained product methyl chlorosilane and chloromethane gases return to the fluidized bed reactor to participate in the reaction; the dust trapped by the inorganic film filter and bag filter returns to the fluidized bed reactor to participate in the reaction. The experiment is carried out for 20 hours and the film needs not to be blown back; the dust removal rate of gas mixture is up to 99.90% in this example.
Example 5
[0037] Dust and chloromethane enter a fluidized bed reactor, where reaction occurs to generate methyl chlorosilane gas mixture with the effect of catalyst copper powder; the high-temperature flue gas containing silicon powder and copper powder is sent into the inorganic film cross-flow filter for separation with a centrifugal fan. Film filter element is of 6 pieces of single prorus symmetrical FeAl alloy film, with pore diameter being 20 μm, inner diameter 50 mm, cross-flow velocity 40 m/s, film-crossing pressure differential 0.02 MPa. The dust content of the gas at feed side is 3.2343 g/m 3 , the dust content of the gas at the film penetration side is 4.2 mg/m 3 . Partial gas mixture containing large-sized dust is sent into the bag filter with a fan; the clean leaving the inorganic film cross-flow filter is used as blowback gas for blowing back the film filter after being compressed with compressor; the remaining purified gas is condensed and rectified, and then is used to separate chloromethane gas and methyl chlorosilane, and the purity of the obtained product methyl chlorosilane is 99.95%; chloromethane gas returns to the fluidized bed reactor to participate in the reaction; the trapped dust returns to the fluidized bed reactor to participate in the reaction. The experiment is carried out for 20 hours and the film needs not to be blown back; the dust removal rate of gas mixture is up to 99.87% in this example.
Example 6
[0038] Dust and chloromethane enter a fluidized bed reactor, where reaction occurs to generate methyl chlorosilane gas mixture with the effect of copper catalyst; the high-temperature flue gas containing silicon powder and copper powder is sent into the inorganic film cross-flow filter for separation with a centrifugal fan. A piece of single symmetrical FeCrAl alloy film is used, with the pore diameter being 50 μm, inner diameter 60 mm, cross-flow velocity 20 m/s and film-crossing pressure differential 0.008 MPa. The dust content of the gas at the feed side is 2.2353 g/m 3 ; the dust content of the gas at the film penetration side is 3.8 mg/m 3 . Partial gas mixture containing large-sized dust is sent into the bag filter with a fan; the clean leaving the inorganic film cross-flow filter is used as blowback gas for blowing back the film filter after being compressed with compressor; the remaining purified gas is condensed and rectified, and then is used to separate chloromethane gas and methyl chlorosilane, and the purity of the obtained product methyl chlorosilane is 99.94%; chloromethane gas returns to the fluidized bed reactor to participate in the reaction; the dust trapped by inorganic film filter and bag filter return to the fluidized bed reactor to participate in the reaction. The experiment is carried out for 30 hours and the film needs not to be blown back; the dust removal rate of gas mixture is up to 99.83% in this example. | Dry dust removal method in organic chlorosilane production is provided, in which the detailed steps are as follows: delivering high-temperature flue gas (a) from fluidized bed reactor (I) into inorganic film cross-flow filter (E) to remove dust for the first time; delivering the concentrated dust gas (c) trapped by inorganic film cross-flow filter (II) into bag filter (III) to remove dust for the second time; returning the gas mixture (f) of passing through bag filter (EI) to the air intake of inorganic film cross-flow filter (II); condensing the residual clean gas (b) from the osmotic side of inorganic film in condenser (A), and then rectifying in rectifying column (B) to separate the products of chloromethane (g) and methyl chlorosilane (h) to obtain the product of methyl chlorosilane (h); returning chloromethane to fluidized bed reactor to take part in reaction; retreating the dust (e) trapped by inorganic film cross-flow filter and bag filter, and then returning it to fluidized bed reactor (I) to take part in reaction. | 2 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is the National Phase of PCT/AU2009/000074 filed on Jan. 23, 2009, which claims priority under 35 U.S.C. 119(e) to U.S. Provisional Application No. 61/022,902 filed on Jan. 23, 2008. The entire contents of all the above applications are hereby incorporated by reference.
FIELD OF THE INVENTION
The present invention relates to a mobile delivery platform for flowable explosive.
BACKGROUND OF THE INVENTION
Flowable explosive, such as emulsion explosive, is conventionally delivered in surface and underground applications using gravity tanks. Gravity tanks have a high centre of gravity and are not easily transportable. They also require a top access structure for cleaning and maintenance of the inside walls to prevent crystallization of the emulsion explosive. The top access structure limits tank capacity and is a fall hazard for workers.
A need therefore exists for a mobile, self-cleaning delivery platform for flowable explosive.
SUMMARY OF THE INVENTION
According to the present invention, there is provided apparatus for storing and dispensing flowable explosive, the apparatus including an explosive pump for pumping flowable explosive into an explosive tank having a fluid pressure-actuated piston movable therein for expelling flowable explosive out of the explosive tank through a delivery hose fitted with an injector through which one or more additives from one or more additive tanks can be pumped by an additive pump.
The explosive tank and the piston therein can be cylindrical with a common horizontal longitudinal axis.
The piston can have one or more circumferential seals for cleaningly wiping the inner surface of the explosive tank.
The piston can be a concave piston that is radially expandable to sealingly engage the inner surface of the explosive tank.
The explosive tank can have a detector therein for detecting displacement of the piston and/or monitoring quantities of flowable explosive in the explosive tank.
The one or more additives can be lubricant stored in a lubricant tank, and explosive additive stored in an explosive additive tank.
The delivery hose can be wound on a hose reel.
The tanks, pumps, and hose reel can be arranged on a transportable platform.
The flowable explosive can be selected from emulsion explosive, gel explosive, slurry explosive, blended explosive, and doped explosive.
The present invention also provides a method of delivering flowable explosive using the above apparatus.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be further described by way of example only with reference to the accompanying drawings, in which:
FIG. 1 is a schematic diagram of fluid circuit of an embodiment of a mobile delivery platform for flowable explosive of the invention; and
FIG. 2 are side, plan and end view of the mobile delivery platform.
DETAILED DESCRIPTION
Referring to the FIG. 1 , an embodiment of a mobile delivery platform 26 for flowable explosive generally includes an explosive tank 1 , an explosive pump 10 , an additive pump 14 , an explosive additive tank 15 , a lubricant tank 16 , and a delivery hose 23 wound on a hose reel 22 . Referring to FIG. 2 , these components are arranged together on a transportable platform 24 , for example, a multimodal transport platform with International Standards Organization (ISO) standardised multimodal attachments or fittings.
The explosive tank 1 is cylindrical and is made, for example, of a corrosion resistant or a suitable pressure vessel material. The explosive tank 1 has a capacity, for example, of 3 tonne. A cylindrical piston 6 is axially movable inside the explosive tank 1 . The explosive tank 1 and piston 6 have a common longitudinal axis horizontal to the transportable platform 24 . The piston 6 is a concave piston that is radially expandable when pressurised to sealingly engage the inner surface of the explosive tank 6 . Two circumferential seals 7 are provided on the piston 6 . The piston seals 7 cleaningly wipe the inner surface of the explosive tank 1 during axial movement therein of the piston 6 . Together, the piston 6 and the piston seals 7 provide a “self-cleaning” action that prevents build-up of flowable explosive on the inner surface of the explosive tank 1 . Other equivalent “self-cleaning” piston and seal arrangements may also be used. The piston 6 is made of, for example, corrosion resistant material. The piston seals 7 and the delivery hose 23 are made of, for example, rubber. Together, the piston 6 and piston seals 7 sealingly divide the explosive tank 1 into opposed pressure and explosive ends.
The pressure end of the explosive tank 1 is provided with an inlet manifold 5 , a pressure relief valve 2 , and a piston displacement sensor 4 . The pressure inlet manifold 5 includes a pressure regulator and a pressure gauge. The piston displacement sensor 4 is, for example, a laser detector.
The explosive end of the explosive tank 1 is provided with a pressure relief valve 3 and a selector valve 8 to control flow of flowable explosive to and from an inlet/outlet port in the explosive tank 1 . The flowable explosive is, for example, emulsion explosive, gel explosive, slurry explosive, blended explosive, doped explosive, etc. The flowable explosive has a viscosity of between around 20,000 and 90,000 centipoise (cP), for example, 40,000 cP.
Flowable explosive is drawn from an external supply (not shown) via selector valves 9 , 18 by the explosive pump 10 and pumped via selector valves 11 , 8 into the explosive end of the explosive tank 1 . This displaces the piston 6 backwardly toward the pressure end of the explosive tank 1 . The backward displacement of the piston 6 is monitored by the piston displacement sensor 4 . The pressure relief valve 2 acts as a bleed valve to maintain backpressure against the piston 6 so that it is positively retained next to flowable explosive pumped into the explosive tank 1 . A flow meter 12 is connected to the explosive pump 10 to indicate the flow rate of flowable explosive pumped into the explosive tank 1 . The explosive pump 10 is, for example, a high pressure diaphragm pump.
Flowable explosive is discharged from the explosive tank 1 via the selector valves 8 , 11 to the delivery hose 23 by applying fluid pressure to the piston 6 via the pressure inlet manifold 5 . The fluid pressure is, for example, air pressure from a source of compressed air, for example, a truck compressed air system. The air pressure displaces the piston 6 forwardly toward the explosive end of the explosive tank 1 . The forward displacement of the piston 6 is monitored by the piston displacement sensor 4 . The discharge pressure of flowable explosive is indicated by a pressure meter 13 . The delivery hose 23 is unwound from the hose reel 22 and positioned to deliver the flowable explosive from the explosive tank 1 to a surface or underground delivery site, for example, a blast hole. The delivery rate of the flowable explosive is, for example, up to around 1100 litres per minute. The flowable explosive is substantially fully discharged from the explosive tank 1 by the piston 6 as the “self-cleaning” action of the piston 6 and the piston seals 7 leaves less than around 0.05% by weight of the initial load of flowable explosive remaining in front of the piston 6 .
The pressure required to discharge flowable explosive is selectively reduced by injecting flowable lubricant stored in the lubricant tank 16 into the delivery hose 23 . The lubricant is, for example, water, oil, polymeric lubricant, etc. The flowable lubricant is pumped from the lubricant tank 16 via selector valve 17 by the additive pump 14 to an injector 19 fitted to the delivery hose 23 . The pressure and flow rate of lubricant injected into the delivery hose 23 are respectively indicated by a flow meter 20 and a pressure meter 21 . The additive pump 14 is, for example, a piston pump. The lubricant tank 16 is filled with flowable lubricant via a filler or from an external source (not shown) via the selector valves 9 , 18 . Lubricant, such as water, is selectively pumped by the additive pump 14 from the lubricant tank 16 through the explosive pump 10 for cleaning the explosive pump 10 , injector 19 and delivery hose 23 after flowable explosive has been discharged from the explosive tank 1 . A check valve between the lubricant tank 16 and the selector valve 18 prevents backup of water into the lubricant tank 16 during cleaning.
Explosive additive stored in the explosive additive tank 15 is selectively injectable into the delivery hose 23 by the additive pump 14 via the selector valve 17 . The explosive additive is, for example, gassing solution. The explosive additive tank 15 is filled with explosive additive via a filler. The flow and pressure meters 20 , 21 measure the flow and pressure of explosive additive injected into the delivery hose 23 .
Referring to FIG. 2 , a control panel 25 is provided at one end of the platform 24 for the flow and pressure meters 12 , 13 , 20 , 21 , a display of the piston displacement sensor 4 , and controls for the explosive pump 10 and the additive pump 14 . The selector valves can be solenoid valves having controls provided in the control panel 25 .
The mobile delivery platform 26 can form part of a mobile manufacturing unit (MMU), an underground delivery system, or a plant storage unit.
It will be appreciated that embodiments of the invention advantageously provide a mobile, self-cleaning delivery platform for flowable explosive.
The embodiments have been described by way of example only and modifications are possible within the scope of the claims which follow. | Apparatus for storing and dispensing flowable explosive, the apparatus including an explosive pump for pumping flowable explosive into an explosive tank having a fluid pressure-actuated piston movable therein for expelling flowable explosive out of the explosive tank through a delivery hose fitted with an injector through which one or more additives from one or more additive tanks can be pumped by an additive pump. | 5 |
CROSS-REFERENCE TO RELATED APPLICATIONS AND PATENT
This application is a divisional of the commonly assigned, copending U.S. application Ser. No. 07/359,494, filed: May 31, 1989, now Pat. No. 4,969,234 entitled "METHOD OF AND APPARATUS FOR REDUCING THE STICKINESS OF COTTON FLOCKS."
This application is related to copending U.S. application Ser. No. 07/132,790, filed Dec. 10, 1987, entitled "TREATMENT OF COTTON", and which application is a divisional application to U.S. application Ser. No. 06/833,987, filed Feb. 26, 1986, entitled "TREATMENT OF COTTON", now U.S. Patent No. 4,796,334, granted Jan. 10, 1989, which is related also to copending U.S. application Ser. No. 07/207,252, filed Jun. 15, 1988, entitled "TREATMENT OF COTTON", and which application is a continuation application to the aforementioned parent application, namely U.S. application No. 06/833,987. This application is also related to the commonly assigned U.S. application Ser. No. 07/359,495, filed May 31, 1989, and entitled "METHOD OF AND APPARATUS FOR TREATING COTTON CONTAMINATED WITH HONEYDEW" and is further related to the commonly assigned, copending U.S. application Ser. No. 07/363,784, filed Jun. 9, 1989, entitled "METHOD OF AND APPARATUS FOR REDUCING THE STICKINESS OF THE FIBERS OF COTTON FLOCKS CONTAMINATED WITH HONEYDEW".
BACKGROUND OF THE INVENTION
The present invention broadly relates to treating contaminated cotton fibers or flocks when such are being continuously processed and, more specifically pertains to a new and improved apparatus for reducing the stickiness or tackiness of the fibers of cotton flocks contaminated with honeydew.
Generally speaking, the present invention relates to a new and improved apparatus of the aforementioned type and which entails heating the cotton flocks for a brief period of time.
It is known that cotton flocks of many provenances or origins are more or less contaminated with insect secretions which contain sugar. These sugar-containing secretions are generally termed "honeydew". There is known a laboratory method by means of which such honeydew is allowed to caramelize by heating cotton flock samples or specimens in an oven with the aim of thereby producing a discoloration or change of color of the cotton, in order to determine the degree of contamination thereof with honeydew from the resulting change in the color of the cotton flocks. This is namely very important because, in the event of heavy contamination of the cotton flocks, the cotton flocks become sticky and tend to adhere to various parts of the yarn production plant or to form laps or coils at rolls or rollers or at other rotatable members. This result is very undesirable since it causes frequent interruptions of the yarn manufacturing process.
A method of the aforementioned type is disclosed in European Pat. application No. 86102352.1, published Oct. 8, 1986, under Publication No. 196,449. The object of this known method is to convert any contaminating honeydew into a non-tacky or non-adhesive and brittle state or condition by supplying heat for a short period of time, but without causing any discoloration or change of color of the cotton flocks, so that the brittle sugar or caramellized deposits can be crushed and removed in the course of the subsequent treatment.
A number of devices or apparatus for performing this prior art method have been proposed in the abovementioned European Pat. application No. 86102352.1, published under Publication No. 196,449. The object of one disclosed device or apparatus is to heat the cotton flocks already in the course of opening the raw cotton bales, i.e. directly at the start of the yarn manufacturing process. Other devices or apparatus are intended for treating fiber slivers before drafting.
SUMMARY OF THE INVENTION
Therefore, with the foregoing in mind it is a primary object of the present invention to provide a new and improved apparatus for reducing the stickiness or tackiness or adhesiveness of the fibers of cotton flocks, which apparatus can be performed or applied at any processing or treatment stage of the cotton flocks, i.e. during ginning and cleaning as well as before carding and drafting.
Another and more specific object of the present invention aims at providing a new and improved apparatus for reducing the stickiness or tackiness of cotton flocks and by means of which a uniform and rapid heat transfer into the fiber batt is attainable and detrimental or undesired effects of uncontrolled heating are obviated.
To achieve the aforementioned objects, the inventive apparatus, in its more specific aspects, among other things, comprises a fiber feeding device by means of which the fiber flocks are compressed into a fiber batt or web and fed in this condition or form to a plurality of heatable rolls or rollers following thereupon. Downstream of such heatable rolls or rollers, as viewed in the conveying direction of the fiber batt or web, there are provided opening and infeeding means for opening the fiber batt or web again into fiber flocks and infeeding such fiber flocks to fiber conveyor means.
The inventive apparatus for reducing the stickiness or tackiness of cotton flocks is based on the finding that the amount of heat that can be applied to or brought into a fiber batt or web at a press nip or clamping location between two heatable rolls or rollers or at locations directly upstream or directly downstream of the press nip or clamping location is far greater than the amount of heat that can be applied to or brought into the very same fiber batt or web, when the latter simply embraces or wraps around a heated roll or roller.
This is due not only to the fact that the fiber batt or web in the press nip or clamping location is heated from both sides, but rather also due to the fact that the conductivity of the fiber batt or web in the compressed state is higher, by virtue of the reduction of the amount of air contained in the fiber batt or web, than in a fiber batt or web which is only wrapped around a heated roll or roller and thus freely exposed on one side.
According to the invention, the best results are obtained when cotton in the press nip or clamping location of the rolls or rollers is compressed to a density of 100 to 400 kg/m 3 , preferably about 250 kg/m 3 .
A particularly preferred variant of the method according to the invention comprises the steps of applying at least one belt or band which revolves around at least two rotating heated rolls or rollers, providing at least one further rotating heated roll or roller forming press nip or clamping locations with the at least two rotating heated rolls or rollers, and clamping the fiber batt or web against the at least one further rotating heated roll over a part of the surface thereof. The resulting improvement in heat transfer is due to the fact that the length of the press nip or clamping location is artificially extended or enlarged by the revolving belt or band.
A further particularly preferred variant of the method according to the invention comprises the step of at least partially exposing or laying bare at least one surface of the fiber batt or web, preferably the upper or top surface thereof, to allow water vapor to escape during the heating operation. If this step is omitted and no provision is made for the vapors generated during the heating process to escape, there is the risk of the cotton flocks remaining sticky or tacky even after the heat treatment has been effected.
In a preferred embodiment of the apparatus constructed according to the invention for reducing the stickiness or tackiness of the fibers of cotton flocks, the plurality of heatable rolls or rollers are arranged in a preferably ascending chimney or flue through which an air current or flow is effected by means of a blower or fan. In this manner, any generated vapors are sucked out or blown away.
The chimney is preferably located between a flock feed chute and an opening roll or roller which opens the fiber batt or web into fiber flocks. Such an arrangement renders possible the space-saving and economical integration of the inventive apparatus in an existing feeder of a card or carding machine.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood and objects other than those set forth above will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings wherein throughout the various figures of the drawings, there have been generally used the same reference characters to denote the same or analogous components and wherein:
FIG. 1 shows a schematic side view of an exemplary embodiment of the inventive apparatus for reducing the stickiness or tackiness of cotton flocks;
FIG. 2 schematically shows a side view of a modified embodiment of the heatable rolls or rollers of the apparatus illustrated in FIG. 1;
FIG. 3 schematically shows a side view of a further embodiment of heatable rolls or rollers which can be used instead of the heatable rolls or rollers in the exemplary embodiment of the inventive apparatus illustrated in FIGS. 1 and 2; and
FIG. 4 schematically shows a variant of the apparatus illustrated in FIG. 1.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Describing now the drawings, it is to be understood that to simplify the showing thereof, only enough of the structure of the apparatus for realizing the inventive method of reducing the stickiness or tackiness of the fibers of cotton flocks contaminated with honeydew or the like has been illustrated therein as is needed to enable one skilled in the art to readily understand the underlying principles and concepts of the present invention. Turning attention now specifically to FIG. 1 of the drawings, the apparatus illustrated therein by way of example and not limitation will be seen to comprise a lower or bottom part of a flock chute or shaft 11 such as is normally used upstream of a card or carding machine. At the lower end of this flock chute or shaft 11, which is disposed in a flock chute housing 12, there are arranged two take-up or delivery rolls or rollers 13 and 14. While the axis of rotation of the take-up or delivery roll or roller 14 is fixedly arranged in space, the axis of rotation of the other take-up or delivery roll or roller 13 is displaceable in the direction of the double-headed arrow 15, in order to adjust the desired thickness of a fiber feed or fiber batt.
A further rotatable roll or roller 16 is provided upstream of the take-up or delivery roll or roller 13 and is arranged in spaced relationship with respect to the take-up or delivery roll or roller 14. This further rotatable roll or roller 16 performs a guide function for the cotton flocks in the flock chute or shaft 11. A fiber batt or web 17 produced by the take-up or delivery rolls or rollers 13 and 14 is conducted, instantly downstream of the take-up or delivery rolls 13 and 14, between clamping means and a counter element here shown as two clamping rolls 18 and 19 which serve to clamp the fiber batt or web 17 in the event of any interruption or stoppage of the manufacturing process and thus prevent any further conveyance of cotton flocks. The take-up or delivery rolls 13 and 14 are stopped during this operation.
In normal operation, the fiber batt or web 17 then passes on through an exit slot or opening 21 located at the bottom end of the flock chute housing 12 and over a guide plate 22 to an arrangement or array of heatable rolls or rollers. This heatable roll arrangement or array here comprises, for instance, five individual heatable rolls or rollers 23, 24, 25, 26 and 27 which are alternately arranged in a downwardly inclined row on both sides of the fiber batt or web 17. All five heatable rolls or rollers 23 through 27 are driven so that the fiber batt or web 17 is drawn or pulled through the rolls or rollers 23 through 27.
As will be apparent from FIG. 1, four press nip or clamping locations 28, 29, 31 and 32 are provided between the five heatable rolls or rollers 23 through 27. These four press nip or clamping locations 28, 29, 31 and 32 preferably have a press nip or clamping width of 4 mm or less. Before entering the press nip or clamping location 28, the fiber batt or web 17 on the guide plate 22 has a thickness of about 100 mm. Therefore, the fiber or flock batt or web 17 undergoes a 20 to 25 times compression in the press nip.
Between the heatable rolls or rollers 23 through 27 and downstream of the heatable roll or roller 27 there are free or exposed regions or areas 33, 34, 35 and 36 of the fiber batt or web 17 where the vapors produced by the heating operation can escape. This can be assisted by an air current or flow 37 produced by a suitable blower or fan which is not particularly shown in the drawing, but which could be, for instance, flanged at a pipe connection or spigot 40. This pipe connection or spigot 40 is located at the top or upper end of a chimney or flue 38 in which the heatable roll or roller arrangement or array is accommodated. This chimney 38 vertically extends or ascends between the flock chute or shaft 11 and a feeding device or system for a card or carding machine.
After leaving the last heatable roll or roller 27, the compressed and heated fiber batt or web 17 passes over a guide plate 39 to an opening roll or roller 41 of an infeeding or infeed device 56. Here, the fiber batt or web 17 is again opened into individual cotton flocks, which are blown or sucked into a rising or ascending line or conduit 42 which finally leads to a subsequent machine in the ginning process or in the cleaning department of the spinning mill. A line or conduit 43 serves to admit or allow for the ingress of an air current or flow substantially tangentially in the direction of movement of the opening roll or roller 41, in order to promote the pneumatic conveyance or transport of the loosened cotton flocks in a line or conduit 42. The opening roll or roller 41 is located at the lower or bottom end of a separating or partition wall 60 which forms a lateral or side wall of the chimney 38.
FIG. 2 shows a modified embodiment of the heatable roll or roller arrangement or array of FIG. 1 in which a revolving belt or band 44 wraps around the three heatable rolls or rollers 23, 25 and 27 arranged below the fiber batt or web 17. This revolving belt or band 44 is driven at the same speed as the circumferential speed of the heatable rolls or rollers 23 through 27, either by the heatable rolls or rollers 23 through 27 themselves or by a driven deflection roll or roller 45. Two further deflection rolls or rollers 46 and 47 as well as a tension roll or roller 48 provide uniform movement or travel of the revolving belt or band 44 and the desired or required tension of such revolving belt or band 44. Extended press nip or clamping locations or zones 49 and 51 between the revolving belt or band 44 and the top or upper heatable rolls or rollers 24 and 26, respectively, are formed by the revolving belt or band 44.
In this embodiment, the tension of the revolving belt or band 44 is selected such that the fiber batt or web 17 in the press nip locations or clamping locations or zones 49 and 51 has a thickness of about 4 mm or less. The revolving belt or band 44 is preferably made of metal and is itself heated by the heatable rolls or rollers 23, 25 and 27 so that the heat input or transfer into the fiber batt or web 17 is accomplished from both sides.
FIG. 3 shows a further possibility of heating a fiber batt or web 17 in the clamped condition or state thereof. Four rotating heatable rolls or rollers 23.1, 24.1, 27.1 and 26.1 are provided. The revolving belt or band 44 passes over the first rotating heatable roll or roller 23.1, beneath the second rotating heatable roll or roller 24.1, over the third rotating heatable roll or roller 27.1 and then over two deflection rolls or rollers 45 and 46. Also in this case, there is provided a tension roll or roller 48. Above the second rotating heatable roll or roller 24.1 there is located the fourth rotating heatable roll or roller 26.1 which forms two press nip or clamping locations 28.1 and 32.1 with the surfaces of the two lower rotating heatable rolls or rollers 23.1 and 27.1 or with the surface of the revolving belt or band 44 wrapped around these two lower rotating heatable rolls or rollers 23.1 and 27.1, respectively. The fiber batt or web 17 runs over the guide plate 22, beneath a stationary guide or guide member 52 and through the press nip or clamping location 28.1, then along a further stationary guide or guide member 53, over the surface of the rotating heatable roll or roller 24.1 while being clamped by the revolving belt or band 44, past a stationary guide or guide element 54, through the press nip or clamping location 32.1 and finally beneath a further stationary guide or guide member 55 to the guide plate 39. The heated fiber batt or web 17 then passes to the opening roll or roller 41.
In this embodiment, the fiber batt or web 17 is heated over a considerable length in the clamped state or condition by means of just four rotating heatable rolls or rollers. The stationary guides or guide members 52 and 55 can also be replaced by rotatable guide rolls or rollers 57 and 58 or by a further revolving belt or band 59 which is guided or trained around the corresponding heatable rolls or rollers and guide rolls or rollers 57, 23.1, 24.1, 27.1, 58 and 26.1. The guide roll or roller 57 or the guide roll or roller 58 can be provided as a tension roll or roller.
It should be mentioned that the described apparatus or installations use heatable rolls which are heated to a temperature of about 220° C. Heating can be accomplished by means of oil, steam, electric current or any other heat source capable of supplying the required amount of heat in the required time. The fiber batt or web 17 moves through the plant or installation at a speed of between 0.02 m/sec and 0.1 m/sec. If the cotton being processed is not contaminated with honeydew, the heating can be simply turned off or the entire plant or installation can be by-passed.
FIG. 4 shows a variant of the apparatus of FIG. 1 inasmuch as a cooling zone or area 70 is provided between the chimney or flue 38 and the infeeding device 56, in order to cool the heated fiber batt or web 17 between two cooling conveyor belts or bands 71 and 72.
The cooling zone or area 70 is separated, by a separating or partition wall 60.1 and by a separating or partition wall 73 arranged opposite thereto, from the chimney 38 and from the region or area containing the infeeding device 56. The separating or partition walls 60.1 and 73 shown in FIG. 4 are of course closed by two end sides or walls to form a closed room or space.
On the other hand, these end sides or walls not particularly designated by reference characters in the drawing of FIG. 4 are provided with air inlet openings (not shown) to admit an air flow or current L which, for the purpose of cooling the fiber batt or web 17 located between the two cooling conveyor belts or bands 71 and 72, flows, for instance, substantially perpendicular through these two cooling conveyor belts or bands 71 and 72 which consist of lattice work or mesh structure. The air flow or current L is generated by a suitable suction fan (not shown), which is connected to a connection pipe or spigot or stud 74. The airflow or current L should have a relative air humidity which is able to absorb humidity from the fiber flocks.
The cooling conveyor belts or bands 71 and 72 are synchronously driven by a suitable single drive not particularly shown in the drawing of FIG. 4 and convey the fiber batt or web 17 at the outlet speed thereof prevailing in the press nip or clamping location 32 between the two last heated rolls or rollers 26 and 27.
It is readily conceivable that the fiber flocks can also be cooled in the next following unit for conveying or otherwise acting upon the fiber flocks, such unit being arranged downstream of the opening roll 56.
Finally, reference is made to the stripping or stripper knives 75 which are provided at the rolls or rollers or at the conveyor belts or bands for the purpose of removing or picking up any honeydew deposits. These stripping or stripper knives 75 can also be heated to effect a caramelization of the honeydew adhering thereto.
While there are shown and described present preferred embodiments of the invention, it is to be distinctly understood that the invention is not limited thereto, but may be otherwise variously embodied and practiced within the scope of the following claims. ACCORDINGLY, | The invention relates to an apparatus for reducing the stickiness or tackiness of cotton flocks. For this purpose, cotton flocks delivered by any suitable conveyor structure are received in a flock chute and brought, by rolls or rollers, as a fiber batt between a number of heated rolls or rollers, in order to be heated such that the stickiness or tackiness of the honeydew on the cotton is thus reduced to an extent which no longer has an adverse effect on subsequent machinery. Downstream of the heated rolls or rollers the fiber batt is again opened into cotton flocks by an opening roll or roller and fed to a pneumatic conveyor line through which the cotton flocks are fed to the subsequent machine. | 3 |
This application is a Divisional application Ser. No. 09/766,587, filed Jan. 23, 2001, which is a Divisional application of application Ser. No. 09/461,432, filed Dec. 16, 1999, now U.S. Pat. No. 6,330,755, which is a Continuation application of application Ser. No. 09/177,495, filed Oct. 23, 1998, now U.S. Pat. No. 6,012,235, which is a continuation application of application Ser. No. 09/061,062, filed Apr. 16, 1998, now U.S. Pat. No. 5,950,330 which is a Continuation application of application Ser. No. 08/882,731, filed Jun. 26, 1997, now U.S. Pat. No. 5,784,799, which is a Divisional application of application Ser. No. 08/593,870, filed Jan. 30, 1996, now U.S. Pat. No. 5,661,913, which is a Continuing application of application Ser. No. 08/443,039, filed May 17, 1995, now U.S. Pat. No. 5,553,396, which is a Divisional application of application Ser. No. 08/302,443, filed Sep. 9, 1994, now U.S. Pat. No. 5,457,896, which is a Continuing application of application Ser. No. 08/096,256, filed Jul. 26, 1993, now U.S. Pat. No. 5,349,762, which is a Continuing application of application Ser. No. 07/751,951, filed Aug. 29, 1991 now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a vacuum processing apparatus and operating method therefor. More specifically, the present invention relates to a vacuum processing apparatus having vacuum processing chambers the inside of which must be cleaned, and its operating method.
2. Description of the Prior Art
In a vacuum processing apparatus such as a dry etching apparatus, a CVD apparatus or a sputtering apparatus, a predetermined number of substrates to be treated are stored as one unit (which is generally referred to as a “lot”) in a substrate cassette and are loaded in the apparatus. The substrates after being processed are likewise stored in the same unit in the substrate cassette and are recovered. This is an ordinary method of operating these apparatuses to improve the productivity.
In such a vacuum processing apparatus described above, particularly in an apparatus which utilizes a reaction by an active gas, as typified by a dry etching apparatus and a CVD apparatus, reaction products adhere to and are deposited on a vacuum processing chamber with the progress of processing. For this reason, problems such as degradation of vacuum performance, the increase of dust, the drop of the levels of optical monitoring signals occur. To solve these problems, conventionally the insides of the vacuum processing chambers are cleaned periodically. Cleaning operations include so-called “wet cleaning” which is wiping-off of the adhering matters by use of an organic solvent, etc., and so-called “dry cleaning” in which an active gas or plasma is used for decomposing adhering matters. Dry cleaning is superior from the aspect of the working factor and efficiency. These features of the dry cleaning have become essential with the progress in automation of production lines.
An example of vacuum processing apparatuses having such a dry cleaning function is disclosed in Japanese Utility Model Laid-Open No. 127125/1988. This apparatus includes a preliminary vacuum chamber for introducing wafers to be treated into a processing chamber from an atmospheric side to a vacuum side, which is disposed adjacent to the processing chamber through a gate valve, dummy wafers are loaded in the preliminary vacuum chamber and are transferred into the processing chamber by exclusive conveyor means before the processing chamber is subjected to dry cleaning, and the dummy wafer is returned to the vacuum preparatory chamber by the conveyor means after dry cleaning is completed.
SUMMARY OF THE INVENTION
In the prior art technology described above, the structure of the vacuum processing apparatus is not much considered. The preliminary vacuum chamber for storing the dummy wafers must have a large capacity, the exclusive conveyor means is necessary for transferring the dummy wafers and thus, the apparatus is complicated in structure.
Dummy wafers used for plasma cleaning are again returned to the preliminary vacuum chamber and are made to stand by. In this instance, reaction products generated during plasma cleaning and residual gas used for plasma cleaning adhere on the used dummy wafers. Thereafter, normal processing for wafers is resumed. Therefore, the used dummy wafers and unprocessed wafers exist in mixture inside the preliminary vacuum chamber and this state is not desirable from the aspect of contamination of unprocessed wafers.
The present invention provides a vacuum processing apparatus which solves the problems described above, is simple in structure, prevents contamination of unprocessed substrates and accomplishes a high production yield. A vacuum processing apparatus having vacuum processing chambers the insides of which are dry-cleaned after substrates to be treated are processed in vacuum is provided with first storage means for storing substrates to be treated, second storage means for storing dummy substrates, the first and second storage means being disposed in the air, conveyor means for transferring the substrates to be processed between the first storage means and the vacuum processing chambers and for transferring the dummy substrates between the second storage means and the vacuum processing chambers, and control means for controlling the conveyor means so as to transfer the dummy substrates between the second storage means and the vacuum processing chambers before and after dry cleaning of the vacuum processing chambers. A method of operating a vacuum processing apparatus having vacuum processing chambers the insides of which are dry-cleaned after substrates to be processed are processed in vacuum comprises the steps of disposing first storage means for storing the substrates to be processed together with second storage means for storing dummy substrates in the air atmosphere, transferring the substrates to be processed between the first storage means and the vacuum processing chambers and vacuum-processing the substrates to be processed, and transferring the dummy substrates between the second storage means and the vacuum processing chambers before and after dry-cleaning of the vacuum processing chambers.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plan view of a dry etching apparatus as an embodiment of a vacuum processing apparatus in accordance with the present invention; and
FIG. 2 is a vertical sectional view taken along line 1 — 1 of FIG. 1
DESCRIPTION OF THE PREFERRED EMBODIMENTS
As substrates to be processed are processed in a vacuum processing apparatus, reaction products adhere to and are deposited in vacuum processing chambers. The reaction products adhering to and deposited in the vacuum processing chambers are removed by disposing dummy wafers inside the vacuum processing chambers and by conducting dry-cleaning. To carry out dry cleaning, the timings of dry cleaning of the vacuum processing chambers are determined and during or after the processing of a predetermined number of substrates to be processed, dummy substrates are conveyed by substrate conveyor means from dummy substrate storage means disposed in the air atmosphere together with processed substrate storage means, and are then disposed inside the vacuum processing chambers. After the dummy substrates are thus disposed, a plasma is generated inside each of the vacuum processing chambers to execute dry-cleaning inside the vacuum processing chamber. After dry-cleaning inside the vacuum processing chambers is completed, the dummy substrates are returned from the vacuum processing chambers to the dummy substrate storage means by the substrate conveyor means. In this manner, a preliminary vacuum chamber and an exclusive transfer mechanism both necessary in prior art techniques become unnecessary, and the apparatus structure gets simplified. The dummy substrates used for the dry-cleaning and the substrates to be processed do not co-exist inside the same chamber, so that contamination of substrates to be processed due to dust and remaining gas is prevented and a high production yield can be achieved.
Hereinafter, an embodiment of the present invention will be explained with reference to FIGS. 1 and 2.
FIGS. 1 and 2 show a vacuum processing apparatus of the present invention which is, in this case, a dry-etching apparatus for etching wafers, i.e., substrates to be processed by plasma.
Cassette tables 2 a to 2 c are disposed in an L-shape in this case in positions such that they can be loaded into and unloaded from the apparatus without changing their positions and postures. In other words, the cassettes 1 a to 1 c are fixed always in predetermined positions on a substantially horizontal plane, while the cassette tables 2 a and 2 b are disposed adjacent to and in parallel with each other on one of the sides of the L-shape. The cassette table 2 c is disposed on the other side of the L-shape. The cassettes 1 a and 1 b are for storing unprocessed wafers and for recovering the processed wafers. They can store a plurality (usually 25) of wafers 20 as the substrates to be treated. The cassette 1 c in this case is for storing the dummy wafers for effecting dry-cleaning using plasma (hereinafter referred to as “plasma-cleaning”) and recovering the dummy wafers after plasma-cleaning. It can store a plurality of (usually twenty-five pieces) dummy wafers 30 .
A load lock chamber 5 and unload lock chamber 6 are so disposed as to face the cassette tables 2 a and 2 b , and a conveyor 13 is disposed between the cassette tables 2 a , 2 b and the load lock chamber 5 and the unload lock chamber 6 . The load lock chamber 5 is equipped with an evacuating device 3 and a gas introduction device 4 , and can load unprocessed wafers in the vacuum apparatus through a gate valve 12 a . The unload lock chamber 6 is similarly equipped with the evacuating device 3 and the gas introduction device 4 , and can take out processed wafers to the atmosphere through a gate valve 12 d . The conveyor 13 is equipped with a robot having X, Y, Z and θ axes, which operates so as to deliver and receive the wafers 20 between the cassettes 1 a , 1 b and the load lock and unload lock chambers 5 and 6 and the dummy wafers 30 between the cassette 1 c and the load lock and unload lock chambers 5 and 6 .
The load lock chamber 5 and the unload lock chamber 6 are connected to a transfer chamber 16 through the gate valves 12 b and 12 c . The transfer chamber 16 is rectangular, in this case, and etching chambers 11 a , 11 b and 11 c are disposed on the three side walls of the transfer chamber 16 through gate valves 15 a , 15 b and 15 c , respectively. A conveyor 14 capable of delivering the wafers 20 or the dummy wafers 30 from the load lock chamber 5 to the etching chambers 11 a , 11 b , 11 c and of delivering them from the chambers 11 a , 11 b , 11 c to the unload lock chamber 6 is disposed inside the transfer chamber 16 . The transfer chamber 16 is equipped with an evacuating device 17 capable of independent evacuation.
The etching chambers 11 a , 11 b , 11 c have the same structure and can make the same processing. The explanation will be given on the etching chamber 11 b by way of example. The etching chamber 11 b has a sample table 8 b for placing the wafers 20 thereon, and a discharge chamber is so provided as to define a discharge portion 7 b above the sample table 8 b . The etching chamber 11 b includes a gas introduction device 10 b for introducing a processing gas in the discharge portion 7 b and an evacuating device 9 b for decreasing the internal pressure of the etching chamber 11 b to a predetermined pressure. The etching chamber 11 b further includes generation means for generating a microwave and a magnetic field for converting processing gas in the discharge portion 7 b to plasma.
A sensor 18 for measuring the intensity of plasma light is disposed at an upper part of the etching chamber. The measured value of the sensor 13 is inputted to a controller 19 . The controller 19 compares the measured value from the sensor 18 with a predetermined one and determines the timing of cleaning inside the etching chamber. The controller 19 controls the conveyors 13 and 14 to control the transfer of the dummy wafers 30 between the cassette 1 c and the etching chambers 11 a to 11 c.
In a vacuum processing apparatus having the construction described above, the cassettes 1 a , 1 b storing unprocessed wafers are first placed onto the cassette tables 2 a , 2 b by a line transfer robot which operates on the basis of the data sent from a host control apparatus, or by an operator. On the other hand, the cassette 1 c storing the dummy wafers is placed on the cassette table 2 c . The vacuum processing apparatus executes the wafer processing or plasma cleaning on the basis of recognition by itself of the production data provided on the cassettes 1 a to 1 c , of the data sent from the host control apparatus, or of the command inputted by an operator.
For instance, the wafers 20 are sequentially loaded in the order from above into the etching chambers 11 a , 11 b , 11 c by the conveyors 13 and 14 , and are etched. The etched wafers are stored in their original positions inside the cassette 1 a by the conveyors 14 and 13 . In this case, from the start to the end of the operation, without changing the position and posture of the cassettes, the unprocessed wafers are taken out from the cassettes and are returned in their original positions where the wafers have been stored, and are stored there. In this manner, the apparatus can easily cope with automation of the production line, contamination of the wafers due to dust can be reduced and high production efficiency and high production yield can thus be accomplished.
As etching is repeated, the reaction products adhere to and are deposited on the inner wall of the etching chambers 11 a to 11 c . Therefore, the original state must be recovered by removing the adhering matters by plasma cleaning. The controller 19 judges the timing of this plasma cleaning. In this case, a portion through which the plasma light passes is provided in each of the etching chambers 11 a to 11 c . The sensor 18 measures the intensity of the plasma light passing through this portion and when the measured value reaches a predetermined one, the start timing of plasma cleaning is judged. Alternatively, the timing of plasma cleaning may be judged by counting the number of wafers processed. In each etching chamber by the controller 19 and judging the timing when this value reaches a predetermined value. The actual timing of plasma cleaning that is carried out may be during a processing of a predetermined number of wafers in the cassette 1 a or 1 b , after the processing of all the wafers 20 in a cassette is completed and before the processing of wafers in the next cassette.
Plasma cleaning is carried out in the following sequence. In this case, the explanation will be given about a case where the etching chambers 11 a to 11 c are subjected to plasma cleaning by using three dummy wafers 30 among the dummy wafers 30 (twenty-five dummy wafers are stored in this case) stored in the cassette. 1 c.
Dummy wafers 30 which are stored in the cassette 1 c and are not used yet or can be used because the number of times of use for plasma cleaning is below a predetermined one are drawn by the conveyor 13 . At this time, dummy wafers 30 stored in any position in the cassette 1 c may be used but in this case, the position numbers of the dummy wafers in the cassette and their number of times of use are stored in the controller 19 , and accordingly dummy wafers having smaller numbers of times of use are drawn preferentially. Then, the dummy wafers 30 are loaded in the load lock chamber 5 disposed on the opposite side to the cassette 1 a by the conveyor 13 through the gate valve 12 a in the same way as the transfer at the time of etching of wafers 20 . After the gate valve 12 a is closed, the load lock chamber 5 is evacuated to a predetermined pressure by the vacuum exhaust device 3 and then the gate valves 12 b and 15 a are opened. The dummy wafers 30 are transferred by the conveyor 14 from the load lock chamber 5 to the etching chamber 11 a through the transfer chamber 16 and are placed on the sample table 8 a . After the gate valve 15 a is closed, plasma cleaning is carried out in the etching chamber 11 a in which the dummy wafers 30 are disposed, under a predetermined condition.
In the interim, the gate valves 12 a , 12 b are closed and the pressure of the load lock chamber 5 is returned to the atmospheric pressure by the gas introduction device 4 . Next, the gate valve 12 a is opened and the second dummy wafer 30 is loaded in the load lock chamber 5 by the conveyor 13 in the same way as the first dummy wafer 30 , and evacuation is effected again by the evacuating device 3 to a predetermined pressure after closing the gate valve 12 a . Thereafter, the gate valves 12 b and 15 b are opened and the second dummy wafer 30 is transferred from the load lock chamber 5 to the etching chamber 11 b through the transfer chamber 16 by the conveyor 14 . Plasma cleaning is started after the gate valve 15 b is closed.
In the interim, the third dummy wafer 30 is transferred into the etching chamber 11 c in the same way as the second dummy wafer 30 and plasma cleaning is carried out.
After plasma cleaning is completed in the etching chamber 11 a in which the first dummy wafer 20 is placed, the gate valves 15 a and 12 c are opened. The used dummy wafer 30 is transferred from the etching chamber 11 a to the unload lock chamber 6 by the conveyor 14 . Then, the gate valve 12 c is closed. After the pressure of the unload lock chamber 6 is returned to the atmospheric pressure by the gas introduction device 4 , the gate valve 12 d is opened. The used dummy wafer 30 transferred to the unload lock chamber 6 is taken out in the air by the conveyor 13 through the gate valve 12 d and is returned to its original position in the cassette 1 c in which it is stored at the start.
When plasma cleaning of the etching chambers 11 b and 11 c is completed, the second and third dummy wafers 20 are returned to their original positions in the cassette 1 c.
In this way, the used dummy wafers 30 are returned to their original positions in the cassette 1 c and the dummy wafers 30 are always stocked in the cassette 1 c . When all the dummy wafers 30 in the cassette 1 c are used for plasma cleaning or when the numbers of times of use of the wafers 30 reach the predetermined ones after the repetition of use, the dummy wafers 30 are replaced as a whole together with the cassette 1 c . The timing of this replacement of the cassette is managed by the controller 19 and the replacement is instructed to the host control apparatus for controlling the line transfer robot or to the operator.
Although the explanation given above deals with the case where the etching chambers 11 a to 11 c are continuously plasma-cleaned by the use of three dummy wafers 30 among the dummy wafers 30 in the cassette 1 c , other processing methods may be employed, as well.
For example, the etching chambers 11 a to 11 c are sequentially plasma-cleaned by the use of one dummy wafer 30 . In the case of such plasma cleaning, unprocessed wafers 20 can be etched in etching chambers other than the one subjected to plasma cleaning, and plasma cleaning can thus be carried out without interrupting etching.
If the processing chambers are different, for example, there are an etching chamber, a post-processing chamber and a film-formation chamber, and wafers are sequentially processed while passing through each of these processing chambers, each of the processing chambers can be subjected appropriately to plasma cleaning by sending dummy wafers 30 during the processing of the wafers 20 which are stored in the cassette 1 a or 2 a and drawn and sent sequentially, by passing merely the dummy wafers 30 through the processing chambers for which plasma cleaning is not necessary, and by executing plasma cleaning only when the dummy wafers 30 reach the processing chambers which need plasma cleaning.
According to the embodiment described above, the cassette storing the dummy wafers and the cassettes storing the wafers to be processed are disposed together in the air, the dummy wafers are loaded from the cassette into the apparatus by the same conveyor as the conveyor for transferring the wafers, at the time of cleaning, and the used dummy wafers are returned to their original positions in the cassette. In this way, a mechanism for conducting exclusively plasma cleaning need not be provided, and the construction of the apparatus can be simplified. It is not necessary to handle plasma cleaning as aparticular processing sequence, but the plasma cleaning can be incorporated in an ordinary etching processing and can be carried out efficiently in a series of operations.
The dummy wafers used for plasma cleaning are returned to their original positions in the cassette placed in the air. Accordingly, the used dummy wafers and the wafers before and after processing do not exist mixedly in the vacuum chamber, so that contamination of wafers due to dust and remaining gas does not occur unlike conventional apparatuses.
The used dummy wafers are returned to their original positions in the cassette and the numbers of times of their use is managed. Accordingly, it is possible to prevent the confusion of the used dummy wafers with the unused dummy wafers and the confusion of the dummy wafers having small numbers of times of use with the dummy wafers having large numbers of times of use. For these reasons, the dummy wafers can be used effectively without any problem when plasma cleaning is carried out.
Furthermore, in accordance with the present invention, the apparatus can have a plurality of processing chambers and can transfer wafers and dummy wafers by the same conveyor. Since plasma cleaning can be carried out by managing the timing of cleaning of each processing chamber by the controller, the cleaning cycle can be set arbitrarily, dry cleaning can be carried out without interrupting the flow of the processing, the processing can be efficiently made and the productivity can be improved.
As described above, according to the present invention, there are effects that the construction of the apparatus is simple, the substrates to be processed are free from contamination and the production yield is high. | A vacuum processing apparatus which includes a cassette mount table for holding a cassette, a conveying structure for transferring a wafer from the held on the cassette mount table, a robot, and a vacuum loader. The vacuum loader is provided with a vacuum conveyor chamber and a conveying structure which further include an additional robot. | 8 |
FIELD OF THE INVENTION
[0001] The invention relates to a method for the treatment of material containing at least one valuable metal and arsenic to form a valuable metal-depleted scorodite sediment and a pure aqueous solution to be removed from the process. According to the method, the valuable metals are first removed from the material to be treated and then arsenic precipitation from the solution is performed in two stages. The aim is to use the method to obtain as low a valuable metal content as possible in the scorodite sediment that will be formed. Likewise, the arsenic and valuable metal content of the aqueous solution that is formed during arsenic precipitation also remains so low that the water can be released into the environment.
BACKGROUND OF THE INVENTION
[0002] Arsenic appears in nature in many different formations. Very commonly arsenic appears with iron and copper, but also with nickel, cobalt, gold and silver. Arsenic is also the most important impurity to remove during recovery of non-ferrous metals. During pyrometallurgical processes the majority of arsenic remains in the fly ash of the waste heat boiler and electric furnace. The utilisation of arsenic has not grown in relation to its recovery, so the majority of arsenic has to be stored in the form of waste. Since arsenic and its compounds are toxic, they must be turned into as poorly soluble a form as possible before they are removed from the process. The less soluble arsenic compounds in the neutral pH zone are for instance zinc, copper and lead arsenates, but the binding of arsenic to these valuable metals is not under serious consideration, specifically because of the valuable metal content that remains in the waste. One current arsenic precipitation method that is frequently used is to precipitate arsenic with iron as ferric arsenate, which is fairly insoluble. In particular, the crystalline form of ferric arsenate, scorodite, FeAsO 4 .2H 2 O, is less soluble than its other form, amorphous ferric arsenate. One arsenic recovery method is described in CA patent application 2384664, which presents a method for the recovery of arsenic from an acidic solution that also contains copper and divalent and trivalent iron. Arsenic precipitation is performed in one stage, wherein the stage comprises several stirred tank reactors into which air is passed. The temperature of the reactors is held in the range of 60-100° C. to prevent the co-precipitation of copper. In order to precipitate the ferric arsenate, a neutralizing agent is fed into the reactors, helping to maintain the pH value between 1.5-1.9. The precipitated ferric arsenate is recycled to the first reactor and ferric arsenate compounds are fed into the solution as seeds. Arsenic recovery is connected to sulphidic concentrate leaching, which occurs by means of trivalent iron. The solution from concentrate leaching is routed to the arsenic removal described above, and the solution exiting arsenic removal is routed in turn to copper extraction.
[0003] U.S. Pat. No. 6,406,676 describes a method for removing arsenic and iron from an acidic solution that is generated in the hydrometallurgical treatment of concentrate. Arsenic and iron precipitation are performed in two steps, where the pH is kept in the range of 2.2-2.8 in the first precipitation step and between 3.0-4.5 in the second step. Lime is added to both precipitation steps and in addition air is injected in the second step. Each step produces its own iron-arsenic residue, and the residue from the second step is recycled to the first step where any unreacted lime can be exploited in the first stage. The residue from the second step can also be recycled to the beginning of the same step to improve the crystallisation of the residue. According to the example, the method is applicable for a zinc-containing solution and it is stated that zinc is not precipitated with the iron and arsenic, but can be recovered after this treatment.
[0004] The article by Wang, Q. et al entitled “Arsenic Fixation in Metallurgical Plant Effluents in the Form of Crystalline Scorodite via a Non-Autoclave Oxidation-Precipitation Process”, Society for Mining Metallurgy and Exploration, Inc, 2000, describes a method for removing arsenic from fly ash, in which arsenic is recovered as scorodite. The first treatment stage of the arsenic-containing material is the oxidation of trivalent arsenic (As(III)) into pentavalent arsenic (As(V)) with a gas containing sulphur dioxide and oxygen in oxidising conditions, in which arsenic does not precipitate. After this, arsenic is precipitated in atmospheric conditions, in which the Fe(III)/As(V) mole ratio is specified as 1. Precipitation is carried out either in one or several stages, but precipitation as scorodite demands the over-saturation of the solution, which is achieved by recycling scorodite crystals to the first precipitation reactors and simultaneously neutralising the suspension. A beneficial pH range is around 1-2 and this is maintained by feeding a suitable neutralising agent into the precipitation stage. In these conditions, arsenic can be precipitated to the level of 0.5 g/l. The final arsenic removal to a level below 0.1 mg/l is done by means of a second purification stage, in which the iron and arsenic Fe(III)/As(V) mole ratio is adjusted to a value in a range of 3-5 and the pH to a value between 3.5-5. The amorphous precipitate generated in this stage is routed back to the first precipitation stage, where it dissolves and precipitates again as scorodite. It is stated in the article that if valuable metals are present in the solution, they can be recovered after arsenic precipitation.
[0005] The tests described in the article mentioned above give a good understanding of arsenic precipitation, but in all the tests carried out, arsenic precipitation was done first and recovery of valuable metals afterwards. The disadvantage of these methods is that water-soluble valuable metals originating from an alkaline solution remain in the ferric arsenate residue precipitated from the solution containing valuable metals, and cannot be recovered even after thorough washing.
PURPOSE OF THE INVENTION
[0006] The purpose of the present invention is to eliminate the drawbacks that have appeared in the methods described above and thus to achieve a better recovery of valuable metals. In the method according to the invention, the recovery of valuable metals such as copper from the material to be treated is carried out first and arsenic removal is performed after this, so that in addition the concentration of the valuable metals and arsenic in the aqueous solution to be removed from the process is made so low that it can be discharged into the environment.
SUMMARY OF THE INVENTION
[0007] The characteristic features of the method according to the invention are presented in the attached claims.
[0008] The invention relates to a method for treating material that contains at least one valuable metal and arsenic, and the purpose is to produce a scorodite residue that can be stored, which has a low valuable metal content, and a pure aqueous solution that can be removed from the process. A dilute acidic solution is formed of a material containing a valuable metal and arsenic and first at least one valuable metal is removed from the solution by means of liquid-liquid extraction and/or precipitation, after which the valuable metal-depleted solution is routed to two-stage arsenic removal. In the first stage of arsenic removal the majority of the arsenic in the solution is precipitated as scorodite FeAsO 4 .2H 2 O and the solution exiting precipitation is routed to the second precipitation stage, in which the rest of the arsenic is precipitated as amorphous ferric arsenate, which is recycled to the first precipitation stage. The arsenic content of the aqueous solution removed from the precipitation stage is in the range of 0.01-0.2 mg/l.
[0009] According to one preferred embodiment of the invention, the material containing a valuable metal and arsenic is the fly ash formed in the pyrometallurgical treatment of non-ferrous metals.
[0010] According to another embodiment of the invention, the material containing a valuable metal and arsenic is the calcine formed in pyrometallurgical treatment of non-ferrous metals.
[0011] According to one embodiment of the invention, at least some of the dilute acid used in leaching material which contains a valuable metal and arsenic is the arsenic-containing dilute acid generated in the treatment of non-ferrous metals. Such is for instance the dilute acid generated in scrubbing arsenic-containing gases. The acid is preferably sulphuric acid, with a concentration of 10-200 g/l.
[0012] According to one preferred embodiment of the invention, the valuable metal to be recovered is copper.
[0013] In an embodiment according to the invention, the Fe/As mole ratio in the first arsenic precipitation stage is adjusted to be between 1-1.1 and an oxidant is fed into the stage to oxidise the arsenic to pentavalent and the iron if necessary to trivalent, the pH of the stage is adjusted to between 1-2 and the temperature to between 85-135° C. in order to precipitate the arsenic as scorodite. The Fe/As mole ratio is adjusted by means of arsenic analysis and/or by adjusting the ratio of the solution streams. The pH adjustment is carried out preferably by means of limestone or lime. The scorodite formed in the precipitation stage is recycled to the front end of the precipitation stage to form seed crystals.
[0014] The overflow solution exiting the thickening of the first precipitation stage is routed to the second precipitation stage, in which the Fe/As mole ratio is adjusted to be over three, the pH value to between 4-7 and the temperature to between 40-60° C. in order to precipitate the arsenic as amorphous ferric arsenate. The Fe/As mole ratio is adjusted by adding divalent or trivalent iron into the precipitation stage and the pH adjustment is preferably carried out by means of lime.
LIST OF DRAWINGS
[0015] FIG. 1 presents a diagram of the method according to the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0016] The invention relates to a method for the treatment of material containing a valuable metal and arsenic, whereby the valuable metals are first removed from the material and then the arsenic as poorly soluble scorodite. The material to be treated may be for example the fly ash generated in the pyrometallurgical treatment of non-ferrous metals or a calcine that contains for instance copper, iron and arsenic. As a result of both pyrometallurgical and hydrometallurgical treatment an arsenic-containing dilute acid may also be generated, having a low valuable metal content, but its treatment may be combined with the treatment of other arsenic-containing solids such as dust. Such is for instance the dilute acid generated in scrubbing arsenic-containing gases.
[0017] FIG. 1 presents the principle diagram of the process according to the invention. It is worth noting that although we talk of fly ash in the description below, the treatment according to the invention is also highly suitable for treating other arsenic-containing material.
[0018] Where fly ash generated during the fabrication of non-ferrous metals is concerned, the majority of it is sulphate-based, so it dissolves easily in the leaching stage into a dilute acid such as dilute sulphuric acid, preferably with a concentration of 10-200 g/l. If some of the valuable metals in the fly ash are in sulphide form, leaching can be intensified by feeding oxygen-containing gas into the leaching stage (not shown in detail in the diagram). When leaching is carried out using the arsenic-containing dilute acid formed in the process, arsenic recovery can be performed simultaneously from two different intermediate products. In leaching performed in stirred tank reactors in atmospheric conditions, almost all of the arsenic and the majority of the copper dissolves, and about half of the iron. The concentrations of the various metals in this kind of solution are typically in the following range: 20-40 g of copper, iron and arsenic per litre. The metal-containing leaching residue is recycled back for instance to pyrometallurgical treatment of non-ferrous metal production.
[0019] The acidic aqueous solution containing valuable metals and arsenic is first routed to the valuable metal recovery stage. When the most important valuable metal in the fly ash is copper, copper removal is performed first. Copper removal is preferably made by means of liquid-liquid extraction, where the copper-rich aqueous solution obtained from stripping is routed to electrolysis. The acid concentration of the aqueous solution entering extraction is for example 30 g/l H 2 SO 4 and the copper concentration 20 g/l. Over 97% copper is recovered via extraction and electrolysis.
[0020] The remainder of the copper, which is not recovered in extraction, can if necessary be removed from the aqueous solution of extraction i.e. the raffinate, by sulphide precipitation for example. Sulphide precipitation is carried out preferably in two stages using hydrogen sulphide gas or some suitable hydroxide as neutralising agent. In the first stage the pH value is adjusted to be between 1.5-2 and in the second stage to 2-2.5. If the amount of copper is too small, in other words if it is only a matter of e.g. dilute acid formed in the process, sulphide precipitation is sufficient as the only form of copper recovery.
[0021] According to the method, arsenic is precipitated from a solution free of valuable metals in two stages. When the intermediate product that contains arsenic is fly ash, iron is in its aqueous solution in order to precipitate arsenic as scorodite FeAsO 4 .2H 2 O, but if there is insufficient amount of iron, it is added to the precipitation stage. The arsenic in the solution exiting copper recovery is mostly trivalent. An oxidant is routed to the first stage of precipitation, which is strong enough to oxidise all the arsenic to pentavalent. The iron in the solution is trivalent. The oxidant used may be for instance oxygen, hydrogen peroxide or another suitable oxidant. Arsenic precipitation occurs in accordance with the following formula:
[0000] Fe 3+ +H 3 AsO 4 +H 2 O→FeAsO 4 .2H 2 O (solid) +3 H + (1)
[0022] As the formula shows, arsenic precipitation forms acid in the solution and this must be neutralised. The preferred neutralising agent is limestone or lime. As mentioned in the description of the prior art, the Fe(III)/As(V) mole ratio should be around 1-1.1 in the first precipitation stage, the pH value between 1-2 and the temperature in the range of 85-135° C. The correct iron/arsenic ratio is formed by arsenic analysis and ratio control of the solution streams. In the precipitation stage, which occurs in several consecutive stirred reactors although only one reactor is shown in the flow chart, the scorodite crystals formed are recycled as underflow from the tail end of the stage, particularly from thickening, into the first reactor to ensure that the reaction proceeds.
[0023] Typically the amount of arsenic in the solution entering arsenic removal is around 20-30 g/l and the arsenic concentration of the solution removed from the process may be a maximum of 0.2 mg/l. In the first precipitation stage the arsenic concentration of the solution falls to a value of around 0.1-1 g/l. The rest of the arsenic is precipitated in the second precipitation stage, in which the Fe(III)(As(V) mole ratio is adjusted to be over three. The adjustment usually occurs by adding ferrous or ferric iron to this precipitation stage. If divalent iron is added as in the diagram, it is oxidised with air to trivalent. The pH value is adjusted to the range 4-7, preferably using lime as neutralising agent. The temperature of the second precipitation stage can be adjusted to be lower than the temperature of the first stage, to about 40-60° C. Since the conditions differ from those of the first precipitation stage, the arsenic residue generated is not scorodite, but amorphous ferric arsenate. The residue separated from thickening after the second precipitation stage is recycled to the first precipitation stage, in which conditions it dissolves and the arsenic is precipitated again as scorodite. The arsenic concentration of the aqueous solution removed from the second precipitation stage is typically around 0.01-0.2 mg/l, in other words the solution meets environmental requirements and can be discharged from the process, since the valuable metals have been removed from the solution earlier.
EXAMPLES
Example 1
[0024] Dusts from a copper smelter are leached into a solution containing sulphuric acid, so that the copper concentration of the solution is 20 g/l, the iron concentration 4 g/l, the arsenic concentration 15 g/l and the sulphuric acid concentration 30 g/l. The solution is routed to liquid-liquid copper extraction, after which the concentrations of the aqueous solution raffinate are as follows: Cu 0.4 g/l, Fe 4 g/l, As 15 g/l and sulphuric acid 60 g/l.
[0025] The raffinate (10 m 3 /h), from which the valuable metals have been recovered, is routed to arsenic removal. The purpose is to precipitate the arsenic in a stable form suitable for landfill (as scorodite FeAsO 4 .2H 2 O) and to obtain a final solution suitable for removal (As <0.01 mg/l). This takes place by means of continuous two-stage precipitation.
[0026] The solution, which includes 15 g arsenic/l, 4 g iron/l and 60 g sulphuric acid/l, is routed to the first precipitation stage, where the pH value is kept at around 1.5 by means of lime milk (CaCO 3 759 kg/h). The additional iron required for scorodite precipitation is obtained with the addition of ferrous sulphate (392 kg/h FeSO 4 .7H 2 O) to the desired Fe/As mole ratio of 1.1. The oxidation of arsenic and iron are ensured by using hydrogen peroxide or some other suitable oxidant.
[0027] The first precipitation stage comprises three oxidation reactors connected in series, in which the temperature is maintained in the range 85-95° C. and the pH value between 1-1.5. After the first precipitation stage the slurry is thickened and the overflow is routed to the second precipitation stage. Some of the underflow of the first precipitation stage (0.5 m 3 /h, solids content 200 g/l) is recycled to the beginning of the reactor series as seed crystals. The sediment obtained, which contains 7.8% arsenic in scorodite form and 0.2% copper, is filtered and stored. Over 95% of the arsenic is precipitated in this precipitation stage and the solution now only contains 0.6 g arsenic/l.
[0028] Arsenic precipitation is continued in the second stage, which in principle is the same chain of three oxidation reactors. Neutralisation is continued with lime milk (Ca(OH) 2 5 kg/h) up to a pH value of 7. The temperature is adjusted to be in the range of about 50° C. Ferrous sulphate (7 kg/h FeSO 4 .7H 2 O) is again added to the second precipitation stage, the iron equivalent of which is three times that of stoichiometric arsenic in order to ensure the most complete separation of arsenic possible. Air bubbles are used to oxidise ferrous iron. Arsenic is precipitated as amorphous ferric arsenate in this stage, and is then settled and returned to the first stage as underflow (0.14 m 3 /h and a solids content of 200 g/l), where it transforms into crystalline scorodite. After this precipitation stage the solution only contains approx. 0.01 mg/l arsenic, less than 0.1 mg/l iron and less than 1 mg/l copper, and its pH value is 7. Thus the impurity level of the solution is such that it can be freely discharged from the circuit. | The invention relates to a method for the treatment of material containing at least one valuable metal and arsenic to form a valuable metal-depleted scorodite sediment and a pure aqueous solution to be discharged from the process. According to the method, the valuable metals are first removed from the material to be treated and then arsenic precipitation from the solution is performed in two stages. By means of the method, the aim is to obtain as low a valuable metal content as possible in the scorodite sediment that will be formed. Likewise, the arsenic and valuable metal content of the aqueous solution that is formed during arsenic precipitation also remains so low that the water can be released into the environment. | 8 |
FIELD OF THE INVENTION
[0001] The present invention relates to 7a-heterocycle substituted 6,6-difluro bicyclic himbacine derivatives, which are useful as protease activated receptor-1 (PAR-1) antagonists and might be expected to be cannabinoid (CB 2 ) receptor inhibitors. PAR-1 receptors are also known in the art as thrombin receptor antagonists (TRA). The inventive compounds have utility in treating disease states such as acute coronary syndrome (ACS) (unstable angina, non-ST-segment elevation [NSTE] myocardial infarction [MI], and ST segment-elevation myocardial infarction [STEMI]), secondary prevention of myocardial infarction or thrombotic stroke (secondary prevention) or peripheral artery disease (PAD), which is also know in the art as peripheral vascular disease. The present invention also relates to pharmaceutical compositions comprising the inventive compounds as well as processes for their preparation.
BACKGROUND OF THE INVENTION
[0002] Thrombin is known to have a variety of activities in different cell types. PAR-1 receptors are known to be present in such cell types as human platelets, vascular smooth muscle cells, endothelial cells and fibroblasts. The art indicates that PAR-1 receptor antagonists would be expected to be useful in the treatment of thrombotic, inflammatory, atherosclerotic and fibroproliferative disorders, as well as other disorders in which thrombin and its receptor play a pathological role.
[0003] Thrombin receptor antagonist peptides have been identified based on structure-activity studies involving substitutions of amino acids on thrombin receptors. In Bernatowicz et al., J. Med. Chem., 39 (1996), p. 4879-4887, tetra- and pentapeptides are disclosed as being potent thrombin receptor antagonists, for example N-trans-cinnamoyl-p-fluoroPhe-p-guanidinoPhe-Leu-Arg-NH 2 and N-trans-cinnamoyl-p-fluoroPhe-p-guanidinoPhe-Leu-Arg-Arg-NH 2 . Peptide thrombin receptor antagonists are also disclosed in WO 94/03479.
[0004] Cannabinoid receptors belong to the superfamily of G-protein coupled receptors. They are classified into the predominantly neuronal CB 1 receptors and the predominantly peripheral CB 2 receptors. These receptors exert their biological actions by modulating adenylate cyclase and Ca +2 and K + currents. While the effects of CB 1 receptors are principally associated with the central nervous system, CB 2 receptors are believed to have peripheral effects related to bronchial constriction, immunomodulation and inflammation. As such, the art suggests that a selective CB 2 receptor binding agent might be expected to have therapeutic utility in the control of diseases associated with rheumatoid arthritis, systemic lupus erythematosus, multiple sclerosis, diabetes, osteoporosis, renal ischemia, cerebral stroke, cerebral ischemia, nephritis, inflammatory disorders of the lungs and gastrointestinal tract, and respiratory tract disorders such as reversible airway obstruction, chronic asthma and bronchitis (R. G. Pertwee, Curr. Med. Chem. 6(8), (1999), 635; M. Bensaid, Molecular Pharmacology, 63 (4), (2003), 908).
[0005] Himbacine, a piperidine alkaloid of the formula
[0000]
[0000] has been identified as a muscarinic receptor antagonist. The total synthesis of (+)-himbacine is disclosed in Chackalamannil et al., J. Am. Chem. Soc., 118 (1996), p. 9812-9813.
[0006] Substituted bi- and tricyclic thrombin receptors antagonists are known in the art to treat thrombin receptor mediated disorders such as thrombosis, atherosclerosis, restenosis, hypertension, angina pectoris, angiogenesis related disorders, arrhythmia, a cardiovascular or circulatory disease or condition, heart failure, ACS, myocardial infarction, glomerulonephritis, thrombotic stroke, thromboembolytic stroke, PAD, deep vein thrombosis, venous thromboembolism, a cardiovascular disease associated with hormone replacement therapy, disseminated intravascular coagulation syndrome and cerebral infarction, as well as CB 2 receptor mediated disorders. U.S. Pat. No. 6,645,987 and U.S. Pat. No. 6,894,065 disclose PAR-1 receptor antagonists of the structure:
[0000]
[0000] where R 10 may be groups such as H, alkyl, haloalkyl, hydroxyl, etc. and R 22 may be groups such as H, optionally substituted alkyl, hydroxyl, etc. Other known substituted thrombin receptor antagonists are disclosed in WO2001/96330, U.S. Pat. No. 6,063,847, U.S. Pat. No. 6,326,380, U.S. Pat. No. 7,037,920, U.S. Pat. No. 7,488,742, U.S. Pat. No. 7,713,999, U.S. Pat. No. 7,442,712, U.S. Pat. No. 7,488,752, U.S. Pat. Nos. 7,776,889, 7,888,369, U.S. Pat. No. 8,003,803 and U.S. Pat. No. 8,022,088. US 2008/0090830 and Chackalamannil et al., J. Med. Chem., 49 (2006), p. 5389. A PAR-1 receptor antagonist that exhibits good thrombin receptor antagonist activity (potency) and selectivity is vorapaxar (Merck & Co., Inc.), which has the following structure:
[0000]
[0000] This compound underwent clinical trials and is disclosed in U.S. Pat. No. 7,304,048. A crystalline form of the bisulfate salt of vorapaxar is disclosed in U.S. Pat. No. 7,235,567.
[0007] WO2011/162,562 to LG Life Sciences LTD. describes a series of [6+5] fused bicycle derivatives of the general structure:
[0000]
[0000] where R 5 and R 6 are inter alia both fluoro groups, as inhibitors of the PAR-1 receptor. The compounds are taught to be useful in the treatment and prevention of thrombus, platelet aggregation, atherosclerosis, restenosis, blood coagulation, hypertension, arrhythmia, angina pectoris, heart failure, inflammation and cancer when used alone or with other cardiovascular agents.
[0008] WO2011/28420 and WO2011/28421, both to Sanofi-Aventis, disclose compounds that are reported to be PAR-1 receptor antagonists. The compounds disclosed in WO2011/28420 are pyridyl-vinyl pyrazoloquinolines derivatives and have the following general structure:
[0000]
[0000] WO2011/28421 discloses tryicyclic pyridyl-vinyl-pyrrole derivatives of the following general structure:
[0000]
[0000] PCT/US13/027383 to Merck Sharpe & Dohme Corp. discloses bicyclic himbacine derivatives of the following general structure
[0000]
[0000] where R 10 and R 11 may both be fluoro groups. These compounds are PAR-1 receptor antagonists.
[0009] Applicants discovered in accordance with the present invention that the inventive compounds act as inhibitors of PAR-1 receptor and, based upon their structure, might also act as inhibitors of the CB 2 receptor. Therefore, the inventive compounds might be expected to be useful in treating disease states associated with the inhibition of these receptors.
[0010] There is a need for new compounds, formulations, treatment and therapies to treat diseases associated with the PAR-1 and CB 2 receptors. Moreover, there is a need to develop therapeutics that exhibit improved therapeutic profiles; for example, desirable half-life or reduced unintended effects, such as reduced drug-drug interactions (DDIs). DDIs are potentially undesirable as they can reduce the therapeutic effectiveness of an agent or increase the incidence of unintended effects associated with the drug. It is, therefore, an object of this invention to provide compounds useful in the treatment, prevention or amelioration of such diseases or disorders with improved therapeutic profiles. These and other objectives will become evident from the following description.
SUMMARY OF THE INVENTION
[0011] In its many embodiments, the present invention provides for a novel group of bicyclic himbacine derivatives, which are PAR-1 receptor antagonists, or metabolites, stereoisomers, salts, solvates or polymorphs thereof, processes of preparing such compounds, pharmaceutical compositions comprising one or more such compounds, processes of preparing pharmaceutical compositions comprising one or more such compounds and potentially methods of treatment, inhibition or amelioration of one or more disease states associated with the PAR-1 receptor by administering an effective amount at least one of the inventive bicyclic himbacine derivatives to a patient in need thereof.
[0012] In one aspect, the present application discloses a compound or a pharmaceutically acceptable salt, metabolite, solvate, prodrug or polymorph of said compound, said compound or pharmaceutically acceptable salt thereof having the general structure shown in Formula I
[0000]
[0013] wherein:
R 1 is
[0000]
W is
[0000]
R a is independently H or C 1 -C 4 alkyl;
R b is H; C 1 -C 4 alkyl; cycloalkyl (e.g., cyclopropyl); —N(R 3 )(R 4 ); or phenyl, which is independently optionally substituted once or twice by alkyl, haloalkyl, —OH, or alkoxy;
R 2 is independently halo; —CN; alkyl; or haloalkyl;
R 3 is H or alkyl;
R 4 is H or alkyl;
R 5 is H, alkyl or —CN; and
a is 0, 1 or 2.
[0023] Another aspect of the present invention is pharmaceutical compositions comprising a therapeutically effective amount of at least one compound of Formula I or a pharmaceutically acceptable salt thereof and a pharmaceutically acceptable carrier.
[0024] Another aspect of the present invention is pharmaceutical compositions comprising a therapeutically effective amount of at least one compound of Formula I or a pharmaceutically acceptable salt thereof, at least one additional cardiovascular agent and a pharmaceutically acceptable carrier.
[0025] Another aspect of the present invention is the possible prevention of one or more disease state associated with inhibiting the PAR-1 receptor by administering an effective amount of a compound of Formula I or a pharmaceutically acceptable salt thereof to a patient in need thereof.
[0026] Another aspect of the present invention is a method of inhibiting platelet aggregation comprising administering to a mammal an effective amount of a compound of Formula I or a pharmaceutically acceptable salt thereof.
[0027] It is further contemplated that the combination of the invention could be provided as a kit comprising in a single package at least one compound of Formula I or a pharmaceutically acceptable salt thereof in a pharmaceutical composition, and at least one separate pharmaceutical composition, such as, for example a separate pharmaceutical composition comprising a cardiovascular agent.
[0028] The compounds of the present invention can potentially be useful in the treatment, amelioration or prevention of one or more conditions associated with inhibiting the PAR-1 receptor by administering at least one compound of Formula I or a pharmaceutically acceptable salt thereof to a mammal in need of such treatment. Conditions that could potentially be treated or prevented by inhibiting the PAR-1 receptor include thrombosis, atherosclerosis, restenosis, hypertension, angina pectoris, angiogenesis related disorders, arrhythmia, a cardiovascular or circulatory disease or condition, heart failure, ACS, myocardial infarction, glomerulonephritis, thrombotic stroke, thromboembolytic stroke, PAD, deep vein thrombosis, venous thromboembolism, a cardiovascular disease associated with hormone replacement therapy, disseminated intravascular coagulation syndrome and cerebral infarction.
[0029] Another embodiment is the possible treatment, amelioration or prevention of ACS, secondary prevention of myocardial infarction or stroke, urgent coronary revascularization, or PAD by administering at least one compound of Formula I or a pharmaceutically acceptable salt thereof to a mammal in need of such treatment.
[0030] Another embodiment of this invention is in the possible treatment, amelioration or prevention of one or more conditions associated with cardiopulmonary bypass surgery (CPB) by administering effective amount of at least one compound of Formula I or a pharmaceutically acceptable salt thereof to a subject of said CPB surgery. CPB surgery includes coronary artery bypass surgery (CABG), cardiac valve repair and replacement surgery, pericardial and aortic repair surgeries. The conditions associated with CABG include bleeding, thrombotic vascular events (such as thrombosis or restenosis), vein graft failure, artery graft failure, atherosclerosis, angina pectoris, myocardial ischemia, acute coronary syndrome, myocardial infarction, heart failure, arrhythmia, hypertension, transient ischemic attack, cerebral function impairment, thromboembolic stroke, cerebral ischemia, cerebral infarction, thrombophlebitis, deep vein thrombosis and PAD.
[0031] Another embodiment of the present invention is the possible use of a compound of Formula I or a pharmaceutically acceptable salt thereof for the manufacture of a medicament for the treatment, amelioration or prevention of one or more conditions associated with inhibiting the PAR-1 receptor in a patient.
DETAILED DESCRIPTION
[0032] In an embodiment, the present invention provides compounds represented by structural Formula I, or pharmaceutically acceptable salt thereof, wherein the various moieties are as described as above.
[0033] Another embodiment is the following compounds:
2-(6-((E)-2-((3R,3aS,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-1-oxo-7a-(5-oxo-4,5-dihydro-1,3,4-oxadiazol-2-yl)octahydroisobenzofuran-4-yl)vinyl)pyridin-3-yl)benzonitrile (1); 2-(6-((E)-2-((3R,3aS,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-1-oxo-7a-(5-oxo-4,5-dihydro-1,3,4-oxadiazol-2-yl)octahydroisobenzofuran-4-yl)vinyl)pyridin-3-yl)-6-methylbenzonitrile (2); 2-(6-((E)-2-((3R,3aS,4R,5S,7aR)-7a-(5-amino-1,3,4-oxadiazol-2-yl)-6,6-difluoro-3,5-dimethyl-1-oxooctahydroiso benzofuran-4-yl)vinyl)pyridin-3-yl)-6-methylbenzonitrile (3); 2-(6-((E)-2-((3R,3aS,4R,5S,7aR)-7a-(5-amino-1,3,4-oxadiazol-2-yl)-6,6-difluoro-3,5-dimethyl-1-oxooctahydroiso benzofuran-4-yl)vinyl)pyridin-3-yl)benzonitrile (4); 2-(6-((E)-2-((3R,3aS,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-7a-(5-methyl-1,3,4-oxadiazol-2-yl)-1-oxooctahydroisobenzofuran-4-yl)vinyl)pyridin-3-yl)-6-methylbenzonitrile (5); 2-(6-((E)-2-((3R,3aS,4R,5S,7aR)-7a-(5-cyclopropyl-1,3,4-oxadiazol-2-yl)-6,6-difluoro-3,5-dimethyl-1-oxooctahydroisobenzofuran-4-yl)vinyl)pyridin-3-yl)-6-methylbenzonitrile (6); 2-(6-((E)-2-((3R,3aS,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-1-oxo-7a-(5-phenyl-1,3,4-oxadiazol-2-yl) octahydroisobenzofuran-4-yl)vinyl)pyridin-3-yl)-6-ethylbenzonitrile (7); 5-((1R,3aR,6S,7R,7aS)-5, 5-difluoro-7-((E)-2-(5-(3-fluorophenyl)pyridin-2-yl)vinyl)-1,6-dimethyl-3-oxooctahydroisobenzofuran-3a-yl)-1,3,4-oxadiazol-2(3H)-one (8); 2-(6-((E)-2-((3R,3aS,4R,5S,7aR)-7a-(5-(tert-butyl)-1H-pyrazol-3-yl)-6,6-difluoro-3,5-dimethyl-1-oxooctahydroisobenzofuran-4-yl)vinyl)pyridin-3-yl)benzonitrile (9); 2-(6-((E)-2-((3R,3aS,4R,5S,7aR)-7a-(5-(tert-butyl)-1-methyl-1H-pyrazol-3-yl)-6,6-difluoro-3,5-dimethyl-1-oxooctahydroisobenzofuran-4-yl)vinyl)pyridin-3-yl)benzonitrile (10); 2-(6-((E)-2-((3R,3aS,4R,5S,7aR)-7a-(1,5-dimethyl-1H-pyrazol-3-yl)-6,6-difluoro-3,5-dimethyl-1-oxooctahydroiso benzofuran-4-yl)vinyl)pyridin-3-yl)benzonitrile (11); 6′-((E)-2-((3R,3aS,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-1-oxo-7a-(1H-pyrazol-3-yl)octahydroisobenzofuran-4-yl)vinyl)-[3,3′-bipyridine]-2-carbonitrile (13)
or a pharmaceutically acceptable salt thereof.
[0046] Another embodiment of the present invention is the following compounds or a pharmaceutically acceptable salt thereof wherein R 1 is
[0000]
[0047] Another embodiment of the present invention is the following compounds or a pharmaceutically acceptable salt thereof wherein R 1 is
[0000]
[0000] and R b is —NH 2 , alkyl (e.g., methyl or ethyl), cyclopropyl or phenyl.
[0048] Another embodiment of the present invention is the following compounds or a pharmaceutically acceptable salt thereof wherein R 1 is
[0000]
[0000] and R a independently is H or alkyl (e.g., methyl, ethyl, n-propyl, n-butyl, iso-butyl or tert-butyl).
[0049] Another embodiment is a compound of Formula I or a pharmaceutically acceptable salt thereof wherein W is
[0000]
[0050] Another embodiment is a compound of Formula I or a pharmaceutically acceptable salt thereof wherein W is
[0000]
[0051] Another embodiment is a compound of Formula I or a pharmaceutically acceptable salt thereof wherein W is
[0000]
[0052] Another embodiment is a compound of Formula I or a pharmaceutically acceptable salt thereof wherein W is
[0000]
[0053] As used above, and throughout this disclosure, the following terms, unless otherwise indicated, shall be understood to have the following meanings:
[0054] “Patient” or “subject” includes both humans and animals.
[0055] “Mammal” means humans and other mammalian animals.
[0056] “Alkyl” means an aliphatic hydrocarbon group which may be straight or branched and comprising about 1 to about 20 carbon or about 1 to 12 atoms in the chain. “Lower alkyl” means a group having about 1 to about 6 carbon atoms in the chain which may be straight or branched. Non-limiting examples of “alkyl” include those have about 1 to 4 carbon atoms in the chain, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, and tert-butyl. Branched means that one or more lower alkyl groups such as methyl, ethyl or propyl, are attached to a linear alkyl chain.
[0057] “Alkoxy” means an alkyl-O— group in which the alkyl group is as previously described. Non-limiting examples of suitable alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy and n-butoxy. The bond to the parent moiety is through the ether oxygen.
[0058] “Halo” refers to fluorine, chlorine, bromine or iodine radicals. Non-limiting examples include fluoro, chloro or bromo, or fluoro and chloro.
[0059] “Halogen” means fluorine, chlorine, bromine, or iodine. Non-limiting examples include fluorine or chlorine.
[0060] “Haloalkyl” means a halo-alkyl-group in which the alkyl group is as previously described. The bond to the parent moiety is through the alkyl. Non-limiting examples of suitable haloalkyl groups include fluoromethyl, difluoromethyl, —CH 2 CF 3 , —CH 2 CHF 2 or —CH 2 CH 2 F.
[0061] “Cycloalkyl” is a cyclized alkyl ring having 3-12 or 3-6 carbon atoms. Examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
[0062] The term “isolated” or “in isolated form” for a compound refers to the physical state of said compound after being isolated from a synthetic process or natural source or combination thereof. The term “purified” or “in purified form” for a compound refers to the physical state of said compound after being obtained from a purification process or processes described herein or well known to the skilled artisan, in sufficient purity to be characterizable by standard analytical techniques described herein or well known to the skilled artisan.
[0063] When a functional group in a compound is termed “protected”, this means that the group is in modified form to preclude undesired side reactions at the protected site when the compound is subjected to a reaction. Suitable protecting groups will be recognized by those with ordinary skill in the art as well as by reference to standard textbooks such as, for example, T. W. Greene et al, Protective Groups in Organic Synthesis (1991), Wiley, New York.
[0064] “Effective amount” or “therapeutically effective amount” is meant to describe an amount of compound or a composition of the present invention effective as PAR-1 or thrombin receptor antagonists, thereby producing the desired therapeutic, ameliorative, inhibitory or preventative effect.
[0065] The compounds of Formula I can form salts which are also within the scope of this invention. Reference to a compound of Formula I herein is understood to include reference to salts thereof, unless otherwise indicated. The term “salt(s)”, as employed herein, denotes acidic salts formed with inorganic and/or organic acids, as well as basic salts formed with inorganic and/or organic bases. In addition, when a compound of Formula I contains both a basic moiety, such as, but not limited to a pyridine or imidazole, and an acidic moiety, such as, but not limited to a carboxylic acid, zwitterions (“inner salts”) may be formed and are included within the term “salt(s)” as used herein. Pharmaceutically acceptable (i.e., non-toxic, physiologically acceptable) salts are preferred, although other salts are also useful. Salts of the compounds of the Formula I may be formed, for example, by reacting a compound of Formula I with an amount of acid or base, such as an equivalent amount, in a medium such as one in which the salt precipitates or in an aqueous medium followed by lyophilization.
[0066] Exemplary acid addition salts include acetates, ascorbates, benzoates, benzenesulfonates, bisulfates, borates, butyrates, citrates, camphorates, camphorsulfonates, fumarates, hydrochlorides, hydrobromides, hydroiodides, lactates, maleates, methanesulfonates, naphthalenesulfonates, nitrates, oxalates, phosphates, propionates, salicylates, succinates, sulfates, tartarates, thiocyanates, toluenesulfonates (also known as tosylates,) and the like. Additionally, acids which are generally considered suitable for the formation of pharmaceutically useful salts from basic pharmaceutical compounds are discussed, for example, by P. Stahl et al, Camille G. (eds.) Handbook of Pharmaceutical Salts. Properties, Selection and Use . (2002) Zurich: Wiley-VCH; S. Berge et al, Journal of Pharmaceutical Sciences (1977) 66(1) 1-19; P. Gould, International J. of Pharmaceutics (1986) 33 201-217; Anderson et al, The Practice of Medicinal Chemistry (1996), Academic Press, New York; and in The Orange Book (Food & Drug Administration, Washington, D.C. on their website). These disclosures are incorporated herein by reference thereto.
[0067] Exemplary basic salts include ammonium salts, alkali metal salts such as sodium, lithium, and potassium salts, alkaline earth metal salts such as calcium and magnesium salts, salts with organic bases (for example, organic amines) such as dicyclohexylamines, t-butyl amines, and salts with amino acids such as arginine, lysine and the like. Basic nitrogen-containing groups may be quarternized with agents such as lower alkyl halides (e.g. methyl, ethyl, and butyl chlorides, bromides and iodides), dialkyl sulfates (e.g. dimethyl, diethyl, and dibutyl sulfates), long chain halides (e.g. decyl, lauryl, and stearyl chlorides, bromides and iodides), aralkyl halides (e.g. benzyl and phenethyl bromides), and others.
[0068] All such acid salts and base salts are intended to be pharmaceutically acceptable salts within the scope of the invention and all acid and base salts are considered equivalent to the free forms of the corresponding compounds for purposes of the invention.
[0069] In this application, unless otherwise indicated, whenever there is a structural formula provided, such as those of Formula I, this formula is intended to encompass all forms of a compound such as, for example, any solvates, hydrates, stereoisomers, tautomers, co-crystals, polymorphs etc.
[0070] Compounds of Formula I, and salts, solvates, co-crystals and prodrugs thereof, may exist in their tautomeric form (for example, as an amide or imino ether). All such tautomeric forms are contemplated herein as part of the present invention.
[0071] Prodrugs, solvates and co-crystals of the compounds of the invention are also contemplated herein. The term “prodrug”, as employed herein, denotes a compound that is a drug precursor which, upon administration to a subject, undergoes chemical conversion by metabolic or chemical processes to yield a compound of Formula I or a salt thereof. A discussion of prodrugs is provided in T. Higuchi and V. Stella, Pro - drugs as Novel Delivery Systems (1987) 14 of the A.C.S. Symposium Series, and in Bioreversible Carriers in Drug Design , (1987) Edward B. Roche, ed., American Pharmaceutical Association and Pergamon Press, both of which are incorporated herein by reference thereto.
[0072] “Solvate” means a physical association of a compound of this invention with one or more solvent molecules. This physical association involves varying degrees of ionic and covalent bonding, including hydrogen bonding. In certain instances the solvate will be capable of isolation, for example when one or more solvent molecules are incorporated in the crystal lattice of the crystalline solid. “Solvate” encompasses both solution-phase and isolatable solvates. Non-limiting examples of suitable solvates include ethanolates, methanolates, and the like. “Hydrate” is a solvate wherein the solvent molecule is H 2 O.
[0073] A co-crystal is a crystalline superstructure formed by combining an active pharmaceutical intermediate with an inert molecule and provides crystallinity to the combined form. Co-crystals are often made between a dicarboxlyic acid such as fumaric acid, succinic acid etc. and a basic amine, such as the one represented by a compound of this invention in different proportions depending on the nature of the co-crystal. (Remenar, J. F. et. al. J Am. Chem. Soc. 2003, 125, 8456).
[0074] All stereoisomers (for example, geometric isomers, optical isomers and the like) of the present compounds (including those of the salts, solvates, co-crystals and prodrugs of the compounds as well as the salts and solvates, co-crystals of the prodrugs), such as those which may exist due to asymmetric carbons on various substituents, including enantiomeric forms (which may exist even in the absence of asymmetric carbons), rotameric forms, atropisomers, and diastereomeric forms, are contemplated within the scope of this invention, as are positional isomers (such as, for example, 4-pyridyl and 3-pyridyl). Individual stereoisomers of the compounds of the invention may, for example, be substantially free of other isomers, or may be admixed, for example, as racemates or with all other, or other selected, stereoisomers. The chiral centers of the present invention can have the S or R configuration as defined by the IUPAC 1974 Recommendations. The use of the terms “salt”, “solvate” “prodrug” and the like, is intended to equally apply to the salt, solvate and prodrug of enantiomers, stereoisomers, rotamers, tautomers, positional isomers, racemates or prodrugs of the inventive compounds.
[0075] The present invention also embraces isotopically-labelled compounds of the present invention which are identical to those recited herein, 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, phosphorus, fluorine and chlorine and iodine, such as 2 H, 3 H, 11 C, 13 C, 14 C, 15 N, 18 O, 17 O, 31 P, 32 P, 35 S, 18 F, 36 Cl and 123 I, respectively.
[0076] Certain isotopically-labelled compounds of Formula (I) (e.g., those labeled with 3 H and 14 C) are useful in compound 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. Certain isotopically-labelled compounds of Formula (I) can be useful for medical imaging purposes. E.g., those labeled with positron-emitting isotopes like 11 C or 18 F can be useful for application in Positron Emission Tomography (PET) and those labeled with gamma ray emitting isotopes like 123 I can be useful for application in Single photon emission computed tomography (SPECT). Further, substitution with heavier isotopes such as deuterium (i.e., 2 H) may afford certain therapeutic advantages resulting from greater metabolic stability (e.g., increased in vivo half-life or reduced dosage requirements) and hence may be preferred in some circumstances. Additionally, isotopic substitution at a site where epimerization occurs may slow or reduce the epimerization process and thereby retain the more active or efficacious form of the compound for a longer period of time. Isotopically-labeled compounds of Formula (I), in particular those containing isotopes with longer half lives (T1/2>1 day), can generally be prepared by following procedures analogous to those disclosed in the Schemes and/or in the Examples herein below, by substituting an appropriate isotopically labeled reagent for a non-isotopically labeled reagent.
[0077] As discussed above, the compounds of Formula I may be used to treat, ameliorate or prevent conditions associated with inhibiting the PAR-1 receptor. In addition to the conditions mentioned above, other conditions could include migraine, erectile dysfunction, rheumatoid arthritis, rheumatism, astrogliosis, a fibrotic disorder of the liver, kidney, lung or intestinal tract, systemic lupus erythematosus, multiple sclerosis, osteoporosis, renal disease, acute renal failure, chronic renal failure, renal vascular homeostasis, renal ischemia, bladder inflammation, diabetes, diabetic neuropathy, cerebral stroke, cerebral ischemia, nephritis, cancer, melanoma, renal cell carcinoma, neuropathy, malignant tumors, neurodegenerative and/or neurotoxic diseases, conditions or injuries, Alzheimer's disease, an inflammatory disease or condition, asthma, glaucoma, macular degeneration, psoriasis, endothelial dysfunction disorders of the liver, kidney or lung, inflammatory disorders of the lungs and gastrointestinal tract, respiratory tract disease or condition, radiation fibrosis, endothelial dysfunction, periodontal diseases or wounds, or a spinal cord injury, or a symptom or result thereof, viral infections, including infections from human respiratory syncytial virus (hRSV), human metapneumovirus (hMPV) and influenza virus type A, as well as other disorders in which thrombin and its receptor play a pathological role.
[0078] In addition to their PAR-1 receptor antagonist properties, the compounds of Formula I or the pharmaceutically acceptable salts might be expected to be used to treat, ameliorate or prevent one or more conditions associated with inhibiting the CB 2 receptor by administering at least one compound of Formula I or a pharmaceutically acceptable salt thereof to a mammal in need of such treatment. Conditions might include, for example, rheumatoid arthritis, systemic lupus erythematosus, multiple sclerosis, diabetes, osteoporosis, renal ischemia, cerebral stroke, cerebral ischemia, nephritis, inflammatory disorders of the lungs and gastrointestinal tract, and respiratory tract disorders such as reversible airway obstruction, chronic asthma and bronchitis.
[0079] In another embodiment, compounds of the present invention might be expected to be useful in a method for treating, ameliorating or preventing radiation- and/or chemical-induced toxicity in non-malignant tissue in a patient comprising administering a therapeutically effective amount of at least one compound of Formula I or a pharmaceutically acceptable salt thereof. In particular, the radiation- and/or chemical-induced toxicity is one or more of intestinal fibrosis, pneumonitis, and mucositis. In one embodiment, the radiation- and/or chemical-induced toxicity is intestinal fibrosis. In another embodiment, the radiation- and/or chemical-induced toxicity is oral mucositis. In yet another embodiment, the radiation- and/or chemical-induced toxicity is intestinal mucositis, intestinal fibrosis, intestinal radiation syndrome, or pathophysiological manifestations of intestinal radiation exposure.
[0080] The present invention might also be expected to provides for methods for reducing structural radiation injury in a patient that will be exposed, is concurrently exposed, or was exposed to radiation and/or chemical toxicity, comprising administering a therapeutically effective amount of at least one compound of Formula I or a pharmaceutically acceptable salt thereof. The present invention might also be expected to provide for methods for reducing inflammation in a patient that will be exposed, is concurrently exposed, or was exposed to radiation and/or chemical toxicity, comprising administering a therapeutically effective amount of at least one compound of Formula I or a pharmaceutically acceptable salt thereof. The present invention might also be expected to provide for methods for adverse tissue remodeling in a patient that will be exposed, is concurrently exposed, or was exposed to radiation and/or chemical toxicity, comprising administering a therapeutically effective amount of at least one compound of Formula I or a pharmaceutically acceptable salt thereof. The present invention might also be expected to provide for methods for reducing fibroproliferative tissue effects in a patient that will be exposed, is concurrently exposed, or was exposed to radiation and/or chemical toxicity, comprising administering a therapeutically effective amount of at least one compound of Formula I or a pharmaceutically acceptable salt thereof.
[0081] The present invention might also be expected to provide for methods useful for treating a cell proliferative disorder in a patient suffering therefrom comprising administering a therapeutically effective amount of at least one compound of Formula I or a pharmaceutically acceptable salt thereof. In one embodiment, the cell proliferative disorder is pancreatic cancer, glioma, ovarian cancer, colorectal and/or colon cancer, breast cancer, prostate cancer, thyroid cancer, lung cancer, melanoma, or stomach cancer. In one embodiment, the glioma is an anaplastic astrocytoma. In another embodiment, the glioma is a glioblastoma multiforme.
[0082] As used above, the term “inflammatory disease or condition” includes irritable bowel syndrome, Crohn's disease, nephritis or a radiation- or chemotherapy-induced proliferative or inflammatory disorder of the gastrointestinal tract, lung, urinary bladder, gastrointestinal tract or other organ. The term respiratory tract disease or condition includes reversible airway obstruction, asthma, chronic asthma, bronchitis or chronic airways disease. “Cancer” includes renal cell carcinoma or an angiogenesis related disorder. “Neurodegenerative disease” includes Parkinson's disease, amyotropic lateral sclerosis, Alzheimer's disease, Huntington's disease or Wilson's disease.
[0083] The term “pharmaceutical composition” is also intended to encompass both the bulk composition and individual dosage units comprised of more than one (e.g., two) pharmaceutically active agents such as, for example, a compound of the present invention and an additional agent selected from the lists of the additional agents described herein, along with any pharmaceutically acceptable carrier. The bulk composition and each individual dosage unit can contain fixed amounts of the afore-said “more than one pharmaceutically active agents”. The bulk composition is material that has not yet been formed into individual dosage units. An illustrative dosage unit is an oral dosage unit such as tablets, pills and the like. Similarly, the herein-described method of treating a patient by administering a pharmaceutical composition of the present invention is also intended to encompass the administration of the afore-said bulk composition and individual dosage units.
[0084] The amount and frequency of administration of the compound of this invention and/or their pharmaceutically acceptable salts will be regulated according to the judgment of the attending clinician considering such factors as age, condition and size of the patient as well as the severity of the symptoms being treated.
[0085] The quantity of active compound in a unit dose of preparation may be varied or adjusted from about 1 mg to about 150 mg, preferably from about 1 mg to about 75 mg, more preferably from about 1 mg to about 50 mg, according to the particular application.
[0086] The term “patient” includes animals, preferably mammals and especially humans, who use the instant active agents for the prevention or treatment of a medical condition. Administering of the drug to the patient includes both self-administration and administration to the patient by another person. The patient may be in need of treatment for an existing disease or medical condition, or may desire prophylactic treatment to prevent or reduce the risk of said disease or medical condition.
[0087] The term “therapeutically effective amount” is intended to mean that amount of a drug or pharmaceutical agent that will elicit the biological or medical response of a tissue, a system, animal or human that is being sought by a researcher, veterinarian, medical doctor or other clinician. A “prophylactically effective amount” is intended to mean that amount of a pharmaceutical drug that will prevent or reduce the risk of occurrence of the biological or medical event that is sought to be prevented in a tissue, a system, animal or human by a researcher, veterinarian, medical doctor or other clinician. The terms “preventing” or “prevention” are used herein to refer to administering a compound before the onset of clinical symptoms.
[0088] The compounds of this invention may also be useful in combination (administered together or sequentially) with one or more therapeutic agents, such as, for example, another cardiovascular agent. Cardiovascular agents that could be used in combination with the compounds for Formula I or their pharmaceutically acceptable salts include drugs that have anti-thrombotic, anti-platelet aggregation, antiatherosclerotic, antirestenotic and/or anti-coagulant activity. Such drugs are useful in treating thrombosis-related diseases including thrombosis, atherosclerosis, restenosis, hypertension, angina pectoris, arrhythmia, heart failure, myocardial infarction, glomerulonephritis, thrombotic and thromboembolic stroke, peripheral vascular diseases, other cardiovascular diseases, cerebral ischemia, inflammatory disorders and cancer, as well as other disorders in which thrombin and its receptor play a pathological role. Suitable cardiovascular agents are selected from the group consisting of thromboxane A2 biosynthesis inhibitors such as aspirin; thromboxane antagonists such as seratrodast, picotamide and ramatroban; adenosine diphosphate (ADP) inhibitors such as clopidogrel; cyclooxygenase inhibitors such as aspirin, meloxicam, rofecoxib and celecoxib; angiotensin antagonists such as valsartan, telmisartan, candesartran, irbesartran, losartan and eprosartan; endothelin antagonists such as tezosentan; phosphodiesterase inhibitors such as milrinoone and enoximone; angiotensin converting enzyme (ACE) inhibitors such as captopril, enalapril, enaliprilat, spirapril, quinapril, perindopril, ramipril, fosinopril, trandolapril, lisinopril, moexipril and benazapril; neutral endopeptidase inhibitors such as candoxatril and ecadotril; anticoagulants such as ximelagatran, fondaparin and enoxaparin; diuretics such as chlorothiazide, hydrochlorothiazide, ethacrynic acid, furosemide and amiloride; platelet aggregation inhibitors such as abciximab and eptifibatide; and GP IIb/IIIa antagonists.
[0089] Other possible combinations might include lipid lowering agents (e.g., simvastatin, lovastatin, pravastatin, atorvastatin rosuvastatin, pitavastatin, ezetimibe); niacin in immediate-release or controlled release forms or niacin in combination with a DP antagonist, such as laropiprant and/or with an HMG-CoA reductase inhibitor; niacin receptor agonists such as acipimox and acifran, as well as niacin receptor partial agonists; metabolic altering agents including insulin sensitizing agents and related compounds (e.g., muraglitazar, glipizide, stigliptin, metformin, rosiglitazone statins, e.g., simvastatin, atorvastatin and rosovastatin), PCSK9 inhibitors, e.g. antibodies—REGN727, AMG-145, RN316, RG7652; and small molecule inhibitors and CETP inhibitors, e.g., anacetrapib, evacetrapib, etc. Other possible combinations include AMPK agonists (e.g., ETC-1002); glucagon receptor antagonists; Lp-PLA2 inhibitors (e.g., darapladib) and anti-IL-1beta antibodies (canakinumab).
[0090] The dosage of the cardiovascular agent can be determined from published material, and may range from 1 to 1000 mg per dose.
[0091] An embodiment of this invention is combinations comprising an effective amount of a compound of Formula I or a pharmaceutically acceptable salt thereof and an ADP antagonist and/or cyclooxygenase inhibitor.
[0092] Non-limiting combinations comprise an effective amount of a compound according to Formula I or a pharmaceutically acceptable salt thereof and aspirin, ticagrelor, cangrelor, clopidogrel (either as a free base or as a pharmaceutically acceptable salt, such as its bisulfate salt), prasugrel, ticlopidine or fragmin.
[0093] Other therapeutic agents could include drugs that are known and used in the treatment of inflammation, rheumatism, asthma, glomerulonephritis, osteoporosis, neuropathy and/or malignant tumors, angiogenesis related disorders, cancer, disorders of the liver, kidney and lung, melanoma, renal cell carcinoma, renal disease, acute renal failure, chronic renal failure, renal vascular homeostasis, glomerulonephritis, chronic airways disease, bladder inflammation, neurodegenerative and/or neurotoxic diseases, conditions, or injuries, radiation fibrosis, endothelial dysfunction, periodontal diseases and wounds. Further examples of therapeutically effective agents which may be administered in combination with a compound of Formula I or a pharmaceutically acceptable salt thereof include resistance factors for tumor cells towards chemotherapy and proliferation inhibitors of smooth muscle cells, endothelial cells, fibroblasts, kidney cells, osteosarcoma cells, muscle cells, cancer cells and/or glial cells.
[0094] For treating and/or preventing radiation- and/or chemical-induced toxicity in non-malignant tissue, the present invention includes administering to a patient in need of such treatment an effective amount of a combination of one or more compounds of formula I and one or more radiation-response modifiers selected from the group consisting of Kepivance™ (palifermin), L-glutamine, teduglutide, sucralfate mouth rinses, iseganan, lactoferrin, mesna and trefoil factor.
[0095] For treating a cell proliferative disorder the present invention includes administering to a patient in need of such treatment an effective amount of a combination of one or more compounds of Formula I or a pharmaceutically acceptable salt thereof and another antineoplastic agent. In one embodiment, the other antineoplastic agent is temozolomide and the cell proliferative disorder is glioma. In another embodiment, the other antineoplastic agent is interferon and the cell proliferative disorder is melanoma. In one embodiment, the other antineoplastic agent is PEG-Intron (peginterferon alpha-2b) and the cell proliferative disorder is melanoma.
[0096] Pharmaceutical compositions comprising a therapeutically effective amount of a combination of at least one compound of Formula I or a pharmaceutically acceptable salt thereof and a radiation-response modifier in a pharmaceutically acceptable carrier are also provided.
[0097] Pharmaceutical compositions comprising a therapeutically effective amount of a combination of at least one compound of Formula I or a pharmaceutically acceptable salt thereof and an antineoplastic agent in a pharmaceutically acceptable carrier are also provided.
[0098] For preparing pharmaceutical compositions from the compounds described by this invention, inert, pharmaceutically acceptable carriers can be either solid or liquid. Solid form preparations include powders, tablets, dispersible granules, capsules, cachets and suppositories. The powders and tablets may be comprised of from about 5 to about 95 percent active ingredient. Suitable solid carriers are known in the art, e.g. magnesium carbonate, magnesium stearate, talc, sugar or lactose. Tablets, powders, cachets and capsules can be used as solid dosage forms suitable for oral administration. Examples of pharmaceutically acceptable carriers and methods of manufacture for various compositions may be found in A. Gennaro (ed.), The Science and Practice of Pharmacy, 20 th Edition, (2000), Lippincott Williams & Wilkins, Baltimore, Md.
[0099] Liquid form preparations include solutions, suspensions and emulsions. As an example may be mentioned water or water-propylene glycol solutions for parenteral injection or addition of sweeteners and opacifiers for oral solutions, suspensions and emulsions. Liquid form preparations may also include solutions for intranasal administration.
[0100] Aerosol preparations suitable for inhalation may include solutions and solids in powder form, which may be in combination with a pharmaceutically acceptable carrier, such as an inert compressed gas, e.g. nitrogen.
[0101] Also included are solid form preparations which are intended to be converted, shortly before use, to liquid form preparations for either oral or parenteral administration. Such liquid forms include solutions, suspensions and emulsions.
[0102] The compounds of the invention may also be deliverable transdermally. The transdermal compositions can take the form of creams, lotions, aerosols and/or emulsions and can be included in a transdermal patch of the matrix or reservoir type as are conventional in the art for this purpose.
[0103] Preferably the compound is administered orally.
[0104] Preferably, the pharmaceutical preparation is in a unit dosage form. In such form, the preparation is subdivided into suitably sized unit doses containing appropriate quantities of the active component, e.g., an effective amount to achieve the desired purpose.
[0105] In general, the compounds in the invention may be produced by a variety of processes know to those skilled in the art and by know processes analogous thereto. The invention disclosed herein is exemplified by the following preparations and examples which should not be construed to limit the scope of the disclosure. Alternative mechanistic pathways and analogous structures will be apparent to those skilled in the art. The practitioner is not limited to these methods.
[0106] Moreover, one skilled in the art would have resources such as Chemical Abstracts or Beilstein at his or her disposal to assist in preparing a specific compound.
[0107] One skilled in the art will recognize that one route will be optimized depending on the choice of appendage substituents. Additionally, one skilled in the art will recognize that in some cases the order of steps has to be controlled to avoid functional group incompatibility.
[0108] The prepared compounds may be analyzed for their composition and purity as well as characterized by standard analytical techniques such as, for example, elemental analysis, NMR, mass spectroscopy and IR spectra.
[0109] One skilled in the art will recognize that reagents and solvents actually used may be selected from several reagents and solvents well known in the art to be effective equivalents. Hence, when a specific solvent or reagent is mentioned, it is meant to be an illustrative example of the conditions desirable for that particular reaction scheme and in the preparations and examples described below.
[0110] Where NMR data are presented, 1H spectra were obtained, for example, on either a Varian Inova (400 or 500 mHz), Varian Mercury VX-400 (400 MHz), or Bruker-Biospin AV-500 (500 MHz), and are reported as ppm with number of protons and multiplicities indicated parenthetically. Where LC/MS data are presented, analyses was performed, for example, using an Agilent 1100 series or Applied Biosystems® API-100 mass spectrometer and C18 column, 5-95% CH 3 CN—H 2 O (with 0.05% TFA) gradient. The observed parent ion is given
[0111] Throughout the synthetic schemes, abbreviations are used with the following meaning unless otherwise indicated:
[0000] ACN or MeCN=acetonitrile; Ac 2 O=acetic anhydride; Aq.=aqueous; t-Butyl=tert-butyl; t-BuOH=tert-butyl alcohol; cat.=catalyst; DBU=1,8-Diazabicyclo[5.4.0]undec-7-ene; DCC=N,N′-bicyclohexylcarbodiimide; DCM=dichloromethane; DAST=diethylaminosulfur trifluoride; DMAC=N,N-dimethylacetamide; DMAP=4-dimethylamino pyridine; DMEM=Dulbecco's modified eagle medium, DMF=dimethylformamide; DMP=Dess-Martin periodinane; DMSO=dimethylsulfoxide; DIEA=N,N-Diisopropylethylamine or Hünig's base; Et=ethyl; EtOH=ethanol; EtOAc=ethyl acetate; g=gas HATU=O-(7-azabenzotriazol-1-yl)-N,N,N′,N′-tetramethyluronium hexafluorophosphate; HEPES=(4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid); HPLC=high pressure liquid chromatography; HOAc=acetic acid; LCMS=liquid chromatorgraphy-mass spectrometry; KHMDS=Potassium bis(trimethylsilyl)amide; LiHMDS=lithium bis(trimethylsilyl)amide; Me=methyl; MeOH=methanol; MeI=methyl iodide; mmol=millimoles MPLC=medium pressure liquid chromatography; Ms=mesylate; MS ESI=electrospray ionixation mass spectrometry; MTBE=methyl tert-butyl ether; NMM=M-methylmorpholine; NMP=N-methyl-2-pyrrolidone; Ph=phenyl; piv-cl=pivaloyl chloride; i-Pr=iso-propyl; RT or rt=room temperature TEA=triethanolamine; TFA=trifluoroacetic acid; THF=tetrahydrofuran; TLC=thin layer chromatography.
INTERMEDIATE SYNTHESES
[0112] Intermediate compounds of the present invention can be synthesized according to the schemes and procedures outlined below. Since the schemes are an illustration, the invention should not be construed as being limited by the chemical reactions and conditions expressed. The preparation of the various starting materials used in the schemes is well within the ordinary skill level of a practitioner of this art. Unless otherwise indicated, the definition for a variable is the same as that provided in Formula I.
[0000]
[0113] Intermediate A can be prepared from commercially available and known starting materials according to Scheme A. 2-Ethylfuran (A-1) was oxidized to the corresponding hydroxyfuranone, which under the action of base is opened to carboxylic acid (A-2). Alkynylalcohol (A-3) was reduced to the corresponding cis-alkene (A-4) using Lindlar's catalyst under an atmosphere of hydrogen gas. DCC-mediated coupling of prepared intermediates (A-2) and (A-4) provided the complete carbon framework for intermediate A in compound (A-5). Formation of the enol acetate (A-6) set the stage for an intramolecular Diels-Alder reaction to form lactone (A-7). Hydrolysis and subsequent reaction of ketone (A-8) with DAST provided the C6-difluoro lactone (A-9). Saponification of the amide provided carboxylic acid (A-10), which was then chemoselectively reduced via a two-step protocol to yield Intermediate A.
Intermediate A
[0114]
Step 1: 5-ethyl-5-hydroxyfuran-2(5H)-one
[0115] NaH 2 PO 4 (243 g, 3.12 mol) was added to a solution of 2-ethylfuran (100 g, 1.04 mol) in t-BuOH (1.0 L) and H 2 O (200 mL) at room temperature. After 30 min, NaClO 2 (312 g, 3.12 mol) was added portionwise. The temperature was controlled between 10-30° C. After the addition, the reaction was stirred for another 2 h until the reaction goes to completion. The reaction solution was purged with N 2 overnight until it turned to white. The precipitate was filtered and t-BuOH was removed under vacuo. The reaction was extracted with CH 2 Cl 2 and dried with anhydrous Na 2 SO 4 . After combining all thirteen reactions and concentration, the title compound was obtained and was used directly for the next step without further purification.
Step 2: (E)-4-oxohex-2-enoic acid
[0116] To a solution of 5-ethyl-5-hydroxyfuran-2(5H)-one (130 g, 1.02 mol) in THF (645 mL) was added acetone (520 mL), water (130 mL), pyridine (8.1 mL, 0.1 mol) at room temperature. The reaction was stirred overnight. TLC (petroleum ether/ethyl acetate, 3:1) showed the reaction was completed. The mixture was concentrated under vacuo. The residue was treated with 10% K 2 CO 3 to pH >10 at 0° C. and extracted with ethyl acetate (500 mL×3). The aqueous layer was acidified with concentrated HCl at 0° C. to pH <2. After extraction with ethyl acetate (500 mL×6) and washing with brine, the organic layer was dried with anhydrous Na 2 SO 4 and concentrated to give the title compound. It was washed with methyl tert-butyl ether to provide the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 7.12 (d, 1H, J=16.0 Hz), 6.66 (d, 1H, J=15.6 Hz), 2.68 (q, 2H, J=7.2 Hz), 1.13 (q, 2H, J=7.2 Hz).
Step 3: (R,Z)-4-hydroxy-N,N-diphenylpent-2-enamide
[0117] To a solution of (R)-4-hydroxy-N,N-diphenylpent-2-ynamide (200 g, 0.75 mol) and Lindlar catalyst (13.6 g, 7.5 mmol) in CH 3 OH (2 L) was added quinoline (21.6 mL, 182 mmol) at room temperature. The reaction was evacuated and recharged with a balloon of H 2 . After stirring at room temperature for 1 h, TLC (petroleum ether/ethyl acetate, 3:1) showed the reaction was complete. Solvent was removed under reduced pressure at 35° C. THF (1 L) was added which was followed by the addition of petroleum ether (1 L). After removing half amount of the solvent, petroleum ether (1 L) was added. A precipitate formed during concentration, which was filtered and washed with methyl tert-butyl ether to afford the title compound. The combined filtrate residues were purified by silica gel column chromatography (petroleum ether:ethyl acetate, 5:1) to yield another batch of (R,Z)-4-hydroxy-N,N-diphenylpent-2-enamide. 1 H NMR (400 MHz, CDCl 3 ) δ 7.38-7.23 (m, 10H), 6.09 (dd, 1H, J=12.0, 6.0 Hz), 5.82 (d, 1H, J=12.0 Hz), 4.88-4.85 (m, 1H), 1.35 (d, 1H, J=6.8 Hz).
Step 4: (E)-(R,Z)-5-(diphenylamino)-5-oxopent-3-en-2-yl 4-oxohex-2-enoate
[0118] NMM (91 mL, 814 mmol) was added to (E)-4-oxohex-2-enoic acid (58 g, 450 mmol) in anhydrous toluene (800 mL) at 0° C. Then, pivaloyl chloride (55 mL, 450 mmol) was added dropwise while maintaining the internal temperature between 0-5° C. After the addition, the reaction was stirred at 0° C. for 30 min. (R,Z)-4-Hydroxy-N,N-diphenylpent-2-enamide (100 g, 370 mmol) and DMAP (4.57 g, 37 mmol) in anhydrous toluene (400 mL) and anhydrous THF (200 mL) were added dropwise to the reaction mixture while maintaining the temperature between 0-5° C. under N 2 . After 2 hours, the TLC (petroleum ether:ethyl acetate, 5:1) showed that the reaction was complete. 9 N H 2 SO 4 (330 mL) was added dropwise to quench the reaction, while the temperature was kept between 0-5° C. The reactions were combined together and extracted with methyl tert-butyl ether and washed with saturated NaHCO 3 . The crude product was purified by silica gel column chromatography (petroleum ether:ethyl acetate, 15:1) to give the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 7.34-7.24 (m, 10H), 7.06 (dd, 1H, J=16.0, 4.0 Hz), 6.66 (dd, 1H, J=16.0, 4.0 Hz), 6.35-6.32 (m, 1H), 5.88-5.80 (m, 2H), 2.68-2.63 (m, 2H), 1.49-1.47 (m, 3H), 1.13-1.08 (m, 3H).
Step 5: (2E,4Z)-(R,Z)-5-(diphenylamino)-5-oxopent-3-en-2-yl 4-acetoxyhexa-2,4-dienoate
[0119] (E)-(R,Z)-5-(Diphenylamino)-5-oxopent-3-en-2-yl 4-oxohex-2-enoate (100 g, 265 mmol) and DMAP (9.5 g, 79 mmol) in Ac 2 O (100 mL, 1.06 mol) were stirred at 50° C. for 19 h. TLC (petroleum ether:ethyl acetate, 5:1) showed the reaction was complete. The reaction was concentrated under reduced pressure at 45° C. The reaction was extracted with methyl tert-butyl ether and washed with 10% citric acid (5 L). The organic layer was washed with sat. NaHCO 3 , brine, dried over Na 2 SO 4 and filtered, the reaction was concentrated to give the title compound, which was used without further purification in the next step. 1 H NMR (400 MHz, CDCl 3 ) δ 7.25-7.15 (m, 10H), 6.26-6.23 (m, 1H), 5.87-5.73 (m, 4H), 2.27 (s, 3H), 1.69 (d, 1H, J=6.8 Hz), 1.46 (d, 1H, J=6.4 Hz).
Step 6: (1R,3aS,6S,7R,7aS)-7-(diphenylcarbamoyl)-1,6-dimethyl-3-oxo-1,3,3a,6,7,7a-hexahydroisobenzofuran-5-yl acetate
[0120] (2E,4Z)-(R,Z)-5-(Diphenylamino)-5-oxopent-3-en-2-yl 4-acetoxyhexa-2,4-dienoate (100 g, 0.24 mol) in NMP (2.5 L) was stirred at 145° C. for 2 h. The TLC (petroleum ether:ethyl acetate, 3:1) showed the reaction was almost complete. The reaction was cooled to 50° C. and DBU (3.6 mL, 2.39 mmol) was added in one portion. After 1 h, the reaction was cooled to 20° C. and was poured to cold water (22 L). The reaction was extracted with ethyl acetate (22 L). The organic layer was washed with water (22 L×2). The combined aqueous layers were extracted with ethyl acetate (5 L×3). The organic layers were then combined together, washed with brine and dried with anhydrous Na 2 SO 4 . After concentration, a precipitate that had formed was washed with methyl tert-butyl ether to give the title compound. The filtrate was concentrated and purified by silica gel column chromatography (petroleum ether:CH 2 Cl 2 , 6:1) to give another batch of the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 7.51-7.23 (m, 10H), 5.26 (s, 1H), 4.90-4.86 (m, 1H), 3.21-3.10 (m, 2H), 2.83 (dd, 1H, J=10.8, 3.6 Hz), 2.52-2.50 (m, 1H), 2.16 (s, 3H), 1.58 (d, 3H, J=6.0 Hz), 1.09 (d, 3H, J=6.4 Hz).
Step 7: (3R,3aS,4R,5S,7aR)-3,5-dimethyl-1,6-dioxo-N,N-diphenyloctahydroisobenzo furan-4-carboxamide
[0121] HCl (298 mL, 4 M in water) was added dropwise to (1R,3aS,6S,7R,7aS)-7-(diphenylcarbamoyl)-1,6-dimethyl-3-oxo-1,3,3a,6,7,7a-hexahydroisobenzofuran-5-yl acetate (100 g, 238 mmol) in CH 3 OH (1 L) at 0° C. After the addition, the reaction was warmed to room temperature and stirred for another 36 h. The TLC (petroleum ether:ethyl acetate, 3:1) showed the reaction was almost complete. Methanol was removed under reduced pressure at 35° C. The reaction was extracted with CH 2 Cl 2 and the organics was washed with sat. NaHCO 3 , brine, dried over Na 2 SO 4 and concentrated. The resultant residue was purified on multiple 15 g scale silica gel columns (petroleum ether:CH 2 Cl 2 , 6:1) to yield the title compound. MS ESI calcd. for C 23 H 24 NO 4 [M+H] + 378, found 378. 1 H NMR (400 MHz, CDCl 3 ) δ 7.50-7.46 (m, 3H), 7.35-7.33 (m, 2H), 7.29-7.22 (m, 5H), 5.16-5.10 (m, 1H), 2.98-2.90 (m, 3H), 2.65-2.63 (m, 1H), 2.55-2.46 (m, 2H), 1.56 (d, 3H, J=5.6 Hz), 1.18-1.14 (m, 3H).
Step 8: (3R,3aS,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-1-oxo-N,N-diphenyloctahydroisobenzofuran-4-carboxamide
[0122] To a solution of (3R,3aS,4R,5S,7aR)-3,5-dimethyl-1,6-dioxo-N,N-diphenyloctahydroisobenzofuran-4-carboxamide (300.0 g, 0.79 mol) in CH 2 Cl 2 (anhyd., 3 L) was added DAST (180 mL, 2.37 mol) dropwise slowly at 15-30° C. The resulting mixture was stirred overnight at 25° C. After LCMS showed the mixture was complete, the mixture was slowly poured to a solution of K 3 PO 4 .3H 2 O (0.4 mol/L, 3 L) and was partitioned with water and CH 2 Cl 2 . The aqueous layer was extracted with CH 2 Cl 2 (1000 mL×2). The combined organic layers were washed with NaHCO 3 (500 mL), brine (500 mL), dried over Na 2 SO 4 , filtered and concentrated under reduced pressure. The residue was oxidized by KMnO 4 (100 g) in DMAC for 2 hours, then filtered. The filtrate was extracted by EtOAc, washed with 10% CaCl 2 aqueous solution, and brine. The combined organic solution was dried by Na 2 SO 4 and concentrated. The residue was further purified by recrystallization with ethanol (3 V) to give the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 7.40 (m, 3H), 7.24 (m, 7H), 4.84 (m, 1H), 2.76 (m, 1H), 2.45 (m, 3H), 2.18 (m, 1H), 1.71 (m, 1H), 1.5 (d, 3H, J=5.6 Hz), 1.1 (d, 3H, J=6.5 Hz).
Step 9: (3R,3aR,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-1-oxooctahydroisobenzofuran-4-carboxylic acid
[0123] To a solution of the (3R,3aS,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-1-oxo-N,N-diphenyloctahydroisobenzofuran-4-carboxamide (260 g, 0.653 mol) in THF (1300 mL) was added a solution of LiOH.H 2 O (55 g, 1.31 mol) in H 2 O (650 mL) at room temperature. The mixture was heated to 60° C. and stirred for 2 h. Upon completion of reaction, the mixture was diluted with LiOH.H 2 O solution (1.3 L, 10% in water). The THF layer was removed in vacuo. The aqueous phase was extracted with MTBE (800 mL×3). The aqueous layer was acidified to pH 1-2 with 1N HCl and extracted with EtOAc (800 mL mL×3). The combined organic layers were washed with water (500 mL), brine (500 mL), dried over Na 2 SO 4 , filtered and concentrated to give the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 4.73 (m, 1H), 2.99 (m, 1H), 2.89 (m, 1H), 2.64 (m, 1H), 2.53 (m, 1H), 2.33 (m, 1H), 1.86 (m, 1H), 1.39 (d, 3H), 1.15 (d, 3H).
Step 10: (3R,3aS,4R,5S,7aR)-6,6-difluoro-4-(hydroxymethyl)-3,5-dimethylhexahydroisobenzofuran-1(3H)-one
[0124] To a solution of (3R,3aR,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-1-oxooctahydroisobenzofuran-4-carboxylic acid (81.0 g, 0.326 mol) in CH 2 Cl 2 (800 mL) was added (COCl) 2 (58.8 mL, 0.66 mol) and DMF (1 mL) at 20-25° C. under nitrogen. The mixture was stirred for 4 hours. Upon reaction completion, the mixture was concentrated under reduced pressure. The residue was dissolved with THF (400 mL×2) and then concentrated twice. The residue was dissolved in THF (500 mL), and a solution of LiAlH(t-BuO) 3 (653 mL, 0.653 mol, 1 M in THF) was added dropwise slowly below −55° C. under nitrogen. The mixture was slowly warmed to room temperature and stirred overnight. Upon reaction completion, the mixture was quenched with 1N HCl (1 L) and extracted with EtOAc (500 mL×3). The combined organic layers were washed with water (500 mL), brine (500 mL), dried over Na 2 SO 4 , filtered and concentrated to give the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 4.77 (m, 1H), 3.83 (m, 2H), 2.85 (m, 1H), 2.45 (m, 2H), 2.07 (m, 2H), 1.83 (m, 1H), 1.59 (d, 3H), 1.13 (d, 3H).
[0000]
[0125] Intermediate B can be prepared according to Scheme B through a two-step process. Oxidation of intermediate A to aldehyde (B-1) and Horner-Wadsworth-Emmons olefination reaction with known or synthesized phosphonate esters provided Intermediate B.
Intermediate B
[0126]
Step 1: (3R,3aS,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-1-oxooctahydroisobenzofuran-4-carbaldehyde
[0127] To a stirred solution of (3R,3aS,4R,5S,7aR)-6,6-difluoro-4-(hydroxymethyl)-3,5-dimethylhexahydroisobenzofuran-1(3H)-one (56 g, 0.24 mol) in MeCN (600 mL) was added Dess-Martin reagent (122 g, 0.287 mol) and NaHCO 3 (60.3 g, 227 mol) under nitrogen at 0° C. The mixture was stirred for 4 h at 25° C. Upon reaction completion, the mixture was transferred to into L-ascorbic acid (5% aq., 1500 mL) under nitrogen, and then was filtered. The filtrate was quenched with Na 2 SO 3 (5% aq., 750 mL). The solvent was removed and the product was extracted with EtOAc (750 mL×3). The combined organic layers were washed with brine (900 mL), dried over Na 2 SO 4 , filtered and concentrated to give the title compound, which was directly used in the next step without further purification.
Step 2: (3R,3aS,4R,5S,7aR)-4-((E)-2-(5-bromopyridin-2-yl)vinyl)-6,6-difluoro-3,5-dimethylhexahydroisobenzofuran-1(3H)-one
[0128] To a solution of diethyl ((5-bromopyridin-2-yl)methyl)phosphonate (95.6 g, 0.310 mol) in THF (400 mL) was added LiHMDS (310 mL, 0.310 mol, 1 M in THF) dropwise at 0° C. under nitrogen. The mixture was stirred for 30 min at 0° C., and then warmed up to about 25° C. Ti(OiPr) 4 (110 g, 0.3103 mmol) was added and the reaction was stirred for 30 min at 25° C. A solution of (3R,3aS,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-1-oxooctahydroisobenzofuran-4-carbaldehyde (36 g, 0.1552 mmol) in THF (400 mL) was added into the mixture, and stirred overnight at room temperature. Upon reaction completion, the mixture was quenched with saturated solution of potassium sodium tartrate (1 L), and then filtered. The filtrate was extracted with EtOAc (500 mL×3). The combined organic layers were washed with brine (500 mL), dried over Na 2 SO 4 , filtered and concentrated. The residue was purified by column chromatography with PE/EtOAc (20:1) to give the title compound. MS ESI calcd. for C 17 H 19 BrF 2 NO 2 [M+H] + 386/388, found 386/388. 1 H NMR (500 MHz, CDCl 3 ) δ 8.61 (d, 1H, J=2 Hz), 7.78 (dd, 1H, J=2.4, 8.4 Hz), 7.09 (d, 1H, J=8.4 Hz), 6.55 (m, 2H), 4.74 (m, 1H), 2.95 (m, 1H), 2.73 (m, 1H), 2.38-2.53 (m, 2H), 1.83-2.04 (m, 2H), 1.45 (d, 3H, J=6 Hz), 1.07 (d, 3H, J=6.8 Hz).
[0000]
[0129] Intermediate C can be prepared according tosscheme C through an oxidation to aldehyde C-1 and a Horner-Wadsworth-Emmons olefination reaction using known or synthesized phosphonate esters from Intermediate A.
Intermediate C1
[0130]
Step 1: (3R,3aS,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-1-oxooctahydroisobenzofuran-4-carbaldehyde
[0131] To a solution of (3R,3aS,4R,5S,7aR)-6,6-difluoro-4-(hydroxymethyl)-3,5-dimethylhexahydroisobenzofuran-1(3H)-one (3.21 g, 13.70 mmol) in CH 2 Cl 2 (100 mL) stirred at 0° C. under nitrogen was added DMP (8.72 g, 20.56 mmol). The reaction mixture was stirred for 2 h. Upon reaction completion, the mixture was quenched with NaHCO 3 (5% aq., 200 mL) and Na 2 SO 3 (5% aq., 200 mL) and extracted with CH 2 Cl 2 (3×150 mL). The combined organic layers were washed with brine (80 mL), dried over anhyd. Na 2 SO 4 and concentrated under reduced pressure to afford the title compound. MS ESI calcd. for C 11 H 15 F 2 O 3 [M+H] + 233, found 233.
Step 2: 2-(6-((E)-2-((3R,3aS,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-1-oxooctahydroisobenzofuran-4-yl)vinyl)pyridin-3-yl)benzonitrile
[0132] To a solution of diethyl ((5-(2-cyanophenyl)pyridin-2-yl)methyl)phosphonate (1.98 g, 6.0 mmol) in THF (10 mL) at 0° C. was added lithium bis(trimethylsilyl)amide (6.0 mL, 6.0 mmol, 1 M in THF). The reaction was stirred for 30 minutes at 0° C. before allowing it to warm to RT. Titanium(IV) isopropoxide (1.76 mL, 6.0 mmol) was added to the reaction mixture. The reaction mixture was stirred for 5 min., then a solution of (3R,3aS,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-1-oxooctahydroisobenzofuran-4-carbaldehyde (0.697 g, 3.0 mmol) in THF (10 mL) was added and stirred at RT for 1 hour. The reaction was quenched with aqueous sat. potassium sodium tartrate and the product was extracted with EtOAc. The organic phase was dried with Na 2 SO 4 , concentrated and purified by silica gel chromatography (0-40% EtOAc in hexanes) to provide 2-(6-((E)-2-((3R,3aS,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-1-oxooctahydro isobenzofuran-4-yl)vinyl)pyridin-3-yl)benzonitrile. MS ESI calcd. for C 24 H 23 F 2 N 2 O 2 [M+H] + 409, found 409. 1 H NMR (500 MHz, CDCl 3 ) δ8.75 (d, J=2.3 Hz, 1H); 7.97 (d, J=8.0 Hz, 1H); 7.86 (d, J=7.8 Hz, 1H); 7.75 (t, J=7.7 Hz, 1H); 7.56 (t, J=7.7 Hz, 2H); 7.37 (d, J=8.1 Hz, 1H); 6.69-6.71 (m, 2H); 4.80 (m, 1H); 2.97-3.02 (m, 1H); 2.79-2.84 (m, 1H); 2.53-2.60 (m, 1H); 2.41-2.49 (m, 1H); 2.02-2.16 (m, 1H); 1.85-1.99 (m, 1H); 1.53 (d, J=6.0 Hz, 3H), 1.13 (d, J=6.6 Hz, 3H).
[0133] The following compound in Table 1 was prepared according to Scheme C using the procedure outlined in the synthesis intermediate C1 using known or synthesized phosphonate esters.
[0000]
TABLE 1
Inter-
Exact
medi-
Mass
ate
Structure
IUPAC Name
[M + H]+
C2
(3R,3aS,4R,5S,7aR)- 6,6-difluoro-4-((E)- 2-(5-(3- fluorophenyl)pyridin- 2-yl)vinyl)-3,5- dimethylhexahydro isobenzofuran-1(3H)- one
402
[0000]
[0134] Intermediate D can be prepared via a Miyaura reaction with Intermediate B to yield boronic ester (D-1) according to scheme D. Subsequent palladium-mediated coupling provides intermediate D.
Intermediate D1
[0135]
Step 1: (3R,3aS,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-4-((E)-2-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-yl)vinyl)hexahydroisobenzofuran-1(3H)-one
[0136] In a reaction vessel (3R,3aS,4R,5S,7aR)-4-((E)-2-(5-bromopyridin-2-yl)vinyl)-6,6-difluoro-3,5-dimethylhexahydroisobenzofuran-1(3H)-one (2.0 g, 5.18 mmol), bispinacolatodiboron (1.64 g, 6.47 mmol), and potassium acetate (1.01 g, 10.4 mmol) were combined. This mixture was then evacuated and backfilled with N 2 (3 times). Then dry, degassed dioxane (25.9 mL) was added to this flask. This mixture was then heated at 90° C. for 12 h. The mixture was cooled, diluted with acetonitrile (40 mL) and filtered through a 10 g plug of C18 silica gel pad. The solvent was evaporated under reduced pressure to provide the title compound, which was used without further purification. MS ESI calcd. for C 17 H 21 BF 2 NO 4 [M+H] + (ionizes for boronic acid) 352, found 352.
Step 2: 6′-((E)-2-((3R,3aS,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-1-oxooctahydroiso benzofuran-4-yl)vinyl)-[3,3′-bipyridine]-2-carbonitrile
[0137] To a mixture of (3R,3aS,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-4-((E)-2-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-yl)vinyl)hexahydroisobenzofuran-1(3H)-one (1.0 g, 2.31 mmol), 3-bromopicolinonitrile (0.549 g, 3.00 mmol) and potassium carbonate (0.96 g, 6.92 mmol) in dioxane (12 mL) was added 1,1′-bis(di-tert-butylphosphino)ferrocene palladium dichloride (0.150 g, 0.231 mmol) at rt. The reaction mixture was stirred at 60° C. for 1 hour. After cooling to 25° C., the reaction was diluted with EtOAc (200 mL) and partitioned with brine (200 mL). The organics were washed again with brine, dried over anhydrous sodium sulfate, filtered and evaporated. Purification by silica gel chromatography (25-75% EtOAc/hexanes) provided the title compound. MS ESI calcd. for C 23 H 22 F 2 N 3 O 2 [M+H] + 410, found 410.
[0138] The following intermediate in Table 2 was prepared according to scheme D using the procedure outlined in the synthesis intermediate D1 using known or commerically available aryl bromides.
[0000]
TABLE 2
Inter-
Exact
medi-
Mass
ate
Structure
IUPAC Name
[M + H]+
D2
2-(6-((E)-2- ((3R,3aS,4R, 5S,7aR)- 6,6-difluoro-3,5- dimethyl-1- oxooctahydro isobenzo furan-4-yl)vinyl) pyridin-3-yl)-6- methylbenzonitrile
423
General Synthetic Schemes
[0139] Representative compounds of the present invention can be synthesized according to the general schemes outlined below as well as the representative examples that follow. Since the schemes are an illustration, the invention should not be construed as being limited by the chemical reactions and conditions expressed. The preparation of the various starting materials used in the schemes is well within the ordinary skill level of a practitioner of this art.
[0000]
[0140] Compounds of Formula (1) can be prepared via modification of intermediate B, C or D by generating the corresponding anion of using bases such as LiHMDS and reaction with an appropriate electrophile to yield (1-1). Subsequent exposure to hydrazine yielded the corresponding hydrazide (1-2) and reaction with CDI or cyanogen bromide provided compounds of Formula 1.
[0000]
[0141] Compounds of Formula (2) can be prepared from hydrazide (1-2), which was a synthetic intermediate formed in Scheme 1. Amide coupling conditions using HATU and various carboxylic acids provides oxazole precursor (2-1). Condensation under the action of Burgess reagent, furnished compound of Formula (2).
[0000]
[0142] Compounds of Formula (3) can be prepared via modification of intermediate B, C or D by generating the corresponding anion using bases, such as LiHMDS and reaction with an appropriate electrophile to yield (3-1). Subsequent oxidation to ynone (3-2) and exposure to a hydrazine yielded compounds of Formula (3).
[0000]
[0143] Compounds of Formula 4 can be prepared from intermediates generated using in Schemes 1 or 3 from intermediate B. A palladium-mediated Suzuki coupling reaction of bromide (4-1) with known or commerically available boronic acids or esters furnished compounds of the Formula 4.
EXAMPLES
[0144] The following schemes and examples are provided so that the invention will be more fully appreciated and understood. Starting materials are made using known procedures or as illustrated below.
Example 1
[0145]
Step 1: (1R,3aR,6S,7R,7aS)-7-((E)-2-(5-(2-cyanophenyl)pyridin-2-yl)vinyl)-5,5-difluoro-1,6-dimethyl-3-oxooctahydroisobenzofuran-3a-carboxamide
[0146] To 2-(6-((E)-2-((3R,3aS,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-1-oxooctahydroiso benzofuran-4-yl)vinyl)pyridin-3-yl)benzonitrile (0.90 g, 2.20 mmol) in 2-Me-THF (7 mL) at 0° C. under N 2 (g) was added lithium bis(trimethylsilyl)amide (461 mg, 2.75 mmol). The reaction mixture was stirred at 0° C. for 30 min before cooling the system to −78° C., and adding methyl cyanoformate (0.244 g, 2.86 mmol). After stirring for 40 min at −78° C., the reaction mixture was allowed to warmed to RT and was stirred for 20 min. The reaction mixture was cooled to 0° C., quenched with saturated NH 4 Cl (aq) , and the product was extracted with EtOAc. The organic phase was washed with brine, dried with Na 2 SO 4 , and was concentrated. The residue was purified by column chromatography on silica (0-40% EtOAc in hexanes) to afford the title compound. MS ESI calcd. for C 26 H 25 F 2 N 2 O 4 [M+H] + 467, found 467.
Step 2: (1R,3aR,6S,7R,7aS)-7-((E)-2-(5-(2-cyanophenyl)pyridin-2-yl)vinyl)-5,5-difluoro-1,6-dimethyl-3-oxooctahydroisobenzofuran-3a-carbohydrazide
[0147] To a solution of (1R,3aR,6S,7R,7aS)-7-((E)-2-(5-(2-cyanophenyl)pyridin-2-yl)vinyl)-5,5-difluoro-1,6-dimethyl-3-oxooctahydroisobenzofuran-3a-carboxamide (161 mg, 0.345 mmol) in ethanol (2.5 mL) was added hydrazine (0.108 mL, 3.45 mmol). The reaction was heated and stirred at 60° C. for 30 min. Upon completion of the reaction, the system was cooled to RT and was diluted with EtOAc, was washed with water, and brine. The organic phase was dried with Na 2 SO 4 before concentrating and the residue was purified by column chromatography on silica (0-65% EtOAc in hexanes) to provide the title compound. MS ESI calcd. for C 25 H 25 F 2 N 4 O 4 [M+H] + 467, found 467.
Step 3: 2-(6-((E)-2-((3R,3aS,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-1-oxo-7a-(5-oxo-4,5-dihydro-1,3,4-oxadiazol-2-yl)octahydroisobenzofuran-4-yl)vinyl)pyridin-3-yl)benzonitrile
[0148] A solution of (1R,3aR,6S,7R,7aS)-7-((E)-2-(5-(2-cyanophenyl)pyridin-2-yl)vinyl)-5,5-difluoro-1,6-dimethyl-3-oxooctahydroisobenzofuran-3a-carbohydrazide (35 mg, 0.075 mmol) and 1,1′-carbonyldiimidazole (48.7 mg, 0.300 mmol) in THF (0.75 mL) was stirred at 25° C. for 1 hour. Upon reaction completion, the solvent was removed under reduced pressure and the residue was purified by reverse phase HPLC (acetonitrile/water with 0.1% TFA modifier) to yield the title compound as a TFA salt. MS ESI calcd. for C 26 H 23 F 2 N 4 O 4 [M+H] + 493, found 493. 1 H NMR (500 MHz, CDCl 3 ) δ 9.12 (br s, 1H); 8.98 (d, J=8.35, 1H); 8.30 (d, J=8.3 Hz, 1H); 7.90 (d, J=7.8 Hz, 1H); 7.80 (d, J=7.7 Hz, 1H); 7.64 (t, J=7.6 Hz, 3H); 6.90 (d, J=9.7 Hz, 1H); 6.81-6.95 (m, 1H); 4.84-4.96 (m, 1H); 3.06-3.18 (m, 2H); 2.84-2.96 (m, 1H); 2.12-2.33 (m, 2H); 1.60 (d, J=9.0, 3H); 1.12 (d, J=6.6 Hz, 3H). PAR-1 FLIPR IC 50 =4.22 nM.
[0149] The following examples in Table 3 were prepared according to Scheme 1 using the procedure outlined in the synthesis of Example 1. Intermediate C or D may be used in step 1. In step 3, cyanogen bromide (1 equivalent) with aqueous sodium bicarbonate (1 equivalent, 2 M) can be utilized to provide the corresponding 1,3,4-oxadiazol-2-amine.
[0000]
TABLE 3
PAR-1
Exact Mass
FLIPR
Ex
Structure
IUPAC Name
[M + H]+
IC 50 (nM)
2
2-(6-((E)-2- ((3R,3aS,4R,5S,7aR)- 6,6-difluoro-3,5- dimethyl-1-oxo-7a-(5- oxo-4,5-dihydro-1,3,4- oxadiazol-2- yl)octahydroisobenzo furan-4-yl)vinyl) pyridin-3-yl)-6- methylbenzonitrile
507
1.34
3
2-(6-((E)-2- ((3R,3aS,4R,5S,7aR)- 7a-(5-amino-1,3,4- oxadiazol-2-yl)-6,6- difluoro-3,5-dimethyl- 1-oxooctahydroiso benzofuran-4- yl)vinyl)pyridin-3-yl)- 6-methylbenzonitrile
506
1.22
4
2-(6-((E)-2- ((3R,3aS,4R,5S,7aR)- 7a-(5-amino-1,3,4- oxadiazol-2-yl)-6,6- difluoro-3,5-dimethyl- 1-oxooctahydroiso benzofuran-4- yl)vinyl)pyridin-3- yl)benzonitrile
492
3.08
Example 5
[0150]
Step 1: (1R,3aR,6S,7R,7aS)-N′-acetyl-7-((E)-2-(5-(2-cyano-3-methylphenyl)pyridin-2-yl)vinyl)-5,5-difluoro-1,6-dimethyl-3-oxooctahydroisobenzofuran-3a-carbohydrazide
[0151] A solution of HATU (32.9 mg, 0.087 mmol), DIEA (0.023 mL, 0.133 mmol), acetic acid (4.77 μL, 0.083 mmol) in DMF (0.5 mL) was stirred at 25° C. for 10 min. (1R,3aR,6S,7R,7aS)-7-((E)-2-(5-(2-Cyano-3-methylphenyl)pyridin-2-yl)vinyl)-5,5-difluoro-1,6-dimethyl-3-oxooctahydroisobenzofuran-3a-carbohydrazide (32 mg, 0.067 mmol) was added to the reaction mixture and was stirred for 1 hour at 25° C. The reaction was then diluted with EtOAc, washed with water and brine. The organic phase was dried with Na 2 SO 4 and was concentrated. The crude residue was purified by column chromatography (0 to 5% MeOH in DCM) to provide the title compound. MS ESI calcd. for C 30 H 33 F 2 N 2 O 4 [M+H] + 523, found 523.
Step 2: 2-(6-((E)-2-((3R,3aS,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-7a-(5-methyl-1,3,4-oxadiazol-2-yl)-1-oxooctahydroisobenzofuran-4-yl)vinyl)pyridin-3-yl)-6-methylbenzonitrile
[0152] In a microwave vial, was added Burgess reagent (21.89 mg, 0.092 mmol), (1R,3aR,6S,7R,7aS)-N′-acetyl-7-((E)-2-(5-(2-cyano-3-methylphenyl)pyridin-2-yl)vinyl)-5,5-difluoro-1,6-dimethyl-3-oxooctahydroisobenzofuran-3a-carbohydrazide (16 mg, 0.031 mmol) and THF (0.75 mL). The microwave tube was capped and heated at 150° C. for 30 min. in a microwave. The reaction mixture was diluted with EtOAc, washed with water and brine. The organic phase was dried with Na 2 SO 4 , concentrated and the crude was purified by reverse phase HPLC (acetonitrile/water with 0.1% TFA modifier) to provide the title compound as a TFA salt. MS ESI calcd. for C 28 H 27 F 2 N 4 O 3 [M+H] + 505, found 505. 1 H NMR (500 MHz, CD 3 OD) δ 8.88 (d, J=6.1 Hz, 1H); 8.39 (t, J=8.9 Hz, 1H); 8.01 (t, J=9.2 Hz, 1H); 7.72 (td, J=7.8, 3.7 Hz, 1H); 7.50-7.57 (m, 2H); 6.90-6.99 (m, 2H); 5.19 (m, 1H); 3.33 (br m, 2H); 3.00 (d, J=10.6 Hz, 2H); 2.63-2.65 (m, 6H); 2.49 (br m, 1H); 1.56 (dd, J=5.6, 2.5 Hz, 3H); 1.04 (dd, J=5.01, 2.98 Hz, 3H). PAR-1 FLIPR IC 50 =2.45 nM.
[0153] The following examples in Table 4 were prepared according to Scheme 2 using the procedure outlined in the synthesis of Example 5. Intermediate C or D may be used in step 1.
[0000]
TABLE 4
PAR-1
Exact Mass
FLIPR
Ex
Structure
IUPAC Name
[M + H]+
IC 50 (nM)
6
2-(6-((E)-2- ((3R,3aS,4R,5S,7aR)- 7a-(5-cyclopropyl- 1,3,4-oxadiazol-2-yl)- 6,6-difluoro-3,5- dimethyl-1- oxooctahydroisobenzo furan-4-yl)vinyl) pyridin-3-yl)-6- methylbenzonitrile
531
2.07
7
2-(6-((E)-2- ((3R,3aS,4R,5S,7aR)- 6,6-difluoro-3,5- dimethyl-1-oxo-7a-(5- phenyl-1,3,4- oxadiazol-2-yl) octahydroisobenzofuran- 4-yl)vinyl)pyridin-3- yl)-6-ethylbenzonitrile
567
5.01
Example 8
[0154]
Step 1: (1R,3aR,6S,7R,7aS)-methyl-7-((E)-2-(5-bromopyridin-2-yl)vinyl)-5,5-difluoro-1,6-dimethyl-3-oxooctahydroisobenzofuran-3a-carboxylate
[0155] To (3R,3aS,4R,5S,7aR)-4-((E)-2-(5-bromopyridin-2-yl)vinyl)-6,6-difluoro-3,5-dimethylhexahydroisobenzofuran-1(3H)-one (3.86 g, 10.0 mmol) in THF (30 mL) at 0° C. under N 2 (g) was added lithium bis(trimethylsilyl)amide (12.5 mL, 12.5 mmol, 1 M in THF). The reaction mixture was stirred at 0° C. for 30 min before cooling the system to −78° C., and adding methyl cyanoformate (1.11 g, 13.0 mmol). After stirring for 40 min at −78° C., the reaction mixture was allowed to warmed to RT and was stirred for 20 min. The reaction mixture was cooled to 0° C., quenched with saturated NH 4 Cl (aq) , and the product was extracted with EtOAc. The organic phase was washed with brine, dried with Na 2 SO 4 , and was concentrated. The residue was purified by column chromatography on silica (0-40% EtOAc in hexanes) to afford the title compound. MS ESI calcd. for C 19 H 21 BrF 2 NO 4 [M+H] + 444/446, found 444/446.
Step 2: (1R,3aR,6S,7R,7aS)-7-((E)-2-(5-bromopyridin-2-yl)vinyl)-5,5-difluoro-1,6-dimethyl-3-oxooctahydroisobenzofuran-3a-carbohydrazide
[0156] To a solution of (1R,3aR,6S,7R,7aS)-methyl-7-((E)-2-(5-bromopyridin-2-yl)vinyl)-5,5-difluoro-1,6-dimethyl-3-oxooctahydroisobenzofuran-3a-carboxylate (311 mg, 0.7 mmol) in ethanol (3.0 mL) was added hydrazine (0.264 mL, 8.40 mmol). The reaction was heated and stirred at 50° C. for 30 min. Upon completion of the reaction, the system was cooled to RT and was diluted with EtOAc, was washed with water, and brine. The organic phase was dried with Na 2 SO 4 before concentrating and the residue was purified by column chromatography on silica (0-40% EtOAc in hexanes) to provide the title compound. MS ESI calcd. for C 18 H 21 BrF 2 N 3 O 3 [M+H] + 444/446, found 444/446.
Step 3: 5-((1R,3aR,6S,7R,7aS)-7-((E)-2-(5-bromopyridin-2-yl)vinyl)-5,5-difluoro-1,6-dimethyl-3-oxooctahydroisobenzofuran-3a-yl)-1,3,4-oxadiazol-2(3H)-one
[0157] A solution of ((1R,3aR,6S,7R,7aS)-7-((E)-2-(5-bromopyridin-2-yl)vinyl)-5,5-difluoro-1,6-dimethyl-3-oxooctahydroisobenzofuran-3a-carbohydrazide (133 mg, 0.3 mmol) and 1,1′-carbonyldiimidazole (195 mg, 1.200 mmol) in THF (1.5 mL) was stirred at 25° C. for 1 hour. Upon reaction completion, the solvent was removed under reduced pressure and the residue was purified by silica gel chromatography (0-30% EtOAc in hexanes) to yield the title compound. MS ESI calcd. for C 19 H 19 BrF 2 N 3 O 4 [M+H] + 470/472, found 470/472.
Step 4: 5-((1R,3aR,6S,7R,7aS)-5,5-difluoro-7-((E)-2-(5-(3-fluorophenyl)pyridin-2-yl)vinyl)-1,6-dimethyl-3-oxooctahydroisobenzofuran-3a-yl)-1,3,4-oxadiazol-2(3H)-one
[0158] To a mixture of 5-((1R,3aR,6S,7R,7aS)-7-((E)-2-(5-bromopyridin-2-yl)vinyl)-5,5-difluoro-1,6-dimethyl-3-oxooctahydroisobenzofuran-3a-yl)-1,3,4-oxadiazol-2(3H)-one (51.7 mg, 0.11 mmol), (3-fluorophenyl)boronic acid (23.09 mg, 0.165 mmol) and tribasic potassium phosphate (0.165 mL, 0.330 mmol, 2 M in water) in THF (0.7 mL) was added 1,1′-bis(di-tert-butylphosphino)ferrocene palladium dichloride (3.58 mg, 5.50 μmol) at RT. The system was purged and flushed with N 2(g) and the reaction mixture was stirred at 50° C. for 2 hours. The reaction mixture was diluted with EtOAc, and the organic was washed with water and brine. The organic phase was dried with Na 2 SO 4 , and was concentrated under reduced pressure. The crude was purified by silica gel chromatography (0-25% EtOAc in hexanes) to provide the title compound. MS ESI calcd. for C 25 H 23 F 3 N 3 O 4 [M+H] + 486, found 486. 1 H NMR (500 MHz, CDCl 3 ) δ 8.81 (s, 1H); 8.08 (d, J=8.3 Hz, 1H); 7.59 (dd, J=7.95, 3.05 Hz, 1H); 7.49-7.54 (m, 2H); 7.47 (d, J=10.2 Hz, 1H); 7.12-7.21 (m, 1H); 6.75-6.78 (m, 2H); 5.11-5.19 (m, 1H); 3.08 (s, 1H); 2.88 (m, 2H); 2.37-2.59 (m, 2H); 1.53 (dd, J=6.1, 3.0 Hz, 3H); 1.05 (dd, J=6.8, 3.0 Hz, 3H). PAR-1 FLIPR IC 50 =28.7 nM.
Example 9
[0159]
Step 1: (3R,3aS,4R,5S,7aR)-4-((E)-2-(5-bromopyridin-2-yl)vinyl)-6,6-difluoro-7a-((R)-1-hydroxy-4,4-dimethylpent-2-yn-1-yl)-3,5-dimethylhexahydroisobenzofuran-1(3H)-one
[0160] To (3R,3aS,4R,5S,7aR)-4-((E)-2-(5-bromopyridin-2-yl)vinyl)-6,6-difluoro-3,5-dimethylhexahydroisobenzofuran-1(3H)-one (600 mg, 1.55 mmol) in 2-Me-THF (6 mL) at 0° C. under N 2 (g) was added lithium bis(trimethylsilyl)amide (325 mg, 1.94 mmol). The reaction mixture was stirred at 0° C. for 30 min before cooling the system to −78° C. and adding 4,4-dimethylpent-2-ynal (222 mg, 2.02 mmol). After stirring for 30 min at −78° C., the reaction mixture was allowed to warmed to RT and was stirred for 30 min. The reaction mixture was cooled to 0° C., quenched with saturated NH 4 Cl (aq) , and the product was extracted with EtOAc. The organic phase was washed with brine, dried with Na 2 SO 4 , and was concentrated. The residue was purified by column chromatography on silica (0-20% EtOAc in hexanes) to afford the title compound. MS ESI calcd. for C 24 H 29 BrF 2 NO 3 [M+H] + 496/498, found 496/498.
Step 2: (3R,3aS,4R,5S,7aR)-4-((E)-2-(5-bromopyridin-2-yl)vinyl)-7a-(4,4-dimethylpent-2-ynoyl)-6,6-difluoro-3,5-dimethylhexahydroisobenzofuran-1(3H)-one
[0161] To a solution of (3R,3aS,4R,5S,7aR)-4-((E)-2-(5-bromopyridin-2-yl)vinyl)-6,6-difluoro-7a-(1-hydroxy-4,4-dimethylpent-2-yn-1-yl)-3,5-dimethylhexahydroisobenzofuran-1(3H)-one (153 mg, 0.308 mmol) in DCM (1 mL) was added sodium bicarbonate (38.8 mg, 0.462 mmol) and Dess-Martin Periodinane (327 mg, 0.771 mmol) at RT. After 2 hours, the solvent was removed under reduced pressure and the residue was directly purified by silica gel chromatography (0-20% EtOAc in hexanes) to provide the title compound. MS ESI calcd. for C 24 H 27 BrF 2 NO 3 [M+H] + 494/496, found 494/496.
Step 3: (3R,3aS,4R,5S,7aR)-4-((E)-2-(5-bromopyridin-2-yl)vinyl)-7a-(5-(tert-butyl)-1H-pyrazol-3-yl)-6,6-difluoro-3,5-dimethylhexahydroisobenzofuran-1(3H)-one
[0162] To a solution of (3R,3aS,4R,5S,7aR)-4-((E)-2-(5-bromopyridin-2-yl)vinyl)-7a-(4,4-dimethylpent-2-ynoyl)-6,6-difluoro-3,5-dimethylhexahydroisobenzofuran-1(3H)-one (150 mg, 0.303 mmol) in EtOH (0.9 mL) was added hydrazine (0.029 mL, 0.910 mmol) at RT. After 30 min., the solvent was removed under reduced pressure and the crude residue was purified by silica gel chromatography (0-30% EtOAc in hexanes) to provide the title compound. MS ESI calcd. for C 24 H 29 BrF 2 N 3 O 2 [M+H] + 508/510, found 508/510.
Step 4: 2-(6-((E)-2-((3R,3aS,4R,5S,7aR)-7a-(5-(tert-butyl)-1H-pyrazol-3-yl)-6,6-difluoro-3,5-dimethyl-1-oxooctahydroisobenzofuran-4-yl)vinyl)pyridin-3-yl)benzonitrile
[0163] To a mixture (3R,3aS,4R,5S,7aR)-4-((E)-2-(5-bromopyridin-2-yl)vinyl)-7a-(5-(tert-butyl)-1H-pyrazol-3-yl)-6,6-difluoro-3,5-dimethylhexahydroisobenzofuran-1(3H)-one (80 mg, 0.16 mmol), (2-cyanophenyl)boronic acid (34.7 mg, 0.236 mmol) and tribasic potassium phosphate (0.236 mL, 0.472 mmol, 2 M in water) in THF (1.0 mL) was added 1,1′-bis(di-tert-butylphosphino)ferrocene palladium dichloride (5.13 mg, 7.87 μmol) at RT. The system was purged and flushed with N 2(g) and the reaction mixture was stirred at 50° C. for 4 hours. The reaction mixture was diluted with EtOAc, and the organic was washed with water and brine. The organic phase was dried with Na 2 SO 4 , and was concentrated under reduced pressure. The crude was purified by silica gel chromatography (0-45% EtOAc in hexanes) to provide the title compound. MS ESI calcd. for C 31 H 33 F 2 N 4 O 2 [M+H] + 531, found 531. 1 H NMR (500 MHz, CDCl 3 ) δ 9.77-9.57 (br s, 1H); 8.76 (d, J=2.3 Hz, 1H); 7.95 (dd, J=8.1, 2.4 Hz, 1H); 7.85 (d, J=7.7 Hz, 1H); 7.74 (t, J=7.7 Hz, 1H); 7.54-7.58 (m, 2H); 7.35 (d, J=8.1 Hz, 1H); 6.76 (d, J=4.7 Hz, 2H); 6.33 (s, 1H); 4.85 (dd, J=10.4, 5.8 Hz, 1H); 3.22-3.32 (m, 1H); 3.02-3.11 (m, 1H); 2.81-2.93 (m, 1H); 2.18-2.33 (m, 2H); 1.59 (d, J=12, 3H); 1.39 (s, 9H); 1.09 (d, J=6.6 Hz, 3H). PAR-1 FLIPR IC 50 =14.5 nM.
[0164] The following examples in Table 5 were prepared according to Schemes 3 and 4 using the procedure outlined in the synthesis of Example 9 using 4,4-dimethylpent-2-ynal, but-2-ynal, or 3-trimethylsilylpropynal in step 1 and known or commercially available boronic acids and esters in step 4.
[0000]
TABLE 5
PAR-1
Exact Mass
FLIPR
Ex
Structure
IUPAC Name
[M + H]+
IC 50 (nM)
10
2-(6-((E)-2- ((3R,3aS,4R,5S,7aR)- 7a-(5-(tert-butyl)-1- methyl-1H-pyrazol-3- yl)-6,6-difluoro-3,5- dimethyl-1- oxooctahydroisobenzo furan-4-yl)vinyl) pyridin-3- yl)benzonitrile
545
25.3
11
2-(6-((E)-2- ((3R,3aS,4R,5S,7aR)- 7a-(1,5-dimethyl-1H- pyrazol-3-yl)-6,6- difluoro-3,5-dimethyl- 1-oxooctahydroiso benzofuran-4- yl)vinyl)pyridin-3- yl)benzonitrile
517
6.30
12
2-(6-((E)-2- ((3R,3aS,4R,5S,7aR)- 6,6-difluoro-3,5- dimethyl-1-oxo-7a- (1H-pyrazol-3-yl)octa hydroisobenzofuran- 4-yl)vinyl)pyridin-3- yl)benzonitrile
475
0.99
Example 13
[0165]
Step 1: 6′-((E)-2-((3R,3aS,4R,5S,7aR)-6,6-difluoro-7a-((S and R)-1-hydroxy-3-(trimethylsilyl)prop-2-yn-1-yl)-3,5-dimethyl-1-oxooctahydroisobenzofuran-4-yl)vinyl)-[3,3′-bipyridine]-2-carbonitrile
[0166] A solution of 6′-((E)-2-((3R,3aS,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-1-oxooctahydroisobenzofuran-4-yl)vinyl)-[3,3′-bipyridine]-2-carbonitrile (102 mg, 0.25 mmol) was dissolved in THF (2 mL). The solution was cooled to −78° C. and degassed by bubbling in nitrogen for 20 minutes followed by vacuum purging and flushing with nitrogen (3×). LiHMDS (1.0 M in THF, 325 μL, 0.325 mmol) was added and after 10 minutes, 3-trimethylsilylpropynal (51.7 μL, 0.350 mmol) was added. After 20 minutes at −78° C., the system was warmed to room temperature for an hour. The reaction was quenched with saturated aqueous NH 4 Cl, then diluted with ethyl acetate and partitioned. The organic layer was washed with water, then with brine, dried over anhydrous sodium sulfate, filtered and concentrated. The residue was purified by chromatography (15-45% EtOAc/hexanes) to yield the title compound. MS ESI calcd. for C 29 H 32 F 2 N 3 O 3 Si [M+H] + 536, found 536.
Step 2: 6′-((E)-2-43R,3aS,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-1-oxo-7a-(3-trimethylsilyl) propioloyl)octahydroisobenzofuran-4-yl)vinyl)-[3,3′-bipyridine]-2-carbonitrile
[0167] To a solution of 6′-((E)-2-((3R,3aS,4R,5S,7aR)-6,6-difluoro-7a-((S and R)-1-hydroxy-3-(trimethyl silyl)prop-2-yn-1-yl)-3,5-dimethyl-1-oxooctahydroisobenzofuran-4-yl)vinyl)-[3,3′-bipyridine]-2-carbonitrile (94 mg, 0.175 mmol) in DCM (877 μL) was added Dess-Martin periodinane (112 mg, 0.263 mmol) at 0° C. After 90 min, the reaction was quenched with saturated aqueous NaHCO 3 , diluted with DCM and partitioned. The organic was washed with saturated aqueous NaHCO 3 again, then dried over anhydrous sodium sulfate, filtered and evaporated. The residue was purified by silica chromatography (15-60% EtOAc/hexanes) to yield the title compound. MS ESI calcd. for C 29 H 30 F 2 N 3 O 3 Si [M+H] + 534, found 534.
Step 3: 6′-((E)-2-((3R,3aS,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-1-oxo-7a-(1H-pyrazol-3-yl)octahydroisobenzofuran-4-yl)vinyl)-[3,3′-bipyridine]-2-carbonitrile
[0168] To a solution of 6′-((E)-2-((3R,3aS,4R,5S,7aR)-6,6-difluoro-3,5-dimethyl-1-oxo-7a-(3-(trimethylsilyl)propioloyl) octahydroisobenzofuran-4-yl)vinyl)-[3,3′-bipyridine]-2-carbonitrile (80.5 mg, 0.151 mmol) in ethanol (1 mL) was added hydrazine (14.2 μL) at rt. After 45 minutes, the reaction was partitioned between water and ethyl acetate. The organic was water and then with brine, dried over anhydrous sodium sulfate, filtered and evaporated. The residue was purified by silica chromatography (20-100% EtOAc/hexanes) and to yield the title compound. MS ESI calcd. for C 26 H 24 F 2 N 5 O 2 [M+H] + 476, found 476. 1 H NMR (500 MHz, CDCl 3 ) δ 8.76 (dd, 1H, J=4.7 Hz, 1.3 Hz), 8.73 (d, 1H, J=2.2 Hz), 7.95 (dd, 1H, J=8.0 Hz, 2.3 Hz), 7.89 (dd, 1H, J=8.0 Hz, 1.3 Hz), 7.64 (m, 2H), 7.36 (d, 1H, J=8.2 Hz), 6.75 (m, 2H), 6.59 (d, 1H, J=2.4 Hz), 4.85 (m, 1H), 3.24 (m, 1H), 3.02 (m, 1H), 2.87 (m, 1H), 2.32-2.14 (m, 2H), 1.57 (d, 3H, J=5.8 Hz), 1.05 (d, 3H, J=6.6 Hz). PAR-1 FLIPR IC 50 =6.2 nM L-005346192.
Assays
[0169] The following assays were used to evaluate the ability of the inventive compounds to act as PAR-1 receptor antagonists and their interactions with other therapeutic agents in the body.
PAR-1 FLIPR Assay
[0170] This assay measures the potency of the inventive compounds as PAR-1 receptor antagonists.
[0171] Frozen HEK 293 Cells were plated in 384-well PDL coated plates at 12000 cells/well in 50 uL of DMEM media containing 10% FBS, pen/strep/L-Glutamine and non-essential amino acids, incubated overnight at 37° C./5% CO 2 . Media was then removed from the cells, incubated with 33 uL of Calcium-5 dye in assay buffer (Hank's buffer containing 20 mM HEPES, 0.04% Chaps and 2.5 mM Probenecid) for 60 minutes at 37° C. 2 uL of varying concentrations of compound in 40% DMSO in assay buffer (final DMSO concentration is 2.3%) were then added to the cells and incubated at 25° C. for 30 minutes. The plates were added to the FLIPR Tetra®, the device added 5 μL of PAR-1 selective receptor-activating peptide (sequence Ala-parafluoroPhe-Arg-Cha-Cit-Try-NH 2 , prepared in water) at a concentration equal to the effective concentration that achieved 80% activation of signaling on the day of the experiment. The range of peptide was from 1.5-3 μM. The final volume is 40 uL/well, with 2% DMSO. The FLIPR was read at an excitation wavelength of 480 nm and an emission wavelength of 535 nm, and performed 60 scans over a 1-2 min reading time. The data were analyzed by taking the peak signal over a portion of the range of the 60 scans and dividing this signal by the minimum signal for that same range. The data were expressed as percent inhibition of the maximum divided by the minimum signal achieved at 80% activation produced by the PAR1 activating peptide on the test day. The compounds of Examples 1-13 were tested in the assay described above and the data collected for these compounds is provided.
CYP MUX (3A4) RI
[0172] This assay measures inhibition of CYP3A4 by a compound. Cytochromes P450 (CYPs) constitute a superfamily of heme-containing enzymes that recognize and metabolize a large number structurally diverse xenobiotics in the human body. CYP3A4 constitutes the largest portion of CYP enzymes in the liver that accounts for the metabolism of almost 50% of all drugs. This assay is used to evaluate the potential of a compound for developing DDIs. (Clarke, S. E.; Jones B. C. Drug - Drug Interactions , New York: Marcel Dekker; 2002. pp. 53-88).
[0173] Compound dilutions and assay-ready plates were prepared on a TTP Labtech mosquito® HTS. Assay conduction was fully automated on a customized Screening Platform from Caliper (now PerkinElmer) containing a Mitsubishi robotic plate handler, Liconic incubators, a Caliper Zephyr® liquid handling workstation equipped with temperature-controlled deck positions, a Biotek MultiFlo™ dispenser and an Agilent PlateLoc heat sealer. Assay plates were Corning Costar® 384 well PP plates. High throughput mass spectrometric readout was performed on a RapidFire® 300 system coupled to an AB Sciex API 4000™ triple quadrupole device. CYP isoform 3A4 was incubated in a separate reaction of 50 μL final volume. 25 μL of HLM (human liver microsomes, BD UltraPool™ 150, 0.25 mg/mL final concentration) and the respective substrate, testosterone (75 μM) for 3A4, in potassium phosphate buffer (100 mM, pH=7.4) were added to 250 nL of stamped compound solution (10 mM in DMSO). The reactions were started upon addition of 25 μL of a co-factor solution containing magnesium chloride (3.3 mM), glucose-6-phosphate (3.3 mM), glucose-6-phosphate dehydrogenase (1.4 units) and NADP (1 mM) in potassium phosphate buffer (100 mM, pH=7.4) and incubated on deck at 37° C. for 10 min. 8 μL of each reaction were transferred to the same readout plated filled with 48 μL of stop solution containing internal standards (concentration in final readout plate), 6-hydroxytestosterone-D7 (0.5 μM), 4′-hydroxydiclofenac-D4 (0.2 and dextrorphan-D3 (0.01 in acetonitrile with 0.5% formic acid. After heat sealing, plates were stored at −20° C. for at least 30 min, centrifuged and subjected directly to RapidFire®/MS analysis.
[0174] The selectivity of the inventive compounds in CPY3A4 assay is summarized in Table 6 below.
[0000]
TABLE 6
Ex
CYP3A4 IC 50 (μM)
1
21.8
2
22.8
3
10.4
4
9.9
5
16.9
6
50
7
50
8
50
9
50
10
50
11
17.6
12
2.4
13
8.8
[0175] While the invention has been described with reference to certain particular embodiments thereof, numerous alternative embodiments will be apparent to those skilled in the art from the teachings described herein. Recitation or depiction of a specific compound in the claims (i.e., a species) without a specific stereo configuration designation, or with such a designation for less than all chiral centers, is intended to encompass the racemate, racemic mixtures, each individual enantiomer, a diastereoisomeric mixture and each individual diastereomer of the compound where such forms are possible due to the presence of one or more asymmetric centers. All patents, patent applications and publications cited herein are incorporated by reference in their entirety. | The present invention relates to bicyclic himbacine derivatives of the formula
or a pharmaceutically acceptable salt thereof
wherein:
R 1 is
W is
and the remaining variables are described herein. The compounds of the invention are effective inhibitors of the PAR-1 receptor. The inventive compounds may be used for the treatment or prophylaxis of disease states such as ASC, secondary prevention of myocardial infarction or stroke, or PAD. | 0 |
FIELD OF THE INVENTION
This invention relates to labels having a removable section, the labels being particularly adapted for use with printing processes for the in-mold labeling of injection- or blow-molded plastic containers. More particularly, the present invention relates to two-part, one removable and the other permanent, labels for use in printing processes of white opaque, transparent, translucent or contact clear films having a heat activatible adhesive on one side and, under the adhesive, a patterned anti-adhesive (abhesive) coating corresponding to the removable section so as make labels from which a section ultimately can be readily removed, the labels in the meantime being functional through the entire label converting and molding process.
BACKGROUND OF THE INVENTION
Plastic containers or bottles are prevalent today in a wide variety of shapes and sizes for holding many different kinds of materials such as light duty liquids (e.g., dishwashing detergent), heavy duty liquids (e.g., laundry detergents), motor oil, vegetable oil, herbicides, etc. Generally, these containers are fabricated from layers or a plurality of layers of plastic, particularly polypropylene, polyethylene and polyesters, by means of blow molding or injection molding.
Generally, such containers are provided with a label which designates the trade name of the product and may contain other information as well. In some instances, the label is merely attached to the container after molding by means of adhesive or the like. However, the label may also be attached to the container during the container molding process. This technology by which the label is associated with the container during the molding operation is generally referred to as an in-mold label process.
Methods and articles describing same are known for performing in-mold labeling of a plastic container. For example, Dronzek, Jr., U.S. Pat. Nos. 5,711,839 and 5,925,208, in the name of one of the applicants herein, and commonly assigned, teach that polymeric sheets or rolls suitable for printing and forming, at high rates of production, blown or injection in-mold labeled plastic containers if made from a polymeric transparent, translucent or contact clear substrate, preferably monoaxially or biaxially oriented, and having a thickness in the range of 0.002 to 0.008 inches which is reverse printed and overcoated on the container-facing side with a heat activatable adhesive and coated or extruded on the opposite side with an antistatic and/or slip coating. Optionally, these Patents teach that such sheets or rolls can be printed and then cut into individual labels for affixing to the container as part of an in-molding process. Recyclable containers are provided at high speed without missing labels or doubled labels due to feeding problems. The labels are firmly adherent, and squeeze-release resistant and the indicia, because they are viewable through the labels themselves, are protected against spillage and abrasion.
Also relevant for its teachings, regarding in-mold labeling with a removable coupon portion, is Sullivan et al, U.S. Pat. No. 5,172,936, the label having a permanent portion and a removable portion, a printed face, and an adhesive-coated back, the permanent areas of the label having a degree of adhesion resulting in a permanent bond and the removable areas being covered with an adhesive with a lower degree of adhesion so as to allow the removable portion to be removed from the surface. The labels provided by the teachings of U.S. Pat. No. 5,172,936 are not made by a process which uses, as its final step, overcoating the patterned adhesive with the permanent adhesive. Moreover the removable portions are disclosed to tend to wrinkle, crease and blister. It would be desirable to eliminate such shortcomings, while at the same time providing a coupon which is different in use and appearance, but maintains all functional advantages.
Also relevant for its teachings with respect to machine-direction oriented label films and die-cut labels prepared therefrom is Josephy et al, U.S. Pat. No. 5,585,193, which discloses labels prepared from a multilayer composite cast extruded and oriented in the machine direction. The composite also comprises an adhesive layer for adhering the label to a substrate. The advantage provided by such composites is improved die-cuttability.
The present state of the art thus shows that white opaque, transparent, translucent, clear or contact clear polymeric films having judiciously selected characteristics of thickness, specific gravity and coefficient of expansion and contraction and provided with a heat activatable adhesive coating have improved and surprising characteristics of adhesion to in-mold blown plastic containers with resistance to damage from cracking, tearing, creasing, wrinkling or shrinking due to physical abuse and flexing of the plastic container material. Furthermore, it has been shown in U.S. Pat. No. 5,192,936 that labels with removable coupons can be provided from polymeric face stock by pattern printing with a permanent adhesive the area to be permanently affixed and pattern-printing with a lesser strength adhesive with selectively removable features under the coupon-removable area. This patent teaches the use of less adhesive, a different adhesive or a modified adhesive to achieve the desired objectives. In addition, the prior art teaches, in U.S. Pat. No. 5,585,193, that using a machine-direction oriented film improves the die-cuttability of labels prepared from such films.
It has now been found that making an in-mold label having a removable coupon portion is unexpectedly improved if the film used is oriented uniaxially in the machine direction and is axially in line with the direction of tear when the coupon is ultimately removed.
It has also been found that the process for making the labels with removable features is simplified, and an improved coupon is obtained, if a patterned “abhesive” (i.e., an anti-adhesive; non-stick, anti-adherent properties) is laid down on the substrate in the shape of the coupon and the entire side facing the in-mold article is overcoated with the permanent adhesive to insure that there is no wrinkling or creasing in the removable area making a permanent bond between the adhesive and the container interface.
Accordingly, a principal object of the present invention is to provide for the use of surface- or backside-printable polymeric sheets or rolls to make labels for in-mold use without the problems discussed above. It is a further object of the invention to provide a method for in-mold labeling of hollow plastic containers using printed labels made from such sheets. It is still another object of the invention to provide articles labeled with printed labels which have the unexpectedly superior properties described above.
These and other objects of the invention will become apparent from the present specification.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 is a flow diagram of a process employed to make sheets or rolls from which to die-cut labels according to the present invention;
FIG. 2 . illustrates, in perspective view, a bottle 2 labeled in accordance with the present invention, the label 4 having permanent sections 4 a and 4 b and having removable section 6 partially pulled away, facilitated by notches 8 a and 8 b ; and
FIGS. 2 a – 2 c show magnified cross sections of the container 2 and the label 4 , both with the label 4 attached to the container 2 and with the coupon 6 partially removed. FIG. 2 a shows air 12 , abhesive 14 , and coupon 6 . FIG. 2 b shows container 2 , adhesive 10 , air 12 . FIG. 2 c shows container 2 , adhesive 10 , abhesive 14 , and label 4 .
SUMMARY OF THE INVENTION
According to this invention, there is provided a label having at least one removable section and at least one permanent section, the removable section being defined by two or more discontinuities spaced apart on an edge of the label, the label being made from a polymeric film that is uniaxially oriented in the machine direction, and the discontinuities being located so that a line which is extended to connect the discontinuities is substantially perpendicular to the axis of orientation of the polymeric film.
In preferred labels:
the polymeric film is selected from a monolayer film or an extrusion-cast multilayer film, the monolayer film and the multilayer film being uniaxially-oriented and the multilayer film comprising at least one skin layer and a core layer, each of the layers being formed from at least one polymer, the monolayer films and the multilayer films also being selected from films which are surface printable and films which are capable of being rendered surface printable, and having a thickness between 0.002 and 0.008 inches; those wherein the monolayer film comprises one selected from any of polypropylene, polyethylene or polyester; those wherein the multilayer film comprises one selected from at least one skin layer comprising any of polypropylene, polyethylene and polyester, a core layer comprising any of polypropylene, polyethylene and polyester, and at least one skin layer comprising any of polypropylene, polyethylene and polyester; such labels in which the polymeric film comprises a monolayer or multiple coextruded layers selected from opaque or clear virgin olefin homopolymer, opaque or clear recycled olefin homopolymer, opaque or clear reprocessed olefin homopolymer, opaque or contact clear virgin olefin copolymer, contact clear recycled olefin copolymer, opaque or contact clear reprocessed olefin copolymer or blends of any of the foregoing; and special mention is made of: such labels in which the print-receiving face of the polymeric film includes at least one print enhancing surface to enhance the anchorage of ink, the print surface layer comprising a corona-treated, print-receiving surface.
In another of its major aspects, the present invention contemplates, a label having at least one removable section and at least one permanent section, the removable section being defined by two or more discontinuities spaced apart on an edge of the label, the label being made from a polymeric film that is uniaxially oriented in the machine direction, and the discontinuities being located so that a line which is extended to connect the discontinuities is substantially perpendicular to the axis of orientation of the polymeric film;
wherein a print-receiving face of the polymeric film includes at least one print enhancing surface to enhance the anchorage of ink, the print enhancing surface comprising a primer, a product of flame-treatment, corona-treatment or chemical treatment, a coextruded print receiving layer or a combination of any of the foregoing layers; and
wherein the permanent and the removable sections are provided with a continuous adhesive layer for anchoring the permanent section to a surface; and
wherein the removable section is provided first with a removable-section-defining abhesive layer for stripping the removable section from a surface.
Preferred embodiments include:
such labels wherein the polymeric film is selected from a monolayer film or an extrusion-cast multilayer film, the monolayer film and the multilayer film being uniaxially-oriented and the multilayer film comprising at least one skin layer and a core layer, each of the layers being formed from at least one polymer, the monolayer films and the multilayer films also being selected from films which are surface printable and films which are capable of being rendered surface printable, and having a thickness between 0.002 and 0.008 inches; such labels wherein the monolayer film comprises one selected from any of polypropylene, polyethylene or polyester; such labels wherein the multilayer film comprises one selected from at least one skin layer comprising any of polypropylene, polyethylene and polyester, a core layer comprising any of polypropylene, polyethylene and polyester, and at least one skin layer comprising any of polypropylene, polyethylene and polyester; such labels in which the polymeric film comprises a monolayer or multiple coextruded layers selected from opaque or clear virgin olefin homopolymer, opaque or clear recycled olefin homopolymer, opaque or clear reprocessed olefin homopolymer, opaque or contact clear virgin olefin copolymer, contact clear recycled olefin copolymer, opaque or contact clear reprocessed olefin copolymer or blends of any of the foregoing; and special mention is made of such labels in which the print-receiving face of the polymeric film includes at least one print enhancing surface to enhance the anchorage of ink, said print surface layer comprising a corona-treated, print-receiving surface.
In its embodiments, the invention includes containers having a label as defined above and articles of manufacture having a label as defined above.
DETAILED DESCRIPTION OF THE INVENTION
The terms “virgin”, “recycled” or “reprocessed” when used herein and in the appended claims mean, respectively, new resin, reground resin, and resin sheets and the like which have been prepared for other uses, and after-treated to remove coatings, etc.
The term “regrind compatible” when used herein and in the appended claims means that containers with in-mold labels can be reground and molded after being mixed with virgin material. Regrind compatibility is determined by regrinding, mixing and molding.
The term “contact clear” when used herein and in the appended claims means a hazy material difficult to see through, but which, in intimate contact with a surface, transmits an underlying image. Polyethylene films are a common example. Contact clarity is determined by a simple trial and error test.
The terms “primer”, “flame-treatment”, “corona treatment”, and “chemical treatment” when used herein and in the appended claims mean, respectively, a deposited coating for promoting adhesion generally comprising a filled or unfilled polymer, surface activation by carefully exposing to a bank of flames, without burning or distortion, exposure to high voltage direct current to microscopically etch the surface, and carefully etching the surface with chemicals known to be effective for this purpose.
The labels of the invention comprise a substrate which has characteristics substantially similar to the plastic container with which the label is to be used with special reference to the polymers used. This prevents loosening of the label, especially at its edges after the in-mold processing and facilitates recycling.
The substrate film must be oriented. As is well known, cast film can or cannot be oriented, but is usually oriented to a minor degree in the machine direction (MD). Blown film is usually oriented due to the manufacturing process, but is not usually sold as oriented because it is an unbalanced orientation. Extruded film is usually oriented to a major degree, and orientation can be monoaxial or biaxial. Although many such films, monolayered and multilayered, can be used in the present invention, it is important to select and to use monoaxially oriented film as the substrate. The substrate should have “a coefficient of thermal expansion or contraction under the conditions which the container sees the same or substantially the same as that of the plastic from which said container is made.” Some variability is permissible, and the characteristic seems to be a factor in preventing lifting of the edges of the in-molded containers bearing the in-mold labels of the invention. Coefficient of thermal expansion or contraction is measured by standard methods, such as by ASTM Method D696, which expresses the values in units of 10 −6 in/in/° C., or in values of %/° C. from which the permissible variations mentioned hereinabove are measured. However, the best test is a practical one: make a test container and subject it to a heat and cooling cycling in a controlled temperature oven. Those combinations of label materials and bottle plastics free of edge lifting are suitable.
A heat activated adhesive is applied from a printing roll, screen, extrusion die, and the like, in a single all-in-one process to a surface of the substrate which will come into contact with the container. Selected inkwork comprising printed indicia will be, as part of the same process, reverse printed on the back surface, i.e., under the adhesive and abhesive for clear or contact-clear labels or on the opposite surface of opaque labels by a printing process as described above or an art-recognized equivalent. Similarly, the abhesive (as well as optional non-coextruded antistatic and/or slip compositions) will be applied from the roll or screen in known ways and when indicia are applied as part of the printing process. If a coextruded substrate is used an antistatic and/or slip layer can be coextruded with the base polymer sheet during the extrusion process and is matched with the adhesive to provide the proper antistatic and slip for optional feeding into the mold. After die-cutting, as will be described later, each individual label will be picked up by high speed machinery of well-known types for positioning in an injection mold or a blow mold prior to container formation. As the container is formed, the adhesive is activated by the heat in the mold and its contents and adheres the label to an outer surface of the container.
The preferred embodiments of the labels of the present invention are fabricated from white opaque extruded, cast or blown films of polyolefin, e.g., polyethylene or polypropylene, or polyester and these may optionally be provided with a print enhancing coating or coextruded layer such as those well known to those skilled in this art. Opaque films are preferred to mask indicia printed on the back side of the removable area so that they are not visible until the coupon is removed. The films can be e.g., provided in rolls which may be printed with conventional label indicia on conventional printing equipment and furthermore can be die cut and applied to plastic containers using conventional in-mold equipment. Although for purposes of exemplary showing, the present invention is described and illustrated in connection with a polyethylene container, it will be understood that in-mold labeling may also be applied in the formation of propylene multi-layer bottles, polyethylene terephthalate bottles and other types of plastic containers formed by blow or injection molding.
The preferred construction of the improved in-mold labels of the present invention uses a solid, i.e., non-multicellular thermoplastic film comprised of a monoaxially extruded polypropylene polymer. Such films are marketed under the name “PRINTRITE®” by Trico Industries, Davisville, R.I., 02854, U.S.A. Preferred multilayered films include PRIMAX® NA-R 400, a corona-treated, semi-rigid matte white polyolefin film, PRIMAX® NA 400, a corona-treated flexible matte white polyolefin film by Avery Dennison, Concord, Ohio 44077, U.S.A. In order to enhance the printing qualities of the thermoplastic film it may be provided with, for example, a print receptive coextruded layer known to those skilled in the art, filled, e.g., lightly filled with clay/calcium carbonate, silica and/or china clay, etc., or, preferably, an unfilled primer coating, such as an acrylic type resin. Typically such primers are available commercially from sources well known to those skilled in this art. For example, polyester primers are marketed by Rohm & Haas, Philadelphia, Pa., U.S.A., and acrylic or polyurethane primers by Neo Resins, Wilmington, Mass. 01887, U.S.A. The coating helps insure that the surface of the film will accept high quality printing and may also improve the abrasion and scuff resistant qualities of the finished label.
The physical properties of the aforementioned monoaxially oriented thermoplastic polypropylene film (PRINTRITE®), are set forth in Table 1:
TABLE 1
Density
0.905 g/cm 3
Thickness
0.0024–0.0038 inches
Folding Endurance
Excellent
Coefficient of Expansion**
81–100 × 10 −6 in/in/° C.
% Shrink at 212° F., MD, TD
<2%
Surface treatment
Corona-discharge
*MD = machine direction; TD = transverse direction
**Modern Plastics Encyclopedia, October 1989, page 606
A heat activated adhesive is applied to such label sheets in a conventional manner. The use of such coatings for in-mold labels is reviewed in detail by D. H. Wiesman in Tappi Journal, Vol 69, No. 6, June 1986. A preferred adhesive comprises an organic polymeric resin such as an ethylene/vinyl acetate copolymer gel or dispersion. A suitable source of such adhesives is Rohm & Haas Corp. which sells such products under the name “ADCOTE®” 31DW1974 (Solvent-based) and “ADCOTE® 57WW654 (Water-based). Also suitable is a warm melt adhesive designated Product No. S11723 and sold by Selective Coatings & Inks, Inc., Farmingdale, N.J., U.S.A. Before (if reverse printing is employed), applying the adhesive, the film is printed with suitable label indicia in a conventional manner. The adhesive is preferably applied from, for example, a gravure roll, or screen or flexographic plate, so as to produce a continuous coating. It has been found that the printing quality of the present thermoplastic film labels is equivalent to the printing quality of conventional paper labels. Finally, individual labels may be die cut from the sheets or rolls in the conventional manner e.g., by rotary die cutting, by square cutting, and the like.
With respect to printing, although various methods are used in this art to apply information or decorations to plastics, traditional equipment is used herein. To avoid unnecessarily detailed description, reference is made to Modern Plastics Encyclopedia, Mid-October Issue, 1989, “Printing” by Hans Deamer, pages 381–383.
Selection of the printing inks for use, and formation of print-enhancing surfaces and the production of images or indicia are well within the skill of workers in this field. Also, it is easily obvious to the artisan to produce the films of this invention with direct printed and reverse printed indicia on any print-receiving surface and to carry out the printing operation in the stages set forth in the description above. The inclusion of primers for sealing the printed image and to enhance ink and adhesive bonding is also conventional in this art.
The antistatic and/or slip agents preferred if used herein are applied as coatings or as coextruded layers, incorporated in the resin used for the labels. Such coatings are also applied by techniques known to those skilled in this art. For example, a thin coat of antistatic agent can be applied to one surface of the film which may already have been printed in reverse. Suitable such coatings can be selected from the many commercially-available materials known in this art, such as listed, for example in Modern Plastics Encyclopedia, Mid-October Issue, 1987, “Antistatic Agents” by J. L. Rogers, pages 130 and 132, as well as pages 579–581. Preferred for use herein are commercially-available antistatic coating compositions available, for example, from Akzo Chemie America, Chicago, Ill., under the trade name or designation Armostat® Aqueous Ethoquad CY12, from distributors of a product of the successors to Union Carbide Corp., Danbury, Conn., under the trade name or designation Silwet® L-77, a modified silicone, or from Flint Ink, Ann Arbour, Mich. 48105 U.S.A. under the tradename “FLEXCON” a proprietary mixture which is gravure, flexographic and screen applicable or from Process Resources Corp., Thornwood, N.Y., U.S.A. under the tradename or designation PD 945, a mixture which is gravure, flexographic or screen applicable and having the typical properties described in Table 2:
TABLE 2
Solids
4%
pH
8.5–9.5
Viscosity
10–50 CPS 2/20 RPM @ 77° F.
Weight/gallon
8.5 LBS/GAL
Color
Off White
Diluent
Water
Clean-Up
Water
Shelf-Life
90 Days
The antistatic coating can be applied as part of the printing process and it may be applied either before or after application of the adhesive layer.
As is shown in FIG. 1 , the adhesive layer is preferably put on last, although the adhesive layer can be laid down at an earlier stage. But it is critical to the present invention that the abhesive layer is always put down before the adhesive layer, although intervening steps can be employed. In preferred embodiments, a patterned roller or screen will be used, although preferably just before, as illustrated in the flow diagram in FIG. 1 . However, as mentioned above, the abhesive layer can also, if desired, be laid down earlier in the process, as part of printing, backside printing, an independent station, and the like. The abhesive composition employed can be a commercially-available product or can be prepared by one skilled in this art. Presently preferred, is a product sold under the trade designation “FLEXCON ABSEEEAL LACQUER” by Flint Ink, Ann Arbour, Mich. 48105, U.S.A. This composition includes heptane (10–30%), n-propanol (10–30%), hydrotreated paraffin wax and water. See also the teachings regarding water-based, non-silicone-containing slip enhancers in U.S. Pat. No. 5,792,734.
With respect to the coextruded slip layers, migratory slip aids such as fatty acid amides (soaps) can be used in extruded or coextruded layers, such as but not limited to erucamide, oleoamide or steramide. Other types of migratory slip additives are silicone oils. Examples of non-migratory slip aids are talc platelets, silicone spheres or waxes. In any event, migratory, non-migratory, and combinations thereof, can be used as slip agents.
The in-mold labels of the present invention may be utilized on conventional in-mold labeling apparatus in the same manner as conventional paper labels. See, for example, the article in Tappi Journal, cited above.
To save unnecessarily detailed description, devices for performing in-mold labeling on a container, which are well known, are the subject matters of U.S. Pat. No. 3,759,643 to Langecker, 1973, and U.S. Pat. No. 4,479,644 to Bartlmee et al, 1984. In general, all such apparatus use a injection mold or a blow mold having a cavity for containing a hollow body, and a member which is movable toward the cavity. The member includes a section for carrying a label to be placed in the mold during movement of the member toward the cavity. Ventilation openings are provided in the mold for venting any air between the mold and label. Variations in the apparatus that may be employed include using rotating mold units and oscillating means for picking up individual labels and depositing them in the rotating molds at appropriate intervals to automate the process.
A labeled bottle in accordance with the invention is shown in FIGS. 2 ( 2 a , 2 b and 2 c ) and has been explained in detail above.
The patents, applications, publications and test methods mentioned above are incorporated herein by reference.
Many variations of the present invention will suggest themselves to those skilled in the art in light of the above detailed description. For example, instead of virgin oriented polypropylene as the face film, virgin poly(ethylene terephthalate), polyamide, polyethylene, polycarbonate, fluoropolymers and polyimide films can be used. Instead of 0.007 inch polyester film, 0.004 inch polyester film can be used. Instead of ethylene/vinyl acetate as the heat activated adhesive layer, low density polyethylene can be used. Instead of an acrylic printing enhancing coating, another coating, such as a polyester or urethane resin, can be printed in selected areas on the print receiving face of the polymeric sheet or roll. Instead of a polyethylene container, a polypropylene container or a polyester container, the labels can be applied to containers made by injection molding or by blow molding single or multi-layers of barex, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, ionomer resin, K-resin, polystyrene and polyvinyl chloride. Polypropylene labels can be put on polyethylene containers and polyethylene labels can be put on polypropylene containers.
As antistatic agents of the nonionic type there can be used ethoxylated, propoxylated or glycerol compounds. Alkyl amines can be used as antistats of the amine type. Alkyl ammonium quaternary salts can be used as antistats of the quaternary type. The antistats can be applied in the gravure, flexographic or screen printing process as an aqueous and/or alcoholic solution at 1 or 2% concentration, by weight.
Instead of a single layer label, the labels can comprise two, or more, layers. For example, the outer layer can comprise a reverse printed transparent substrate, comprising at least one layer, through which the indicia is viewed, and this can be laminated to at least one second film (transparent or opaque), and which is unprinted, but which bears the heat activatable adhesive layer, the second film having all of the thermodynamic characteristics required for the first, and serving to anchor the composite label to the blow molded container.
All such obvious modifications are within the full intended scope of the appended claims. | Labels having a permanent section and at least one removable coupon section are made from polymeric sheets or rolls suitable for printing and forming, at high rates of production, blown or injection in-mold labeled plastic containers are based on a polymeric white opaque, transparent, translucent or contact clear substrate monoaxially oriented and having a thickness in the range of 0.002 to 0.008 inches. The polymer film is reverse pattern-printed with an abhesive coextensive with the detachable portion then overcoated on the container-facing side with a continuous coating of heat activatable adhesive. Such sheet or roll can be printed and then cut into individual labels for affixing to the container as part of a in-molding process. Recyclable containers are provided at high speed without missing labels or doubled labels due to feeding problems. The labels are firmly adherent, except for the removable coupon, and squeeze-release resistant and the indicia, because, in clear and contact-clear versions, are viewable through the labels themselves, are protected against spillage and abrasion. | 1 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an organic compound decomposing method having a small load on an environment and with a high decomposition ratio and preferable composition amount.
[0003] 2. Description of the Related Art
[0004] Recently, various substances are pointed out as having a high possibility to become environmental hormones causing a new environment problem such as bisphenol A which is a raw material of plastic, phthalate ester contained in plastic as plasticizer, dioxin generated when waste is burnt, and nonyl phenol which is a surface active agent exhausted from factories and households.
[0005] A significant amount of the aforementioned organic compounds is already mixed in the ambient atmosphere, water, and soil. These chemical compounds cannot easily be decomposed in the ecological system. Accordingly, it is expected that these compounds are widely diffused in the entire world through the water circulation and the food chain for a long period of time. This is considered to bring about contamination of the atmosphere, water, and soil, affecting the human body. To cope with this, a technique for purifying the aforementioned organic compounds is strongly required.
[0006] For purifying the aforementioned organic compounds, there have been suggested a so-called bio-remediation method for decomposing organic materials by the microbes in the soil and a method for decomposing organic compounds contained in water using supercritical water as disclosed in Japanese Patent Publication 10-84947.
[0007] However, the bio-remediation has a problem that the organic compound decomposition speed is slow and it is necessary to continuously supply nutriments for microbes until the organic compound decomposition is complete. There is also a problem that dead bodies of microbes remain after the organic compound decomposition is complete. Moreover, the method for decomposing organic compounds in water using supercritical water requires a large-scale facility and a plenty of energy and cannot be implemented in practice because of the low decomposition capability.
SUMMARY OF THE INVENTION
[0008] It is therefore an object of the present invention to provide an organic compound decomposing method having a preferable decomposition efficiency and decomposition amount with a low load on the environment.
[0009] The organic compound decomposing method according to the present invention decomposes an organic compound using ascorbic acid and/or ascorbic acid salt together with oxygen.
[0010] Ascorbic acid and ascorbic acid salt is well known as vitamin C, available in the natural world, and not harmful. Accordingly, by using these, it is possible to decompose a harmful organic compound without giving a useless load on the environment.
[0011] Moreover, the organic compound decomposition is significantly promoted by using the aforementioned substances together with oxygen. That is, this method provides a high decomposition efficiency and can be applied to decomposition of a large amount of organic compound. Moreover, the decomposition operation is quite simple without requiring any large-scale facility, large amount of energy or complicated management.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] [0012]FIG. 1 shows components contained in an aqueous solution of bisphenol A before a treatment using L-sodium ascorbate.
[0013] [0013]FIG. 2 shows components contained in an aqueous solution of bisphenol A after a treatment using L-sodium ascorbate.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0014] Description will now be directed to embodiments of the present invention. It should be noted that while explanation will be given on decomposition of organic compounds, the present invention is not to be limited to the organic compounds used as examples.
[0015] The organic compound decomposing method according to the present invention uses ascorbic acid and/or ascorbic acid salt together with oxygen applied to an organic compound to be treated.
[0016] Here, an oxygen gas may be blown directly to the ascorbic acid and/or ascorbic acid salt and the organic compound. However, in order to increase the organic compound decomposition efficiency and decomposition amount, it is preferable to employ a method in which the oxygen is dissolved in a solution together with the ascorbic acid and/or ascorbic acid salt and the organic compound or a method in which oxygen and air are blown into a solution containing ascorbic acid and/or ascorbic acid salt and the organic compound.
[0017] Moreover, when considering the handling convenience, it is preferable to add ascorbic acid salt such as sodium salt. The ascorbic acid and the ascorbic acid salt may be extracted from a natural material or synthesized. It should be noted that ascorbic acid extracted from a natural material may contain other components but they will not cause a particular problem.
[0018] The amounts of the ascorbic acid and the ascorbic acid salt to be added with respect to an organic compound differ depending on the amount of the organic compound and the decomposition efficiency required. However, it is preferable to be about 1/1000 to 1000 times of the amount of the organic compound and more preferably, about 1/100 to 100 times.
[0019] Moreover, the oxygen used here may be an oxygen gas supplied from an oxygen cylinder, or may be the oxygen contained in the air, or may be oxygen contained in a solution. It should be noted that as the oxygen amount is increased, the decomposition efficiency and the decomposition amount of the organic compound are increased. Moreover, when oxygen is dissolved in a solution, for example, as the oxygen concentration is increased such as a saturated concentration, the decomposition efficiency and the decomposition amount of the organic compound are increased.
[0020] Moreover, the temperature for the decomposition is preferable from about −20°C. to 120°C. and more preferably, from about 0°C. to 60°C., and most preferably, from about 20° C. to 40°C. When the temperature exceeds 120°C., an enormous energy is required for decomposing the organic compound. Moreover, when the temperature is below −20°C., the decomposition speed is drastically lowered. It should be noted that pH for the decomposition is preferably from about pH 4 to pH 11.
[0021] Here, the organic compounds to be decomposed are not limited to particular compounds, but especially aromatic compounds can be decomposed easily such as nonylphenol, bisphenol A, dioxin, polychlorinated biphenyl, polybromobiphenyl, alkyl benzene, alkylbenzene derivative, alkylphenol, alkylphenol derivative, phthalate ester, benzophenone, benzophenone derivative, benzoic acid, halogenated benzene derivative, cresol, cresol derivative, aromatic amino acid (such as phenylalanine), agricultural chemicals containing the aromatic ring, resin containing the aromatic ring (such as polystyrene, ABS resin, PET, PC, phenol resin, epoxy resin, polyphenylene oxide, low molecular weight version of polyphenylene oxide, polyphenylene oxide derivative, and the like), dyes containing the aromatic ring, aromatic agent, and the like.
[0022] It should be noted that the aforementioned organic compounds can be decomposed with a higher decomposition efficiency and a higher decomposition amount when exposed to the ascorbic acid and/or ascorbic acid salt and oxygen contained in water, i.e., via water, than when exposed directly to the ascorbic acid and/or ascorbic acid salt and oxygen.
[0023] Moreover, when the aforementioned organic compounds exist in a gas, it is preferable that the organic compounds in gas be dissolved in an aqueous solution when applied to the ascorbic acid and/or ascorbic acid salt together with oxygen.
[0024] As has been described above, by applying the ascorbic acid and/or ascorbic acid salt together with oxygen to the organic compounds, the organic compounds are decomposed. Thus, it is possible to decompose organic compounds harmful to the environment using a method having a high decomposition efficiency and decomposition amount as well as a small load on the environment. Moreover, among the organic compounds, especially those having the aromatic ring can be decomposed.
[0025] Moreover, when decomposing the aforementioned organic compounds, it is preferable to add at least one of hydrogen peroxide solution, ozone, ammonium, inorganic alkali, inorganic alkali salt, inorganic acid, inorganic acid salt, porphyrin, and metalloporphyrin.
[0026] It should be noted that the amount of the aforementioned substances to be added varies depending on the type and concentration of the organic compound to be decomposed and the temperature during the decomposition. However, the amount to be added is preferably about 1/100 to 100 times with respect to the ascorbic acid and/or ascorbic acid salt and more preferably, from about 1/10 to 10 times.
[0027] Thus, by adding the aforementioned substances, the decomposition efficiency and the decomposition amount of an organic compounds are increased.
[0028] Moreover, when decomposing an organic compound, it is preferable to apply light. When light is applied, the decomposition efficiency and the decomposition amount of the organic compound are increased.
[0029] As has been described above, the organic compound decomposing method according to the present invention enables to decompose harmful organic compounds contained in the domestic waste water, factory waste water, these waste water after disposal, the sea, rivers, soil, exhaust gas, waste, compost, and the like with a high decomposition efficiency and a high decomposition amount as well as with a low energy and a small load on the environment. Moreover, it becomes possible to decompose organic compounds containing the aromatic ring.
[0030] Thus, the present invention enables to promote the waste water disposal and changing of waste into compost, purify the soil and the atmosphere, thereby purifying the environment, contributing to the ecology of the earth.
[0031] Moreover, since the present invention provides a high decomposition efficiency and a high decomposition amount, it is possible to decompose a large amount of organic compounds. The decomposition operation is quite simple, not requiring a large-scale facility, a large amount of energy, or a complicated management.
[0032] Next, explanation will be given on specific examples of the decomposition efficiency and the decomposition amount of organic compounds when the aforementioned organic compound decomposing method is applied.
EXAMPLE 1
[0033] Firstly, bisphenol A was added to an aqueous solution of 10 mM sodium hydroxide so as to have a concentration of 2 mM. Next, L-sodium ascorbate was added to this solution so as to have a concentration of 100 mM. Next, this solution was subjected to air bubbling for 4 hours.
[0034] Next, compounds contained in the aforementioned solution and compounds contained in the bisphenol A solution not subjected to the aforementioned treatment were detected by using a high performance liquid chromatography (HPLC). Here each of these solutions was added by a benzoic acid solution having a predetermined concentration solved in a mixture of identical amounts of water and ethanol was added as an internal standard liquid.
[0035] An HPLC analysis of the bisphenol A solution not subjected aforementioned treatment resulted in peak 1 of the benzoic acid and peak 2 of the bisphenol A as shown in FIG. 1. Moreover, an HPLC analysis of the bisphenol A solution subjected to the aforementioned treatment resulted in FIG. 2 where the peak 2 of the bisphenol A is lowered, which means that 75% of the bisphenol A was decomposed.
[0036] Moreover, other peaks were observed in addition to peak 1 of the benzoic acid and peak 2 of the bisphenol A. These peaks are considered to be products obtained by decomposition of the bisphenol A.
EXAMPLE 2
[0037] Firstly, nonyl phenol ethylene oxide was added to be solved so as to have a concentration of 5 mM. It should be noted that the nonyl phenol ethylene oxide is one of the surface active agents. Next, this solution was added by L-sodium ascorbate with a concentration of 20 mM. Next, this solution was subjected to air bubbling for 6 hours. Here, the water temperature was set to 40°C. As a result, it has been found that 52% of the nonyl phenol ethylene oxide was decomposed.
EXAMPLE 3
[0038] Firstly, dodecabromodiphenyl ether is dissolved in a hydrophilic organic solvent, to which a small amount water was added to obtain a concentration of 0.01 mM. Next, to this solution was added L-sodium ascorbate and hydrogen peroxide solution to obtain a concentration of 0.01 mM. Next, this solution was subjected to air bubbling for 12 hours. Here, the water temperature was set to a room temperature. As a result, it has been found that 63% of the dodecabromodiphenyl ether was decomposed.
EXAMPLE 4
[0039] Firstly, aqueous solution of diethyl phthalate was dissolved in a hydrophilic organic solvent, to which a small amount of water was added to obtain a concentration of 0.05 mM. Next, to this solution was added L-sodium ascorbate to obtain a concentration of 0.01 mM. Next, this solution was subjected to air bubbling for 6 hours while applying light radiation by a high-pressure mercury lamp to the solution. Here, the water temperature was set to a room temperature. As a result, it has been found that 84% of the aqueous solution of diethyl phthalate was decomposed.
EXAMPLE 5
[0040] Firstly, two analytes of strip-shaped polylactic acid were buried in a soil. One of them was kept as it was. The other was subjected to spray of an aqueous solution of L-sodium ascorbate and then the soil containing the sample was subjected to air bubbling for 3 days. As a result, the strip-shaped polylactic acid subjected to the treatment by L-sodium ascorbate was significantly deformed by decomposition.
EXAMPLE 6
[0041] After L-sodium ascorbate was added to obtain a concentration of 50 ppm, cation flocculant was added to a contaminated soil subjected to the air season and to a contaminated soil not subjected to the air season. Next, dehydration was performed to each of the soil samples. It should be noted that the contaminated soil is soil in a domestic waste. As a result, it has been found that the dehydration speed of the contaminated soil subjected to treatment by the L-sodium ascorbate was 1.5 times faster than the soil not subjected to the treatment. Moreover, the cake amount after the dehydration was smaller by 2.5%.
EXAMPLE 7
[0042] Firstly, L-sodium ascorbate and magnesium porphyrin were added to a colored dye waste water. Here the L-sodium ascorbate was added to obtain a concentration of 20 ppm and the magnesium porphyrin was added to obtain a concentration of 1 ppm. Next, air bubbling was performed for 2 hours. As a result, decoloration of the dye waste water was promoted.
EXAMPLE 8
[0043] Firstly, L-sodium ascorbate was added to a semiconductor factory waste water containing 80 ppm of organic carbon (OC) and 30 ppm of hydrogen peroxide solution, so as to obtain a concentration of 5 ppm. Next, air bubbling was performed for 1 hour. As a result, the concentrations of the organic carbon and the hydrogen peroxide solution became equal to or below 10 ppm.
EXAMPLE 9
[0044] Firstly, an aqueous solution of L-sodium ascorbate was sprayed to a domestic waste in a treatment machine. Next the waste was agitated sufficiently to mix oxygen in the waste. As a result, the compostization speed was increased by twice as compared in the prior art.
EXAMPLE 10
[0045] An organic compound was decomposed by using supercritical water. Here, L-sodium ascorbate having a concentration of 1/10 with respect to the organic compound concentration was added. It should be noted that dissolved oxygen exists in the supercritical water. As a result, the decomposition speed of the organic compound was increased by twice.
EXAMPLE 11
[0046] An organic compound was decomposed by using a subcritical water. Here, L-sodium ascorbate having a concentration of 1/10 with respect to the concentration of the organic compound was added. It should be noted that dissolved oxygen exists in the subcritical water. As a result, the decomposition speed of the organic compound was increased by twice.
[0047] As is clear from the above-given explanation, the organic compound decomposing method according to the present invention enables to decompose organic compounds contained in domestic waste water, factor waste water, the remaining matters after treatment of these waste waters, in the sea, rivers, soil, exhaust gas, garbage, compost, and the like, with a high decomposition efficiency and a high decomposition amount as well as with a small load on the environment. Thus, it becomes possible to promote waste water treatment and garbage compostization, and purify soils and exhaust gas, thereby promoting purification of the environment, contributing to maintenance of the earth ecology.
[0048] Moreover, since the decomposition efficiency and the decomposition amount are preferable, the present invention can also be applied to decomposition of a large amount of organic compounds. Furthermore, the decomposition operation is very simple, not requiring a large-scale facility, large amount of energy, or a complicated management. | Ascorbic acid and/or ascorbic acid salt is made to act together with oxygen on an organic compound. Alternatively, light radiation is applied during chemical action with oxygen so as to improve a composition efficiency of an organic compound and obtain a preferable decomposition amount. This reduces the load caused by an organic compound decomposition on the environment. | 0 |
TECHNICAL FIELD
[0001] This invention relates to novel compounds which are selective inhibitors of matrix metalloproteinases, especially metalloproteinase 12 (MMP-12), processes for their preparation, pharmaceutical compositions containing them and their use in therapy.
BACKGROUND TO THE INVENTION
[0002] Metalloproteinases represent a super family of proteinases (enzymes), whose numbers have increased dramatically in recent years. Based on structural and functional considerations, these enzymes have been classified into families and subfamilies N. M. Hooper, FEBS letters 354, 1-6 (1994). Examples of metalloproteinases include the matrix metalloproteinases (MMPs), which is a family of zinc containing endopeptidases, such as the collagens (MMP-1, MMP-8, MMP-13, MMP-18), the gelatinases (MMP-2, MMP-9), the stromelysins (MMP-3, MMP-10, MMP-11), matrilysin (MMP-7, MMP-26), metalloelastase (MMP-12) enamelysin (MMP-20), the MT-MMPs (MMP-14, MMP-15, MMP-16, MMP-17, MMP-24, MMP-25).
[0003] The MMPs is a family of zinc containing endopeptidases which are capable of cleaving large biomolecules like the collagens, proteoglycans and fibronectins, a process necessary for the growth and remodelling of tissues such as embryonic development and bone formation under normal physiological conditions. Expression is upregulated by pro-inflammatory cytokines and/or growth factors. The MMP's are secreted as inactive zymogens which, upon activation, are subject to control by endogenous inhibitors, for example, tissue inhibitor of metalloproteinases (TIMP) and α-macroglobulin. Chapman, K. T. et al., J. Med. Chem. 36, 4293-4301 (1993); Beckett, R. P. et al., DDT 1, 16-26 (1996). The characterizing feature of diseases involving the enzymes appears to be a stoichiometric imbalance between active enzymes and endogenous inhibitors, leading to excessive tissue disruption, and often degradation. McCachren, S. S., Arthritis Rheum. 34, 1085-1093 (1991).
[0004] Over-expression and activation of MMPs have been linked with a wide range of diseases such as cancer, tumour metastasis, rheumatoid arthritis, osteoarthritis, chronic inflammatory disorders such as emphysema, cardiovascular disorders such as atherosclerosis, corneal ulceration, dental diseases such as gingivitis and periodontal disease, and neurological disorders such as multiple sclerosis. Chirivi, R. G. S. et al., Int. J. Cancer, 58, 460-464 (1994); Zucker, S., Cancer Research, 53, 140-144 (1993). In addition, a recent study indicates that MMP-12 is required for the development of smoking-induced emphysema in mice. Science, 277, 2002 (1997). MMP-12, also known as macrophage elastase or metalloelastase, was initially cloned in the mouse by Shapiro et al., J. Biological Chemistry, 267, 4664 (1992) and in man by the same group in 1995. Structurally, the proMMP-12 consists of a pro-domain, a catalytic domain containing the zinc binding site and a C-terminal hemopexin-like domain. Recombinant human MMP-12 can be activated by autocatalysis as described below and reviewed by Shapiro et al “Macrophage Elastase” in Handbook of Proteolytic Enzymes 2004 (Eds A J Barrett et al) pp 540-544 Academic Press, San Diego.
[0005] MMP-12 is preferentially expressed in activated macrophages and its expression in monocytes can be induced by cytokines such as GM-CSF and CD-40 signalling. In addition to elastin, MMP-12 can degrade a broad spectrum of substrates, including type IV collagen, fibronectin, laminin, vitronectin, proteoglycans, chondroitin sulphate, myelin basic protein, alpha-one chymotrypsin and plasminogen. It can also activate MMP-2 and MMP-3. MMP-12 is required for macrophage mediated proteolysis and matrix invasion in mice. MMP-12 is proposed to have a direct role in the pathogenesis of aortic aneurisms and in the development of pulmonary emphysema that results from chronic inhalation of cigarette smoke, wood smoke and urban smogs.
[0006] MMP-12 has been shown to be secreted from alveolar macrophages from smokers Shapiro et al., J. Biological Chemistry, 268, 23824, (1993) as well as in foam cells in atherosclerotic lesions Matsumoto et al., Am. J. Pathol, 153, 109, (1998). A mouse model of COPD is based on challenge of mice with cigarette smoke for six months, two cigarettes a day six days a week. Wildtype mice developed pulmonary emphysema after this treatment. When MMP-12 knock-out mice were tested in this model they developed no significant emphysema, strongly indicating that MMP-12 is a key enzyme in the COPD pathogenesis. The role of MMPs such as MMP-12 in COPD (emphysema and bronchitis) is discussed in Anderson and Shinagawa, Current Opinion in Anti-inflammatory and Immunomodulatory Investigational Drugs: 29-38 (1999). It was recently discovered that smoking increases macrophage infiltration and macrophage-derived MMP-12 expression in human carotid artery plaques Kangavari (Matetzky S, Fishbein M C et al., Circulation 102, (18), 36-39 Suppl. S, Oct. 31, (2000).
[0007] Apart from the role of these potentially very destructive enzymes in pathology, the MMPs play an essential role in cell regrowth and turnover in healthy tissue. Broad spectrum inhibition of the MMPs in the clinical setting results in musculoskeletal stiffness and pain. H. S. Rasmussen and P. P. McCann, Pharmacol. Ther., 75, 69-75 (1997). This side effect and others associated with broad spectrum inhibition may be enhanced in chronic administration. Thus, it would be advantageous to provide selective MMP inhibitors.
[0008] The inhibition of such MMP-12 activities is considered to contribute to the improvement and prevention of the above discussed diseases caused by or related to the activity of MMP-12. Therefore, the development of MMP-12 inhibitors has been desired.
[0009] A number of metalloproteinase inhibitors are known and described in the literature, (see for example the reviews of MMP inhibitors by Beckett R. P. and Whittaker M., 1998, Exp. Opin. Ther. Patents, 8 (3):259-282. Whittaker M. et al, 1999, Chemical Reviews 99 (9): 2735-2776) review a wide range of known MMP inhibitor compounds. They state that an effective MMP inhibitor requires a zinc binding group, i.e. a functional group capable of chelating the active site zinc(II) ion, at least one functional group which provides a hydrogen bond interaction with the enzyme backbone, and one or more side chain which undergo effective van der Waals interactions with the enzyme subsites. Zinc binding groups in known MMP inhibitors include carboxylic acid groups, hydroxamic acid groups, sulfhydryl groups or mercapto groups.
[0010] Despite the potent affinity of hydroxamic acid as zinc coordinator, hydroxamic acid inhibitors demonstrate a considerable degree of specificity within the MMP family: a potent inhibitor of one member of the MMP family, may have only minimal potency against another MMP family member. This exhibited specificity typically relies on the identity of the other parts of the inhibitors, e.g. the P1, P2, P3 and P4 units. Without in any way wishing to be bound by theory, or the ascription of tentative binding modes for specific variables, the notional concepts P1, P2, P3 and P4 are used herein for convenience only and have substantially their conventional meanings, as illustrated by Schechter & Berger, (1976) Biochem Biophys Res Comm 27 157-162, and denote those portions of the inhibitor believed to fill the S1, S2, S3 and S4 subsites respectively of the enzyme, where S1 is adjacent the cleavage site and S4 remote from the cleavage site.
[0011] There are several patents which disclose hydroxamate-based inhibitors of metalloproteases or analogous enzymes.
[0012] WO02/028829 describes inhibitors of peptide deformylase (PDF) useful for example in the development of new antibacterial drugs. PDF is a bacterial enzyme which shares several structural features in common with zinc metalloproteases. PDF does not cleave a peptide bond, but rather cleaves off the N-formyl group from the terminal N-formyl methionine which characterises the nascent bacterial polypeptide chain. Despite the fact that the compounds of WO02/028829 comprise a hydroxamic acid group the SAR (structure activity relationship) exhibited by these inhibitors is not helpful to the design of specific inhibitors of the endopeptidase MMP-12. An endopeptidase cleaves within a peptide chain, and therefore the protease typically recognises a number of amino acid residues around the intended cleavage site. In contrast PDF is intended to cleave a terminal group on the first amino acid of bacterial proteins of very different sequence. Accordingly the selectivity of PDF is predicated on recognition of the N-formyl.methionine terminal residue rather than the identity of the adjacent amino acids.
[0013] US 3003/0134827 discloses compounds having a hydroxyacetamide moiety linked to a broad range of cyclic amides as inhibitors of MMPs in particular MMP-3, aggrecanase and TNF-α-converting enzyme (TACE). Although hydantoin is postulated as one of many such cyclic amides, US 2003/0134827 discloses no concrete examples of compounds within the scope of this invention. As demonstrated in the following biological examples, the compounds of the invention achieve potent MMP-12 inhibition while at the same time being highly selective against the enzymes addressed in US 2003/0134827.
[0014] U.S. Pat. No. 6,462,063 discloses substituted hydantoin hydroxamates capable of inhibiting C-proteinase. In contrast to the compounds of the invention defined below, the compounds of U.S. Pat. No. 6,462,063 have a hydroxamic acid linked to a carbon atom of the hydantoin ring via a chain comprising, apart from the acid function, at least three atoms. By varying the length of the hydroxamic acid carrying chain and the substitution pattern of the hydantoin ring, the binding properties to the enzyme and hence the specificity of the inhibitor will be altered. The hydroxamate function of U.S. Pat. No. 6,462,063 is thus sitting on the other side of the hydantoin ring compared to the compounds of the invention defined below and is also disposed further out from the hydantoin These kind of structural variations between the class of compounds disclosed in U.S. Pat. No. 6,462,063 and inhibitors based on hydantoin hydroxamates wherein the hydroxamic acid is linked to a nitrogen atom of a hydantoin group via a one atom chain, will render the SAR exhibited by the compounds of U.S. Pat. No. 6,462,063 of no relevance to the design of specific inhibitors of MMP-12
[0015] WO02/074750 discloses a new class of compounds that act as MMP inhibitors wherein the zinc binding group of the inhibitor is constituted of a five membered ring structure such as a hydantoin group. The zinc binding ring structure is attached to one or more functional groups or side chains which are disposed at an appropriate angle and distance to recognise the characteristic sequence around the appropriate MMP12 cleavage site. The mode of binding to the enzyme of this class of zinc-binding inhibitors will thus differ substantially from that of compounds having other zinc binding groups, such as hydroxamic acid adjacent a hydantoin core, in that coordination of the hydroxamate zinc binding group will displace the hydantoin away from the structural zinc. Any further substituents opposed from the hydroxamate will also be displaced away from the structural zinc and will interact with other parts of the enzyme. Due to this different binding mode of the compounds disclosed in WO02/074750 compared to hydantoin hydroxamates, the SAR found for the P1, P2, P3 and P4 units of the compounds of WO02/074750 is not relevant to the design of new MMP inhibitors based on a hydantoin hydroxamate scaffold.
[0016] Similarly, US 2005/0171096 discloses hydantoin derivatives alleged to be inhibitors of matrix metalloproteinases and TACE although no guidance as to the specificity of the inhibitors is given. The compounds of US 2005/0171096 do not bear a hydroxamic acid or conventional zinc-binding group. This suggests that that the hydantoin is the zinc binding group and hence the SAR exhibited by the P1, P2 and P3 units of these compounds is different from that of an inhibitor based on a hydantoin substituted with a hydroxamic acid carrying side chain.
[0017] As foreshadowed above, we have now discovered a particular configuration of hydroxamic hydantoins that are inhibitors of metalloproteinases and are of particular interest in selectively inhibiting MMPs such as MMP-12 and have desirable activity profiles. The compounds of this invention have beneficial potency, selectivity and/or pharmacokinetic properties.
DISCLOSURE OF THE INVENTION
[0018] In accordance with the present invention, there is provided a compound of formula (I) or a pharmaceutically acceptable salt or solvate thereof:
[0000]
[0000] wherein;
R 1 is C 1 -C 6 alkyl, C 0 -C 3 alkandiylcarbocyclyl, C 0 -C 3 alkandiylheterocyclyl, R 2 is carbocyclyl or heterocyclyl; R 3 is H or C 1 -C 4 alkyl; R 4 is H or C 1 -C 4 alkyl; each R 5 and R 5′ is independently H, C 1 -C 4 alkyl or halo; or R 4 and an adjacent R 5′ together define a double bond; each R 6 and R 6′ is independently H, C 1 -C 4 alkyl or halo; or R 5 and an adjacent R 6 together define a double bond; or R 5 , R 5′ and an adjacent R 6 and R 6′ together define a triple bond; n is 1-3, m is 0-3; D is absent, or D is an ether, thioether, amine, amide, carbamate, urea or sulphonamide linkage; whereby the group (CR 5 R 5′ ) n -D-(CR 6 R 6′ ) m has at least 2 chain atoms; X and Y are independently O or S;
and wherein
each C 1 -C 4 alkyl is optionally substituted with 1 to 3 halo or an hydroxyl; each C 1 -C 6 alkyl, carbocyclyl or heterocyclyl (including those in any C 0 -C 3 alkanediylcarbocyclyl or C 0 -C 3 alkanediylheterocyclyl group) is independently optionally substituted with 1 to 3 substituents selected from halo, oxo, cyano, azido, nitro, C 1 -C 6 alkyl, C 0 -C 3 Alkdiylcarbocyclyl, C 0 -C 3 Alkdiylheterocyclyl, Z—NRaRb, Z—O-Rb, Z—S—Rb, Z—C(═NOH)Rb, Z—C(═O)Rb, Z—(C═O)NRaRb, Z—NRaC(═O)Rb, Z—NRaSO p Rb, Z—S(═O) p Rb, Z—S(═O) p NRaRb, Z—C(═O)ORb, Z—OC(═O)Rb, Z—NRaC(═O)ORb or Z—OC(═O)NRaRb; wherein; each C 0 -C 3 Alkdiyl is independently a bond, a C 1 -C 3 straight or branched, saturated carbon chain or a C 2 -C 3 straight or branched unsaturated carbon chain; the carbocyclyl or heterocyclyl moiety of any C 0 -C 3 Alkdiylcarbocyclyl, C 0 -C 3 Alkdiylheterocyclyl is optionally substituted 1 to 3 times with substituents selected from halo, oxo, cyano, azido, nitro, C 1 -C 4 alkyl, Z—NRaRc, Z—O-Rc, Z—S—Rc, Z—C(═O)Rc, Z—(C═O)NRaRc, Z—NRaC(═O)Rc, Z—NRaSO p Rc, Z—S(═O) p Rc, Z—S(═O) p NRaRc, Z—C(═O)ORc, Z—OC(═O)Rc, Z—NRaC(═O)ORc or Z—OC(═O)NRaRc;
each Z is independently a bond or C 1 -C 3 alkanediyl;
each Ra is independently H or C 1 -C 4 alkyl;
[0036] each Rb is independently H or C 1 -C 6 alkyl, C 0 -C 3 Alkdiylcarbocyclyl, C 0 -C 3 Alkdiylheterocyclyl;
or Ra and Rb together with an adjacent N atom define pyrrolidine, piperidine, morpholine, piperazine or N-methyl piperazine; Rc is H or C 1 -C 4 alkyl; or Rc and Ra together with an adjacent N atom define pyrrolidine, piperidine, morpholine, piperazine or N-methyl piperazine each p is independently 1 or 2;
and pharmaceutically acceptable salts and solvates thereof.
[0041] In one embodiment of the invention the R 1 group comprises an optionally substituted alkyl chain, especially branched C 2 -C 6 alkyl chains. Preferably the branch occurs at position 1, adjacent the backbone of the inhibitor, as shown in the partial structure:
[0000]
[0000] where R1′ is CH 3 , CH 2 CH 3 , C 1 haloalkyl, halo, hydroxy;
R1″ is H, CH 3 , CH 2 CH 3 , C 1 haloalkyl, halo, hydroxyl; R 1 * is C 1 -C 5 optionally substituted alkyl, for example substituted with 1-3 substituents independently selected from carbocyclyl, heterocyclyl, ZNRaRb, nitro, hydroxyl, cyano, carboxy, oxo, halo, C 1 -haloalkyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C r C 4 alkanoyl or carbamoyl groups.
[0044] Representative values of R 1 thus include 1-methylpropyl, 1,1-dimethylpropyl, 1-ethyl-1-methyl propyl, 1,1 di methyl butyl, 1,1-diethyl propyl, 1-ethyl propyl, 1-methyl butyl, 1,2-dimethylpropyl. Currently preferred values of R 1 include i-propyl, sec.butyl and tert.butyl.
[0045] A moiety such as an optionally substituted carbocyclyl or an optionally substituted heterocyclyl distanced 1-5 atoms from the backbone of the inhibitor at the position of R 1 can be used to alter the lipophilicity of the compounds of the invention. It is believed that an appropriate choice of this moiety will confer any lipophilic/hydrophilic characteristics to the inhibitors required to improve certain properties, i.a. their DMPK properties.
[0046] Accordingly, suitable values for R 1 * are C 1 -C 5 alkyl substituted with carbocyclyl or C 1 -C 5 alkyl substituted with heterocyclyl wherein said carbocyclyl and heterocyclyl are optionally substituted 1-4 times with substituents selected from C 1 -C 3 alkyl, oxo and halo. Preferred structures for R 1 thus include:
[0000]
[0000] wherein n is 0, 2, 3 or 4.
[0047] In other embodiments of the invention, the C 0 -C 3 alkandiylcarbocyclyl as R 1 has methylene as the C 0 -C 3 alkandiyl component and a C 5 or C 6 monocyclic ring as the carbocyclyl component. Representative values of R 1 in this embodiment thus include (optionally substituted): benzyl, cyclohexylmethyl-, 1-methylcyclohexylmethyl-, cyclopentylmethyl-, 1-methylcyclopentylmethyl, where the optional substituents are as outlined above.
[0048] In a preferred embodiment of the invention, the C 0 -C 3 alkandiylcarbocyclyl as R 1 has a bond as the C 0 -C 3 alkandiyl component and a C 5 or C 6 monocyclic ring as the carbocyclyl component. Representative values of R 1 in this embodiment thus include (optionally substituted): phenyl, or preferably cyclohexyl or cyclopentyl, where the optional substituents are as outlined above.
[0049] In other embodiments of the invention, the C 0 -C 3 alkandiylheterocyclyl as R 1 has methylene as the C 0 -C 3 alkandiyl component and a 5 or 6 membered aromatic, partially saturated, or unsaturated monocyclic ring as the heterocyclyl component. Representative values of R 1 in this embodiment thus include (optionally substituted): pyrrolylmethyl-, pyrrolinylmethyl-, pyrrolidinylmethyl-, thiazolylmethyl, pyridylmethyl-, pyrimidinylmethyl-, piperidylmethyl-, piperazinylmethyl- or morpholinylmethyl, where the optional substituents are as outlined above.
[0050] In other embodiments of the invention, the C 0 -C 3 alkandiylheterocyclyl as R 1 has a bond as the C 0 -C 3 alkandiyl component and a 5 or 6 membered aromatic, partially saturated, or unsaturated monocyclic ring as the heterocyclyl component. Representative values of R 1 in this embodiment thus include (optionally substituted): pyrrolyl, pyrrolinyl, pyrrolidinyl, thiazolyl, pyridyl, pyrimidinyl, piperidyl-, piperazinyl or morpholinyl; where the optional substituents are as outlined above.
[0051] In typical embodiments of the invention the chiral center to which the R 1 group is attached has the R stereochemistry as shown in the partial structure:
[0000]
[0052] This stereochemistry corresponds to a D-amino acid, which is unexpected in the context of an inhibitor of an enzyme such as a protease. Such enzymes cleave proteins which are universally composed of L-amino acids. The recognition sites of most proteases thus prefer L-configurations. The compounds of the invention may be administered as the racemate at R 1 , but are preferably administered as pure or substantially enantiomerically pure preparations, such as at least 90% ee at R 1 , preferably at least 95%, such as >97% ee.
[0053] In some embodiments of the invention both of X and Y are ═S or one of X and Y is ═S and the other is ═O, especially wherein X is ═O. It is currently preferred that both X and Y are ═O.
[0054] In typical embodiments of the invention, the steric center of the imidazoline ring to which the —(CR 5 R 5′ ) n -D-(CR 6 R 6′ ) m —R 2 group is attached has the S stereochemistry, as depicted in the partial structure:
[0000]
[0055] The compounds of the invention may be administered as the racemate at this position, but are preferably administered as pure or substantially enantiomerically pure preparations, such as at least 90% ee at this position, preferably at least 95%, such as >97% ee.
[0056] In other embodiments of the invention, R 4 and an adjacent R 5 together define an olefinic bond forming part of the linkage to R 2 :
[0000]
[0057] In this embodiment, D will typically be absent, m will be 1 or 2 and each R 6 /R 6′ is H.
[0058] It is currently preferred that the stereochemistry at the chiral center to which R 1 is attached and at the chiral center to which the —(CR 5 R 5′ ) n -D-(CR 6 R 6′ ) m —R 2 group is attached have the R and S stereochemistries respectively.
[0059] Representative values of D include S, NH, NMe, NH(C═O)C(═O)NH, NH(═O)NH, NH(C═O)O and OC(═O)NH.
[0060] Currently preferred values for D include O, i.e. an ether linkage or D is absent (i.e. the (CR 5 R 5′ ) n -D-(CR 6 R 6′ ), function is a C 1 -C 6 alkandiyl chain.
[0061] Conveniently the —(CR 5 R 5′ ) n -D-(CR 6 R 6′ ) m — group has in total 2 or 3 chain atoms, especially:
—CH 2 CH 2 — (2), —CH 2 CH 2 CH 2 — (3), —CH 2 O— (2), —CH 2 OCH 2 — (3), —CH 2 CH 2 O— (3), —CH 2 —NH— (2), —CH 2 CH 2 NH— (2), —CH 2 OC(═O)NH— (4), —CH 2 NH(C═O)O— (4).
[0066] The numbers in brackets after each —(CR 5 R 5′ ) n -D-(CR 6 R 6′ ), group indicate the number of chain atoms.
[0067] It is currently preferred that n and m are each 1 and D is absent, i.e. the —(CR 5 R 5′ ) n -D-(CR 6 R 6′ ) m — group is —CH 2 CH 2 —.
[0068] In some embodiments of the invention each R 5 , R 5′ and each R 6 , R 6′ (if present) are H, but the invention extends to branched or substituted structures, such as those wherein R 5 and/or R 5′ on any one carbon atom is, for example methyl, i-propyl, t-butyl or fluoro. To avoid asymmetric centers it can be advantageous that both R 5 and R 5′ and/or R 6 and R 6′ on any one carbon atom are the same, typically, H, F or Me.
[0069] In some embodiments of the invention, D is absent and adjacent R 5 and R 6 together define a cis or trans double bond:
[0000]
[0070] In this embodiment n and m are typically 1 and the adjacent R 5′ and R 6′ are H. In the event that n or m is >1 the R 5 , R 5′ R 6 and R 6′ of any such further chain atoms are generally H.
[0071] In other embodiments of the invention, D is absent and adjacent R 5 , R 5′ R 6 and R 6′ together define a triple bond:
[0000]
[0072] In one embodiment of the invention R 2 as carbocyclyl is an optionally substituted aromatic ring structure, such as naphthyl or indanyl and especially phenyl.
[0073] In another embodiment of the invention R 2 as heterocyclyl is an optionally substituted, aromatic ring structure, such as a monocyclic ring selected from pyrrole, furan, thiophene, pyrazole, pyrazoline, imidazole, oxazole, isooxazole, thiazole, isothiazole, triazole, oxadiazole, furazan, thiadiazole, tetrazole, pyridine, pyridazine, pyrimidine, pyrazine, thiazine, triazine; or a bicyclic ring selected from thienobifuran, indole, isoindole, benzofuran, isobenzofuran, indoline, isoindoline, benzothiophene, isobenzothiophene, indazole, benzimidazole, benzthiazole, purine, quinoline, isoquinoline, chromane, isochromane, cinnolene, quinazoline, quinoxaline, napthyridine, phthalazine or pteridine.
[0074] It is currently preferred that R 2 is an optionally substituted, aromatic monocyclic ring, especially optionally substituted: pyrrolyl, thiazolyl, pyridyl or pyrimidinyl, and particularly optionally substituted phenyl.
[0075] In some embodiments an optional substituent to R 2 is located at the para, ortho or meta position relative to the —(CR 5 R 5′ ) n -D-(CR 6 R 6 ) m — linkage. Typical such substituents include C 1 -C 4 alkyl, such as methyl, haloC 1 -C 2 alkyl, such as fluoromethyl and trifluoromethyl, —OC 1 -C 4 alkyl, such as methoxy, —C(═O)C 1 -C 4 alkyl, such as acetyl, or halo, such as fluoro. A preferred structure for R 2 is phenyl substituted with fluoro in the ortho position which phenyl is optionally further substituted in the meta or preferably para position.
[0076] In some embodiments an optional substituent to R 2 is in the para position relative to the —(CR 5 R 5′ n ,-D-(CR 6 R 6′ ) m -linkage and comprises an aromatic, monocyclic ring such as those defined above for R 2 , especially optionally substituted: phenyl, pyrrolyl, thiazolyl, pyridyl or pyrimidinyl. This optional substituent is typically bonded directly to the R 2 ring or via a methylene, ethylene or ether linkage; as shown below
[0000]
[0077] In the structure II, the R 2 ring has been depicted for the purposes of illustration only as phenyl, but other ring systems will be equally applicable. It will be seen that the ring R 2 has one, but may also have two additional substituents R 2′ which is the ortho or meta substituent described in the immediately preceding paragraph.
[0078] Where R 2 is a 5-membered ring, the ring substituent of this aspect of the invention will, of course not be at the para position, but rather at a corresponding position disposed distally from the —(CR 5 R 5′ ) n -D-(CR 6 R 6′ H 2 ) m — linkage.
[0079] In structure II, the ring substituent of this aspect of the invention is depicted as R 7 and has been illustrated for the purposes of illustration only as phenyl, but other heteroaromatic monocyclic ring systems will also be applicable. Typical R 7 rings include phenyl, pyrrolyl, thiazolyl, pyridyl or pyrimidinyl. As elaborated below, the ring R 7 and its linkage D′ constitutes a value for C 0 -C 3 Alkdiylcarbocyclyl, C 0 -C 3 Alkdiylheterocyclyl or —Z—ORb, where Rb is O 0 —C 3 Alkdiylcarbocyclyl, C 0 -C 3 Alkdiylheterocyclyl. Ring R 7 is thus optionally substituted with 1 to 3 substituents selected from halo, oxo, cyano, azido, nitro, C 1 -C 4 alkyl, Z—NRaRc, Z—O-Rc, Z—S—Rc, Z—C(═O)Rc, Z—(C═O)NRaRc, Z—NRaC(═O)Rc, Z—NRaSO p Rc, Z—S(═O) p Rc, Z—S(═O) p NRaRc, Z—C(═O)ORc, Z—OC(═O)Rc, Z—NRaC(═O)ORc or Z—OC(═O)NRaRc.
[0080] Representative substituents for ring R 7 include, for example one or two substituents selected from C 1 -C 4 alkyl, such as methyl, haloC 1 -C 2 alkyl, such as fluoromethyl and trifluoromethyl, —OC 1 -C 3 alkyl, such as methoxy, —C(═O)C 1 -C 3 alkyl, such as acetyl, or halo, such as fluoro.
[0081] The linkage to ring R 7 is marked D′ in structure II and typically comprises a bond, methylene or ethylene linkage (i.e. R 7 is C 0 -C 3 Alkdiylcarbocyclyl or C 0 -C 3 Alkdiylheterocyclyl as a substituent to R 2 ) or an ether linkage (i.e. R 7 is Z—O—Rb, where Z is a bond or methylene, O is the ether linkage and Rb is C 0 -C 3 Alkdiylcarbocyclyl or C 0 -C 3 Alkdiylheterocyclyl). Further preferred structures for the linkage D′ include C(═O)CH 2 and CH 2 C(═O).
[0082] Unless otherwise defined, the scientific and technological terms and nomenclature used in the foregoing and hereinafter have the same meaning as commonly understood by a person of ordinary skill to which this invention pertains, in addition, the following definitions apply unless otherwise noted.
[0083] ‘C 1 -C 6 alkyl’ (occasionally abbreviated to C 1 -C 6 alk and also used in compound expressions such as C 1 -C 6 alkyloxy etc) as applied herein is meant to include straight and branched aliphatic carbon chain substituents containing from 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl and any simple isomers thereof. Me denotes a methyl group.
[0084] ‘C 1 -C 4 alkyl’ (occasionally abbreviated to O 1 —C 4 alk, and used in composite expressions) as applied herein is meant to include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, 1-methyl-cyclopropyl.
[0085] ‘C 0 -C 3 alkanediyl’ as applied herein is meant to include a bond (C 0 )bivalent straight and branched saturated carbon chains such as methylene, ethanediyl, 1,3-propanediyl and 1,2-propanediyl.
[0086] ‘C 0 -C 3 Alkdiyl’ as applied herein is meant to include a bond (C 0 ), bivalent C 1 -C 3 straight and branched saturated carbon chains such as methylene, ethanediyl, 1,3-propanediyl and 1,2-propanediyl, or C 2 -C 3 straight and branched unsaturated carbon chains such as ethenediyl, ethynediyl, 1,3-propenediyl and 1,2-propenediyl and propynediyl.
[0087] ‘C 0 -C 3 alkanediyl-O—C 1 -C 4 alkyl’ (occasionally abbreviated to C 0 -C 3 alk-O—C 1 -C 4 alk) as applied herein is meant to include C 1 -C 4 alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy directly bonded (i.e. C 0 ) or through an intermediate methylene, ethanediyl, 1,3-propanediyl or 1,2-propanediyl chain.
[0088] ‘amide linkage’ as applied herein is meant to include —NRfC(═O)— and —C(═O)NRf— wherein Rf is C 1 -C 4 alkyl such as Me, or preferably H.
[0089] ‘amine linkage’ as applied herein is meant to include —NH— or —NRe—, where Re is C 1 -C 4 alkyl or C(═O)C 1 -C 4 alkyl.
[0090] ‘carbamate linkage’ as applied herein is meant to include —OC(C═O)NRf— and —NRfC(═O)O—, wherein Rf is C 1 -C 4 alkyl such as Me, or preferably H.
[0091] ‘sulphonamide linkage’ as applied herein is meant to include —NRfS(═O) 2 — and —S(═O) 2 NRf— wherein Rf is C 1 -C 4 alkyl such as Me, or preferably H.
[0092] ‘Amino’ is meant to include NH 2 , and mono- and dialkylamino such as NHC 1 -C 6 alkyl and N(C 1 -C 6 alkyl) 2 groups especially NHC 1 -C 3 alkyl and N(C 1 -C 3 alkyl) 2 , or the two alkyl groups of dialkylamino together form a saturated cyclic amine such as pyrrolidinyl, piperidinyl, piperazinyl, N-methylpiperazinyl and morpholinyl.
[0093] ‘Amido’ is meant to include NHC(═O)C 1 -C 6 alkyl, NC 1 -C 6 alkylC(═O)C 1 -C 6 alkyl.
[0094] ‘Carbamoyl’ is meant to include C(═O)NH 2 , and mono- and dialkylcarbamoyl, such as C(═O)NHC 1 -C 6 alkyl and C(═O)N(C 1 -C 6 alkyl) 2 , especially C(═O)NHC 1 -C 3 alkyl and C(═O)N(C 1 -C 3 alkyl) 2 , or the two C 1 -C 6 alkyl groups of the dialkylcarbamoyl together form a saturated cyclic amine such as pyrrolidinyl, piperidinyl, piperazinyl and morpholniyl.
[0095] ‘Halo’ or halogen as applied herein is meant to include F, Cl, Br, I, particularly chloro and preferably fluoro.
[0096] Haloalkyl as applied herein means an alkyl in which 1-3 hydrogen atoms per carbon have been replaced with halo, preferably fluoro. Representative examples include difluoromethyl and 2,2-difluoroethyl, 2,2,2-trifluoroethyl and 2-fluoroethyl. Preferred examples include trifluoromethyl and fluoromethyl.
[0097] ‘C 0 -C 3 alkanediylaryl’ as applied herein is meant to include a phenyl, naphthyl or phenyl fused to C 3 -C 7 cycloalkyl such as indanyl, which aryl is directly bonded (i.e. C 0 ) or through an intermediate methylene, ethanediyl, 1,3-propanediyl or 1,2-propanediyl group as defined for C 0 -C 3 alkaneyl above. Unless otherwise indicated the aryl and/or its fused cycloalkyl moiety is optionally substituted with 1-3 substituents selected from halo, hydroxy, nitro, cyano, carboxy, C 1 -C 6 alkyl, C 1 -C 4 alkoxy, C 0 -C 3 alkanediylC 1 -C 4 alkoxy, C 1 -C 4 alkanoyl, amino, amido, carbamoyl, azido, oxo, mercapto, C 0 -C 3 alkanediylcarbocyclyl, C 0 -C 3 alkanediylheterocyclyl, it being understood that when the substituent is C 0 -C 3 alkanediylcarbocyclyl or C 0 -C 3 alkanediylheterocyclyl said carbocyclyl or heterocyclyl is typically not further substituted with C 0 -C 3 alkanediylcarbocyclyl or C 0 -C 3 alkanediylheterocyclyl.“Aryl” has the corresponding meaning, i.e. where the C 0 -C 3 alkanediyl linkage is absent.
[0098] ‘C 0 -C 3 alkanediylcarbocyclyl’ as applied herein is meant to include C 0 -C 3 alkanediylaryl and C 0 -C 3 alkanediylC 3 -C 7 cycloalkyl, and C 0 -C 3 alkanediylC 3 -C 7 cycloalkyl further comprising an additional fused C 3 -C 7 cycloalkyl ring. Unless otherwise indicated the aryl or cycloalkyl group is optionally substituted with 1-3 substituents selected from halo, hydroxy, nitro, cyano, carboxy, C 1 -C 6 alkyl, C 1 -C 4 alkoxy, C 0 -C 3 alkanediylC 1 -C 4 alkoxy, C 1 -C 4 alkanoyl, amino, amido, carbamoyl, azido, oxo, mercapto, C 0 -C 3 alkanediylcarbocyclyl and C 0 -C 3 alkanediylheterocyclyl, it being understood that when the substituent is C 0 -C 3 alkanediylcarbocyclyl or C 0 -C 3 alkanediylheterocyclyl said carbocyclyl or heterocyclyl is typically not further substituted with C 0 -C 3 alkanediylcarbocyclyl or C 0 -C 3 alkanediylheterocyclyl. “Carbocyclyl” has the corresponding meaning, i.e. where the C 0 -C 3 alkanediyl linkage is absent.
[0099] ‘C 0 -C 3 alkanediylheterocycylyl’ as applied herein is meant to include a mono- or bicyclic, saturated or unsaturated, heteroatom-containing ring system, bonded directly i.e. (C 0 ), or through an intermediate methylene, ethanediyl, 1,3-propanediyl, or 1,2-propanediyl group as defined for C 0 -C 3 alkanediyl above. The ring system is derived by abstraction of a hydrogen from a monocyclic heteroatom containing ring such as pyrrole, furan, pyrroline, pyrrolidine, tetrahydrofuran, thiophene, tetrahydrothiophene, pyrrazole, imidazole, oxazole, isoxazole, pyrazoline, imidazoline, pyrazolidine, imidazolidine, dioxolane, thiazole, isothiazole, thiazolidine, isoxazolidine, 1,2,3-triazole, 1,2,4-triazole, 1,2,3-oxadiazole, furazan, thiadiazole, tetrazole, pyridine, pyran, dihydropyran, piperidine, pyridazine, pyrimidine, pyrazine, piperazine, morpholine, dioxane, thiazine, thiomorpholine, or from a saturated or unsaturated, heteroatom-containing bicyclic ring system such as pyrrolizine, thienofurane, indole, isoindole, benzofuran, isobenzofuran, indoline, isoindoline, benzothiophene, isobenzothiophene, indazole, benzimidazole, benzthiazole, purine, quinoline, isoquinoline, 4H-quinolizine, chromene, chromane, isochromane, cinnoline, quinazoline, quinoxazoline, naphtyridine, phtalazine, pteridine etc. Any such non-saturated ring system having an aromatic character may be referred to as heteroaryl herein. Unless otherwise indicated the hetero ring system is optionally substituted with 1-3 substituents selected from halo, hydroxy, nitro, cyano, carboxy, C 1 -C 6 alkyl, C 1 -C 4 alkoxy, C 0 -C 3 alkanediylC 1 -C 4 alkoxy, C 1 -C 4 alkanoyl, amino, amido, carbamoyl, azido, oxo, mercapto, C 0 -C 3 alkanediylcarbocyclyl, C 0 -C 3 alkanediylheterocyclyl, it being understood that when the substituent is C 0 -C 3 alkanediylcarbocyclyl or C 0 -C 3 alkanediylheterocyclyl said carbocyclyl or heterocyclyl is typically not further substituted with C 0 -C 3 alkanediylcarbocyclyl or C 0 -C 3 alkanediylheterocyclyl. “Heterocyclyl” and “Heteroaryl” has the corresponding meaning, i.e. where the C 0 -C 3 alkanediyl linkage is absent.
[0100] Typically the terms ‘optionally substituted C 0 -C 3 alkanediylcarbocyclyl’ and ‘optionally substituted C 0 -C 3 alkanediylheterocyclyl’ refers preferably to substitution of the carbocyclic or heterocyclic ring.
[0101] Typically heterocyclyl and carbocyclyl groups are thus a monocyclic ring with 5 or especially 6 ring atoms, or a bicyclic ring structure comprising a 6 membered ring fused to a 4, 5 or 6 membered ring.
[0102] Typical such groups include C 3 -C 8 cycloalkyl, phenyl, benzyl, tetrahydronaphthyl, indenyl, indanyl, heterocyclyl such as from azepanyl, azocanyl, pyrrolidinyl, piperidinyl, morpholinyl, thiomorpholinyl, piperazinyl, indolinyl, pyranyl, tetrahydropyranyl, tetrahydrothiopyranyl, thiopyranyl, furanyl, tetrahydrofuranyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, imidazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, tetrazolyl, pyrazolyl, indolyl, benzofuranyl, benzothienyl, benzimidazolyl, benzthiazolyl, benzoxazolyl, benzisoxazolyl, quinolinyl, tetrahydroquinolinyl, isoquinolinyl, tetrahydroisoquinolinyl, quinazolinyl, tetrahydroquinazolinyl and quinoxalinyl, any of which may be optionally substituted as defined herein.
[0103] The saturated heterocycle thus includes radicals such as pyrrolinyl, pyrrolidinyl, pyrazolinyl, pyrazolidinyl, piperidinyl, morpholinyl, thiomorpholinyl, pyranyl, thiopyranyl, piperazinyl, indolinyl, azetidinyl, tetrahydropyranyl, tetrahydrothiopyranyl, tetrahydrofuranyl, hexahydropyrimidinyl, hexahydropyridazinyl, 1,4,5,6-tetrahydropyrimidinylamine, dihydro-oxazolyl, 1,2-thiazinanyl-1,1-dioxide, 1,2,6-thiadiazinanyl-1,1-dioxide, isothiazolidinyl-1,1-dioxide and imidazolidinyl-2,4-dione, whereas the unsaturated heterocycle include radicals with an aromatic character such as furanyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, tetrazolyl, thiadiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl, indolyl, isoindolyl. In each case the heterocycle may be condensed with a phenyl or carbocyclyl ring to form a bicyclic ring system.
[0104] It should be noted that the radical positions on any molecular moiety used in the definitions may be anywhere on such a moiety as long as it is chemically stable.
[0105] Radicals used in the definitions of the variables include all possible isomers unless otherwise indicated. For instance pyridyl includes 2-pyridyl, 3-pyridyl and 4-pyridyl; pentyl includes 1-pentyl, 2-pentyl and 3-pentyl.
[0106] When any variable occurs more than one time in any constituent, each definition is independent.
[0107] The invention relates to the compounds of formula (I) per se, the prodrugs, N-oxides, addition salts, quaternary amines, metal complexes, and stereochemically isomeric forms thereof.
[0108] The invention further relates to methods for the preparation of the compounds of formula (I), the prodrugs, N-oxides, addition salts, quaternary amines, metal complexes, and stereochemically isomeric forms thereof, its intermediates, and the use of the intermediates in the preparation of the compounds of formula (I).
[0109] It will be appreciated that the compounds according to the invention may contain one or more asymmetrically substituted carbon atoms. The presence of one or more of these asymmetric centres (chiral centres) in compounds according to the invention can give rise to stereoisomers, and in each case the invention is to be understood to extend to all such stereoisomers, including enantiomers and diastereomers, and mixtures including racemic mixtures thereof. Racemates may be separated into individual optically active forms using known procedures (cf. Advanced Organic Chemistry: 3rd Edition: author J March, pp 104-107) including for example the formation of diastereomeric derivatives having convenient optically active auxiliary species followed by separation and then cleavage of the auxiliary species.
[0110] Where optically active centres exist in the compounds of the invention, we disclose all individual optically active forms and combinations of these as individual specific embodiments of the invention, as well as their corresponding racemates.
[0111] Where tautomers exist in the compounds of the invention, we disclose all individual tautomeric forms and combinations of these as individual specific embodiments of the invention. The compounds of the invention may be provided as pharmaceutically acceptable salts, solvates, prodrugs, N-oxides, quaternary amines, metal complexes, or stereochemically isomeric forms. These include acid addition salts such as hydrochloride, hydrobromide, citrate, tosylate and maleate salts and salts formed with phosphoric and sulphuric acid. In another aspect suitable salts are base salts such as an alkali metal salt for example sodium or potassium, an alkaline earth metal salt for example calcium or magnesium, or organic amine salt for example triethylamine. Examples of solvates include hydrates.
[0112] The compounds of formula (I) have activity as pharmaceuticals. As previously outlined the compounds of the invention are metalloproteinase inhibitors, in particular they are inhibitors of MMP-12 and may be used in the treatment of diseases or conditions mediated by MMP-12 such as asthma, rhinitis, chronic obstructive pulmonary diseases (COPD), arthritis (such as rheumatoid arthritis and osteoarthritis), atherosclerosis and restenosis, cancer, invasion and metastasis, diseases involving tissue destruction, loosening of hip joint replacements, periodontal disease, fibrotic disease, infarction and heart disease, liver and renal fibrosis, endometriosis, diseases related to the weakening of the extracellular matrix, heart failure, aortic aneurysms, CNS related diseases such as Alzheimer's disease and Multiple Sclerosis (MS), psoriasis and hematological disorders.
[0113] The compounds of the invention typically show a favourable selectivity profile. Whilst we do not wish to be bound by theoretical considerations, the compounds of the invention are believed to show selective inhibition for any one of the above indications relative to any MMP-1 inhibitory activity, by way of non-limiting example they may show in excess of 100 fold selectivity over any MMP-1 inhibitory activity.
[0114] Accordingly, the present invention provides a compound of formula (I), or a pharmaceutically acceptable salt, a solvate, prodrug, N-oxide, quaternary amine, metal complex, or stereochemically isomeric form thereof, as hereinbefore defined for use in therapy. In another aspect, the invention provides the use of a compound of formula (I), or a pharmaceutically acceptable salt, a solvate, prodrug, N-oxide, quaternary amine, metal complex, or stereochemically isomeric form thereof, as hereinbefore defined in the manufacture of a medicament for use in therapy.
[0115] In the context of the present specification, the term “therapy” also includes “prophylaxis” unless there are specific indications to the contrary. The terms “therapeutic” and as “therapeutically” should be construed accordingly.
[0116] The invention further provides a method of treating a disease or condition mediated by MMP-12 which comprises administering to a patient a therapeutically effective amount of a compound of formula (I) or a pharmaceutically acceptable salt, a solvate, prodrug, N-oxide, quaternary amine, metal complex, or stereochemically isomeric form thereof, as hereinbefore defined.
[0117] The invention also provides a method of treating an obstructive airways disease (e.g. asthma or COPD) which comprises administering to a patient a therapeutically effective amount of a compound of formula (I) or a pharmaceutically acceptable salt or solvate thereof as hereinbefore defined.
[0118] For the above-mentioned therapeutic uses the dosage administered will, of course, vary with the compound employed, the mode of administration, the treatment desired and the disorder indicated. The daily dosage of the compound of formula I/salt/solvate (active ingredient) may be in the range from 0.001 mg/kg to 75 mg/kg, in particular from 0.5 mg/kg to 30 mg/kg. This daily dose may be given in divided doses as necessary. Typically unit dosage forms will contain about 1 mg to 500 mg of a compound of this invention.
[0119] The compounds of formula (I) and pharmaceutically acceptable salts, solvates, prodrugs, N-oxides, quaternary amines, metal complexes, or stereochemically isomeric forms thereof may be used on their own but will generally be administered in the form of a pharmaceutical composition in which the formula (I) compound/salt/solvate (active ingredient) is in association with a pharmaceutically acceptable adjuvant, diluent or carrier. Depending on the mode of administration, the pharmaceutical composition will preferably comprise from 0.05 to 99% w (percent by weight), more preferably from 0.10 to 70% w, of active ingredient, and, from 1 to 99.95% w, more preferably from 30 to 99.90% w, of a pharmaceutically acceptable adjuvant, diluent or carrier, all percentages by weight being based on total composition. A representative tablet within the scope of the pharmaceutical composition of the invention could have a mass of 500-1500 mg with a loading of active ingredient in the range 35-75%, with the balance being excipients, such as binders, disintegrants, antioxidants and the like.
[0120] Thus, the present invention also provides a pharmaceutical composition comprising a compound of formula (I) or a pharmaceutically acceptable salt or solvate thereof as hereinbefore defined in association with a pharmaceutically acceptable adjuvant, diluent or carrier. The invention further provides a process for the preparation of a pharmaceutical composition of the invention which comprises mixing a compound of formula (I) or a pharmaceutically acceptable salt or, a solvate, prodrug, N-oxide, quaternary amine, metal complex, or stereochemically isomeric form, thereof as hereinbefore defined with a pharmaceutically acceptable adjuvant, diluent or carrier.
[0121] The pharmaceutical compositions of this invention may be administered in standard manner for the disease or condition that it is desired to treat, for example by oral, topical, parenteral, buccal, nasal, vaginal or rectal administration or by inhalation. For these purposes the compounds of this invention may be formulated by means known in the art into the form of, for example, tablets, capsules, aqueous or oily solutions, suspensions, emulsions, creams, ointments, gels, nasal sprays, suppositories, finely divided powders or is aerosols for inhalation, and for parenteral use (including intravenous, intramuscular or infusion) sterile aqueous or oily solutions or suspensions or sterile emulsions.
[0122] The inhaled (including aerosol & nebulised) route is convenient, especially for compounds of formula I with a rapid metabolism. A large number of appropriate devices able to dose and entrain the pharmaceutical active and deliver it to the lungs of the patient are now available, even for COPD patients with a reduced respiratory capacity. See for example Byron's review in Proc. Am. Thorac. Soc. 2004:1(4) 321-328 or Caprioti's review in Medsurg. Nurs.2005: 14(3) 185-194.
[0123] The oral delivery route, particularly capsules or tablets is favoured, especially for advanced COPD patients with severely compromised respiratory capacity.
[0124] In addition to the compounds of the present invention the pharmaceutical composition of this invention may also contain, or be co-administered (simultaneously or sequentially) with, one or more pharmacological agents of value in treating one or more diseases or conditions referred to hereinabove. A representative example is inhaled steroids such as are conventionally used in asthma, for example budesonide and “Symbicort” (trade mark).
[0125] A general route to compounds according to the present invention wherein X and Y are both 0 is shown in scheme 1.
[0000]
[0126] Coupling of two amino acids(1a) and (1b) carrying the appropriate side chains, R 1 and (CR 5 R 5′ ) n D(CR 6 R 6′ ) m R 2 , by standard peptide coupling conditions like using couplings agents such as HOBt and EDCI or the like in the presence of a base such as DIEA, NaHCO 3 or the like in a solvent like DMF provides the dipeptide (1c). The hydantoin derivative (1e) can then be achieved by removal of the Boc group according to conventional procedures such as treatment with an acid for instance TFA or formic acid or the like in a solvent like dichloromethane, followed by formylation of the formed primary amine with a formylating agent such as phenyl chloroformate or phosgene or the like in the presence of a base like DIEA or NaHCO 3 and finally ring closure of the dipeptide effected for example by treatment of the afforded formyl derivative (1d) with a base such as DIEA or the like and subsequent hydrolysis of the methyl ester by treatment with an acid such as HCl. If an alkyl substituent, R 3 on the secondary nitrogen of the hydantoin ring is desired, this alkylation is conveniently performed subsequent to the ring closure of compound 1d and prior to the ester hydrolysis, by reaction with a desired alkylating agent such as R 3 -Lg, wherein Lg is a leaving group such as a halide like a chloride, bromide or iodide or Lg is a derivative of sulphonic acid such as a triflate, tosylate mesylate or the like, optionally in the presence of a base such as t-BuOK. Coupling of hydroxylamine hydrochloride or a suitably protected hydroxylamine, for example, O-tritylhydroxylamine or O-bensylhydroxylamine using standard peptide coupling conditions such as using coupling agents like BOP and NMM in a solvent like DMF or as described above or by using any other convenient reagents, provides the hydroxamic acid derivative (1f). The free acid (1g) is then achieved after removal of the optional hydroxy protecting group carried out by using the appropriate conditions according to the protecting group, such as by acidic treatment in the case of a trityl protecting group.
[0127] Amino acids carrying the appropriate side chains for use in scheme 1 are commercially available or they can be prepared by the skilled person according to literature procedures. For example, amino acids carrying a side chain containing a thioether, amine, ether or carbamate group suitable for the preparation of compounds of general formula I wherein D is a thioether, amine, ether or amide linkage respectively, can be prepared from suitably protected, commercially available α-hydroxyalkyl amino acids as illustrated in scheme 2.
[0000]
[0128] The hydroxy group of amino acid (2a) can be converted to a thioether, amine or ether function for instance by way of a Mitsunobu reaction, i.e. reaction of the hydroxy group of the alcohol (2a) with an azodicarboxylate such as DIAD or the like in the presence of triphenylphosphine or the like followed by displacement with a desired thiol, amine or alcohol to provide the thioether derivative (2b), the amine (2c) or the ether (2d) respectively. A big variety of thiols, amines and alcohols are available commercially or in the literature. An alternative method to obtain the amine derivative (2c) is to oxidize the hydroxy group of the alcohol (2a) to the corresponding aldehyde, effected for example by treatment with Dess-Martin periodinane or by any other suitable oxidation reagent, followed by a reductive amination with the desired amino derivative R 2 (CH 2 ) m NH 2 . Ether derivatives (2d) can alternatively be achieved by alkylation of the hydroxy group of the alcohol (2a) by a displacement reaction with a suitable alkylating agent R 2 -Lg, where Lg is a leaving group such as a trichloroimidate, a halide like a chloride, bromide or iodide, or a derivative of sulphonic acid such as a mesylate, triflate, tosylate or the like, in the presence of a base such as sodium hydride, Ag 2 O, t.BuOK or the like in a solvent like DMF or THF or the like. Amino acids carrying a carbamate containing side chain can be prepared by reaction of amino acid (2a) with a suitable isocyanate R 2 N═C═O in the presence of a base like t.BuOK in a solvent like DMF or THF. Alternatively, compounds carrying a carbamate containing side chain can be prepared by reacting the hydroxy group of the amino acid (2a) with a formylating agent such phosgene or a suitable chlorocarbamate in the presence of a base like sodium hydrogen carbonate in a solvent like dichloromethane or toluene, followed by reaction with a desired amine R 2 —(CH 2 ) m NH 2 . Derivatives substituted with the groups R 4 , R 5 , R 5′ , R 6 and/or R 6′ , can be prepared according to the above described method by using the appropriately substituted amino acids and alkylating agents.
[0129] Amino acids carrying an amide, carbamate, urea or sulponamide containing side chain, i.e. D is an amide, carbamate urea or sulpnonamide linkage respectively in compound (1b), can be prepared from α-aminoalkyl amino acids as illustrated in scheme 3. α-Aminoalkyl amino acids are commercially available or they can be prepared from the corresponding α-hydroxyalkyl amino acids according to literature procedures.
[0000]
[0130] Reaction of the α-aminoalkyl amino acid (3a) with an appropriate acid chloride R 2 (CH 2 ) m (C═O)Cl in a solvent like pyridine or dichloromethane optionally in the presence of a base like 4-dimethylaminopuridine or the like provides the amide (3b), reaction of the amine (3a) with a desired chloroformate R 2 (CH 2 ) m O(C═O)Cl provides the carbamate (3c), whereas formylation of the amine (3a) using a convenient formylating agent for instance phosgene, p-nitrochloroformate, CD or the like optionally in the presence of a base such as sodium hydrogen carbonate followed by reaction with the desired amino derivative NH 2 (CH 2 ) m R 2 provides the urea (3d) and finally, sulphonamides (3e) are obtained by reaction of the amine (3a) with a suitable sulphonyl chloride R 2 (CH 2 ) m (S═O) 2 Cl in a solvent like pyridine or dichloromethane optionally in the presence of a base like 4-dimethylaminopyridine. Secondary amines may also be achieved from the primary amine (3a) by alkylation of the nitrogen using any suitable alkylating agent such as an alkyl halide or an alkyl derivative of sulphonic acid as described above. Derivatives substituted with the groups R 4 , R 5 , R 5′ , R 6 and/or R 6′ , can be prepared according to the above described method by using the appropriately substituted amino acids and alkylating, acylating, sulphonylating or aminating agents.
[0131] Amino acids (1b) used in scheme 1 carrying a saturated or unsaturated all carbon side chain suitable for the preparation of compounds according to general formula I wherein D is absent and R 2 is a carbocyclic or heterocyclic aromatic system, are commercially available or they can be prepared from suitably protected α-amino-ω-hydroxy acids or the corresponding α-amino-w-carboxy acids. An example is shown in scheme 3A.
[0000]
[0132] The acid (3Aa) which is available commercially or in the literature, can be reduced to the corresponding alcohol (3Ab) by any suitable method known in the field of synthetic organic chemistry, for example the acid can be transformed to a suitable ester or acid halide like the N-hydroxysuccinimide followed by treatment with a reducing agent such as LiBH 4 . The afforded alcohol (3Ab) can then be further reacted with iodine in the presence of triphenylphosphine and imidazole to provide the iodo derivative (3Ac). Conversion of the iodo derivative to the corresponding zink derivative by reaction with zink activated with 1,2-dibromoethane and chlorotrimethylsilane followed by a palladium catalyzed displacement reaction with a desired aryl iodide derivative, using for example tris(dibenzylideneacetone)palladium(0) as catalyst in the presence of a phosphine ligand like tri(o-tolyl)phosphine, gives the arylated amino acid (3Ad). Removal of the Boc group, coupling of an amino acid, ring closure, hydrolysis of the benzyl ester and introduction of the hydroxylamine moiety as described in scheme 1 gives the hydantoin derivative (3Ae).
[0133] Amino acids containing an α,β-unsaturated all carbon side chain useful for the preparation of compounds according to general formula I wherein R 4 and R 5 together form an olefinic bond, can be prepared for example as shown in scheme 3B.
[0000]
[0134] Oxidation of the alcohol (3Ab) using an oxidizing agent such as Dess Martin periodinate to the corresponding aldehyde followed by a Grignard reaction or the like of with a desired Grignard reagent, R 2 (CH 2 ) m MgBr provides the hydroxy derivative (3Ba). Dehydration effected for instance by acidic treatment provides the unsaturated compound (3Bb) which subsequently can be treated as described in scheme 1 to give the desired hydantoin derivative (3Bc). The same strategy can also be applied in order to obtain compounds with other side chains such as alternative position of the olefinic bond or heteroatom containing side chains by choosing the appropriate hydroxyalkyl substituted amino acid and Grignard reagent.
[0135] Compounds containing a substituted R 2 moiety can be achieved by using an amino acid (1b) carrying the desired R 2 -substituent in scheme 1, or the substituent can be introduced at a later stage of the synthesis. When the substituent is linked to R 2 by a carbon-carbon bond, it is conveniently introduced by a palladium catalyzed coupling reaction. Scheme 3C illustrates a method employing a Suzuki coupling.
[0000]
[0136] Coupling of the dipeptide (3Ca) with the boronic acid derivative R 7 B(OH) 2 of the desired substituent in the presence of a palladium catalyst such as Pd(PPh 3 ) 2 Cl 2 or the like and a base like sodium carbonate provides the R 7 -substituted dipeptide (3Cb). Removal of the Boc group, coupling of an amino acid, ring closure, hydrolysis of the benzyl ester and introduction of the hydroxylamine moiety as described in scheme 1 gives the hydantoin derivative (3Cc). Other palladium catalyzed coupling reactions known from the literature may alternatively be used for the introduction of a carbon linked substituent to R 2 . For instance, a Heck coupling reaction wherein a desired activated alkene is coupled to an aromatic or vinylic R 2 moiety using a catalyst such as Pd(OAc) 2 or the like in the presence of a base such as triethylamine or potassium carbonate or the like provides alkene substituted compounds.
[0137] Although the method in scheme 3C is illustrated with a bromobenzene ring as R 2 group it should be understood that the same strategy is applicable to other R 2 groups such as substituted and unsubstituted carbocycles and heterocycles.
[0138] An alternative strategy for the preparation of the compounds of the invention is to first prepare a suitable hydantoin derivative and subsequently elongate the side chain and thus introduce the desired linkage D. Hydantoin derivatives carrying a hydroxyalkyl or aminoalkyl side chain whereto the various functional groups can be attached are suitable intermediates for this strategy. An example of their preparation is illustrated in scheme 4.
[0000]
[0139] The hydantoin derivative (4c) can be prepared from the two amino acids (4a) and (4b) as described in scheme 1. Removal of the benzyl group for example by catalytic hydrogenation using a catalyst such as palladium on carbon optionally in the presence of a base like sodium hydrogen carbonate and in the case of R 3 being hydrogen, protection of the ring nitrogen with any suitable amino protecting group such as a boc group using standard methods well known in the art, gives the hydroxyalkyl derivative (4d). The corresponding aminoalkyl derivative (4e) can then be prepared by conversion of the hydroxy group to an amino group for example by transforming the hydroxy group to a leaving group such as a mesylate or the like by treatment with mesylchloride in a solvent like pyridine optionally in the presence of a base such as triethylamine followed by displacement of the leaving group with azide and finally reduction of the azide to an amine by any suitable reduction method such as treatment with Ph 3 P. Derivatives substituted with the groups R 4 , R 5 and/or R 5′ can be prepared according to the above described method by using the appropriately substituted amino acid instead of the unsubstituted amino acid (4b).
[0140] Subsequent elongation of the hydroxyalkyl side chain in order to obtain a thioether, amine, ether or carbamate containing side chain can be performed as illustrated in scheme 5.
[0000]
[0141] The hydroxy group of the hydantoin (4d) can be converted to a thioether, amine or ether function for instance by way of a Mitsunobu reaction, i.e. reaction of the hydroxy group of the alcohol (4d) with an azodicarboxylate such as DIAD or the like in the presence of triphenylphosphine or the like followed by displacement with a desired thiol, amine or alcohol to provide the thioether, amine or the ether derivative respectively. A big variety of thiols, amines and alcohols are available commercially or in the literature. An alternative method to obtain amine derivatives, i.e. D′ is NH, is to oxidize the hydroxy group of the alcohol (4d) to the corresponding aldehyde, effected for example by treatment with Dess-Martin periodinane or by any other suitable oxidation reagent, followed by a reductive amination with the desired amino derivative R 2 (CH 2 ) m NH 2 . Ether derivatives, i.e. D′ is O, can alternatively be achieved by alkylation of the hydroxy group of the alcohol (4d) by a displacement reaction with a suitable alkylating agent R 2 -Lg, where Lg is a leaving group such as a trichloroimidate or a halide like a chloride, bromide or iodide, or a derivative of sulphonic acid such as a mesylate, triflate, tosylate or the like, in the presence of a base such as sodium hydride, Ag 2 O t.BuOK or the like in a solvent like DMF or THF or the like. Amino acids carrying a carbamate containing side chain can be prepared by reaction of hydantoin (4d) with a suitable isocyanate R 2 (CH 2 ) m N═C═O in the presence of a base like t.BuOK in a solvent like DMF or THF. Alternatively, compounds carrying a carbamate containing side chain can be prepared by reacting the hydroxy group of the hydantoin (4d) with a formylating agent such phosgene in the presence of a base like sodium hydrogen carbonate in a solvent like dichloromethane or toluene, followed by reaction with a desired amine R 2 (CH 2 ) m NH 2 .
[0142] Hydantoins carrying an amide, carbamate, urea or sulphonamide containing side chain, i.e. D is an amide, carbamate, urea or sulphonamide linkage respectively in general formula (I), can be prepared from α-aminoalkyl amino acids (4e) as illustrated in scheme 6.
[0000]
[0143] Reaction of the α-aminoalkyl hydantoin (4e) with an appropriate acid chloride R 2 (CH 2 ) m (C═O)Cl in a solvent like pyridine or dichloromethane optionally in the presence of a base like 4-dimethylaminopyridine or the like provides the amide (6a), reaction with a desired chloroformate R 2 (CH 2 ) m O(C═O)Cl provides the carbamate (6b) whereas formylation of the amine (4e) using a convenient formylating agent, for instance phosgene, p-nitrochloroformate, CDI or the like optionally in the presence of a base such as sodium hydrogen carbonate followed by reaction with the desired amino derivative NH 2 (CH 2 ) m R 2 provides the urea (6c) and finally, sulpnonamides (6d) are obtained by reaction of the amine (4e) with a suitable sulphonyl chloride R 2 (CH 2 ) m (S═O) 2 Cl in a solvent like pyridine or dichloromethane optionally in the presence of a base like 4-dimethylaminopuridine. Secondary amines, i.e. D is an amino linkage in general formula I, may also be prepared from the primary amine (4e) by alkylation of the nitrogen using any suitable alkylating agent such as an alkyl halide or an alkyl derivative of sulphonic acid as described above. Removal of the protecting groups, boc and trityl, by standard methods such as acidic treatment then provides the unprotected hydroxamic acids. Derivatives substituted with the groups R 4 , R 5 , R 5′ , R 6 and/or R 6′ , can be prepared according to the above described method by using the appropriately substituted amino acid and acylating, sulphonylating or aminating agents.
[0144] Compounds according to the present invention wherein one or both of the carbonyl groups of the hydantoin moiety is replaced by thiocarbonyl are conveniently prepared from thiopeptides. Various methods for the preparation of thiopeptides are described in the literature and one example, described by R. Michelot et al. in Bioorganic & Medicinal Chemistry Vol. 4, No 12 1996 p. 2201-2209, is shown in Scheme 7.
[0000]
[0145] The amino thioacid (7a) can be achieved from the corresponding amino acid (2b, 2c, 2d or 2e) by activation of the amino acid with isobutylchloroformate and N-methylmorpholine in a solvent like THF followed by treatment with H 25 and subsequent acidifying with for instance HCl. Coupling of the afforded amino thioacid with a natural or unnatural amino acid (7b) under standard peptide coupling conditions such as using a coupling reagent like BOP-CI or PyBOP or the like in the presence of a base such as DIEA or the like in a solvent like THF provides the thiodipeptide (7c).
[0146] Alternatively, the thiodipeptide (7c) can be achieved from the amino acid (2b, 2c, 2d or 2e) by converting the acid function to a nitrile by using for instance a reagent like trimethylsilanecarbonitrile in the presence of a Lewsis acid such as BF 3 —OEt 2 followed by treatment as described by C. H. Williams et al. in J. Chem. Soc. Perkin Trans. I, 1988, p. 1051-1055 and finally coupling of the second amino acid (7b) as described above.
[0147] A further alternative to the thiodipeptide (7c) is by conversion of the dipeptide (1c) by using the thionation reagent 2,4-bis(4-methoxyphenyl)-1,2,3,4-dithiadiphosphetane 2,4-disulfide described by K. Clausen et al. in Tetrahedron, Vol. 37, 1981, p. 3635-3639.
[0148] Amino thioacids substituted with the groups R 4 , R 5 , R 5′ , R 6 and/or R 6′ , can be prepared according to the above described methods by starting from the appropriately substituted compounds corresponding to amino acids (2b-2e) carrying the desired substituents.
[0149] A thiohydantoin derivative can then be formed by taking the thiodipeptide (7c) through the steps described for the dipeptide (1c) in scheme 1. An example is shown in scheme 8.
[0000]
[0150] Removal of the Boc group from thiodipeptide (8a) by treatment with an acid for instance TFA or formic acid in a solvent like dichloromethane, followed by formylation of the formed primary amine with a formylating agent such as phenyl chloroformate or phosgene or the like in the presence of a base like DIEA or NaHCO 3 yields the carbamate (8b). Ring closure of the thiodipeptide effected for example by treatment with a base such as DIEA or the like and subsequent hydrolysis of the methyl ester by treatment with an acid such as HCl gives the carboxylic acid (8c). Coupling of hydroxylamine hydrochloride or a suitably protected hydroxylamine, for example, O-tritylhydroxylamine or O-bensylhydroxylamine using standard peptide coupling conditions such as using coupling reagents like BOP and NMM in a solvent like DMF or as described above or any other convenient reagents, provides the hydroxamic acid (8c). The free acid (8e) is then achieved after removal of the optional hydroxy protecting group carried out by using the appropriate conditions according to the protecting group, such as by acidic treatment in the case of a trityl protecting group.
[0151] Scheme 9 illustrates a method to prepare compounds according to general formula I wherein Y is S and X is O or S.
[0000]
[0152] Removal of the Boc group from thiodipeptide (9a), prepared as described in scheme 1 or 7, by treatment with an acid for instance TFA or formic acid or the like in a solvent like dichloromethane, followed by ring closure effected for example by reaction with thiocarbonyl diimidazole or the like provides the hydantoin derivative (9b). Subsequent hydrolysis of the methyl ester by treatment with an acid such as HCl gives the carboxylic acid (9c). Coupling of hydroxylamine hydrochloride or a suitably protected hydroxylamine, for example, O-tritylhydroxylamine or O-bensylhydroxylamine using standard peptide coupling conditions such as using coupling reagents like BOP and NMM in a solvent like DMF or as described above or any other convenient reagents, provides the hydroxamic acid (9d). The free acid (9e) is then achieved after removal of the optional hydroxy protecting group carried out by using the appropriate conditions according to the protecting group, such as by acidic treatment in the case of a trityl protecting group.
[0153] It will be readily apparent that the above described methods are not limited to the stereochemistries indicated. The same methods are also applicable to reactants having other sterochemistries and to racemates, the obtained product will have the configuration corresponding to the one of the reactants.
[0154] Any functional groups present on any of the constituent compounds used in the preparation of the compounds of the invention are appropriately protected where necessary. For example functionalities on the natural or non-natural amino acids are typically protected as is appropriate in peptide synthesis. Those skilled in the art will appreciate that the selection and use of appropriate protecting groups depend upon the reaction conditions. Suitable protecting groups are described in Greene, “Protective Groups in Organic Synthesis”, John Wiley & Sons, New York (1981) and “The Peptides: Analysis, Synthesis, Biology”, Vol. 3, Academic Press, New York (1981), the disclosure of which are hereby incorporated by reference.
DETAILED DESCRIPTION
[0155] Various embodiments of the compounds of the invention and key intermediates towards such compounds will now be described by way of illustration only with reference to the accompanying non-limiting chemistry and biology examples.
[0156] Method A
[0000]
Example 1
Step a
[0157]
2-(2-Tert-butoxycarbonylamino-4-phenyl-butyrylamino)-3-methylbutyric acid methyl ester (1a)
[0158] To an ice-cooled solution of D-valine methyl ester hydrochloride (1000 mg, 3.58 mmol) and HOBt (in DMF (14 mL) was added EDCI (755 mg, 3.94 mmol). After the mixture was stirred for 30 min, N-boc-L-homophenylalanine (600 mg, 3.58 mmol) and N-methylmorpholine (1 mL, 8.95 mmol) were added. The mixture was warmed to room temperature and stirred overnight. The solvent was removed and the residue was partitioned between water and EtOAc. The aqueous layer was extracted with EtOAc and the combined organic phases were dried over anhydrous Na 2 SO 4 . After concentration under reduced pressure, the crude title compound (2000 mg) was obtained and used in the next step without further purification.
[0000]
Step b
2-(2-Amino-4-phenyl-butyrylamino)-3-methylbutyric acid methyl ester (1b)
[0159] To a solution of the crude compound obtained in step a above (2000 mg) in CH 2 Cl 2 (10 mL) was added TFA(10 mL). After stirring for 1.5 h at room temperature, the mixture was concentrated. The residue was diluted with EtOAc whereafter 10% NaOH was added to adjust the pH to 14. The aqueous layer was extracted with EtOAc and the combined organic phases were dried over anhydrous Na 2 SO 4 . After concentration under reduced pressure, the crude title product (1400 mg) was obtained for next step without further purification.
Step c
[0160]
3-Methyl-2-(2-phenoxycarbonylamino-4-phenyl-butyrylamino)-butyric acid methyl ester (1c)
[0161] To a mixture of the crude compound obtained in step b above (1400 mg) in dioxane (18 mL) and water (2 mL) was added phenyl chloroformate (0.9 mL, 7.16 mmol) and DIEA (1.6 mL, 8.95 mmol). The mixture was stirred at room temperature for 3 h and concentrated under reduced pressure. The residue was partitioned between water and EtOAc. The aqueous layer was extracted with EtOAc, the combined organic phases were dried and concentrated. The residue was purified by silica gel column chromatography to afford the title compound as a white solid (1165 mg, 79% yield, three steps).
[0162] 1 H NMR (300 MHz, CDCl 3 ): δ 0.89 (d, J=6.6 Hz, 3H); 0.94 (d, J=6.6 Hz, 3H); 2.00-2.35 (m, 3H); 2.70-2.80 (m, 2H); 3.73 (s, 3H); 4.30-4.45 (m, 1H); 4.30-4.45 (m, 1H); 4.57 (dd, J=8.1, 9.0 Hz, 1H); 5.84 (d, J=8.1Hz, 1H); 5.84 (d, J=8.1Hz, 1H); 6.65 (d, J=9.0 Hz, 1H); 7.10-7.40 (m, 10H).
Step d
[0163]
2-(2,5-Dioxo-4-phenethyl-imidazolidin-1-yl-3-methyl-butyric acid methyl ester (1d)
[0164] To a solution of the compound obtained in step c above (1140 mg) in DMF (14 mL) was added DIEA (0.6 mL, 3.30 mmol). After stirring overnight at room temperature, the solvent was removed. The residue was diluted with EtOAc and washed with water. The organic layer was dried and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to afford the title compound as a colourless oil (672 mg, 77%).
[0165] 1 H NMR (300 MHz, CDCl 3 ): δ 0.92 (d, J=6.9 Hz, 3H); 1.12 (d, J=6.9 Hz, 3H); 1.95-2.35 (m, 2H); 2.60-2.85 (m, 3H); 3.71 (s, 3H); 4.00-4.10 (m, 1H); 4.35 (d, J=8.4 Hz, 1H); 7.00 (s, 1H); 7.10-7.35 (m, 5H).
Step e
[0166]
2-(2,5-Dioxo-4-phenethyl-imidazolidin-1-yl-3-methyl-butyric acid (1e)
[0167] A mixture of the compound obtained in step d above (482 mg, 1.52 mmol) and 6 N HCl (20 mL) was stirred at 70° C. for 3 h. The reaction mixture was cooled to room temperature and extracted with CH 2 Cl 2 . The combined organic phases were washed with brine, dried and concentrated. The residue was purified by silica gel column chromatography to afford the title compound as a colorless oil (210 mg, 46% yield) with a recover of starting material (200 mg).
[0168] 1 H NMR (300 MHz, CD 3 OD): δ 0.86 (d, J=6.8 Hz, 3H); 1.01 (d, J=6.8 Hz, 3H); 1.94-2.20 (m, 2H); 2.50-2.80 (m, 3H); 4.10-4.15 (m, 1H); 4.27 (d, J=8.4 Hz, 1H); 7.10-7.30 (m, 5H).
[0000]
Step f
2-(2,5-Dioxo-4-phenethyl-imidazolidin-1-yl-N-hydroxy-3-methyl-butyramide (1f)
[0169] To a solution of the compound obtained in step e above (109 mg, 0.36 mmol) in DMF (1.8 mL) was added BOP (190 mg, 0.43 mmol) at 0° C. After stirring for 30 min, HONH 2 xHCl (50 mg, 11.38 mmol) and N-methylmorpholine (0.16 mL, 1.44 mmol) were added. The mixture was warmed to room temperature and stirred overnight. The solvent was removed and the residue was partitioned between EtOAc and a saturated solution of NH 4 Cl. The aqueous layer was extracted with EtOAc, dried and concentrated. The residue was purified by silica gel column chromatography to afford the title compound as a white solid (63 mg, 55% yield).
[0170] 1 H NMR (300 MHz, CD 3 OD): δ0.89 (d, J=6.8 Hz, 3H); 1.01 (d, J=6.8 Hz, 3H); 1.94-2.20 (m, 2H); 2.60-2.80 (m, 2H); 2.80-3.00 (s, 1H); 4.00-4.10 (m, 2H); 7.10-7.30 (m, 5H).
Example 2
[0171]
2-(2,5-Dioxo-4-phenethyl-imidazolidin-1-yl-N-hydroxy-propionamide (2)
[0172] The procedure described in method A was followed but using D-alanine methyl ester hydrochloride instead of D-valine methyl ester hydrochloride which gave the title compound (8 mg)
[0173] 1 H NMR (300 MHz, CD 3 OD): δ 1.56 (dd, J=2.7, 7.2 Hz, 3H), 1.90-2.20 (m, 2H), 2.72 (dd, J=7.8, 7.8 Hz, 2H), 4.00-4.15 (m, 1H), 4.60-4.15 (m, 1H), 7.10-7.35 (m, 5H).
Example 4
[0174]
3-Cyclohexyl-2-(2,5-dioxo-4-phenethyl-imidazolidin-1-yl-N-hydroxy-propionamide (4)
[0175] The procedure described method A was followed but using D-cyclohexyl-alanine methyl ester hydrochloride instead of D-valine methyl ester hydrochloride which gave the title compound (3 mg).
[0176] 1 H NMR (300 MHz, CDCl 3 ): δ 0.80-2.10 (m, 16H), 2.72 (s, 2H), 4.09 (s, 1H), 4.70-4.75 (m, 1H), 6.98 (s, 1H), 7.10-7.35 (m, 5H), 10.06 (s, 1H).
Example 5
[0177]
2-[4-(2-Biphenyl-4-yl-ethyl)-2,5-dioxo-imidazolidin-1-yl]-N-hydroxy-3-methyl-butyramide (5)
[0178] The procedure described method A was followed but using 4-biphenyl-4-yl-2-tert-butoxycarbonylamino-butyric acid instead of N-boc-L-homophenylalanine, which gave the title compound (6 mg).
[0179] 1 H NMR (300 MHz, CDCl 3 ): δ0.84 (d, J=6.0 Hz, 3H), 1.03 (d, J=6.0 Hz, 3H), 1.94-2.30 (m, 2H), 2.50-2.80 (m, 3H), 4.10-4.15 (m, 1H), 4.25 (d, J=11.4 Hz, 1H), 6.30-6.50 (m, 1H), 7.10-7.60 (m, 9H), 10.10 (s, 1H).
Example 6
[0180]
2-[2,5-Dioxo-4-(3-phenylpropyl)-imidazolidin-1-yl]-N-hydroxy-3-methyl-butyramide (6)
[0181] The procedure described method A was followed but using 2-tert-butoxycarbonylamino-5-phenyl-pentanoic acid instead of N-boc-L-homophenylalanine, which gave the title compound (8 mg).
[0182] 1 H NMR (300 MHz, CDCl 3 ): δ 0.93 (d, J=6.6 Hz, 3H), 1.03 (d, J=6.6 Hz, 3H), 1.90-2.10 (m, 4H), 2.55-2.85 (m, 3H), 4.00-4.15 (m, 1H), 4.27 (d, J=11.4 Hz, 1H), 6.30 (s, 1H), 7.15-7.35 (m, 5H), 8.12 (s, 1H).
[0000]
Example 7
2-(2,5-Dioxo-4-phenethyl-imidazolidin-1-yl)-N-hydroxy-3-methyl-butyramide (7)
[0183] The procedure described method A was followed but using N-boc-D-homophenylalanine instead of N-boc-L-homophenylalanine, which gave the title compound (10 mg).
[0184] 1 H NMR (300 MHz, CDCl 3 ): δ 0.83 (d, J=6.6 Hz, 3H), 1.03 (d, J=6.6 Hz, 3H), 1.90-2.10 (m, 1H), 2.20-2.30 (m, 1H), 2.60-2.80 (m, 3H), 4.00-4.20 (m, 1H), 4.27 (d, J=11.4 Hz, 1H), 6.30 (s, 1H), 7.15-7.40 (m, 5H), 8.12 (s, 1H).
[0000]
Example 8
N-Hydroxy-3-methyl-2-[4-(2-naphtalen-1-yl-ethyl)-(2,5-dioxo-imidazolidin-1-yl)-butyramide (8)
[0185] The procedure described method A was followed but using 2-tert-butoxycarbonylamino-4-naphtalen-1-yl-butyric acid instead of N-boc-L-homophenylalanine, which gave the title compound (20 mg).
[0186] 1 H NMR (300 MHz, CDCl 3 ): δ 0.85 (d, J=6.6 Hz, 3H), 1.04 (d, J=6.6 Hz, 3H), 2.00-2.30 (m, 2H), 2.50-2.70 (m, 1H), 3.10-3.30 (m, 2H), 4.10-4.25 (m, 1H), 4.29 (d, J=11.1Hz, 1H), 6.03 (s, 1H), 7.10-8.00 (m, 9H), 10.10 (s, 1H).
Example 9
[0187]
2-(2,5-Dioxo-4-phenethyl-imidazolidin-1-yl)-N-hydroxy-3-methyl-butyramide (9)
[0188] The procedure described method A was followed but using L-valine methyl ester hydrochloride instead of D-valine methyl ester hydrochloride, which gave the title compound (15 mg).
[0189] 1 H NMR (300 MHz, CD 3 OD): δ 0.88 (d, J=6.4 Hz, 3H), 1.02 (d, J=6.5 Hz, 3H), 1.97-1.92 (m, 1H), 2.11-2.06 (m, 1H), 2.72-2.67 (m, 2H), 2.92-2.86 (m, 1H), 4.10-4.03 (m, 2H), 7.30-7.18 (m, 5H).
Example 10
[0190]
2-(2,5-Dioxo-4-phenethyl-imidazolidin-1-yl)-N-hydroxy-3-phenhyl-propionamide (10)
[0191] The procedure described method A was followed but using D-phenylalanine methyl ester hydrochloride instead of D-valine methyl ester hydrochloride, which gave the title compound (3 mg).
[0192] 1 H NMR (300 MHz, CD 3 OD): δ 1.64-1.61 (m, 1H), 1.95-1.91 (m, 1H), 2.49-2.45 (m, 2H), 3.42-3.39 (m, 2H), 3.93-3.85 (m, 1H), 4.97-4.90 (m, 1H), 6.90-6.75 (m, 1H), 7.26-7.00 (m, 10H).
Example 11
[0193]
2-Cyclohexyl-2-(2,5-dioxo-4-phenethyl-imidazolidin-1-yl)-N-hydroxy-acetamide (11)
[0194] The procedure described method A was followed but using D-cyclohexylglycine methyl ester hydrochloride instead of D-valine methyl ester hydrochloride, which gave the title compound (4 mg).
[0195] 1 H NMR (300 MHz, CDCl 3 ): δ 1.49-0.84 (m, 6H), 1.81-1.66 (m, 4H), 2.06-1.96 (m, 1H), 2.38-2.23 (m, 2H), 2.80-2.76 (m, 2H), 4.11-3.99 (m, 1H), 4.32-4.28 (m, 1H), 6.79 (s, 1H), 7.34-7.20 (m, 5H).
Example 12
[0196]
2-(2,5-Dioxo-4-phenethyl-imidazolidin-1-yl)-N-hydroxy-3,3-dimethyl-butyramide (12)
[0197] The procedure described method A was followed but using D-tert.butylglycine methyl ester hydrochloride instead of D-valine methyl ester hydrochloride, which gave the title compound (2 mg).
[0198] 1 H NMR (300 MHz, CD 3 OD): δ 1.11 (s, 9H), 2.01-1.89 (m, 1H), 2.18-2.07 (m, 1H), 2.75-2.70 (m, 2H), 4.05 (dd, J 1 =6.9 Hz, 4.1 2 =2.1Hz, 1H), 4.41 (s, 1H), 7.30-7.15 (m, 5H).
[0199] Method B
[0000]
Example 13
Step a
[0200]
2-Tert-butoxycarbonylamino-3-hydroxy-propionic acid methyl ester (13a)
[0201] To a solution of L-serine methyl ester hydrochloride (10.00 g, 64.5 mmol) and Boc 2 O (28.12 g, 129 mmol) in THF (258 mL) was slowly added Et 3 N (27 mL, 194 mmol) at room temperature. The reaction was stirred overnight, then quenched with saturated NaHCO 3 and brine, concentrated under vacuum and diluted with CH 2 Cl 2 and brine. The mixtures were separated and the aqueous layers were extracted with CH 2 Cl 2 three times, the combined organic phases were washed with brine, dried and concentrated, the residue was purified by silica gel column chromatography which gave the title compound as colourless oil (14.147 g, 86% yield).
Step b
[0202]
O-(4-bromo)-benzyl-boc-L-serine methyl ester (13b)
[0203] A solution of 1-bromo-4-(bromomethyl)benzene (7.5 g, 30.24 mmol) in Et 2 O (60 ml) was added to a mixture of the compound obtained in step a above (2.27 g, 10.30 mmol) and Ag 2 O (7.007 g, 30.24 mmol) in Et 2 O (400 ml) at room temperature. After being stirred for 4 days, the reaction mixture was filtered through celite and washed with CH 2 Cl 2 , concentrated under vacuum to give crude product. The crude product was purified by silica gel column chromatography to give the title compound as colourless oil (2.567 g, 64%).
Step c
[0204]
O-(4-bromo)-benzyl-boc-L-serine (13c)
[0205] To a solution of O-(4-bromo)-benzyl-boc-L-serine (13b) (2567 mg, 6.633 mmol.) in THF (40 mL) was added a solution of LiOH (238 mg, 9.95 mmol) in water (10 mL) at 0° C., the reaction was stirred for 5 h. 0.5 N HCl was added to neutralize, the mixture was then concentrated under vacuum. The residue was diluted with EtOAc and washed with brine. The combined organic layers were dried and concentrated; the crude product was purified by silica gel column chromatography which gave the title compound as colourless oil (2330 mg, 91%).
Step d
[0206]
2-[3-(4-Bromobenzyloxy)-2-tert-butoxycarbonylamino]-3-methylbutyric acid methyl ester (13d)
[0207] To a mixture of the compound obtained in step c above (2.330 g, 6.25 mmol), NMM (1.5 mL, 13.4 mmol) and HOBt (1.433 g, 10.62 mmol) in DMF (15 mL) at −15° C. was added EDCI (1.017 g, 6.87 mmol). After the reaction was stirred for 30 minutes, it was allowed to warm to room temperature, (R)-methyl 2-amino-3-methylbutanoate hydrochloride (1.147 g, 6.87 mmol) was then added and the reaction was stirred overnight. The solvent was removed under vacuum; the residue was diluted with EtOAc and washed with brine. The combined organic layers were dried and concentrated; the crude product was purified by silica gel column chromatography which gave the title compound as colourless oil (2.246 g, 74%).
Step e
[0208]
2-[4-(4-Bromobenzyloxymethyl)-2,5-dioxo-imidazolidin-1-yl]-3-methyl-butyric acid methyl ester (13e)
[0209] The compound obtained in step d above (1246 mg, 2.56 mmol) was stirred in TFA (5 mL) at 0° C. for 5 h, then concentrated under vacuum. The residue was diluted with CH 2 Cl 2 , washed with saturated NaHCO 3 and brine, dried over anhydrous Na 2 SO 4 , concentrated to give crude product. The obtained crude product was stirred in dioxane (9 mL) and water (1 mL) at 0° C., DIEA (990 mg, 7.68 mmol) and phenyl chloroformate (479 mg, 3.07 mmol) were added and the mixture was stirred for 2 h. The solvent was removed under vacuum; the residue was diluted with EtOAc and washed with brine. The combined organic layers were dried and concentrated to give yellow oil. The obtained oil was then stirred with DIEA (990 mg, 7.68 mmol) in DMF (10 mL) for 24 h. After general workup, the crude product was purified by silica gel column chromatography which gave the title compound as colourless oil (623 mg, 59%).
Step f
[0210]
2-[4-(4-Bromobenzyloxymethyl)-2,5-dioxo-imidazolidin-1-yl]-3-methyl-butyric acid (13f)
[0211] A mixture of the compound obtained in step e above (623 mg, 1.512 mmol) and 2 N HCl (20 mL) was refluxed for 2 h. The reaction mixture was cooled down and then extracted with EtOAc. The combined organic layers were dried and concentrated; the crude product was purified by silica gel column chromatography which gave the title compound as colourless oil (409 mg, 68%).
Step q
[0212]
N-Benzyloxy-2-[4-(4-bromobenzyloxymethyl)-2,5-dioxo-imidazolidin-1-yl]-3-methyl-butyramide (13g)
[0213] To a mixture of the compound obtained in step f above (409 mg, 1.020 mmol), NMM (0.4 mL, 3.58 mmol) and HOBt (234 mg, 1.734 mmol) in DMF (10 mL) at −15° C. was added EDCI (214 mg, 1.123 mmol). After the reaction was stirred for 30 minutes, it was allowed to warm to room temperature, BnONH 2 HCl (179 mg, 1.123 mmol) was then added and the reaction was stirred overnight. The solvent was removed under vacuum; the residue was diluted with EtOAc and washed with brine. The combined organic layers were dried and concentrated; the crude product was purified by silica gel column chromatography which gave the title compound as an oil (426 mg, 83% yield).
Step h
[0214]
2-[4-(4-Bromobenzyloxymethyl)-2,5-dioxo-imidazolidin-1-yl]-N-hydroxy-3-methyl-butyramide (13h)
[0215] The oil obtained in step g above and 10% Pd/C (42 mg) were stirred in MeOH (15 mL) at room temperature for 2 h under H 2 atmosphere, the mixture was filtered through celite, washed with MeOH for several times and then concentrated. The residue was purified by silica gel column chromatography which gave the title compound as an oil (217 mg, 62% yield).
[0216] 1 H NMR (300 MHz, CD 3 OD): δ 0.79 (d, J=6.6 Hz, 3H), 0.97 (d, J=6.6 Hz, 3H), 2.79-2.95 (m, 1H), 3.71-3.78 (m, 1H), 3.84-3.92 (m, 1H), 4.02 (d, J=10.8 Hz, 1H), 4.18-4.22 (m, 1H), 4.61 (s, 2H), 7.48 (d, J=8.4 Hz, 2H), 7.62 (d, J=8.4 Hz, 2H).
Example 14
[0217]
2-[2,5-Dioxo-4-(4-trifluoromethyl-bezyloxymethyl)-imidazolidin-1-yl]-N-hydroxy-3-methyl-butyramide (14)
[0218] The procedure described in method B was followed, but using 4-(trifluoromethyl)benzyl bromide instead of 4-bromobenzyl bromide, which gave the title compound (10 mg).
[0219] 1 H-NMR (300 Hz, CD 3 OD): δ 0.80 (m, 3H), 0.98 (m, 3H), 2.87 (m, 1H), 3.74 (m, 1H), 3.88 (m, 1H), 4.00 (m, 1H), 4.21, (m, 1H), 4.61, (m, 2H), 7.64-7.47 (m, 5H).
[0000]
Example 15
2-[4-(3-Fluorobenzyloxymethyl)-2,5-dioxo-imidazolidin-1-yl]-N-hydroxy-3-methyl-butyramide (15)
[0220] The procedure described in method B was followed, but using 3-fluorobenzyl bromide instead of 4-bromobenzyl bromide, which gave the title compound (16 mg).
[0221] 1 H-NMR (300 Hz, CD 3 OD): δ 0.80 (m, 3H), 0.98 (m, 3H), 2.87 (m, 1H), 3.72 (m, 1H), 3.85 (m, 1H), 4.01 (m, 1H), 4.19, (m, 1H), 4.55, (m, 2H), 7.40-6.96 (m, 4H).
[0000]
Example 16
2-[4-(2-Fluorobenzyloxymethyl)-2,5-dioxo-imidazolidin-1-yl]-N-hydroxy-3-methyl-butyramide (16)
[0222] The procedure described in method B was followed, but using 2-fluorobenzyl bromide instead of 4-bromobenzyl bromide, which gave the title compound (21 mg).
[0223] 1 H-NMR (300 Hz, CD 3 OD): δ 0.77 (m, 3H), 0.96 (m, 3H), 3.30 (m, 1H), 3.75 (m, 1H), 3.84 (m, 1H), 4.18 (m, 1H), 4.60, (m, 2H), 7.37-7.05 (m, 4H).
Example 17
[0224]
2-[4-(4-Fluorobenzyloxymethyl)-2,5-dioxo-imidazolidin-1-yl]-N-hydroxy-3-methyl-butyramide (15)
[0225] The procedure described in method B was followed, but using 4-fluorobenzyl bromideinstead of 4-bromobenzyl bromide, which gave the title compound (9 mg).
[0226] 1 H-NMR (300 Hz, CD 3 OD): δ 0.78 (m, 3H), 0.93 (m, 3H), 2.82 (m, 1H), 3.72 (m, 1H), 3.84 (m, 1H), 4.06 (m, 1H), 4.18, (m, 1H), 4.52, (m, 2H), 7.12-7.03 (m, 2H), 7.38-7.29 (m, 2H).
[0000]
Example 18
2-[2,5-Dioxo-4-(3-trifluoromethyl-bezyloxymethyl)-imidazolidin-1-yl]-N-hydroxy-3-methyl-butyramide (18)
[0227] The procedure described in method B was followed, but using 3-(trifluoromethyl)benzyl bromide instead of 4-bromobenzyl bromide, which gave the title compound (14 mg).
[0228] 1 H-NMR (300 Hz, CD 3 OD): δ 0.76 (m, 3H), 0.96 (m, 3H), 2.84 (m, 1H), 3.77 (m, 1H), 3.87 (m, 1H), 4.00 (m, 1H), 4.21, (m, 1H), 4.60, (m, 2H), 7.60-7.54 (m, 4H).
[0000]
Example 19
2-(4-Benzyloxymethyl-2,5-dioxo-imidazolidin-1-yl)-N-hydroxy-3-methyl-butyramide (19)
[0229] The procedure described in method B was followed, but using benzyl bromide instead of 4-bromobenzyl bromide, which gave the title compound (11 mg).
[0230] 1 H-NMR (300 Hz, CDCl 3 ): δ 0.83 (d, J=6.6 Hz, 3H), 1.04 (d, J=6.6 Hz, 3H), 2.61 (m, 1H), 3.75 (m, 2H), 4.22 (m, 1H), 4.32 (d, J=11.4 Hz, 1H), 4.54 (m, 2H), 7.34 (m, 5H).
[0231] Method C
[0000]
Example 20
Step a
[0232]
2-[2-tert-Butoxycarbonylamino-3-(3′-fluorobiphenyl-4-ylmethoxy)-propionylamino]-3-methylbutyric acid methyl ester (20a)
[0233] A mixture of the compound obtained in Example 13, step d (948 mg, 1.951 mmol), Pd (PPh 3 ) 2 Cl 2 (136 mg, 0.1951 mmol) and 3-fluorophenylboronic acid (328 mg, 2.341 mmol) in toluene (10 mL) were stirred under an atmosphere of argon at room temperature. A solution of 2 M Na 2 CO 3 aqueous (4 mL) was added and the reaction were heated to reflux for 5 h. After cooling, the reaction was diluted with EtOAc and brine, the aqueous layer was extracted with EtOAc, and the combined organic layers were dried over anhydrous NaSO 4 and concentrated. The residue was purified by silica gel column chromatography to give the title compound as a white solid (813 mg, 83%).
Step b
[0234]
2-[4-(3′-Fluorobiphenyl-4-ylmethoxymethyl)-2,5-dioxo-imidazolidin-1-yl-3-methyl-butyric acid methyl ester (20b)
[0235] The compound obtained in step a above (20a) (813 mg, 1.619 mmol) was stirred in TFA (4 mL) at 0° C. for 5 h, then concentrated under vacuum. The residue was diluted with CH 2 Cl 2 , washed with saturated NaHCO 3 and brine, dried over anhydrous Na 2 SO 4 and concentrated which gave the crude product. The obtained crude product was stirred in dioxane (9 mL) and water (1 mL) at 0° C. DIEA (610 mg, 4.86 mmol) and phenyl chloroformate (379 mg, 2.429 mmol) were added, and the mixture was stirred for 2 h. The solvent was removed under vacuum; the residue was diluted with EtOAc and washed with brine. The combined organic layers were dried and concentrated to give a yellow oil. The obtained oil was then stirred with DIEA (610 mg, 4.86 mmol) in DMF (10 mL) for 24 h. After general workup, the crude product was purified by silica gel column chromatography which gave the title compound as a white solid (374 mg, 54% yield).
Step c
[0236]
2-[4-(3′-Fluorobiphenyl-4-ylmethoxymethyl)-2,5-dioxo-imidazolidin-1-yl-3-methyl-butyric acid (20c)
[0237] A mixture of the compound obtained in step b above (20b) (374 mg, 0.874 mmol) and 2 N HCl (15 mL) was refluxed for 2 h. The reaction mixture was cooled down and then extracted with EtOAc. The combined organic layer was dried and concentrated; the crude product was purified by silica gel column chromatography to give the title compound as colorless oil (166 mg, 46%).
Step d
[0238]
2-[4-(3′-Fluorobiphenyl-4-ylmethoxymethyl)-2,5-dioxo-imidazolidin-1-yl-N-hydroxy-3-methyl-butyramide (20d)
[0239] To a solution of the compound obtained in step c above (20c) (166 mg, 0.401 mmol) in DMF (5 mL) was added BOP reagent (213 mg, 0.481 mmol) at 0° C. After stirring for 30 min, HONH 2 xHCl (50 mg, 11.38 mmol) and N-methylmorpholine (0.15 mL, 1.34 mmol) were added. The mixture was warmed to room temperature and stirred overnight. The solvent was removed and the residue was partitioned between EtOAc and saturated NH 4 Cl solution. The aqueous layer was extracted with EtOAc, the organic layer was dried and concentrated. The residue was purified by silica gel column chromatography to afford the title compound as a white solid (60 mg, 35%).
[0240] 1 H-NMR (300 Hz, CD 3 OD): 0.82 (d, J=6.6 Hz, 3H), 0.97 (d, J=6.3 Hz, 3H), 2.82 (m, 1H), 3.76 (m, 1H), 3.84 (m, 1H), 4.03 (m, 1H), 4.20, (m, 1H), 4.58, (m, 2H), 7.61-7.58 (m, 3H), 7.45-7.37 (m, 5H).
Example 21
[0241]
2-[2,5-Dioxo-4-(4′-trifluoromethylbiphenyl-4-ylmethoxymethyl)-imidazolidin-1-yl-N-hydroxy-3-methyl-butyramide (21)
[0242] The procedure described in method C was followed, but using 4-(trifluoromethyl)phenylboronic acid instead of 3-fluorophenylboronic acid, which gave the title compound (6 mg).
[0243] 1 H-NMR (300 Hz, CD 3 OD): 0.82 (m, 3H), 0.96 (m, 3H), 2.82 (m, 1H), 3.72 (m, 1H), 3.76 (m, 1H), 4.01 (m, 1H), 4.21, (m, 1H), 4.59, (m, 2H), 7.43-7.40 (m, 2H), 7.82-7.64 (m, 4H).
[0244] Method D
[0000]
Example 22
Step a
[0245]
3-Hydroxy-2-(tritylamino)-propionic acid methyl ester (22a)
[0246] A solution of Et 3 N (13.4 mL, 96.78 mmol) in CH 2 Cl 2 (40 mL) was added to a solution of L-serine methyl ester hydrochloride (5.0 g, 32.26 mmol) and Ph 3 CCl (13.5 g, 48.39 mmol) in CH 2 Cl 2 (129 mL) at 0° C. under N 2 atmosphere. The reaction was then allowed to warm to room temperature and was stirred overnight. The reaction was quenched with saturated NaHCO 3 , the aqueous layer was extracted with CH 2 Cl 2 , and the combined organic layers were washed with brine, dried and concentrated, the residue was purified by silica gel column chromatography which gave the title compound as a colourless solid (11.41 g, 98%).
Step b
[0247]
3-(4-Bromophenoxy)-2-(tritylamino)-propionic acid methyl ester (22b)
[0248] Under N 2 atmosphere, to a solution of the solid obtained in step a above (4.17 g, 11.55 mmol), PPh 3 (3.72 g, 12.71 mmol) and 4-bromophenol (2.20 g, 12.71 mmol) in toluene (25 mL) was slowly added a solution of DEAD (2.21 g, 12.71 mmol) in toluene (20%). The reaction mixture was heated to 80° C. After being stirred for 3 days, the reaction was diluted with EtOAc, the organic layer was washed with 0.3 N HCl, saturated NaHCO 3 and brine. The solvent was removed under vacuum, and the residue was purified by silica gel column chromatography to give the title compound (4.41 g, 74%).
Step c
[0249]
2-Amino-3-(4-bromophenoxy)-propionic acid methyl ester (22c)
[0250] The compound obtained in step b above (22b) (2.21 g, 4.10 mmol) was stirred in TFA (8 mL) and CH 2 Cl 2 (10 mL) at 0° C.→rt for 1 h, the solvent was removed under vacuum. MeOH (10 mL) was added and then NaHCO 3 (344 mg, 4.10), the mixture was stirred at room temperature for 4 h and then concentrated. The residue was dissolved in CH 2 Cl 2 and washed with brine, dried and concentrated to give crude title compound (1.07 g, 91%).
Step d
[0251]
3-(4-Bromophenoxy)-2-tert-butoxycarbonylamino-propionic acid methyl ester (22d)
[0252] The crude product obtained in step c above (22c) was dissolved in CH 2 Cl 2 (30 mL), a solution of Boc 2 O (1.34 g, 6.15 mmol) in CH 2 Cl 2 (10 mL) and Et 3 N (1.15 mL, 8.20 mmol) was slowly added. After being stirred for 20 h, the reaction was quenched with saturated NaHCO 3 ; the aqueous phase was extracted with CH 2 Cl 2 . The combined organic layers were dried and concentrated. The residue was purified by silica gel column chromatography to give the title compound (1.32 g, 86% yield).
Step e
[0253]
3-(4-Bromophenoxy)-2-tert-butoxycarbonylamino-propionic acid (22e)
[0254] To a solution of the compound obtained in step d above (22d) (1.087 g, 2.91 mmol.) in THF (40 mL) at 0° C. was added a solution of LiOH H 2 O (244 mg, 5.82 mmol) in water (10 mL). After being stirred for 6 h, 0.5 N HCl (5 mL) was added and the reaction was concentrated under vacuum. The residue was diluted with EtOAc and washed with brine. The combined organic layers were dried over Na 2 SO 4 and concentrated; the residue was purified by silica gel column chromatography to give the title compound as a colourless oil (816 mg, 78% yield).
Step f
[0255]
2-[3-(4-Bromophenoxy)-2-tert-butoxycarbonylamino-propionylamino]-3-methyl-butyric acid methyl ester (22f)
[0256] A solution of the compound obtained in step e above (22e) (816 mg, 2.27 mmol), NMM (0.55 mL, 4.922 mmol) and HOBt (521 mg, 3.864 mmol) in DMF (10 mL) was stirred at 0° C. for 10 minutes, then the reaction was cooled to −15° C., and EDCI (478 mg, 2.497 mmol) was added. The reaction was stirred for 30 minutes at −15° C. and then allowed to warm to room temperature, (R)-methyl 2-amino-3-methylbutanoate hydrochloride (417 mg, 2.497 mmol) was added. After being stirred overnight, the reaction mixture was concentrated under vacuum; the residue was diluted with EtOAc and washed with brine. The combined organic layers were dried and concentrated; the residue was purified by silica gel column chromatography to give the title compound as colourless oil (900 mg, 84%).
Step g
[0257]
2-[4-(4-Bromophenoxymethyl)-2,5-dioxo-imidazolidin-1-yl]-3-methyl-butyric acid methyl ester (22g)
[0258] The compound obtained in step f above (22f) (900 mg, 1.907 mmol) was stirred in TFA (8 mL) at 0° C. for 5 h, and then concentrated under vacuum. The residue was diluted with CH 2 Cl 2 , washed with saturated NaHCO 3 and brine, dried over anhydrous Na 2 SO 4 , concentrated to give the crude product. The obtained crude product was stirred in dioxane (9 mL) and water (1 mL) at 0° C., DIEA (737 mg, 5.72 mmol) and phenyl chloroformate (446 mg, 2.861 mmol) were added, and the mixture was stirred for 1.5 h. The solvent was removed under vacuum; the residue was diluted with EtOAc and washed with brine. The combined organic layers were dried and concentrated to give a yellow oil. The obtained oil was then stirred with DIEA (737 mg, 5.72 mmol) in DMF (10 mL) for 24 h. After general workup, the crude product was purified by silica gel column chromatography to give the title compound as colorless oil (245 mg, 32% from step f).
[0259] Step h
[0000]
2-[4-(4-Bromophenoxymethyl)-2,5-dioxo-imidazolidin-1-yl]-3-methyl-butyric acid (22h)
[0260] A mixture of the compound obtained in step g above (22g) (759 mg, 1.907 mmol) and 3 N HCl (20 mL) was stirred at 80° C. for 2 h. The reaction mixture was cooled down and then extracted with EtOAc. The combined organic layers were dried and concentrated; the crude product was purified by silica gel column chromatography which gave the title compound as colorless oil (300 mg, 41%).
Step i
[0261]
N-benzyloxy-2-[4-(4-bromophenoxymethyl)-2,5-dioxo-imidazolidin-1-yl]-3-methylbutyramide (22i)
[0262] A solution of the compound obtained in step h above (22h) (300 mg, 0.782 mmol), NMM (0.19 mL, 1.72 mmol) and HOBt (179 mg, 1.329 mmol) in DMF (11 mL) were stirred at 0° C. for 10 minutes, then the reaction was cooled to −15° C., and EDCI (165 mg, 0.860 mmol) was added. The reaction was stirred for 30 minutes at −15° C. and then allowed to warm to room temperature, BnONH 2 HCl (137 mg, 0.860 mmol) was added. After being stirred overnight, the reaction mixture was concentrated under vacuum, and the residue was diluted with EtOAc and washed with brine. The combined organic layers were dried and concentrated; the residue was purified by silica gel column chromatography which gave the title compound as colorless oil (426 mg, 83% yield).
Step j
[0263]
2-[4-(4-Bromophenoxymethyl)-2,5-dioxo-imidazolidin-1-yl]-N-hydroxy-3-methylbutyramide (22j)
[0264] The oil obtained in step i above (22i) (271 mg, 0.571 mmol)and 10% Pd/C (31 mg) were stirred in MeOH (25 mL) at room temperature for 3 h under H 2 atmosphere, the mixture was filtered through celite, washed with MeOH for several times and then concentrated. The residue was purified by silica gel column chromatography which gave the title compound as an oil (118 mg, 52% yield). % yield).
[0265] 1 H NMR (300 MHz, CD 3 OD): δ 0.95 (d, J=6.6 Hz, 3H), 1.02 (d, J=6.6 Hz, 3H), 2.83-3.01 (m, 1H), 4.07 (d, J=10.8 Hz, 1H), 4.23-4.29 (dd, J 1 =2.7 Hz, J 2 =13.5 Hz, 2H), 4.40 (s, 1H), 6.84 (d, J=9.3 Hz, 2H), 7.38 (d, J=9.3 Hz, 2H).
Example 23
[0266]
2-(2,5-Dioxo-4-phenoxymethyl-imidazolidin-1-yl)-N-hydroxy-3-methyl-butyramide (23)
[0267] The procedure described in method D was followed, but using phenol instead of 4-bromophenol, which gave the title compound (7 mg).
[0268] 1 H-NMR (300 Hz, CD 3 OD): 1.04-0.96 (m, 6H), 2.95 (m, 1H), 4.10 (m, 1H), 4.29-4.24 (m, 21H), 4.40 (m, 1H), 7.28-6.87 (m, 5H).
[0269] Method E
[0000]
Example 24
Step a
[0270]
2-[2-tert-Butoxycarbonylamino-3-(4-phenyl-cyclohexa-1,5-dienyloxy)-propionylamino]-3-methylbutyric acid methyl ester (24a)
[0271] A solution of 2 M Na 2 CO 3 (4 mL)was added at room temperature under an atmosphere of Argon to a mixture of the compound obtained in Example 22, step f (401 mg, 0.848 mmol), Pd(PPh 3 ) 2 Cl 2 (154 mg, 0.22 mmol) and phenylboronic acid (145 mg, 1.1872 mmol) in toluene (10 mL) and the reaction was heated to reflux. After 5 h, the reaction was cooled to room temperature. The mixture was diluted with EtOAc, and washed with brine. The combined organic layers were dried over anhydrous NaSO 4 and concentrated under vacuum. The residue was purified by silica gel column chromatography which gave the title compound as a white solid (255 mg, 64%).
Step b
[0272]
2-[4-(Biphenyl-4-yloxymethyl)-(2,5-dioxo-imidazolidin-1-yl]-3-methyl-butyric acid methyl ester (24b)
[0273] The compound obtained in step a (24a) above (764 mg, 1.626 mmol) was stirred in TFA (10 mL) at 0° C. for 5 h, then concentrated under vacuum. The residue was diluted with CH 2 Cl 2 , washed with saturated NaHCO 3 and brine, dried over anhydrous Na 2 SO 4 and concentrated which gave the crude product. The obtained crude product was stirred in dioxane (9 mL) and water (1 mL) at 0° C., DIEA (629 mg, 4.878 mmol) and phenyl chloroformate (382 mg, 2.43 mmol) were added, and the mixture was stirred for 2 h. The solvent was removed under vacuum; the residue was diluted with EtOAc and washed with brine. The combined organic layers were dried and concentrated to give a yellow oil. The obtained oil was then stirred with DIEA (629 mg, 4.878 mmol) in DMF (10 mL) for 30 h. After general workup, the crude product was purified by silica gel column chromatography which gave the title compound as colourless oil (328 mg, 51%).
Step c
[0274]
2-[4-(Biphenyl-4-yloxymethyl)-(2,5-dioxo-imidazolidin-1-yl]-3-methyl-butyric acid (24c)
[0275] A mixture of the compound obtained in step b above (24b) (320 mg, 0.808 mmol) and 3 N HCl (15 mL) was stirred at 80° C. for 4 h. The reaction mixture was cooled down and then extracted with EtOAc. The combined organic layers were dried and concentrated; the crude product was purified by silica gel column chromatography which gave the title compound as colourless oil (96 mg, 31%).
Step d
[0276]
N-Benzyloxy-2-[4-(biphenyl-4-yloxymethyl)-(2,5-dioxo-imidazolidin-1-yl]-3-methylbutyramide (24d)
[0277] A solution of the compound obtained in step c above (96 mg, 0.250 mmol), NMM (0.05 mL, 0.448 mmol) and HOBt (58 mg, 0.426 mmol) in DMF (6 mL) were stirred at 0° C. for 10 minutes, then the reaction was cooled to −15° C., and EDCI (53 mg, 0.275 mmol) was added. The reaction was stirred for 30 minutes at −15° C. and then allowed to warm to room temperature, BnONH 2 HCl (44 mg, 0.275 mmol) was added. After being stirred overnight, the reaction mixture was concentrated under vacuum, the residue was diluted with EtOAc and washed with brine. The combined organic layers were dried and concentrated, the residue was purified by silica gel column chromatography which gave the title compound as colourless oil (92 mg, 76%).
Step e
[0278]
2-[4-(Biphenyl-4-yloxymethyl)-(2,5-dioxo-imidazolidin-1-yl]-N-hydroxy-3-methylbutyramide (24e)
[0279] The oil obtained in step d above (24d) (90 mg, 0.185 mmol) and 10% Pd/C (12 mg) were stirred in MeOH (15 mL) at room temperature for 3 h under H 2 atmosphere. The mixture was filtered through celite, washed with MeOH several times and then concentrated. The residue was purified by silica gel column chromatography which gave the title compound as an oil (32 mg, 44%).
[0280] 1 H NMR (300 MHz, CD 3 OD): δ 0.99 (d, J=6.6 Hz, 3H), 1.04 (d, J=6.6 Hz, 3H), 2.82-2.98 (m, 1H), 4.11 (d, J=10.8 Hz, 1H), 4.25-4.40 (m, 2H), 4.43 (s, 1H), 6.98 (d, 2H), 7.22-7.42 (m, 3H), 7.50-7.58 (m, 4H).
Method F
[0281]
Example 25
Step a
[0282]
2-Amino-6-benzoylamino-hexanoic acid (25a)
[0283] To a solution of L-lysine (1) (3.65 g, 0.02 mol) in water (50 mL) at 90° C. was added CuCO 3 (2.5 g) portionwise. After being refluxed for 40 min, the mixture was cooled and filtered. The filtrate was further cooled to 0° C., and a solution of BzCl (3.5 mL, 0.03 mol) and NaOH (2.7 g, 0.0685 mol) in water (20 mL) were added. The reaction was stirred at 0° C. for 1 h and then allowed to warm to room temperature. After 2 days, the reaction mixture was filtered and the solid was washed with water and Et 2 O. This obtained solid was then added to a solution of EDTA (7.0 g) in water (350 mL), the mixture was heated to reflux until the reaction solution became clear blue. The reaction was cooled which gave a white precipitate. This precipitate was collected and washed with water and Et 2 O and dried which afforded the title compound as a white solid (1.8 g, 36%).
Step b
[0284]
6-Benzoylamino-2-tert-butoxycarbonylamino-hexanoic acid (25b)
[0285] To a solution of the compound obtained in step a above (1.0 g, 4.0 mmol) Et 3 N (0.92 mL, 6.6 mmol) and dioxane/H 2 O (1:1, v/v) (40 mL) at 0° C. was added Boc 2 O (0.96 g, 4.4 mmol). The reaction was allowed to warm to room temperature and stirred overnight. The solvent was removed and the residue was partitioned between water and EtOAc. The aqueous layer was acidified and extracted with EtOAc, and the combined organic phases were dried over anhydrous Na 2 SO 4 . After concentration under vacuum, the crude title compound (1.4 g) was obtained and used in the next reaction without further purification.
Step c
[0286]
6-Benzoylamino-2-tert-butoxycarbonylamino-hexanoylamino)-3-methyl-butyric acid methyl ester (25c)
[0287] EDCI (1.26 g, 6.6 mmol) was added at −15° C. to a mixture of the compound obtained in step b above (25b) (1.0 g, 3.0 mmol), NaHCO 3 (0.83 g, 9.8 mmol) and HOBt (1.15 g, 7.5 mmol) in DMF (30 mL). The reaction was stirred for 30 minutes, and then it was allowed to warm to room temperature. (R)-Methyl 2-amino-3-methylbutanoate hydrochloride (0.58 g, 3.3 mmol) was then added and the reaction was stirred overnight. The solvent was removed under vacuum; the residue was diluted with EtOAc and washed with brine. The combined organic layers were dried and concentrated; the crude product was purified by silica gel column chromatography which gave the title compound as a white solid (1.1 g, 79%).
Step d
[0288]
2-(2-Amino-6-benzoylamino-hexanoylamino)-3-methyl-butyric acid methyl ester (25d)
[0289] A mixture of the compound obtained in step c above (1.0 g, 2.1 mmol) and HCO 2 H (20 mL) in CHCl 3 (15 mL) was stirred at room temperature overnight. The reaction was diluted with CH 2 Cl 2 and NaHCO 3 was added to adjust the pH to 8. The organic layer was washed with brine, dried and concentrated to give crude title compound as a colorless oil (0.6 g, 78% yield).
Step e
[0290]
2-[4-(Benzoylamino-butyl)-(2,5-dioxo-imidazolidin-1-yl]-3-methyl-butyric acid methyl ester (25e)
[0291] To a mixture of the crude compound obtained in step d above (25d) (0.6 g, 1.65 mmol) in dioxane (18 mL) and water (2 mL) was added phenyl chloroformate (0.21 mL, 1.65 mmol) and DIEA (0.6 mL, 3.3 mmol). The mixture was stirred at room temperature for 3 h and concentrated under reduced pressure. The residue was partitioned between water and EtOAc. The aqueous layer was extracted with EtOAc, the combined organic phases were dried and concentrated which gave a white solid (0.79 g). This white solid was dissolved in DMF (20 mL), and DIEA (0.28 mL, 1.6 mmol) was added. After stirring overnight at room temperature, the solvent was removed. The residue was diluted with EtOAc and washed with water. The organic layer was dried and concentrated under reduced pressure. The residue was purified by silica gel column chromatography which afforded the title compound as a colorless oil (0.43 g, 69%).
[0000]
Step f
2-[4-(Benzoylamino-butyl)-(2,5-dioxo-imidazolidin-1-yl]-3-methyl-butyric acid (25f)
[0292] A mixture of the compound obtained in step e above (25f) (0.21 g, 0.54 mmol) and 6 N HCl (5 mL) was heated at 70° C. for 6 h. The reaction was diluted with water and extracted with CH 2 Cl 2 . The organic layer was washed with brine, dried over Na 2 SO 4 , and concentrated under vacuum which gave the title compound as a crude oil (0.2 g, 98%).
Step g
[0293]
N-{4-[1-(1-Benzyloxycarbamoyl-2-methyl-propyl)-(2,5-dioxo-imidazolidin-4-yl]-butyl}-benzamide (25g)
[0294] A solution of the compound obtained in step f above (25f) (200 mg, 0.53 mmol), NMM (0.15 mL, 1.3 mmol) and HOBt (98 mg, 0.64 mmol) in DMF (5 mL) was stirred at 0° C. for 15 minutes, then the reaction was cooled to −15° C., and EDCI (123 mg, 0.64 mmol) was added. The reaction was stirred for 30 minutes at −15° C. and then allowed to warm to room temperature and BnONH 2 HCl (102 mg, 0.64 mmol) was added. After being stirred overnight, the reaction mixture was concentrated under vacuum; the residue was diluted with EtOAc and washed with brine. The combined organic layers were dried and concentrated, the residue was purified by silica gel column chromatography which gave the title compound as a white solid (150 mg, 59%).
Step h
[0295]
N-{4-[1-(1-Hydroxycarbamoyl-2-methyl-propyl)-(2,5-dioxo-imidazolidin-4-yl]-butyl}-benzamide (25h)
[0296] The compound obtained in step g above (25g) (150 mg, 0.312 mmol) and 10% Pd/C (20 mg) were stirred in MeOH (10 mL) at room temperature for 15 h under H 2 atmosphere, the mixture was filtered through celite, washed with MeOH several times and then concentrated. The residue was purified by silica gel column chromatography which gave the title compound as a white solid (50 mg, 41%).
[0297] 1 H NMR (300 MHz, CD 3 OD+CDCl 3 ): δ 0.86 (d, 3H, J=6.9 Hz,), 1.02 (d, 2H, J=6.9 Hz), 1.46-1.91 (m, 6H), 2.83-2.86 (m, 1H), 3.34-3.42 (m, 2H), 4.04-4.08 (m, 2 H), 7.41-7.82 (m, 5H).
Example 26
[0298]
2-{2,5-Dioxo-4-[2-(4-phenoxyphenyl)-ethyl]-imidazolidin-1-yl}-N-hydroxy-3-methyl-butyramide (26)
[0299] The procedure described in method A was followed but using 2-tert-butoxycaronylamino-4-(4-phenyoxyphenyl)-butyric acid instead of N-boc-homophenylalanine which gave the title compound (8 mg).
[0300] 1 H NMR (300 MHz, CDCl 3 ): δ 0.82-1.02 (dd, J 1 =6.3 Hz, J 2 =53.4 Hz, 6H),1.90-2.30 (m, 2H), 2.60-2.80 (m, 3H), 4.00-4.08 (m, 1H), 4.19-4.24 (d, J=10.8 Hz, 1H), 6.59 (s, 1H), 6.91-6.99 (m, 4H), 7.05-7.4-0 (m, 5H).
Example 27
Preparation of Substituted N-Boc-L-Homophenylalanine Derivatives
[0301]
Step a
[0302] A series of substituted homophenylalanine derivatives were synthesized by coupling of the corresponding substituted aryl iodide to 2-tert-butoxy-carbonylamino-4-iodobutyric acid according to the procedure described in J. Org. Chem. 1998, 63, 7875.
Step b
[0303] To a solution of the compound obtained in step a above in 1,4-dioxane was added 2N NaOH. After stirring at room temperature for 3 h, the reaction was diluted with EtOAc. The mixture was acidified by slow addition of 1N HCl to PH 6, and then extracted with EtOAc. The organic phases were washed with brine, dried and concentrated. The residue was purified by silica gel column chromatography to afford the acid derivatives 27a-27m.
[0000]
Example 28
[0304]
2-[2,5-Dioxo-4-(2-o-tolylethyl)-imidazolidin-1-yl]-N-hydroxy-3-methyl-butyramide (28)
[0305] The procedure described in method A was followed but using 27a instead of N-boc-L-homophenylalanine which gave the title compound (8 mg).
[0306] 1 H NMR (300 MHz, CDCl 3 ): δ 0.90 (d, J=6.6 Hz, 3H), 1.12 (d, J=6.6 Hz, 3H), 1.91-2.03 (m, 1H), 2.07-2.23 (m, 1H), 2.29 (s, 3H), 2.60-2.80 (m, 3H), 4.09-4.16 (m, 1H), 4.37 (d, J=8.7 Hz, 1H), 6.78 (s, 1H), 7.13 (m, 4H).
Example 29
[0307]
2-[2,5-Dioxo-4-(2-m-tolylethyl)-imidazolidin-1-yl]-N-hydroxy-3-methyl-butyramide (29)
[0308] The procedure described in method A was followed but using 27b instead of N-boc-L-homophenylalanine which gave the title compound (13 mg).
[0309] 1 H NMR (300 MHz, CDCl 3 ): δ 0.83 (d, J=6.6 Hz, 3H), 1.01 (d, J=6.6 Hz, 3H), 1.90-2.01 (m, 1H), 2.21-2.29 (m, 1H), 2.32 (s, 3H), 2.62-2.76 (m, 3H), 4.02-4.04 (m, 1H), 4.21 (d, J=11.4 Hz, 1H), 6.52 (s, 1H), 6.98-7.05 (m, 3H), 7.17-7.27 (m, 1H), 8.32 (s, br, 1H), 10.11 (s, 1H).
Example 30
[0310]
2-[2,5-Dioxo-4-(2-p-tolylethyl)-imidazolidin-1-yl]-N-hydroxy-3-methyl-butyramide (30)
[0311] The procedure described in method A was followed but using 27c instead of N-boc-L-homophenylalanine which gave the title compound (12 mg).
[0312] 1 H NMR (300 MHz, CD 3 OD): δ 0.88 (d, J=6.6 Hz, 3H), 1.01 (d, J=6.6 Hz, 3H), 1.86-1.93 (m, 1H), 2.04-2.09 (m, 1H), 2.28 (s, 3H), 2.66 (t, J=7.8 Hz, 2H), 2.86-2.92 (m, 1H), 4.01-4.06 (m, 2H), 7.08 (s, 4H).
[0000]
Example 31
N-Hydroxy-2-{4-[2-(2-methoxyphenyl)-ethyl]-2,5-dioxo-imidazolidin-1-yl}-3-methyl-butyramide (31)
[0313] The procedure described in method A was followed but using 27d instead of N-boc-L-homophenylalanine which gave the title compound (11 mg).
[0314] 1 H NMR (300 MHz, CD 3 OD): δ 0.89 (d, J=6.6 Hz, 3H), 1.04 (d, J=6.6 Hz, 3H), 1.84-1.97 (m, 1H), 2.09-2.21 (m, 1H), 2.72-2.91 (m, 3H), 3.84 (s, 3H), 3.97-4.01 (m, 1H), 4.08 (d, J=10.8 Hz, 1H), 6.87-6.91 (m, 2H), 7.14-7.23 (m, 2H), 7.58 (s, 1H).
[0000]
Example 32
N-Hydroxy-2-{4-[2-(3-methoxyphenyl)-ethyl]-2,5-dioxoimidazolidin-1-yl}-3-methylbutyramide (32)
[0315] The procedure described in method A was followed but using 27e instead of N-boc-L-homophenylalanine which gave the title compound (8 mg).
[0316] 1 H NMR (300 MHz, CD 3 OD): δ 0.91 (d, J=6.6 Hz, 3H), 1.04 (d, J=6.6 Hz, 3H), 1.91-1.98 (m, 1H), 2.09-2.14 (m, 1H), 2.71 (t, J=8.1Hz, 2H), 2.91-2.95 (m, 1H), 3.79 (s, 3H), 4.05-4.09 (m, 2H), 6.76-6.82 (m, 3H), 7.18-7.23 (m, 1H).
Example 33
[0317]
N-Hydroxy-2-{4-[2-(4-methoxyphenyl)-ethyl]-2,5-dioxoimidazolidin-1-yl}-3-methylbutyramide (33)
[0318] The procedure described in method A was followed but using 27f instead of N-boc-L-homophenylalanine which gave the title compound (11 mg).
[0319] 1 H NMR (300 MHz, CD 3 OD): δ 0.91 (d, J=6.6 Hz, 3H), 1.04 (d, J=6.6 Hz, 3H), 1.88-1.95 (m, 1H), 2.04-2.11 (m, 1H), 2.68 (t, J=8.1Hz, 2H), 2.90-2.98 (m, 1H), 3.78 (s, 3H), 4.06-4.09 (m, 2H), 6.86 (d, J=8.1Hz, 2H), 7.15 (d, J=8.1Hz, 2H).
Example 34
[0320]
2-{4-[2-(4-Ethylphenyl)-ethyl]-2,5-dioxoimidazolidin-1-yl}-N-hydroxy-3-methyl-butyramide (34)
[0321] The procedure described in method A was followed but using 27g instead of N-boc-L-homophenylalanine which gave the title compound (14 mg).
[0322] 1 H NMR (300 MHz, CDCl 3 ): δ 0.82 (d, J=6.6 Hz, 3H), 1.00 (d, J=6.6 Hz, 3H), 1.21 (t, J=7.5 Hz, 3H), 1.90-2.03 (m, 1H), 2.21-2.27 (m, 1H), 2.61 (q, J=7.5 Hz, 2H), 2.68-2.76 (m, 3H), 4.03 (s, br, 1H), 4.22 (d, J=11.4 Hz, 1H), 6.42 (s, 1H), 7.10-7.26 (m, 4H), 8.24 (s, br, 1H), 10.09 (s, br, 1H).
Example 35
[0323]
2-{4-[2-(4-tert-Butylphenyl)-ethyl]-2,5-dioxoimidazolidin-1-yl}-N-hydroxy-3-methylbutyramid (35)
[0324] The procedure described in method A was followed but using 27h instead of N-boc-L-homophenylalanine which gave the title compound (13 mg).
[0325] 1 H NMR (300 MHz, CDCl 3 ): δ 0.82 (d, J=6.3 Hz, 3H), 1.00 (d, J=6.3 Hz, 3H), 1.29 (s, 9H), 1.90-2.04 (m, 1H), 2.20 (m, 1H), 2.62-2.73 (m, 3H), 4.05-4.10 (m, 1H), 4.18-4.28 (m, 1H), 6.64 (s, 1H), 7.12 (d, J=8.1Hz, 2H), 7.31 (d, J=8.1Hz, 2H), 8.35 (s, br, 1H), 10.12 (s, br, 1H).
Example 36
[0326]
2-{4-[2-(2-Fluorophenyl)-ethyl]-2,5-dioxoimidazolidin-1-yl}-N-hydroxy-3-methylbutyramide (36)
[0327] The procedure described in method A was followed but using 27i instead of N-boc-L-homophenylalanine which gave the title compound (7 mg).
[0328] 1 H NMR (300 MHz, CD 3 OD): δ 0.91 (d, J=6.6 Hz, 3H), 1.04 (d, J=6.6 Hz, 3H), 1.91-2.02 (m, 1H), 2.05-2.13 (m, 1H), 2.75-2.81 (m, 2H), 2.90-2.98 (m, 1H), 4.06-4.13 (m, 2H), 7.03-7.14 (m, 2H), 7.21-7.29 (m, 2H).
Example 37
[0329]
2-{4-[2-(3-Fluoro-phenyl)-ethyl]-2,5-dioxoimidazolidin-1-yl}-N-hydroxy-3-methylbutyramide (37)
[0330] The procedure described in method A was followed but using 27j instead of N-boc-L-homophenylalanine which gave the title compound (15 mg).
[0331] 1 H NMR (300 MHz, CD 3 OD): δ 0.87 (d, J=6.9 Hz, 3H), 1.00 (d, J=6.9 Hz, 3H), 1.88-1.96 (m, 1H), 2.06-2.10 (m, 1H), 2.71 (t, J=8.1Hz, 2H), 2.86-2.92 (m, 1H), 4.01-4.06 (m, 2H), 6.87-7.03 (m, 3H), 7.24-7.29 (m, 1H).
Example 38
[0332]
2-{4-[2-(4-Fluoro-phenyl)-ethyl]-2,5-dioxoimidazolidin-1-yl}-N-hydroxy-3-methylbutyramide (38)
[0333] The procedure described in method A was followed but using 27k instead of N-boc-L-homophenylalanine which gave the title compound (11 mg).
[0334] 1 H NMR (300 MHz, CD 3 OD): δ 0.88 (d, J=6.9 Hz, 3H), 1.01 (d, J=6.9 Hz, 3H), 1.91-1.95 (m, 1H), 2.05-2.10 (m, 1H), 2.70 (t, J=7.8 Hz, 2H), 2.89-2.93 (m, 1H), 4.03-4.06 (m, 2H), 6.97-7.03 (m, 2H), 7.20-7.24 (m, 2H).
Example 39
[0335]
2-{4-[2-(4-Benzylphenyl)-ethyl]-2,5-dioxoimidazolidin-1-yl}-N-hydroxy-3-methylbutyramide (39)
[0336] The procedure described in method A was followed but using 271 instead of N-boc-L-homophenylalanine which gave the title compound (12 mg).
[0337] 1 H NMR (300 MHz, CDCl 3 ): δ 0.82 (d, J=6.6 Hz, 3H), 1.01 (d, J=6.6 Hz, 3H), 1.88-2.00 (m, 1H), 2.15-2.28 (m, 1H), 2.60-2.76 (m, 3H), 3.95 (s, 2H), 4.00-4.04 (m, 1H), 4.22 (d, J=11.7 Hz, 1H), 6.23 (s, 1H), 7.12-7.31 (m, 9H), 8.12 s, br, 1H), 10.10 (s, 1H).
Example 40
[0338]
2-{2,5-Dioxo-4-[2-(4-phenylacetyl-phenyl)-ethyl]-imidazolidin-1-yl}-N-hydroxy-3-methylbutyramide (40)
[0339] The procedure described in method A was followed but using 27m instead of N-Boc-L-homophenylalanine which gave the title compound (7 mg.)
[0340] 1 H NMR (300 MHz, CD 3 OD): δ 0.91 (d, J=6.6 Hz, 3H), 1.04 (d, J=6.6 Hz, 3H), 1.98-2.03 (m, 1H), 2.12-2.16 (m, 1H), 2.78-2.83 (m, 2H), 2.91-2.95 (m, 1H), 4.05-4.11 (m, 2H), 4.33 (s, 2H), 7.23-7.38 (m, 7H), 8.01 (d, J=7.8 Hz, 2H).
[0000]
Example 41
N-Hydroxy-2-(4-{2-[4-(1-hydroxyimino-2-phenyl-ethyl)-phenyl]-ethyl}-2,5-dioxoimidazolidin-1-yl)-3-methylbutyramide (41)
[0341] To a solution compound 40 (140 mg, 0.32 mmol) in CHCl 3 /CH 3 OH (10 mL) was added HONH 2 ×HCl (44 mg, 0.64 mmol) and N-methylmorpholine (0.071 mL, 0.64 mmol). After stirring for 5 min, one drop of CH 3 COOH was added and the reaction was stirred overnight at room temperature. The solvent was removed and the residue was purified by preparative thin layer chromatography to afford the title compound as a white solid (20 mg).
[0342] 1 H NMR (300 MHz, CD 3 OD): δ 0.89 (d, J=6.6 Hz, 3H), 1.03 (d, J=6.6 Hz, 3H), 1.89-1.96 (m, 1H), 2.08-2.11 (m, 1H), 2.68-2.73 (m, 2H), 2.91-2.94 (m, 1H), 4.04-4.07 (m, 2H), 4.19 (s, 2H), 7.17-7.24 (m, 7H), 7.57 (d, J=7.5 Hz, 2H).
[0000]
Example 42
2-(2,5-Dioxo-4-phenethyl-imidazolidin-1-yl)-N-hydroxy-3-methoxybutyramide (42)
[0343] The procedure described in method A was followed but using (R)-methyl 2-amino-3-methoxybutanoate instead of D-valine methyl ester hydrochloride which gave the title compound (6 mg).
[0344] 1 H NMR (300 MHz, CDCl 3 ): δ 1.13 (d, J=6.3 Hz, 3H), 2.01-1.91 (m, 1H), 2.19-2.10 (m, 1H), 2.74-2.69 (m, 2H), 3.40 (s, 3H), 4.11-4.04 (m, 1H), 4.33-4.26 (m, 1H), 4.51-4.46 (m, 1H), 6.83 (s, 1H), 7.30-7.16 (m, 5H), 8.46-8.24 (m, 1H), 9.77 (s, 1H).
Example 43
[0345]
N-hydroxy-3-methyl-2-hydroxy-(5-oxo-4-phenethyl-2-thioxo-imidazolidin-1-yl)-butyramide
[0346] Method H
[0000]
Step a
[0347]
[0348] Under nitrogen, to a solution of 1b (440 mg, 1.50 mmol) in CH 2 Cl 2 (15 mL) prepared according to Method A above, was added 1,1′-thiocarbonyldiimidazole (1.34 g, 7.52 mmol). The mixture was stirred at room temperature for 3 h and concentrated under reduced pressure. The residue was diluted with EtOAc and washed with brine. The putative diastereomers at the valine alpha carbon co-migrate under TLC and were confirmed by NMR below. The organic layer was dried and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to afford the title compound as a pale yellow oil (200 mg, 40%).
[0349] 1 H NMR (300 MHz, CDCl 3 ): δ 0.87, 0.88 (for two epimers, d, J=6.6 Hz, 3H), 1.20, 1.21 (for two epimers, d, J=6.6 Hz, 3H), 2.01-2.12 (m, 1H), 2.21-2.33 (m, 1H), 2.72-2.85 (m, 3H), 3.71 (s, 3H), 4.08-4.16 (m, 1H), 4.92, 4.94 (for two epimers, d, J=9.0 Hz, 1H), 7.19-7.36 (m, 5H).
[0000]
Step b
[0350] To a solution of the above obtained compound (200 mg, 0.6 mmol) in dioxane (2.5 mL) was added 10 mL of 6N HCl. The mixture was stirred at 90° C. for 2 days. The reaction solvent was removed under reduced pressure. The residue was purified by flash silica gel column chromatography to afford the title compound as a pale yellow oil (160 mg, 83%).
[0351] 1 H NMR (300 MHz, CDCl 3 ): δ 0.88 (d, J=6.6 Hz, 3H), 1.21 (d, J=6.6 Hz, 3H), 1.94-2.06 (m, 1H), 2.16-2.30 (m, 1H), 2.57-2.88 (m, 3H), 4.04-4.14 (m, 1H), 4.99, 5.01 (for two epimers, d, J=9.3 Hz, 1H), 7.16-7.32 (m, 5H), 8.57 (d, J=10.8 Hz, 1H), 9.84 (s, br, 1H).
Step c
[0352]
[0353] A solution of the above obtained compound (160 mg, 0.50 mmol) in DMF (5 mL) was added N-methylmorpholine (0.23 mL, 2.09 mmol). The mixture was cooled to 0 degrees and BOP (250 mg, 0.57 mmol) added. After stirring for 30 min at 0 degrees HONH 2 ×HCl (73 mg, 1.04 mmol) was added. The reaction was then allowed to warm to room temperature and stirred overnight. The reaction solvent was removed under reduced pressure. The residue was diluted with EtOAc, washed with 1N HCl, saturated NaHCO 3 and brine, dried over anhydrous Na 2 SO 4 , and concentrated under reduced pressure. The obtained residue was carefully purified by silica gel column chromatography to afford two epimers of the title compound both as a pale yellow oil (60+60 mg, 72%). Conventional preparative HPLC would allow purification of the diastereomers.
[0354] Less polar epimer: 1 H NMR (300 MHz, CD 3 OD): δ 0.88 (d, J=6.6 Hz, 3H), 1.07 (d, J=6.6 Hz, 3H), 1.95-2.17 (m, 2H), 2.61-2.76 (m, 2H), 3.06-3.14 (m, 1H), 4.16 (t, J=5.1Hz, 1H), 4.79 (d, J=11.1Hz, 1H), 7.15-7.30 (m, 5H).
[0355] More polar epimer: 1 H NMR (300 MHz, CD 3 OD): δ 0.88 (d, J=6.6 Hz, 3H), 1.07 (d, J=6.6 Hz, 3H), 1.91-2.18 (m, 2H), 2.65-2.77 (m, 2H), 3.01-3.11 (m, 1H), 4.10 (dd, J=5.1Hz, 7.2 Hz, 1H), 4.89 (d, J=11.1Hz, 1H), 7.16-7.32 (m, 5H).
Biological Examples
[0356] A typical MMP-12 enzyme assay employs recombinant human MMP-12 catalytic domain expressed and purified as described by Parkar A. A. et al, (2000), Protein Expression and Purification, 20:152. The purified enzyme can be used to monitor inhibitors of activity as follows: MMP-12 (50 ng/ml final concentration) is incubated for 60 minutes at room temperature with the synthetic substrate Mac-Pro-Cha-Gly-Nva-His-Ala-Dpa-NH 2 in assay buffer (0.1 M “Tris-HCl” (trade mark) buffer, pH 7.3 containing 0.1 M NaCl, 20 mM CaCl 2 , 0.020 mM ZnCl and 0.05% (w/v) “Brij 35” (trade mark) detergent) in the presence (5 concentrations) or absence of inhibitors. Activity is determined by measuring the fluorescence at λ ex 320 nm and λ em 405 nm. Percent inhibition is calculated as follows: % Inhibition is equal to the (Fluorescence plus inhibitor −Fluorescence background ); divided by the (Fluorescence minus inhibitor −Fluorescence background );
[0357] A favoured assay employs full length recombinant human MMP-12, amino acid residues 1 to 470 (Shapiro et al 1993, J Biol Chem 268:23824-23829) expressed in mouse myeloma cell line NS-40. The purified rhMMP-12 typically has the N terminal sequence L 17 PLNSSTSLE and an SDS-PAGE apparent molecular mass of approx. 56 kDa. Such proteins are available from R&D Systems, USA as a lyophilised 0.2 um filtered solution of 25 mM MES, 0.15M NaCl, 10 mMCaCl 2 , 0.15% Brij 35, pH 5.5. Auto-activation of the rhMMP-12 can be achieved by dilution to 0.05 mg/ml into TCNB buffer (50 mMTris, 10 mM CaCl 2 , 0.15M NaCl, 0.05% Brij 35, pH 7) and incubation at 37 degrees for 30 hours. A preferred buffer for MMP work is 50 mM Tris.HCl, pH 7.5, 200 mM Ca acetate.
[0358] Suitable FRET substrates include (7-methoxycoumarin-4-yl)acetyl-Pro-Leu-Gly-Leu-(3-(2,4-dinitrophenoyl)-L-2,3-diaminopropionyl)-Ala-Arg-NH 2 , commercially available from R&D Systems, USA. Typical specific activities are >500 picomol/min/ug, with rhMMP-12 measured with 10 uM of this substrate, 20 ng activated enzyme in 100 ul TCNB buffer at room temperature.
[0359] An alternative general MMP substrate is Dnp-PLGLWλ D —R—NH 2 .
[0360] Counterscreening for MMP selectivity is carried out analogously to the above using commercially available recombinant enzymes (R& D Systems USA) such as MMP-1, 2 & 9 (same substrate as MMP-12) or 3 & 10 (substrate: Mca-RPKPVE-Nva-WRK(Dnp)-AR-NH 2 ).
[0361] For example, Table 1 shows the Ki-value expressed in nM for a representative selection of compounds according to the invention when tested in an MMP-12 enzyme assay such as those described above. Category A indicates ≦50 nM inhibition, category B indicates 51-200 nM inhibition and category C indicates >200 nM:
[0000]
Example No.
Ki
7
B
10
A
14
A
15
B
25h
C
26
A
28
A
29
A
30
A
31
A
33
A
34
A
36
A
37
A
38
A
39
A
40
A
Selectivity Profiles
[0362] To evaluate the enzymatic inhibition of Tumour Necrosis Factor-α Converting Enzyme (TACE) exhibited by the compounds, an assay wherein a FRET substrate was utilized to generate a spectroscopic response to peptidase cleavage. The activity was measured by a continuous detection of increased fluorescence intensity during 12 min. The substrate consisted of a peptide with a fluorescent donor 7-methoxycoumarin (Mca) and a quenching acceptor 2,4-dinitrophenyl group (Dpa), typically Mca-P-L-A-Q-A-V-Dpa-R-S-S-S-R-NH 2 (R&D Systems, ES003).The cleavage site by TACE is the peptide bond between Ala and Val. The compounds were tested at a range of concentrations while the enzyme and substrate concentrations were fixed. A typical TACE assay employs recombinant human TACE (supplied by R&D Systems) in an assay buffer (25 mM Tris-HCl, pH=9.0, 2.5 μM ZnCl 2 , 0.005% Brij 35). The enzyme concentration (TACE) used was 100 ng/ml, the substrate was prepared at a 100 μM stock solution in DMSO and a 96-well polypropylene plate was used for the reaction mixtures. To each well of the plate was added assay buffer 90,00, enzyme (TACE) 0,09 μl and inhibitor 10. The reactions were started by addition of substrate 10 μl/well, giving a substrate concentration of 10 μM and a total volume of 100 μl/well. The total concentration of DMSO was not above 1%. The assay was performed at ambient temperature. Product fluorescence (emission filter 320 nM, excitation filter 405 nM) was monitored with a Thermo Labsystems Fluoroskan Ascent plate reader. The Ki was determined by Prism Software.
[0363] To evaluate the enzymatic inhibition of Human Matrix Metalloproteinase (MMP-3) exhibited by the compounds, an assay wherein FRET was utilized to generate a spectroscopic response to peptidase cleavage, was used. The activity was measured by a continuous detection of increased fluorescence intensity during 12 min. The substrate consisted of a peptide with a fluorescent donor 7-methoxycoumarin (Mca) and a quenching acceptor 2,4-dinitrophenyl group (Dpa), typically Mca-Arg-Pro-Lys-Pro-Val-Glu-Nval-Trp-Arg-Lys(Dnp)-NH 2 (R&D Systems, ES002).The cleavage site by MMP-3 is the peptide bond between Glu and Nval. The compounds were tested at a range of concentrations, the enzyme concentration (MMP-3) was fixed at 400 ng/ml and the substrate concentrations was 10 μM. The MMP-3 assay used employs recombinant human MMP-3 (supplied by R&D Systems) in an assay buffer of 50 mM Tris-HCl, 200 mM calcium acetate at pH=7.5. The MMP-3 enzyme was preactivated by dilution to 0.119 mg/ml into 1 mM APMA (p-aminophenylmercuric acetate) followed by incubation at 37° C. for 24 hours. The substrate was prepared at a 100 μM stock solution in DMSO and a 96-well polypropylene plate was used for the reaction mixtures. To each well of the plate was added assay buffer 90.00, enzyme (MMP-3) 0.3 μl and inhibitor 1 μl. The reactions were started by addition of substrate, 10 μl/well, to a total volume of 100 μl/well. The total concentration of DMSO was not above 1%. The assay was performed at ambient temperature. Product fluorescence (emission filter 320 nM, excitation filter 405 nM) was monitored with a Thermo Labsystems Fluoroskan Ascent plate reader. The Ki was determined by Prism Software.
[0364] The selectivity for MMP-12 over MMP-3 and TACE was evaluated for a representative selection of the compounds of the invention by comparing the Ki figures obtained when tested in the corresponding enzyme assays, such as those described above. The selectivity is presented as the fold difference in Ki for TACE and MMP-3 compared to MMP-12 and is calculated as the ratio Ki (TAcE) /Ki MMP-12 and Ki MMP-3) /Ki MMP-12 respectively. The result is summarized in Table 2.
[0000]
Ki (TACE) /
Ki (MMP-3) /
Example
Ki (MMP-12)
Ki (MMP-12)
1
380
140
5
>4500
71
7
>80
53
10
>150
34
12
245
122
13i
>190
>190
14
>500
>500
15
>700
120
30
2200
75
32
140
>200
36
280
240
38
390
150 | The invention provides compounds of the formula (I)
wherein the variables are as defined in the specification.
The compounds of the invention are inhibitors of metalloproteinase MMP-12 and are among other things useful for the treatment of obstructive airway diseases, such as chronic obstructive pulmonary disease (COPD). | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of application Ser. No. 07/760,917 now U.S. Pat. No. 5,201,601 for Board Mat Construction, filed Sep. 17, 1991.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to mat structures to be constructed preferably of wood or wood products and a temporary roadway or platform lying upon soft ground formed from such mat structures.
2. Description of Related Art
Various different forms of board mat constructions heretofore have been provided such as those disclosed in U.S. Pat. Nos: 1,970,037, 2,639,650, 2,652,753, 2,819,026, 2,912,909, 4,289,420, 4,462,712, 4,600,336, 4,875,800, 4,889,444 and 5,020,937. However, these various different forms of mat constructions, in many instances, do not provide sufficient ground traction between the mat constructions and the underlying ground surface and between the upper surface of the mat construction and a vehicle moving thereover. Furthermore, these previously known mat constructions may not be readily mass produced at low cost and the spacing of multiple transverse boards thereof spaced along the length of the mat require relatively precise spacing jigs in order to effect mass production. In addition, many of these previously known forms of mat constructions require extensive cleaning after each usage on soft ground and are difficult to correctly assemble when laying down a mat construction.
SUMMARY OF THE INVENTION
The mat construction of the instant invention, basically, includes a rectangular planar surface defining member and a pair of transverse member structures, which may be formed from logs or boards, secured to and extending transversely at the opposite ends of the surface defining member. The transverse members, or panels, form edge surfaces substantially perpendicular to the planar surface member. These edge surfaces are located at opposite ends of the mat and at locations slightly less than approximately one-quarter the length of the mat from each mat end.
When forming a roadway or platform, a plurality of mat constructions or structures are disposed with their surface defining member uppermost and their transverse members lowermost. Other mat constructions of the roadway or platform are inverted and disposed beneath the first mentioned mat constructions.
The mat constructions or structures may all be of the same length and width and the transverse members each have a length, i.e. the dimension along the length or major axis of the mat structure, slightly less than one-quarter the length of the planar surface defining member. The transverse members, or panels, are spaced apart to define an open space therebetween slightly greater than one-half the length of the planar surface defining member.
The inverted mat constructions, or structures, with the surface defining member lowermost and the transverse members uppermost are first laid upon the ground lengthwise in end-to-end aligned relation. The uppermost mat structures are then disposed over the inverted mat structures with the spacing between the transverse members of each of the upper mat constructions receiving therein the adjacent transverse members of adjacent ends of the inverted mat structures. The spacing between the transverse members of each lower mat construction receive therein the adjacent transverse end members of adjacent ends of the upper mat structures.
A main object of this invention is to provide a mat construction for use in forming a roadway or platform on soft ground with a minimum amount of expense, transportation costs, difficulty in assembling the individual mat constructions in order to form a roadway or platform, and ease of removal of the mat constructions after usage and cleaning thereof prior to subsequent usage.
Another object of this invention is to provide a mat construction in accordance with the preceding objects which will afford ground traction between the lower mat constructions and the ground upon which they are disposed.
Another object of this invention is to provide mat constructions formed in a manner such that surface traction of the upper mat constructions of a roadway or platform being with the wheels of vehicles traveling thereover may be increased.
Another very important object of this invention is to provide a mat construction which may be produced at low cost.
Still another object of this invention is to provide a mat construction of simple design which does not require the use of sophisticated jigs during mass production.
A further object of this invention is to provide a mat construction which may be of one piece, molded construction.
A still further object of this invention is to provide a mat construction which will require minimum cleaning after each usage upon soft ground.
Yet another object of this invention is to provide a mat construction which may be molded primarily of wood products and resin.
Another object of this invention is to provide a platform mat construction of substantially eight feet in width and which may be made double wide to provide for a single lane roadway with the usual less than eight foot spacing between the wheels of vehicles serving to minimize downward depression of the outer margins of the roadway beneath soft ground over which the roadway is formed.
Yet another object of this invention is to provide a mat construction which will conform to conventional forms of manufacture, be of simple construction and easy to use so as to provide a device that will be economically feasible, long-lasting and relatively trouble free in operation.
These together with other objects and advantages which will become subsequently apparent reside in the details of construction and operation as more fully hereinafter described and claimed, reference being had to the accompanying drawings forming a part hereof, wherein like numerals refer to like parts throughout.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is fragmentary perspective view of a double wide roadway constructed through the utilization of a plurality of right side up and inverted mat constructions of the instant invention and wherein the rectangular planar surface defining member of each mat construction is formed by a single unbroken panel member;
FIG. 2 is a perspective view of a modified form of mat construction wherein the rectangular planar surface defining member is constructed of four plank-type members and wherein each transverse member at the opposite ends of rectangular surface defining member is formed of a pair of closely spaced transverse planks or boards;
FIG. 3 is an enlarged end elevational view of the mat construction illustrated in FIG. 2;
FIG. 4 is an end elevational view of a one piece mat construction wherein the rectangular planar surface defining member and the transverse members are integrally formed by, for example, a molding process;
FIG. 5 is a reduced bottom plan view of a mat construction of the type illustrated in FIG. 1;
FIG. 6 an enlarged fragmentary vertical sectional view taken substantially upon the plane indicated by the section line 6--6 of FIG. 1; and
FIG. 7 is a reduced side elevational view of the one piece mat construction in FIG. 4.
FIG. 8 a perspective view of another form of mat construction or structure wherein the rectangular planar surface defining member is constructed of a plurality of planks and wherein each of the transverse members is formed of three spaced-apart transverse planks, boards or logs.
FIG. 9 is a perspective view of a portion of a temporary roadway formed from a plurality of mat structures of the type shown in FIG. 8.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now more specifically to the drawings the numeral 10 generally designates a roadway which has been constructed over soft ground utilizing a plurality of mat constructions, or structures, of the instant invention.
Each mat structure is referred to in general by the reference numeral 12 or 12' and includes a rectangular substantially planar surface defining member 14 or 14' and a pair of opposite end elongated transverse members 16 or 16'.
Each rectangular surface defining member 14 defines a first rectangular surface 18 and a second rectangular surface 20 facing opposite, or underside, and paralleling the first surface 18. In addition, each transverse member 16 (sometimes referred to as a transverse end member) is secured to the opposite ends of the rectangular surface defining member 14 in any convenient manner, such as by nails, glue, etc.
The mat constructions 12' are identical to the mat constructions 12, except that the mat constructions 12' are one-half the width of the mat constructions 12. The mat constructions 12 and 12' utilize one piece rectangular surface defining members 14 and 14' and one piece transverse logs or members 16 and 16'.
When the mat constructions 12 and 12' have their first rectangular surfaces 18 and 18' disposed uppermost, the transverse logs or end members 16 and 16' are secured to the undersides of the rectangular surface defining members 14 and 14'. When constructing the roadway 10, some mat structures 12 and also the mat structures 12' are disposed with their first rectangular surfaces 18 disposed uppermost and other mat structures 12 are disposed with their first rectangular surfaces 18 disposed lowermost to lie on the ground.
The transverse members or panels 16, 16' define edge surfaces that extend substantially perpendicular from the underside of the planar surfaces 14, 14'. As shown in FIG. 6, a first edge surface 15, 15' is substantially flush with one end of the mat structure 12, 12'. A second edge surface 17, 17' is substantially flush with the opposite end of the mat structure 12, 12'. A third edge surface 19, 19' is located at a distance no greater than, and approximately, one-quarter the overall length of the mat structure from the first edge surface 15, 15'. A fourth edge surface 21, 21' is located at a distance no greater than, and approximately, one-quarter the overall length of the mat structure from the second edge surface 17, 17'. Similar edge surfaces 115', 117', 119', and 121' are shown in the FIG. 2 embodiment, wherein each transverse member, or panel, is formed from two logs or planks 116 spaced closely together, in a manner to be described.
The overall length of the transverse logs or members 16 and 16', i.e. from the edge surface flush with the end of the mat to the innermost edge surface, is slightly less than one-quarter the length of the rectangular surface defining member 14 and 14'. As a result, the spacing between the transverse logs or members 16 and 16' of each mat structure 12 and 12' is slightly greater than one-half the length of the corresponding rectangular surface defining member 14 and 14'. That is, the distance between the edge surfaces 19 and 21 (or 19' and 21', or 119' and 121') is slightly greater than one-half the distance between the edge surfaces 15 and 17 (or 15' and 17', or 115' and 117'). In this manner, when constructing the roadway 10, a double row of mat structures 12 are disposed lengthwise in end-to-end aligned and abutted relation with their second rectangular surfaces 20 and their transverse logs or members 16 disposed uppermost, see FIG. 6. Thereafter, a first row of mat structures 12' with their first rectangular surfaces 18' disposed uppermost and their transverse logs or members 16' disposed lowermost are centered over the first laid two rows of mat structures 12 in end-to-end aligned and abutting relation with the adjacent transverse logs or members of end abutted upper mat sections 12' received between the transverse logs or members 16 of the lower mats 12 and the transverse logs or members 16 of abutted ends of lower mats 12 received in the spacing between the transverse logs or members 16' of the upper mat structures 12'. Two rows of one-half width mat constructions 12' may be disposed over the exposed remote side half marginal portions of the first laid two rows of mat constructions 12 with the half width mat constructions 12' aligned transversely of the roadway 10 with the corresponding upper mat structures. In this manner, the upper and lower mat structures 12 and 12' are relatively tightly interlocked or interconnected together against relative longitudinal shifting and the friction between the upper and lower mat structures 12 and 12' strongly resists relative lateral shifting between upper and lower mat sections 12 and 12'. Further, when a vehicle with slightly less than eight foot spacing between opposite side wheels is driven down the center of the roadway 10 on the center row of upper mat structures 12, the weight of the vehicle is supported more from the adjacent margins of the underlying bottom mat structures 12 and, thus, there is little tendency for soft mud at the longitudinal margins of the roadway 10 to bulge up and overflow the roadway longitudinal margins.
The mat sections 12 and 12' may be constructed entirely of wood with the transverse logs or members 16 and 16' comprising large transverse planks or panels and with the rectangular surface defining members comprising heavy plywood panel sections, both the rectangular surface defining members 14 and 14' and the transverse log or members 16 and 16' being treated against rot.
The overall dimensions of the mat structure can vary. One preferred dimension is that width of the mat structure be approximately 8 feet and the length either 12 feet or 8 feet. The length and width dimension is substantially greater than the thickness dimension, as is apparent from the drawings.
With attention now invited more specifically to FIG. 2 of the drawings, there may be seen a modified form of mat structure 112 which utilizes plural individual plank sections 113 as the rectangular surface defining member thereof and a pair of plank members 116 defining each of the transverse end logs or end members thereof. Although four planks are depicted to define the planar surface, it should be apparent that more or less planks may be utilized depending on the desired width of the mat. Similarly, although two planks 116 are depicted to define each transverse log or end member, more than two planks may be utilized. The significant design criterion is the distance between edge surfaces 115' and 119' (and 117' and 121') so that this distance is less than, but approximately equal to, one-quarter the length of the mat. The space between edge surfaces 119' and 121' is open, i.e. free of any edge surfaces and equal to at least approximately one-half the length of the mat.
The plank members 113 are slightly spaced apart to allow heavily laden rubber tire areas aligned with the spacing between adjacent plank members 113 to be depressed downwardly between adjacent planks 113 in order to increase traction between the tires of wheeled vehicles and the first rectangular surface 118 of the mat structure 112. Here again, the plank members 113 and 116 may be constructed of wood or even molded of wood products mixed with resin. Of course, the mat structure 112 also may be constructed as a one-half mat structure and used in the same manner as the mat structure 12'.
Referring now more specifically to FIGS. 4 and 7, the reference numeral 212 refers to a third form of mat structure which is of one piece construction and constructed of a mixture of wood chips and resin, or the like. The first rectangular surface 218 of the mat structure 212 is substantially planar and includes four integral longitudinally extending, transversely spaced and generally inverted V-shaped ridges 219 for increasing traction between a wheeled vehicle and the first rectangular surface 218. Of course, these ridges are optional. The transverse logs or members 216 or formed integrally with the rectangular surface defining member 214 of the mat structure 212. The ridges 219, in addition to affording increased traction between the first rectangular surface 218 and wheeled vehicles moving thereover, also provide longitudinal stiffening for the mat structure 212. Also, as before, the mat structure 212 may be constructed as a one-half width mat structure.
It has been found that utilizing only two transverse members or panels at the opposite ends of each mat section 12 or 12' results in simplified construction of the mat sections 12 and 12', as opposed to mat sections previously known which incorporate more than two transverse log members or planks and which are interdigitated with relatively inverted mat sections of the same type. Previous mat sections utilizing more than two members must be constructed through the utilization of jigs to insure proper spacing between the transverse log members and they are more difficult to clean after usage on soft ground to insure that the interdigitation of the log members of relatively inverted mat sections subsequently may be accomplished.
With applicant's invention it is only necessary to provide the rectangular surface defining members 14 and 14' and transverse logs or members 16 and 16' of the correct dimensions. Then, the transverse logs or members 16 and 16' may be readily secured to the opposite ends of the rectangular surface defining members 14 and 14', inasmuch as the transverse logs or members are substantially aligned with the end edges of the rectangular surface defining members 14 and 14' and the opposite side longitudinal margins of the rectangular surface defining members 14 and 14'. This type of construction enables the mat structures 12 and 12' to be assembled by persons having minimum education and instruction while still providing a product which is superior in its ability to be quickly erected in order form a roadway such as the roadway 10 and also its ability to be readily cleaned for subsequent usage.
Another embodiment of the present invention is shown in FIGS. 8 and 9. FIG. 8 shows an inverted mat structure 312 having a substantially planar surface defining member 314 formed of a plurality of planks 313 arranged in a lengthwise direction similar to that of the FIG. 2 embodiment. Extending from the underside of the planar surface member 314 along the width dimension, are a pair of transverse structures, beams or end members 316. Each of the transverse structures or members 316 are formed from a plurality of planks, specifically three planks 318, that are spaced apart from each other in the lengthwise direction of the mat. That is, the three planks 318 form a single transverse structure beam or end member 316 that collectively provide the same function as the transverse members 16, 116, 216 of the earlier-described embodiments. The transverse structures 316 define edge surfaces 315, 317, 319 and 321 that extend substantially perpendicularly from the planar surface member 314. As with the above described embodiments, the distance lengthwise from the first edge surface 315 to the third edge surface 319 is slightly less than one-quarter the length of the mat structure 312 from the edge 315 to the edge 317. The distance between the edge surface 317 to edge surface 321 is also slightly less than one-quarter the length of the mat structure 312. The space between the edge surfaces 319 and 321 is thus slightly greater than one-half the length of the mat structure and is open or free of any additional edge surfaces, or planks, or other protrusions. As is shown in FIG. 9, a roadway is formed such that the transverse end members 316 of adjacent mat structures (part of a set of mat structures) disposed on the ground abut with each other and fit relatively freely yet snugly, within the space between the pair of transverse end members, beams or panels, of a single mat structure disposed on top of the bottommost set. The topmost mat structures similarly define a set of mat structures arranged lengthwise in end-to-end relationship, although for purposes of illustration, only a single topmost mat structure is shown.
The primary advantage of utilizing spaced-apart beams or planks 318, instead of a single solid member or panel 16 or a pair of closely spaced end members or beams 116, as shown in FIGS. 1 and 2, respectively, is for weight savings. Because the significant design criterion requires only two edge surfaces 315, 319 or 317, 321 at opposite ends of the mat structure, the construction lying between the edge surfaces 315, 319 is not critical. For example, instead of three beams or planks 318, only two beams can be used with spacing therebetween. It has been found, however, that by using at least three spaced-apart beams, the central beam provides structural rigidity and minimizes potential bending, and possible breakage, of the upper planar surface.
It should also be realized that the transverse end members, beams or panels 316 formed of spaced apart beams 318 can also be utilized with a planar surface that is a solid rectangular panel, such as plywood, instead of parallel beams 313. Similarly, the entire construction can be formed as a molded unit or a one-piece unit formed of wood chips or wood products mixed with a suitable resin.
The foregoing is considered as illustrative only of the principles of the invention. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation shown and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention. | A roadway/platform mat construction is provided for disposition over soft ground. The mat construction includes a rectangular, panel-like mat structure including opposite transverse end margins and opposite side longitudinal margins. The mat construction defines a first rectangular surface and a second rectangular surface facing opposite and paralleling the first surface and including elongated transverse members carried by the opposite ends of the mat structure and projecting outwardly of the second surface thereof. The transverse members are of a length measured longitudinally of the mat construction equal to substantially one-quarter the length of the overall mat structure and the spacing between opposite end members of each mat structure measured longitudinally thereof is equal to substantially one-half the length of the mat structure. | 4 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to face-pumped slab lasers of the type that have laser head assemblies constructed of individual components, which are rigidly attached together, in order to form an integral structure. Such structures of this type, generally, allow a face-pumped slab laser component to be assembled and disassembled easily and quickly.
2. Description of the Related Art
Up to the present invention, complete dismantling of a face-pumped slab laser head is required in order to repair, replace or service a face-pumped laser. The complete dismantling typically requires a total optical alignment to properly restore the laser performance. A typical "down time" for a face-pumped slab laser which usually involves complete dismantling, re-assembly and realignment is about two days. Obviously, such a lengthy "down time" is expensive and time consuming. Therefore, a new advantageous system, therefore, would be presented if such amounts of "down time" could be reduced.
It is known, in commercial rod lasers, to utilize a rod, an end cap, and a flow tube replacement assembly to reduce "down time". While this replacement assembly performs adequately for a rod laser, a face-pumped slab laser requires a far more complex replacement or modular assembly, such as, for example, the cooling integration and cooling passage design. Also, the optical alignment requirements of a rod laser are not as stringent as those of a face-pumped slab laser. Therefore, modular slab laser assembly which reduced "down time" would be advantageous.
It is apparent from the above that there exists a need in the art for a laser system which has a modular construction to reduce "down time", and which at least equals the safety and performance characteristics of other known lasers, but which at the same time is capable of being used with a face-pumped slab laser. It is a purpose of this invention to fulfill this and other needs in the art in a manner more apparent to the skilled artisan once given the following disclosure.
SUMMARY OF THE INVENTION
Generally speaking, this invention fulfills these needs by providing a face-pumped slab laser head, comprising a lamp means, at least two guide means operatively connected to said lamp means, a removable modular slab assembly substantially located adjacent to said lamp means and slidably engaging said guide means wherein said modular slab assembly is further comprising a face-pumped laser slab means and a holding means for holding said slab means in a predetermined orientation and a reflector containment means which substantially encloses said lamp means, said guide means and said removable modular slab assembly.
In certain preferred embodiments, the reflector means include upper and lower reflector halves. Also, the laser slab means includes a slab located within a glass tube. Finally, the holding means includes at least two outer end caps, at least two inner end caps and gaskets.
In another further preferred embodiment, the modular slab assembly can be easily removed and installed in the face-pumped slab laser system without adversely affecting the "down time" of the laser system.
The preferred face-pumped slab laser head, according to this invention, offers the following advantages: quick assembly, disassembly and reassembly of the modular components; reduced down time; good stability; good durability; maintains slab and optical alignment; and good economy. In fact, in many of the preferred embodiments, these factors of assembly, disassembly and reassembly, reduced down time, and slab and optical alignment are optimized to an extent that is considerably higher than heretofore achieved in prior, known laser systems.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other features of the present invention which will be more apparent as the description proceeds are best understood by considering the following detailed description in conjunction with the accompanying drawings wherein like character represent like parts throughout the several veins and in which:
FIG. 1 is an exploded view of the component parts of a modular face-pumped slab laser, according to the present invention;
FIG. 2 is a schematic view of an alignment assembly jig, according to the present invention;
FIG. 3 is a isometric view of the assembly jig with the inner end caps in place;
FIG. 4 is an isometric view of the assembly jig with the slab flow tube, gaskets and outer end caps in place;
FIG. 5 is an exploded, top view of the modular face-pumped laser head, according to the present invention;
FIG. 6 is an isometric view of the assembly jig with the handle and the compression device in place;
FIG. 7 is an isometric view of the modular slab component prior to insertion into the lower reflector half;
FIG. 8 is an isometric view of the assembled component parts shown in FIG. 1 without the upper reflector half;
FIG. 9 is an isometric view of the modular face-pumped slab laser head completely assembled with the upper reflector half installed;
FIG. 10 is an exploded side plan view of the positioning, compression and storage assembly prior to being assembled, according to the present invention;
FIG. 11 is a side plan view of an assembled positioning, compression and storage assembly; and
FIG. 12 is an end view of a self-draining coolant manifold for a modular slab laser assembly, according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
With reference first to FIG. 1, there is illustrated some of the component parts of modular face-pumped slab laser head 2. Head 2 includes, in part, lower reflector half 4, guide posts 6, outer end cap 8 having slab alignment slot 10, slab 12, inner end cap 14, gaskets 16, slab tube 18, slab seal gasket 84, slab seal retainer 85. Reflector half 4 and guide posts 6, preferably, are constructed of aluminum which are then coated by conventional coating techniques with gold. End caps 8, preferably, are constructed of brass which are then coated by conventional coating techniques with gold. Slab 12, preferably, is constructed of any suitable solid state lasing material such as Nd:YAG. Inner end cap 14, preferably, is constructed of copper which is then coated by conventional coating techniques with gold. Gaskets 16, preferably, are constructed of any suitable elastomeric material. Slab tube 18, preferably, is constructed of any suitable heat-resistant transparent material, such as glass.
With respect to FIG. 2, there is illustrated jig assembly 30 for constructing modular face-pumped slab laser head 2. Jig assembly 30 includes, in part, bottom plate 32, supports 34 and 36, and end plates 42 and 48. Plates 32, 42 and 48 and supports 34 and 36, preferably, are constructed of aluminum. Bottom plate 32 is rigidly attached end plate 42 by conventional fasteners (not shown). Support 34 is rigidly attached to end plate 48 by conventional fasteners 50. Supports 36 are rigidly attached to bottom plate 32 by conventional fasteners 38. Support 36 is also rigidly attached to end plate 42 by conventional fasteners 40.
Located on top of end plate 42 are alignment blocks 46a and 46b. Blocks 46a and 46b, preferably, are constructed of aluminum and are rigidly attached to end plate 42 by conventional fasteners (not shown). Slot 44, which is machined in end plate 42 by conventional machining techniques, is located on the upper half of end plate 42. Block 46a is, preferably, precisely aligned by conventional techniques, pinned by conventional pins (not shown) and fastened to plate 42 by conventional fasteners (not shown). Block 46b is then rigidly attached to plate 42 by conventional fasteners (not shown).
End plate 48 is rigidly attached to bottom plate 32 by a conventional fastener 60. Fastener 60 is located in slot 58 in end plate 48. Slot 58 is machined into end plate 48 by conventional machining techniques. Located on top of end plate 48 are alignment blocks 54a and 54b. Blocks 54a and 54b, preferably, are constructed of aluminum and are rigidly attached to end plate 48 by conventional fasteners 56. Block 54a is, preferably, precisely aligned by conventional techniques, pinned by conventional pins (not shown) and fastened to plate 48 by conventional fasteners (not shown). Block 54b is then rigidly attached to plate 48 by conventional fasteners (not shown). Slot 52 is machined into the upper half of end plate 48 by conventional machining techniques.
FIG. 3 shows inner end caps 14 located on jig assembly 30. In particular, inner end caps 14 are located on end plates 42 and 48. Inner end caps 14 are rigidly retained on end plates 42 and 48 by conventional fasteners 61. As can be seen, inner end caps 14 are located on end plate 42 between alignment blocks 46 and on end plate 48 between alignment blocks 54.
FIG. 4 shows outer end cap 8 with alignment slot 10 just prior to insertion into slab 12. In particular, slab 12 is placed within slab tube 18 (FIG. 1). Gaskets 16 (FIG. 1 and FIG. 9) are then placed around tube 18. Tube 18 is then placed within jig assembly 30 such that slab 12 fits in alignment holes 10 of outer end caps 8. Outer end caps 8 are then fastened to inner caps 14 by conventional fasteners 62. Retainer 85 and seal 84 are placed around slab 12.
FIG. 5 illustrates a top, exploded view of laser head 2 with upper reflector half 10 removed. In particular, in this view laser head 2 includes, in part, lower reflector half 4, guide posts 6, outer end cap 8, slab 12, inner end cap 14, gasket 16, conventional excitation lamps 112, manifolds 151, plugs 152, manifold tubes 162. Manifolds 151, plugs 152 and tubes 162 will be described in greater detail with respect to FIGS. 9 and 12.
Head 2 also includes conventional lamp holders 70, O-ring 72, conventional lamp fastener 74, lamp O-ring 76, conventional lamp electrical connection 78, slab seal gasket 84, slab seal retainer 85, conventional fasteners 86, flow screens 87, flow conduits 83, O-ring 89, conduits 90 and 91 and a conventional electrical connector 97. Lamp holders 70, preferably, are constructed of any suitable polymeric material. O-rings 72, 76, 84 and 89, preferably, are constructed of any suitable elastomeric material. Flow screens 87 and conduits 83, preferably, are constructed by any suitable machining techniques. Conduits 90 and 91, preferably, are constructed by any suitable machining techniques.
As can be seen in FIG. 5, when outer end cap 8 contacts slab 12, this connection allows coolant, which, typically, is water to circulate from manifold 151, through conduits 90 and 91 through flow screens 87 through flow conduits 83 around slab 12 and out through flow conduits 83 and flow screen 87, through conduits 90 and 91 and manifold 151. Also, excitation lamps 112 can be electrically connected to a conventional power source (not shown) in order to excite slab 12. Finally, O-rings 16, 72, 76, 84 and 89 should substantially prevent leakage of the coolant from laser head 2.
With respect to FIG. 6, there is illustrated positioning, compression and storage device 100. Device 100 is rigidly secured to outer end caps 8. In particular, as can be more clearly shown in FIGS. 9 and 10, assembly 100 includes, in part, handle 102 and compression flanges 104. Handle 102 and flanges 104, preferably, are constructed of aluminum. As shown more clearly in FIG. 10, handle 102 is placed over head 2 and rigidly attached to outer end cap 8 by conventional fasteners 112. Handle 102 is also rigidly attached to outer end cap 8 and inner end cap 14 by conventional fasteners 110. Compression flanges 104 are rigidly attached to outer end cap 8 by conventional fasteners 106. Also, flanges 104 are rigidly attached to handle 102 by conventional fasteners 108.
FIG. 7 shows a partially constructed modular face-pumped slab laser head 2. In particular, in this illustration, compression assembly 100 is still attached to outer end caps 8 such that compression assembly 100 can be stored. In this manner, if a defect occurs in slab 12 due to, for example, a contamination or fracture of slab 12, the operator merely has to remove compression assembly 100 from slab laser head 2 and replace the defective compression assembly 100 with a new compression assembly 100. The defective compression assembly 100 can then be repaired. It is to be understood that compression assembly 100 allows outer end caps 8 and 14 to be rigidly held in place while providing proper alignment for slab 12. This allows compression assembly 100 to be placed in a proper storage area so that it can be used later if by chance the compression assembly 100 that is currently being used in the laser head fails.
With respect to FIG. 8 there is illustrated the insertion of compression assembly 100 into lower reflector half 4. In this illustration, handle 102 and compression flanges 104 have been removed after compression assembly 100 has been placed in lower reflector half 4.
FIG. 9 illustrates the complete assembly of modular face-pumped slab laser head 2 having cooling manifold assembly 150 attached. Also, as can be seen, upper reflector half 110 has been placed on top of lower reflector half 4. Upper reflector half 110, preferably, is constructed in the same manner as lower reflector half 4. Finally, located within laser head 2 are conventional excitation lamps 112 (FIG. 5) which are attached within lower reflector half 4 and upper reflector half 10 and adjacent to slab 12 and tube 18 (FIG. 5) by conventional attachments (not shown).
As can be seen more clearly in FIGS. 9 and 12, self-draining manifold coolant assembly 150 includes, in part, manifold 151, draining caps 152, coolant inlet 154, coolant outlet 156, and conventional fasteners 158 and 160. Manifold 151 and draining caps 152, preferably, are constructed of any suitable coolant water-contamination resistant material such as LEXAN®. Inlet 154, preferably, is constructed of stainless steel.
It is to be understood that the self-draining feature requires that the slab coolant reservoir 164 is mounted lower than the laser head 2 itself so that siphoning does not occur. Note, since both manifolds 151 are identical, that when attached to laser head 2, the self draining plugs 152 face in opposing directions (one up, one down). When it is necessary to drain the slab coolant from laser head 2, removal of these plugs 152 (down facing plug first) quickly drains the coolant into a waiting receptacle (not shown) under the downward facing drain plug. During removal of plugs 152, one plug 152 (the one facing down) acts as a drain while the other plug 152 (the one facing up) acts as a vent. Removal of the manifolds 151 from laser head 2 may now be performed without spillage onto nearby optical components of the laser head 2.
During the operation of manifold assembly 150, coolant, such as, water is fed from a source (not shown) to inlet 154. The coolant traverses manifold tubes 162 to outlet 156. The coolant then enters laser head 2 such that coolant is traversed through tube 18 along slab 12 according to conventional slab cooling techniques.
Once given the above disclosure, many other features, modification or improvements will become apparent to the skilled artisan. Such features, modifications or improvements are, therefore, considered to be a part of this invention, the scope of which is to be determined by the following claims. | This invention relates to face-pumped slab lasers of the type that have laser head assemblies constructed of individual components, which are rigidly attached together, in order to form an integral structure. Such structures of this type, generally, allow a face-pumped slab laser component to be assembled and disassembled easily and quickly. | 7 |
This is a continuation of copending application Ser. No. 08/018,771 filed on Feb. 17, 1993, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to creped sanitary tissues which are extremely soft, absorbent and drapeable making them especially suitable for such products as bathroom tissue, facial tissue and napkins.
2. Description of Background Art
In the manufacture of sanitary tissue, a significant challenge to the papermaker is to make tissues which are not only soft, absorbent and thick but also strong. Typically, softness, absorbency, and thickness are inversely related to strength. Several avenues are available to the papermaker for improving product quality. For example, to improve sheet absorbency and thickness, one can use a thru air dried process as disclosed in U.S. Pat. No. 3,301,746 by Sanford and Sisson or one can incorporate bulking fibers into the web as disclosed in U.S. Pat. No. 3,434,918 by Bernardin, U.S. Pat. No. 4,204,504 by Lesas et al., U.S. Pat. No. 4,431,481 by Drach et al., U.S. Pat. No. 3,819,470 by Shaw et al., and U.S. Pat. No. 5,087,324 by Awofeso et al. Bulking fibers can take the form of mechanical pulp or other thermally/chemically cross-linked fiber. Thicker more absorbent structures can be made using a low batting papermaking felt as described in U.S. Pat. No. 4,533,457 by Curran et al.
To improve tissue softness, several approaches are available to the papermaker such as using certain species of hardwood like eucalyptus in stratified webs as discussed in U.S. Pat. No. 4,300,981 by Carstens and U.S. Pat. No. 3,994,771 by Morgan et al. U.S. Pat. No. 3,821,068 by Shaw discloses a technique for producing a soft tissue structure by avoiding mechanical compression until the sheet has been dried to at least 80% solids. U.S. Pat. No. 3,812,000 by Salvucci et al. discloses a technique for producing a soft tissue structure by avoiding mechanical compression of an elastomer containing fiber furnish until the consistency of the web is at least 80% solids. U.S. Pat. No. 3,301,746 by Sanford and Sisson discloses a thru air dried papermaking technology for producing soft tissue structures. U.S. Pat. No. 5,164,045 by Awofeso et al. discloses a technique for making a soft tissue product by combining foam forming, stratification, and bulking fibers. Finally, U.S. Pat. No. 4,063,995 by Grossman discloses advanced creping technologies for improving the softness of tissue products.
Numerous references suggest the broad use of a myriad of alternative fibers for making generic "paper". High strength specialty papers have been made using non-woody fibers (usually termed "hard" or "cordage" fibers) such as sisal, abaca, hemp, flax and kenaf. As described in McLaughlin and Schuck, Econ. Bot 45 (4), pp 480-486, 1991; such fibers are commonly used for such products as currency paper, bank notes, tea bags, rope paper, filters, air cleaners and other products requiring "scruff" and tear resistance along with high endurance for folding. McLaughlin and Schuck suggested that such specialty products can also be formed from fibers derived from the genera Hesperaloe and Yucca in the family Agavaceae and that "their long, narrow fibers may be superior to other species currently used for pulping." Surprisingly, in light of the literature described and discussed above suggesting that these hard or cordage fibers be used for specialty papers requiring high strength and scruff resistance, we have found that chemically pulped fibers derived from the leaves of the genus Hesperaloe in the family Agavaceae are especially suitable for making extremely high quality creped tissue paper having outstanding softness and drapeability coupled with extremely high strength. McLaughlin and Schuck report neither fiber coarseness for the fibers under considerations nor the strength of papers made from these fibers making predictions about suitability for tissue-making at least very problematic, if not impossible. Accordingly, the present invention is directed to a creped tissue paper product having extremely high strength along with outstanding bulk, absorbency and softness wherein at least about 20% by weight of the fiber is derived by chemical pulping from leaves of the genus Hesperaloe, preferably Hesperaloe funifera. Preferably, the sanitary tissue paper product may consist essentially of at least about 40% Hesperaloe funifera fibers, the remainder being a fiber blend chosen from the group consisting of softwoods, hardwoods, anfractuous (bulking) fibers and recycled fiber.
SUMMARY AND OBJECTS OF THE PRESENT INVENTION
The present invention provides for the use of long low coarseness fibers derived from the leaves of the genus Hesperaloe, preferably Hesperaloe funifera for use in creped tissue products to obtain extremely high product strength without unduly sacrificing bulk, absorbency and softness.
Further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will become more fully understood from the detailed description given hereinbelow and the accompanying drawings which are given by way of illustration only, and thus are not limitative of the present invention, and wherein:
FIG. 1 is a graph illustrating the relationship between bulk and breaking length for Hesperaloe funifera and northern softwood kraft handsheets;
FIG. 2 is a graph illustrating the relationship between Hesperaloe funifera fiber in webs intended for applications requiring wet strength wherein caliper is plotted against wet geometric mean tensile for a 50% northern softwood kraft and a 50% northern hardwood kraft web as compared to a 50% Hesperaloe funifera and a 50% northern hardwood kraft web;
FIG. 3 is a graph illustrating Hesperaloe funifera fiber in web structures intended for applications requiring both wet strength and absorbency wherein water-holding capacity is plotted versus wet geometric mean tensile strength for a 50% northern softwood kraft and a 50% northern hardwood kraft web as compared to a 50% Hesperaloe funifera and a 50% northern hardwood kraft web.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Tissue production is a relatively mature industry in the United States. Extremely large expensive paper machines are used to produce tissue from various wood pulps at very high speeds and in tremendous quantities. Even though large sums of money are expended in research directed to improving tissue products, advances are typically relatively subtle. In contrast to the often subtle distinctions between tissues made from wood pulps, we have found that it is possible to dramatically increase the quality of tissue made on existing machinery by replacing at least about 20% by weight of the furnish with chemically pulped fibers derived from the leaves of plants in the genus Hesperaloe in the family Agavaceae. Plants in the genus Hesperaloe, such as Hesperaloe funifera, are non-woody plants from the family Agavaceae (as are yucca and sisal) which yield long, fine fibers of low coarseness (i.e. weight per unit length). These fibers were identified as being especially suitable for tissue making in a study of the Agavaceae family where a number of species of the genera Agave, Dasylirion, Furcraea, Hesperaloe, Nolina, and Yucca were screened for suitability for use in tissuemaking. In this study, plants in the genus Hesperaloe from the family Agavaceae were found to be especially desirable for use in tissuemaking as tissues incorporating these fibers proved to provide an unexpected combination of high strength coupled with softness, bulk and absorbency properties not typically encountered in tissues having that degree of strength. When fibers such as Hesperaloe funifera are used in sanitary tissue products such as bathroom, facial and related tissue products, attributes such as strength, absorbency and softness are improved unexpectedly. Other examples of Hesperaloe species and hybrids are known and these have been found to show promise of good suitability for tissue-making. Hereinafter, when we refer to the genus "Hesperaloe" in the family Agavaceae, the term should be understood to include not only Hesperaloe funifera but also the species H. nocturna, H. parviflova, H. changii, H. sp. nova (Alamos), various hybrids, and the numerous varieties as if all were individually named.
Table I shows typical fiber properties of NSWK (northern softwood kraft), SSWK (southern softwood kraft), WCSW (west coast softwood kraft), NHWK (northern hardwood kraft), eucalyptus kraft, and several non-woody fibers including samples of fiber from the genus Hesperaloe. These data show that the fibers from the genus Hesperaloe have coarseness values comparable to eucalyptus and NHWK with fiber length values greater than NSWK.
TABLE I______________________________________Fiber Properties of Typical Furnishes Coarseness Fiber LengthFiber Type mg/100 m mm______________________________________NSWK 14.2 2.92SSWK 26.7 3.46WCSW 23.2 3.38NHWK 11.0 1.02Eucalyptus 7.6 0.99M. textilis* 17.4 3.65C. sativa* 13.8 3.36A. sisalana* 14.0 2.45Y. elata* 6.7 1.89H. changii* 9.0 4.58H. funifera* 8.0 2.96______________________________________ *Non-woody plant fibers
Fibers suitable for the practice of the present invention can be prepared from the leaves of the Hesperaloe by conventional chemically based pulping methods including traditional chemical processes such as the sulfite and kraft processes, as well as semi-chemical means such as neutral sulfite and by chemi-mechanical or chemi-thermo-mechanical pulping procedures. Accordingly, pulp produced by any of the foregoing processes should be understood to be comprehended within the term "chemically pulped fibers".
Several experiments were performed showing the utility of the Hesperaloe funifera in sanitary tissue products. The first experiment was a handsheet study comparing a 100% chemically pulped Hesperaloe funifera handsheet to a 100% NSWK handsheet, both being formed according to TAPPI standards. As illustrated in FIG. 1, at the same breaking length (7.2 km), Hesperaloe funifera sheets have a bulk of 2.18 cc/g while the NSWK handsheets have a bulk of only 1.54 cc/g. It appears that the Hesperaloe funifera fiber causes a bulking effect in the handsheet structure.
Several trials were executed on a papermachine using a 50/50 blend of NSWK/NHWK, and a 50/50 blend of chemically pulped Hesperaloe funifera/NHWK. FIG. 2 shows the relationship between caliper and wet geometric mean tensile strength for two-ply 29.6 lb/3000 sq ft ream structures made from the two furnish blends while FIG. 3 shows the relationship between water holding capacity and wet geometric mean tensile strength. Both FIGS. 2 and 3 illustrate that the Hesperaloe funifera containing web possesses outstanding wet strength coupled with high absorbency, the Hesperaloe fiber providing a bulking effect versus a control furnish.
Homogeneously formed tissue samples having the composition: chemically pulped H. funifera 50%; and NHWK 50% were prepared on a papermachine, creped then compared to tissue containing 50% NSWK fibers and 50% NHWK fibers and also samples of commercially produced tissue. Specifically, the tissue samples were evaluated for basis weight, caliper, tensile strength properties, stiffness modulus, and mean deviation in the coefficient of friction. As set forth in Table II, it can be seen that the tissues incorporating chemically pulped H. funifera were both extremely strong and extremely flexible as evidenced by the excellent tensile strength values and the very low ratio of dry geometric mean tensile strength to geometric mean stiffness modulus.
TABLE II__________________________________________________________________________Properties of Tissue Samples GM Dry Dry GMT Stiffness GM DrySample Basis Wt. Caliper Dry GMT Modulus Friction StiffnessIdentification (lbs/rm) (mils) (gm/3") (gm/% str) Deviation Modulus__________________________________________________________________________50% H. Funifera/ 19.1 61.0 1837 27.5 0.193 6750% NHWKTissue50% NSWK/ 18.1 72.2 630 16.7 0.145 3850% NHWKTissueNorthern ® 19.1 68.7 603 22.3 0.165 27Bathroom TissueNorthern ® 18.4 65.3 725 21.4 0.163 34Bathroom TissueKleenex ® 17.3 63.5 586 17.7 0.185 33Bathroom TissueWhite Cloud ® 21.1 91.0 547 20.3 0.122 30Bathroom TissueCharmin ® Free 17.9 76.5 598 17.8 0.172 34Bathroom Tissue__________________________________________________________________________
Accordingly, it can be seen that tissues of the present invention are exceedingly strong for a given stiffness, exhibiting a ratio of dry geometric mean tensile strength (in g per 3") to geometric mean stiffness modulus (in g per % strain measured at a load of 50 g for a one inch strip) above about 40, preferably above about 50 and more preferable above about 65.
With such pronounced softness advantages over tissues formed from premium furnishes like northern softwood, it is evident that furnishes comprising non-woody fibers like Hesperaloe funifera are unexpectedly desirable for creating tissue with dramatically improved quality advantages. Our studies indicate that other more recently studied non-woody fibers in the genus Hesperaloe, Hesperaloe changii and Hesperaloe sp. nova (Alamos) offer similar, potentially more desirable, benefits in tissuemaking as they have coarseness values of about 9.0 mg/100 m combined with average fiber lengths in the range of 3.5 to 4.6 mm.
The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the following claims. | A paper product having increased thickness, absorbency, and softness without altering product strength wherein a fiber blend is provided being up to 50% softwood fibers and up to 100% Hesperaloe funifera fibers. | 3 |
FIELD OF THE INVENTION
[0001] The present invention is related to motorcycles, and pertains more particularly to oil cooling for air-cooled and other motorcycle engines.
BACKGROUND OF THE INVENTION
[0002] Many types of motorcycles exist which utilize a variety of engine types and operating temperature regulating apparatus and methods. Some motorcycles employ water cooling systems through the use of radiators and water passages within the engine block and other engine or transmission components. By far the most common type of motorcycle engine today, however, is an air-cooled engine comprising a lightweight aluminum engine block and cooling fins integrated around cylinders to dissipate accumulated heat from the engine generated from combustion and component friction within the engine.
[0003] Notably, motorcycles manufactured by Harley-Davidson Motorcycle Company of Milwaukee, Wis. have large displacement, air-cooled four stroke engines which, as is true for the vast majority of motorcycle engines, comprise an engine lubrication system comprising a least one oil pump which circulates oil through the engine for lubricating the components thereof, and for carrying away the accumulated heat of combustion and friction generated within the engine during operation.
[0004] Such large displacement, air-cooled four-stroke engines of current art, such as those manufactured by Harley-Davidson Motorcycle Company, typically utilize two different types of oil pumps for circulating oil through the lubrication system, namely a scavenge pump and a lubricating pump. The scavenge pump draws oil from the crank case area, then returns the oil to the oil reservoir, and the lubrication pump is utilized for circulating oil through the remainder of the system. To maintain adequate oil flow the scavenge pump is typically designed to operate at approximately 120 percent of the pump capacity of the lubricating pump, which is the supply pump of the system.
[0005] It is well-known in the art that, for such large displacement, air-cooled engines as described above, it is important that the operating temperature of the engine and lubricating oil reach a certain temperature after start-up from a cold start before operating the motorcycle on the road. Lubricating engine oil at ambient temperature has higher viscosity than at engine operating temperature, and because of this heavier consistency of cold oil, it does not flow easily through small oil passages within the engine block or oil cooling system. Further, upon cold start up, lubricating oil from the crank case takes a finite time to reach the components within the engine, and until such time after startup, cold metal-to-metal contact may occur between components within the engine, known as “hammer effect” in the art.
[0006] During operation of such a large displacement, air-cooled motorcycle as described above, the temperature range of the engine and therefore the lubricating oil may vary greatly depending on the circumstances of operation. For example, if the running motorcycle is stopped at a stop light or in traffic, or for any other reason during engine operation, cooling air is not adequately flowing around the finned cylinders and other portions of the engine, the temperature of the engine and lubricating oil may rise quickly to the point of oil thermal breakdown temperature, which quickly accelerates engine component friction and wear, significantly shortening the life of the engine.
[0007] It has been empirically determined by testing in the industry that the recommended minimum temperature for the lubricating oil for safely operating and maintaining engine life in such large displacement air-cooled four stroke engines as described above, should be at least 100 degrees Fahrenheit before operating the motorcycle. Empirical testing has also determined that the oil temperature should reach at least 100 degrees Fahrenheit before significantly raising the engine rpm and adding significant stress to the engine components, and after complete warm up and during operation of the motorcycle, a typical recommended temperature range for the oil is between approximately 170 degrees and 210 degrees Fahrenheit.
[0008] It is therefore desirable to maintain the oil operating temperature within the recommended range during all of the operating time of the motorcycle. It is also therefore desirable to be able to quickly raise the oil temperature upon start-up from a cold start, so as to shorten the potential time of “hammer effect” of cold metal-to-metal engine component contact.
[0009] Many motorcycles such as those described above manufactured by Harley-Davidson Motorcycle Company, for example, utilize oil cooling systems for attempting to maintain oil temperature. In such systems the lubricating oil is pumped from the crank case by a scavenge pump, first circulating through an oil filter, and is then diverted to a simple radiator-type oil cooler for cooling, and the cooled oil then circulates back to the reservoir.
[0010] In such systems, the oil cooler is typically mounted horizontally to the down tubes at the front of the frame of the motorcycle, transverse to the direction of travel of the motorcycle. Such an arrangement, however, has significant drawbacks in that oil cooling unit, for example, by being mounted unprotected on the front of the frame of the motorcycle, is exposed to damage from rocks, tar, and other road debris that may be kicked by the front tire of the motorcycle during operation, or by other vehicles sharing the road with the motorcycle. Further, depending on speed of travel of the motorcycle, conventional oil coolers mounted in such a way are not subjected to as much of the air circulation as may be required, due to the air flowing over a motorcycle traveling forward tending to divert under, over and around the front of the engine.
[0011] Another drawback in current art oil coolers and diverter apparatus is that, as equal amounts of oil are diverted to the oil cooler and by-passed back to the reservoir, the relatively excessive amount of oil pumped through the oil cooler at cold startup extends the period of time required for reaching the recommended operating temperature of the oil. The inventor has discovered that it is desirable, particularly at cold startup, to by-pass as much of the oil as possible back to the oil reservoir, provided that there remains at least a small portion of the total flow out of the oil filter diverted sufficient for dissipating condensation from within the crank case at cold start up, as typically happens with air-cooled aluminum block engines such as described.
[0012] It is therefore desirable to provide an oil cooling unit, system and method which overcomes all of several drawbacks described above for such current art oil cooling systems. An improved oil cooling unit, system and method is herein provided by the inventor, and is described below in enabling detail.
SUMMARY OF THE INVENTION
[0013] In a preferred embodiment of the present invention an oil-cooling system for lubricating oil of a vehicle engine is provided, the system comprising a radiator having an oil inlet and an oil outlet communicating with internal passages of the radiator, an electrically-operated fan interfaced to the radiator in a manner to urge air through the radiator over the internal passages, the fan turned on and off by a temperature sensitive switch sensing oil temperature, a valve having a first inlet, a first passage through the valve through a first chamber to a first outlet, a second inlet, a second passage through the valve through a second chamber to a second outlet, and a translatable valve closure element controlling a passage from the first chamber to the second chamber, and a temperature-operated translation element positioned in the first chamber in the path of oil entering the valve through the first inlet, and connected to the translatable valve element in a manner to progressively close the passage from the first chamber to the second chamber at higher oil temperature, and to progressively open the passage from the first chamber to the second chamber at lower oil temperature. The system is characterized in that, below a first oil temperature the passage between the first and the second chamber remains open allowing oil coming in the first inlet to bypass the radiator to the second outlet, the passage closes gradually as oil temperature rises, closes completely at the first oil temperature so that all oil coming in the first inlet must pass through the radiator and none may bypass, and in that the temperature-sensitive switch operating the fan causes the fan to start at a second oil temperature higher than the first oil temperature, enhancing ability of the radiator to cool the oil.
[0014] In some preferred embodiments there is a volume between the fan and the radiator, providing a positive pressure chamber for air prior to passing over the radiator internal passages, such that air urged by the fan into the positive pressure chamber is distributed evenly over the internal oil passages. Also in some preferred embodiments the radiator comprises a stack-tube design.
[0015] In some embodiments the translatable valve closure element is preloaded in both translation directions by springs of differing spring rate, thereby providing a controlled force bias keeping the valve open at oil temperatures below the first temperature. Also in some embodiments the temperature-operated translation element comprises a volume of temperature-sensitive wax that expands with increasing temperature.
[0016] In some embodiments, at maximum opening of the passage between the first and second chamber, the opening allows at least seventy percent of oil from the vehicle engine to bypass the radiator and return to the vehicle engine. In some other embodiments, at maximum opening of the passage between the first and second chamber, the opening allows at least ninety percent of oil from the vehicle engine to bypass the radiator and return to the vehicle engine. The invention is especially suited for cooling oil for motorcycle engines. In some cases there is a shroud protecting the radiator when mounted on a vehicle. Also in some cases the system further comprises a mounting plate, one or more downtube mounting elements, and connectors and conduits compatible with a motorcycle, thereby providing an aftermarket kit for integrating the system to a motorcycle.
[0017] In another aspect of the invention a method for managing oil temperature for a vehicle engine is provided, comprising the steps of (a) determining a preferred temperature window for oil in operation of the vehicle, comprising a first, lower temperature, and a second, higher temperature; (b) pumping oil from the vehicle engine to a control valve controlling oil passage into a radiator, and bypassing the radiator via a by-pass passage in the control valve more than seventy-percent of the oil to return to the vehicle engine without passing through the radiator upon cold start-up; (c) closing the bypass passage at the first oil temperature, forcing all oil entering the control valve to pass through he radiator before returning to the vehicle engine; (d) starting a forced-air fan at the second temperature to urge ambient air through air passages of the radiator, thereby enhancing ability of the radiator to cool the oil passing though; and (e) as oil temperature falls, opening the bypass passage again at the first temperature.
[0018] 12. The method of claim 11 wherein a volume is provided between the fan and the radiator, providing a positive pressure chamber for air prior to passing over the radiator internal passages, such that air urged by the fan into the positive pressure chamber is distributed evenly over the internal oil passages.
[0019] In some preferred embodiments the radiator comprises a stack-tube design, and in some preferred embodiments the translatable valve closure element is preloaded in both translation directions by springs of differing spring rate, thereby providing a controlled force bias keeping the valve open at oil temperatures below the first temperature. In other preferred embodiments the temperature-operated translation element comprises a volume of temperature-sensitive wax that expands with increasing temperature.
[0020] In some embodiments, at maximum opening of the passage between the first and second chamber, the opening allows at least seventy percent of oil from the vehicle engine to bypass the radiator and return to the vehicle engine. In other embodiments, at maximum opening of the passage between the first and second chamber, the opening allows at least ninety percent of oil from the vehicle engine to bypass the radiator and return to the vehicle engine. The method is particularly adaptable a motorcycle engine.
[0021] In some embodiments a shroud protects the radiator when mounted on a vehicle. Further, in some embodiments there is a mounting plate, one or more downtube mounting elements, and connectors and conduits compatible with a motorcycle, thereby providing an aftermarket kit for integrating the system to a motorcycle.
BRIEF DESCRIPTION OF THE DRAWING FIGURES
[0022] FIG. 1 a is a front elevation view of a mounting plate for an oil cooling unit according to an embodiment of the present invention.
[0023] FIG. 1 b is a side elevation view of the mounting plate of FIG. 1 a.
[0024] FIG. 2 a is a perspective rear view of an oil cooling unit according to an embodiment of the present invention.
[0025] FIG. 2 b is a perspective front view of the oil cooling unit of FIG. 2 a.
[0026] FIG. 3 is an elevation view of an improved oil cooler by-pass valve according to an embodiment of the present invention.
[0027] FIG. 4 is an elevation front view of motorcycle frame members and the oil cooling unit of FIG. 2 a attached thereto.
[0028] FIG. 5 is a side view of a motorcycle illustrating the oil cooling unit of FIG. 2 a , and an oil cooler shroud attached to the motorcycle frame according to an embodiment of the present invention.
[0029] FIG. 6 is a simplified flow diagram of an oil cooling system according to an embodiment of the present invention.
[0030] FIG. 7 is a simplified chart illustrating oil cooling system component operation relative to oil temperature in accordance with an embodiment of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0031] Referring now to FIG. 1 a , the inventor first illustrates a mounting plate 101 provided for mounting an improved oil cooling unit to the front of a motorcycle. Plate 101 is in this example roughly trapezoidal in shape, the nonparallel sides extending upward from the bottom edge to form a smaller upper edge, and has four rounded corners. Plate 101 is designed for mounting to the front frame members of a motorcycle frame, particularly a pair of down tubes at the front of the frame, and the non-parallel sides are accordingly angled to align approximately with the angle between the pair of down tubes of the motorcycle frame. Since such an angle may vary from motorcycle model to model, and it is desirable for the edges of the plate to align with the edges of the frame when the plate is attached to the frame, the angle of the non-parallel sides of plate 101 may vary accordingly in alternative embodiments, and is therefore not particularly important in the scope and spirit of the present invention.
[0032] Plate 101 comprises a body 103 preferably manufactured of strong, lightweight material resistant to bending and warping, such as sheet metal, aluminum plate, or in some alternative embodiments plasticized or fiberglass materials, or some other similar material of suitable properties. It can be seen in FIG. 1 b that body 103 of plate 101 is substantially thin compared to it's width, and it is desirable to utilize a material in the manufacture of plate 101 which allows for it's thickness to be minimal with maximum resistance to bending or warping.
[0033] Plate 101 is provided with a large opening 105 through body 103 for the purpose of enabling air circulation through body 103 , when the improved air cooling unit of the present invention is mounted thereupon, as is subsequently described below. Opening 105 in this example has rounded sides extending upward from a straight bottom edge to a straight top edge, and the width of the opening is approximately equal to it's height, in this embodiment about 4½ inches.
[0034] A series of through-holes 111 are provided through body 103 near each corner, facilitating attachment of plate 101 to the motorcycle frame. A pair of through-holes 107 , one located on each side of opening 105 , and a series of four through-holes 119 , one located near each corner of opening 105 , enable attachment of the improved oil cooling unit assembly of the present invention, utilizing known attachment means, as is further described below.
[0035] A portion of body 103 located at each top and bottom edge of opening 105 , protrudes outwardly from body 103 in this example, these being upper guard 113 extending from the upper edge of opening 105 , and lower guard 114 extending outwardly from the lower edge of opening 105 , both to a distance of approximately {fraction (3/4)} inch. The upper and lower guards have both the purpose of providing a conduit for maximum air circulation through oil cooler 203 when mounted, as well as providing protection to the cooling passages within oil cooler 203 from outside debris.
[0036] FIG. 1 b is a side elevation view of mounting plate 101 of FIG. 1 a , which better illustrates the thickness of body 103 , in this embodiment approximately {fraction (1/8)} inch. Upper guard 113 and lower guard 114 are seen in this view extending outwardly from the surface of body 103 , as described for FIG. 1 a . Body 103 in this embodiment has a vertical height of approximately 6¾ inches, and a width of approximately 8½ inches as it's base, and approximately 7 inches at it's height. As mentioned, however, all of these dimensions may vary in all embodiments, at least partly in accordance with the dimensions between the motorcycle frame members to which plate 101 is attached, and those of the improved oil cooling unit which attaches thereto as described below.
[0037] FIGS. 2 a and 2 b are perspective views of the rear and front of an improved oil cooling unit 201 according to a preferred embodiment of the present invention. Oil cooling unit 201 is provided as part of an improved oil cooling system and method which overcomes all of the drawbacks of current art oil cooling systems as described previously in the background section.
[0038] Oil cooling unit 201 comprises the main components of mounting plate 101 of FIG. 1 a , and improved oil cooler radiator 203 , and, as shown in FIG. 2 b , a cooling fan assembly mounted to the rear side of plate 101 , and a plurality of mounting brackets 205 for attaching plate 101 to the front of the motorcycle frame.
[0039] Referring now back to FIG. 2 a , oil cooling unit 201 is provided with an improved oil cooler radiator 203 , adapted for mounting to the surface of plate 101 utilizing a pair of mounting flanges 211 , one on either side of oil cooler 203 , through which mounting holes extend which align with holes 107 of plate 101 . Standard fasteners are shown attaching oil cooler 203 to plate 101 . Each mounting flange 211 also has a portion that extends upward from the surface of plate 101 , along the sides of oil cooler 203 , to a distance approximately equal to that of upper guard 113 and lower guard 114 . The side upwardly-extending portions of mounting flanges 211 , together with upper guard 113 and lower guard 114 , form a protective shield which extends around the circumference of oil cooler 203 , protecting the cooling fins and tubes internal to oil cooler 203 from damaging debris which may be possibly kicked up from the road during motorcycle operation.
[0040] Conventional oil coolers of current art as described previously, in addition to the several drawbacks outlined above, lack sufficient oil cooling capacity due to the inherent nature of their design. Specifically, such conventional oil coolers have an inlet leading to a series of tubes running within the framework of the oil cooler, leading then to an outlet. Heat is drawn from the oil passing through the tubes of the oil cooler by way of cooling fins welded or otherwise formed on the outer surface of the oil passage tubes. Such an oil cooler configuration and arrangement is known in the art as a tube-fin design, and is limited in the capacity for drawing heat from the oil passing through tubes, due to its inherent design.
[0041] Notably, motorcycle engines of motorcycles manufactured by Harley-Davidson Motorcycle Company, when outfitted with oil cooling systems, typically utilize simple oil coolers of such simple tube-fin design, which are somewhat large in overall dimension, approximately 3 inches tall by 8 inches wide by 1¼ inches deep, and which are usually mounted directly across the front of the engine or frame utilizing standard mounting brackets. As mentioned previously, however, such a mounting arrangement provides for no protection of the oil cooler itself from road debris or other road hazards inherent when operating a motorcycle, and its close proximity to the engine further curtails the oil cooling capacity of the oil cooler when the engine is hot.
[0042] Through empirical testing, the inventor has determined that a much smaller and more compact oil cooler may be utilized by increasing the oil cooling capacity of the oil cooler itself, and integrating the improved oil cooler into the oil cooling unit and system as described herein. For this purpose, the inventor utilizes a new and improved oil passage cooling system for oil cooler 203 . In this embodiment, although not shown in great detail in the present illustrations, cooler 203 utilizes an improved cooling system for the oil passages of cooler 203 , known in the art as a stack-tube configuration, but improved upon by the inventor for the specific applications.
[0043] As mentioned above, in a tube-fin configuration, the oil to be cooled flows through tubes which have fins attach thereto which draw heat from the oil, and dissipate the heat to the surrounding circulating air by radiation and convection. The present invention, however, utilizes a stack-tube configuration, wherein the tubes are multilayered such that cooling air circulating through the first layer of tubes directly meets, and tends to flow around a layer of tubes directly behind the first layer. Further, in the stack-tube configuration utilized for oil cooler 203 , not only does oil flow through each tube, but also flows through the “cooling fins”, which are actually bulbous extensions of the tubes themselves. Oil flowing through said bulbous extensions tends to accumulate somewhat as it flows thorough, allowing much more heat to be drawn from the oil due to the greatly increased surface area of each fin oil passage, and the extended time in which the oil spends in the bulbous cooling “fins” as it flows thorough. Further, each separate tube is also connected to its adjacent tube by means of the bulbous fins, and oil within is therefore enabled to pass between tubes, in addition to through each tube, further enhancing cooling capacity of the oil cooler.
[0044] Such a configuration enables the use of a much smaller, compact oil cooler which is more efficient in oil cooling capacity, and more economically manufactured than conventional motorcycle oil coolers of current art. Oil cooler 203 is approximately 4 inches wide by 4 inches high by {fraction (3/4)} inches deep, which is a small percentage of the overall dimensions of a conventional motorcycle oil cooler as referenced previously.
[0045] Oil cooler 203 has an inlet 207 for receiving oil to be cooled, which is pumped from the engine through the oil filter of the motorcycle engine. Inlet 207 allows incoming oil into a large horizontal upper passage 216 , down through a series of vertical interconnected cooling fins 217 , each of which have bulbous cooling extensions 218 as described above, and into a large lower passage 220 , and finally to outlet 209 .
[0046] Oil cooling unit 201 is adapted for mounting to the down tubes of the front of the frame of the motorcycle, transversely to the direction of travel of the motorcycle, with oil cooler 203 facing the motorcycle engine. Mounting brackets 205 are provided for this purpose, and are fixedly attached to plate 101 near each corner. Mounting brackets 205 are preferably manufactured of metal but may be manufactured of a variety of strong, lightweight materials in various embodiments. Mounting brackets 205 each have a pair of elongated through holes 213 arranged on brackets 205 such that a bridge is formed between them, allowing passage of an unsecured end of a standard hose clamp which may is used to secure brackets 205 to the down tubes of the frame of the motorcycle. The aforementioned mounting method is better illustrated in subsequent disclosure below.
[0047] To provide additional cooling for oil according to this embodiment of the present invention, oil cooling unit 201 is provided with a cooling fan 206 , mountable to the front side of mounting plate 101 (away from the engine direction), which provides substantial additional cooling of the oil when required, automatically, and according to oil temperature. Fan 206 is mounted to plate 101 utilizing through holes 119 ( FIG. 1 a ) and standard fasteners, and is a commercially available cooling fan well known in the industry. In the preferred embodiment illustrated fan 206 is of a standard size, and has an opening with a circumference substantially equal to that of opening 105 of plate 101 ( FIG. 1 a ), for the purpose of maximizing air flow through plate 101 during operation of the fan. Fan 206 in a preferred embodiment has a circulation capacity of approximately 150 cubic feet per minute (CFM), at approximately 1.7 meters of air pressure. In alternative embodiments, however, this air flow capacity may vary depending upon the application and oil cooling capacity required.
[0048] Oil cooling unit 201 is further provided with a spacer 215 disposed between fan 206 and plate 101 , having a depth approximately {fraction (1/2)} that of fan 206 , and an outside circumference slightly greater, approximately {fraction (1/4)} inch on each side. Spacer 215 effectively seals the opposing surfaces of fan 206 and plate 101 , has an opening (not shown) having dimensions substantially equal to that of fan 206 providing air passage, and is provided in this embodiment also for creating a positive air pressure chamber during operation of fan 206 . In such a way, during operation of the fan, air is collected in a plenum ahead of the radiator at an increased pressure, before passing through oil cooler radiator 203 , which provides for more even distribution of cooling air over the cooling elements of oil cooler radiator 203 during operation.
[0049] Fan 206 receives power for operation via power lead 217 which leads to a power source. In a preferred embodiment as illustrated herein, fan 206 is automatically operated by means of a normally-open thermostatically controlled electrical switch which senses oil temperature and either remains open or closes accordingly to operate the fan, depending on the oil temperature before the oil goes through the cooler. Further illustration and disclosure is provided below pertaining to the operation of the cooling fan and thermostatically controlled fan operating switch.
[0050] As mentioned in the background section, some oil cooling systems of current art may utilize a simple diverter unit disposed between the oil filter and oil cooler for bypassing all or a portion of the circulating oil from the oil filter away from the oil cooler, bypassing all or a portion directly back to the oil reservoir. Also, it is desirable to be able to regulate the temperature of the motorcycle engine's lubricating oil after start-up from a cold start and during operation to achieve optimum oil viscosity which occurs in the recommended operating temperature range, in the least amount of time, and maintaining the recommended oil operating temperature within the range specified by the manufacturer during extended operation of the motorcycle in a variety of extreme conditions.
[0051] Current art diverter apparatus used in oil cooling systems for large displacement, air-cooled four stroke engines, such as those for motorcycle's manufactured by Harley-Davidson Motorcycle Company, as described above, typically have a total flow capacity of approximately 2.5 gallons per minute (GPM), and when activated, divert approximately 50 percent of the total oil flow out of the oil filter to the oil cooler, bypassing the remaining 50 percent back to the reservoir. In other applications the diverter apparatus in a normally-open condition either diverts 100 percent of the oil flow back to the reservoir, such as during start-up, or, when the engine or oil reaches a certain temperature, diverts 100 percent of the oil flow through the oil cooler. Such current art diverters have an internal thermostatically controlled valve approximately {fraction (1/4)} inch in diameter, and having a total travel distance between lands within the diverter apparatus of approximately {fraction (1/16)} inch. The oil by-pass capability is therefore limited in such diverter valve apparatus of current art.
[0052] It has been determined, however, through empirical testing by the inventor, that, particularly under extreme conditions during operation of the motorcycle after warm up, diverting equal amounts of the total oil flow to the cooler and reservoir, or either all or none of the oil flow, as in current art, is insufficient for ensuring optimum oil temperature for quick startup and oil and engine protection during operation of the motorcycle.
[0053] To provide for automatically controlling and regulating the oil flow through the oil cooling system in a much more effective and efficient manner, an improved by-pass valve is provided by the inventor, which, when used in conjunction with other elements of the oil cooling unit and system described herein, overcomes all of the drawbacks mentioned above in oil diverters of current art systems.
[0054] Referring now to FIG. 3 , an elevation view is given of a unique and improved oil cooler by-pass valve according to an embodiment of the present invention. By-pass valve 301 is provided for automatically regulating oil flow to the oil cooler depending on oil and engine operating temperature, to achieve and maintain optimum oil viscosity and recommended temperature range after cold startup and during motorcycle operation. By-pass valve 301 is of a type known in the industry in which a thermally responsive element within the valve actuates a closure element to allow oil to flow to an oil cooler. By-pass valve 301 , however, has been modified and adapted to be utilized with the oil cooling unit of the present invention, to allow for more effective and efficient oil temperature regulation under all operating conditions.
[0055] By-pass valve 301 has a main body 303 comprising an internal chamber 326 having a land (shoulder) 319 at the bottom of the chamber, and directly below chamber 326 , a smaller chamber 325 opens to chamber 326 , and also has a small land (shoulder) 327 at the bottom of the chamber. Land 319 functions as a valve seat for sealing off chamber 326 from chamber 325 , while land 327 functions as a spring stop.
[0056] By-pass valve 301 has a total of four nozzles providing inlets and outlets connectable to oil passage conduits for oil flowing to and from by-pass valve 301 . In the embodiment illustrated, inlet 305 and outlet 311 are shown as the upper conduits. Inlet 305 provides oil passage into chamber 326 , provided typically from the output of an oil filter (not shown) of an engine. An oil passage conduit (not shown) connects the output of the oil filter to inlet 305 . A passage 336 extends through the inlet 305 , into and through chamber 326 , and then passing out outlet 311 , enabling oil flow to flow into and out of chamber 326 .
[0057] The lower nozzles of by-pass valve 301 are inlet 307 and outlet 309 , and also comprise a similar passage 338 providing a conduit enabling oil flow from the oil cooler, through by-pass valve 301 , and out to the oil reservoir. Passage 338 also opens into chamber 325 directly above, such that oil may be allowed to flow from passage 336 , down through chamber 327 and chamber 325 , and into passage 338 . Oil passage conduits (not shown) are typically connected between outlet 311 and the inlet of the oil cooler, inlet 307 and the outlet of an oil cooler, and outlet 309 to the inlet of an oil reservoir.
[0058] By-pass valve 301 also comprises a valve actuating mechanism which is similar to those utilized in by-pass valves of current art, with the exception of certain key differences which enable by-pass valve 301 to operate in a much more efficient manner. The valve actuating mechanism of by-pass valve 301 utilizes a thermally responsive element which expands to urge an actuating element against a compression spring which urges against a valve seat and thereby causes oil to flow through the oil cooler. The thermally reactive element comprises a special wax-filled chamber 335 within a gland 317 , and an expansion rod 331 within wax-filled chamber 335 . Expansion of the special wax within chamber 335 caused by increased temperature of oil flowing around gland 317 , causes gland 317 to urge downward against compression spring 329 , and the increased tension of spring 329 thereby urges valve 323 downward towards land 319 against resistance from spring 340 . As oil temperature and wax expansion increases, valve 323 is further urged downward by gland 317 until seated on land 319 , thereby sealing chamber 326 from lower chamber 325 .
[0059] Following the discussion above, when the oil is cold the valve element 323 is retracted and oil can freely flow from chamber 326 to chamber 325 , as well as to outlet 311 and then through the oil cooler. As the temperature increases more oil is caused to go through the cooler, and less through the bypass route. Finally, at a specific temperature the valve is closed, and all oil goes through the cooler.
[0060] The valve actuating mechanism described above for by-pass valve 301 is secured within body 303 utilizing an aluminum seal 313 , secured with a standard circlip 333 , and sealed with O-ring 315 to oil passage through seal 313 . A compression spring 329 is disposed between valve 323 , and seats within an adapted bottom portion of gland 317 , preventing lateral movement of spring 329 .
[0061] The valve actuating mechanism illustrated in FIG. 3 is shown in the normally open position, which is the preset condition of by-pass valve 301 . The thermally-responsive valve actuator mechanism of by-pass valve 301 is held in the normally open position by compression spring 340 disposed between the bottom of valve 323 and land 327 , the spring pressure urging valve 323 upward. The dual action of springs 329 and 340 , with the springs selected for spring rate and amount of precompression, allow for ability to easily move valve element 323 .
[0062] In a departure from current art, by-pass valve 301 has been adapted in several ways to better regulate oil temperature in a variety of conditions including cold startup and extreme operating heat, such that optimum oil viscosity and temperature range is maintained, which greatly increases oil performance and ultimately engine life.
[0063] Specifically, as mentioned above, current art by-pass apparatus used in conventional oil cooling systems typically have a total flow capacity limit of approximately 2.5 gallons per minute (GPM), and when closed, may divert approximately 50 percent of the total oil flow out of the oil filter to the oil cooler, bypassing the remaining 50 percent back to the reservoir, or some may divert 100 percent of the oil flow back to the reservoir, such as during start-up, or, when the engine or oil reaches a certain temperature, diverting 100 percent of the oil flow through the oil cooler. Such current art diverter apparatus have an internal thermostatically controlled valve approximately about {fraction (1/4)} inch in diameter, and having a total travel distance between lands within the apparatus of approximately {fraction (1/16)} inch. The oil by-pass capability is therefore limited in such diverter valve apparatus of current art.
[0064] The valve actuating mechanism within by-pass valve 301 of FIG. 3 is shown in the normally open position, that is, compression spring 340 urges valve 323 upward above land 319 , creating a space between land 319 and the bottom of valve element 323 , which enables oil to flow from chamber 326 down to chamber 325 . In this position gland 317 is urged to the farthest upper position limited by aluminum seal 313 , by the compressive force of spring 329 disposed between space or 323 and gland 317 .
[0065] Gland 317 is positioned to directly intersect the oil flow through passage 336 between inlet 305 and outlet 311 . Gland 317 is of special design and circumference such that in its position between inlet 305 and outlet 307 during the normally open valve actuator mechanism position, approximately 10 percent of the total flow rate from the oil filter is automatically and at a consistent level, diverted out through outlet 311 . Such large displacement, air-cooled four stroke engines as described herein typically utilize an aluminum engine block, and it is well-known that water condensation within the crank case, or oil reservoir, after a hot engine has cooled is undesirable, but a factor that must be dealt with. It has been determined by the inventor that, upon startup from a cold start, 10 percent of the total oil flow rate from the oil cooler is sufficient for carrying away air and moisture from within the crank case upon startup and by bringing the oil to a temperature of at least 180 degrees F., for dissipation outside of the engine through various means.
[0066] In the normally open position the valve actuator mechanism of by-pass valve 301 , at cold startup, thereby allows oil flow from the oil filter through inlet 305 , wherein the flowing oil tends to flow around gland 317 within chamber 326 . Approximately 10 percent of the total oil flow into by-pass valve 301 is thereby diverted to outlet 311 and out to the inlet for an oil cooling unit. In this open position the remaining 90 percent of oil flow enters down into and through chambers 326 , and chamber 325 since valve 323 is unseated from land 319 in this position, and finally to passage 338 where it merges with the 10 percent flow returning from oil cooling unit via inlet 307 , all of which is returned to the reservoir, but only 10 percent of which has been cooled by the oil cooling unit. In this manner the dual benefit is provided of significantly reducing the time period required for warming the engine oil to operating temperature after a cold startup, and minimizing a condition known in the industry as airlock, whereby air is left in the crankcase during engine cooling, containing moisture which is not adequately expressed from the engine very quickly after startup.
[0067] It is emphasized that the descriptions herein are exemplary, and the percentages and other characteristics described are not limiting to the invention. In some cases more than 90 percent of the oil will be bypassed in the situation just described above, and in some other cases less. The inventor believes that to provide an adequate run-up sequence from a cold-start that at least 70 percent of the oil should be by-passed.
[0068] As oil temperature increases during operation of the engine of the motorcycle, the specialized wax within chamber 335 expands, urging gland 317 downward, compressing spring 329 , thereby urging valve 323 downward towards land 319 , which is a valve seat for valve element 323 . As the valve actuating mechanism begins to close as the oil temperature rises the flow ratio between supply passage 336 and return passage 338 begins to change quickly and dramatically, until valve 323 is urged securely into land 319 , thereby sealing chamber 325 from oil flow within chamber 326 and passage 336 , and causing all oil from the filter to pass through the oil cooler.
[0069] With valve element 323 securely seated oil can no longer flow into chamber 325 and thereby into passage 338 , so 100 percent of the oil flow entering valve 301 from an oil filter output is now diverted directly to an oil cooling unit via output 311 , thereby cooling 100 percent of the oil before it is circulated out of by-pass valve 301 back to the oil reservoir of the engine.
[0070] As mentioned previously the valve actuating mechanism of by-pass valve 301 has modifications which greatly enhance the flow control and capacity through by-pass valve 301 . Specifically, valve element 323 and the openings of chambers 326 and 325 are significantly larger than those of by-pass valves of current art. For example, valves and valve actuating mechanisms of by-pass valve of current art are typically approximately {fraction (1/4)} inch in diameter, and the valve seat in such a by-pass valve is slightly smaller. Further, the travel distance of current valves between the valve seat and the uppermost valve position in the fully open condition is approximately {fraction (1/16)} inch.
[0071] Valve element 323 of by-pass valve 301 , on the other hand, is significantly larger than those of current art, up to {fraction (5/8)} inch in diameter in a preferred embodiment, and land 327 , which functions as the valve seat for valve 323 , is only slightly smaller in diameter, and the travel distance of valve 323 between the normally open position and land 327 is significantly greater than that of current by-pass valve actuating apparatus, preferably at least {fraction (1/8)} inch, thereby providing an oil passage significantly larger than current art valves, which significantly increases oil bypass flow rate comparative to current models.
[0072] Referring now back to FIG. 2 b , a fan 206 is provided which enhances oil cooling for cooling unit 201 , fan 206 mountable to the front side of mounting plate 101 . Fan 206 receives power for operation via power lead 217 which connects to a power source. In a preferred embodiment as illustrated herein, fan 206 is automatically operated by way of a normally open thermostatically controlled electrical switch which senses oil temperature and either remains open or closes to control the functions of an oil cooling fan, depending on the oil temperature.
[0073] Now referring again to FIG. 3 , thermostat switch 337 is provided in this embodiment for controlling the on/off condition of cooling fan 206 . Switch 337 is a normally open thermostatically controlled electrical switch which is known in the art and commercially available, which is sensitive to the temperature of the oil flowing through passage 338 of by-pass valve 301 , and either opens or closes the electrical switch to actuate cooling fan in response to the temperature of the flowing oil. Switch 337 is adapted in this embodiment for attachment to the lower portion of body 303 of by-pass valve 301 , utilizing a threaded male portion 344 of switch 337 , which is threaded into the female threaded opening 343 formed into the bottom surface of body 303 of by-pass valve 301 .
[0074] Thermostat switch 337 , as is typical in similar temperature-sensitive electrical switches known in the art, closes an electrical circuit utilizing known switch actuation means, when a certain oil temperature threshold is met. Oil passage 338 between inlet 307 and outlet 309 is open to a chamber 341 provided within thermostat 337 , enabling switch 337 to sense the temperature of the oil flowing through passage 338 , and operate the electrical switch accordingly.
[0075] Referring ahead now to FIG. 7 , a simplified table 701 is provided illustrating the operation of the valve actuating mechanism of by-pass valve 301 and cooling fan 206 , relative to sensed oil temperature in accordance with an embodiment of the present invention. It is noted herein that in the table provided, oil temperature is illustrated in degrees Fahrenheit, and the stated temperatures may vary as much as approximately plus or minus two percent, without changing the associated component operation.
[0076] From cold startup, the engine of the motorcycle engine is at ambient temperature, variable depending on the surrounding environment. Regardless of the ambient temperature, however, it can be assumed that the temperature of the engine oil may be the same as, or close to that of the engine, particularly if the motorcycle has not been operated for an extended period of time, etc. It is desirable, therefore, that upon engine startup, the engine oil reach its recommended operating temperature range as quickly as possible in order to achieve the optimum oil viscosity and lubricating and flowing capability.
[0077] As illustrated in the simplified table 701 , the valve actuating mechanism within by-pass valve 301 remains in the normally open position until the oil temperature reaches 170 degrees Fahrenheit, allowing a 90 percent oil flow by-pass directly back to the reservoir, the remaining 10 percent being diverted by by-pass valve to the oil cooling unit. As previously mentioned, it is desirable to always divert approximately 10 percent of the total oil flow at cold startup to prevent the known condition of air lock.
[0078] As the oil temperature exceeds 170 degrees Fahrenheit the valve actuating mechanism of by-pass valve 301 begins to close, and the amount of oil flow diverted to the oil cooling unit compared to that by-passed back to the reservoir increases accordingly. The valve actuating mechanism continues to close as the oil temperature rises towards 180 degrees Fahrenheit.
[0079] When the oil temperature flowing through passage 336 of by-pass valve 301 reaches 180 degrees, the valve actuating mechanism of by-pass valve 301 is fully closed, diverting 100 percent of the oil flow into by-pass valve 301 , directly to the oil cooling unit.
[0080] As mentioned previously, the temperature of the oil in the engine of a motorcycle, unequipped with an embodiment of the present invention, may quickly exceed the recommended operating temperature range due to the motorcycle traveling slowly in heavy traffic or idling at a traffic light, and the resulting lack of air circulation around the engine and oil cooling unit if so equipped. Table 701 illustrates that once the oil temperature reaches 210 degrees Fahrenheit during such extreme operating conditions, additional cooling to oil flowing through the oil cooling unit is provided with an oil cooler fan running, as previously described herein. Thermostat switch 337 ( FIG. 3 ) closes when the oil temperature reaches 210 degrees Fahrenheit, which actuates oil cooling fan 206 .
[0081] Once activated by the closed thermostat electrical switch 337 , cooling fan 206 operates to cool the oil flowing through the oil cooling unit, until the temperature of the oil decreases to 190 degrees Fahrenheit, at which point the thermostatically controlled electrical switch opens, which switches off the cooling fan.
[0082] FIG. 4 is an elevation front view of motorcycle frame members and oil cooling unit 201 of FIG. 2 a attached thereto, according to an embodiment of the present invention. In this illustration oil cooling unit 201 is shown as it is fixedly attached to down tubes 402 of the front of a frame of a motorcycle, down tubes 402 supported by frame cross member 405 . Mounting plate 101 of cooling unit 201 has a mounting bracket 205 affixed at each of the four corners of plate 101 which, when utilized with standard hose clamps or other standard fasteners as previously mentioned, enable the attachment mechanism for oil cooling unit 201 .
[0083] Cooling fan 206 faces forward in the mounting configuration in the preferred embodiment shown, and when operating, draws air from in front of the fan and circulates it rearward through the opening of body 101 , and around and through the multilayered cooling passages of oil cooler 203 (not shown).
[0084] Oil cooling unit 201 in one preferred embodiment is provided as an aftermarket kit designed for retrofitting to an existing motorcycle, and all necessary mounting hardware as described above, and any conduits and connectors necessary for making all connections are also preferably provided in the retrofit kit. For some current models of motorcycles of the type described above, the presence of components of the motorcycle which may not readily accommodate mounting of oil cooler unit 201 , as shown in FIG. 4 , including such as voltage regulator heat sinks, electrical boxes, crank position sensors, and so on, which are typically mounted at or near the front of the frame of the motorcycle, may need to be repositioned in their mounting position to accommodate oil cooling unit 201 . In this case an aftermarket oil cooling unit kit may also include all of the necessary hardware for performing such repositioning of existing components of the motorcycle, the kit comprising a different set of components depending on the model of the motorcycle and the application. Oil cooling unit 201 may also be installed to the motorcycle frame, as described above, during manufacture and assembly of the motorcycle.
[0085] FIG. 5 is a side view of a motorcycle illustrating oil cooling unit 201 of FIG. 2 a , and an oil cooler shroud attached to the motorcycle frame according to an embodiment of the present invention. It is the purpose of this simplified illustration to show the mounting positions of oil cooling unit 201 and by-pass valve 301 , and to introduce an oil cooler shroud which enhances oil cooling and heat disbursement of the oil cooling unit and engine during operation of the motorcycle, as well as protects components thereof.
[0086] Motorcycle 501 represents the type of motorcycle previously described herein which is suitable for application of the oil cooling unit and system of the present invention. Motorcycle 501 has a large displacement, air-cooled four stroke engine with an aluminum engine block, and although in this simplified view many components are not shown for simplicity purposes, it can be assumed that motorcycle 501 has all of said components of such an engine, including an oil crank case, oil pumps, oil filter, and all necessary fittings and conduits for connecting to oil cooling unit 201 and by-pass valve 301 .
[0087] Oil cooling unit 201 is shown in the hidden view mounted to the angled down tubes 402 of the front of the frame of motorcycle 501 , secured to each down tube (only one shown) utilizing mounting bracket 205 and standard hose clamps 208 as described previously with reference to FIG. 4 . By virtue of the angle of the set of down tubes, oil cooling unit 201 is angled at approximately 10 degrees from vertical plum.
[0088] Oil conduits connecting components of the engine to by-pass valve 301 and oil cooling unit 201 are not shown in this view for purposes of simplicity. The inventor notes, however, that it can be assumed, as will be further detailed in simplified illustrative form below, that there is a conduit connection between output of the oil filter and the supply side inlet of by-pass valve 301 , between the supply side outlet of by-pass valve 301 and inlet 207 of oil cooling unit 201 , between the return side outlet of by-pass valve 301 and the engine's oil reservoir, and between outlet 207 of oil cooling unit 201 and the return side inlet of by-pass valve 301 .
[0089] Oil cooler shroud 503 is designed for protecting oil cooling unit 201 and components thereof from damage caused by road debris, tar, and so on, which may be thrown into the air by the front tire of the motorcycle while traveling down the road, or by those of vehicles operating nearby. Oil cooler shroud 503 is also of aerodynamic design, aiding in airflow redirection, optimizing the cooling capacity of the air flowing across and around the engine when maintained forward motion of at least 10 miles per hour. The shroud has screened openings 505 on each side for admitting air to a volume within the shroud, where the air may then be drawn into and urged through the oil cooler radiator by action of the automatically-switched fan.
[0090] FIG. 6 is a simplified flow diagram showing the oil flow in a motorcycle engine and a cooling system according to an embodiment of the present invention. Scavenge oil pump 603 pumps oil from the engine via path 629 to the oil filter 605 via path 613 . Oil passes from the filter to by-pass valve 607 via path 615 , and, in the case of oil at a temperature below the lower temperature of a preferred temperature window, oil also bypasses oil cooler system 609 via path 631 . As oil temperature rises to the first temperature of the temperature window, the bypass path closes, and all oil from filter 605 must pass through the oil cooler system.
[0091] From the oil cooler system oil follows path 619 to reservoir 611 , and lubricating pump 623 takes oil via path 621 and urges the oil through lubricating passages of engine 627 via paths 625 .
[0092] In a preferred embodiment of the invention described herein the oil cooling system is provided as an after-market kit, and may be applied to a wide range of existing motorcycles. This description, however, should not be thought of as a limitation to the invention, as the inventor intends the system for original equipment manufacture (OEM) as well.
[0093] It will be apparent to the skilled artisan that there are many alterations that might be made to embodiments described herein without departing from the spirit and scope of the invention. The nature of the radiator, the relative sizes of components, the size of conduits and the style of connectors; all of these characteristics and many more may be changed, and may vary considerably, all within the spirit and scope of the invention. The breadth of the invention is defined only by the claims which follow. | A method for managing oil temperature for a vehicle engine comprises the steps of (a) determining a preferred temperature window for oil in operation of the vehicle, comprising a first, lower temperature, and a second, higher temperature; (b) pumping oil from the vehicle engine to a control valve controlling oil passage into a radiator, and bypassing the radiator via a by-pass passage in the control valve more than seventy-percent of the oil to return to the vehicle engine without passing through the radiator upon cold start-up; (c) closing the bypass passage at the first oil temperature, forcing all oil entering the control valve to pass through he radiator before returning to the vehicle engine; (d) starting a forced-air fan at the second temperature to urge ambient air through air passages of the radiator, thereby enhancing ability of the radiator to cool the oil passing though; and (e) as oil temperature falls, opening the bypass passage again at the first temperature. | 5 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a diet earring of tragus engagement type, and more particularly to an earring attached to a tragus of the human ear capable of stimulating particularly the two acupuncture points called a "thirst point" and a "hunger point" for achieving the "diet" effect. The "tragus" herein referred to is a flattened, somewhat tongue-like projection of the auricle in front of the opening of the external auditory meatus of the human ear. The "acupuncture points" are the points to each of which, conventionally, a needle such as a "circular subcutaneous needle" or an "intradermal needle" is punctured or which is cauterized with such as "moxa" for diagnostic or remedial purposes.
2. Brief Description of the Prior Art
As a method of stimulating the tragus to achieve a diet effect, there has been known a method such as using a "circular subcutaneous needle" or an "intradermal needle", in which such a needle is punctured to a "thirst point" and a "hunger point" which are acupuncture points located at the tragus effective for achieving the diet effect and an adhesive tape is attached to prevent escapement of the needle.
However, in order to retain the needle, the needle is in the state to be subcutaneously punctured, and accordingly there have been various disadvantages as follows:
(1) Puncture of the needle causes pains;
(2) Therefore, not preferable for the person hardly endure such pains or for children;
(3) Replacement of needles is inevitable in every 3 or 4 days in view of the effective life of needles;
(4) Repeated consults for the doctor is necessary because the use of needles requires special acupuncture techniques by the professional person;
(5) The expense necessary merely for replacing needles is even so high that frequent consultations require an extremely high costs;
(6) Even if one desires to conduct personally the therapy, he is likely to remove the needles once being on purpose pricked; and
(7) The stabilization of needles using adhesive tape causes uncleanness as the time lapses and there is a danger that the needles are likely to be possibly removed.
SUMMARY OF THE INVENTION
Accordingly, an object of the present invention is to provide a diet earring of the tragus engagement type capable of achieving the diet effect for maintaining human's health merely retained to the human's tragus without using such needles as mentioned above.
A diet earring of tragus engagement type of the invention comprises a pressing member to be attached to an outer surface of a human tragus; a retaining member to engage an opposite surface of the tragus; a connecting member formed of a resilient material for connecting the pressing member and the retaining member so that the earring is retained to the tragus with the pressing member and retaining member; and a plurality of projections provided on at least one surface of either one of the pressing member and the retaining member which is opposed to each other, thereby the tragus being stimulated during the state of the tragus being retained between the pressing member and the retaining member.
In one aspect of the present invention, the plurality of projections are two projections for stimulating a thirst point and a hunger point of the tragus.
In another aspect of the present invention, the connecting member is a spring urged clip or a resilient member; and each of the pressing member and retaining member are a plate-like member formed in a shape selected from the group consisting of an ellipse, a regular circle, a polygon and any other figure.
A further object of the invention is to provide a diet earring for being worn on the human tragus to be retained on the tragus with pressing and retaining members capable of pressing the thirst and hunger points by means of a plurality of projections formed on the surface of the pressing member, and also for suspending the wearer's thirst and hunger to achieve food limiting (diet) effect, because of by pressing the thirst and hunger points to suspend thirsty feeling and appetite, respectively.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a diet earring R 1 of tragus engagement type according to a first embodiment of the invention;
FIG. 2 is a front view illustrating a tragus of the human ear including a "thirst point" and a "hunger point" therein;
FIG. 3 is a front view of a left ear to which tragus the earring is attached;
FIG. 4 is a front view of a right ear to which tragus the earring is attached;
FIG. 5 is a partially sectioned side elevational view of a diet earring R 2 according to a second embodiment;
FIG. 6 is a sectional view taken along the line Y--Y of FIG. 5; and
FIG. 7 is a front view of a pressing member.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The embodiments of the present invention are hereinafter described.
Embodiment 1
In FIGS.1 and 2, a diet earring R 1 includes a pressing member 1 formed as a circular disk which is to be attached to the outer surface of a human tragus 6, and a retaining member 2 for abutting the opposite surface of the tragus 6. The pressing and retaining members 1 and 2 are connected together by means of a U-shaped connecting member 3 so as to be opposed to each other with a predetermined distance "g". The member 3 is a spring member formed of a resilient material.
A plurality of round projections 4, such as including ten projections, are formed and substantially uniformly distributed on the surface opposed to the surface of retaining member 2. These projections are distributed so that either two of such projections can press on the thirst and the hunger points, respectively, in the normal wearing condition of the earring R 1 onto the tragus 6.
When the earring R 1 is retained to tragus 6 with its pressing member 1 and retaining member 2 by way of resilience of connecting member 3, the thirst and hunger points 7 and 8 of tragus 6 should be positioned so as to be pressed by the projections 4. In the point of view, the distance "g" and the magnitude of the spring force of connecting member 3 are provided, wherein the value of the distance "g" is provided to be smaller than the thickness of tragus 6 in the case of the embodiment.
The diet earring R 1 of such an arrangement is easily attached to tragus 6 so that it is interposed as the pressing member 1 engaging with the outer surface of tragus 6. FIGS. 3 and 4 show the diet earring R 1 which is attached to the tragus 6 of the left and right ears 5, respectively.
In the wearing state of tragus 6, the projections 4 stimulate the thirst and hunger points 7 and 8 to effectively suspend the human's appetite for thirsty and hungry.
Embodiment 2
As illustrated in FIGS. 5 to 7, together with FIG. 2 referred to also, the second embodiment of the diet earring R 2 of the invention includes a pressing member 11 formed in an elliptic figure and a retaining member 12 formed in a circular figure. The pressing member 11 and retaining member 12 are connected to each other so as to be pivoted to each other from a closed position to a open position or vice versa by means of a spring urged clip C.
As precisely, the clip C includes a J-shaped arm 13 formed integrally with the pressing member 11 at the end thereof, and also includes an I-shaped frame 14 to which the base end of the arm 13 is joined through a pin hinge 15, but the free end 13a of arm 13 extends beyond the hinged point and normally abuts a leaf spring 16 and urged by the spring 16.
The leaf spring 16 is mounted to frame 14, and performs the function, for biasing the free end 13a of arm 13 in the direction of an arrow A to hold pressing member 11 in the closed position represented by the solid line; and for biasing the free end 13a of arm 13 in the direction of an arrow B to hold pressing member 11 of its open position in the same open position. In the position of retaining member 12 being closed, the side wall of frame 14 serves as the stopper for the free end 13a of arm 13.
A bearing portion 17 for a thumb wheel 18 coaxially rotatably mounted on retaining member 12 is formed integrally with frame 14 at the opposite end with respect to pin hinge 15 of frame 14.
The pressing member 11 and retaining member 12 are positioned so as to opposed to each other with a predetermined amount "g" of the gap therebetween.
The amount "g" is regulated according to the urging force applied by leaf spring 16 of clip C and the location of retaining member 12 which is moved by the thumb wheel 18, but is basically formed smaller than the wall thickness of tragus 6 in order to effectively press the points 7 and 8. The pressure applied by projections 19 on the points 7 and 8 is determined by the amount of "g" and the urging force of leaf spring 16, and further the fine adjustment of the pressure is performed by the displacement of retaining member 12 caused by manual rotation of thumb wheel 18.
As described above, the clip C of the embodiment is formed of the arm 13, frame 14, pin hinge 15, leaf spring 16, bearing 17 and thumb wheel 18.
The projections 19 are formed on the surface of pressing member 11 so as to be opposed to the retaining member 12, including uniformly distributed seven projections, and are so distributed that either two of these would come in the position capable of pressing the "thirst point" 7 as well as the "hunger point" 8 in the usual wearing condition.
By the arrangement above, the diet earring R 2 is briefly attached, by opening the pressing member 11 to the position shown by the dotted line, then closing the same to the solid lined position as engaging the pressing member 11 with the outer side of tragus 6. The fine adjustment of the pressure applied by projections of pressing member 11 is achieved by manual rotation of thumb wheel 18 in the state of wearing the earring R 2 .
In the wearing state of earring R 2 onto tragus 6, the projections 19 stimulate the thirst and hunger points 7 and 8 to produce the effect for suspending the human's appetite for thirsty and hungry.
Projections 19 may be also provided for both members 11 and 12 on each surface thereof inwardly opposed to each other. In the same manner, also in the first embodiment previously described, the projections 4 may be formed on the opposed surfaces of the members 1 and 2.
Instead of ten projections 4 as in embodiment 1 or seven projections 19 as in embodiment 2, merely but at least two projections may be also formed on the pressing member, corresponding to the thirst and hunger positions, respectively.
As to the shape of the members 1 and 2, not limited in circular or elliptic shape, but any of the other shapes may be freely selected, such as rectilinear, triangular or of a star shape, especially in taking consideration of an ornamental appearance of the earring while wearing the earring onto the human tragus.
Instead of the spring urged clip C as in embodiment 2, a screwed clip may be also employed, which is, for example, formed of an arm 13 and frame 14 are integrally joined and not opened from each other. | Disclosed is a diet earring for stimulating acupuncture points located on the human tragus used in a simple procedure to eliminate disadvantages of the conventional needle puncture process. The earring has a pressing member 1 and a retaining member 2 for engaging the outer surface and the opposite surface of the tragus 9, respectively, and a connecting member 3 provided with an appropriate resilient urging spring for connecting the above-mentioned members, thereby the earring being retained on the both surfaces of the tragus with a suitable pressure with the tragus interposed between the pressing and retaining members. | 0 |
CROSS REFERENCE TO RELATED APPLICATION
This claims the benefit of commonly-assigned U.S. Provisional Patent Application No. 60/946,958, filed Jun. 28, 2007.
BACKGROUND OF THE INVENTION
This invention relates to mediating among media applications on a device, to determine which application should be playing.
In a device capable of a plurality of different media applications, it frequently is the case that only one media application can be played back to the user at any one time. A media application may be defined as any application that causes media to be played, even if only incidentally. Thus, in a multifunction device that may include, for example, at least a mobile telephone, an audio (e.g., music) player, a video player, a calendar application, and an Internet/World Wide Web browser (with, e.g., a wireless broadband connection), there may be several audio applications—e.g., the telephone ringtone generator, the music player, the alarm/reminder tone generator of the calendar application, and the browser (which may invoke its own audio playback session)—that can play audio, just as there may be more than one application—e.g., the video player and the browser (which may invoke its own video playback session)—that can play video. Typically, only one audio playback and/or one video playback can occur at any one time, particularly in a device with limited processing capability such as a handheld device. Therefore, a way is required to determine which application, among competing applications that all want to play, can play.
The problem may be further complicated when one application is already playing and another application wants to begin playing. This, in fact, is more likely the situation, as it is unlikely that multiple applications will both want to begin playing at precisely the same time. For example, in the multifunction device described above, the user may have initiated playback of a music file, and while the music is playing, an incoming telephone call necessitates playback of a ringtone. Whether and when, in fact, the second application can interrupt the first application may be decided based on predetermined priorities. In addition, when a first application is interrupted by a second application, a decision must be made regarding resumption, or not, of the first application upon termination of the second application. A predetermined set of rules may determine when an application is resumed and when it is not.
One known solution to this problem is for every application to “know” about the existence of every other application and when another application wants to play, and for the applications to decide among themselves, based on a predetermined matrix of (a) priorities and (b) rules for resumption, which application can interrupt another and whether the interrupted application will resume. However, such a solution requires complex programming of every application, as well as reprogramming of existing applications when a new application is added. In addition, it requires that each application be kept advised of the status of each other application.
It would be desirable to be able to mediate among various media applications in a device without each application having to be aware of, and having to take into account, each other application.
SUMMARY OF THE INVENTION
Although various media, including at least audio and video media, may be involved, for convenience, the discussion below will focus on audio media. It should be understood, however, that the principles of the invention apply to any media.
In accordance with the present invention, a media server in the device mediates among the various media applications. Thus, any media application that wants to initiate playback must make a request to the media server, which will then grant or deny the request. If the request is granted, and if the granting of the request requires the interruption of playback of another media application, the media server will send a message to the other application at the beginning of the interruption, at the end of the interruption, or both. The interrupted application will use information in one or both of those messages to determine whether or not that other application resumes playback upon completion of playback of the interrupting application.
The media server can be programmed with the aforementioned matrix of priorities and rules. However, that would still require reprogramming of the media server every time a new application is added. While that is better than having to reprogram every application to account for the new application, according to another alternative embodiment, each application, when it intends to play and/or when it finishes playing, sends a message to the media server containing various items of information, or “tags.” Similar messages may be sent on the establishment of the respective connection used by each application, which generally occurs ahead of time. The information or tags of those messages, from either the application or the connection, may relate to the identity of the application or connection, its priority (preferably this relates to the connection), and other information as described below. The media server in this embodiment is programmed with rules as to how to handle various priorities and the other information in the messages. These rules rarely need to be changed, even when additional applications are added to the system. Instead, one might have to change only the message or messages that an existing application or its connection sends (e.g., the application's connection's priority), and then only if the addition of the new application requires changes of those messages.
According to an implementation of this embodiment, when a connection is established between an application and the media server, it sends a message including a tag indicating its priority. When that application subsequently sends a request to the media server to be allowed to play some content on that connection, the media server can grant or deny the request based on the application's priority, as determined when the connection was established, relative to the priorities of other applications that are playing, if any. Thus, according to one variant of this implementation, if the priority is lower than that of an application that is already playing, then the media server will refuse the request. But if the priority is the same or higher than the priority of an application that is already playing, the media server will grant the request and the application that is already playing will be interrupted. This “rule” can be expressed as “higher priority wins, and among equal priorities, most recent wins.” Implicit in this “rule” is that if no other application is already playing, the request is granted (because any priority is higher than no priority).
In one embodiment, the actual decision as to whether or not an interrupted application will resume playback after the interruption is over is made by the interrupted application. That decision, however, can be facilitated by a message or messages that the media server sends to the interrupted application, which in turn may be determined, at least in part, by information sent to the media server by the interrupting application, as described in more detail below.
Therefore, in accordance with the present invention, there is provided a method of controlling which of a plurality of media applications can be played in a device. The method includes providing a media server in the device and establishing a respective connection for each of those applications to that media server, where each respective connection has an assigned priority. Establishment of the connections includes, for each respective connection, sending a message communicating the assigned priority to the media server. A request to play is sent from one of the applications to the media server. When the assigned priority of the respective connection for the requesting application is lower than the assigned priority of the respective connection for another application that is playing, the request is denied at the media server. When the assigned priority of the respective connection for the requesting application is at least equal to the assigned priority of the respective connection for that other application, the request is granted at the media server.
Apparatus operating in accordance with the method is also provided.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other advantages of the invention will be apparent upon consideration of the following detailed description, taken in conjunction with the accompanying drawings, in which like reference characters refer to like parts throughout, and in which:
FIG. 1 is a block diagram of a device or method in accordance with the present invention;
FIG. 2 is a flow diagram illustrating how a media server in the present invention handles a request to begin playback;
FIG. 3 is a flow diagram illustrating how a media server in the present invention handles the ending of playback;
FIG. 4 is a flow diagram illustrating the handling of implicit and explicit interruptions; and
FIG. 5 is a flow diagram illustrating how an interrupted application in the present invention decides whether or not to resume.
DETAILED DESCRIPTION OF THE INVENTION
The invention will now be described in the context of the multifunction device discussed above. It should be understood, however, that the invention is not limited to any one particular type of device.
In a device that includes a mobile telephone, as well as various media playing functions (in addition to the ringtone generator of the mobile telephone), different media playing functions may compete with each other. Thus, because a user will ordinarily want to be advised of incoming telephone calls regardless of whatever else he or she is using the device for, one ordinarily would want the playing of a ringtone to interrupt any other media—e.g., stored music—that might be playing. If the user declines to answer the call, ordinarily one would want the music to resume. Similarly, if the user accepts the call, ordinarily one would want the music to resume after the user completes the call.
However, once a media application, considered generically, has been interrupted, there are various ways to handle resumption of that application, particularly where there have been multiple interruptions. Thus, one could stack all of the applications, resuming each application as the most recent interrupting application terminates, until the stack is clear and the original application resumes. In one embodiment of the invention, however, most applications are not stacked. In fact, in that embodiment, only an alarm or reminder is stacked, so that if an alarm or reminder arrives and plays a sound while another application is already interrupted (e.g., music is interrupted for a telephone call), then the other application that is interrupted will resume after both the alarm/reminder and the original interruption are over. However, if in that embodiment any other media application is initiated during an interruption—e.g., during a phone call, the user browses to a web page and initiates an audio playback for the benefit of the other caller—the original application is not resumed after all other interruptions.
One way of handling this stacking arrangement, without having to have a lot of complicated rules in the media server, is to have connection for the interrupting application, when it sends its initial message to the media server requesting connection and indicating its priority level, also send an indication of whether it is stackable. If the connection for a current interrupting application is stackable, the application will be stacked atop the other interrupted application(s) which will eventually resume when the current interrupting application terminates, but if it is not, the other application(s) will be “pushed out the bottom” of the stack and will not resume when the current interrupting application terminates. In the embodiment described, the connection for an alarm/reminder would include an indication or tag of “stackable” in its message to the media server, while the connection for any other application would indicate that it is not stackable (or alternatively would simply not indicate that it is stackable).
One way of handling this stacking arrangement, without having to have a lot of complicated rules in the media server, is to have the connection for the interrupting application, when it sends its initial message to the media server requesting connection and indicating its priority level, also send an indication of whether it is stackable. If the connection for a current interrupting application is stackable, the application will be stacked atop the other interrupted application(s) which will eventually resume when the current interrupting application terminates, but if it is not, the other application(s) will be “pushed out the bottom” of the stack and will not resume when the current interrupting application terminates. In the embodiment described, the connection for an alarm/reminder would include an indication or tag of “stackable” in its message to the media server, while the connection for any other application would indicate that it is not stackable (or alternatively would simply not indicate that it is stackable).
Not all interrupting applications necessarily send an “interruption name” or “interruption status” tag. For many interruptions, resumption of the interrupted application is not expected. For these types of interruptions, which can be referred to as “implicit” interruptions, the media server could send a generic “interruption has begun” message and a generic “interruption has ended” message. Therefore, for implicit interruptions, it is not necessary for the interrupting application to send an “interruption name” or “interruption status” tag. The media server can simply send the generic “interruption has begun” message at the beginning of the interruption, and the generic “interruption has ended” message when it detects that playback of the interrupting content has stopped.
For certain types of interruptions, however, resumption of the interrupted application would be expected, but it may not be clear implicitly when the interruption is over. For example, if the interruption is an incoming telephone call, the reason to interrupt any media that is playing is that the ringtone, which also is a form of media, must be played. However, the interruption does not end when playing of the ringtone itself is complete. Instead, the interruption ends when the user either declines the incoming call, or accepts and then completes the call. The audio portion of the call itself is handled in this embodiment by other applications in the device and is not considered media. Thus, an explicit indication that the interruption is over is required in this embodiment. Therefore, applications such as incoming telephone calls issue “explicit” interruptions. For an explicit interruption, the message to the media server includes a particular “you have been interrupted by” notification, so that when that message is delivered to the interrupted application, the interrupted application has the necessary information to handle the resume/do-not-resume decision. In addition, because the end of the interruption cannot be inferred from the end of playing of the interrupting media (the ringtone), an explicit “interruption has ended” message is sent in this embodiment by the interrupting application (e.g., the telephone call application) and passed on by the media server to the interrupted application.
When an application that has been interrupted is pushed out of the stack by an unstackable further interruption, of the type described above, it can remain running and resident essentially indefinitely until the user turns off the device or the device battery is depleted, unless the user returns to the application manually. For example, if a music player application is interrupted by a telephone call, which is further interrupted by a web media playback session, the original music player application in this embodiment will not resume automatically on termination of the telephone call, because the web media playback application in this embodiment is not stackable. When the user has completed all of the interrupting activities, and realizes that the music has not resumed, the user can return manually to the music player application, and either terminate it or resume it manually. In the latter case, the music player can remember its position at the time of interruption and resume playing from that position.
The invention will now be described with reference to FIGS. 1-5 .
FIG. 1 shows a method or apparatus 10 in accordance with the present invention. While one embodiment of the invention can be implemented as software in a processor of a device of the type described, it also can be implemented in hardware.
Thus, in a software embodiment, “device” 10 is implemented in a processor of a device of the type described. Media server 11 , I/O module 12 and applications 13 are software modules running on that processor, with I/O module 12 driving I/O hardware including one or more speakers (not shown). Each application 13 may not actually be a separate application; several applications 13 can be individual clients or instances of one application. For example, both the music player and the web audio application can be instances of the same application.
In a hardware embodiment, device 10 can include separate hardware or firmware modules (e.g., separate integrated circuit devices) for media server 11 , I/O module 12 and various applications 13 .
In either embodiment, media server 11 grants or denies permission to any of applications 13 to play based on the requesting application's priority, as communicated by that application to media server 11 , as compared to the priority of any application 13 already playing. Each application 13 makes its own decision on resumption after the interruption, based on information communicated to it by media server 11 . That information can originate with the interrupting application, which can communicate the information to media server 11 .
It should further be noted that the term “media server” is arbitrary in the context of the current invention, and refers to any hardware or firmware, or software application, service or process, in the device, that performs the functions ascribed herein to the media server.
FIG. 2 shows process 20 by which a media server in the present invention handles a request to begin playback. At step 21 , the media server waits for a message. At step 22 , a message is received that a client of one of the system applications that currently has an inactive connection wants to activate that connection. (As previously noted, a connection to each application is defined initially, including the priority assigned to the connection.) Next, at test 23 , the media server determines whether or not a connection with a higher priority is already playing. If so, then activation failure is reported at step 24 , and the media server returns to step 21 to await a further message.
If, at test 23 , a higher-priority connection is not already playing, the media server moves to test 25 to determine whether any connection (of any priority) is playing. If not, then the requesting application can be allowed to play, and at step 26 the connection is marked as “active” and the media server returns to step 21 to await a further message.
If, at test 24 , another connection is playing, then that connection must have the same or lower priority (because this is the “No” branch of test 23 ). Accordingly, at step 27 , that currently-playing connection is interrupted. At step 28 , the now-interrupted “current” connection is marked as most-recently-interrupted” (this is used later for resumption as described below), and also at step 29 as inactive. Any previously interrupted application is forgotten, unless the connection for the current interruption is stackable (not shown). The media server then moves to step 26 and proceeds as above.
FIG. 3 shows process 30 by which a media server in the present invention handles the end of playback. At step 31 , the media server waits for a message. At step 32 , a message is received that the currently-playing client wants to deactivate its connection (e.g., after terminating a telephone call). At step 33 , the media server marks the connection as inactive, and then at test 34 determines if there is another connection marked as most-recently-interrupted (see step 28 ). If not, the playback session that just ended had not interrupted any other session when it began, and so the media server returns to step 31 to await a further message.
However, if at test 34 , the media server determines that there is another connection marked as most-recently-interrupted, then at step 35 , the media server sends a message to that most-recently-interrupted connection that the interruption has ended (so that the application for that connection can determine whether or not to resume). At step 36 , it is noted that now no connection is most-recently-interrupted, and the media server returns to step 31 to await a further message, unless the connection for the just-ended interruption was stackable, in which case the previous most-recently interrupted application rises back to the most-recently interrupted position at the top of the stack (not shown).
FIG. 4 shows how connections are activated and deactivated in the present invention in the case of implicit and explicit interruptions. In either case, a connection must be active to play media. Any attempt to play implicitly requests that the corresponding connection be activated, but a client also may make an explicit request to activate (or deactivate a connection). When a connection is activated or deactivated, the processes of FIGS. 2 and 3 are invoked.
Both explicit interruption path 400 and implicit interruption path 410 begin at step 41 with an inactive connection. In the case 400 of an explicit interruption, the connection is activated at step 401 (see FIG. 2 ) and playback begins at step 402 . Playback step 402 continues, possibly cycling through pauses 403 , until it is completed, and explicitly deactivated at step 404 (see FIG. 3 ), and returns to the inactive state 41 .
In the case 410 of an implicit interruption, an inactive connection (step 41 ) is implicitly activated (no separate step), starts playing at step 412 , and continues, possibly cycling through pauses 413 , until another connection becomes active at step 414 . In the absence of an explicit request by this application to deactivate, this can only happen if another equal or higher-priority connection is activated (see FIG. 2 ). As a result, the current connection implicitly returns to the inactive state 41 .
FIG. 5 shows the process 50 by which an interrupted application in the present invention decides whether or not to resume. At step 51 , the interrupted application receives a message that the interruption has ended (see step 35 ). At step 52 , the interrupted application examines the message and notes the name of the interrupting client and the interruption status. At test 53 , the application, using rules particular to itself, as discussed above, decides whether to resume playback (step 54 ) or not to resume playback (step 55 ).
Thus it is seen that a method or apparatus for playing media applications, with interruptions of one application by another, without the need for complicated rules or knowledge of one application by the other, has been provided. It will be understood that the foregoing is only illustrative of the principles of the invention, and that various modifications can be made by those skilled in the art without departing from the scope and spirit of the invention, and the present invention is limited only by the claims that follow. | In a device that can execute multiple media applications, but only one at a time, a media server coordinates among applications, but neither the media server nor the individual applications maintain rules regarding all of the different applications. Each connection used by an application is assigned a priority and communicates that priority to the media server when the connection is established. When an application requests to begin playback, the request is granted if no other application is playing, or if another application is playing on a connection having a priority at most equal to that of the connection used by the requesting application, but is denied if the connection already in use has a higher priority. Resumption of an application that was interrupted by another application on a connection with higher priority is determined by the interrupted application after the interruption ends, based on information communicated by the media server. | 6 |
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to a gypsum-based building material having increased thermal conductivity and shielding attenuation, a method for producing the building material, a molding containing the building material and a method for producing the molding. More specifically, the molding compositions and moldings have increased thermal conductivity and shielding against electromagnetic rays.
It is to be understood in this context that the word molding carries the broad meaning of any object or structural building part produced by molding, rather than the narrow meaning of a decorative recessed or relieved surface or a decorative plane or curved strip used for ornamentation or finishing.
Gypsum boards, specifically gypsum composite boards, gypsum cardboards, gypsum fiberboards and gypsum non-woven boards, are mainly used as floor, wall and ceiling linings for the interior finishing of buildings. Gypsum is also used in plaster flooring and in gypsum plaster and gypsum fillers.
Gypsum boards and gypsum-based building materials are almost exclusively used in construction engineering for the purpose of thermal insulation, since gypsum has very low thermal conductivity due to its microstructure. According to the prior art, the thermal conductivity of gypsum cardboards is, for example, from approximately 0.18 to 0.22 W/m*K.
However, in addition to the use for the purpose of thermal insulation, there are also other applications in construction engineering for which high thermal conductivity is desirable. Conventional gypsum building materials and gypsum boards are unsuitable for such applications due to their low thermal conductivity.
Furthermore, for many applications, for example for rooms containing EDP (Electronic Data Processing) equipment or for buildings in proximity to mobile communications or other transmitting stations, it is desirable to increase the electromagnetic shielding of the building materials being used. According to the prior art, gypsum cardboards are lined for that purpose with lead foil (see the book entitled: Gips-Datenbuch, Bundesverband der Gipsindustrie [Gypsum-Data Book, Federal Association of the Gypsum Industry] 2003, page 37).
However, it is also known that both objectives may, in principle, be achieved by adding carbon to the building material being used.
For example, International Publication No. WO99/62076 A1 discloses gypsum cardboards having a 30 to 80 μm-thick layer which encases the gypsum core and contains, in addition to cellulose fibers, a dry-mass-based content of preferably from 8 to 15% of carbon fibers having a diameter of from 4 to 10 μm and a length of from 2 to 10 mm. This improves the shielding attenuation against electromagnetic rays.
However, carbon fibers are relatively expensive. In addition, carbon fibers are almost linear structures, i.e. they have a very small surface area. The abutting edges of the boards therefore provide very little contact area for onward conduction of heat or electromagnetic signals: fibers oriented perpendicularly or with an inclination to the butting edge enter into contact only if a fiber end on the edge face of one board precisely abuts a fiber end on the edge face of the following board, and fibers lying on the abutting edge faces of the boards enter into contact only if the fibers meet or intersect one another.
International Publication No. WO 2004/065322 A1 discloses an electrically conductive gypsum-based building material which shields electromagnetic radiation. The electrical conductivity and the shielding effect are achieved by adding a mixture of particles of graphite having a size of less than or equal to 12 μm and amorphous carbon. The content of the mixture of graphite and amorphous carbon is from 25 to 75% of the total mass of the building material. The content of the amorphous carbon is, in turn, from 10 to 95% of the total mass of the mixture of graphite and amorphous carbon. The amorphous carbon contains calcined coke and/or ashes containing amorphous carbon produced by burning an organic component.
The drawbacks of those building materials include the relatively high graphite/carbon content of greater than or at least 25% and the need, in the preparation of the material, to handle substances which have a very fine-grained structure and therefore form a large amount of dust. It is difficult to incorporate fine graphite particles and, in particular, amorphous carbon into an aqueous phase. Due to their relatively low mass at a relatively large surface area and their poor wettability with water, those particles have a marked tendency to float. Although the aforementioned International Patent Application proposed, in the preparation of the material, only mixing the gypsum with the additives, before water is added, there is still the problem, when the gypsum-graphite/carbon mixture is combined with water, of the floating of the carbon and/or the graphite particles and therefore of at least partial segregation of the building material.
German Published, Non-Prosecuted Patent Application DE 100 49 230 A1 proposes the addition of a dry-mass-based content of up to 50%, preferably from 5 to 35%, of graphite to flooring materials such as cement or gypsum, in order to improve the thermal conductivity. The particle size of the graphite should be in the range of from 0.001 to 1 mm, preferably up to 0.5 mm. The use of expandable graphite is particularly recommended, for the following reasons: although expandable graphite has lower thermal conductivity, due to its open-pored foam-like structure, than the solid graphite grain, it combines more intimately with the surrounding binder, as a result of its resilient characteristics and its surface structure. The binder partially penetrates the expandable graphite particle. The resilient characteristics of the expandable graphite compensate for the problem of the different expansion coefficients of the binder and graphite particles and therefore reduce the effect of the thermal contact resistances at the grain boundaries.
The production and characteristics of expandable graphite are described as follows in a technical information document from the firm Graphit Kropfmühl AG: due to the layer lattice structure of graphite, atoms or small molecules may become embedded (intercalated) between the carbon layers. That produces what is known as swelling salt or GIC (Graphite Intercalation Compound). High-grade expandable graphites have a large content of intercalated layers. The embedded molecules are mostly sulfur or nitrogen compounds. Under the effect of heat, the layers are spread apart by thermolysis like an accordion or concertina, and the graphite flakes expand. Depending on the type of expanded graphite, expansion may start at temperatures as low as approximately 150° C. and take place relatively abruptly. In the case of free expansion, the end volume may reach several hundred times the initial volume. The characteristics of the expandable graphite, i.e. starting temperature and swelling capacity, are determined mainly by the intercalation quality (how many of the base-parallel layers were intercalated) and by the intercalation agent.
Within the terminology used in the Graphit Kropfmühl AG publication, the term “expandable graphite” apparently denotes the precursor to the expansion, i.e. the graphite intercalation compound (the graphite salt) which is capable of expansion, and not the expanded state. The use of graphite salts of that type as flame-retarding additives for building materials is known in the art.
However, the reference to the open-pored foam-like structure of the expandable graphite in German Published, Non-Prosecuted Patent Application DE 100 49 230 A1 suggests that it was not the still expandable graphite salt, but rather the already expanded form of the expandable graphite (referred to below as expanded graphite, for the sake of clarity) that was meant in that case. The worm-shaped or accordion or concertina-shaped particles obtained as a result of the thermal expansion are very bulky. The bulk density of expanded graphite, at from 2 to 20 g/l, is very low. The conveyance and metering of particles formed of expanded graphite therefore present considerable technical problems and the incorporation into the aqueous phase is greatly hindered by the floating of the light, bulky particles of expanded material. It would therefore be difficult to achieve homogeneous distribution of expanded graphite in gypsum or cement. A further problem is the marked formation of dust when expanded graphite is used. It is therefore unlikely that heat-conducting additives formed of expanded graphite will, in practice, be found to be suitable for building materials.
Indeed, for the embodiments of the aforementioned patent application, finely ground natural graphite having a particle size of less than 0.05 mm (product supplied by the firm Graphit Kropfmühl AG under the trademark EDM), rather than expanded graphite, was added to the flooring coat. An increase in the thermal conductivity of the flooring coat from 1 to 1.4 W/m*K to from 2 to 2.8 W/m*K was thus achieved.
SUMMARY OF THE INVENTION
It is accordingly an object of the invention to provide a gypsum-based building material having increased thermal conductivity and shielding attenuation, a method for producing the building material, a molding containing the building material and a method for producing the molding, which overcome the hereinafore-mentioned disadvantages of the heretofore-known products and methods of this general type and which provide a thermally conductive and electromagnetically shielding additive for gypsum-based building material molding compositions and moldings produced therefrom.
This additive should bring about a significant increase in thermal conduction and the shielding of electromagnetic radiation, even at relatively low mass fractions. It should also be easy to handle without having to take specific dust extraction measures, etc., and be easy to convey, meter and incorporate, in particular in an aqueous medium. The additive should also affect the characteristics of the gypsum as little as possible and, in particular, should not impair the mechanical stability of the building moldings. It is also desirable that it should be possible to produce the building moldings containing the additive, for example gypsum cardboards, by using substantially the same technology and, apart from the devices required for adding the additive, with the same equipment, as corresponding conventional building moldings.
With the foregoing and other objects in view there is provided, in accordance with the invention, a gypsum-based building material, comprising ground stock formed of compacted expanded graphite being added to the gypsum-based building material. A dry-mass-based proportion of the gypsum building material formed by the ground stock additive is from 5 to 50%, but preferably not more than 25%.
The additive being used in the present invention may be obtained by thermal expansion of a swellable graphite interstitial compound to form expanded graphite and recompression of the expanded graphite to form a two-dimensional structure which is then ground to form particles of the desired size. Plate-like particles having a diameter of from 1 to 5 mm are basically preferred. The bulk density is from 0.12 to 0.25 g/cm 3 .
The graphite-based additive for gypsum-based building material molding compositions according to the present invention has a number of advantages over the carbon or graphite additives known from the prior art.
The additive particles are relatively compact due to the compression. They therefore tend to form little dust and are easy to handle, convey, meter and incorporate. In particular, they may easily be incorporated in gypsum compositions or the like without the problem of floating in the aqueous medium.
With a particle diameter of from 1 to 5 mm, the particles are relatively large compared to those of additives known from the prior art. This is a particular advantage, since a large additive particle size facilitates the formation of a conductive percolation network in a non-conductive matrix.
It is generally known that in particle composite materials formed of a matrix having low electrical or thermal conductivity and an electrically or thermally conductive additive, the electrical or thermal conductivity is a function of the content of this additive. The conductivity does not increase linearly relative to the content of the conductive additive, but rather rises significantly once the percolation threshold has been reached, i.e. as soon as the conductive additive content is sufficiently high to form a continuous network of conduction paths. Further addition of additive beyond the percolation threshold only results in a minor increase in conductivity.
The capability of forming a network, and therefore the conductive additive content required to reach the percolation threshold, is highly dependent on the additive particle size and size distribution. With additives formed of large particles having a broad size distribution, the formation of a continuous network requires a lower content of additive than with an additive formed of small particles having a narrow size distribution.
However, due to their low bulk density, it is difficult to incorporate additives formed of bulky particles, such as expanded graphite, into a molding composition forming the matrix. At from 0.12 to 0.25 g/cm 3 , the bulk density of the additive being used in the present invention is in the range between the two limiting cases of expanded graphite (from 0.002 to 0.02 g/cm 3 ), on one hand and natural graphite (from approximately 0.4 to 0.7 g/cm 3 ) and synthetic graphite (from 0.8 to 0.9 g/cm 3 ), on the other hand.
The compression of the expanded graphite eliminates the disadvantageous characteristics of expanded graphite without losing its advantages. In contrast to the bulky expanded graphite particles, particles are obtained which are easy to handle, and which do not float in the aqueous medium and may therefore easily be incorporated in conventional molding compositions. The compression of the expanded graphite also brings about a significant increase in thermal conductivity in the particles.
On the other hand, even compacted expanded graphite still has to a high degree the advantages, known from German Published, Non-Prosecuted Patent Application DE 100 49 230 A1, of uncompressed expanded graphite, i.e. a certain resilience and ease of saturation with a binder. It should be noted in this regard that graphite foil, which is also produced by the compression of expanded graphite and is known, in particular, from sealing technology, is also to a certain extent resilient and may also be impregnated with binders or similar substances, incorporating up to 100% of its own mass.
A further advantage of the ground stock formed of compacted expanded graphite is that its hygroscopicity is similar to that of gypsum. Therefore, the air-conditioning or climatizing effect of the gypsum-based building materials is not reduced by the additive, as would be the case when other additives are used (carbon fibers, synthetic graphite, carbon black and the like).
The graphite particles also have a binding and lubricating effect. The exposure to dust and degree of tool wear in the mechanical machining of moldings such as, for example, gypsum boards are therefore reduced in accordance with the invention. Additives known from the prior art (carbon black, carbon fibers) have no such effect and the dust produced during machining of moldings containing those substances is harmful due to the content of carbon fibers or very fine carbon particles, so that special protective measures would have to be taken during machining.
With the objects of the invention in view, there is also provided a method for producing gypsum-based building materials. The first two steps of the process for producing the additive are known from the production of graphite foil. An intercalation compound is produced from natural graphite. The compound is thermally expanded. The expanded material particles are then compressed to form a two-dimensional structure having a thickness of between 0.1 and 3 mm, preferably at most 1 mm, and a density of between 0.8 and 1.8 g/cm 3 .
The compressed expanded graphite is ground up in a cutting mill, preferably with screens having a mesh width of between 2 and 4 mm. Particles having a diameter of between 1 and 5 mm are mainly obtained.
The content of the ground stock formed of compacted expanded graphite may be replaced, to a limited extent, by ground natural graphite without significantly detracting from the improvement in thermal conductivity which may be achieved. For example, for a mass-based proportion of the building material formed by the additive of 25%, the proportion of the total mass of the building material formed by the ground stock formed of compacted expanded graphite is 5% and the proportion of the ground natural graphite is 20%. In other words, in this case, 80% of the ground stock formed of compacted expanded graphite is replaced by ground natural graphite. This is economically advantageous, since ground natural graphite is less expensive, because it does not require the expansion and compacting process. A person skilled in the art will select the contents of ground stock formed of compacted expanded graphite and ground natural graphite depending on the individual application, while taking the desired product characteristics (required thermal conductivity, etc.) and the availability of the materials into account.
In addition, the combination of ground stock formed of compacted expanded graphite with other thermally conductive additives, such as natural graphite, is also advantageous because it increases the width of the particle size distribution of the additive. This, in turn, facilitates the formation of a percolation network, since the extended particles obtained by the grinding-up of compacted expanded graphite are able to form conduction bridges between the smaller particles formed of natural graphite.
Other additives which may be added to the ground stock formed of compacted expanded graphite in order to increase the thermal and electrical conductivity of gypsum-based building materials include carbon and metal fibers.
In accordance with the invention, the ground stock formed of compressed expanded graphite is added to gypsum-based building materials. The ground stock is incorporated into the building material in an amount such that it forms a proportion of from 5 to 50% of the dry mass of the building material. The term “gypsum-based building materials” refers, in the present context, to mixtures of gypsum and the conventional additives. These are either used as molding compositions such as gypsum fillers, gypsum plasters, gypsum flooring coat or the like or serve, optionally in combination with other components, as a starting material for the production of moldings such as, for example, gypsum boards, specifically gypsum cardboards, gypsum fiberboards, gypsum non-woven boards and gypsum composite boards. The moldings in accordance with the invention therefore contain a gypsum-based building material to which ground compacted expanded graphite is added in a proportion of from 5 to 50% of the dry mass of the gypsum-based building material.
The invention also relates to composite building components formed of at least one molding containing a gypsum-based building material, to which is added ground stock formed of compacted expanded graphite in a proportion of from 5 to 50% of the dry mass of the building material, and at least one molding containing no gypsum-based building material. This molding containing no gypsum-based building material may, for example, be a hardboard, a board made from a heat insulating material, a tile, a fireclay brick or an aerated concrete brick or the like.
Gypsum boards in accordance with the invention can, for example, be used for the protective sheathing of cable ducts in buildings.
The moldings in accordance with the invention, for example gypsum cardboards, are distinguished not only by significantly higher thermal conductivity, but also by highly uniform heating and heat distribution within the boards or moldings. This effect could be demonstrated by using thermographic tests. The uniform heating of the surface of the gypsum cardboards in accordance with the invention causes effective heat distribution over the entire board, for example in the case of solar irradiation restricted to a partial surface of the board.
Upon simultaneous use of a gypsum filler or gypsum plaster in accordance with the invention, the entire wall surface of a place of residence is thus, for example, heated more rapidly and uniformly and points at which local temperatures are lower that are caused, for example, by cast shadows or junctions between building components, are reduced. In advantageous cases, this even allows the formation of mold or mildew, caused by locally lower component temperatures, to be reduced or prevented. Furthermore, if two-dimensional heating and cooling members or air-conditioning or cooling elements and components are used, the advantage of the very good thermal conduction and the two-dimensional distribution of heat in the moldings and building materials in accordance with the invention is of considerable use, since the improved transfer of heat in turn allows the pipes through which the heating medium flows to be positioned in a configuration (meander, spiral, lattice or the like) with wider meshes than in a conventional building material, so that fewer pipes are required.
The gypsum boards or other moldings in accordance with the invention are optionally impregnated, entirely or in part, with plastics material, for example resins or thermoplastic polymers, in order to improve their impermeability and resistance to mechanical and other environmental influences.
Alternatively or additionally, one or more surfaces of the gypsum boards or other moldings may be provided, entirely or in part, with coats of paint or other forms of coating or covering which perform specific functions, including improving visual appearance, facilitating handleability, fire protection, acting as a barrier against water vapor, improving outward heat insulation and sound absorption, or reducing sensitivity to shocks. Examples of coatings of this type include coats of paint, plastics material coverings, linings with paper, wood veneer, metal foils or plastics material films, metal sheets, metal strips, fabrics or two-dimensional textile structures.
Coatings containing an adhesive, an adhesion promoter or a binder are also possible. These coatings may be used for producing a composite formation between moldings in accordance with the invention or of moldings in accordance with the invention and other building moldings such as, for example, fireclay bricks, aerated concrete bricks or tiles.
Other features which are considered as characteristic for the invention are set forth in the appended claims.
Although the invention is illustrated and described herein as embodied in a gypsum-based building material having increased thermal conductivity and shielding attenuation, a method for producing the building material, a molding containing the building material and a method for producing the molding, it is nevertheless not intended to be limited to the details shown, since various modifications and structural changes may be made therein without departing from the spirit of the invention and within the scope and range of equivalents of the claims.
The construction and method of operation of the invention, however, together with additional objects and advantages thereof will be best understood from the following description of specific embodiment examples.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now in detail to the embodiments of the invention, it is noted that the invention will be described below with reference to gypsum cardboards, by way of example. However, in view of the general suitability of the invention for all types of gypsum-based building materials, this choice is not to be understood as entailing any limitation.
The production of gypsum cardboards is known. Gypsum cardboards are generally produced, on continuously operating belt processing lines, from plaster of Paris and additives for the gypsum core and from high-grade cardboard.
In the production of gypsum cardboards, the cardboard that forms the visible side of the board is initially supplied from below. The cardboard is scored for shaping the edges. Gypsum putty, which is distributed through the use of molding stations, is then supplied. The thermally conductive and electrically shielding additive, the production of which was described above, is added to this gypsum putty. At the same time, the cardboard is supplied from above. The slab of gypsum cardboard, which is still very moist, passes through a setting section, at the end of which individual boards are cut into lengths by using a cutting device. The length and belt speed of the setting section are adapted to the setting behavior of the gypsum core. A turntable feeds the boards to a multistage dryer. Once the boards have been dried, they are trimmed at their transverse edges and stacked.
The gypsum cardboards are optionally provided with grooves, joints or recesses. It is thus known, for example, to provide a gypsum layer which is boarded on one side with joints that extend through the gypsum core and up to the cardboard layer. A rollable gypsum cardboard material is thus obtained.
Embodiment Examples
Particle size distribution of the additive:
A mixture of compacted expanded graphite having a thickness of between 0.1 mm and 1 mm was ground in a cutting mill with a screen having a mesh width of 3 mm. The particle size distribution of the ground stock was determined by screen analysis. Table 1 shows the results of the screen analysis. Approximately two-thirds of all particles had a diameter of greater than 1 mm.
TABLE 1
Particle size distribution of the ground stock
Fraction/mm
Percentage
<0.2
2
0.2 to 0.5
10
0.5 to 1.0
22
1.0 to 2.0
49
2.0 to 3.15
16
3.15 to 5.0
1
5.0 to 8.0
0
>8.0
0
Thermal conductivity of the gypsum cardboards in accordance with the invention:
Thermal conductivity perpendicular to the plane of the board for the cardboard-covered board, thermal conductivity of the gypsum core (i.e. without the effect of the cardboard covering) and thermal conductivity parallel to the plane of the board, were determined for gypsum cardboards in accordance with the invention having a variable content of the thermally conductive additive. Conventional gypsum cardboards and gypsum cardboards in which the additive was replaced, entirely or in part, by ground natural graphite, containing mainly particles in a size range of from 180 to 300 μm, were also examined for the purpose of comparison.
A one-plate apparatus was used for measuring the thermal conductivity perpendicular to the plane of the board. This apparatus was formed of an electrically heated square central plate having a length of 20 cm, surrounded by a 6-cm-wide first frame-like guard ring, a thermostated second guard ring and a thermostated cooling plate. The guard rings ensured a one-dimensional vertical heat flow in the region of the measuring surface. The sample was located between the hot side of the apparatus (including the central plate and the first guard ring) and the cooling plate. The central plate and first guard ring were electrically heated to a temperature T h . The cooling plate was cooled to a temperature T c . The thermal resistance 1/Λ of the sample being examined was calculated from the electrical power P el and the surface area A of the central plate with the temperatures T h and T c , as follows:
1
Λ
=
A
*
(
T
h
-
T
c
)
P
el
If the thickness of the sample is known, the thermal conductivity of the sample perpendicular to the plane of the plate may be calculated from the experimentally determined thermal resistance:
λ
=
Λ
*
d
=
P
el
*
d
A
*
(
T
h
-
T
c
)
The values thus measured invariably include fractions of the cardboard covering which act as a serial resistor.
The thermal conductivity of the core material was determined by using the dynamic hot-wire method. In this method, a hot wire embedded in the sample (platinum wire having a diameter of 100 μm and a length of 6 cm) is used simultaneously as a heating element and as a temperature sensor. During the measurement, the wire was heated by using a constant electrical power source. The development over time of the average temperature of the hot wire, which is dependent on the thermal conductivity of the sample, could be established on the basis of the temperature-dependent wire resistance.
For these measurements, the sample plates were halved and the hot wire was embedded, in each case, between the two halves of the sample plate, from which the cardboard casing had been removed in each case at the surface facing the wire. Table 2 summarizes the test results.
TABLE 2
Thermal conductivity of gypsum cardboards including
various additives
Thermal conductivity
Perpendicular
to the plane of
Composition and mass-based
the board/
Gypsum core/
content/% of the additive
[W/(m * K)]
[W/(m * K)]
0
0.231 ± 0.012
0.385 ± 0.019
5 (compacted expanded
0.373 ± 0.0019
graphite)
10 (compacted expanded
0.466 ± 0.023
1.097 ± 0.055
graphite)
15 (compacted expanded
0.476 ± 0.024
graphite)
15 (ground natural
0.398
graphite)
17 (compacted expanded
0.453 ± 0.023
graphite)
20 (compacted expanded
0.417 ± 0.021
1.090 ± 0.055
graphite)
20 (natural graphite) + 5
0.41 ± 0.03
(compacted expanded
graphite)
Even a dry-mass-based content of 10% of ground stock formed of compacted expanded graphite resulted in a doubling of the thermal conductivity perpendicular to the plane of the cardboard-covered board. If only the thermal conductivity of the core is measured, the effect is even more apparent, due to the absence of the cardboard covering acting as a serial resistor: an additive content of 10% caused the thermal conductivity of the core material perpendicular to the plane of the board to almost triple.
Increasing the mass-based additive content further to up to 20% caused no further significant increase in thermal conductivity (within the limits of experimental error). This indicates that the percolation threshold is reached with a mass-based content of as low as from 10 to 15% of ground stock formed of compacted expanded graphite.
If ground natural graphite was added to the gypsum core instead, no such large increase in thermal conductivity could be achieved at a comparable mass-based additive content (15%).
However, a mixture of ground stock formed of compacted expanded graphite and natural graphite resulted in a similar increase in thermal conductivity as in the case of an additive containing only ground stock formed of compacted expanded graphite. This was due to the facilitation of the formation of percolation networks at a broad particle size distribution.
Shielding attenuation of the gypsum cardboards in accordance with the invention:
The shielding attenuation of conventional gypsum cardboards and gypsum cardboards having various contents of ground stock formed of compacted expanded graphite was measured, in accordance with The German Standard DIN EN 50147-1, at frequencies of the magnetic field, plane wave and microwave field types (see Table 3).
The measuring system included a signal generator, transmitting antenna, receiving antenna and spectrum analyzer. The sample was located between the transmitting and receiving antennae.
For each measurement frequency, a shielding attenuation S of the material to be examined (Table 3) is obtained as a differential of two measurements of the path attenuation, i.e. a path attenuation P 0 without the attenuating material to be examined and a path attenuation P s with the sample of the material to be examined incorporated in the measuring apparatus. The distance, the orientation and the polarization of the antennae and the output power of the signal generator were identical in the two measurements.
TABLE 3
Measured values of the shielding attenuation/[dB]
Mass-
Micro-
based
Magnetic field
Plane wave
wave
additive
10
156
1
10
107
407
997
10
18
content/%
kHz
kHz
MHz
MHz
MHz
MHz
MHz
GHz
GHz
0
0
0
0
0
0
0
0
0
0
5
0
0
0
0
2
9
8
18
34
10
0
0
0
0
6
18
15
31
56
15
0
0
0
0
13
26
23
46
70
17
0
0
0
0
16
28
24
43
60
20
0
0
0
0
18
29
27
51
68
Whereas gypsum cardboards without additive did not have a shielding effect in any of the frequency ranges examined, the addition of graphite allowed shielding attenuation to be achieved in the plane wave and microwave frequency ranges. The shielding attenuation increased in tandem with the content of the additive. However, the increase in shielding attenuation was much lower in the case of mass-based additive contents above 15% than in the case of mass-based additive contents of up to 15%. This indicated that a percolation threshold had been exceeded, as had also been observed for the thermal conductivity. | A gypsum-based building material having increased thermal conductivity and shielding attenuation, a method for producing the building material, a molding containing the building material and a method for producing the molding are provided. The products and methods include adding ground stock formed of compacted expanded graphite to gypsum-based building materials in order to increase the thermal conductivity and the electromagnetic shielding attenuation of the building materials and moldings, for example gypsum cardboards, produced therefrom. | 2 |
FIELD OF THE INVENTION
The present invention relates generally to computer networks, and more particularly to a method of and system for controlling access to the Internet or the world wide web by providing a filtering proxy server that accesses a policy provider for judgments as to the suitability of a particular resource for a particular user.
DESCRIPTION OF THE PRIOR ART
The Internet and the world wide web have experienced explosive growth. Everyday, more content is added to the Internet and more users gain access to the Internet. The Internet enables more people to gain access to more information more quickly than ever before.
Almost everyone sees the tremendous educational, research, and entertainment value of the Internet. Children and other inquisitive people can explore new areas in ways that were not possible before. Similarly, employees and business professionals can explore industry trends, obtain information on competitors and their products, and generally expand their knowledge base. Accordingly, a substantial number of parents, educators, and business leaders provide Internet access to their children, students and employees and encourage them to use the Internet.
For all the information on the Internet that most people consider to be good and valuable, there is a substantial amount of information that some people find objectionable and or inappropriate. Many sites contain adult material such as nudity, violence, and intolerance all disclosed in various degrees of explicitness. While it is unlikely that anyone would want to prevent entirely their child or student from accessing information on the Internet, it is equally unlikely that anyone would want a young child to access scenes of explicit vulgarity or sites advocating violent or hateful action toward members of various groups. Less controversially, while there is nothing objectionable about Internet versions of mainstream newspapers and magazines, most businesses would prefer their employees not to spend their working time reading sports reports and or comics.
Presently, the on-line services market is divided into quite separate camps. On one side are the on-line environments such as AMERICA ONLINE, COMPUSERVE AND PRODIGY. Initially, these services provided their own content. Accordingly, on-line environments had virtually complete control over what was available. The other side of the on-line market is occupied by access providers, which provide little more than access to the Internet without an appreciable amount of their own content. Recently, on-line environments have begun to move toward the access provider side by providing gateways to the Internet. Increasingly, customers of on-line environments are using their service to access the public Internet rather than to obtain content created by the on-line environment provider.
The controversy about limiting access to objectionable material on the Internet, and particularly the world wide web, has put the spotlight squarely on the vacuum between these two service models. On-line environments claim to be “kid-safe”, but they cannot guarantee it, especially insofar as they provide gateways to the whole Internet. Access providers try to avoid any perception that they can control the content or applications their services deliver. Instead, access providers place the burden on parents to install and configure content filtering software, which may be complex or simplistic, on their own.
The platform for content selection (PICS) provides an infrastructure for controlling access to the Internet. PICS allows Internet sites, pages, or other resources to be classified with PICS labels. Each PICS label associated with an Internet site or page classifies the site or page according to the rating specified in the label. A rating provider assigns objective values to the PICS label for a resource. PICS products filter web content according to the PICS labels.
There are a number of shortcomings in presently available PICS products and services. Primarily, current products and services fail to personalize their filtering. Today's firewalls and proxy servers filter everyone's request against a single set of criteria. Thus, currently existing products and services do not recognize the differences in maturity level and sensitivities of different members of an organizations such as a family. Furthermore, the filtering criteria are either simplistic black lists or overly complex multi-dimensional content ratings. In the black list schemes, a binary approach is used to block or not block access by everyone to a particular resource based upon a rater's judgment. Examples of multi-dimensional systems are RSACi, which describes various levels of sex, nudity, violence, and harsh language, and SafeSurf, which provides twelve themes and nine levels within each theme.
The multi-dimensional systems provide great flexibility by which parents can tailor their filtering based upon their values and their children's maturity and sensitivity. However, the multi-dimensional systems tend to be too complex for the average parent to use. Moreover, multi-dimensional systems measure content against several categories but they do not necessarily evaluate the resource as a whole.
SUMMARY OF THE INVENTION
The present invention provides a method of and system for controlling access to the Internet by members of an organization that includes at least one supervisor and at least one non-supervisor for which limited Internet access is desired. The organization may be any commercial or non-commercial organization. In one of its aspects, the organization may be a family, with the supervisor being a parent and the non-supervisor being a child. In another of its aspects the organization may be a school, with the supervisor being a teacher and the non-supervisor being a student. The organization may also be a business, with the supervisor being a manager or a system administrator and the non-supervisor being a regular employee.
The system maintains a user session identifier for each member of the organization. Each user session identifier includes an access level field, which contains an access level set for the organization member, and a supervisor field, which indicates whether or not the organization member is a supervisor. The user session identifier may also include a field that specifies whether not unrated sites or resources are to be blocked. Where the non-supervisor members of the organization are children, the access level is preferably is an age level.
When the system establishes an Internet session between a member of the organization and the Internet, the system initially sets a user session identifier for the session to a default user session identifier. The default user session identifier is the session identifier for the lowest access level member of the organization. When the member requests a resource, the system determines if the requested resource is suitable for an individual with the access level of the current user session identifier. Preferably, in the embodiment in which non-supervisory members are children, the access level is an age rating. The system determines if the access level rating for requested resource is greater than the value of the access level field of the user session identifier. If so, the system blocks the resource and presents the member with choices of logging on to the system as a specific member of the organization with a higher access level, or appealing the blocking to a supervisor.
If the member chooses to appeal the blocking, the locator for the blocked resource is placed in a list of sites awaiting supervisor review. If the member chooses to logon as a specific member of the organization, the system authenticates the logon and sets an updated user session identifier to the session identifier for the specific member of the organization. If the updated user session identifier indicates that the member is a supervisor, the system presents the supervisor with the list of sites awaiting supervisor review. If the supervisor believes that a blocked site is appropriate for access by the non-supervisor, the supervisor can place the blocked site on a exception list. The next time the non-supervisor logs on, the system advises the non-supervisor of the previously blocked sites placed on the exception list.
Whenever a member of the organization requests a resource, the system associates the current user session identifier with the request. In the preferred embodiment, a supervisor or parent has access to any site or resource. Accordingly, if the supervisor field identifies the requestor as a supervisor, the system forwards the requested resource to the requestor. If the requester is not a supervisor, then the system determines if the requested resource is on the exception list for the requester, and if so, the system forwards the requested resource to the requester.
If the requested resource is not on the exception list, then the system determines if the requested resource is appropriate for the user. The present invention introduces the concept of a policy provider. A policy provider provides a subjective judgment as to whether a particular resource is suitable for a particular user. A policy provider is thus different from a rating provider, which provides either (i) an objective binary suitable/not-suitable judgment for a particular resource regardless of the requester, or (ii) a set of ratings that a parent or supervisor may use in determining whether the resource is suitable for the user.
If the organization has designated a policy provider, the system queries the designated policy provider for a determination of the suitability of the requested resource for the user. In the embodiment in which the organization is a family, the policy provider returns an age value, which the system compares to the age set for the user in the access level in the session identifier.
The system may also determine if the requested resource has a ratings label. Since many publishers and rating providers use rating systems based upon criteria other than age, the system of the present invention includes a policy interpreter or reifier that converts multi-variate and non-age-based ratings into an age rating. If the highest or most stringent rating is greater than the level access specified in the user session identifier, the system blocks the resource. Additionally, if the resource is unrated and the user session identifier indicates that unrated resources are to be blocked, the system blocks the resource. Otherwise, the system forwards the resource to the requester.
In the preferred embodiment of the invention in which the non-supervisor members of the organization are children, the access level of a child is specified by an age value. The age value of the child's session identifier may be the child's actual chronological age, or it may be a “virtual age” selected by the parent based upon the maturity level of the child and the parent's experience with ratings provided by the policy provider.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a high level block diagram of a system according to the present invention.
FIG. 2 is a block diagram of a preferred embodiment of a controlled access web service according to the present invention.
FIG. 3 is a high level flowchart of processing performed by the controlled access web service of the present invention.
FIG. 4 is a flowchart of policy evaluation according to the present invention.
FIG. 5 is a flowchart of block processing according to the present invention.
FIG. 6 is a flowchart of appeal processing according to the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawings, and first to FIG. 1, the Internet is designated generally by the numeral 11 . The Internet comprises a plurality of web sites 13 -N and communications facilities, as is well known to those skilled in the art. Web sites 13 provide Internet content in response to requests from users.
In the system of the present invention, users access a plurality of policy providers 15 a-n. Policy providers 15 are services that make subject judgments as to the suitability of the content of particular Internet sites, pages, or other resources for particular individuals. Policy providers are different from the ratings providers 16 of the prior art, the ratings provider 16 give objective ratings to resources without regard to who is requesting the resource. In the preferred embodiment, in which the non-supervisory members are children, the policy provider gives each resource an age rating based upon the content of the resource as a whole. Internet users can use the services of a policy provider that appears to share the values and sensibilities of the user and in whose judgment the user trusts.
According to the present invention, a controlled access web service 17 provides access between a plurality of customers 19 a-n and the Internet 11 . In the preferred embodiment of the present invention, in which customers 19 represent families using home personal computers, customers 19 use dial-up connections through a public switch telephone network PSTN 21 to establish Internet sessions through controlled access web service 17 .
Typically, each customer 19 includes several users. In the family context, one or two of the users are parents and the other users are children. According to the present invention, a parent can use controlled access web service 17 to filter Internet content to each child individually.
Generally, and as will be explained in detail hereinafter, before according a user's path through the system, according to the present invention includes several phases. First, a user 19 dials up controlled access web service 17 through PSTN 21 and provides to controlled access web service a customer account identifier and password, as is well known. Controlled access web service 17 authenticates the customer account identifier and the password and establishes the Internet session. Thereafter, each web request is filtered through a proxy in controlled access web service 17 according to the policies set for the particular customer. If the access policy is violated, controlled access web service 17 manages an exception cycle, which includes blocking the violating web page, reporting the reason for the blocking and prompting the user either to upgrade to a higher access level or to appeal the blocking for later parental review.
Referring now to FIG. 2, controlled access web service 17 includes a filtering proxy 23 and an authentication server 25 . When a customer or family initially establishes a dial-up connection, authentication server 25 accesses an authenticator database 27 , which contains authentication information. Authenticator database 27 also includes for each user associated with the customer, a session identifier. In the preferred family oriented embodiment of the present invention, each session identifier contains a parent field, which contains a bit that indicates whether or not the user is a parent, a block unrated field, which contains a bit that indicates whether or not to block unrated sites, and an access level field, which in the preferred embodiment contains the age of the user. The age may be either the actual chronological age of a child or a virtual age that may be greater than or less than the actual age of the child, depending upon the maturity level of the child and the parent's experience with the rating system. Authenticator database 27 also identifies the third party policy provider that the customer has selected.
Upon authentication of the initial logon, authentication server 25 passes to filtering proxy 23 session parameters and the Internet session is established. The session parameters include the identity of the third party policy provider and the session identifier for the user. Initially, the user session identifier is a default session identifier, which is the session identifier for the youngest member of the family.
During the session, filtering proxy 23 tags each request for a page or resource with the current user session identifier. Filtering proxy 23 fetches the requested resource and then forwards the resource to a policy evaluator 29 for an evaluation. In the preferred embodiment, a parent is entitled to view anything on the web. Accordingly, if the parent bit of the user session identifier is set to parent, the requested page is returned to filtering proxy 23 and forwarded to the customer. Initially, however, since the default user session identifier is the session identifier for the youngest child of the family, the parent bit is not set to parent.
Policy evaluator 29 accesses a database 31 of per household exception lists. An exception list contains, for each user, a list of pages or sites that would otherwise be blocked for the user but, upon parental review, have been determined to be appropriate for access by the user. If the requested page is not in the per household exception list, then the policy evaluator 29 accesses the appropriate third party policy provider 15 . The policy provider returns a judgment as to the suitability of the requested resource for the user. In the preferred embodiment, the policy provider returns an age value, which policy evaluator 29 compares to the user session identifier. Policy evaluator 29 may cache the judgment received from policy provider 15 in a ratings database 33 for later reuse.
Optionally, the system may consult a ratings provider 16 for a conventional PICS label. Accordingly, controlled access web service 17 includes a PICS policy interpreter or reifier 35 , which contains transfer functions that convert the rating received from ratings provider 16 to an age based rating. If the rating received by policy evaluator 29 is greater than the age of the user set forth in the user session identifier, policy evaluator 29 returns a “block” to filtering proxy 23 . If policy evaluator 29 does not receive a rating, then policy evaluator 29 checks whether or not the current session identifier indicates that unrated sites should be blocked. If so, policy evaluator 29 returns a block to filtering proxy 23 .
When filtering proxy 23 receives a block from policy evaluator 29 , filtering proxy 23 forwards to the customer a page that indicates that the requested resource has been blocked. The page forwarded to the customer contains controls that enable the customer to logon at a higher access level, appeal the block, or accept the block. The processes of logging on at a higher access level or appealing are handled by authentication server 25 .
If the user chooses to appeal the block, authentication server 25 passes the appeal to an appeals administrator 37 , which adds the locator for the blocked site to a per household list of sites for parental review contained in a database 39 . If the user chooses to logon as a specific user, then authentication server 25 invokes second level authentication and accesses authenticator database 27 . Second level authentication may be by means of a specific user ID and password or, in the case of younger children with a smartcard or token system. If second level authentication is valid, then authentication server 25 passes the user session identifier for the authenticated user to filtering proxy server 23 . If the specific user is a parent, then appeals administrator 37 fetches the pending list of sites for parental review from database 39 and forwards that list to the parent. The parent may review the list and the sites. The parent may either overrule the blocking, in which case the locator for the blocked site is placed in the appropriate per household exception list in database 31 , or affirm the blocking. According to the present invention, the next time the customer initially logs on to controlled access web service 17 , the customer is presented with a list of sites added to the per household exception list. If the parent finds that he or she consistently overrules the blocking of pages or sites, the parent may raise the age for the child or choose another policy provider.
Referring now to FIG. 3, there is shown a high level flow chart of the processing that occurs in controlled access web service 17 . First, at block 41 , upon initial logon to the account, the system sets the user session identifier to the default values. Then, the system sends to the customer a list of sites added to the exception list in the prior session, at block 43 , and waits for a request at block 45 . When the system receives the request, the system appends the user session identifier to the request and sends the request, at block 47 . Then, the system waits for a response, at block 49 . When the system receives the response, the system performs policy evaluation, indicated generally at block 51 , and shown in detail with respect to FIG. 4 . Policy evaluation returns either a “block” or “not block.” If, at decision block 53 , policy evaluation returns a block, then the system performs block processing, indicated generally at block 55 , and shown in detail with respect to FIG. 5 . If, at decision block 53 , policy evaluation returns not blocked, then the system sends the requested page to the customer, at block 57 , and returns to block 45 to wait for another request.
Referring now to FIG. 4A, there is shown details of policy evaluation processing. The system tests, at decision block 59 , if the user session identifier indicates that the user is a parent. If so, the system returns not block, at terminator 60 . If, on the other hand, the user session identifier indicates that the user is not a parent, then the system tests, at decision block 61 if the resource is in the exception list. If so, the system returns not block at terminator 62 . If the requested resource is not in the exception list, then the system tests, at decision block 63 , whether or not the requested resource is in the rating database. If so, the system tests, at decision block 64 if the rating in the database is greater than the user session identifier. If so, the system returns block at terminator 65 . If, at decision block 63 the rating is not greater than the user session identifier, then the system returns not block at terminator 66 .
If, at decision block 63 , the resource is not in the rating database, then the system determines if the customer has designated a policy provider, at decision block 67 . If so, the system queries the designated policy provider and implicitly waits at block 68 . If, at decision block 69 , the system receives a rating from the policy provider, then the system determines, at block 71 , if the rating receive from the policy provider is greater than the user session identifier. If so, the system returns block at terminator 72 . If, at decision block 71 the rating is not greater than the user session identifier, then the system returns not block at terminator 73 . In addition, if a rating is returned from the policy provider, in step 69 , the rating is stored in a rating data base at step 70 after 73 .
If, at decision block 69 , the customer has not designated a policy provider, then the system determines, at decision block 74 , FIG. 4B if there is a label in the resource. If so, the system tests, at decision block 75 , if the label is an age. If so, the system inserts the rating in the rating database, at block 76 . If the rating is not an age, then the system reifies label to an age rating, at block 77 , and inserts the rating into the rating database, at block 76 . Then, the system tests, at decision block 78 if the rating produced by the reifier is greater than the user session identifier. If so, the system returns block at terminator 79 . If, the rating is not greater than the user session identifier, then the system returns not block at terminator 80 .
If, at decision block 74 , there is not a label in the document, the system determines, at decision block 81 , if the customer has designated a ratings provider. If so, the system queries the designated ratings provider and implicitly waits at block 82 . If, at decision block 83 , the system receives a label from the ratings provider, the system tests, at decision block 85 , if the label is an age. If so, the system inserts the rating in the rating database, at block 86 . If the rating is not an age, then the system reifies the label to an age rating, at block 87 , and inserts the rating into the rating database, at block 86 . Then, the system tests, at decision block 88 if the rating produced by the reifier is greater than the user session identifier. If so, the system returns block at terminator 89 . If, the rating is not greater than the user session identifier, then the system returns not block at terminator 90 .
If, at decision block 81 , the customer has not designated a ratings provider, then the system tests, at decision block 91 , if the current user session identifier indicates that unrated pages should be blocked. If not, the system returns not block at terminator 93 . If, on the other hand, the current user session identifier is set to block unrated sites or resources, then the system returns block at terminator 95 .
Referring now to FIG. 5, there is shown a flow chart of block processing. First, the system sends a “sorry” page, at block 101 , and waits for a response, at block 103 . The sorry page notifies the user that the requested resource has been blocked and includes controls that enable the user to logon at a higher level, appeal the block, or accept the block. If, at decision block 105 , the user selects logon at a higher level, the system authenticates the higher level logon and updates the user session identifier, at block 107 . Then, the system tests, at decision block 109 , if the new user is a parent. If not, processing returns to block 45 of FIG. 3 . If, at decision block 109 , the new user is a parent, then the system performs appeal processing as indicated generally at block 111 and shown in detail with respect to FIG. 6 .
If, at decision block 113 the user selects the appeal control from the sorry page, the system appends a locator for the request to the list of sites for parental review, at block 115 and returns. If, at decision block 117 , the user accepts the block, by selecting an “OK” control, processing returns to block 45 of FIG. 3 .
Referring now to FIG. 6, there is shown a flow chart of appeal processing according to the present invention. Upon determining that the new user is a parent, the system sends a list of sites for parental review, at block 119 , and waits for a response, at block 121 . The parent can review each site on the list if the parent so chooses. If the parent determines that he or she has no objection to the child viewing an appealed site, then the parent can select an unblock control on the list of sites, at decision block 123 . If the parent does select the unblock control, then the system adds the site to the exception list and removes the site from the list of sites for parental review, at block 125 . When the parent is finished with the list of sites for parental review, the parent can select an OK control at decision block 127 . Selection of the OK control clears the list of sites for parental review, at block 129 and the system returns to block 45 of FIG. 3 .
From the foregoing, it may be seen that the present invention provides a method and system that includes authentication components that identify individual end users and filtering tools that manage policy enforcement according to policy evaluations by third parties. With the present invention, Internet access providers can address not only the current objectionable content debate, but future debates over consumer privacy, intellectual property rights, and mobile code safety. Moreover, the present invention provides a flexible, secure, and easy to configure system that allows Internet access providers to provide content filtering to their customers without becoming censors. | A method of and system for controlling access to the Internet by members of an organization that includes at least one supervisor and at least one non-supervisor for which limited Internet access is desired. The system maintains for each member of the organization a session identifier. When the system establishes an Internet session between a member of the organization and the Internet, the system initially sets a user session identifier for said Internet session to a default session identifier, which is the session identifier for the lowest access level member of the organization. When the member requests a resource, the system determines if an access level rating for requested resource is greater than the value of the access level field of the user session identifier. If so, the system blocks the resource and presents member with choices of logging on to the system as a specific member of the organization with a higher access level, or appealing the blocking to a supervisor. | 7 |
BACKGROUND OF THE INVENTION
The present invention relates to a wet spinning process for obtaining polyvinyl alcohol (hereinafter referred to as PVA) fiber containing boric acid or a borate, and more especially to a very stable spinning process for producing a PVA fiber of high tenacity and high modulus.
The process of spinning a PVA solution containing boric acid or a borate into an alkaline coagulation bath to produce PVA fiber has long been known. For example, the specifications of Japanese Patent Publications No. 8918/1956 and No. 2061/1959 disclose the process of spinning a PVA spinning solution containing boric acid or a borate into an alkaline coagulation bath containing different salts.
It is supposed that in these processes the PVA spinning solution may form a fiber by the gelation reaction with the alkaline component, by the dehydrating coagulation reaction with the salts of the coagulation bath and further by the crosslinking reaction with boric acid. Since these reactions proceed simultaneously, the mechanism of the spinning reaction is so delicate that it is affected by slight changes in the spinning conditions and becomes very unstable. Accordingly, the quality of the thus obtained products fluctuates notably and the tendency for the products to degenerate with the lapse of time is extremely apparent and is one of the largest problems associated with this process. Spinning methods for PVA fibers of the above-mentioned type have long been known, and a sufficient number of basic studies have been reported to enable production of fibers of relatively high quality, but this technique has not yet been applied practically to industrial production, evidently because of the above-mentioned unsteadiness of spinning and the unstable quality.
The present inventors, after researching the causes of such unsteadiness of spinning and instability also taking into consideration the change in the quality of the fiber with the lapse of time, have found that these deficiencies are a function of the metal deposit on the backside of the spinning nozzle (on the side of the spinning solution) and of the deposit of scale around the nozzle orifice of the front side of the spinning nozzle (on the side of the coagulation bath).
Since the spinning nozzle for a wet process is generally made of an alloy of gold with platinum, the noble metal when coming in contact with some non-noble metal is apt to create a galvanic cell and itself become a cathode while making the non-noble metal an anode.
The spinning solution contains a fair amount of metal ions derived from the water solvent or from erosion of the apparatus, which metal ions appear to have been deposited on the nozzle acting as a cathode. According to the result of our analysis, the deposited metal consists principally of copper and subsidiary components such as iron.
According to the results of our analysis, it has been found that the scale deposited around the nozzle orifice contains iron and calcium compounds. This fact suggests that the metal ions contained in the spinning solution would become insoluble compounds to deposit as the scale around the nozzle orifice.
SUMMARY OF THE INVENTION
In accordance with the present invention there has been provided a process for producing PVA fibers having an excellent quality and containing boric acid or a borate, which comprises admixing 0.01 - 5% by weight based on the PVA weight of a compound selected from the group consisting of an amino acid, an amine, salicylic acid or a derivative thereof and a derivative of pyridine (hereinafter abbreviated as the additive) with the aqueous polyvinyl alcohol solution containing boric acid or a borate and then spinning the solution into an alkaline coagulation bath to form filaments. When 0.01 - 5% by weight of the additive based on the polyvinyl alcohol is admixed with the spinning solution according to the process of the present invention, the electrodeposition of metals and the formation of scale are completely eliminated to ensure a very stable spinning process and also prevent the degeneration of the fiber quality with lapse of time.
DETAILED DESCRIPTION OF THE INVENTION
The present inventors have previously applied for patents relating to a method of admixing aminopolycarboxylic acid and condensed phosphoric acid to the coagulation bath (Ser. No. 202,384 filed Nov. 26, 1971). Although the above methods were capable of preventing the formation of scale, they were not effective for preventing the electrodeposition of metal on the backside of the spinning nozzle and they failed to assure a complete stabilization of the spinning process. The present invention overcomes this limitation and assures a very high stability of the spinning process. In comparison with the conventional processes in which no additive is added to the spinning solution and the spinning process is gradually worsened with the lapse of time to reduce the product quality and curtail the life of the nozzle to five days, the present invention enables a prolonged nozzle life of more than one month and also prevents the degeneration of the product quality.
When the additive is incorporated only in the spinning bath, the spinning process is maintained stable for about 15 - 20 days, but thereafter the spinning is worsened as electrodeposition occurs on the backside of the nozzle.
It is believed that the effect of incorporating the additive into the spinning solution according to the present invention is achieved because the metal ions in the spinning solution combine with the additive to form chelate compounds and thereby change the redox potential thereof to interrupt the electrodeposition and, thus prevent the formation of such compounds into scale or alternatively immediately dissolve any already formed scale by the action of the additive.
Furthermore it has been discovered that the fiber produced according to the present invention possesses qualities such as tenacity and initial modulus better than the products obtained from a spinning solution not containing the additives.
The reasons why fibers of improved quality are obtainable according to the present invention are not well known yet, but it may be suggested that the additive admixed with the PVA spinning solution containing boric acid or a borate affects directly or indirectly the coagulation of said spinning solution caused by dehydration or gelation and assures that the PVA fibers have a compact and fine microstructure.
It is beyond our expectation that the effect obtained by the present invention has improved not only the spinnability but also the quality of the thus obtained PVA fibers. This result was totally unexpected in view of the conventional process for preparing PVA fibers containing boric acid.
The additives used in the process of the present invention may be the compounds having a solubility in the spinning solution of from about 0.01 - 5% by weight based on the PVA.
Among the amino acids contemplated for use in the present invention, aminopolycarboxylic acids have the greatest effect. Suitable examples of aminopolycarboxylic acids include ethylenediamine-tetraacetic acid and the sodium and potassium salts thereof (hereinafter sodium and potassium aminopolycarboxylates are referred to as the salts thereof), nitrilotriacetic acid and the salts thereof, trimethylene diamine-tetraacetic acid and the salts thereof, methylamine-diacetic acid and the salts thereof, and N-cyclohexylethylenediamine-triacetic acid and the salts thereof.
Amines used in the present invention include ethylene diamine, N-methylethylene diamine, N-n-propylethylene diamine, N,N'-dimethylethylene diamine, 1,2-diaminopropane, trimethylene diamine, 1,2-diaminocyclohexane, 1,2,3-triaminopropane, 1,3-diamino-2-aminomethylpropane, diethylenetriamine, triethylenetetramine, 2-hydroxyethylamine, 2-mercapto ethylamine and bis( 2-aminoethyl) sulfide. Salicylic acid and derivatives thereof include salicylic acid and 5-sulfosalicylic acid. Derivatives of pyridine include 2-aminomethyl pyridine, pyridine-2-carboxylic acid, pyridine-2,6-dicarboxylic acid, pyridoxamine, piperizine and piperizine-2,6-dicarboxylic acid.
The quantity of said additive to be admixed to the spinning solution should be within the range of about 0.01 - 5% by weight based on the PVA, and preferably within the range of about 0.1 - 1.0% by weight. A content less than 0.01% by weight may be less effective and a content larger than 5% may be undesirable because of an adverse effect on the coagulation.
No particular means are necessary to admix the additive, and it may simply be dissolved in the required quantity at the time of preparing the spinning solution.
The PVA employable in the present invention should have a polymerization degree greater than 500 and a degree of saponification greater than 95% and preferably greater than 99 mol per cent, while the aqueous spinning solution should have a PVA concentration of from about 10 - 30% by weight and should contain from about 0.5 - 5% by weight of boric acid or a borate based on the PVA. The solution should preferably have a pH value of from about 3.5 to 7.
The above-described PVA spinning solution can be spun by a usual wet spinning method. The coagulation bath should be an aqueous solution containing about 5 - 200 g/l of caustic alkali and 100 g/l to the saturating concentration of a dehydration salt. Examples of employable caustic alkalis are sodium hydroxide and potassium hydroxide, while examples of dehydration salts include sodium sulfate, ammonium sulfate and sodium carbonate. The spun fiber may be conventionally treated by neutralization with an acid, washing with water, drying, drawing, heat-treatment and acetalization.
The PVA fiber obtained by the process of the present invention has excellent tenacity and initial modulus, particularly at higher temperature, and is useful as an industrial material for tires, belts and other materials to be employed under severe conditions.
Now the present invention will be described in detail with reference to several specific embodiments thereof. The dry breaking tenacity and initial modulus as shown in these examples are determined as follows:
Dry breaking tenacity: This is a value of a sample fiber 20 cm long being twisted 8 turns/10 cm length and then dried for 3 hours at 105° C., measured in accordance with the Japanese Industrial Standard L 1070 by a tensile testing machine (constant rate of extension type) in which an elastic film (Lycra film made by du Pont Company) is stuck to the jaw face of a chuck, and drawing the sample at a drawing speed of 10 cm per minute.
Initial modulus: This is a value measured on the basis of the stress-strain curve obtained by measuring the foregoing dry breaking tenacity in accordance with Japanese Industrial Standard L 1073. when the measurement is made at normal temperature, it is made in a room maintained at 20° C. and when the measurement is made at high temperatures, it is made by setting an electric heater so that the upper and lower chucks and the sample are maintained at 120° C.
EXAMPLE 1
50 kg of PVA having a polymerization degree of 2,200 and a saponification degree of 98.5 mole per cent were dissolved in water to form an aqueous solution containing 13% PVA to which was then added 1 kg of boric acid (2% by weight on the basis of the PVA) and 0.05 kg of ethylenediamine-tetraacetic acid (0.1% by weight based on the PVA) and there was further added acetic acid to adjust the pH to 4.5.
The thus obtained spinning solution was spun into a coagulation bath containing 100 g/l of NaOH and 150 g/l of Na 2 SO 4 through a nozzle having 1000 orifices of 0.06 mm diameter at a extrusion rate of 150 g/min and was removed from the bath at a rate of 8 m/min.
Subsequently, the spun filament was drawn by 100% with rollers and the sodium hydroxide adhered to the fiber was neutralized with sulfuric acid. Then the resultant fiber was wet hot drawn at a ratio of 100%, washed with water, dried, dry hot drawn at a ratio of 250%, heat treated, taken up and thereafter the properties of the fiber were measured.
CONTROL EXAMPLES A AND B
Control Example A; Aside from the fact that no ethylenediamine tetraacetic acid was added to the spinning solution, the treatment was essentially the same as that of Example 1.
Control Example B; Aside from the fact that ethylenediamine tetraacetic acid of 3.4 × 10 - 3 mol/l was added to the coagulation bath instead of to the spinning solution, the treatment was essentially the same as that of Example 1.
Table I shows the results of Example 1 and Control Examples A and B. It is evident from this table that ethylenediamine tetraacetic acid added to the spinning solution offered most excellent effects.
Table I__________________________________________________________________________ Example 1 Control Example B Control Example__________________________________________________________________________ ASpinnability Stable beyond 30 days Stable for 15 days Decreased from 5th dayFiber-breaking in drawing(times/100 kg) 0.33 0.52 6.3Electrodeposition of metal onthe backside of nozzle none yes yesDry breaking tenacity atroom temperature (g/d) after 1 day 10.8 10.7 9.8 after 4 days 10.8 10.8 9.3 after 7 days 10.9 10.5 -- after 15 days 11.0 10.5 -- after 30 days 10.8 10.7 --Initial modulus at roomtemperature (g/d) 280 275 230 at high temperature 140 132 105__________________________________________________________________________
EXAMPLES 2 - 4 AND CONTROL EXAMPLES C AND D
The treatment of Example 1 was repeated except that nitrilotriacetic acid was employed instead of ethylenediaminetetraacetic acid. The quantity of nitrilotriacetic acid added was varied each time as shown in Table III. In control Example C, the spinning solution originally contained a great amount of bubbles, which were difficult to remove and provided an abnormally difficult spinnability. The results are shown in Table II.
Table II__________________________________________________________________________ Example No. Control Example 2 3 4 C D__________________________________________________________________________Nitrilotriacetic acid (% byweight based on PVA) 2 0.5 0.05 8 0.005Spinnability Stable for Stable for Stable for Decreased from Decreased from 30 days 30 days 30 days 3rd day 10th dayFiber-breaking in drawing(times/100 kg) 0.75 0.28 0.65 5.8 3.3Electrodeposition of metal onthe backside of nozzle none none none none a littleDry breaking tenacity atroom temperature (g/d) after 1 day 10.8 11.5 10.7 10.5 10.2 after 4 days 10.9 11.4 10.9 -- 9.8 after 7 days 10.8 11.6 10.9 -- 10.1 after 10 days 10.8 11.2 10.7 -- 9.7 after 15 days 11.0 11.4 11.0 -- --Initial modulus (g/d) at room temperature 275 285 270 255 250 at high temperature 131 145 135 122 120__________________________________________________________________________
EXAMPLE 5
50 kg of PVA having a degree of polymerization of 2400 and a saponification degree of 98.5 mole per cent were dissolved in water to obtain an aqueous solution containing 13 weight per cent PVA, and a spinning solution was prepared from the aqueous solution by adding 1 kg of boric acid (2 weight per cent based on PVA), 0.05 kg of N-methylethylenediamine and acetic acid to adjust the pH to 4.5. This spinning solution was spun into a coagulation bath containing 100 g/l of NaOH and 150 g/l of Na 2 SO 4 through a nozzle having 1000 orifices each 0.06 mm in diameter at an extrusion rate of 150 g/min. and the resultant fiber was removed from the bath at a rate of 8 m/min. Subsequently, the spun fiber was drawn with rollers at a ratio of 100%, and thereafter, NaOH adhered to the fiber was neutralized with sulfuric acid. Then the resulting fiber was wet hot drawn at a ratio of 100%, washed with water, dried, dry hot drawn at a ratio of 250%, heat-treated, taken up and thereafter the properties of the fiber were measured.
CONTROL EXAMPLES E AND F
Control Example E; Aside from the fact that no N-methylethylenediamine was added to the spinning solution, the treatment was essentially the same as that of Example 5.
Control Example F; Aside from the fact that N-methylethylenediamine of 3.4 × 10 - 3 mole/l was added to the coagulation bath instead of to the spinning solution, the treatment was essentially the same as that of Example 5.
The results of Example 5 and control examples E and F are shown in Table III.
TABLE III______________________________________ Example 5 Control Ex. E Control Ex. F______________________________________Spinnability Stable beyond Decreased Stable for 30 days from 5th day 15 daysFiber breakingin drawing 0.31 6.3 0.72(times/100 kg)Electrodepositionof metal on back- none yes yesside of nozzleDry breakingtenacity (g/d)1 day 10.7 9.8 10.64 10.9 9.3 10.87 10.9 -- 10.415 11.0 -- 10.430 10.8 -- 10.4______________________________________
EXAMPLE 6 AND CONTROL EXAMPLE G
50 kg of PVA having a degree of polymerization of 1700 and a degree of saponification of 98.5% were dissolved in water to obtain an aqueous solution containing 18 weight per cent of PVA and a spinning solution was prepared from the aqueous solution by adding 0.75 kg of boric acid (1.5 weight per cent based on PVA), 0.25 kg of salicylic acid (0.5 weight per cent based on PVA) and acetic acid to adjust the pH to 5. The treatment otherwise was essentially the same as that of Example 5.
Control Example G; Aside from the fact that no salicylic acid was added to the spinning solution, the treatment was essentially the same as that of Example 6. The results of Example 6 and Control Example G are shown in Table IV.
Table IV__________________________________________________________________________ Example 6 Control Example G__________________________________________________________________________Spinnability Stable beyond 30 days Decreased from 7th dayFiber-breaking in drawing(times/100 kg) 0.50 4.2Electrodeposition of metalon backside of nozzle none yesDry breaking tenacity atroom temperature (g/d) 1st day 10.8 10.0 4th day 11.0 9.5 10th day 11.0 -- 15th day 10.8 -- 30th day 10.8 --Initial modulus (g/d) at room temperature 280 240 at high temperature 140 110__________________________________________________________________________
EXAMPLES 7 - 9 AND CONTROL EXAMPLES H AND I
Instead of using N-methylethylenediamine, triethylene tetramine was added to the spinning solution. The quantity of the additive was varied as shown in Table V. The treatments were otherwise essentially the same as that of Example 5. The results are shown in Table V.
Table V__________________________________________________________________________ Example No. Control Example 7 8 9 H I__________________________________________________________________________Triethylene tetramine(weight %/PVA) 2 0.5 0.05 8 0.005Spinnability Stable beyond Decreased from Decreased from 30 days same same 3rd day 10th dayFiber-breaking in drawing(times/100 kg) 0.80 0.30 0.75 6.5 2.3Electrodeposition of metal on none none none none a littlebackside of nozzleDry breaking tenacity atroom temperature (g/d) 1st day 10.7 11.3 10.6 10.2 10.1 4th day 10.7 11.3 10.7 -- 10.0 7th day 10.8 11.5 10.9 -- 9.9 10th day 10.7 11.1 10.9 -- 9.8 15th day 10.9 11.3 11.0 -- --Initial modulus (g/d) at room temperature 270 281 272 250 245 at high temperature 131 148 135 122 120__________________________________________________________________________
EXAMPLE 10
Instead of the N-methylethylenediamine used in Example 5, 2-aminomethyl pyridine was added to the spinning solution in the same quantity as that of Example 5. The treatment was essentially the same as that of Example 5. The results obtained are shown in Table VI.
While the present invention has been described and pointed out with reference to certain specific embodiments thereof, it is to be understood that the scope of proprietary rights attendant thereto are not to be limited except by the following claims.
Table VI______________________________________ Example 10______________________________________Spinnability Stable beyond 30 daysFiber-breaking in drawing(times/100 kg) 0.25Electrodeposition of metal onbackside of nozzle noneDry breaking tenacity atroom temperature (g/d) 1st day 10.9 4th day 10.6 7th day 10.4 15th day 11.0 30th day 10.8Initial modulus (g/d) at room temperature 280 at high temperature 138______________________________________ | Disclosed is a method for preparing polyvinyl alcohol fibers which comprises spinning an aqueous solution of polyvinyl alcohol containing boric acid or a borate and from about 0.01-5 weight per cent based on said polyvinyl alcohol of an additive comprising an amino acid, an amine, salicylic acid and derivatives thereof or a derivative of pyridine into an alkaline coagulation bath, and subsequently treating the resultant spun fiber by roller drawing, neutralizing with acid, wet hot drawing, washing with water, drying and dry hot drawing. | 2 |
FIELD OF THE INVENTION
The present invention is a method of using luminal glutamine in the prevention of bacterial translocation and Neonatal Necrotizing Enterocolitis (NEC) in vivo. The same treatment is useful to also protect intestinal cells against injuries caused by other infectious agents, toxins, chemicals, and injurious substances.
BACKGROUND OF THE INVENTION
Glutamine is a "conditionally essential amino acid": Although, glutamine is considered a non-essential amino acid, recent reports and studies from our laboratory support that the presence of intraluminal (apical) glutamine is essential for optimal intestinal epithelial function (Horvath K, Jami M M, Hill I D, Papadimitriou J C, Magder L S, Chanasongcram S. Glutamine-free oral diet and the morphology and function of the rat small intestine, J Parent Ent Nutr 1996;20: 128-134).
Small intestinal epithelial cells (enterocytes) have the third highest rate of cell turnover in the body, and require a constant high energy source. Glutamine is the preferred fuel for enterocytes (Williamson R C N. Intestinal adaptation. Structural, functional and cytokinetic changes, N Engl J Med 1978; 298:1393-1402; Nygaard K. Resection of the small intestine in rats. 3. Morphological changes in the intestinal tract. Acta Chir Scand 1967; 133: 233-248; Windmueller H G., Spaeth A E.: Uptake and metabolism of plasma glutamine by the small intestine. J. Biol. Chem. 1974; 249: 5070-5079).
The enterocytes are strongly dependent on an external glutamine supply, because of the small size of the mucosal glutamine pool in the small intestine (0.2 μmol/g of tissue) compared to liver (5.94 μmol/g) or skeletal muscle (3,3 μmol/g). The activity of mucosal glutamine synthetase is also extremely low (Windmueller H G., Spaeth A E.: Uptake and metabolism of plasma glutamine by the small intestine. J. Biol. Chem. 1974; 249: 5070-5079; Lund P.: A radiochemical assay for glutamine synthetase, and activity of the enzyme in the rat tissues. Biochem. J. 1970; 118:35-39).
Although enterocytes can get glutamine from both the lumen and circulating blood, these two sources of glutamine are not utilized in identical manner. During total parenteral nutrition (TPN) without glutamine, intestinal atrophy and hypofunction occurs within 3 days, despite the fact that L-glutamine levels in serum do not decrease significantly. Although L-glutamine is not regarded as an essential amino acid, its necessity during TPN makes it a conditionally essential amino acid in humans (Hughes C A, Dowling R H. Speed of onset of adaptive mucosal hypoplasia and hypofunction in the intestine of parenterally fed rats. Clin Sci 1980; 59:317-327).
Atrophy of the intestine also involves cells and organelles other than enterocyte. Immunological cells, such as lymphocytes and macrophages, in the mucosa also metabolize glutamine. Fibroblasts require glutamine for optimal function, as well (Ardawi M S M, Newsholme E A. Glutamine metabolism in lymphocytes of the rat. Biochem J. 1983; 212: 835-842; Caldwell M D. Local glutamine metabolism in wound and inflammation. Metabolism 1989; 38(suppl):34-39; Zielke H R, Ozand P T, Tildon J T, Sevdalian D A, Cornblath M. Reciprocal regulation of glucose and glutamine utilization by cultured human diploid fibroblasts. J Cell Physiol 1978; 95:41-48).
In the absence of glutamine the rate of ( 3 H) thymidine incorporation into DNA was very low in mesenteric lymphocytes and even a small amount of glutamine (1 μM) caused a four-fold increase in incorporation. TPN formulas without glutamine result in significant decrease in the secretory IgA level associated with bacterial translocation from the gut. 2% glutamine in TPN significantly decreased the bacterial (E. coli, Proteus mirabilis) translocation to mesenteric lymph nodes in rats (Burke D J, Alverdy J C, Aoys E, Moss G. Glutamine-supplemented total parenteral nutrition improves gut immune function. Arch Surg 1989; 124:1396-1399), although there was no significant difference in the adherence of bacteria to the ileum and colon (Ardawi M S M, Newsholme E A. Glutamine metabolism in lymphocytes of the rat. Biochem J. 1983; 212: 835-842; Alverdy J C, Chi H S, Sheldon G S. The effect of parenteral nutrition on gastrointestinal immunity, the importance of enteral stimulation. Ann. Surg. 1985; 202:681-684; Alverdy J C, Aoys E, Moss G S. Total parenteral nutrition promotes bacterial translocation from the gut. Surgery 1988; 104:185-190).
TPN supplemented with glutamine restored the normal SIgA levels in bile. Glutamine supplementation was also beneficial in models of mucosal damage (radiation, methotrexate) by significantly decreasing the mortality of animals and accelerating mucosal recovery. These data emphasize the importance of glutamine for two distinct functions of the small intestine: (I) nutrient absorption and (II) the mucosal defense (Burke D J, Alverdy J C, Aoys E, Moss G. Glutamine-supplemented total parenteral nutrition improves gut immune function. Arch Surg 1989; 124:1396-1399; Fox A D, Kripke S A, De Paula J, Berman J M, Settle R G, Rombeau J L. Effect of a glutamine-supplemented enteral diet on methotrexate-induced enterocolitis. J Parent Enteral Nutr 1988;12:325-331; Klimberg V S, Souba W W, Dolson D, Copeland E M. Oral glutamine supports crypt cell turnover and accelerates intestinal healing following abdominal radiation. JPEN 1989; 115:38 (abstract)).
Effects of Glutamine on the Small Intestinal Mucosa
Glutamine increases the number of mitoses per crypt in animals fed a glutamine-supplemented elemental diet.
That implies that glutamine supports crypt cell turnover and leads to increased villous height. Burke et al demonstrated that the addition of glutamine to TPN resulted in the maintenance of normal levels of IgA (Barber A E, Jones W G, Minei J P, Moldawer L L, Fahey T J, Lowry S F, Shires G T. Composition and functional consequences of fiber and glutamine supplementation of enteral diets. Surg Forum 1989;40:15-16; Klimberg V S, Souba W W, Dolson D, Copeland E M. Oral glutamine supports crypt cell turnover and accelerates intestinal healing following abdominal radiation. JPEN 1989; 115:38 (abstract)). (Hwang T L, O'Dwyer S, Smith R J, Wilmore D W. Preservation of the small intestinal mucosa using glutamine supplemented parenteral nutrition. Surg Forum 1986; 37:56-58); Burke D J, Alverdy J C, Aoys E, Moss G. Glutamine-supplemented total parenteral nutrition improves gut immune function, 1989; 124:1396-1399).
Underlying mechanism of actions of glutamine on the intestinal mucosa are not known. Li et al reported an elevated concentration of glucagon in the portal vein of rats receiving glutamine containing TPN. Glucagon has an important role in the regulation of glutaminase. O'Dwyer suggested that the trophic effect of glutamine may be related to its secretagogue action, stimulating enteroglucagon secretion (Li S, Nussbaum M S, McFadden D W, Zhang F-S, LaFrance R J, Dayal R, Fischer J E. Addition of L-glutamine to total parenteral nutrition and its effect on portal insulin and glucagon and the development of hepatic steatosis in rats. J Surg Res 1990; 48:421-426); Geer R J, Williams P E, Lairmore T, Abumrad N N. Glucagon: an important stimulator of gut and hepatic glutamine metabolism. Surg Forum 1987; 38:27-28); O'Dwyer S T, Smith R J, Hwang T L, Wilmore D W. Maintenance of small bowel mucosa with glutamine enriched parenteral nutrition. JPEN 1989; 13:579-585).
Glutamine and the Neonatal Intestine
Very little data are available concerning the role of glutamine in the developing intestine. Kimura demonstrated an increased glutamine oxidation in the bowel of newborn rats compared to adult animals, indicating a higher demand for glutamine during development (Kimura R E. Glutamine oxidation by developing rat small intestine. Pediatr Res 1987; 21:214-217).
The glutamate content of human milk protein is very high and it is the most abundant amino acid in a variety of milk proteins (casein, serum albumin, lactoferrin, IgA and a-lactalbumin). Glutamine, glutamic acid and taurine are the most abundant free amino acids in human milk. Presumably, the high glutamate and glutamine content is advantageous for the developing small intestine (Harzer G, Bindels J G. Main compositional criteria of human milk and their implications on nutrition in early infancy. In: New aspects of nutrition in pregnancy, infancy and prematurity. (ed. Xanthou M). Elsevier Science Publishers, Amsterdam, 1987, p. 83-94; Rassin D K. Protein requirements in neonate. In: Textbook of Gastroenterology and Nutrition in Infancy (ed. Lebenthal E.), Raven Press, Ltd., New York, 1989, pp. 281-292; Harzer D, Franzke V, Bindels J G. Human milk nonprotein nitrogen components: changing patterns of free amino acid and urea in the course of early lactation. Am J Clin Nutr 1984; 40:303-309.
Very recently, Neu et al. have studied glutamine metabolism in preterm infants and have shown that preterm infants can tolerate and utilize glutamine when provided orally (enterally). Examining the immunological functions, these authors reported a reduced HLA-DR(+) T cell population and a concomitant increase in nosocomial infection in preterm infants not receiving supplemental oral glutamine.
Bacterial Translocation
Bacterial translocation is defined as the passage of viable intestinal bacteria across the intestinal epithelial cell layer into the normally sterile extra intestinal tissues. The translocated bacteria are usually normal inhabitants of the lower part of the small intestine and the colon. Translocation of bacteria may occur both transcellularly and paracellularly (Alexander J W, Bryce S T, Babock G F et al. The process of microbial translocation. Ann Surg 1990;212:496-512).
The first step in the process of translocation is the traffic of bacteria across the epithelial cell (enterocyte) monolayer. Translocation of few bacteria is a normal process and the mucosal immune system (macrophages as first line of defense) along with the consequent immune activation prevent further translocation. Secretory immunoglobulins may prevent the attachment of the same bacteria into the mucosal surface.
In the absence of glutamine (TPN) expression of secretory IgA is decreased. The Golgi-apparatus plays an important role in secretory IgA production. The production of secretory component takes place in the rough endoplasmic reticulum and it needs further maturation in the Golgi apparatus.
The morphological changes in the Golgi-apparatus described by our group may explain the decreased SIgA production found in patients on TPN. Any decline in immune defense results in deeper invasion of bacteria, and they can be detected in the mesenteric lymph nodes, liver and spleen. (Horvath K, Jami M M, Hill I D, Papadimitriou J C, Magder L S, Chanasongcram S. Glutamine-free oral diet and the morphology and function of the rat small intestine. J Parent Ent Nutr 1996;20: 128-134; Burke D J, Alverdy J C, Aoys E, Moss G. Glutamine-supplemented total parenteral nutrition improves gut immune function. Arch Surg 1989; 124:1396-1399; Brandtzaeg P, Halstensen T S, Kett K, Kraj -- i P, Kvale D, Rognum TO, Scott H, Sollid L M. Immunobiology and immunopathology of human gut mucosa: humoral immunity and intraepithelail lymphocytes. Gastroenterology 1989; 97:1562-84).
Necrotizing Enterocolitis in Premature Infants
NEC is the most serious gastrointestinal disorder of premature infants and one of the leading causes of death in neonatal intensive care units (NICU). It is the most common surgical emergency in the newborn period and the second leading cause of morbidity and mortality in the preterm population. The incidence of NEC in selected studies has ranged from fewer than 1% to as many as 5% of NICU admissions. A recent multicenter study of 2681 infants weighing 501-1500 grams reported that proven NEC (Bell Stage 2-3) occurred in 10.1% and suspected NEC (Bell Stage 1) in a further 17.2% of the cohort; mortality was 54% in infants with severe (Stage 3) NEC.
Those data indicate that NEC is a major public health problem in neonates: given the ˜4 million births/year in the United States, NEC would be expected to develop in 1200-9600 infants, of whom between 9-28% will die as a result of their disease. Earlier studies indicated a mortality of 10-55% in premature infants. Survivors of NEC can also have considerable long-term morbidity resulting from their disease, including short-gut syndrome, failure-to-thrive, intestinal stricture, and the need for repeated surgery.
Clinical Significance
Several studies have demonstrated the beneficial effect of glutamine in the intestine and especially on enterocytes (Barber A E, Jones W G, Minei J P, Moldawer L L, Fahey T J, Lowry S F, Shires G T. Composition and functional consequences of fiber and glutamine supplementation of enteral diets. Surg Forum 1989;40:15-16; Klimberg V S, Souba W W, Dolson D, Copeland E M). Oral glutamine supports crypt cell turnover and accelerates intestinal healing following abdominal radiation. JPEN 1989; 115:38 (abstract); Souba W W, Klimberg V S, Hautamaki R D, Meddenhall W H, Bova F C, Howard R J, Bland K I, Copeland E M. Oral glutamine reduces bacterial translocation following abdominal radiation. J Surg Res 1990; 48:1-5), however, the molecular mechanism of these effects has not been clarified. (Hwang T L, O'Dwyer S, Smith R J, Wilmore D W. Preservation of the small intestinal mucosa using glutamine supplemented parenteral nutrition. Surg Forum 1986; 37:56-58).
In different experimental animal models it has been shown that endotoxemia, ischemia, hemorrhagic shock can cause bacterial translocation. (Deitch E A, Berg R D, Specian R. Endotoxin promotes the translocation of bacteria from the gut. Arch Surg 1987; 122:185; Redan J A, Rush B F, Lysz T W, Smith S, Machiedo G W. Organ distribution of gut-derived bacteria caused by bowel manipulation or ischemia. Am J Surg 1990;159:85-89; Deitch E A, Bridges W, Baker J, Ma J W, Ma I, Grisham M B, Grenger D N, Specian R D, Berg R D). Hemorrhagic shock induced bacterial translocation is reduced by xanthine oxidase inhibition or inactivation. Surgery 1988; 104:191), burn and infection, chemotherapy, abdominal radiation. (Jones II W G, Minei J P, Barber A E, Raybern J, Fahey III T J, Shires III G T, Shires G T. Bacterial translocation and intestinal atrophy after injury and burn wound sepsis. Ann Surg 1990;211:399; Berg R D. Bacterial translocation from the gastrointestinal tract of mice receiving immunosuppressive chemotherapeutic agents. Curr Microbiol 1983; 8: 285-289; Fox A D, Kripke S A, De Paula J, Berman J M, Settle R G, Rombeau J L. Effect of a glutamine-supplemented enteral diet on methotrexate-induced enterocolitis. J Parent Enteral Nutr 1988;12:325-331; Guzman-Stein G, Bonsack M, Liberty J, Delaney J P). Abdominal radiation causes bacterial translocation, total parenteral nutrition, total parenteral nutrition plus narcotics and impaired intestinal motility can cause bacterial translocation to mesenteric lymph nodes, abdominal cavity, liver, spleen and blood resulting in septicemia and death. The cause of such increased bacterial translocation has not been defined. (J Surg Res 1989;46:104; Souba W W, Klimberg V S, Hautamaki R D, Meddenhall W H, Bova F C, Howard R J, Bland K I, Copeland E M. Oral glutamine reduces bacterial translocation following abdominal radiation. J Surg Res 1990; 48:1-5; Alverdy J C, Aoys E, Moss G S. Total parenteral nutrition promotes bacterial translocation from the gut. Surgery 1988; 104:185-190; Kueppers P M, Miller T A, Chen C Y K et al . . . Effect of total parenteral nutrition plus morphine on bacterial translocation in rats. Ann Surg 1993;217:286-292).
Prospective randomized clinical trials have documented that the incidence of major infectious complications is less in enterally fed burn and trauma, patients than in comparable patients fed parenterally. (Alexander J W, MacMillan J C, Stinnet J D. et al. Beneficial effect of aggressive protein feeding in severely burned children. Ann Surg 1980; 192:505-517; Kudsk K A, Groce M A, Fabian T C et al. Enteral versus parenteral feeding: Effects on septic morbidity after blunt and penetrating abdominal trauma. Ann Surg 1992; 215:503-513; Moore F A., Moore E E, Jones T N et al. TEN versus TPN following major torso trauma: reduced septic morbidity. J Trauma 1989; 29:916-923).
Sedman et al examined 242 general surgical patients for bacterial translocation during surgery. 10.3% of the patients had translocation detected on the intestinal serosa or in the mesenteric lymph nodes. Intestinal obstruction and inflammatory bowel disease were predisposing factors for translocation, however, 5% of patients without these conditions had translocation. The development of postoperative septic complications was twice as common in patients with translocation as those without it. (Sedman P C, Macfie J, Sagar P, Mitchell C J, May J, Mancey-Jones B, Johnstone D. The prevalence of gut translocation in humans. Gastroenterology 1994;107:643-649).
SUMMARY OF THE INVENTION
Based on our Caco 2 cell and ileal loop models, the instant invention demonstrates that the absence of luminal glutamine results in NEC and mucosal damage.
An object of the present invention is to treat premature infants with additional glutamine from the enteral side (oral administration) to reduce bacterial translocation and subsequent development of NEC.
A second object is to use similar strategy (high oral glutamine) in adult and pediatric patients in intensive care units under total parenteral nutrition (intravenous feed) to avoid mucosal dysfunction and further bacterial translocation.
A third object is its use in patients undergoing chemotherapy, irradiation and bone marrow transplantation.
Yet another object is to use the preparation to prevent or treat other inflammatory mucosal diseases of the GI tract that may have a bacterial etiologic component.
Another object is the use in post surgical patients during diet restriction and parenteral nutrition. In these patients the translocation of intestinal bacteria may result in systemic sepsis and multi organ failure without glutamine therapy.
A further object is to use the preparation in fullterms, children, and adults, in GI dysfunctions of infective and/or inflammatory origin where bacterial translocation may act as a trigger or aid in disease progression.
A preferred method of preventing necrotizing tissue injury in gastro-intestinal tract comprises orally administering glutamine. The tissues are protected along the gastro-intestinal tract by blocking bacterial translocation with the glutamine.
Preferably, the tissues along the gastro-intestinal tract are protected with the administered glutamine which blocks translocating of bacteria (such as gram (-) bacteria), other infectious agents, toxins, chemicals, and injurious substances. Oral glutamine also optimizes mucosal defense and increases nutrient absorption due to its intraluminal/apical availability. Glutamine is administered for preventing and treating gastro-intestinal dysfunctions and pathologic conditions.
Glutamine may be administered to individuals such as pre-term infants, full-term infants, children and adults. Glutamine may be provided in any form that is orally administrable. That includes powder forms or in a reconstituted mixture with a fluid. Alternately glutamine may be administered as capsules. Preferably, the capsules are acid resistant slow-release release micro-capsules which last long enough to reach the requisite areas in the gastro-intestinal tract such as the intestines. The capsules may be enter coated time-release capsules. Also, other drugs for treatment of ailments may be administered with the glutamine.
A preferred method of treating neonatal necrotizing enterocolitis comprises providing enteral glutamine for reducing inflammation caused by bacterial adherence, invasion and injury.
A preferred method of treating gastro-intestinal dysfunctions includes providing apical glutamine for improving physiological functions.
Preferably, the oral administration allows the glutamine to coat gastro-intestinal mucosa thereby treating infectious and/or inflammatory conditions of the gastro-intestinal tract.
A preferred method of treating pathologic conditions with lowered transepithelial electrical resistance (TEER) is by administering oral glutamine as a curative agent.
These and further and other objects and features of the invention are apparent in the disclosure, which includes the above and ongoing written specification, with the claims and the drawings.
BRIEF DESCRIPTION OF THE ILLUSTRATIONS
FIG. 1 is a schematic representation of an enterocyte with apical and basolateral sides.
FIG. 2 shows the expression of disaccharidases as the Caco-2 cells differentiate.
FIGS. 3A-E illustrate the Disaccharidase and glucoamylase activity during glutamine deprivation and replenishment.
FIG. 4 shows the results of both apical (0/0.6) and basolateral (6.0/0) glutamine deprivation.
FIG. 5 shows the effect of apical vs. basolateral glutamine deprivation on bacterial transcytosis.
FIG. 6 shows the effect of glutamine replenishment.
FIGS. 7A, 7B, and 7C show the histopathology of weanling rabbit ileal loops:
7A: shows control loops inoculated with PBS;
7B: shows loops inoculated with 10 9 CFU of E. coli strain 21-1 isolated from a patient with NEC.
7C: shows loops co-inoculated with 4 mM glutamine and 10 9 CFU of E. coli.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the present invention, supply of glutamine from the luminal side (apically for the enterocytes) has been shown to reduce bacterial translocation and maintain healthy physiological functions.
The present inventors show that supply of glutamine to the enterocytes from the apical side (luminal) is much more important and is critical in the maintenance of physiological functions. Lack of such apical glutamine results in decreased transepithelial resistance, increased passage of inulin, and increased bacterial translocation across intestinal cell monolayers. The present invention also demonstrates that it is not an energy related phenomenon, since, the deleterious effects are most remarkable 24-48 hr after glutamine deprivation. The present invention shows that these effects can be reversed in the same system by replenishment with glutamine, a process that again takes more than 24 hr for full recovery. These data underline that the present inventors have identified a novel phenomenon of glutamine action on enterocytes.
The underlying mechanisms as to why enterocytes cannot utilize glutamine from the basolateral side remains unsolved. However, these tissue culture results have been replicated in a weanling rabbit ileal loop model of NEC.
Effect of Glutamine on enterocytes in general is not critical to the present invention. It is well known that this amino acid is the major energy source for enterocytes. In humans, and experimental animal models the beneficial role of glutamine has been shown to be mediated via improved immunological functions. In the present invention, however, it is demonstrated for the first time, that due to some unknown cellular mechanisms enterocytes use glutamine much more efficiently when supplied from apical (luminal) side.
From a clinical stand point the present invention also demonstrates that lack of apical glutamine results in increased bacterial translocation in tissue culture systems. Translating the effects in vivo, instillation of rabbit loops with glutamine protects them against bactrial infections, such as the Gram (-) bacteria-induced necrotizing enterocolitis.
The accompanying figures illustrate the following:
FIG. 1: Schematic representation of an enterocyte with apical and basolateral sides.
FIG. 2: shows the expression of disaccharidases as the Caco-2 cells differentiate. Note the increase in enzyme expression after day-8 that reaches high levels comparable to human biopsy samples by day-12.
FIGS. 3A-E: FIGS. 3B-E: Disaccharidase and glucoamylase activity during glutamine deprivation and replenishment. There was a decline in the levels of all enzymes after 4 hr deprivation. While the drop in lactase did not reach statistical significance, all other values at time points from 4-48 hr deprivation were significantly different from control, p<0.05 (n=4). There was a linear increase in enzyme expression over the 4-48 hr replenishment period that reached base line level after 48 hr. The 4-48 hr values were not statistically different from the control, p<0.05 (n=4).
FIG. 3A: A drop in Na + /K + -ATPase activity was also noted as early as 4 hr glutamine deprivation, and continued to be significantly lower for 48 hr, p<0.01 (n=4). Replenishment-induced rise was significant only after 12 hr (p,0.01) reaching baselines after 24 hr.
FIG. 4: Both apical (0/0.6) and basolateral (6.0/0) glutamine deprivation resulted in a significantly reduced TEER compared to control monolayers. *=p<0.01, apical deprivation and basolateral deprivation vs. control. There was no statistically significant difference between the apical and basolateral deprivations (n=4-7).
FIG. 5: Effect of apical vs. basolateral glutamine deprivation on bacterial transcytosis. There was a linear rise in bacterial translocation after at 1, 3, and 6 hr after infection following 48 hr of apical glutamine deprivation. At hr 3 and 6 there was a statistically significant rise in transcytosis with apical deprivation; #=p<0.05, 3 hr apical deprivation vs. 3 hr control; *=p<0.01, 6 hr apical deprivation vs. 6 hr control (n=4-7).
FIG. 6: Effect of glutamine replenishment. There was a significant rise in transcytosis after 48 hr of deprivation that continued for 4 hr post-replenishment. Glutamine replenishment for 18 hr causes a significant drop in bacterial translocation, that reaches base line level after 48 hr. *=p<0.01, 48 hr deprivation and 4 hr replenishment vs. control (n=9-18).
FIG. 7: Histopathology of weanling rabbit ileal loops. A: control loops inoculated with PBS showing healthy villi and deeper layers (original magnification 40×). B: Loop inoculated with 10 9 CFU of E. coli strain 21-1 isolated from a patient with NEC. There is severe damage to mucosa with massive submucosal edema and infiltration of polymorphonuclear cells into the lamina propria. C: Loop co-inoculated with 4 mM glutamine and 10 9 CFU of E. coli. Note the near-total protection except a generalized mild submucosal edema.
EXAMPLE 1
Caco-2 Cell Culture Model
Effect of glutamine-deprivation was studied in Caco-2 cells derived from human adenocarcinoma cells which show all the morphological and functional characteristics of mature small intestinal epithelial cells after differentiation. In our system, similar results with high enzyme activity was observed after 10-12 days of growth (FIG. 2). When the fully differentiated Caco-2 cells were kept in a glutamine-free medium for 48 hours, it was found that a significant decrease in the brush border membrane enzyme (disaccharidases and glucoamylase) (FIGS. 3B-E), and in the (Na + , K + -ATPase) (FIG. 3A) enzyme activities (FIG. 3) occurred. The inventors observed a drop in transepithelial electrical resistance across the cell monolayer when the cells were deprived of glutamine either from the apical or basolateral side (FIG. 4). (Panigrahi P, Tall B D, Russell R G, DeTolla L J, Morris Jr J G Development of an in vitro model for study of non-O1 Vibrio cholerae virulence using Caco-2 cells. Infect Immun 1990; 58:3415-3424; Panigrahi P, Gupta S, Gewolb I H, Morris J G. Occurrence of necrotizing enterocolitis may be depenedent on patterns of bacterial adherence and intestinal colonization: studies in Caco-2 tissue culture and weanling rabbit models. Pediatr Res 1994;36:115-121; Panigrahi P, Bamford P, Horvath K, Glenn Morris J, Gewolb I H. E. Coli transcytosis in a Caco-2 cell model: implications in neonatal necrotizing enterocolitis. Ped res 1996; 40:415-421; Pinto M S, Robine-Leon M D, Appay M et al. Enterocyte-like differentiation and polarization of the human colon carcinoma cell line Caco-2 in culture. Biol Cell 1983;47:323-330).
EXAMPLE 2
Bacterial Translocation In Caco-2 Transwell System
Bacterial translocation was measured in the same condition using cells grown on polycarbonate filters. When cells were deprived of glutamine from the apical side, there was a ˜10 and 5-fold increase in bacterial transcytosis in the 1 st and 6 th hr respectively (FIG. 5). Replenishment of apical glutamine resulted in the restoration of the bacterial translocation to the normal level after 18 hours (FIG. 6). E. Coli strain 21-1 isolated from an infant with necrotizing enterocolitis was used for this study. This in vitro system eliminates the confounding effects of immune system, and these results for the first time, demonstrate that glutamine primarily affects the enterocytes and thus influences initial steps of bacterial translocation. Note the effect of replenishment evident only after 18 hrs. The transcytosis level comes to baseline after 48 hrs. To further complement these results, intracellular ATP concentration was assayed using the commercial Sigma kit. There was no significant change in the ATP levels of Caco-2 cells treated with or without glutamine, except a transient increase after 4 hr in the glutamine deprived cells. These results indicate that there is a preferential effect of glutamine when it is supplied to the enterocytes from the apical (luminal) side, and that it is a more complex action on the cells than a simple energy-related phenomenon.
EXAMPLE 3
In vivo Weanling Rabbit Ileal Loop Studies
Following standard protocols ileal loop studies were conducted in weanling rabbits. Weanling rabbits between 350-400 gm were used. Surgical and inoculation procedures, essentially identical to our previously described methods were followed. 1 and 4 mM glutamine was used in the treated loops along with the E. coli strain. Non-infected loops inoculated with PBS and E. coli alone, were maintained in each animal as negative and positive controls. There was total protection against E. coli induced damaged in the loops receiving both concentrations of glutamine (FIG. 7). (Panigrahi P, Gupta S, Gewolb I H, Morris J G. Occurrence of necrotizing enterocolitis may be depenedent on patterns of bacterial adherence and intestinal colonization: studies in Caco-2 tissue culture and weanling rabbit models. Pediatr Res 1994;36:115-121).
An E. coli strain isolated from an infant with necrotizing enterocolitis (NEC) (laboratory strain 21-1) was used for in vitro translocation studies in Caco-2 cells and in the weanling rabbit ileal loop experiments.
Caco-2 Cell Culture System
Caco-2 cells were grown in Dulbecco's modified Eagle's medium (DMEM) supplemented with 1% nonessential amino acids, 1% sodium pyruvate, 10% fetal calf serum (FCS), 100 U of penicillin and 100 μg of streptomycin/mL in a 5% CO 2 atmosphere at 37° C. Glutamine supplementation was done according to the defined experimental conditions. For enzyme analysis, 3×101 cells were seeded onto 60-mm tissue culture dishes and grown for 12 days. For transcytosis studies, 0.2×10 6 cells in 0.3 mL medium were seeded on the apical side of 0.6-cm 2 polycarbonate transwell filters/clusters (Costar, Cambridge, Mass.). Each basolateral chamber received 1 mL of medium. Medium was changed every third day.
Caco-2 Cell Growth and Replication
At different days postconfluence, cells were counted in a hemocytometer after trypsinizing the monolayers. Total DNA content was measured by the perchloric acid method.
Monolaver Permeability and Integrity
Transepithelial electrical resistance (TEER) and inulin transport were examined to evaluate the structural integrity of the Caco-2 cell monolayer during days 2 to 14 postseeding. A Milli Cell ERS (Millipore) apparatus was used according to manufacturer's instructions to record the electrical resistance across cell monolayers. A polycarbonate membrane alone with media on both the apical and basolateral sides was used as control, and resistance was calculated in ohms per square centimeter.
Enzyme Estimation in Caco-2 Cells
Expression of brush border marker enzymes has been reported from various laboratories including ours. For this study, differentiated Caco-2 cells were washed in chilled phosphate buffered saline (PBS), harvested using a rubber policeman, centrifuged at 3000×g for 5 minutes; the cell pellets were stored frozen. Disaccharidase (sucrase, maltase, lactase, and palatinase) activities were determined by the method of Dahlquist. Glucoamylase was assayed by the method of Azad et al using maltooligosaccharide mixture (3 to 10 glucose units) as substrate (ICN, Irvine, Calif.). Protein content of the cell pellets was measured by Bradford Coomassie assay (Pierce Co, Rocldord, Ill.) and was used as an internal control. A time course glutamine deprivation/ replenishment experiment was conducted.
Examination of "Apical vs Basolateral" Effect of Glutamine
Three defined experimental conditions were created and used in the transwell system for transcytosis studies; (1) control (6.0:0.6): 6 mmol/L glutamine in the upper chamber, 0.6 mmol/L in the lower chamber (considering that the basolateral side receives glutamine at a physiologic concentration of 0.6 mmol/L, and the upper chamber receives high glutamine found in the lumen); (2) apical deprivation (0:0.6): 0 mmol/L glutamine in the upper chamber, 0.6 mmol/L in the lower chamber; and (3) basolateral deprivation (6.0:0): 6 mmol/L glutamine in the upper chamber, 0 mmol/L in the lower chamber. After glutamine deprivation and replenishment over different time points, translocation studies were carried out over a I- to 6-hour period. Clusters were transferred to a fresh well containing DMEM at the end of each incubation period.
Bacterial Transcytosis Study
Transwell clusters were washed in sterile PBS and refed with fresh DMEM without antibiotics or FCS. TEER was measured, and 3×101 CFU of the bacterial strains were applied to the apical side in 0.3 mL of DMEM. After gentle agitation for 10 minutes, the clusters were incubated for 6 hours. At the end of each hour, clusters were transferred to a new well containing fresh DMEM; samples were obtained at the end of the different incubation periods from the basolateral side and quantitated by plating dilutions on L-agar plates. Colonies were counted after overnight incubation of the plates at 37° C. S. typhimurium strain SO 1344 and E. coli strain DH5-α were used as controls.
To examine the effect of glutamine replenishment, after 48 hours of glutamine deprivation, monolayers were refed with fresh DMEM containing 6 mmol/L glutamine. Translocation experiments were carried out after 4, 18, 24, and 48 hours of replenishment.
Ileal Loop Model in Weanling Rabbit
Ileal loops were prepared in weanling New Zealand white rabbits weighing <500 g following our previously described methods. E. coli strain 21-1 (10 9 CFU) with or without different concentrations of glutamine (1 and 4 mmol/L) was inoculated in duplicate animals, in duplicate loops. Control loops were maintained in each animal that received PBS only. Rabbits were killed after 16 to 18 hours, gross changes in the loops noted, fluid accumulation measured, and tissue samples fixed in formalin for histopathology. Only the center portion of the loop sufficiently away from the ligature sites was collected to avoid any local inflammatory changes caused by physical trauma. All studies were approved by the Institutional Animal Care and Use Committee of the University of Maryland at Baltimore.
Statistical Analysis
Statistical Analysis was performed using Student's t test and analysis of variance (ANOVA) with Student-Newman-Keuls or Dunnett's (for multiple comparisons to controls) post hoc test using SigmaStat (Jandel Scientific, San Rafael, Calif.). A p value of <0.05 was considered statistically significant.
Effect of Glutamine on Caco-2 Cell Growth and Replication
Glutamine had no effect on cell growth or multiplication. There was no significant difference between the cell count and the DNA content of the monolayers grown with or without glutamine during the 12-day period (data not shown). However, there was a significant decline in the total protein content of the glutamine-deprived cells.
Effect of Glutamine on Enterocyte Enzyme Expression
There was a decline in the expression of all enzymes tested after 4 hours of glutamine deprivation, which reached a nadir at 24 to 48 hours (FIG. 3 top panel). A linear increase in expression of disaccharidases was noted over 4 to 48 hours during replenishment (FIG. 3 top panel). However, the recovery of ATPase occurred only after 12 hours, reaching baselines after 24 to 48 hours (FIG. 3 bottom panel).
Monolayer Permeability and Integrity
Two-day-old postconfluent monolayers showed development of high TEER (172±20.2 Ω/cm 2 ), comparable to the TEER of intact human gastrointestinal mucosa, which was maintained over the 12-day period. Glutamine deprivation resulted in decreased TEER of the monolayers. Both apical and basolateral deprivation resulted in significant decreases in the TEER compared with controls. There was no statistical difference in the TEER between apical and basolateral deprivation (FIG. 4).
Bacterial Translocation
Glutamine deprivation resulted in increased E. coli translocation, and the increase reached statistical significance after 48 hours of deprivation. Further experiments were conducted after 48-hour deprivation only and E. coli translocation were noted over a 1-6 hour period. No difference could be noted between control and glutamine-deprived cells after 1 hour. After 3 and 6 hours, there was a statistically significant increase in bacterial transcytosis with apical deprivation. Although there was a rise in transcytosis, statistical significance was not observed after basolateral deprivation at hours 3 and 6 (FIG. 5). Upon replenishment with glutamine, there was no corrective effect during the first 12-hour period (6- and 12-hour data not shown); however, the level of transcytosis reduced to normal levels after 18 hours. Although the baseline was reached after 48 hours, there was no statistically significant difference between control and 18-, 24- , and 48-hour replenishment (FIG. 6).
Effect of Glutamine in the Mucosal Iniury Model in Weanling Rabbit
E. coli infection produced typical necrotic injury in the ileal loops (FIG. 7). There was severe damage, necrosis, and hemorrhage of mucosa, in cases resulting in total collapse. There was also massive submucosal edema, with infiltration of polymorphonuclear cells into submucosa and lamina propria. Loops receiving 1 and 4 mmol/L glutamine showed an almost total protection against E. coli-induced injury. No further higher concentration of glutamine was used. There were some acute inflammatory changes and mild submucosal edema with intact mucosa and deeper layers. Fluid accumulation was minimal (2 to 3 mL) and was noted in all of the loops including the control loops receiving PBS alone.
A preferred range of oral administration of glutamine is approximately between 0.2-0.9 gm/kg/day in at least three divided doses. Preferably, about 0.3 gm/kg/day is administered. It may be administered in any vehicle, as a mixture, in a reconstituted liquid, or the like. Administration may be orally or via a nasogastric tube. Glutamine may also be given in capsule form. Capsules may be acid-resistant slow-release microcapsules.
While the invention has been described with reference to specific embodiments, modifications and variations of the invention may be constructed without departing from the scope of the invention, which is defined in the following claims. | A method of preventing necrotizing tissue injury in the gastrointestinal tract comprising orally administering glutamine is disclosed. Glutamine protects tissues along the gastrointestinal tract by blocking translocation of bacterial agents such as gram (-) bacteria, other infectious agents, toxins, chemicals and injurious substances. The intraluminal/apical presence of the glutamine optimizes mucosal defense and increases nutrient absorption. Enteral glutamine is useful in treating neonatal necrotizing enterocolitis for reducing inflammation caused by bacterial translocation and injury. Oral glutamine is also useful in treating gastrointestinal dysfunctions. When glutamine is orally administered, it coats gastrointestinal mucosa thereby treating infectious and/or inflammatory conditions of the gastrointestinal tract. It is useful in treating pathologic conditions with lowered transepithelial electrical resistance (TEER) by acting as a curative agent. | 0 |
REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims priority to Provisional U.S. Application No. 61/948,964, filed Mar. 6, 2014, entitled “METHODS AND DEVICES FOR DISPLAYING TREND AND VARIABILITY IN A PHYSIOLOGICAL DATASET,” and is incorporated herein in its entirety.
BACKGROUND
[0002] 1. Field of the Invention
[0003] The invention is directed to devices and methods for displaying a physiological dataset in graphical form. Specifically, the invention is directed toward devices and methods for displaying trend and variability of a physiological dataset in graphical form.
[0004] 2. Background of the Invention
[0005] Medical professionals use charts of physiological data on a regular basis to come to decisions critical to patient care. Patient information charts have historically been written or printed on paper, however with the advent of electronic displays, charts of patient's data are increasingly found in electronic forms. Everything from patient health information to real-time physiological data is transitioning from paper to electronic form. The transition to electronic form, linked to computers or other programmable equipment, enables new and improved visualizations to be applied to patient data, especially physiological data.
[0006] Physiological data is typically acquired from the patient by means of a variety of sensors. Data can be acquired over the course of a patient's life at regularly scheduled exams, or over a series of hours, minutes, or in real-time in the case of continuous monitoring.
[0007] Patients in a hospital may be connected to a variety of sensors, monitors and devices which produce real-time traces of physiological signals, real-time and near-real-time calculations of physiological parameters. For example, an ICU patient could be simultaneously connected to devices which record ECG, EMG, EEG, capnography, pulse oximetry, pneumography, blood pressure, etc., yielding a plethora of physiological parameters including heart rate, end-tidal CO2 or end-expiratory CO2, O2 saturation, respiratory rate, tidal volume, and minute ventilation. The sheer number of physiological datasets measured from a patient in the hospital can easily lead to information overload.
[0008] The information overload can cause healthcare providers to overlook aspects of the data that could indicate important aspects of the patient's condition or the patient's state. Therefore, there is a need to reduce information overload.
SUMMARY OF THE INVENTION
[0009] The present invention overcomes the problems and disadvantages associated with current strategies and designs and provides new tools and methods of displaying a physiological dataset in graphical form.
[0010] One embodiment of the invention is directed to a method of displaying trends and variability in a physiological dataset. The method comprises the steps of obtaining the physiological dataset, applying a smoothing algorithm to the physiological dataset to obtain a trend of the physiological dataset, applying a variability algorithm to the physiological dataset to obtain the variability of the physiological dataset, outputting a graph of the trend of the physiological dataset, and outputting a graph of the variability of the physiological dataset.
[0011] In a preferred embodiment, the physiological dataset is based on data obtained from a patient's respiratory system. Preferably, the smoothing algorithm is one of a moving average algorithm and a digital filter algorithm. The graph of the trend of the physiological dataset and the graph of the variability of the physiological dataset are preferably one of overlaid and graphed adjacently. Preferably, the graph of the variability of the physiological dataset comprises an envelope bounded on the top by a plot of the maximums identified by the variability algorithm and bounded on the bottom by a plot of the minimums identified by the variability algorithm. The space between the bounds is preferably shaded and the graph of the variability of the physiological dataset is preferably used to assess and diagnose apnea.
[0012] In a preferred embodiment, the physiological dataset is interbreath interval data. Preferably, the graph of variability of the physiological dataset is a function of fractal scaling coefficients calculated at various time points and over various time windows of the dataset. Preferably, the graph of variability of the physiological dataset comprises one or more of, error bars, line graphs, momentum bars, shaded areas under a curve, and a stochastic plot. In a preferred embodiment, the magnitude of the variability which is displayed by the graph of variability of the physiological dataset is calculated as a function of at least one of, the raw dataset, the smoothed dataset, multiple smoothed datasets, the fractal scaling coefficients of the dataset, or the stochastic coefficients of the dataset.
[0013] Another embodiment of the invention is directed toward a device comprising a transthoracic impedance measurement device to obtain a physiological dataset, a processor receiving the physiological dataset from the measurement device, and an output device coupled to the processor. The processor is adapted to: apply a smoothing algorithm to the physiological dataset to obtain a trend of the physiological dataset, apply a variability algorithm to the physiological dataset to obtain the variability of the physiological dataset. The output device is adapted to: output a graph of the trend of the physiological dataset and output a graph of the variability of the physiological dataset.
[0014] Another embodiment of the invention is directed toward a system for displaying trends and variability in a physiological dataset. The system comprises a patient monitoring device, at least one sensor coupled to the patient monitoring device, a processor contained within the patient monitoring device and receiving patient data from the at least on sensor, a screen contained within the patient monitoring device and receiving display information from the processor. The processor: obtains the physiological dataset from the at least one sensor, applies a smoothing algorithm to the physiological dataset to obtain a trend of the physiological dataset, applies a variability algorithm to the physiological dataset to obtain the variability of the physiological dataset, outputs a graph of the trend of the physiological dataset to the screen, and outputs a graph of the variability of the physiological dataset to the screen.
[0015] In a preferred embodiment, the physiological dataset is based on data obtained from a patient's respiratory system. Preferably, the smoothing algorithm is one of a moving average algorithm and a digital filter algorithm. The graph of the trend of the physiological dataset and the graph of the variability of the physiological dataset are preferably one of overlaid and graphed adjacently. Preferably, the graph of the variability of the physiological dataset comprises an envelope bounded on the top by a plot of the maximums identified by the variability algorithm and bounded on the bottom by a plot of the minimums identified by the variability algorithm. The space between the bounds is preferably shaded and the graph of the variability of the physiological dataset is preferably used to assess and diagnose apnea.
[0016] In a preferred embodiment, the physiological dataset is interbreath interval data. Preferably, the graph of variability of the physiological dataset is a function of fractal scaling coefficients calculated at various time points and over various time windows of the dataset. Preferably, the graph of variability of the physiological dataset comprises one or more of, error bars, line graphs, momentum bars, shaded areas under a curve, and a stochastic plot. In a preferred embodiment, the magnitude of the variability which is displayed by the graph of variability of the physiological dataset is calculated as a function of at least one of, the raw dataset, the smoothed dataset, multiple smoothed datasets, the fractal scaling coefficients of the dataset, or the stochastic coefficients of the dataset.
[0017] Other embodiments and advantages of the invention are set forth in part in the description, which follows, and in part, may be obvious from this description, or may be learned from the practice of the invention.
DESCRIPTION OF THE DRAWING
[0018] The invention is described in greater detail by way of example only and with reference to the attached drawing, in which:
[0019] FIG. 1 : Example MV trend. (A) Raw data. Note the highly varying signal making it difficult to determine the overall respiratory status. (B) Visualizing a trend in the data. The average trend helps identify general drifts in the measurements. (C) Visualizing the variability in the data. The variability envelope when applied in conjunction with the trend in the data contains all relevant information from the raw signal, yet presents it in an easier-to-comprehend fashion.
[0020] FIG. 2 : Examples of average trends and variance envelopes applied to a variety of respiratory signals (MV, TV, RR)
[0021] FIG. 3 : Example of adequate ventilation (MV) over time, as visualized by a stable trend and a stable envelope.
[0022] FIG. 4 : Example of an agitated patient who may be undermedicated. Note that the trend in the data increases slightly, whereas the envelope increases substantially with time, indicative of increased respiratory variability, likely caused by increase in pain and discomfort.
[0023] FIG. 5 : Example of a patient who is headed towards respiratory compromise. The average MV trend is systematically decreasing and so is the variability in the MV data.
[0024] FIG. 6 : Example of a patient with apneic breathing pattern. Note the increase in variability (with envelope encroaching on the MV=0 line) coupled with a decrease in the overall trend. This is indicative of a repetitive breathing pattern with significant respiratory pauses and interspersed large “rescue” breaths.
[0025] FIG. 7 : Example of a patient with apneic breathing pattern as a result of opioid administration. Note the increase in variability (with envelope encroaching on the MV=0 line) coupled with a decrease in the overall trend. This is indicative of a repetitive breathing pattern with significant respiratory pauses and interspersed “rescue” breaths.
[0026] FIG. 8 : Example of a patient who is headed towards respiratory compromise following opioid administration. The average MV trend is systematically decreasing and so is the variability in the MV data.
[0027] FIG. 9 : Example of a patient who may be undermedicated. Note that, despite receiving a dose of opioids, the trend in the data remains practically unchanged, whereas the envelope increases with time, indicative if increased respiratory variability, likely caused by increase in pain and discomfort.
[0028] FIG. 10 : Example of a patient displaying hypopneic breathing following opioid administration. The decrease in both the trend and variability in the data suggest a regular breathing pattern at lower volumes and rates.
[0029] FIG. 11 : Example of adequate ventilation (MV) over time, as visualized by a small change in the trend (expected result of opioid administration) and a stable envelope.
[0030] FIG. 12 : Example of an embodiment of the structure of the device disclosed herein.
[0031] FIG. 13 : Example of an embodiment of a patient monitoring device.
DESCRIPTION OF THE INVENTION
[0032] As embodied and broadly described herein, the disclosures herein provide detailed embodiments of the invention. However, the disclosed embodiments are merely exemplary of the invention that may be embodied in various and alternative forms. Therefore, there is no intent that specific structural and functional details should be limiting, but rather the intention is that they provide a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention
[0033] It has surprisingly been discovered that a visualization of physiological data aids healthcare providers in quickly assessing important features of a monitored physiological parameter by reducing the perceived complexity of a recorded dataset. The invention achieves this by simultaneously displaying a physiological parameter's trend and variability as well as their evolution over time. This is in contrast to existing methods for displaying physiological datasets, which generally include applying various filtering (smoothing) algorithms. Filters generally reduce the perceived complexity of a dataset, enabling a better assessment of trends in the data, but in the process they reduce variability, impairing the ability to assessment changes in variability in the data. Variability has proven to be an important feature of physiological signals. For example, reduced heart rate variability can predict mortality following a heart attack.
[0034] A caregiver would not be able to assess heart rate variability from a chart of heart rate where the dataset is filtered. A solution to this problem is to overlay the filtered signal with an indication of variability.
[0035] The method described herein is a means of displaying a physiological dataset within a graphical user interface. The dataset is calculated and/or monitored with respect to an independent variable, e.g. time. The dataset is a measurement, calculation or derivation related to a tissue, organ, organ system or physiological system. Features of the time-series analysis including the value, trend of the value and variability of the dataset correlate with specific disease stated related to the monitored tissue, organ or organs system. The features of the time series analysis may also correlate with overall patient health. The method of displaying the dataset enables medical caregivers to quickly assess important time-series features of the dataset.
[0036] The method specifically aids in identifying the trend and variability of the dataset with respect to an independent variable, e.g. time. The assessment of variability combined with the trend aids in assessing patient health or diagnosing or predicting disease states.
[0037] The dataset may be acquired from the patient by a means of an analog or digital sensor. The dataset may represent a physiological signal or a calculated, estimated or derived physiological parameter or health index. A health index is a numerical representation based on one or more physiological parameters, or features of their signals. The health index correlates with patient health, disease state or overall patient status. In one embodiment of the invention the dataset is a respiratory parameter derived from a transthoracic impedance measurement. In one embodiment the dataset is a calculation of minute ventilation, calculated based on a measurement of transthoracic impedance. In one embodiment the dataset is a respiratory health index based on the combination of variability in tidal volume, the trend in minute ventilation and the duty cycle of the respiratory rate. In another embodiment of the invention, the dataset is the rapid shallow breathing index derived from the patient's respiratory parameters over time.
[0038] In one embodiment of the invention, the physiological parameter is Minute Ventilation (MV). The trends in MV combined with an assessment of the variability of MV can assist medical caregivers to identify periods of apnea, hypopnea, hyperventilation, impending respiratory failure/arrest, response to narcotics, pain level, and/or depth of anesthesia.
[0039] The method described herein is preferably applied to the dataset first by implementing a filter to reduce the perceived complexity of the dataset. The filter enables the caregiver to quickly assess trends in the data without suffering from information overload of the entire dataset. The filter applied to the dataset may be applied in software or electrical hardware. The filter applied to the dataset may be a time-domain filter or frequency domain filter. The filter may be moving average, a weighted moving average, a smoothing algorithm, a Chebyshev filter, a Butterworth filter, a Bessel filter, an elliptic filter, constant k filter, m-derived filter, special filter, top-hat filter, or other Fourier-transform-based filter. The window of the filter may be 2 minutes, 5 minutes, 10 minutes, 1 hour, a custom time frame, or another time frame and preferably corresponds to the rate at which trends are likely to appear in the data.
[0040] An embodiment of the invention implements a smoothing average over a two-minute window. This smoothed data is then displayed as the trend over time. The middle panel in FIG. 1 shows an example of the smoothed trend line overlaid on the dataset.
[0041] After the filter highlights the trend in the data, the method preferably adds a visual indication of variability to the graph. The visual indication of variability preferably consists of an envelope which overlays the smoothed trend. The visualization preferably updates in real-time for monitored parameters, but may be applied retroactively on historical data.
[0042] In one embodiment of the invention, the minimum and maximum points within each window are determined and stored in an array of peaks. Preferably once the minimum and maximum points are determined in each window position, all the peaks are plotted on the graph. The maximum peaks are preferably then connected by line segments, with points between the peaks being interpolated. The minimum points are also preferably connected by line segments with points between the minimum peaks being interpolated. The bottom panel in FIG. 1 is an example of this envelope. In this embodiment, the area within the maximum envelope and the minimum envelope may be shaded.
[0043] A quantitative coefficient of variability is preferably calculated for each point on the chart and displayed. The coefficient of variability is preferably calculated from a window of data points which is smaller than the total number of points on the graph. The coefficient of variability is preferably based on the statistics of the dataset calculated within the window. The coefficient of variability is preferably a function of statistical variance, standard deviation, or entropy.
[0044] In one embodiment, error bars are applied behind the smoothed dataset. The error bars are preferably a function of the standard deviation of the dataset within a window of, for example, 2 minutes. The error bar is preferably overlaid on the graph at the last point in the window, the center point in the window, or the first point in the window.
[0045] In one embodiment, a function of one or more fractal scaling coefficients, or a function of a ratio of at least two fractal scaling coefficients is utilized and overlaid on the graph. In one embodiment, a set of fractal scaling coefficients is calculated for the entire dataset (FC 1 ), then again for the window (FC 2 ). The coefficient of variability is preferably calculated as a function of one or more coefficients from the set of FC 1 as compared to FC 2 . One embodiment of the visualization is to display variability as a function of the difference or absolute value of the difference of two or more smoothing algorithms applied to the dataset. In one embodiment of the invention, two moving average algorithms are applied to the dataset, one with a window of ten (10) minutes and one with a window of two (2) minutes. The visualization preferably consists of a graph of the two moving averages overlaid on each other, or both overlaid on the dataset, smoothed or un-smoothed. This may enable the caregiver to see the trend from the smoothed data as well as discern the absolute difference between the smoothed data trends. It is understood that when the two averages cross, i.e. the absolute difference between the two averages reaches zero, the trend in the data has changed direction. This can predict a rapid change in state and trigger an alarm signal.
[0046] In another embodiment, the difference between the results of the two smoothing algorithms is calculated and displayed on a graph. The graph is preferably overlaid on the graph of the smoothed dataset, or appears in its own space. This visualization preferably provides an indicator of the momentum behind a trend, where a large difference between the results indicates a strong trend, and a small difference between the results indicates a stable trend. However, a change in sign indicates a reversal of the previous trend.
[0047] Another visualization that can be applied to the data is a stochastic plot. The stochastic plot may be overlaid on the raw dataset or a smoothed dataset. The stochastic plot can be interpreted by a care provider to predict a patient's future status.
[0048] In one embodiment of the invention, the visualization including a smoothing component and an indication of variability is applied to one or more datasets relating to the respiratory system. The user can interpret the visualization in order to assess or predict patient state, health state, respiratory status, disease state or response to a medical intervention. The user may also use the visualization of variability to diagnose a disease. The user may draw conclusions from the visualization including, an assessment of the patient's response to an opioid, a diagnosis or prediction of respiratory arrest, respiratory failure, apnea or cardiac arrest. The user may assess the patient's respiratory sufficiency, likelihood of successful extubation or the necessity of intubation.
[0049] FIG. 3 illustrates an example of the display of the visualization algorithm on a minute ventilation dataset. The patient in the example maintains a similar minute ventilation and minute ventilation variability over time. A caregiver could draw the conclusion that the patient has a good status, free of various disease states. FIG. 11 shows an example of a healthy response to an opioid dose, with only a slightly downward trend on the MV dataset, and little change in the signal variability. This type of response would lead a caregiver to conclude that the patient is correctly dosed.
[0050] FIG. 4 indicates an example of an agitated patient. In this instance, the increase in MV variability and MV trend as shown in the visualization could lead a caregiver to conclude that the patient is undermedicated and could adjust the patient's dose of pain medication accordingly. FIG. 9 is an example of a patient who responds idiosyncratically to an opioid dose. The variability increases, which could indicate restlessness and discomfort and general inefficacy of the pain medication.
[0051] It is often critical for caregivers to respond to indications of respiratory compromise as quickly as possible. The example in FIG. 5 is a case in which a caregiver could use the visualization to diagnose respiratory compromise and undertake a medical intervention to prevent patient state from worsening. Interventions could include waking the patient, administering an opoid antagonist such as Naloxone, or intubating and ventilating the patient. FIG. 8 is an example of the visualization applied to an MV dataset in a patient suffering respiratory compromise as a result of a dose of an opioid.
[0052] Apnea is a state in which the breathing is interrupted. It may result from a variety of causes, including opioid toxicity. The sooner opiate toxicity can be identified, the sooner a caregiver can undertake measures to prevent the patient's condition from worsening. Periods of apnea are generally followed by a period of rescue breathing which may include larger than normal or faster than normal breaths, which normalize over time. The difference between the breaths during these periods translates to a high index of variability in datasets related to the respiratory system. Apnea can be identified by a downward trend in minute volume, a high variability in respiratory rate, or interbreath interval, and a high variability in tidal volume and minute ventilation. FIG. 6 shows an example of the increased variability and decrease in trend in minute ventilation to indicate the onset of apnea. FIG. 7 shows an example of the onset of apnea as a symptom of opioid toxicity in response to a dose of opioid pain medication.
[0053] FIG. 10 shows an example of the visualization on the MV dataset in a patient suffering hypopnea, or shallow breathing. In terms of the trend, it is difficult to differentiate hypopnea from apnea, however, the variability in each case is very different. The variability in the hypopneic patient's dataset is much lower, which allows a caregiver to differentiate between the two cases.
[0054] The methods disclosed herein may also be applied to parameters associated with the circulatory system including measurements of the heart rate, or its inverse, beat-to-beat interval. Low variability in the heart rate can predict or, indicate, or quantify the progression of many conditions including myocardial infarction, congestive heart failure, diabetic neuropathy, depression or susceptibility to SIDS. In this embodiment, the envelope provides a visualization of heart rate variability to assist the caregiver in identifying, or assessing the risk of the aforementioned conditions.
[0055] FIG. 13 depicts a preferred embodiment of a patient monitoring system 1300 adapted to calculated and display a physiological parameter's trend and variability as well as their evolution over time. Preferably, patient monitoring system 1300 is a portable device that can be mounted on an IV pole, attached to a bed, attached to a wall, placed on a surface or otherwise positioned. Patient monitoring system 1300 may be adapted for use during medical procedures, recovery, and/or for patient monitoring. Preferably, patient monitoring system 1300 is battery powered and/or has a power cable. Patient monitoring system 1300 preferably has at least one input port 1305 . Preferably, each input port 1305 is adapted to receive signals from one or more sensors remote to patient monitoring system 1300 . Additionally, patient monitoring system 1300 may further include wireless communication technology to receive signals from remote and wireless sensors. The sensors may be adapted to monitor for a specific patient characteristic or multiple characteristics. Patient monitoring system 1300 preferably is adapted to evaluate the data received from the sensors and apply the algorithms described herein to the data. Furthermore, the patient monitoring system 1300 may be able to receive custom algorithms and evaluate the data using the custom algorithm.
[0056] Patient monitoring system 1300 preferably further includes a screen or display device 1310 . Preferably, screen 1310 is capable of displaying information about patient monitoring system 1300 and the patient being monitored. Screen 1310 preferably displays at least one graph or window of the patient's condition, as described herein. Each graph may be a fixed size or adjustable. For example, the graph may be customizable based on the number of data points, a desired length and/or time of measurement, or a certain number of features (i.e. breaths, breath pauses, or obstructed breaths). Additionally, the scale of the graph may be adjustable. Furthermore, the patient or caregiver (or clinician) may be able to choose what is displayed on screen 1310 . For example, screen 1310 may be able to display the mean, median, and/or standard deviation of data being monitored; the max, min and or range of data being monitored; an adaptive algorithm based on trend history; a adapted algorithm based on large populations of like patients (i.e. condition, age, weight, and events); and/or patent breathing parameters (i.e. blood pressure, respiratory rate, CO 2 , and/or O 2 rates).
[0057] Patient monitoring system 1300 is preferably equipped with an alarm. The alarm can be an audio alarm and/or a visual alarm. The alarm may trigger based on certain conditions being met. For example, based on trends, real-time conditions, or patient parameter variability. The alarm may be customizable, both in sound/visualization and in purpose. The patient and/or caregiver may be able to navigate through multiple windows that display different information. For example, certain windows may display the graphs described herein, certain windows may display the patient's biographical data, and certain windows may display the system's status. Additionally, custom windows may be added (e.g by the patient, caregiver, or by the system automatically). For example, a custom window may be for clinical use, to mark events, or to display the patient's condition.
[0058] In a preferred embodiment, patient monitoring system 1300 has a plurality of configurations. The configurations are preferably adapted to display relevant information to a caregiver or patient about the patient based on the patient's current condition. For example, for a patient undergoing a surgery, the nurse or doctor may need different information than for a patient recovering from an illness. Preferably, at the initiation of monitoring the patient, the patient monitoring system 1300 allows the patient or caregiver to select a configuration. Selectable configurations may include, but are not limited to specific procedures, specific illnesses, specific afflictions, specific patient statuses, specific patient conditions, general procedures, general illnesses, general afflictions, general patient statuses, and/or general patient conditions. Upon selection, preferably, the patient monitoring system 1300 will automatically display data relevant to the selection. In another embodiment, the patient monitoring system 1300 may automatically determine an appropriate configuration based on the data received from the patient. The patient or caregiver may be able to customize configurations once they are chosen.
[0059] With reference to FIG. 12 , an exemplary system includes at least computing device 1200 , for example contained within the system depicted in FIG. 13 , including a processing unit (CPU) 1220 and a system bus 1210 that couples various system components including the system memory such as read only memory (ROM) 1240 and random access memory (RAM) 1250 to the processing unit 1220 . Other system memory 1230 may be available for use as well. It can be appreciated that the invention may operate on a computing device with more than one CPU 1220 or on a group or cluster of computing devices networked together to provide greater processing capability. The system bus 1210 may be any of several types of bus structures including a memory bus or memory controller, a peripheral bus, and a local bus using any of a variety of bus architectures. A basic input/output (BIOS) stored in ROM 1240 or the like, may provide the basic routine that helps to transfer information between elements within the computing device 1200 , such as during start-up. The computing device 1200 further includes storage devices such as a hard disk drive 1260 , a magnetic disk drive, an optical disk drive, tape drive or the like. The storage device 1260 is connected to the system bus 1210 by a drive interface. The drives and the associated computer readable media provide nonvolatile storage of computer readable instructions, data structures, program modules and other data for the computing device 1200 . The basic components are known to those of skill in the art and appropriate variations are contemplated depending on the type of device, such as whether the device is a small, handheld computing device, a desktop computer, a computer server, a handheld scanning device, or a wireless devices, including wireless Personal Digital Assistants (“PDAs”), tablet devices, wireless web-enabled or “smart” phones (e.g., Research in Motion's Blackberry™, an Android™ device, Apple's iPhone™), other wireless phones, a game console (e.g, a Playstation™, an Xbox™, or a Wii™), a Smart TV, a wearable internet connected device, etc. Preferably, the system is technology agnostic.
[0060] Although the exemplary environment described herein employs the hard disk, it should be appreciated by those skilled in the art that other types of computer readable media which can store data that are accessible by a computer, such as magnetic cassettes, flash memory cards, digital versatile disks, cartridges, random access memories (RAMs), read only memory (ROM), a cable or wireless signal containing a bit stream and the like, may also be used in the exemplary operating environment.
[0061] To enable user interaction with the computing device 1200 , an input device 1290 represents any number of input mechanisms, such as a microphone for speech, a touch-sensitive screen for gesture or graphical input, keyboard, mouse, motion input, speech, game console controller, TV remote and so forth. The output device 1270 can be one or more of a number of output mechanisms known to those of skill in the art, for example, printers, monitors, projectors, speakers, and plotters. In some embodiments, the output can be via a network interface, for example uploading to a website, emailing, attached to or placed within other electronic files, and sending an SMS or MMS message. In some instances, multimodal systems enable a user to provide multiple types of input to communicate with the computing device 1200 . The communications interface 1280 generally governs and manages the user input and system output. There is no restriction on the invention operating on any particular hardware arrangement and therefore the basic features here may easily be substituted for improved hardware or firmware arrangements as they are developed.
[0062] For clarity of explanation, the illustrative system embodiment is presented as comprising individual functional blocks (including functional blocks labeled as a “processor”). The functions these blocks represent may be provided through the use of either shared or dedicated hardware, including, but not limited to, hardware capable of executing software. For example the functions of one or more processors presented in FIG. 12 may be provided by a single shared processor or multiple processors. (Use of the term “processor” should not be construed to refer exclusively to hardware capable of executing software.) Illustrative embodiments may comprise microprocessor and/or digital signal processor (DSP) hardware, read-only memory (ROM) for storing software performing the operations discussed below, and random access memory (RAM) for storing results. Very large scale integration (VLSI) hardware embodiments, as well as custom VLSI circuitry in combination with a general purpose DSP circuit, may also be provided.
[0063] Embodiments within the scope of the present invention may also include computer-readable media for carrying or having computer-executable instructions or data structures stored thereon. Such computer-readable media can be any available media that can be accessed by a general purpose or special purpose computer. By way of example, and not limitation, such computer-readable media can comprise RAM, ROM, EEPROM, CD-ROM or other optical disk storage, magnetic disk storage or other magnetic storage devices, or any other medium which can be used to carry or store desired program code means in the form of computer-executable instructions or data structures. When information is transferred or provided over a network or another communications connection (either hardwired, wireless, or combination thereof) to a computer, the computer properly views the connection as a computer-readable medium. Thus, any such connection is properly termed a computer-readable medium. Combinations of the above should also be included within the scope of the computer-readable media.
[0064] Computer-executable instructions include, for example, instructions and data which cause a general purpose computer, special purpose computer, or special purpose processing device to perform a certain function or group of functions. Computer-executable instructions also include program modules that are executed by computers in stand-alone or network environments. Generally, program modules include routines, programs, objects, components, and data structures, etc. that perform particular tasks or implement particular abstract data types. Computer-executable instructions, associated data structures, and program modules represent examples of the program code means for executing steps of the methods disclosed herein. The particular sequence of such executable instructions or associated data structures represents examples of corresponding acts for implementing the functions described in such steps.
[0065] Those of skill in the art will appreciate the preferred embodiments of the invention may be practiced in network computing environments with many types of computer system configurations, including personal computers, hand-held devices, multi-processor systems, microprocessor-based or programmable consumer electronics, network PCs, minicomputers, mainframe computers, and the like. Networks may include the Internet, one or more Local Area Networks (“LANs”), one or more Metropolitan Area Networks (“MANs”), one or more Wide Area Networks (“WANs”), one or more Intranets, etc. Embodiments may also be practiced in distributed computing environments where tasks are performed by local and remote processing devices that are linked (either by hardwired links, wireless links, or by a combination thereof) through a communications network, e.g. in the “cloud.” In a distributed computing environment, program modules may be located in both local and remote memory storage devices.
[0066] Other embodiments and uses of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. All references cited herein, including all publications, U.S. and foreign patents and patent applications, are specifically and entirely incorporated by reference. It is intended that the specification and examples be considered exemplary only with the true scope and spirit of the invention indicated by the following claims. Furthermore, the term “comprising of” includes the terms “consisting of” and “consisting essentially of.” | Embodiments of the invention are directed to methods and devices for displaying trends and variability in a physiological dataset. The method comprises obtaining the physiological dataset, applying a smoothing algorithm to the physiological dataset to obtain a trend of the physiological dataset, applying a variability algorithm to the physiological dataset to obtain the variability of the physiological dataset, outputting a graph of the trend of the physiological dataset, and outputting a graph of the variability of the physiological dataset. | 6 |
BACKGROUND
[0001] Deepwater accumulators provide a supply of pressurized working fluid for the control and operation of subsea equipment, such as through hydraulic actuators and motors. Typical subsea equipment may include, but is not limited to, blowout preventers (BOPs) that shut off the well bore to secure an oil or gas well from accidental discharges to the environment, gate valves for the control of flow of oil or gas to the surface or to other subsea locations, or hydraulically actuated connectors and similar devices. Accumulator fluid power may be used to operate underwater process valves and connectors, as well as supply of non-continuous process chemicals into a process stream at the seafloor. Applications may also include management of fluid power and electrical power on subsea drilling BOP stacks, subsea production Christmas trees, workover and control systems (WOCS), and subsea chemical injection systems.
[0002] Accumulators are typically divided vessels with a gas section and a hydraulic fluid section that operate on a common principle. The principle is to precharge the gas section with pressurized gas to a pressure at or slightly below the anticipated minimum pressure required to operate the subsea equipment. Fluid can be added to the accumulator in the separate hydraulic fluid section, increasing the pressure of the pressurized gas and the hydraulic fluid. The hydraulic fluid introduced into the accumulator is therefore stored at a pressure at least as high as the precharge pressure and is available for doing hydraulic work.
[0003] Accumulators generally come in three styles—the bladder type having a balloon type bladder to separate the gas from the fluid, the piston type having a piston sliding up and down a seal bore to separate the fluid from the gas, and the float type with a float providing a partial separation of the fluid from the gas and for closing a valve when the float approaches the bottom to prevent the escape of the charging gas. A fourth type of accumulator is pressure compensated for depth and adds the nitrogen precharge pressure plus the ambient seawater pressure to the working fluid.
[0004] The precharge gas can be said to act as a spring that is compressed when the gas section is at its lowest volume/greatest pressure and released when the gas section is at its greatest volume/lowest pressure. Accumulators are typically precharged in the absence of hydrostatic pressure and the precharge pressure is limited by the pressure containment and structural design limits of the accumulator vessel under surface ambient conditions. Yet, as accumulators are used in deeper water, the efficiency of conventional accumulators decreases as application of hydrostatic pressure causes the gas to compress, leaving a progressively smaller volume of gas to charge the hydraulic fluid. The gas section must consequently be designed such that the gas still provides enough power to operate the subsea equipment under hydrostatic pressure even as the hydraulic fluid approaches discharge and the gas section is at its greatest volume/lowest pressure.
[0005] For example, accumulators at the surface typically provide 3000 psi working fluid maximum pressure. In 1000 feet of seawater the ambient pressure is approximately 465 psi. For an accumulator to provide a 3000 psi differential at 1000 ft. depth, it must actually be precharged to 3000 psi plus 465 psi, or 3465 psi.
[0006] At slightly over 4000 ft. water depth, the ambient pressure is almost 2000 psi, so the precharge would be required to be 3000 psi plus 2000 psi, or 5000 psi. This would mean that the precharge would equal the working pressure of the accumulator and any fluid introduced for storage may cause the pressure to exceed the working pressure and accumulator failure.
[0007] At progressively greater hydrostatic operating pressures, the accumulator thus has greater pressure containment requirements at non-operational (no ambient hydrostatic pressure) conditions.
[0008] The accumulator design must also take into account human error contingencies. For example, removal of the external ambient hydrostatic pressure without evacuating the fluid section of the accumulator to reestablish the original gas section precharge pressure may result in failure due to gas section pressures exceeding the original precharge pressures.
[0009] Accumulators may be included, for example, as part of a subsea BOP stack assembly assembled onto a subsea wellhead. The BOP assembly may include a frame, BOPs, and accumulators to provide back up hydraulic fluid pressure for actuating the BOPs. The space available for other BOP package components such as remote operated vehicle (ROV) panels and mounted controls equipment becomes harder to establish due to an increasing number and size of the accumulators required to be considered for operation in deeper water depths. The accumulators are also typically installed in series where the failure of any one accumulator prevents the additional accumulators from functioning.
[0010] The inefficiency of precharging accumulators under non-operational conditions thus requires large aggregate accumulator volumes that increase the size and weight of the subsea equipment. Yet, offshore rigs are moving further and further offshore to drill in deeper and deeper water. Because of the ever increasing envelope of operation, traditional accumulators have become unmanageable with regards to quantity and location. In some instances, it has even been suggested that in order to accommodate the increasing demands of the conventional accumulator system, a separate subsea skid may have to be run in conjunction with the subsea equipment in order to provide the required volume necessary at the limits of the water depth capability of the equipment. With rigs operators increasingly putting a premium on minimizing size and weight of the drilling equipment to reduce drilling costs, the size and weight of all drilling equipment must be optimized.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] For a more detailed description of the embodiments, reference will now be made to the following accompanying drawings:
[0012] FIG. 1 is a system arrangement layout;
[0013] FIG. 2 is a table listing examples of typical system operating depths;
[0014] FIG. 3 is a diagram of a system architecture;
[0015] FIG. 4 is an intensifier based system state transition diagram;
[0016] FIG. 5 is a system architecture with fluid recovery;
[0017] FIG. 6 is an accumulator system configuration;
[0018] FIG. 7 is a hybrid system configuration;
[0019] FIG. 8 is an intensifier configuration;
[0020] FIG. 9 is an intensifier with a recharge pump configuration;
[0021] FIG. 10 is an intensifier with regenerative electrical power;
[0022] FIG. 11 is an intensifier with regenerative electrical power and fluid recovery;
[0023] FIG. 12 is a screen assembly;
[0024] FIG. 13 is a regulator assembly;
[0025] FIG. 14 is an exploded view of a regulator;
[0026] FIG. 15 is a cutaway view of a regulator;
[0027] FIG. 16 is a reference assembly;
[0028] FIG. 17 is a schematic of a reference pump;
[0029] FIG. 18 is a schematic of a reference pump module;
[0030] FIG. 19 is a schematic of a reference pilot accumulator and reservoir;
[0031] FIG. 20 is an exploded view of an intensifier;
[0032] FIG. 21 is a cross section view of an intensifier;
[0033] FIG. 22 is a comparison of intensifying cylinders;
[0034] FIG. 23 is a cross section view of an inner barrel instrument package;
[0035] FIG. 24 is a schematic of an intensifier without fluid recovery;
[0036] FIG. 25 is a schematic of an intensifier with fluid recovery;
[0037] FIG. 26 is an exploded view of an accumulator;
[0038] FIG. 27 is a caged float valve arrangement;
[0039] FIG. 28 is a schematic of an accumulator;
[0040] FIG. 29 is a recharge pump assembly;
[0041] FIG. 30 is an exploded view of a recharge pump;
[0042] FIG. 31 is a schematic of a recharge pump;
[0043] FIG. 32 is a power pack assembly;
[0044] FIG. 33 is a cutaway view of a power pack assembly;
[0045] FIG. 34 is a schematic of a power pack;
[0046] FIG. 35 is a regenerator assembly;
[0047] FIG. 36 is an exploded view of a regenerator assembly;
[0048] FIG. 37 is an embodiment of an accumulator in a subsea blowout preventer stack;
[0049] FIG. 38 is a hybrid embodiment in a subsea blowout preventer stack;
[0050] FIG. 39 is an embodiment of intensifier with no recharge pump in a subsea blowout preventer stack;
[0051] FIG. 40 is an embodiment of an intensifier with a recharge pump in a subsea blowout preventer stack;
[0052] FIG. 41 is an embodiment of an intensifier with regeneration in a subsea blowout preventer stack; and
[0053] FIG. 42 is an embodiment of an intensifier with regeneration on a subsea mudmat.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0054] In the drawings and description that follows, like parts are marked throughout the specification and drawings with the same reference numerals, respectively. The drawing figures are not necessarily to scale. Certain features of the invention may be shown exaggerated in scale or in somewhat schematic form and some details of conventional elements may not be shown in the interest of clarity and conciseness. The present invention is susceptible to embodiments of different forms. Specific embodiments are described in detail and are shown in the drawings, with the understanding that the present disclosure is to be considered an exemplification of the principles of the invention, and is not intended to limit the invention to that illustrated and described herein. It is to be fully recognized that the different teachings of the embodiments discussed below may be employed separately or in any suitable combination to produce desired results. 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 elements and may also include indirect interaction between the elements described. The various characteristics mentioned above, as well as other features and characteristics described in more detail below, will be readily apparent to those skilled in the art upon reading the following detailed description of the embodiments, and by referring to the accompanying drawings.
[0055] FIG. 1 illustrates an embodiment of an apparatus to manage underwater hydraulic and electrical power from fluid source 1900 and electrical source 0015 ; to fluid load 1900 and electrical load 6000 ; under remote hydraulic pilot control and remote electronic control. As shown in FIGS. 1 and 2 , the accumulator 2000 is used to store fluid energy in water depths above the minimum hydrostatic operating depth. In water depths below the minimum hydrostatic operating depth, the intensifier 1000 is used to generate fluid energy. In water depths above the minimum hydrostatic operating depth, the fluid source 1900 is used to recharge the accumulator 2000 . In water depths below the minimum hydrostatic operating depths and above the hydrostatic recharge depth, fluid source 1900 is used to recharge the intensifier 1000 . In water depths below the hydrostatic recharge depth; fluid source 1900 , the recharge pump 6000 , and power pack 7000 are used to recharge the intensifier. During intensifier 1000 operation (generating fluid power), the regenerator 8000 is used to cogenerate electrical energy that is stored in the power pack 7000 for subsequent use. The power pack 7000 is otherwise charged from electrical source 0015 from a surface supply. The reference pilot accumulator 3200 is used to control the regulator 5000 to achieve desired fluid pressure from the intensifier 1000 when operated below the minimum hydrostatic operating depth. The screen 4000 is used to filter seawater that is used by the regulator 5000 , intensifier 1000 , and recharge pump 6000 .
[0056] FIGS. 3 and 5 illustrate the system schematic without and with the use of an external delivery fluid recovery system.
[0057] FIG. 3 shows the arrangement of intensifier 1000 , accumulator 2000 , screen 4000 , regulator 5000 , regenerator 8000 , reference reservoir 3100 , reference pilot accumulator 3200 , reference pump 3300 , recharge pump 6000 , seawater at ambient pressure, and subsea fluid header 1900 . The subsea fluid header 1900 operates at the maximum delivery fluid pressure of the accumulator 2000 . As pressure in the subsea fluid header 1900 drops to below the intensifier 1000 delivery pressure, the regulator 5000 allows seawater to enter the intensifier 1000 , sufficient to generate and maintain the intensifier 1000 delivery pressure as delivery fluid is consumed from the intensifier 1000 by operation of the underwater equipment.
[0058] FIG. 3 also illustrates interconnections between the equipment. The reservoir 3100 is connected to the reference pump 3300 via instrument tubing run 3133 . The pilot accumulator 3200 is connected to the reference pump 3300 via instrument tubing run 3233 . The reservoir 3100 is connected to the regulator 5000 via instrument tubing run 3320 . The pilot accumulator 3200 is connected to the regulator 5000 via instrument tubing run 3220 . The regulator 5000 is connected to the intensifier 1000 by instrument tubing run 1905 and large diameter tubing run 5010 . The power pack 7000 is connected to the recharge pump 6000 via pressure balanced multiconductor electrical cable 6970 . The recharge pump 6000 is connected to the intensifier 1000 via medium diameter tubing run 1960 . The regenerator 8000 is connected to the power pack 7000 via high current medium voltage pressure balanced electrical power cable 7940 .
[0059] The regenerator 8000 utilizes the seawater consumed by the intensifier 1000 when developing delivery fluid power, to cogenerate electrical power which is stored by the power pack 7000 . The seawater exhaust of the regenerator 8000 is connected to the screen 4000 input bell flange.
[0060] The screen 4000 filters seawater that flows from the surrounding ambient environment to flow through the regenerator 8000 and subsequently to the regulator 5000 .
[0061] The regulator 5000 regulates the flow of seawater 0001 to the intensifier 1000 to maintain intensifier 1000 delivery pressure; utilizing a pilot pressure reference 3220 from the reference pilot accumulator 3200 , feedback 1905 from the intensifier 1000 delivery fluid pressure, and hydrostatic ambient pressure. The regulator 5000 uses, for example, a one-atmosphere reference reservoir 3100 to allow the regulator 5000 to respond to changes in intensifier delivery fluid pressure 1905 . The output pressure from the regulator 5000 is at or below ambient hydrostatic pressure.
[0062] The reference pilot accumulator 3200 pressure is adjustable through the use of the reference pump 3300 , which allows hydraulic control fluid to be pumped from the reference reservoir 3100 to the reference pilot accumulator 3200 and vice versa via connections 3133 and 3233 ; in order to change the pressure within the gas charged reference pilot accumulator 3200 . The reference pump 3300 is operated by an external underwater control system through hydraulic valve pilot signals Ref Pump Stroke A 3310 and Ref Pump Stroke B 3311 , the direction of pressure increase through hydraulic valve pilot signals pilot accumulator pressure increase/decrease 3312 .
[0063] The reference pilot accumulator 3200 and reference reservoir 3100 incorporate pressure transducers to allow an external control system to monitor reference pressures via the pilot pressure transducer cable 3210 and the reservoir pressure transducer cable 3110 .
[0064] The intensifier 1000 is operated as a pressure intensifying pump, where regulated seawater pressure (below ambient hydrostatic pressure) is multiplied to a delivery fluid pressure exceeding ambient hydrostatic pressure. Based on installed geometry constraints, desired minimum hydrostatic operating depth, and volumetric delivery constraints, this embodiment uses an intensification factor of 2.2. However, other intensification factors may be appropriate depending on the operating parameters and environment. The intensifier 1000 may be isolated from the regulator 5000 utilizing the regulator isolation valve pilot line 1920 from an external control system. The intensifier 1000 may be isolated from the delivery fluid output and fill header 1900 utilizing the intensifier isolation valve pilot control from an external control system. The intensifier 1000 may be isolated from the recharge pump 6000 utilizing the recharge pump isolation valve pilot 1930 control from an external control system. The intensifier 1000 delivery pressure and volume measurement is available to an external control system via the intensifier instrument communications and power cable 1910 .
[0065] The recharge pump 6000 is used to evacuate seawater from the intensifier 1000 , in order to refill the intensifier 1000 from the subsea fluid header 1900 , when the intensifier 1000 is used below the minimum hydrostatic recharge water depth. The recharge pump 6000 utilizes electrical power stored in the power pack 7000 . The recharge pump 6000 operation is controlled via the recharge pump instrument power and communications cable 6910 to an external underwater control system.
[0066] The power pack 7000 is used to store electrical power from either or both surface electrical supply 0015 and from the regenerator 8000 . The power pack 7000 is controlled via the power pack instrument power and communications cable 7910 to an external underwater control system.
[0067] Once the intensifier 1000 is depleted of delivery fluid, the regulator 5000 is isolated from the intensifier 1000 via operation of the intensifier isolation pilot hydraulic signal 1950 from an external underwater control system. The recharge pump 6000 is operated via the recharge pump instrument communications and power control interface 6910 , to evacuate seawater from the intensifier 1000 and allowing the intensifier 1000 to withdraw delivery fluid from the subsea fluid header 1900 under pressure from the surface. In water depths below minimum hydrostatic delivery operation and above minimum hydrostatic recharge operation, the use of the recharge pump 6000 is not required, as a sufficient pressure differential exists between the surface supplied delivery fluid output and fill header 1900 and ambient hydrostatic pressure to allow the delivery fluid output and fill header 1900 to push the seawater out of the Intensifier. Below the minimum hydrostatic recharge depth, it is necessary to augment the delivery fluid output and fill header 1900 pressure, through evacuation of seawater from the intensifier 1000 by the recharge pump 6000 .
[0068] FIG. 4 describes the operation of the intensifier 1000 in the form of a state transition diagram, with the following states: idle full 9101 , idle empty 9102 , idle transit 9103 , hydro discharge 9100 , header overpressure recharge 9104 , and header underpressure recharge 9105 . Idle full 9101 indicates a state where the intensifier 1000 is full of delivery fluid and under pressure control of the regulator 5000 and capable of discharging delivery fluid, but under no delivery fluid demand from the underwater control system. Idle empty 9102 indicates a state where the intensifier 1000 is empty of fluid and under pressure control of the regulator 5000 , but no longer able to discharge delivery fluid to the underwater control system. Idle transit 9103 indicates a state where the intensifier 1000 is discharging delivery fluid under regulator 5000 control to the underwater control system. Overpressure recharge 9104 is a state where the intensifier 1000 is no longer under regulator 5000 control and withdrawing delivery fluid from delivery fluid output and fill header 1900 . Underpressure recharge 9105 is a state where the intensifier 1000 is no longer under regulator 5000 control, and withdrawing delivery fluid from the delivery fluid output and fill header 1900 with assistance from the recharge pump 6000 evacuating seawater from the intensifier 1000 . Transitions between states are described as causes for the transition. Transition 9115 occurs when the intensifier 1000 is not full and the regulator isolation valve pilot 1920 is not active or engaged. Transition 9114 occurs when the intensifier 1000 is full and the regulator isolation valve pilot 1920 is not active or engaged and the recharge pump 6000 is not running. Transition 9117 occurs when the regulator isolation valve pilot 1920 is not active or engaged and the recharge pump 6000 is not running. Transition 9118 occurs when the regulator isolation valve pilot 1920 is active or engaged and the pump isolation valve pilot 1930 is active or engaged and the recharge pump 6000 is not running. Transition 9119 occurs when the regulator isolation valve pilot 1920 is not active or engaged. Transition 9116 occurs when the regulator isolation valve pilot 1920 is active or engaged and the recharge pump 6000 is running. Transition 9120 occurs when no change in intensifier 1000 volume is detected. Transition 9121 occurs when a decrease in intensifier 1000 volume is detected. Transition 9123 occurs when the intensifier 1000 volume is empty. Transition 9124 occurs when the regulator isolation valve pilot 1920 is active or engaged. Transition 9122 occurs when the regulator isolation valve pilot 1920 is not active or engaged. Transition 9112 occurs when the regulator isolation valve pilot 1920 is active or engaged and the recharge pump 6000 is running. Transition 9111 occurs when the intensifier 1000 volume is full and the regulator isolation valve pilot 1920 is not active or engaged. Transition 9113 occurs when the recharge pump 6000 is running.
[0069] FIG. 5 shows a variation of the system that incorporates the capability of withdrawing delivery fluid from either the delivery fluid output and fill line 1900 , or from an external fluid recovery underwater storage tank line 0020 that feeds from an underwater storage tank (not shown).
[0070] FIG. 6 illustrates a system configuration to be used exclusively above the minimum hydrostatic operating depth of the system, where the accumulators 2000 are used to store delivery fluid at the operating pressure of the delivery fluid input and fill header 1900 . Hydraulic accumulator isolation valve pilots 1940 are provided from the external underwater control system to allow for individual isolation capabilities. The accumulator instrument communications and power cable 1910 to the external underwater control system allows for communication of individual pressure measurement and individual fluid level measurement within the accumulators 2000 .
[0071] FIG. 7 illustrates a system configuration to be may used above the minimum hydrostatic recharge depth of the system, where the accumulators 2000 are used to store delivery fluid at the operating pressure of the delivery fluid input and fill header 1900 and intensifiers 1000 are used to generate delivery fluid power below the minimum hydrostatic operating depth. Hydraulic accumulator isolation valve pilot signals 1940 are provided from the external underwater control system to allow for individual accumulator isolation capabilities. Hydraulic regulator isolation valve pilot 1920 signals are provided from the external underwater control system to allow for individual recharge capabilities of the intensifiers 1000 . Hydraulic recharge pump isolation valve pilot 1930 signals are provided from the external underwater control system to allow for individual recharge capabilities of the intensifiers 1000 . Hydraulic intensifier isolation valve pilot 1950 signals are provided from the external underwater control system to allow for individual intensifier isolation capabilities. The intensifier accumulator instrument communications and power cable 1910 to the external underwater control system allows for communication of individual pressure measurement and individual fluid level measurement within the accumulators 2000 , and individual pressure and volume measurement within the intensifiers 1000 .
[0072] FIG. 8 illustrates a system configuration to be may used exclusively below the minimum hydrostatic operating depth and above the minimum hydrostatic recharge depth of the system, where the intensifiers 1000 are used to generate delivery fluid power. Hydraulic regulator isolation valve pilot 1920 signals are provided from the external underwater control system to allow for individual recharge capabilities of the intensifiers 1000 . Hydraulic recharge pump isolation valve pilot 1930 signals are provided from the external underwater control system to allow for individual recharge capabilities of the intensifiers 1000 . Hydraulic intensifier isolation valve pilot 1950 signals are provided from the external underwater control system to allow for individual intensifier isolation capabilities. The intensifier instrument communications and power cable 1910 to the external underwater control system allows for communication of individual pressure measurement and individual fluid level measurement within the intensifiers 1000 .
[0073] FIG. 9 illustrates a system configuration to be used below the minimum hydrostatic operating depth, where the intensifiers 1000 are used to generate delivery fluid power and the recharge pump 6000 and power pack 7000 are used to individually recharge the intensifiers 1000 . Hydraulic regulator isolation valve pilot 1920 signals are provided from the external underwater control system to allow for individual recharge capabilities of the intensifiers 1000 . Hydraulic recharge pump isolation valve pilot 1930 signals are provided from the external underwater control system to allow for individual recharge capabilities of the intensifiers 1000 . The hydraulic intensifier isolation valve pilot 1950 signals are provided from the external underwater control system to allow for individual intensifier isolation capabilities. The intensifier instrument communications and power cable 1910 to the external underwater control system allows for communication of individual pressure measurement and volume measurement within the intensifiers 1000 .
[0074] FIG. 10 illustrates a system configuration to be used below the minimum hydrostatic operating depth, where the intensifiers 1000 are used to generate delivery fluid power and the recharge pump 6000 and power pack 7000 are used to individually recharge the intensifiers 1000 . The regenerator 8000 is used to augment power pack 7000 recharge time and surface electrical supply current demand 0015 . Hydraulic regulator isolation valve pilot 1920 signals are provided from the external underwater control system to allow for individual recharge capabilities of the intensifiers 1000 . Hydraulic recharge pump isolation valve pilot 1930 signals are provided from the external underwater control system to allow for individual recharge capabilities of the Intensifiers. The hydraulic intensifier isolation valve pilot 1950 signals are provided from the external underwater control system to allow for individual intensifier isolation capabilities. The intensifier instrument communications and power cable 1910 to the external underwater control system allows for communication of individual pressure measurement and volume measurement within the Intensifiers. The regenerator instrument communications and power cable 8910 is used to monitor and control the regenerator 8000 . The power pack instrument communications and power cable 7910 is used to monitor and control the power pack 7000 . The recharge pump instrument communications and power cable 6910 is used to monitor and control the recharge pump 6000 .
[0075] FIG. 11 illustrates a system configuration to be used below the minimum hydrostatic operating depth, where the intensifiers 1000 are used to generate delivery fluid power and the recharge pump 6000 and power pack 7000 are used to individually recharge the intensifiers 1000 . The intensifiers 1000 utilize a replacement subplate mounted valve, in lieu of the hydraulic isolation valve to allow selection of delivery fluid for recharge, from either the subsea fluid header 1900 , or from an external fluid recovery reservoir via the recovery fluid header 1901 . The regenerator 8000 is used to augment power pack 7000 recharge time and surface electrical supply current demand 0015 . Hydraulic regulator isolation valve pilot 1920 signals are provided from the external underwater control system to allow for individual recharge capabilities of the Intensifiers. Hydraulic recharge pump isolation valve pilot 1930 signals are provided from the external underwater control system to allow for individual recharge capabilities of the intensifiers 1000 . Hydraulic intensifier selection valve pilot 1950 signals are provided from the external underwater control system to allow for individual intensifier isolation and recharge capabilities. The intensifier instrument communications and power cable 1910 to the external underwater control system allows for communication of individual pressure measurement and volume measurement within the intensifiers 1000 .
[0076] FIG. 12 illustrates the arrangement of the screen 4000 comprised of as assembly of coarse housing 4100 , medium housing 4200 , and fine housing 4300 . The coarse housing 4100 and medium housing 4200 are joined by flange 4100 , and the medium housing 4200 and fine housing 4300 are joined by flange 4102 . The inlet to the screen 4000 is indicated by the inlet flange 4003 . The outlet from the screen 4000 is indicated by the outlet flange 4005 . The coarse housing 4100 , medium housing 4200 , and fine housing 4300 have mounting feet 4104 to allow the housings to be permanently mounted to a supporting structure. The housings have maintenance lids 4102 , 4202 , and 4302 to allow access to replaceable filter media in the respective housings. The coarse housing 4100 contains a replaceable coarse filter 4110 , designed to accommodate a flow rate of 600 gallons per minute, with a volume of 60,000 gallons throughput, and hold 2 lbs of particulate matter, and a Taylor mesh size of 250. The medium housing 4200 contains a replaceable medium filter 4210 , designed to accommodate a flow rate of 600 gallons per minute, with a volume of 60,000 gallons throughput, and hold 3 lbs of particulate matter, and a Taylor mesh size of 28. The fine housing 4300 contains a replaceable fine filter 4310 , designed to accommodate a flow of 600 gallons per minute, with a volume of 60,000 gallons, hold 5 lbs of particulate matter, and a Taylor mesh size of 9. The screen 4000 is designed for a flow rate of 600 gallons per minute, a total volume of 60,000 gallons throughput; hold a total of 10 lbs of seawater particulate contaminants, with a total pressure drop of 100 psi. It should be appreciated that these filter configurations are examples and that other filter configurations may be used as well.
[0077] The regulator 5000 is a non-relieving, seawater service flow and negative pressure regulator. It is used in conjunction with the Intensifier to supply regulated seawater pressure at or below hydrostatic pressure to cause the Intensifier to deliver hydraulic control fluid at a specific pressure above hydrostatic pressure. The regulator 5000 utilizes hydrostatic pressure, feed forward differential pressure reference, and feed back intensifier 1000 fluid pressure to maintain downstream seawater pressure at or below hydrostatic pressure during low or high flow conditions during delivery fluid consumption by the subsea control system. The regulator 5000 is designed to relieve to ambient (hydrostatic pressure) when the downstream pressure exceeds hydrostatic pressure. The regulator 5000 utilizes the pilot accumulator 3220 pressure reference for its feed forward reference. The regulator 5000 utilizes the hydraulic pressure delivery 1950 of the intensifier 1000 to provide monotonical sum of error and gain associated with reductions of delivery fluid pressure 1900 .
[0078] FIG. 13 illustrates the field connections of the regulator 5000 . Unregulated ambient pressure seawater enters the regulator 5000 from the screen 4000 at the inlet split flange 5020 and inlet seal sub 5016 . Seawater at regulated pressure at or below ambient pressure conditions exits the regulator 5000 at the outlet split flange 5025 and outlet seal sub 5016 . Gage reference pressure is applied from the pilot accumulator 3200 at tubing port 5220 . Feedback pressure from the intensifier 1000 delivery fluid port is applied at tubing port 5905 . Reservoir 3300 circulation at one atmosphere pressure is applied at tubing port 5320 .
[0079] FIG. 14 illustrates an exploded view of the regulator 5000 , comprised of an end cylinder cap 5113 with seawater inlet port 5001 ; a cylinder body 5109 internally chambered for end piston 5112 and front piston 5108 with piston rod 5111 through subdividing bulkhead; an end cap seal 5110 ; a front cylinder cap 5107 ; a flow body 5150 ; a flow body cap; an inlet flow body seal sub 5101 ; an inlet regulator split flange port 5020 ; an outlet flow body seal sub 5106 ; and an outlet regulator split flange port 5025 . The internal arrangement of an end piston 5112 connected to piston rod 5111 ; front piston 5108 connected to piston rod 5111 and poppet assembly 5105 . Seawater inlet port 5001 has access to a volume of seawater between the end piston 5112 and end cylinder cap 5113 . Reservoir port 5320 has access to a volume of hydraulic fluid between the subdividing bulkhead of the cylinder body 5109 and the end piston 5112 . Pilot pressure port 5220 has access to a volume of hydraulic fluid between the subdividing bulkhead of the cylinder body 5109 and the front piston 5108 . Feedback port 5905 has access to a volume of hydraulic fluid between the front piston 5108 and the front cylinder cap. The poppet assembly 5105 rod passes through the front cylinder cap.
[0080] FIG. 15 illustrates a cutaway of the regulator 5000 . End piston 5112 , piston rod 5111 , front piston 5108 , and the poppet assembly 5105 are interconnected. Moving of this assembly towards the seawater inlet port causes the poppet to open and allow seawater to move into the flow body 5150 and vice versa. A constant hydrostatic force F end is applied to the end piston 5112 via the seawater inlet port 5001 biasing the poppet assembly 5105 to open. A constant gage pressure force F acc derived from the pilot accumulator 3200 pressure is applied to the front piston 5108 biasing the poppet assembly 5105 to open. A variable absolute pressure force F int derived from the intensifier delivery pressure 1905 is applied to the front piston 5108 biasing the poppet assembly to close. A variable hydrostatic absolute pressure force F flow derived from the seawater hydrostatic pressure with dynamic pressure loss due to flow through the flow body 5150 is applied to the poppet assembly 5105 .
[0081] The force balance equation is (F end +F acc )*Bias−F int −F flow =0. Where the resultant force of F end +F acc represents the delivery pressure in absolute pressure (gage+hydrostatic), a decrease in F int will cause the poppet assembly 5105 to open and begin flowing until F int increases to close the poppet assembly 5105 . During flow through the flow body 5150 , a decrease in the apparent hydrostatic pressure is observed causing a reduction in F flow causing a further bias to open the poppet assembly 5105 further. As flow through the flow body 5150 is a consequence of delivery fluid demand on the intensifier 1000 on feedback line 1905 causing F int to reduce, as the intensifier catches up with flow demand, F int will increase and bias the poppet assembly 5105 to close; further reducing flow through the flow body 5150 , consequently reducing the hydrodynamic reduction of F flow , further biasing the poppet assembly to close. In order to bias the regulator to maintain a constant closing pressure, F acc is decreased by reducing the pilot accumulator 3200 pressure below the desired gage pressure of the intensifier delivery fluid and output 1900 header.
[0082] FIG. 16 illustrates the assembly of the reference pump module 3300 and reference reservoir 3100 and pilot accumulator 3200 in reference assembly 3000 . The pilot accumulator 3200 , reference reservoir 3100 , reservoir pressure transmitter 3121 , and pilot accumulator pressure transmitter 3221 are mounted into a manifold block with internal porting to connect to pilot accumulator reference tubing 3220 , reservoir circulation tubing 3120 , reference pump reservoir tubing 3133 , and reference pump accumulator tubing 3233 . The reference pump double acting pump module 3520 ; check valves 3530 , 3531 , 3532 , 3533 ; and subplate mounted 3-way valve 3510 are mounted into a manifold block with internal porting between the mounted components and connections to reference pump reservoir tubing 3133 , reference pump accumulator tubing 3233 , reference pump stroke pilot tubing 3310 , reference pump stroke pilot tubing 3311 , and pilot accumulator increase/decrease selector pilot tubing 3312
[0083] FIG. 17 illustrates the schematic of the reference pump module where pilot signals 3310 and 3311 cause a double acting axial pump 3520 to back and forth as the respective pilot signals 3310 and 3311 are pressurized and vented in a mutually exclusive manner (e.g. both pilots are not energized at the same time). The check valves cause fluid to be moved through the 3 -way valve 3510 resulting in moving fluid between 3133 and 3233 . The direction of movement is governed by the pilot signal 3312 acting on the 3-way valve 3510 .
[0084] FIG. 18 shows the action of pump 3520 . As hydraulic pilots 3310 and 3311 move the center piston in each direction, fluid at ports 3522 and 3523 is displaced in and out of the center chambers. The differential area between the piston 3511 rod end and piston end results in an intensification of pressure between that exerted at 3310 and an resultant at 3523 , allowing the pump to generate a pressure in excess of the piloting pressure. The swept volume of the pump is approximately 0.25 cubic inches per stroke, allowing pilot accumulator pressure to be adjusted in small increments.
[0085] FIG. 19 illustrates the schematic of the reference reservoir 3100 and pilot accumulator 3200 . The pilot accumulator 3200 provides a gage pressure reference (relative to the reference reservoir 3100 absolute pressure (one atmosphere)) for the regulator 5000 . The reservoir gross volume is a function of the accumulator net volume. The pressure transducers allow monitoring of the respective reservoir pressures for diagnostic purposes. A maximum of 2.5 gallons gross accumulator volume can satisfy regulator 5000 operation. The reference assembly 3000 is a closed system and does not discharge hydraulic fluid from the reservoir or pilot accumulator.
[0086] As fluid is pumped into the pilot accumulator 3200 from the reference reservoir 3100 , the precharge gas in the pilot accumulator 3200 is compressed and its hydraulic pressure increases. As fluid is pumped from the pilot accumulator 3200 to the reference reservoir 3100 , the gas expands and the accumulator hydraulic pressure decreases. The use of incremental increase and decrease of pilot accumulator 3200 pressure allows intensifier 1000 pressure delivery 1900 to be increased or decreased in a controlled manner without violent swings. The precharge pressure of the gas when the pilot accumulator 3200 is near half capacity, establishes it's median. The range of pressure adjustment is a function of the gross volume of the pilot accumulator 3200 . The gross volume of the reference reservoir 3100 is a function of the gross volume of the pilot accumulator 3200 .
[0087] FIG. 20 illustrates an exploded view of the intensifier 1000 . The intensifier 1000 is comprised of an outer barrel 1010 , elastomer mounting rings 1013 , an inner barrel 1020 , an inner barrel instrument package 1040 , an inner barrel instrument jumper 1058 , two inner barrel proximity sensors 1022 , a piston 1030 , a piston inner diameter seal 1031 , a piston outer diameter seal 1032 , an upper outer barrel flange 1011 , a regulator isolation valve 1053 , a pump isolation valve 1053 , a regulator pressure transducer 1054 , a lower outer barrel flange 1021 , a delivery pressure transducer 1054 , a instrumentation and power connector 1055 , a delivery pressure transducer instrument jumper 1056 , a regulator pressure instrument jumper 1050 , and a pump recharge tubing jumper 1057 . The inner barrel 1020 is attached to the lower outer barrel flange by means of a locking breach 1023 . The outer barrel flanges 1021 and 1011 are attached to the top and bottom of the outer barrel 1010 . The lower outer barrel flange 1021 incorporates a dry-mate subsea bulkhead connector 1055 to provide connection between the inner barrel instrumentation package and the intensifier junction box 1070 . The upper outer barrel flange 1011 incorporates subplate mounted piloted control valves 1053 for isolation of the seawater section of the intensifier 1000 from the regulator 5000 and the recharge pump 6000 . A subplate mounted pressure transducer 1054 is mounted to the upper outer barrel flange 1011 to provide pressure measurement of the internal seawater pressure in the intensifier 1000 . The lower outer barrel flange 1021 incorporates a subplate mounted control valve 1051 for isolating the delivery fluid section of the intensifier 1000 from the delivery fluid output and fill header. An alternative subplate mounted control valve 1059 may be substituted to allow the intensifier 1000 to be filled from either fluid delivery output and fill header 1900 or from an external fluid recovery reservoir 1901 . A subplate mounted pressure transducer 1054 is mounted to the lower outer barrel flange 1021 . The subplate mounted pressure transducers incorporate dry mate connectors, allowing the use of pressure balanced oil filled (PBOF) cables 1056 and 1050 to be interconnected to the intensifier junction box 1070 near the bottom of the intensifier 1000 . The instrument junction box 1070 is comprised of pressure housing with dry mate connections for; the seawater pressure instrument PBOF cable 1058 , the delivery fluid supply pressure instrument PBOF cable 1050 , the intensifier bulkhead PBOF cable 1060 , and the external underwater control system intensifier PBOF cable 1910 . The intensifier bulkhead PBOF cable is comprised of a multiconductor (copper) cable supporting separate conductors for 24 volt DC power and serial communications from the external underwater control system to the inner barrel communications port module 1120 . The external underwater control system intensifier PBOF cable 1910 is comprised of a multiconductor (copper and fiberoptic) cable supporting separate conductors for 24 volt DC power, fiber optic signal lines, and serial communications to the external underwater control system.
[0088] The geometry of the piston 1030 allows for a seawater annulus between the outer piston 1030 wall above the seal locations of the piston 1030 , and the inner diameter of the outer barrel above the highest position the seals may reach (inches above the seal location with the piston in its highest position). An extraction port 1060 and washout port 1060 are located slightly above these levels to allow the annular volume exposed to seawater to be evacuated or cleaned. The extraction port 1060 and annulus longitudinal cross-sectional area are sized to ensure turbulent flow is realized across the outer piston 1030 walls when seawater is pumped from the recharge port at low extraction flow rates. The turbulent flow provides for a self-cleaning action to the seawater interior of the intensifier 1000 when it is being recharged for subsequent operation.
[0089] Piston 1030 position is measured within the one-atmosphere conjoined chamber of the inner barrel 1020 and piston 1030 to derive remaining hydraulic volume of the hydraulic annulus. Piston 1030 position is measured relative to the inner barrel instrumentation package 1040 . Piston 1030 position at the full and empty position is measured by inductive proximity sensors 1022 . No sensor for measuring piston 1030 position crosses a pressure boundary, in contrast to prior art intensifier instrumentation. Fluid level in the inner barrel 1020 (as a consequence of unintended leakage across dynamic Piston seals) is measured relative to the inner barrel instrumentation package 1040 .
[0090] FIG. 21 illustrates the cross section view of the intensifier 1000 showing the piston 1030 in a fully retracted state, full of delivery fluid in 9800 . The intensifier 1000 is an annular piston pressure intensifier axial pump, which provides for pressure multiplication between the seawater supply side of the pump 1054 and the fluid delivery volume 9800 .
[0091] FIG. 22 illustrates a comparison of pressure intensifiers, intensifier 9814 and intensifier 1000 embodied in this apparatus. Intensifier 9814 uses a rod and piston arrangement 9802 which requires an annular volume 9801 between the piston and rod seal which must be vented to ambient pressure, otherwise leakage into this volume 9801 will cause the intensifier to hydraulically lock in place. Intensifier 9814 used for the generation of hydraulic power require the use of external one-atmosphere chambers 9814 to provide the vent required.
[0092] The intensifier 1000 of this embodiment uses a rod-less piston design utilizing dynamic seals on the inner and outer diameter of the piston 1030 skirt to provide the intensification area of the delivery fluid supply side 9800 of the intensifier 1000 relative to the piston 1030 head area. The piston skirt/seal travels between the outer barrel 1010 and inner barrel 1030 and over the inner barrel 1030 to define the hydraulic annular volume 9800 in which delivery fluid is pressurized.
[0093] The internal volume of the inner barrel 1020 and the piston 1030 provide a conjoined volume 9801 that increases and decreases as the piston 1030 moves up and down the outer barrel 1010 . This conjoined volume is a significant multiple of the hydraulic delivery volume, as opposed to a fraction of the volume seen in prior art intensifiers 9814 , and does not require the use of an external accumulator 9814 . Due to the configuration of this rod-less design, the volume of 9814 is utilized to incorporate position sensing instrumentation to measure piston 1030 elevation to derive volumetric measurement of 9800 without requiring the use of sensors operating at pressure within either 9811 , 9800 , or ambient hydrostatic pressures.
[0094] FIG. 23 illustrates a cross section view of the inner barrel instrument package 1040 . The package 1040 is comprised of a cage 1042 containing a piston position sensor 1010 , fluid level sensor 1110 , cable and connector 1121 to the inner barrel 1020 piston down position proximity sensor 1022 , connector cable 1121 to the inner barrel 1020 piston up position proximity sensor 1022 , intensifier remote input/output computer node 1120 . The cage 1042 is secured to the top of the inner barrel 1020 . The inner barrel package 1042 is connected to the lower intensifier barrel flange bulkhead connector 1055 , via the inner barrel instrumentation cable 1058 . The interconnection cable 1055 is routed along the inside wall of the inner barrel 1020 to allow sensor 1110 visibility of the bottom for purposes of fluid incursion detection and measurement.
[0095] FIG. 24 illustrates the schematic view of the intensifier without the option of recharge from an external fluid recovery tank.
[0096] FIG. 25 illustrates the schematic view of the intensifier with the option of recharge from an external fluid recovery tank via 1910 .
[0097] FIG. 26 illustrates and exploded view of the accumulator 2000 . The accumulator 2000 is comprised of the same outer barrel 1010 as used in the intensifier 1000 , two elastomer mounting rings 1013 , an upper outer barrel flange 2200 , a lower outer barrel flange 2100 , a delivery pressure transducer 1054 , a delivery pressure transducer instrument jumper 1056 , a liquid level sensor 2110 , an accumulator junction box 2070 , and a caged poppet valve 2120 . The outer barrel flanges 2200 and 2100 are attached to the top and bottom of the outer barrel 1010 . The lower outer barrel flange 2100 incorporates a subplate mounted control valve 2050 for isolating the delivery fluid section of the accumulator 2000 from the delivery fluid output and fill header. A subplate mounted pressure transducer 1054 is mounted to the lower outer barrel flange 2100 . The subplate mounted pressure transducers incorporate dry mate connectors, allowing the use of pressure balanced oil filled (PBOF) cables 1056 and 1050 to be interconnected to the accumulator junction box 2070 near the bottom of the accumulator 2000 . The accumulator junction box 2070 is comprised of pressure housing with dry mate connections for the delivery fluid supply pressure instrument PBOF cable 2061 , the accumulator liquid level sensor PBOF cable 2062 , and the external underwater control system PBOF cable 1910 . The external underwater control system intensifier PBOF cable 1910 is comprised of a multiconductor (copper and fiberoptic) cable supporting separate conductors for 24 volt DC power, fiber optic signal lines, and serial communications to the external underwater control system. The upper outer barrel flange 2200 incorporates a gas charge valve 2210 to allow the accumulator to be precharged with nitrogen at a pressure appropriate to the deployment depth required.
[0098] FIG. 27 illustrates the caged float valve 2120 used in the accumulator to isolate the delivery fluid output and prevent loss of precharge gas at low liquid levels. The poppet valve 2123 is spring loaded to open without the weight of the float 2121 .
[0099] When the liquid level rises, the float 2121 rises and allows the poppet valve to open. Use of the cage 2122 , allows the use of this assembly 2120 without the need for mechanical interconnections between the caged float valve 2120 and the upper outer barrel flange 2200 .
[0100] FIG. 28 illustrates the arrangement of the liquid level sensor 2110 , pressure transducer 1054 , caged poppet valve 2120 , and accumulator isolation valve 2050 . Accumulator junction box 2070 allows interconnection of the accumulator 2000 instrumentation to the external underwater control system via 1910 , allowing for consistency of mechanical interface between use of accumulator 2000 and intensifier 1000 . The liquid level sensor 2110 utilizes a time-of-flight acoustic ranging technique to measure the distance to the liquid free surface in the accumulator. On discharge and recharging of the accumulator 2000 , the delivery fluid may develop foam or froth at the free surface. Ranging upward to the free surface allows an accurate measurement of distance sufficient to derive useable fluid volume in the accumulator.
[0101] FIG. 29 illustrates the recharge pump 6000 assembly. The recharge pump 6000 is comprised of an electric motor and drive unit 6030 , a positive displacement pump 6003 that exhausts to ambient seawater, a pressure compensation assembly 6010 with sea water inlet 6960 , a dry-mate underwater electrical power connector 6971 , and a dry mate underwater instrument power and communications connector 6911 . The recharge pump 6000 allows seawater to be pumped from equipment that is at or lower than ambient seawater pressure, to exhaust the seawater at ambient seawater pressure.
[0102] FIG. 30 illustrates an exploded view of the recharge pump 6000 . The recharge pump 6000 comprises a seawater exhaust port 6001 ; seawater suction port 6013 , seawater pump and housing 6003 , pump shroud 6004 , shaft coupler and housing 6005 , lower motor housing and motor 6006 , upper motor housing 6007 , electronics housing 6009 , and suction balance bladder 6010 . The seawater suction port provides fluid communication to the seawater pump 6003 suction as well as pressure communication to the seawater pump 6003 case drain port and lower motor housing 6006 . The electric motor contained in the split housing 6006 is immersed in dielectric lubricant and operates at suction pressure as communicated to the housings by port 6012 . A coupling and housing 6005 mechanically connect the motor and pump through a rotating seal. The seawater pump 6003 , coupler housing 6005 and motor housing 6006 and 6007 operate with a case pressure as communicated through the coupling housing 6005 .
[0103] FIG. 31 illustrates a schematic view of the recharge pump 6000 . The controller/driver 6930 utilizes DC voltage 6970 to generate 3-phase stator voltage and frequency on 6932 to rotate the motor 6100 with feedback from resolver signals 6933 from the motor 6100 . The motor temperature is monitored through RTD leads 6931 from the motor windings 6100 . The controller/driver 6930 has the capability of controlling speed and torque developed by the motor 6100 , in order to maintain a constant speed and torque with the DC voltage at nominal values. As the DC voltage 6970 level drops, the controller/driver 6930 will reduce motor speed while maintaining torque. This allows the pump 6003 to maintain operation with diminishing DC voltage while pumping seawater suction 6013 to ambient pressure 0001 . The motor 6100 and pump 6003 are mechanically coupled through the coupler housing 6005 that provides a protection from seawater intrusion into the pump 6003 case and motor. Insulating dialectric fluid is used in the motor housing 6006 and 6007 , as well as in the pump 6003 crankcase. The dielectric lubricating fluid is pressure compensated relative to the pump suction pressure at 6013 which is connected to the intensifier recharge connection 1057 through the compensation bladder 6010 . The controller/driver 6930 is located in housing 6009 which is operated at one atmosphere pressure. The connections 6931 , 6932 , 6933 are connected through the intervening bulkhead between 6009 and 6007 , through the use of dry-mate electrical bulkhead connectors. The controller/driver 6930 is thermally bonded to the housing 6009 wall to maximize heat transfer to the ambient seawater. The controller/driver 6930 is connected to the external underwater control system via a dry-mate bulkhead connector for 6910 , and dry-mate bulkhead connector for 6970 for connection to the power pack 7000 .
[0104] FIG. 32 illustrates an assembly view of the power pack 7000 . The power pack 7000 utilizes incoming surface supply voltage at 160 - 250 volts AC at a 1.6 amps to develop DC voltage for capacitive storage. The capacitive storage is maintained at a level to allow operation of the recharge pump for a limited period of time. The power pack 7000 also utilizes regenerated DC voltage from the regenerator 8000 to charge capacitive storage at a faster rate than surface supplied voltage. The power pack is monitored and controlled by an external underwater control system to allow for isolation of incoming surface supply voltage, isolation of outgoing DC voltage to the recharge pump 6000 , and isolation of incoming regenerator power. The power pack 7000 incorporates an LED which allows for visual confirmation that the capacitive storage of the assembly is null and safe for removal of the upper flange. The electrical components of the power pack are housed in pressure housing with a upper flange to allow the electrical components to be removed as a complete assembly.
[0105] FIG. 33 illustrates a cutaway view of the power pack 7000 . The power pack 7000 is comprised of a pressure housing 7005 ; an upper flange 7006 , an instrument package hanger 7200 , a power converter/relay 7300 , and an array of ultracapacitor modules 7400 . The upper flange is comprised of a sight glass 7113 , an instrumentation power and communications connector 7111 , a surface power connector 7112 , a DC power input connector 7113 , and a DC power output connector 7114 . The power converter/relay 7300 assembly is comprised of an incoming relay module 7310 , a power controller module 7330 , and an outgoing relay module 7330 . The power converter/relay 7300 assembly incorporates structures 7301 that mechanically fasten 7401 to the instrument package hanger 7200 and mechanically fasten to the uppermost ultracapacitor module 7400 in the ultracapacitor array. The power converter/relay 7300 incorporates a DC voltage connection (power and ground) 7402 to the uppermost ultracapacitor module 7400 in the ultracapacitor array. The power converter/relay incorporates cable connections to the upper flange 7006 connectors 7111 , 7112 , 7113 , and 7114 . The power converter/relay assembly incorporates a LED indicator on top of the assembly that is visible through the sight glass 7113 . The ultracapacitor modules 7400 are vertically interconnected mechanically and electrically through mechanical fasteners 7401 and electrical connectors 7402 . The electrical connections 7402 allow for a series connection of modules to form a single capacitive device. The ultracapacitor module 7400 is formed of a plurality of ultracapacitor elements electrically connected in series to form a single capacitive unit. The individual ultracapacitors 7405 are mechanically arranged to fit in a cylindrical form, and mechanically linked to structural elements allowing for mechanical connection to fasteners 7401 .
[0106] FIG. 34 illustrates a schematic view of the power pack 7000 . Incoming surface AC power 0015 can be isolated through relay 7311 . Incoming DC power from the regenerator 8000 or other power packs 7000 can be isolated through relay 7312 . The LED 7313 provides an indication of stored voltage present in the ultracapacitor array of 7400 . The power controller module 7330 receives instrumentation power and communications on 7910 , and is capable of operating in the absence of DC or AC power to the power pack. The module 7330 controls the incoming and outgoing relays.
[0107] The power packs can be used in multiple arrangements with parallel input power from 0015 , and parallel output power to 6970 to extend operating times of the recharge pump 6000 .
[0108] FIG. 35 illustrates an assembly view of the regenerator. The regenerator 8000 utilizes the flow of seawater through impeller inlet and outlets 8014 to the screen, in order to parasitically drive a flywheel alternator 8010 for generation of electrical power in use of recharging the power pack 7000 . The flow rate through the regenerator 8000 is approximately 600 gpm for a period of 2 minutes, generating significant power from a small pressure drop across the regenerator 8000 . Electrical power is made available through connection 8012 , and the regenerator 8000 is connected to the external underwater control system via connector 8013 .
[0109] FIG. 36 illustrates an exploded view of the regenerator 8000 . The regenerator 8000 is comprised of an Impeller housing 8005 with inlet and outlet ports 8014 ; an impeller transmission housing 8006 ; a flywheel/alternator housing 8007 , and a power converter/controller housing 8009 . The impeller housing 8005 contains an impeller and magnetic coupling to eliminate mechanical losses the pressure seals across the pressure bulkhead of the impeller transmission housing 8006 . The impeller transmission housing 8006 contains a step-up transmission to multiply impeller speed, an overrunning clutch, and a flywheel/alternator to generate three phase AC voltage. The power converter/controller housing 8009 contains a rectifying buck boost DC power supply to provide DC voltage output 6970 to the power pack 7000 . The power converter/controller provides for remote monitoring and control via 8910 to an external underwater control system.
[0110] FIG. 37 illustrates the apparatus configured for use with only accumulators 2000 (refer to FIG. 6 ) in water depths less than 6000 feet as used in a subsea blowout preventer stack. The benefit of this configuration is the ability to utilize a BOP stack frame design to accommodate the four accumulators for shallow waters, and extend the operating depth by replacement of the accumulators 2000 with intensifiers 1000 . The ease of replacement is supported by the use of a common outer barrel 1010 with common mounting accessories.
[0111] FIG. 38 illustrates the apparatus configured for use with accumulators 2000 and intensifiers 1000 (refer to FIG. 7 ) in water depths less than 9000 feet as used in a subsea blowout prevent stack. This embodiment extends the accumulator 2000 on configuration of FIG. 37 , through the addition of the screen 4000 , regulator 5000 , reference 3000 , and replacement of two accumulators 2000 with two intensifiers 1000 .
[0112] FIG. 39 illustrates the apparatus configured for use with intensifiers 1000 (refer to FIG. 8 ) in water depths less than 9000 feet as used in a subsea blowout prevent stack. This embodiment extends the hybrid configuration of FIG. 37 , through the replacement of the two remaining accumulators 2000 for two intensifiers 1000 .
[0113] FIG. 40 illustrates the apparatus configured for use with intensifiers 1000 (refer to FIG. 9 ) in water depths greater than 9000 feet as used in a subsea blowout prevent stack. This embodiment utilizes the configuration shown in FIG. 39 , and adds the recharge pump 6000 and power pack 7000 to further extend the operating depth of the stack.
[0114] FIG. 41 illustrates the apparatus configured for use with intensifiers 1000 (refer to FIG. 10 ) in water depths greater than 9000 feet as used in a subsea blowout prevent stack. Recharge times are decreased in this embodiment through the addition of the regenerator 8000 to the BOP stack.
[0115] FIG. 42 illustrates the apparatus configured for use with intensifiers 1000 (refer to FIG. 10 ) in water depths greater than 6000 feet as used to support subsea BOP stack, subsea production tree, subsea distribution unit, subsea production manifold, and other subsea electro-hydraulic consumers of hydraulic and electric power. This configuration utilizes a mudmat foundation 0100 with protective framework. External access to the configuration is via Remote Operated Vehicle (ROV) utilizing the panel 0110 , and hydraulic flying lead stabplate 0111 and electric flying lead stabplate 0112 to connect between the apparatus and the external subsea equipment.
[0116] While specific embodiments have been shown and described, modifications can be made by one skilled in the art without departing from the spirit or teaching of this invention. The embodiments as described are exemplary only and are not limiting. Many variations and modifications are possible and are within the scope of the invention. Accordingly, the scope of protection is not limited to the embodiments described, but is only limited by the claims that follow, the scope of which shall include all equivalents of the subject matter of the claims. | A subsea system including a frame including an intensifier, the intensifier providing structural support to the frame and capable of providing pressurized delivery fluid. The intensifier includes an intensifier chamber and a delivery fluid chamber separated by a piston, the intensifier chamber capable of receiving ambient pressure to provide a pressure on the delivery fluid through the piston. Also, a regulation system regulates the amount of ambient pressure communicated to the intensifier chamber to maintain the delivery fluid pressure substantially constant as the delivery fluid is depleted. | 4 |
[0001] This application claims priority from U.S. Provisional Application No. 61/120,440, filed Dec. 6, 2008, the contents of which are hereby incorporated by reference in their entirety.
TECHNICAL FIELD
[0002] The present invention relates to optionally substituted 4,5,7,8-tetrahydro-(optionally 4-oxo, 4-thioxo or 4-imino)-2H-imidazo[1,2-a]pyrrolo[3,4-e]pyrimidine or 4,5,7,8,9-pentahydro-(optionally 4-oxo, 4-thioxo or 4-imino)-2H-pyrimido[1,2-a]pyrrolo[3,4-e]pyrimidine, for example, compounds of Formula II (Formula II-A and II-B) and Formula I (Formula I-A and I-B) as described below, processes for their production, their use as pharmaceuticals and pharmaceutical compositions comprising them. Of particular interest are novel compounds useful as inhibitors of phosphodiesterase 1 (PDE1), e.g., in the treatment of diseases involving disorders of the dopamine D1 receptor intracellular pathway, such as Parkinson's disease, depression, narcolepsy, damage to cognitive function, e.g., in schizophrenia, or disorders that may be ameliorated through enhanced progesterone-signaling pathway, e.g., female sexual dysfunction as well as other disease or conditions characterized by low levels of cAMP and/or cGMP in cells expressing PDE1 and those characterized by reduced dopamine D1 receptor signaling activities.
BACKGROUND OF THE INVENTION
[0003] Eleven families of phosphodiesterases (PDEs) have been identified but only PDEs in Family I, the Ca 2+ -calmodulin-dependent phosphodiesterases (CaM-PDEs), have been shown to mediate both the calcium and cyclic nucleotide (e.g. cAMP and cGMP) signaling pathways. The three known CaM-PDE genes, PDE1A, PDE1B, and PDE1C, are all expressed in central nervous system tissue. PDE1A is expressed throughout the brain with higher levels of expression in the CA1 to CA3 layers of the hippocampus and cerebellum and at a low level in the striatum. PDE1A is also expressed in the lung and heart. PDE1B is predominately expressed in the striatum, dentate gyms, olfactory tract and cerebellum, and its expression correlates with brain regions having high levels of dopaminergic innervation. Although PDE1B is primarily expressed in the central nervous system, it may be detected in the heart. PDE1C is primarily expressed in olfactory epithelium, cerebellar granule cells, and striatum. PDE1C is also expressed in the heart and vascular smooth muscle.
[0004] Cyclic nucleotide phosphodiesterases decrease intracellular cAMP and cGMP signaling by hydrolyzing these cyclic nucleotides to their respective inactive 5′-monophosphates (5′AMP and 5′GMP). CaM-PDEs play a critical role in mediating signal transduction in brain cells, particularly within an area of the brain known as the basal ganglia or striatum. For example, NMDA-type glutamate receptor activation and/or dopamine D2 receptor activation result in increased intracellular calcium concentrations, leading to activation of effectors such as calmodulin-dependent kinase II (CaMKII) and calcineurin and to activation of CaM-PDEs, resulting in reduced cAMP and cGMP. Dopamine D1 receptor activation, on the other hand, leads to activation of nucleotide cyclases, resulting in increased cAMP and cGMP. These cyclic nucleotides in turn activate protein kinase A (PKA; cAMP-dependent protein kinase) and/or protein kinase G (PKG; cGMP-dependent protein kinase) that phosphorylate downstream signal transduction pathway elements such as DARPP-32 (dopamine and cAMP-regulated phosphoprotein) and cAMP responsive element binding protein (CREB). Phosphorylated DARPP-32 in turn inhibits the activity of protein phosphates-1 (PP-1), thereby increasing the state of phosphorylation of substrate proteins such as progesterone receptor (PR), leading to induction of physiologic responses. Studies in rodents have suggested that inducing cAMP and cGMP synthesis through activation of dopamine D1 or progesterone receptor enhances progesterone signaling associated with various physiological responses, including the lordosis response associated with receptivity to mating in some rodents. See Mani, et al., Science (2000) 287: 1053, the contents of which are incorporated herein by reference.
[0005] CaM-PDEs can therefore affect dopamine-regulated and other intracellular signaling pathways in the basal ganglia (striatum), including but not limited to nitric oxide, noradrenergic, neurotensin, CCK, VIP, serotonin, glutamate (e.g., NMDA receptor, AMPA receptor), GABA, acetylcholine, adenosine (e.g., A2A receptor), cannabinoid receptor, natriuretic peptide (e.g., ANP, BNP, CNP), DARPP-32, and endorphin intracellular signaling pathways.
[0006] Phosphodiesterase (PDE) activity, in particular, phosphodiesterase 1 (PDE1) activity, functions in brain tissue as a regulator of locomotor activity and learning and memory. PDE1 is a therapeutic target for regulation of intracellular signaling pathways, preferably in the nervous system, including but not limited to a dopamine D1 receptor, dopamine D2 receptor, nitric oxide, noradrenergic, neurotensin, CCK, VIP, serotonin, glutamate (e.g., NMDA receptor, AMPA receptor), GABA, acetylcholine, adenosine (e.g., A2A receptor), cannabinoid receptor, natriuretic peptide (e.g., ANP, BNP, CNP), endorphin intracellular signaling pathway and progesterone signaling pathway. For example, inhibition of PDE should act to potentiate the effect of a dopamine D1 agonist by protecting cGMP and cAMP from degradation, and should similarly inhibit dopamine D2 receptor signaling pathways, by inhibiting PDE1 activity. Chronic elevation in intracellular calcium levels is linked to cell death in numerous disorders, particularly in neurodegerative diseases such as Alzheimer's, Parkinson's and Huntington's Diseases and in disorders of the circulatory system leading to stroke and myocardial infarction. PDE1 inhibitors are therefore potentially useful in diseases characterized by reduced dopamine D1 receptor signaling activity, such as Parkinson's disease, restless leg syndrome, depression, narcolepsy and cognitive impairment. PDE1 inhibitors are also useful in diseases that may be alleviated by the enhancement of progesterone-signaling such as female sexual dysfunction.
[0007] There is thus a need for compounds that selectively inhibit PDE1 activity, especially PDE1A and/or PDE1B activity.
SUMMARY OF THE INVENTION
[0008] The invention provides optionally substituted 4,5,7,8-tetrahydro-2H-imidazo[1,2-a]pyrrolo[3,4-e]pyrimidine or 4,5,7,8,9-pentahydro-2H-pyrimido[1,2-a]pyrrolo[3,4-e]pyrimidine, e.g., a Compound of Formula II, e.g., II-A or II-B:
[0000]
[0000] wherein
(i) Q is C(═O), C(═S), C(═N(R 20 )) or CH 2 ; (ii) L is a single bond, —N(H)—, —CH 2 —, —S—, —S(O)— or —S(O 2 )—; (iii) R 1 is H or C 1-4 alkyl (e.g., methyl); (iv) R 4 is H or C 1-6 alkyl (e.g., methyl or isopropyl) and R 2 and R 3 are, independently,
H C 1-6 alkyl (e.g., methyl, isopropyl) optionally substituted with halo or hydroxy (e.g., R 2 and R 3 are both methyl, or R 2 is H and R 3 is methyl, ethyl, isopropyl or hydroxyethyl), aryl, heteroaryl, (optionally hetero)arylalkoxy, (optionally hetero)arylC 1-6 alkyl; or R 2 and R 3 together form a 3- to 6-membered ring;
or R 2 is H and R 3 and R 4 together form a di-, tri- or tetramethylene bridge (pref. wherein the R 3 and R 4 together have the cis configuration, e.g., where the carbons carrying R 3 and R 4 have the R and S configurations, respectively); or (v) R 5 is
a) -D-E-F, wherein:
D is C 1-4 alkylene (e.g., methylene, ethylene or prop-2-yn-1-ylene); E is a single bond, C 2-4 alkynylene (e.g., —C≡C—), arylene (e.g., phenylene) or heteroarylene (e.g., pyridylene); F is
H, aryl (e.g., phenyl), heteroaryl (e.g., pyridyl, diazolyl, triazolyl, for example, pyrid-2-yl, imidazol-1-yl, 1,2,4-triazol-1-yl), halo (e.g., F, Br, Cl), haloC 1-4 alkyl (e.g., trifluoromethyl), —C(O)—R 15 , —N(R 16 )(R 17 ), or C 3-7 cycloalkyl optionally containing at least one atom selected from a group consisting of N or O (e.g., cyclopentyl, cyclohexyl, pyrrolidinyl (e.g., pyrrolidin-3-yl), tetrahydro-2H-pyran-4-yl, or morpholinyl);
wherein D, E and F are independently and optionally substituted with one or more halo (e.g., F, Cl or Br), C 1-4 alkyl (e.g., methyl), haloC 1-4 alkyl (e.g., trifluoromethyl), C 1-4 alkoxy (e.g., methoxy), hydroxy, C 1-4 carboxy, or an additional aryl or heteroaryl (e.g., biphenyl or pyridylphenyl), for example, F is heteroaryl, e.g., pyridyl substituted with one or more halo (e.g., 6-fluoropyrid-2-yl, 5-fluoropyrid-2-yl, 6-fluoropyrid-2-yl, 3-fluoropyrid-2-yl, 4-fluoropyrid-2-yl, 4,6-dichloropyrid-2-yl), haloC 1-4 alkyl (e.g., 5-trifluoromethylpyrid-2-yl) or C 1-4 alkyl (e.g., 5-methylpyrid-2-yl), or F is aryl, e.g., phenyl, substituted with one or more halo (e.g., 4-fluorophenyl) or F is a C 3-7 heterocycloalkyl (e.g., pyrrolidinyl) optionally substituted with a C 1-6 alkyl (e.g., 1-methylpyrrolidin-3-yl); or
b) a substituted heteroarylalkyl, e.g., substituted with haloC 1-4 alkyl; c) attached to the nitrogen on the pyrrolo portion of Formula II-A or II-B and is a moiety of Formula A
[0000]
wherein X, Y and Z are, independently, N or C, and R 8 , R 9 , R 11 and R 12 are independently H or halogen (e.g., Cl or F), and R 10 is
halogen, C 1-4 alkyl, haloC 1-4 alkyl (e.g., triflouromethyl) C 1-4 alkoxy (e.g. methoxy), C 3-7 cycloalkyl, heteroC 3-7 cycloalkyl (e.g., pyrrolidinyl or piperidinyl), C 1-4 haloalkyl (e.g., trifluoromethyl), aryl (e.g., phenyl), heteroaryl (e.g., pyridyl (for example pyrid-2-yl or pyrid-4-yl), or thiadiazolyl (e.g., 1,2,3-thiadiazol-4-yl)), diazolyl (e.g., imidazol-1-yl), triazolyl (e.g., 1,2,4-triazol-1-yl), tetrazolyl, arylcarbonyl (e.g., benzoyl), alkylsulfonyl (e.g., methylsulfonyl), heteroarylcarbonyl, or alkoxycarbonyl;
wherein the aryl, heteroaryl, cycloalkyl or heterocycloalkyl is independently, optionally substituted with one or more C 1-4 alkyl (e.g., methyl), halogen (e.g., chloro or fluoro), haloC 1-4 alkyl (e.g., trifluoromethyl), hydroxy, C 1-4 carboxy, —SH or an additional aryl, heteroaryl (e.g., biphenyl or pyridylphenyl) or C 3-8 cycloalkyl,
preferably R 10 is phenyl, pyridyl, piperidinyl or pyrrolidinyl optionally substituted with the substituents previously defined, e.g. optionally substituted with halo or alkyl
provided that when X, Y, or Z is nitrogen, R 3 , R 9 , or R 10 , respectively, is not present;
(vi) R 6 is
H, C 1-4 alkyl (e.g., methyl, ethyl, n-propyl, isobutyl), C 3-7 cycloalkyl (e.g., cyclopentyl or cyclohexyl), heteroC 3-7 cycloalkyl (e.g., pyrrolidinyl, piperidinyl, morpholinyl), aryl (e.g., phenyl), heteroaryl (e.g., pyrid-4-yl), arylC 1-4 alkyl (e.g., benzyl), arylamino (e.g., phenylamino), heteroarylamino, N,N-diC 1-4 alkylamino, N,N-diarylamino, N-aryl-N-(arylC 1-4 alkyl)amino (e.g., N-phenyl-N-(1,1′-biphen-4-ylmethyl)amino), or —N(R 18 )(R 19 ), wherein the aryl and heteroaryl are optionally substituted with one or more C 1-4 alkyl (e.g., methyl), halogen (e.g., chloro or fluoro), haloC 1-4 alkyl (e.g., trifluoromethyl), hydroxy, C 1-4 carboxy, or an additional aryl, heteroaryl (e.g., biphenyl or pyridylphenyl) or C 3-8 cycloalkyl;
(vii) R 7 is H, C 1-6 alkyl (e.g., methyl or ethyl), halogen (e.g., Cl), —N(R 18 )(R 19 ), hydroxy or C 1-6 alkoxy;
(viii) n=0 or 1;
(ix) when n=1, A is —C(R 13 R 14 )—, wherein R 13 and R 14 , are, independently, H or C 1-4 alkyl, aryl, heteroaryl, (optionally hetero)arylC 1-4 alkoxy, (optionally hetero)arylC 1-4 alkyl or R 14 can form a bridge with R 2 or R 4 ;
(x) R 15 is C 1-4 alkyl, haloC 1-4 alkyl, —OH or —OC 1-4 alkyl (e.g., —OCH 3 )
(xi) R 16 and R 17 are independently H or C 1-4 alkyl;
(xii) R 18 and R 19 are independently
H, C 1-4 alky (e.g., methyl, ethyl, n-propyl, isobutyl), C 3-8 cycloalky (e.g., cyclohexyl or cyclopenyl), heteroC 3-8 cycloalky (e.g., pyrrolidinyl, piperidinyl, morpholinyl), aryl (e.g., phenyl) or heteroaryl (e.g., pyridyl), wherein said aryl and heteroaryl are optionally substituted with one or more
halo (e.g., fluorophenyl, e.g., 4-fluorophenyl), hydroxy (e.g., hydroxyphenyl, e.g., 4-hydroxyphenyl or 2-hydroxyphenyl), C 1-4 alkyl (e.g., methyl), haloC 1-4 alkyl (e.g., trifluoromethyl), C 1-4 carboxy, or an additional aryl, heteroaryl (e.g., biphenyl or pyridylphenyl) or C 3-8 cycloalkyl,
(xiii) R 20 is H, C 1-4 alkyl or C 3-7 cycloalkyl;
in free or salt form.
[0091] In another aspect, the invention provides a Compound of Formula I, e.g. Formula I-A and I-B:
[0000]
[0000] wherein
(i) Q is C(═O), C(═S), C(═N(R 20 )) or CH 2 ; (ii) L is a single bond, —N(H)—, —CH 2 —, —S—, —S(O)— or —S(O 2 )—; (iii) R 1 is H or C 1-4 alkyl (e.g., methyl); (iv) R 4 is H or C 1-6 alkyl (e.g., methyl or isopropyl) and R 2 and R 3 are, independently,
H or C 1-6 alkyl (e.g., methyl, isopropyl) optionally substituted with halo or hydroxy (e.g., R 2 and R 3 are both methyl, or R 2 is H and R 3 is methyl, ethyl, isopropyl or hydroxyethyl), aryl, heteroaryl, (optionally hetero)arylalkoxy, or (optionally hetero)arylC 1-6 alkyl;
or R 2 is H and R 3 and R 4 together form a di-, tri- or tetramethylene bridge (pref. wherein the R 3 and R 4 together have the cis configuration, e.g., where the carbons carrying R 3 and R 4 have the R and S configurations, respectively); (v) R 5 is
a) -D-E-F, wherein:
D is C 1-4 alkylene (e.g., methylene, ethylene or prop-2-yn-1-ylene); E is a single bond, C 2-4 alkynylene (e.g., —C≡C—), arylene (e.g., phenylene) or heteroarylene (e.g., pyridylene); F is
H, aryl (e.g., phenyl), heteroaryl (e.g., pyridyl, diazolyl, triazolyl, for example, pyrid-2-yl, imidazol-1-yl, 1,2,4-triazol-1-yl), halo (e.g., F, Br, Cl), haloC 1-4 alkyl (e.g., trifluoromethyl), —C(O)—R 15 , 'N(R 16 )(R 17 ), or C 3-7 cycloalkyl optionally containing at least one atom selected from a group consisting of N or O (e.g., cyclopentyl, cyclohexyl, pyrrolidinyl (e.g., pyrrolidin-3-yl), tetrahydro-2H-pyran-4-yl, or morpholinyl);
wherein D, E and F are independently and optionally substituted with one or more halo (e.g., F, Cl or Br), C 1-4 alkyl (e.g., methyl), haloC 1-4 alkyl (e.g., trifluoromethyl), for example, F is heteroaryl, e.g., pyridyl substituted with one or more halo (e.g., 6-fluoropyrid-2-yl, 5-fluoropyrid-2-yl, 6-fluoropyrid-2-yl, 3-fluoropyrid-2-yl, 4-fluoropyrid-2-yl, 4,6-dichloropyrid-2-yl), haloC 1-4 alkyl (e.g., 5-trifluoromethylpyrid-2-yl) or C 1-4 alkyl (e.g., 5-methylpyrid-2-yl), or F is aryl, e.g., phenyl, substituted with one or more halo (e.g., 4-fluorophenyl) or F is a C 3-7 heterocycloalkyl (e.g., pyrrolidinyl) optionally substituted with a C 1-6 alkyl (e.g., 1-methylpyrrolidin-3-yl); or
b) a substituted heteroarylalkyl, e.g., substituted with haloalkyl; c) attached to the nitrogen on the pyrrolo portion of Formula I-A or I-B and is a moiety of Formula A
[0000]
wherein X, Y and Z are, independently, N or C, and R 8 , R 9 , R 11 and R 12 are independently H or halogen (e.g., Cl or F), and R 10 is
halogen, C 3-7 cycloalkyl, C 1-4 haloalkyl (e.g., trifluoromethyl), aryl (e.g., phenyl), heteroaryl (e.g., pyridyl (for example pyrid-2-yl), or thiadiazolyl (e.g., 1,2,3-thiadiazol-4-yl)), diazolyl, triazolyl, tetrazolyl, arylcarbonyl (e.g., benzoyl), alkylsulfonyl (e.g., methylsulfonyl), heteroarylcarbonyl, or alkoxycarbonyl;
provided that when X, Y, or Z is nitrogen, R 8 , R 9 , or R 10 , respectively, is not present;
(vi) R 6 is
H, C 1-4 alkyl, C 3-7 cycloalkyl (e.g., cyclopentyl), aryl (e.g., phenyl), heteroaryl (e.g., pyrid-4-yl), arylC 1-4 alkyl (e.g., benzyl), arylamino (e.g., phenylamino), heteroarylamino, N,N-diC 1-4 alkylamino, N,N-diarylamino, N-aryl-N-(arylC 1-4 alkyl)amino (e.g., N-phenyl-N-(1,1′-biphen-4-ylmethyl)amino), or —N(R 18 )(R 19 ); wherein the aryl or heteroaryl is optionally substituted with one or more halo (e.g., F, Cl), hydroxy or C 1-6 alkoxy;
(vii) R 7 is H, C 1-6 alkyl, halogen (e.g., Cl), —N(R 18 )(R 19 );
(viii) n=0 or 1;
(ix) when n=1, A is —C(R 13 R 14 )—, wherein R 13 and R 14 , are, independently, H or C 1-4 alkyl, aryl, heteroaryl, (optionally hetero)arylC 1-4 alkoxy or (optionally hetero)arylC 1-4 alkyl;
(x) R 15 is C 1-4 alkyl, haloC 1-4 alkyl, —OH or —OC 1-4 alkyl (e.g., —OCH 3 )
(xi) R 16 and R 17 are independently H or C 1-4 alkyl;
(xii) R 18 and R 19 are independently H, C 1-4 alky or aryl (e.g., phenyl) wherein said aryl is optionally substituted with one or more halo (e.g., fluorophenyl, e.g., 4-fluorophenyl) or hydroxy (e.g., hydroxyphenyl, e.g., 4-hydroxyphenyl or 2-hydroxyphenyl)
(xiii) R 20 is H, C 1-4 alkyl or C 3-7 cycloalkyl;
in free, salt or prodrug form.
[0151] The invention further provides compounds of Formula I (I-A and I-B) as follows:
1.1 Formula I-A or I-B, wherein Q is C(═O), C(═S), C(═N(R 20 )) or CH 2 ; 1.2 Formula I-A or I-B or 1.1, wherein Q is C(═S); 1.3 Formula I-A or I-B or 1.1, wherein Q is C(═N(R 20 )); 1.4 Formula I-A or I-B or 1.1, wherein Q is CH 2 ; 1.5 Formula I-A or I-B or 1.1, wherein Q is C(═O); 1.6 Formula I-A or I-B, or any of 1.1-1.5, wherein L is a single bond, —N(H)—, —CH 2 —, —S—, —S(O)— or —S(O 2 )—; 1.7 Formula 1.6, wherein L is a single bond; 1.8 Formula 1.6, wherein L is —N(H)—; 1.9 Formula 1.6, wherein L is —CH 2 —; 1.10 Formula 1.6, wherein L is —S—; 1.11 Formula 1.6, wherein L is —S(O)—; 1.12 Formula 1.6, wherein L is —S(O 2 )—; 1.13 Formula I-A or I-B, or any of 1.1-1.12, wherein R 1 is H or C 1-4 alkyl (e.g., methyl); 1.14 Formula 1.13, wherein R 1 is H; 1.15 Formula 1.13, wherein R 1 is C 1-4 alkyl (e.g., methyl); 1.16 Formula I-A or I-B, or any of 1.1-1.15, wherein R 4 is H or C 1-6 alkyl (e.g., methyl, isopropyl) and R 2 and R 3 are, independently,
H or C 1-6 alkyl optionally substituted with halo or hydroxy (e.g., R 2 and R 3 are both methyl, or R 2 is H and R 3 is methyl, ethyl, isopropyl or hydroxyethyl), aryl, heteroaryl, (optionally hetero)arylalkoxy, or (optionally hetero)arylC 1-6 alkyl;
1.17 Formula I-A or I-B, or any of 1.1-1.15, wherein R 2 is H and R 3 and R 4 together form a di-, tri- or tetramethylene bridge (pref. wherein the R 3 and R 4 together have the cis configuration, e.g., where the carbons carrying R 3 and R 4 have the R and S configurations, respectively); 1.18 Formula I-A or I-B or any of 1.1-1.17, wherein R 5 is -D-E-F; 1.19 Formula 1.18, wherein D is C 1-4 alkylene (e.g., methylene, ethylene or prop-2-yn-1-ylene); 1.20 Formula 1.19, wherein D is methylene; 1.21 Any of formulae 1.18-1.20, wherein E is a single bond, C 2-4 alkynylene (e.g., arylene (e.g., phenylene) or heteroarylene (e.g., pyridylene); 1.22 Any of formulae 1.18-1.20, wherein E is arylene (e.g., phenylene); 1.23 Any of formulae 1.18-1.20, wherein E is phenylene; 1.24 Any of formulae 1.18-1.20, wherein E is heteroarylene (e.g., pyridylene); 1.25 Any of formulae 1.18-1.20, wherein E is phenylene wherein F is para-substituted; 1.26 Any of formulae 1.18-1.20, wherein E is heteroarylene (e.g., pyridylene); 1.27 Any of formulae 1.18-1.20, wherein E is a single bond; 1.28 Any of formulae 1.18-1.27, wherein F is H, aryl (e.g., phenyl), heteroaryl (e.g., pyridyl, e.g., pyrid-2-yl), halo (e.g., F, Br, Cl), haloC 1-4 alkyl (e.g., trifluoromethyl), —C(O)—R 15 , —N(R 16 )(R 17 ), or C 3-7 cycloalkyl optionally containing at least one atom selected from a group consisting of N or O (e.g., cyclopentyl, cyclohexyl, pyrrolidinyl (e.g., pyrrolidin-3-yl), tetrahydro-2H-pyran-4-yl, or morpholinyl); 1.29 Formula 1.28, wherein F is haloC 1-4 alkyl (e.g., trifluoromethyl); 1.30 Formula 1.28, wherein F is trifluoromethyl; 1.31 Formula 1.28, wherein F is halo (e.g., F, Br, Cl); 1.32 Formula 1.28, wherein F is Cl; 1.33 Formula 1.28, wherein F is heteroaryl (e.g., pyridyl, e.g., pyrid-2-yl); 1.34 Formula 1.28, wherein F is pyridyl; 1.35 Formula 1.28, wherein F is pyrid-2-yl; 1.36 Formula 1.28, wherein F is C 3-7 cycloalkyl optionally containing at least one atom selected from a group consisting of N or O (e.g., cyclopentyl, cyclohexyl, pyrrolidinyl (e.g., pyrrolidin-3-yl), tetrahydro-2H-pyran-4-yl, morpholinyl); 1.37 Formula 1.28, wherein F is cyclohexyl; 1.38 Formula 1.28, wherein F is pyrrolidinyl (e.g., pyrrolidin-3-yl); 1.39 Formula 1.28, wherein F is cyclopentyl; 1.40 Formula 1.28, wherein F is tetrahydro-2H-pyran-4-yl; 1.41 Formula 1.28, wherein F is aryl (e.g., phenyl); 1.42 Formula 1.28, wherein F is phenyl; 1.43 Formula 1.28, wherein F is 4-fluorophenyl; 1.44 Formula 1.28, wherein F is —C(O)—R 15 and R 15 is C 1-4 alky (e.g., methyl), haloC 1-4 alkyl (e.g., trifluoromethyl), —OH or —OC 1-4 alkyl (e.g., —OCH 3 ); 1.45 Any of formulae 1.18-1.44, wherein D, E and F are independently and optionally substituted with one or more halo (e.g., F, Cl or Br), C 1-4 alkyl (e.g., methyl), haloC 1-4 alkyl (e.g., trifluoromethyl), for example, F is heteroaryl, e.g., pyridyl substituted with one or more halo (e.g., 6-fluoropyrid-2-yl, 5-fluoropyrid-2-yl, 6-fluoropyrid-2-yl, 3-fluoropyrid-2-yl, 4-fluoropyrid-2-yl, 4,6-dichloropyrid-2-yl), haloC 1-4 alkyl (e.g., 5-trifluoromethylpyrid-2-yl) or C 1-4 alkyl (e.g., 5-methylpyrid-2-yl), or F is aryl, e.g., phenyl, substituted with one or more halo (e.g., 4-fluorophenyl), or F is a C 3-7 heterocycloalkyl (e.g., pyrrolidinyl) optionally substituted with a C 1-6 alkyl (e.g., 1-methylpyrrolidin-3-yl); 1.46 Formula 1.45, wherein F is substituted with one or more halo (e.g., F, Cl or Br), C1-4 alkyl (e.g., methyl), halo C1-4 aalkyl (e.g., trifluoromethyl); 1.47 Formula 1.45, wherein F is 6-fluoropyrid-2-yl; 1.48 Formula 1.45, wherein F is 3-fluoropyrid-2-yl; 1.49 Formula 1.45, wherein F is 4-fluoropyrid-2-yl; 1.50 Formula 1.45, wherein F is 5-fluoropyrid-2-yl; 1.51 Formula 1.45, wherein F is heteroaryl, e.g., pyridyl, optionally substituted with one or more haloC 1-4 alkyl (e.g., 5-trifluoromethylpyrid-2-yl; 1.52 Formula 1.45, wherein F is 5-trifluoromethylpyrid-2-yl; 1.53 Formula 1.45, wherein F is heteroaryl, e.g., pyridyl, optionally substituted with one or more C 1-4 alkyl (e.g., 5-methylpyrid-2-yl); 1.54 Formula 1.45, wherein F is 5-methylpyrid-2-yl; 1.55 Formula 1.28, wherein F is —C(O)—R 15 and R 15 is methyl; 1.56 Formula 1.28, wherein F is —C(O)—R 15 and R 15 is trifluoromethyl; 1.57 Formula 1.28, wherein F is —C(O)—R 15 and R 15 is —OH; 1.58 Formula 1.28, wherein F is —C(O)—R 15 and R 15 is —OC 1-4 alkyl (e.g., —OCH 3 ); 1.59 Formula 1.28, wherein F is —C(O)—R 15 and R 15 is —OCH 3 ; 1.60 Formula 1.28, wherein F is —N(R 16 )(R 17 ); 1.61 Formula I-A or I-B or any of 1.1-1.17, wherein R 5 is a substituted heteroarylalkyl, e.g., substituted with haloalkyl; 1.62 Formula I-A or I-B or any of 1.1-1.17, wherein R 5 is attached to one of the nitrogens on the pyrazolo portion of Formula I-A or I-B and is a moiety of Formula A
[0000]
wherein X, Y and Z are, independently, N or C, and R 8 , R 9 , R 11 and R 12 are independently H or halogen (e.g., Cl or F), and R 10 is halogen, C 1-4 alkyl, C 3-7 cycloalkyl, C 1-4 haloalkyl (e.g., trifluoromethyl), aryl (e.g., phenyl), heteroaryl (e.g., pyridyl (for example pyrid-2-yl), or thiadiazolyl (e.g., 1,2,3-thiadiazol-4-yl)), diazolyl, triazolyl, tetrazolyl, arylcarbonyl (e.g., benzoyl), alkylsulfonyl (e.g., methylsulfonyl), heteroarylcarbonyl, or alkoxycarbonyl; provided that when X, Y, or Z is nitrogen, R 8 , R 9 , or R 10 , respectively, is not present
1.63 Formula 1.62, wherein R 5 is a substituted heteroarylmethyl, e.g., para-substituted with haloalkyl;
1.64 Formula 1.62, wherein R 5 is a moiety of Formula A wherein R 8 , R 9 , R 11 , and R 12 are H and R 10 is phenyl;
1.65 Formula 1.62, wherein R 5 is a moiety of Formula A wherein R 8 , R 9 , R 11 , and R 12 are H and R 10 is pyridyl or thiadiazolyl;
1.66 Formula 1.62, wherein R 5 is a moiety of Formula A wherein R 8 , R 9 , R 11 , and R 12 are, independently, H or halogen, and R 10 is haloalkyl;
1.67 Formula 1.62, wherein R 5 is a moiety of Formula A wherein R 8 , R 9 , R 11 , and R 12 are, independently, H, and R 10 is alkyl sulfonyl;
1.68 Formula I-A or I-B or any of 1.1-1.67, wherein R 6 is H, C 1-4 alkyl, C 3-7 cycloalkyl (e.g., cyclopentyl), aryl, heteroaryl, arylC 1-4 alkyl (e.g., benzyl), arylamino (e.g., phenylamino), heteroarylamino, N,N-diC 1-4 alkylamino, N,N-diarylamino, N-aryl-N-(arylC 1-4 alkyl)amino (e.g., N-phenyl-N-(1,1′-biphen-4-ylmethyl)amino), or —N(R 18 )(R 19 ), wherein the aryl or heteroaryl is optionally substituted with one or more halo (e.g., F, Cl), hydroxy or C 1-6 alkoxy;
1.69 Formula 1.68, wherein R 6 is H;
1.70 Formula 1.68, wherein R 6 is aryl (e.g., phenyl) optionally substituted with one or more halo (e.g., F, Cl), hydroxy or C 1-6 alkoxy;
1.71 Formula 1.68, wherein R 6 is C 1-4 alkyl;
1.72 Formula 1.68, wherein R 6 is C 3-7 cycloalkyl (e.g., cyclopentyl);
1.73 Formula 1.68, wherein R 6 is fluorophenyl (e.g., 4-fluorophenyl) or hydroxyphenyl (e.g., 4-hydroxyphenyl or 2-hydroxyphenyl);
1.74 Formula I-A or I-B or any of 1.1-1.73, wherein R 7 is H, C 1-6 alkyl (e.g., methyl), halogen, —N(R 18 )(R 19 );
1.75 Formula 1.74, wherein R 7 is H;
1.76 Formula 1.74, wherein R 7 is C 1-6 alkyl (e.g., methyl);
1.77 Formula 1.74, wherein R 7 is methyl;
1.78 Formula 1.74, wherein R 7 is ethyl;
1.79 Formula I-A or I-B or any of 1.1-1.78, wherein n=0;
1.80 Formula I-A or I-B or any of 1.1-1.78, wherein n=1;
1.81 Formula 1.80, wherein n=1, A is —C(R 13 R 14 )—, wherein R 13 and R 14 , are, independently, H or C 1-4 alkyl, aryl, heteroaryl, (optionally hetero)arylC 1-4 alkoxy or (optionally hetero)arylC 1-4 alkyl;
1.82 any of the preceding formulae wherein the compound is Formula I-A;
1.83 any of the preceding formulae wherein the compound is selected from a group consisting of:
[0000]
1.84 any of the preceding formulae wherein the compounds inhibit phosphodiesterase-mediated (e.g., PDE1-mediated, especially PDE1B-mediated) hydrolysis of cGMP, e.g., with an IC 50 of less than 1 μM, preferably less than 750 nM, more preferably less than 500 nM, more preferably less than 50 nM in an immobilized-metal affinity particle reagent PDE assay, for example, as described in Example 16,
in free or salt form.
[0242] In still another embodiment, the invention provides a compound as follows:
2.1 a Compound of Formula I-A, I-B, II-A or II-B, or any of 1.1-1.6, 1.14-1.67, 1.74-1.84, wherein L is a single bond or —CH 2 —; 2.2 formula 2.1, wherein R 6 is
H, arylamino (e.g., phenylamino), heteroarylamino, N,N-diC 1-4 alkylamino, N,N-diarylamino, N-aryl-N-(arylC 1-4 alkyl)amino (e.g., N-phenyl-N-(1,1′-biphen-4-ylmethyl)amino), or —N(R 18 )(R 19 ), wherein the aryl and heteroaryl are optionally substituted with one or more C 1-4 alkyl (e.g., methyl), halogen (e.g., chloro or fluoro), haloC 1-4 alkyl (e.g., trifluoromethyl), hydroxy, C 1-4 carboxy, or an additional aryl, heteroaryl (e.g., biphenyl or pyridylphenyl) or C 3-8 cycloalkyl;
2.3 a Compound of Formula I-A, I-B, II-A or II-B, or any of 1.1-1.6, 1.14-1.67, 1.74-1.84, wherein L is a single bond, 'CH 2 —, —N(H)—, —S—, —S(O)— or —S(O 2 )—; 2.4 a formula 2.3, wherein R 6 is
H, C 1-4 alkyl (e.g., methyl, ethyl, n-propyl, isobutyl), C 3-7 cycloalkyl (e.g., cyclopentyl or cyclohexyl), heteroC 3-7 cycloalkyl (e.g., pyrrolidinyl, piperidinyl, morpholinyl), aryl (e.g., phenyl), heteroaryl (e.g., pyrid-4-yl), arylC 1-4 alkyl (e.g., benzyl), wherein the aryl and heteroaryl are optionally substituted with one or more C 1-4 alkyl (e.g., methyl), halogen (e.g., chloro or fluoro), haloC 1-4 alkyl (e.g., trifluoromethyl), hydroxy, C 1-4 carboxy, or an additional aryl, heteroaryl (e.g., biphenyl or pyridylphenyl) or C 3-8 cycloalkyl;
2.5 a Compound of Formula I-A, I-B, II-A or II-B, or any of 2.1[0010]-2.4, wherein R 5 is attached to the nitrogen on the pyrrolo portion of Formula I-A, I-B, II-A or II-B and is a moiety of Formula A
[0000]
wherein X, Y and Z are, independently, N or C, and R 8 , R 9 , R 11 and R 12 are independently H or halogen (e.g., Cl or F), and R 10 is
C 3-7 cycloalkyl, heteroC 3-7 cycloalkyl (e.g., pyrrolidinyl or piperidinyl), aryl (e.g., phenyl), or heteroaryl (e.g., pyridyl (for example pyrid-2-yl or pyrid-4-yl), or thiadiazolyl (e.g., 1,2,3-thiadiazol-4-yl)), diazolyl (e.g., imidazol-1-yl), triazolyl (e.g., 1,2,4-triazol-1-yl), tetrazolyl, wherein the aryl, heteroaryl, cycloalkyl or heterocycloalkyl is independently, optionally substituted with one or more C 1-4 alkyl (e.g., methyl), halogen (e.g., chloro or fluoro), haloC 1-4 alkyl (e.g., trifluoromethyl), hydroxy, C 1-4 carboxy, —SH or an additional aryl or heteroaryl (e.g., biphenyl or pyridylphenyl), provided that when X, Y, or Z is nitrogen, R 8 , R 9 , or R 10 , respectively, is not present;
2.6 Formula I-A, I-B, II-A or II-B or any of 2.1-2.5, wherein n=0;
2.7 Formula I-A, I-B, II-A or II-B or any of 2.1-2.5, wherein n=1;
2.8 Any of the preceding formulae wherein L is —N(H)—, —S—, —S(O)— or —S(O 2 )-and R 6 is:
H, C 1-4 alkyl (e.g., methyl, ethyl, n-propyl, isobutyl), C 3-7 cycloalkyl (e.g., cyclopentyl or cyclohexyl), heteroC 3-7 cycloalkyl (e.g., pyrrolidinyl, piperidinyl, morpholinyl), aryl (e.g., phenyl), heteroaryl (e.g., pyrid-4-yl), arylC 1-4 alkyl (e.g., benzyl),
wherein the aryl and heteroaryl are optionally substituted with one or more C 1-4 alkyl (e.g., methyl), halogen (e.g., chloro or fluoro), haloC 1-4 alkyl (e.g., trifluoromethyl), hydroxy, C 1-4 carboxy, or an additional aryl, heteroaryl (e.g., biphenyl or pyridylphenyl) or C 3-8 cycloalkyl;
2.9 a Compound of Formula I-A, I-B, II-A or II-B, or any of the preceding formulae, wherein the remaining substituents are as defined in any of formula 1.1-1.84;
2.10 any of the preceding formulae, wherein the compound is selected from any of the following:
[0000]
2.11 any of the preceding formulae, wherein the compound is selected from any of the following
[0000]
2.12 any of the preceding formulae, wherein the compound is selected from any of the following:
[0000]
2.13 any of the preceding formulae, wherein the compounds inhibit phosphodiesterase-mediated (e.g., PDE1-mediated, especially PDE1A-and/or PDE1B-mediated) hydrolysis of cGMP, e.g., with an IC 50 of less than 10 μM, preferably less than 1 μM, still preferably less than 750 nM, more preferably less than 500 nM, more preferably less than 50 nM especially less than 10 nM in an immobilized-metal affinity particle reagent PDE assay, for example, as described in Example 16,
in free or salt form.
[0287] In one embodiment, the Compound of the Invention is a Compound of Formula I-A, I-B, II-A or II-B, wherein:
(i) Q is C(═O), C(═S), C(═N(R 20 )) or CH 2 ; (ii) L is a single bond, —CH 2 —, —N(H)—, —S—, —S(O)— or —S(O 2 )—; (iii) R 1 is H or C 1-4 alkyl (e.g., methyl); (iv) R 4 is H or C 1-6 alkyl (e.g., methyl or isopropyl) and R 2 and R 3 are, independently,
H C 1-6 alkyl (e.g., methyl, isopropyl) optionally substituted with halo or hydroxy (e.g., R 2 and R 3 are both methyl, or R 2 is H and R 3 is methyl, ethyl, isopropyl or hydroxyethyl), aryl, heteroaryl, (optionally hetero)arylalkoxy, (optionally hetero)arylC 1-6 alkyl, or R 2 and R 3 together form a 3-6-membered ring;
or R 2 is H and R 3 and R 4 together form a di-, tri- or tetramethylene bridge (pref. wherein the R 3 and R 4 together have the cis configuration, e.g., where the carbons carrying R 3 and R 4 have the R and S configurations, respectively); (v) R 5 is
a) -D-E-F, wherein:
D is C 1-4 alkylene (e.g., methylene, ethylene or prop-2-yn-1-ylene); E is a single bond, C 2-4 alkynylene (e.g., —C≡C—), arylene (e.g., phenylene) or heteroarylene (e.g., pyridylene); F is
H, aryl (e.g., phenyl), heteroaryl (e.g., pyridyl, diazolyl, triazolyl, for example, pyrid-2-yl, imidazol-1-yl, 1,2,4-triazol-1-yl), halo (e.g., F, Br, Cl), haloC 1-4 alkyl (e.g., trifluoromethyl), —C(O)—R 15 , 'N(R 16 )(R 17 ), or C 3-7 cycloalkyl optionally containing at least one atom selected from a group consisting of N or O (e.g., cyclopentyl, cyclohexyl, pyrrolidinyl (e.g., pyrrolidin-3-yl), tetrahydro-2H-pyran-4-yl, or morpholinyl);
wherein D, E and F are independently and optionally substituted with one or more halo (e.g., F, Cl or Br), C 1-4 alkyl (e.g., methyl), haloC 1-4 alkyl (e.g., trifluoromethyl), C 1-4 alkoxy (e.g., methoxy), hydroxy, C 1-4 carboxy, or an additional aryl or heteroaryl (e.g., biphenyl or pyridylphenyl), for example, F is heteroaryl, e.g., pyridyl substituted with one or more halo (e.g., 6-fluoropyrid-2-yl, 5-fluoropyrid-2-yl, 6-fluoropyrid-2-yl, 3-fluoropyrid-2-yl, 4-fluoropyrid-2-yl, 4,6-dichloropyrid-2-yl), haloC 1-4 alkyl (e.g., 5-trifluoromethylpyrid-2-yl) or C 1-4 alkyl (e.g., 5-methylpyrid-2-yl), or F is aryl, e.g., phenyl, substituted with one or more halo (e.g., 4-fluorophenyl) or F is a C 3-7 heterocycloalkyl (e.g., pyrrolidinyl) optionally substituted with a C 1-6 alkyl (e.g., 1-methylpyrrolidin-3-yl); or
b) a substituted heteroarylalkyl, e.g., substituted with haloC 1-4 alkyl; c) attached to the nitrogen on the pyrrolo portion of Formula I-A, I-B, II-A or II-B and is a moiety of Formula A
[0000]
wherein X, Y and Z are, independently, N or C, and R 8 , R 9 , R 11 and R 12 are independently H or halogen (e.g., Cl or F), and R 10 is
halogen, C 1-4 alkyl, haloC 1-4 alkyl (e.g., triflouromethyl) C 1-4 alkoxy (e.g. methoxy), C 3-7 cycloalkyl, heteroC 3-7 cycloalkyl (e.g., pyrrolidinyl or piperidinyl), hetero C 1-4 haloalkyl (e.g., trifluoromethyl), aryl (e.g., phenyl), heteroaryl (e.g., pyridyl (for example pyrid-2-yl or pyrid-4-yl), or thiadiazolyl (e.g., 1,2,3-thiadiazol-4-yl)), diazolyl (e.g., imidazol-1-yl), triazolyl (e.g., 1,2,4-triazol-1-yl), tetrazolyl, arylcarbonyl (e.g., benzoyl), alkylsulfonyl (e.g., methylsulfonyl), heteroarylcarbonyl, or alkoxycarbonyl;
wherein the aryl, heteroaryl, cycloalkyl or heterocycloalkyl is independently, optionally substituted with one or more C 1-4 alkyl (e.g., methyl), halogen (e.g., chloro or fluoro), haloC 1-4 alkyl (e.g., trifluoromethyl), hydroxy, C 1-4 carboxy, —SH or an additional aryl or heteroaryl (e.g., biphenyl or pyridylphenyl),
provided that when X, Y, or Z is nitrogen, R 8 , R 9 , or R 10 , respectively, is not present;
(vi) R 6 is
H, C 1-4 alkyl (e.g., methyl, ethyl, n-propyl, isobutyl), C 3-7 cycloalkyl (e.g., cyclopentyl or cyclohexyl), heteroC 3-7 cycloalkyl (e.g., pyrrolidinyl, piperidinyl, morpholinyl), aryl (e.g., phenyl), heteroaryl (e.g., pyrid-4-yl), arylC 1-4 alkyl (e.g., benzyl), wherein the aryl and heteroaryl are optionally substituted with one or more C 1-4 alkyl (e.g., methyl), halogen (e.g., chloro or fluoro), haloC 1-4 alkyl (e.g., trifluoromethyl), hydroxy, C 1-4 carboxy, or an additional aryl, heteroaryl (e.g., biphenyl or pyridylphenyl) or C 3-8 cycloalkyl; when L is a single bond, —CH 2 —, —N(H)—, —S—, —S(O)— or S(O 2 )—,
or
R 6 is
H, arylamino (e.g., phenylamino), heteroarylamino, N,N-diC 1-4 alkylamino, N,N-diarylamino, N-aryl-N-(arylC 1-4 alkyl)amino (e.g., N-phenyl-N-(1,1′-biphen-4-ylmethyl)amino), or —N(R 18 )(R 19 ), wherein the aryl and heteroaryl are optionally substituted with one or more C 1-4 alkyl (e.g., methyl), halogen (e.g., chloro or fluoro), haloC 1-4 alkyl (e.g., trifluoromethyl), hydroxy, C 1-4 carboxy, or an additional aryl, heteroaryl (e.g., biphenyl or pyridylphenyl) or C 3-8 cycloalkyl;
when L is a single bond or —CH 2 —;
(vii) R 7 is H, C 1-6 alkyl (e.g., methyl or ethyl), halogen (e.g., Cl), —N(R 18 )(R 19 ), hydroxy or C 1-6 alkoxy;
(viii) n=0 or 1;
(ix) when n=1, A is —C(R 13 R 14 )—, wherein R 13 and R 14 , are, independently, H or C 1-4 alkyl, aryl, heteroaryl, (optionally hetero)arylC 1-4 alkoxy, (optionally hetero)arylC 1-4 alkyl or R 14 can form a bridge with R 2 or R 4 ;
(x) R 15 is —OH or —OC 1-4 alkyl (e.g., —OCH 3 );
(xi) R 16 and R 17 are independently H or C 1-4 alkyl;
(xii) R 18 and R 19 are independently H, C 1-4 alky (e.g., methyl, ethyl, n-propyl, isobutyl), C 3-8 cycloalky (e.g., cyclohexyl or cyclopenyl), heteroC 3-8 cycloalky (e.g., pyrrolidinyl, piperidinyl, morpholinyl), aryl (e.g., phenyl) or heteroaryl, wherein said aryl and heteroaryl are optionally substituted with one or more halo (e.g., fluorophenyl, e.g., 4-fluorophenyl), hydroxy (e.g., hydroxyphenyl, e.g., 4-hydroxyphenyl or 2-hydroxyphenyl) C 1-4 alkyl (e.g., methyl), haloC 1-4 alkyl (e.g., trifluoromethyl), C 1-4 carboxy, or an additional aryl, heteroaryl (e.g., biphenyl or pyridylphenyl) or C 3-8 cycloalkyl;
(xiii) R 20 is H, C 1-4 alkyl or C 3-7 cycloalkyl;
in free or salt form.
[0362] In still another embodiment, the Compound of the Invention is a Compound of Formula I-A, I-B, II-A or II-B, wherein:
Q is C(═O), C(═S), C(═N(R 20 )) or CH 2 ; (ii) L is a single bond, —CH 2 —, —N(H)—, —S—, —S(O)— or —S(O 2 )—; (iii) R 1 is H or C 1-4 alkyl (e.g., methyl); (iv) R 4 is H or C 1-6 alkyl (e.g., methyl or isopropyl) and R 2 and R 3 are, independently,
H C 1-6 alkyl (e.g., methyl, isopropyl) optionally substituted with halo or hydroxy (e.g., R 2 and R 3 are both methyl, or R 2 is H and R 3 is methyl, ethyl, isopropyl or hydroxyethyl), aryl, heteroaryl, (optionally hetero)arylalkoxy, (optionally hetero)arylC 1-6 alkyl, or R 2 and R 3 together form a 3- to 6-membered ring;
or R 2 is H and R 3 and R 4 together form a di-, tri- or tetramethylene bridge (pref. wherein the R 3 and R 4 together have the cis configuration, e.g., where the carbons carrying R 3 and R 4 have the R and S configurations, respectively); (v) R 5 is attached to the nitrogen on the pyrrolo portion of Formula I-A, I-B, II-A or II-B and is a moiety of Formula A
[0000]
wherein X, Y and Z are, independently, N or C, and R 8 , R 9 , R 11 , and R 12 are independently H or halogen (e.g., Cl or F), and R 10 is
halogen, C 1-4 alkyl, haloC 1-4 alkyl (e.g., triflouromethyl) C 1-4 alkoxy (e.g. methoxy), C 3-7 cycloalkyl, heteroC 3-7 cycloalkyl (e.g., pyrrolidinyl or piperidinyl), C 1-4 haloalkyl (e.g., trifluoromethyl), aryl (e.g., phenyl), heteroaryl (e.g., pyridyl (for example pyrid-2-yl or pyrid-4-yl), or thiadiazolyl (e.g., 1,2,3-thiadiazol-4-yl)), diazolyl (e.g., imidazol-1-yl), triazolyl (e.g., 1,2,4-triazol-1-yl), tetrazolyl, arylcarbonyl (e.g., benzoyl), alkylsulfonyl (e.g., methylsulfonyl), heteroarylcarbonyl, or alkoxycarbonyl;
wherein the aryl, heteroaryl, cycloalkyl or heterocycloalkyl is independently, optionally substituted with one or more C 1-4 alkyl (e.g., methyl), halogen (e.g., chloro or fluoro), haloC 1-4 alkyl (e.g., trifluoromethyl), hydroxy, C 1-4 carboxy, —SH or an additional aryl or heteroaryl (e.g., biphenyl or pyridylphenyl),
provided that when X, Y, or Z is nitrogen, R 8 , R 9 , or R 10 , respectively, is not present;
(vi) R 6 is
H, C 1-4 alkyl (e.g., methyl, ethyl, n-propyl, isobutyl),
C 3-7 cycloalkyl (e.g., cyclopentyl or cyclohexyl),
heteroC 3-7 cycloalkyl (e.g., pyrrolidinyl, piperidinyl, morpholinyl), aryl (e.g., phenyl), heteroaryl (e.g., pyrid-4-yl), arylC 1-4 alkyl (e.g., benzyl), wherein the aryl and heteroaryl are optionally substituted with one or more C 1-4 alkyl (e.g., methyl), halogen (e.g., chloro or fluoro), haloC 1-4 alkyl (e.g., trifluoromethyl), hydroxy, C 1-4 carboxy, or an additional aryl, heteroaryl (e.g., biphenyl or pyridylphenyl) or C 3-8 cycloalkyl; when L is a single bond, —CH 2 —, —N(H)—, —S—, —S(O)— or S(O 2 )—,
or
R 6 is
H, arylamino (e.g., phenylamino), heteroarylamino, N,N-diC 1-4 alkylamino, N,N-diarylamino, N-aryl-N-(arylC 1-4 alkyl)amino (e.g., N-phenyl-N-(1,1′-biphen-4-ylmethyl)amino), or —N(R 18 )(R 19 ), wherein the aryl and heteroaryl are optionally substituted with one or more C 1-4 alkyl (e.g., methyl), halogen (e.g., chloro or fluoro), haloC 1-4 alkyl (e.g., trifluoromethyl), hydroxy, C 1-4 carboxy, or an additional aryl, heteroaryl (e.g., biphenyl or pyridylphenyl) or C 3-8 cycloalkyl;
when L is a single bond or —CH 2 —;
(vii) R 7 is H, C 1-6 alkyl (e.g., methyl or ethyl), halogen (e.g., Cl), —N(R 18 )(R 19 ), hydroxy or C 1-6 alkoxy;
(viii) n=0 or 1;
(ix) when n=1, A is —C(R 13 R 14 )—, wherein R 13 and R 14 , are, independently, H or C 1-4 alkyl, aryl, heteroaryl, (optionally hetero)arylC 1-4 alkoxy, (optionally hetero)arylC 1-4 alkyl or R 14 can form a bridge with R 2 or R 4 ;
(x) R 18 and R 19 are independently H, C 1-4 alky (e.g., methyl, ethyl, n-propyl, isobutyl), C 3-8 cycloalky (e.g., cyclohexyl or cyclopenyl), heteroC 3-8 cycloalky (e.g., pyrrolidinyl, piperidinyl, morpholinyl), aryl (e.g., phenyl) or heteroaryl, wherein said aryl and heteroaryl are optionally substituted with one or more halo (e.g., fluorophenyl, e.g., 4-fluorophenyl), hydroxy (e.g., hydroxyphenyl, e.g., 4-hydroxyphenyl or 2-hydroxyphenyl) C 1-4 alkyl (e.g., methyl), haloC 1-4 alkyl (e.g., trifluoromethyl), C 1-4 carboxy, or an additional aryl, heteroaryl (e.g., biphenyl or pyridylphenyl) or C 3-8 cycloalkyl;
(xi) R 20 is H, C 1-4 alkyl or C 3-7 cycloalkyl;
in free or salt form.
[0419] In yet another embodiment, the Compound of the Invention is a Compound of Formula I-A, I-B, II-A or II-B, wherein:
(i) Q is C(═O), C(═S), C(═N(R 20 )) or CH 2 ; (ii) L is —N(H)—, —S—, —S(O)— or —S(O 2 )—; (iii) R 1 is H or C 1-4 alkyl (e.g., methyl); (iv) R 4 is H or C 1-6 alkyl (e.g., methyl or isopropyl) and R 2 and R 3 are, independently,
H C 1-6 alkyl (e.g., methyl, isopropyl) optionally substituted with halo or hydroxy (e.g., R 2 and R 3 are both methyl, or R 2 is H and R 3 is methyl, ethyl, isopropyl or hydroxyethyl), aryl, heteroaryl, (optionally hetero)arylalkoxy, (optionally hetero)arylC 1-6 alkyl, or R 2 and R 3 together form a 3- to 6-membered ring;
or R 2 is H and R 3 and R 4 together form a di-, tri- or tetramethylene bridge (pref. wherein the R 3 and R 4 together have the cis configuration, e.g., where the carbons carrying R 3 and R 4 have the R and S configurations, respectively); (v) R 5 is attached to the nitrogen on the pyrrolo portion of Formula I-A, I-B, II-A or II-B and is a moiety of Formula A
[0000]
wherein X, Y and Z are, independently, N or C, and R 8 , R 9 , R 11 and R 12 are independently H or halogen (e.g., Cl or F), and R 10 is
C 1-4 alkoxy (e.g. methoxy), C 3-7 cycloalkyl, heteroC 3-7 cycloalkyl (e.g., pyrrolidinyl or piperidinyl), aryl (e.g., phenyl), heteroaryl (e.g., pyridyl (for example pyrid-2-yl or pyrid-4-yl), or thiadiazolyl (e.g., 1,2,3-thiadiazol-4-yl)), diazolyl (e.g., imidazol-1-yl), triazolyl (e.g., 1,2,4-triazol-1-yl), tetrazolyl,
wherein the aryl, heteroaryl, cycloalkyl or heterocycloalkyl is independently, optionally substituted with one or more C 1-4 alkyl (e.g., methyl), halogen (e.g., chloro or fluoro), haloC 1-4 alkyl (e.g., trifluoromethyl), hydroxy, C 1-4 carboxy, —SH or an additional aryl or heteroaryl (e.g., biphenyl or pyridylphenyl),
provided that when X, Y, or Z is nitrogen, R 8 , R 9 , or R 10 , respectively, is not present;
(vi) R 6 is
H, C 1-4 alkyl (e.g., methyl, ethyl, n-propyl, isobutyl), C 3-7 cycloalkyl (e.g., cyclopentyl or cyclohexyl), heteroC 3-7 cycloalkyl (e.g., pyrrolidinyl, piperidinyl, morpholinyl), aryl (e.g., phenyl), heteroaryl (e.g., pyrid-4-yl), arylC -4 alkyl (e.g., benzyl), wherein the aryl and heteroaryl are optionally substituted with one or more C 1-4 alkyl (e.g., methyl), halogen (e.g., chloro or fluoro), haloC 1-4 alkyl (e.g., trifluoromethyl), hydroxy, C 1-4 carboxy, or an additional aryl, heteroaryl (e.g., biphenyl or pyridylphenyl) or C 3-8 cycloalkyl;
(vii) R 7 is H, C 1-6 alkyl (e.g., methyl or ethyl), halogen (e.g., Cl), —N(R 18 )(R 19 ), hydroxy or C 1-6 alkoxy;
(viii) n=0 or 1;
(ix) when n=1, A is —C(R 13 R 14 )—, wherein R 13 and R 14 , are, independently, H or C 1-4 alkyl, aryl, heteroaryl, (optionally hetero)arylC 1-4 alkoxy, (optionally hetero)arylC 1-4 alkyl or R 14 can form a bridge with R 2 or R 4 ;
(x) R 18 and R 19 are independently H, C 1-4 alky (e.g., methyl, ethyl, n-propyl, isobutyl), C 3-8 cycloalky (e.g., cyclohexyl or cyclopenyl), heteroC 3-8 cycloalky (e.g., pyrrolidinyl, piperidinyl, morpholinyl), aryl (e.g., phenyl) or heteroaryl, wherein said aryl and heteroaryl are optionally substituted with one or more halo (e.g., fluorophenyl, e.g., 4-fluorophenyl), hydroxy (e.g., hydroxyphenyl, e.g., 4-hydroxyphenyl or 2-hydroxyphenyl) C 1-4 alkyl (e.g., methyl), haloC 1-4 alkyl (e.g., trifluoromethyl), C 1-4 carboxy, or an additional aryl, heteroaryl (e.g., biphenyl or pyridylphenyl) or C 3-8 cycloalkyl;
(xi) R 20 is H, C 1-4 alkyl or C 3-7 cycloalkyl;
in free or salt form.
[0456] If not otherwise specified or clear from context, the following terms herein have the following meanings:
(a) “Alkyl” as used herein is a saturated or unsaturated hydrocarbon moiety, preferably saturated, preferably having one to six carbon atoms, which may be linear or branched, and may be optionally mono-, di- or tri-substituted, e.g., with halogen (e.g., chloro or fluoro), hydroxy, or carboxy. (b) “Cycloalkyl” as used herein is a saturated or unsaturated nonaromatic hydrocarbon moiety, preferably saturated, preferably comprising three to nine carbon atoms, at least some of which form a nonaromatic mono- or bicyclic, or bridged cyclic structure, and which may be optionally substituted, e.g., with halogen (e.g., chloro or fluoro), hydroxy, or carboxy. Wherein the cycloalkyl optionally contains one or more atoms selected from N and O and/or S, said cycloalkyl may also be a heterocycloalkyl. (c) “Heterocycloalkyl” is, unless otherwise indicated, saturated or unsaturated nonaromatic hydrocarbon moiety, preferably saturated, preferably comprising three to nine carbon atoms, at least some of which form a nonaromatic mono- or bicyclic, or bridged cyclic structure, wherein at least one carbon atom is replaced with N, O or S, which heterocycloalkyl may be optionally substituted, e.g., with halogen (e.g., chloro or fluoro), hydroxy, or carboxy. (d) “Aryl” as used herein is a mono or bicyclic aromatic hydrocarbon, preferably phenyl, optionally substituted, e.g., with alkyl (e.g., methyl), halogen (e.g., chloro or fluoro), haloalkyl (e.g., trifluoromethyl), hydroxy, carboxy, or an additional aryl or heteroaryl (e.g., biphenyl or pyridylphenyl). (e) “Heteroaryl” as used herein is an aromatic moiety wherein one or more of the atoms making up the aromatic ring is sulfur or nitrogen rather than carbon, e.g., pyridyl or thiadiazolyl, which may be optionally substituted, e.g., with alkyl, halogen, haloalkyl, hydroxy or carboxy. (f) For ease of reference, the atoms on the pyrazolo-pyrimidine core of the Compounds of the Invention are numbered in accordance with the numbering depicted in Formula I, unless otherwise noted. (g) Wherein E is phenylene, the numbering is as follows:
[0000]
(h) It is intended that wherein the substituents end in “ene”, for example, alkylene, phenylene or arylalkylene, said substitutents are intended to bridge or be connected to two other substituents. Therefore, methylene is intended to be —CH 2 — and phenylene intended to be —C 6 H 4 — and arylalkylene is intended to be —C 6 H 4 —CH 2 — or 'CH 2 —C 6 H 4 —.
(i) The Compounds of the Invention are intended to be numbered as follows:
[0000]
[0466] Compounds of the Invention, e.g., substituted 4,5,7,8-tetrahydro-2H-imidazo[1,2-a]pyrrolo[3,4-e]pyrimidine or 4,5,7,8,9-pentahydro-2H-pyrimido[1,2-a]pyrrolo[3,4-e]pyrimidine, e.g., Compounds of Formula I (Formula I-A and I-B), e.g., any of formulae 1.1-1.84, or a Compound of Formula II (e.g., II-A or II-B), any of formulae 2.1-2.13 may exist in free or salt form, e.g., as acid addition salts. In this specification unless otherwise indicated, language such as “Compounds of the Invention” is to be understood as embracing the compounds in any form, for example free or acid addition salt form, or where the compounds contain acidic substituents, in base addition salt form. The Compounds of the Invention are intended for use as pharmaceuticals, therefore pharmaceutically acceptable salts are preferred. Salts which are unsuitable for pharmaceutical uses may be useful, for example, for the isolation or purification of free Compounds of the Invention or their pharmaceutically acceptable salts, are therefore also included.
[0467] Compounds of the Invention may in some cases also exist in prodrug form. A prodrug form is compound which converts in the body to a Compound of the Invention. For example when the Compounds of the Invention contain hydroxy or carboxy substituents, these substituents may form physiologically hydrolysable and acceptable esters. As used herein, “physiologically hydrolysable and acceptable ester” means esters of Compounds of the Invention which are hydrolysable under physiological conditions to yield acids (in the case of Compounds of the Invention which have hydroxy substituents) or alcohols (in the case of Compounds of the Invention which have carboxy substituents) which are themselves physiologically tolerable at doses to be administered. Therefore, wherein the Compound of the Invention contains a hydroxy group, for example, Compound-OH, the acyl ester prodrug of such compound, i.e., Compound-O—C(O)—C 1-4 alkyl, can hydrolyze in the body to form physiologically hydrolysable alcohol (Compound-OH) on the one hand and acid on the other (e.g., HOC(O)—C 1-4 alkyl). Alternatively, wherein the Compound of the Invention contains a carboxylic acid, for example, Compound-C(O)OH, the acid ester prodrug of such compound, Compound-C(O)O—C 1-4 alkyl can hydrolyze to form Compound-C(O)OH and HO—C 1-4 alkyl. As will be appreciated the term thus embraces conventional pharmaceutical prodrug forms.
[0468] The invention also provides methods of making the Compounds of the Invention and methods of using the Compounds of the Invention for treatment of diseases and disorders as set forth below (especially treatment of diseases characterized by reduced dopamine D1 receptor signaling activity, such as Parkinson's disease, Tourette's Syndrome, Autism, fragile X syndrome, ADHD, restless leg syndrome, depression, cognitive impairment of schizophrenia, narcolepsy and diseases that may be alleviated by the enhancement of progesterone-signaling such as female sexual dysfunction, or a disease or disorder such as psychosis or glaucoma). This list is not intended to be exhaustive and may include other diseases and disorders as set forth below.
[0469] In another embodiment, the invention further provides a pharmaceutical composition comprising a Compound of the Invention, in free, pharmaceutically acceptable salt or prodrug form, in admixture with a pharmaceutically acceptable carrier.
DETAILED DESCRIPTION OF THE INVENTION
Methods of Making Compounds of the Invention
[0470] The compounds of the Invention and their pharmaceutically acceptable salts may be made using the methods as described and exemplified herein and by methods similar thereto and by methods known in the chemical art. Such methods include, but not limited to, those described below. If not commercially available, starting materials for these processes may be made by procedures, which are selected from the chemical art using techniques which are similar or analogous to the synthesis of known compounds. Various starting materials and/or Compounds of the Invention may be prepared using methods described in WO 2006/133261 and PCT/US2007/070551. All references cited herein are hereby incorporated by reference in their entirety.
[0471] The Compounds of the Invention include their enantiomers, diastereoisomers and racemates, as well as their polymorphs, hydrates, solvates and complexes. Some individual compounds within the scope of this invention may contain double bonds. Representations of double bonds in this invention are meant to include both the E and the Z isomer of the double bond. In addition, some compounds within the scope of this invention may contain one or more asymmetric centers. This invention includes the use of any of the optically pure stereoisomers as well as any combination of stereoisomers.
[0472] It is also intended that the Compounds of the Invention encompass their stable and unstable isotopes. Stable isotopes are nonradioactive isotopes which contain one additional neutron compared to the abundant nuclides of the same species (i.e., element). It is expected that the activity of compounds comprising such isotopes would be retained, and such compound would also have utility for measuring pharmacokinetics of the non-isotopic analogs. For example, the hydrogen atom at a certain position on the Compounds of the Invention may be replaced with deuterium (a stable isotope which is non-raradioactive). Examples of known stable isotopes include, but not limited to, deuterium, 13 C, 15 N, 18 O. Alternatively, unstable isotopes, which are radioactive isotopes which contain additional neutrons compared to the abundant nuclides of the same species (i.e., element), e.g., 123 I, 131 I, 125 I, 11 C, 18 F, may replace the corresponding abundant species of I, C and F. Another example of useful isotope of the compound of the invention is the 11 C isotope. These radio isotopes are useful for radio-imaging and/or pharmacokinetic studies of the compounds of the invention.
[0473] Melting points are uncorrected and (dec) indicates decomposition. Temperature are given in degrees Celsius (° C.); unless otherwise stated, operations are carried out at room or ambient temperature, that is, at a temperature in the range of 18-25° C. Chromatography means flash chromatography on silica gel; thin layer chromatography (TLC) is carried out on silica gel plates. NMR data is in the delta values of major diagnostic protons, given in parts per million (ppm) relative to tetramethylsilane (TMS) as an internal standard. Conventional abbreviations for signal shape are used. Coupling constants (J) are given in Hz. For mass spectra (MS), the lowest mass major ion is reported for molecules where isotope splitting results in multiple mass spectral peaks Solvent mixture compositions are given as volume percentages or volume ratios. In cases where the NMR spectra are complex, only diagnostic signals are reported.
[0474] Terms and abbreviations:
[0475] BuLi=n-butyllithium
[0476] Bu t OH=tert-butyl alcohol,
[0477] CAN=ammonium cerium (IV) nitrate,
[0478] DIPEA=diisopropylethylamine,
[0479] DMF=N,N-dimethylforamide,
[0480] DMSO=dimethyl sulfoxide,
[0481] Et 2 O=diethyl ether,
[0482] EtOAc=ethyl acetate,
[0483] equiv.=equivalent(s),
[0484] h=hour(s),
[0485] HPLC=high performance liquid chromatography,
[0486] LDA=lithium diisopropylamide
[0487] MeOH=methanol,
[0488] NBS=N-bromosuccinimide
[0489] NCS=N-chlorosuccinimide
[0490] NaHCO 3 =sodium bicarbonate,
[0491] NH 4 OH=ammonium hydroxide,
[0492] Pd 2 (dba) 3 =tris[dibenzylideneacetone]dipalladium(O)
[0493] PMB=p-methoxybenzyl,
[0494] POCl 3 =phosphorous oxychloride,
[0495] SOCl 2 =thionyl chloride,
[0496] TFA=trifluoroacetic acid,
[0497] THF=tetrahedrofuran.
[0498] The synthetic methods in this invention are illustrated below. The significances for the R groups are as set forth above for formula I unless otherwise indicated.
[0499] In an aspect of the invention, Compounds (I)-A and (I)-B may be formed by reacting a compound of 1-A and 1-B respectively with for example a R 5 —X in a solvent such as DMF and a base such as K 2 CO 3 at room temperature or with heating:
[0000]
[0000] wherein all the substitutents are as defined previously in Formula I-A, I-B, II-A or II-B above; X is a leaving group such as a halogen, mesylate, or tosylate.
[0500] Alternatively, compounds I-A, I-B, II-A and II-B, wherein L is —N(H)—, —S—, —S(O)— or S(O) 2 — may be synthesized by reacting a compound of 1-C and 1-D respectively with for example a R 6 -L-H in a solvent such as DMF or in neat condition with heating:
[0000]
[0000] wherein all the other substituents are as defined previously in Formula I-A, I-B, II-A or II-B above; X is a leaving group such as a halogen group.
[0501] Compound 1-C, e.g., wherein Q is C(═O) and X is a chloro group, may be prepared by, e.g., reacting compound 1-E with a chlorinating reagent such as hexachloroethane in the presence of a strong base or lithium reagent such as LiHMDS. Compound 1-D, e.g., wherein Q is C(═O) and X is a chloro group, may be prepared by, e.g., reacting compound 1-F with a chlorinating reagent such NCS (N-chlorosuccinimide) in a solvent such as CCl 4 . Sometimes, when R 5 is H, a protective group such as a para-methoxybenzyl (PMB) group may be added prior to the reaction. Under this circumstance, compound 1-C or 1-D with the PMB at the pyrrolo nitrogen can be deprotected using a reagent such as TFA/TFMSA, and then reacts the resulting (deprotected pyrrolo compound) with R 5 X wherein X is a leaving group such as a halogen, mesylate or tosylate, under basic conditions to yield 1-C or 1-D analogs.
[0000]
[0502] Compounds (I)-E and (I)-F may be formed by reacting a compound of 1-G and 1-H respectively with for example a R 5 —X in a solvent such as DMF and a base such as K 2 CO 3 at room temperature or with heating:
[0000]
[0000] wherein all the substituents are as defined previously in Formula I-A, I-B, II-A or II-B; X is a leaving group such as a halogen group, mesylate or tosylate.
[0503] Intermediate 2, e.g., wherein Q is C(═O) may be prepared by, e.g., reacting Intermediate 3 with sodium hydride and para-toluenesulfonylmethyl isocyanide.
[0000]
[0504] Alternatively and preferably, Intermediate 2, e.g., wherein Q is C(═O) is prepared by, e.g., reacting Intermediate 3 with a strong base such as sodium hydride and a reagent such as TsCHR 7 NC in a solvent such as THF:
[0000]
[0505] Intermediate 3 may be prepared by, e.g., reacting Intermediate 4 with diethyl azodicarboxylate in the presence of triphenylphosphine.
[0000]
[0506] Alternatively and preferably, Intermediate 3 may be prepared by, e.g., reacting Intermediate 4 with a dehydrating reagent such as diethyl azodicarboxylate in the presence of phosphine ligand such as triphenylphosphine.
[0000]
[0507] Intermediate 4 may, in turn be made as similarly disclosed in WO 2006/133261, e.g., by reacting a compound of 5-A with an amino alcohol, e.g., (1R,2R)-(−)-2-hydroxycyclopentylamine hydrochloride, e.g., in the presence of, for example, DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene).
[0000]
[0000] wherein all the substituents are as defined previously; X is a leaving group such as a halogen or methylthio group.
[0508] Alternatively and preferably, Intermediate 4 is prepared, e.g., by reacting a compound of 5-A with an amino alcohol in the presence of a strong base, for example, DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene),
[0000]
[0000] wherein all the substituents are as defined previously; X is a leaving group such as a halogen or methylthio group.
[0509] Still alternatively, intermediate 4 may be made, e.g., by reacting a compound of 5-B with an amino alcohol in the presence of a strong base, for example, DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) and a coupling reagent such as BOP at toom temperature.
[0000]
[0510] Intermediate 6 wherein X is halo, e.g., Cl, can be prepared by reacting halogenating Compound 7, e.g., reacting Compound 7 with, e.g., N-chlorosuccinimide, N-bromosuccinimide, or I 2 in the presence of, e.g., carbontetrachloride in a solvent such as DMF.
[0000]
[0511] Compound 8 may be formed by reacting a compound of 9 with for example an amine such as aniline in the present of, e.g., TFA.
[0000]
[0512] The thione compounds of the invention, e.g., Compounds of Formula I-A or I-B or II-A or II-B wherein Q is C(═S) may then be prepared by reacting the Compounds of the Invention wherein Q is C(═O) with P 4 S 10 in a microwave vial in the presence of a base, e.g., pyridine, and heating the mixture to an elevated temperature, e.g., in a microwave, e.g., to about 150° C. The imine compounds of the Invention, e.g., Compounds of Formula I-A or I-B or II-A or II-B wherein Q is C(═N(R 20 )) may in turn be converted from the thione derivative (i.e., Compounds of Formula I-A or I-B or II-A or II-B wherein with Q is C(═S) by reacting the thione derivative with NH 2 (R 20 ) in the presence of HgCl 2 , e.g., in a solvent such as THF, and heating the reaction mixture to an elevated temperature, e.g., in a microwave, e.g., to about 110° C.
[0513] The Compounds of the Invention, e.g., Compounds of Formula I-A or I-B or II-A or II-B wherein Q is C(R 14 )(R 15 ) may also be prepared by reacting the ketone derivative, e.g., Formula I-A or I-B or II-A or II-B wherein Q is C(═O), with a reducing agent, e.g., diisobutylaluminum hydride (DIBAL-H), lithium aluminum hydride, sodium borohydride, preferably, DIBAL-H.
[0514] Wherein L of the compounds of the invention is —S— (thiol) or Compound (I)-C, these compounds may be prepared by reacting Compound (IVb), e.g., with phenyl disulfide and lithium bis(trimethylsilyl)azanide (LiHMDS).
[0000]
[0515] wherein R 6 is phenyl.
[0516] Alternatively and preferably, wherein L of the compounds of the invention is —S— (thiol) or Compound (I)-C, these compounds may be prepared by reacting Compound 1-G, with a disulfide in the presence of a base such as lithium bis(trimethylsilyl)azanide (LiHMDS).
[0000]
[0517] The sulfinyl derivatives of the Invention, e.g., Formula I wherein L is SO or SO 2 may be prepared by the oxidation of (I)-C using a oxidizing reagent such as oxone or a peroxide in a solvent such as acetonitrile and methanol.
[0518] The invention thus provides methods of making Compounds of Formula I-A, I-B or II-A or II-B, for example, comprising
(i) reacting Intermediate 1-A or 1-B with a compound of formula R 5 —X wherein X is a leaving group, e.g., halogen, mesylate, or tosylate, R 5 is as defined above in Formula I, e.g., under basic conditions, for example:
[0000]
[0520] Methods of Using Compounds of the Invention
[0521] The Compounds of the Invention, any of the compounds disclosed herein e.g., any of Compounds of Formula I-A, I-B, e.g., any of 1.1-1.84, or Formula II-A or II-B, e.g., any of 2.1-2.13, in free or salt form are useful in the treatment of diseases characterized by disruption of or damage to cAMP and cGMP mediated pathways, e.g., as a result of increased expression of PDE1 or decreased expression of cAMP and cGMP due to inhibition or reduced levels of inducers of cyclic nucleotide synthesis, such as dopamine and nitric oxide (NO). By preventing the degradation of cAMP and cGMP by PDE1B, thereby increasing intracellular levels of cAMP and cGMP, the Compounds of the Invention potentiate the activity of cyclic nucleotide synthesis inducers.
[0522] The invention provides methods of treatment of any one or more of the following conditions:
(i) Neurodegenerative diseases, including Parkinson's disease, restless leg, tremors, dyskinesias, Huntington's disease, Alzheimer's disease, and drug-induced movement disorders; (ii) Mental disorders, including depression, attention deficit disorder, attention deficit hyperactivity disorder, bipolar illness, anxiety, sleep disorders, e.g., narcolepsy, cognitive impairment, dementia, Tourette's syndrome, autism, fragile X syndrome, psychostimulant withdrawal, and drug addiction; (iii) Circulatory and cardiovascular disorders, including cerebrovascular disease, stroke, congestive heart disease, hypertension, pulmonary hypertension, and sexual dysfunction; (iv) Respiratory and inflammatory disorders, including asthma, chronic obstructive pulmonary disease, and allergic rhinitis, as well as autoimmune and inflammatory diseases; (v) Any disease or condition characterized by low levels of cAMP and/or cGMP (or inhibition of cAMP and/or cGMP signaling pathways) in cells expressing PDE1; and/or (vi) Any disease or condition characterized by reduced dopamine D1 receptor signaling activity,
comprising administering an effective amount of a Compound of the Invention, e.g., a compound according to any of Formula I or 1.1-1.84, in free, pharmaceutically acceptable salt or prodrug form, to a human or animal patient in need thereof In another aspect, the invention provides a method of treatment of the conditions disclosed above comprising administering a therapeutically effective amount of a Compound of Formula II-A or II-B, e.g., any of 2.1-2.13, in free or salt in free or pharmaceutically acceptable salt form, or a composition comprising the same, to a human or animal patient in need thereof.
[0529] In an especially preferred embodiment, the invention provides methods of treatment or prophylaxis for narcolepsy. In this embodiment, PDE 1 Inhibitors may be used as a sole therapeutic agent, but may also be used in combination or for co-administration with other active agents. Thus, the invention further comprises a method of treating narcolepsy comprising administering simultaneously, sequentially, or contemporaneously administering therapeutically effective amounts of
(i) a PDE 1 Inhibitor, e.g., a compound according to any of Formula I or any of 1.1-0, and (ii) a compound to promote wakefulness or regulate sleep, e.g., selected from (a) central nervous system stimulants-amphetamines and amphetamine like compounds, e.g., methylphenidate, dextroamphetamine, methamphetamine, and pemoline; (b) modafinil, (c) antidepressants, e.g., tricyclics (including imipramine, desipramine, clomipramine, and protriptyline) and selective serotonin reuptake inhibitors (including fluoxetine and sertraline); and/or (d) gamma hydroxybutyrate (GHB).
in free or pharmaceutically acceptable salt form, to a human or animal patient in need thereof. In still another embodiment, the methods of treatment or prophylaxis for narcolepsy as hereinbefore described, comprises administering a therapeutically effective amount of a Compound of Formula II-A or II-B, or any of Formula 2.1-2.13, in free or pharmaceutically acceptable salt form, as a sole therapeutic agent or use in combination for co-administered with another active agent.
[0532] In another embodiment, the invention further provides methods of treatment or prophylaxis of a condition which may be alleviated by the enhancement of the progesterone signaling comprising administering an effective amount of a Compound of the Invention, e.g., a compound according to any of Formula I, or any of 1.1-1.84, in free, pharmaceutically acceptable salt or prodrug form, to a human or animal patient in need thereof. The invention also provides methods of treatment as disclosed here, comprising administering a therapeutically effective amount of a Compound of Formula II-A or II-B, e.g., any of formulae 2.1-2.13, in free or pharmaceutically acceptable salt form. In still another embodiment, the invention further provides methods of treatment or prophylaxis of a condition which may be alleviated by the enhancement of the progesterone signaling comprising administering an effective amount of a Compound of the Invention, e.g., a compound according to any of Formula I, or any of 1.1-1.84, in free, pharmaceutically acceptable salt or prodrug form, to a human or animal patient in need thereof. In another aspect, the invention provides methods of treatment as disclosed herein, comprising administering an effective amount of a Compound of the Invention, e.g., a compound according to any of Formula II-A or II-B, e.g., e.g., any of formulae 2.1-2.13, in free or pharmaceutically acceptable salt form. Disease or condition that may be ameliorated by enhancement of progesterone signaling include, but are not limited to, female sexual dysfunction, secondary amenorrhea (e.g., exercise amenorrhoea, anovulation, menopause, menopausal symptoms, hypothyroidism), pre-menstrual syndrome, premature labor, infertility, for example infertility due to repeated miscarriage, irregular menstrual cycles, abnormal uterine bleeding, osteoporosis, autoimmmune disease, multiple sclerosis, prostate enlargement, prostate cancer, and hypothyroidism. For example, by enhancing progesterone signaling, the PDE 1 inhibitors may be used to encourage egg implantation through effects on the lining of uterus, and to help maintain pregnancy in women who are prone to miscarriage due to immune response to pregnancy or low progesterone function. The novel PDE 1 inhibitors, e.g., as described herein, may also be useful to enhance the effectiveness of hormone replacement therapy, e.g., administered in combination with estrogen/estradiol/estriol and/or progesterone/progestins in postmenopausal women, and estrogen-induced endometrial hyperplasia and carcinoma. The methods of the invention are also useful for animal breeding, for example to induce sexual receptivity and/or estrus in a nonhuman female mammal to be bred.
[0533] In this embodiment, PDE 1 Inhibitors may be used in the foregoing methods of treatment or prophylaxis as a sole therapeutic agent, but may also be used in combination or for co-administration with other active agents, for example in conjunction with hormone replacement therapy. Thus, the invention further comprises a method of treating disorders that may be ameliorated by enhancement of progesterone signaling comprising administering simultaneously, sequentially, or contemporaneously administering therapeutically effective amounts of
(i) a PDE 1 Inhibitor, e.g., a compound according to any of Formula I-A or I-B or any of 1.1-1.84, and (ii) a hormone, e.g., selected from estrogen and estrogen analogues (e.g., estradiol, estriol, estradiol esters) and progesterone and progesterone analogues (e.g., progestins)
in free or pharmaceutically acceptable salt form, to a human or animal patient in need thereof. In another embodiment, the invention provides the method described above wherein the PDE 1 inhibitor is a Compound of Formula II-A or II-B, e.g., any of formulae 2.1-2.13, in free or pharmaceutically acceptable salt form.
[0536] The invention also provides a method for enhancing or potentiating dopamine D1 intracellular signaling activity in a cell or tissue comprising contacting said cell or tissue with an amount of a Compound of the Invention, e.g., Formula I-A or I-B or any of 1.1-1.84, sufficient to inhibit PDE1B activity. The invention further provides a method for enhancing or potentiating dopamine D1 intracellular signaling activity in a cell or tissue comprising contacting said cell or tissue with an amount of a Compound of Formula II-A or II-B or any of 2.1-2.13, in free or salt form.
[0537] The invention also provides a method for treating a PDE1-related, especially PDE1B-related disorder, a dopamine D1 receptor intracellular signaling pathway disorder, or disorders that may be alleviated by the enhancement of the progesterone signaling pathway in a patient in need thereof comprising administering to the patient an effective amount of a Compound of the Invention, e.g., Formula I, e.g., Formula I-A or I-B or any of 1.1-1.84, that inhibits PDE1B, wherein PDE1B activity modulates phosphorylation of DARPP-32 and/or the GluR1 AMPA receptor. Similarly, the invention provides a method for treating a PDE1-related, especially PDE1B-related disorder, a dopamine D1 receptor intracellular signaling pathway disorder, or disorders that may be alleviated by the enhancement of the progesterone signaling pathway in a patient in need thereof comprising administering to the patient an effective amount of a Compound of Formula II, e.g., II-A or II-B or any of 2.1-2.13, in free or pharmaceutically acceptable salt form.
[0538] “The Compound of the Invention” referred to above includes a Compound of Formula I-A or I-B, e.g., any of 1.1-1.84, or a Compound of Formula II-A or II-B, e.g., any of 2.1-2.13, in free or pharmaceutically acceptable salt form.
[0539] In another aspect, the invention also provides a method for the treatment for glaucoma or elevated intraocular pressure comprising topical administration of a therapeutically effective amount of a phospodiesterase type I (PDE1) Inhibitor of the Invention, e.g., a Compound of Formula I-A or I-B, e.g., any of 1.1-1.84, or a Compound of Formula II-A or II-B, e.g., any of 2.1-2.13, in free or pharmaceutically acceptable salt form, in an opthalmically compatible carrier to the eye of a patient in need thereof. However, treatment may alternatively include a systemic therapy. Systemic therapy includes treatment that can directly reach the bloodstream, or oral methods of administration, for example.
[0540] The invention further provides a pharmaceutical composition for topical ophthalmic use comprising a PDE1 inhibitor; for example an ophthalmic solution, suspension, cream or ointment comprising a PDE1 Inhibitor of the Invention, e.g., a Compound of Formula I-A or I-B, e.g., any of 1.1-1.84, or a Compound of Formula II-A or II-B, e.g., any of 2.1-2.13, in free or ophthamalogically acceptable salt form, in combination or association with an ophthamologically acceptable diluent or carrier.
[0541] Optionally, the PDE1 inhibitor may be administered sequentially or simultaneously with a second drug useful for treatment of glaucoma or elevated intraocular pressure. Where two active agents are administered, the therapeutically effective amount of each agent may be below the amount needed for activity as monotherapy. Accordingly, a subthreshold amount (i.e., an amount below the level necessary for efficacy as monotherapy) may be considered therapeutically effective and also may also be referred alternatively as an effective amount. Indeed, an advantage of administering different agents with different mechanisms of action and different side effect profiles may be to reduce the dosage and side effects of either or both agents, as well as to enhance or potentiate their activity as monotherapy.
[0542] The invention thus provides the method of treatment of a condition selected from glaucoma and elevated intraocular pressure comprising administering to a patient in need thereof an effective amount, e.g., a subthreshold amount, of an agent known to lower intraocular pressure concomitantly, simultaneously or sequentially with an effective amount, e.g., a subthreshold amount, of a PDE1 Inhibitor of the Invention, e.g., a Compound of Formula I-A or I-B, e.g., any of 1.1-1.84, or a Compound of Formula II-A or II-B, e.g., any of 2.1-2.13, in free or pharmaceutically acceptable salt form, such that amount of the agent known to lower intraocular pressure and the amount of the PDE1 inhibitor in combination are effective to treat the condition.
[0543] In one embodiment, one or both of the agents are administered topically to the eye. Thus the invention provides a method of reducing the side effects of treatment of glaucoma or elevated intraocular pressure by administering a reduced dose of an agent known to lower intraocular pressure concomitantly, simultaneously or sequentially with an effective amount of a PDE1 inhibitor. However, methods other than topical administration, such as systemic therapeutic administration, may also be utilized.
[0544] The optional additional agent or agents for use in combination with a PDE1 inhibitor may, for example, be selected from the existing drugs comprise typically of instillation of a prostaglandin, pilocarpine, epinephrine, or topical beta-blocker treatment, e.g. with timolol, as well as systemically administered inhibitors of carbonic anhydrase, e.g. acetazolamide. Cholinesterase inhibitors such as physostigmine and echothiopate may also be employed and have an effect similar to that of pilocarpine. Drugs currently used to treat glaucoma thus include, e.g.,
1. Prostaglandin analogs such as latanoprost (Xalatan), bimatoprost (Lumigan) and travoprost (Travatan), which increase uveoscleral outflow of aqueous humor. Bimatoprost also increases trabecular outflow. 2. Topical beta-adrenergic receptor antagonists such as timolol, levobunolol (Betagan), and betaxolol, which decrease aqueous humor production by the ciliary body. 3. Alpha 2 -adrenergic agonists such as brimonidine (Alphagan), which work by a dual mechanism, decreasing aqueous production and increasing uveo-scleral outflow. 4. Less-selective sympathomimetics like epinephrine and dipivefrin (Propine) increase outflow of aqueous humor through trabecular meshwork and possibly through uveoscleral outflow pathway, probably by a beta 2 -agonist action. 5. Miotic agents (parasympathomimetics) like pilocarpine work by contraction of the ciliary muscle, tightening the trabecular meshwork and allowing increased outflow of the aqueous humour. 6. Carbonic anhydrase inhibitors like dorzolamide (Trusopt), brinzolamide (Azopt), acetazolamide (Diamox) lower secretion of aqueous humor by inhibiting carbonic anhydrase in the ciliary body. 7. Physostigmine is also used to treat glaucoma and delayed gastric emptying.
[0552] For example, the invention provides pharmaceutical compositions comprising a PDE1 Inhibitor of the Invention and an agent selected from (i) the prostanoids, unoprostone, latanoprost, travoprost, or bimatoprost; (ii) an alpha adrenergic agonist such as brimonidine, apraclonidine, or dipivefrin and (iii) a muscarinic agonist, such as pilocarpine. For example, the invention provides ophthalmic formulations comprising a PDE-1 Inhibitor of the Invention together with bimatoprost, abrimonidine, brimonidine, timolol, or combinations thereof, in free or ophthamalogically acceptable salt form, in combination or association with an ophthamologically acceptable diluent or carrier. In addition to selecting a combination, however, a person of ordinary skill in the art can select an appropriate selective receptor subtype agonist or antagonist. For example, for alpha adrenergic agonist, one can select an agonist selective for an alpha 1 adrenergic receptor, or an agonist selective for an alpha 2 adrenergic receptor such as brimonidine, for example. For a beta-adrenergic receptor antagonist, one can select an antagonist selective for either β 1 , or β 2 , or β 3 , depending on the appropriate therapeutic application. One can also select a muscarinic agonist selective for a particular receptor subtype such as M 1 -M 5 .
[0553] The PDE 1 inhibitor may be administered in the form of an ophthalmic composition, which includes an ophthalmic solution, cream or ointment. The ophthalmic composition may additionally include an intraocular-pressure lowering agent.
[0554] In yet another example, the PDE-1 Inhibitors disclosed may be combined with a subthreshold amount of an intraocular pressure-lowering agent which may be a bimatoprost ophthalmic solution, a brimonidine tartrate ophthalmic solution, or brimonidine tartrate/timolol maleate ophthalmic solution.
[0555] In addition to the above-mentioned methods, it has also been surprisingly discovered that PDE1 inhibitors are useful to treat psychosis, for example, any conditions characterized by psychotic symptoms such as hallucinations, paranoid or bizarre delusions, or disorganized speech and thinking, e.g., schizophrenia, schizoaffective disorder, schizophreniform disorder, psychotic disorder, delusional disorder, and mania, such as in acute manic episodes and bipolar disorder. Without intending to be bound by any theory, it is believed that typical and atypical antipsychotic drugs such as clozapine primarily have their antagonistic activity at the dopamine D2 receptor. PDE1 inhibitors, however, primarily act to enhance signaling at the dopamine D1 receptor. By enhancing D1 receptor signaling, PDE1 inhibitors can increase NMDA receptor function in various brain regions, for example in nucleus accumbens neurons and in the prefrontal cortex. This enhancement of function may be seen for example in NMDA receptors containing the NR2B subunit, and may occur e.g., via activation of the Src and protein kinase A family of kinases.
[0556] Therefore, the invention provides a new method for the treatment of psychosis, e.g., schizophrenia, schizoaffective disorder, schizophreniform disorder, psychotic disorder, delusional disorder, and mania, such as in acute manic episodes and bipolar disorder, comprising administering a therapeutically effective amount of a phosphodiesterase-1 (PDE1) Inhibitor of the Invention, e.g., a Compound of Formula I-A or I-B, e.g., any of 1.1-1.84, or a Compound of Formula II-A or II-B, e.g., any of 2.1-2.13, in free or pharmaceutically acceptable salt form, to a patient in need thereof.
[0557] PDE 1 Inhibitors may be used in the foregoing methods of treatment prophylaxis as a sole therapeutic agent, but may also be used in combination or for co-administration with other active agents. Thus, the invention further comprises a method of treating psychosis, e.g., schizophrenia, schizoaffective disorder, schizophreniform disorder, psychotic disorder, delusional disorder, or mania, comprising administering simultaneously, sequentially, or contemporaneously administering therapeutically effective amounts of:
(i) a PDE 1 Inhibitor of the invention, e.g., a a Compound of Formula I-A or I-B, e.g., any of 1.1-1.84, or a Compound of Formula II-A or II-B, e.g., any of 2.1-2.13, in free or pharmaceutically acceptable salt form; and (ii) an antipsychotic, e.g.,
Typical antipsychotics, e.g.,
Butyrophenones, e.g. Haloperidol (Haldol, Serenace), Droperidol (Droleptan); Phenothiazines, e.g., Chlorpromazine (Thorazine, Largactil), Fluphenazine (Prolixin), Perphenazine (Trilafon), Prochlorperazine (Compazine), Thioridazine (Mellaril, Melleril), Trifluoperazine (Stelazine), Meson Periciazine, Promazine, Triflupromazine (Vesprin), Levomepromazine (Nozinan), Promethazine (Phenergan), Pimozide (Orap); Thioxanthenes, e.g., Chlorprothixene, Flupenthixol (Depixol, Fluanxol), Thiothixene (Navane), Zuclopenthixol (Clopixol, Acuphase);
Atypical antipsychotics, e.g.,
Clozapine (Clozaril), Olanzapine (Zyprexa), Risperidone (Risperdal), Quetiapine (Seroquel), Ziprasidone (Geodon), Amisulpride (Solian), Paliperidone (Invega), Aripiprazole (Abilify), Bifeprunox; norelozapine,
in free or pharmaceutically acceptable salt form, to a patient in need thereof.
[0567] In a particular embodiment, the Compounds of the Invention are particularly useful for the treatment or prophylaxis of schizophrenia.
[0568] Compounds of the Invention, e.g., a Compound of Formula I-A or I-B, e.g., any of 1.1-1.84, or a Compound of Formula II-A or II-B, e.g., any of 2.1-2.13, in free or pharmaceutically acceptable salt form, are particularly useful for the treatment of Parkinson's disease, schizophrenia, narcolepsy, glaucoma and female sexual dysfunction.
[0569] In still another aspect, the invention provides a method of lengthening or enhancing growth of the eyelashes by administering an effective amount of a prostaglandin analogue, e.g., bimatoprost, concomitantly, simultaneously or sequentially with an effective amount of a PDE1 inhibitor of the Invention, e.g., a Compound of Formula I-A or I-B, e.g., any of 1.1-1.84, or a Compound of Formula II-A or II-B, e.g., any of 2.1-2.13, in free or pharmaceutically acceptable salt form, to the eye of a patient in need thereof.
[0570] In yet another aspect, the invention provides a method for the treatment or prophylaxis of traumatic brain injury comprising administering a therapeutically effective amount of a Compound of Formula I-A or I-B, e.g., any of 1.1-1.84, or a Compound of Formula II-A or II-B, e.g., any of 2.1-2.13, in free or pharmaceutically acceptable salt form, to a patient in need thereof. Traumatic brain injury (TBI) encompasses primary injury as well as secondary injury, including both focal and diffuse brain injuries. Secondary injuries are multiple, parallel, interacting and interdependent cascades of biological reactions arising from discrete subcellular processes (e.g., toxicity due to reactive oxygen species, overstimulation of glutamate receptors, excessive influx of calcium and inflammatory upregulation) which are caused or exacerbated by the inflammatory response and progress after the initial (primary) injury. Abnormal calcium homeostasis is believed to be a critical component of the progression of secondary injury in both grey and white matter. For a review of TBI, see Park et al., CMAJ (2008) 178(9):1163-1170, the contents of which are incorporated herein in their entirety. Studies have shown that the cAMP-PKA signaling cascade is downregulated after TBI and treatment of PDE IV inhibitors such as rolipram to raise or restore cAMP level improves histopathological outcome and decreases inflammation after TBI. As Compounds of the present invention is a PDE1 inhibitor, it is believed that these compounds are also useful for the treatment of TBI, e.g., by restoring cAMP level and/or calcium homeostasis after traumatic brain injury.
[0571] The present invention also provides
(i) a Compound of the Invention, e.g., Formula I or any of 1.1-1.84, or a Compound of Formula II-A or II-B, e.g., any of 2.1-2.13, in free or pharmaceutically acceptable salt form, for use as a pharmaceutical, for example for use in any method or in the treatment of any disease or condition as hereinbefore set forth, (ii) the use of a Compound of the Invention, e.g., Formula I or any of 1.1-1.84, or a Compound of Formula II-A or II-B, e.g., any of 2.1-2.13, in free or pharmaceutically acceptable salt form, in the manufacture of a medicament for treating any disease or condition as hereinbefore set forth, (iii) a pharmaceutical composition comprising a Compound of the Invention, e.g., Formula I or any of 1.1-1.84, or a Compound of Formula II-A or II-B, e.g., any of 2.1-2.13, in free or pharmaceutically acceptable salt form, in combination or association with a pharmaceutically acceptable diluent or carrier, and (iv) a pharmaceutical composition comprising a Compound of the Invention, e.g., Formula I or any of 1.1-1.84, or a Compound of Formula II-A or II-B, e.g., any of 2.1Error! Reference source not found.-2.13, in free or pharmaceutically acceptable salt form, in combination or association with a pharmaceutically acceptable diluent or carrier for use in the treatment of any disease or condition as hereinbefore set forth.
[0576] Therefore, the invention provides use of a Compound of the Invention, e.g., Formula I or any of 1.1-1.84, or a Compound of Formula II-A or II-B, e.g., any of 2.1-2.13, in free or pharmaceutically acceptable salt or prodrug form, or a Compound of the Invention in a pharmaceutical composition form, for the manufacture of a medicament for the treatment or prophylactic treatment of the following diseases: Parkinson's disease, restless leg, tremors, dyskinesias, Huntington's disease, Alzheimer's disease, and drug-induced movement disorders; depression, attention deficit disorder, attention deficit hyperactivity disorder, bipolar illness, anxiety, sleep disorder, narcolepsy, cognitive impairment, dementia, Tourette's syndrome, autism, fragile X syndrome, psychostimulant withdrawal, and/or drug addiction; cerebrovascular disease, stroke, congestive heart disease, hypertension, pulmonary hypertension, and/or sexual dysfunction; asthma, chronic obstructive pulmonary disease, and/or allergic rhinitis, as well as autoimmune and inflammatory diseases; and/or female sexual dysfunction, exercise amenorrhoea, anovulation, menopause, menopausal symptoms, hypothyroidism, pre-menstrual syndrome, premature labor, infertility, irregular menstrual cycles, abnormal uterine bleeding, osteoporosis, multiple sclerosis, prostate enlargement, prostate cancer, hypothyroidism, estrogen-induced endometrial hyperplasia or carcinoma; and/or any disease or condition characterized by low levels of cAMP and/or cGMP (or inhibition of cAMP and/or cGMP signaling pathways) in cells expressing PDE1, and/or by reduced dopamine D1 receptor signaling activity; and/or any disease or condition that may be ameliorated by the enhancement of progesterone signaling;.
[0577] The invention also provides use of a Compound of the Invention, e.g., a Compound of Formula I-A or I-B, e.g., any of 1.1-1.84, or a Compound of Formula II-A or II-B, e.g., any of 2.1-2.13, in free or pharmaceutically acceptable salt form, for the manufacture of a medicament for the treatment or prophylactic treatment of:
a) glaucoma or elevated intraocular pressure, b) psychosis, for example, any conditions characterized by psychotic symptoms such as hallucinations, paranoid or bizarre delusions, or disorganized speech and thinking, e.g., schizophrenia, schizoaffective disorder, schizophreniform disorder, psychotic disorder, delusional disorder, and mania, such as in acute manic episodes and bipolar disorder, c) traumatic brain injury.
[0581] The words “treatment” and “treating” are to be understood accordingly as embracing prophylaxis and treatment or amelioration of symptoms of disease as well as treatment of the cause of the disease.
[0582] For methods of treatment, the word “effective amount” is intended to encompass a therapeutically effective amount to treat a specific disease or disorder.
[0583] The term “pulmonary hypertension” is intended to encompass pulmonary arterial hypertension.
[0584] The term “patient” include human or non-human (i.e., animal) patient. In particular embodiment, the invention encompasses both human and nonhuman. In another embodiment, the invention encompasses nonhuman. In other embodiment, the term encompasses human.
[0585] The term “comprising” as used in this disclosure is intended to be open-ended and does not exclude additional, unrecited elements or method steps.
[0586] Compounds of the Invention are in particular useful for the treatment of Parkinson's disease, narcolepsy and female sexual dysfunction.
[0587] Compounds of the Invention, e.g., Formula I-A or I-B or any of 1.1-1.84, or II-A or II-B, any of 2.1-2.13, in free or pharmaceutically acceptable salt form may be used as a sole therapeutic agent, but may also be used in combination or for co-administration with other active agents. For example, as Compounds of the Invention potentiate the activity of D1 agonists, such as dopamine, they may be simultaneously, sequentially, or contemporaneously administered with conventional dopaminergic medications, such as levodopa and levodopa adjuncts (carbidopa, COMT inhibitors, MAO-B inhibitors), dopamine agonists, and anticholinergics, e.g., in the treatment of a patient having Parkinson's disease. In addition, the novel PDE 1 inhibitors, e.g., as described herein, may also be administered in combination with estrogerdestradiol/estriol and/or progesterone/progestins to enhance the effectiveness of hormone replacement therapy or treatment of estrogen-induced endometrial hyperplasia or carcinoma.
[0588] Dosages employed in practicing the present invention will of course vary depending, e.g. on the particular disease or condition to be treated, the particular Compound of the Invention used, the mode of administration, and the therapy desired. Compounds of the Invention may be administered by any suitable route, including orally, parenterally, transdermally, or by inhalation, but are preferably administered orally. In general, satisfactory results, e.g. for the treatment of diseases as hereinbefore set forth are indicated to be obtained on oral administration at dosages of the order from about 0.01 to 2.0 mg/kg. In larger mammals, for example humans, an indicated daily dosage for oral administration will accordingly be in the range of from about 0.75 to 150 mg, conveniently administered once, or in divided doses 2 to 4 times, daily or in sustained release form. Unit dosage forms for oral administration thus for example may comprise from about 0.2 to 75 or 150 mg, e.g. from about 0.2 or 2.0 to 50, 75 or 100 mg of a Compound of the Invention, together with a pharmaceutically acceptable diluent or carrier therefor.
[0589] Pharmaceutical compositions comprising Compounds of the Invention may be prepared using conventional diluents or excipients and techniques known in the galenic art. Thus oral dosage forms may include tablets, capsules, solutions, suspensions and the like.
EXAMPLES
[0590] The synthetic methods for various Compounds of the Present Invention are illustrated below. Other compounds of the Invention and their salts may be made using the methods as similarly described below and/or by methods similar to those generally described in the detailed description and by methods known in the chemical art.
Example 1
(6aR,9aS)-5,6a,7,8,9,9a-hexahydro-5-methyl-2-((4-Pyridin-2yl)-benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one
[0591]
1) 2-((1R,2R)-2-hydroxycyclopentylamino)-3-methylpyrimidin-4(3H)-one
[0592] 3-Methyluracil (12.6 mg, 0.1 mmol) was dissolved in 0.5 mL of DMF, and then BOP (71 mg, 0.16 mmol) was added. The mixture was stirred at room temperature for two minutes, then (1R,2R)-(−)-2-hydroxycyclopentylamine hydrochloride salt (22 mg, 0.16 mmol) was added, followed by DBU (51 uL, 3.4 mmol). The mixture was stirred at room temperature overnight. The reaction mixture was purified by a semi-preparative HPLC to give pure product (16 mg, yield 76%). MS (ESI) m/z 210.1 [M+H] + .
2) (3aS,8aR)-7-Methyl-1,2,3,3a,7,8a-hexahydro-3b,7,8-triaza-cyclopenta[a]inden-6-one
[0593] To a solution of 2-((1R,2R)-2-hydroxycyclopentylamino)-3-methylpyrimidin-4(3H)-one (130 mg, 0.62mmol) in anhydrous THF (2 mL) is added triphenylphosphine (163 mg, 0.62 mmol). Five minutes later, diethyl azodicarboxylate (DEAD, 0.45 mL, 0.93 mmol) in toluene is added dropwise. The mixture is stirred at room temperature for 2 hours. Solvent is removed under vacuum, the residue is treated with 0.02 N HCl (40 mL). The precipitate is filtered off, and the filtrate is washed with CH 2 Cl 2 . The aqueous phase is evaporated to dryness under high vacuum to give product as solids (108 mg, yield 92%), which is used for the next reaction without further purification. MS (ESI) m/z 192.1 [M+H] + .
3) (6aR,9aS)-5,6a,7,8,9,9a-hexahydro-5-methyl-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one
[0594] Sodium hydride (95%, 112 mg, 4.44 mmol) is suspended in 3 mL of anhydrous THF, and then a mixture of (3aS,8aR)-7-Methyl-1,2,3,3a,7,8a-hexahydro-3b,7,8-triaza-cyclopenta[a]inden-6-one (283 mg, 1.48 mmol) and p-toluenesulfonylmethyl isocyanide (97%, 347 mg, 1.77 mmol) in 5 mL of anhydrous THF is added dropwise. The mixture is stirred at room temperature for an hour, and then quenched with water. The mixture is extracted with CH 2 Cl 2 (5×10 mL). The combined organic phase is washed with brine, and then dried with anhydrous Na 2 SO 4 . After filtration, the filtrate is evaporated to dryness under reduced pressure to give crude product (320 mg, yield 94%) as brown solids, which is used for the next reaction without further purification. MS (ESI) m/z 231.1 [M+H] + .
4) (6aR,9aS)-5,6a,7,8,9,9a-hexahydro-5-methyl-2-((4-Pyridin-2yl)-benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one
[0595] A suspension of (6aR,9aS)-5,6a,7,8,9,9a-hexahydro-5-methyl-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one (140 mg, 0.61 mmol), 2-(4-(chloromethyl)phenyl)pyridine (0.12 g, 0.61 mmol) and cesium carbonate (400 mg, 1.22 mmol) in anhydrous DMF is stirred at room temperature overnight. The mixture is filtered through a 0.2 μL microfilter. The filtrate is purified by a semi-preparative HPLC to give 41 mg of pure product as off white solids. MS (ESI) m/z 398.2 [M+H] + .
Example 2
(6aR,9aS)-5,6a,7,8,9,9a-hexahydro-5-methyl-2-(4-(6-fluoropyridin-2-yl)benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one
[0596]
[0597] The synthetic procedure of this compound is analogous to EXAMPLE 1 wherein 2-(4-(chloromethyl)phenyl)-6-fluoropyridine is used in step 4 instead of 2-(4-(chloromethyl)phenyl)pyridine. MS (ESI) m/z 416.2 [M+H] + .
Example 3
(6aR,9aS)-5,6a,7,8,9,9a-hexahydro-1,5-dimethyl-2-(4-(6-fluoropyridin-2-yl)benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one
[0598]
[0599] The synthetic procedure of this compound is analogous to EXAMPLE 1 wherein 1-(1-isocyanoethylsulfonyl)-4-methylbenzene is used in step 3 instead of p-toluenesulfonylmethyl isocyanide, and 2-(4-(chloromethyl)phenyl)-6-fluoropyridine is used in step 4 instead of 2-(4-(chloromethyl)phenyl)pyridine. MS (ESI) m/z 416.2 [M+H] + .
Example 4
(6aR,9aS)-5,6a,7,8,9,9a-hexahydro-1-chloro-5-methyl-2-(4-(6-fluoropyridin-2-yl)benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one
[0600]
[0601] (6aR,9aS)-5,6a,7,8,9,9a-hexahydro-5-methyl-2-(4-(6-fluoropyridin-2-yl)benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one (38 mg, 0.082 mmol) is dissolved in a mixture of CCl 4 and DMF (8/1, v/v). The solution is cooled to 0° C., and then a solution of N-chlorosuccinimide (10.9 mg, 0.082 mmol) in CCl 4 and DMF (8/1, v/v) is added dropwise. The reaction mixture is stirred at room temperature for half an hour. Solvents are removed under vacuum, and the residue is purified by a semi-preparative HPLC to give pure product as off white solids (16.5 mg, yield 45%). MS (ESI) m/z 450.1 [M+H] + .
Example 5
(6aR,9aS)-5,6a,7,8,9,9a-hexahydro-5-methyl-1-(phenylamino)-2-(4-(6-fluoropyridin-2-yl)benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one
[0602]
[0603] Crude (6aR,9aS)-5,6a,7,8,9,9a-hexahydro-1-chloro-5-methyl-2-(4-(6-fluoropyridin-2-yl)benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one (approx. 0.03 mmol) is dissolved in anhydrous CH 2 Cl 2 , and then trichloroacetic acid (5.2 mg, 0.03 mmol) is added, followed by aniline (5.8 uL, 0.06 mmol). The reaction mixture is heated in a Biotage microwave instrument at 100° C. for 2 hours. The mixture is purified by a semi-preparative HPLC to give 2.2 mg of product as solids. MS (ESI) m/z 507.2 [M+H] + .
Example 6
(6aR,9aS)-5,6a,7,8,9,9a-hexahydro-5-methyl-2-(4-methoxy-benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one
[0604]
[0605] The synthetic procedure of this compound is analogous to EXAMPLE 1 wherein 1-(chloromethyl)-4-methoxybenzene is used in step 4 instead of 2-(4-(chloromethyl)phenyl)pyridine. MS (ESI) m/z 351.2 [M+H] + .
Example 7
(6aR,9aS)-5,6a,7,8,9,9a-hexahydro-3-chloro-5-methyl-2-(4-methoxy-benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one
[0606]
[0607] 1.0M LiHMDS in THF (4.2 mL, 4.2 mmol) is added dropwise to a solution of (6aR,9aS)-5,6a,7,8,9,9a-hexahydro-5-methyl-2-(4-methoxy-benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one (500 mg, 1.4 mmol) and hexachloroethane (1.69 g, 7.13 mmol) at room temperature under argon. After 30 min, the mixture is quenched with saturated ammonium chloride aqueous solution at 0° C., and then basified with saturated sodium bicarbonate aqueous solution, followed by extractions with methylene chloride. The collected organic phase is washed with brine, dried over anhydrous sodium sulfate, and then evaporated to dryness under reduced pressure. The obtained crude product is purified by silica gel flash chromatography to give 165 mg of pure product as off white solid (yield: 30%). MS (ESI) m/z 385.2 [M+H] + .
Example 8
(6aR,9aS)-5,6a,7,8,9,9a-hexahydro-3-chloro-5-methyl-2-((4-Pyridin-2yl)-benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one
[0608]
[0609] To a solution of (6aR,9aS)-5,6a,7,8,9,9a-hexahydro-3-chloro-5-methyl-2-(4-methoxy-benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one (95 mg, 0.25 mmol) in CH 2 Cl 2 is slowly added TFA and trifluoromethanesulfonic acid (TFMSA). The mixture is stirred at room temperature overnight. Solvents and TFA are removed under reduced pressure. The residue is neutralized and dissolved in DMF, and then purified by a semi-preparative HPLC to give 77 mg of (6aR,9aS)-5,6a,7,8,9,9a-hexahydro-3-chloro-5-methyl-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one. A suspension of (6aR,9aS)-5,6a,7,8,9,9a-hexahydro-3-chloro-5-methyl-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one (79 mg, 0.3 mmol), 2-(4-(chloromethyl)phenyl)pyridine (61 mg, 0.3 mmol) and cesium carbonate (192 mg, 0.6 mmol) in anhydrous DMF is stirred at room temperature for 4 h. The mixture is filtered through a 0.2 μL microfilter. The filtrate is purified by a semi-preparative HPLC to give pure product. MS (ESI) m/z 432.2 [M+H] + .
Example 9
(6aR,9aS)-5,6a,7,8,9,9a-hexahydro-5-methyl-3-(phenylamino)-2-((4-Pyridin-2yl)-benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one
[0610]
[0611] (6aR,9aS)-5,6a,7,8,9,9a-hexahydro-3-chloro-5-methyl-2-((4-Pyridin-2yl)-benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one (5.6 mg, 0.013 mmol) is placed in a Biotage microwave tube, and then aniline (0.2 mL) is added. The mixture is heated at 150° C. for an hour. The mixture is purified by a semi-preparative HPLC to give product. MS (ESI) m/z 489.3 [M+H] + .
Example 10
(6aR,9aS)-5,6a,7,8,9,9a-hexahydro-5-methyl-3-(phenylamino)-2-(4-methoxy-benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one
[0612]
[0613] The synthetic procedure of this compound is analogous to EXAMPLE 9 wherein (6aR,9aS)-5,6a,7,8,9,9a-hexahydro-3-chloro-5-methyl-2-(4-methoxy-benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one is used instead of (6aR,9a S)-5,6a,7,8,9,9a-hexahydro-3-chloro-5-methyl-2(4-Pyridin-2yl)-benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one. MS (ESI) m/z 442.2 [M+H] + .
Example 11
(6aR,9aS)-5,6a,7,8,9,9a-hexahydro-5-methyl-3-(phenylamino)-2-(4-(1H-1,2,4-triazol-1-yl)-benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one
[0614]
[0615] The synthetic procedure of this compound is analogous to EXAMPLE 9 wherein (6aR,9aS)-5,6a,7,8,9,9a-hexahydro-3-chloro-5-methyl-2-(4-(1H-1,2,4-triazol-1-yl)-benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one is used instead of (6aR,9aS)-5,6a,7,8,9,9a-hexahydro-3-chloro-5-methyl-2-((4-Pyridin-2yl)-benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one. MS (ESI) m/z 479.3 [M+H] + .
Example 12
(6aR,9aS)-5,6a,7,8,9,9a-hexahydro-5-methyl-1-(phenylamino)-2-(4-(pyridin-2-yl)benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one
[0616]
[0617] The synthetic procedure of this compound is analogous to EXAMPLE 9 wherein (6aR,9aS)-5,6a,7,8,9,9a-hexahydro-5-methyl-1-chloro-2-(4-(pyridin-2-yl)benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one is used instead of (6aR,9aS)-5,6a,7,8,9,9a-hexahydro-3-chloro-5-methyl-2-((4-Pyridin-2yl)-benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one. MS (ESI) m/z 489.2 [M+H] + .
Example 13
(6aR,9aS)-5,6a,7,8,9,9a-hexahydro-5-methyl-3-(phenylamino)-2-(4-(pyridin-4-yl)benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one
[0618]
[0619] The synthetic procedure of this compound is analogous to EXAMPLE 9 wherein (6aR,9aS)-5,6a,7,8,9,9a-hexahydro-5-methyl-3-chloro-2-(4-(pyridin-4-yl)benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one is used instead of (6aR,9aS)-5,6a,7,8,9,9a-hexahydro-3-chloro-5-methyl-2-((4-Pyridin-2yl)-benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one. MS (ESI) m/z 489.3 [M+H] + .
Example 14
(6aR,9aS)-5,6a,7,8,9,9a-hexahydro-5-methyl-3-(phenylamino)-2-(4-(1H-imidazol-1-yl)benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one
[0620]
[0621] The synthetic procedure of this compound is analogous to EXAMPLE 9 wherein (6aR,9aS)-5,6a,7,8,9,9a-hexahydro-5-methyl-3-chloro-2-(4-(1H-imidazol-1-yl)benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one is used instead of (6aR,9aS)-5,6a,7,8,9,9a-hexahydro-3-chloro-5-methyl -2-((4-Pyridin-2yl)-benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one. MS (ESI) m/z 478.2 [M+H] + .
Example 15
(6aR,9aS)-5,6a,7,8,9,9a-hexahydro-5-methyl-3-(phenylthio)-2-(4-(pyridin-2-yl)benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one
[0622]
[0623] (6aR,9aS)-5,6a,7,8,9,9a-hexahydro-5-methyl-2-((4-Pyridin-2yl)-benzyl)-cyclopent[4,5]imidazo[1,2-a]pyrrolo[4,3-e]pyrimidin-4(2H)-one (20 mg, 0.05 mmol) and phenyl disulfide (22 mg, 0.10 mmol) are dissolved in 400 μL of anhydrous THF, and then 1.0 M LiHMDS in THF (150 μL, 0.15 mmol) is added dropwise. The mixture is stirred at room temperature for 10 min, and then quenched with ammonium chloride aqueous solution. The mixture is diluted with DMF, and then purified by a semi-preparative HPLC to give pure product as pale yellow solid. MS (ESI) m/z 506.2 [M+H] + .
Example 16
[0624] Measurement of PDE1B Inhibition in Vitro using IMAP Phosphodiesterase Assay Kit
[0625] Phosphodiesterase 1B (PDE1B) is a calcium/calmodulin dependent phosphodiesterase enzyme that converts cyclic guanosine monophosphate (cGMP) to 5′-guanosine monophosphate (5′-GMP). PDE1B can also convert a modified cGMP substrate, such as the fluorescent molecule cGMP-fluorescein, to the corresponding GMP-fluorescein. The generation of GMP-fluorescein from cGMP-fluorescein can be quantitated, using, for example, the IMAP (Molecular Devices, Sunnyvale, Calif.) immobilized-metal affinity particle reagent.
[0626] Briefly, the IMAP reagent binds with high affinity to the free 5′-phosphate that is found in GMP-fluorescein and not in cGMP-fluorescein. The resulting GMP-fluorescein—IMAP complex is large relative to cGMP-fluorescein. Small fluorophores that are bound up in a large, slowly tumbling, complex can be distinguished from unbound fluorophores, because the photons emitted as they fluoresce retain the same polarity as the photons used to excite the fluorescence.
[0627] In the phosphodiesterase assay, cGMP-fluorescein, which cannot be bound to IMAP, and therefore retains little fluorescence polarization, is converted to GMP-fluorescein, which, when bound to IMAP, yields a large increase in fluorescence polarization (Δmp). Inhibition of phosphodiesterase, therefore, is detected as a decrease in Δmp.
[0628] Enzyme Assay
[0629] Materials: All chemicals are available from Sigma-Aldrich (St. Louis, Mo.) except for IMAP reagents (reaction buffer, binding buffer, FL-GMP and IMAP beads), which are available from Molecular Devices (Sunnyvale, Calif.).
[0630] Assay: 3′,5′-cyclic-nucleotide-specific bovine brain phosphodiesterase (Sigma, St. Louis, Mo.) is reconstituted with 50% glycerol to 2.5 U/ml. One unit of enzyme will hydrolyze 1.0 μmole of 3′,5′-cAMP to 5′-AMP per min at pH 7.5 at 30° C. One part enzyme is added to 1999 parts reaction buffer (30 μM CaCl 2 , 10 U/ml of calmodulin (Sigma P2277), 10 mM Tris-HCl pH 7.2, 10 mM MgCl 2 , 0.1% BSA, 0.05% NaN 3 ) to yield a final concentration of 1.25 mU/ml. 99 μl of diluted enzyme solution is added into each well in a flat bottom 96-well polystyrene plate to which 1 μl of test compound dissolved in 100% DMSO is added. The compounds are mixed and pre-incubated with the enzyme for 10 min at room temperature.
[0631] The FL-GMP conversion reaction is initiated by combining 4 parts enzyme and inhibitor mix with 1 part substrate solution (0.225 μM) in a 384-well microtiter plate. The reaction is incubated in dark at room temperature for 15 min. The reaction is halted by addition of 60 μl of binding reagent (1:400 dilution of IMAP beads in binding buffer supplemented with 1:1800 dilution of antifoam) to each well of the 384-well plate. The plate is incubated at room temperature for 1 hour to allow IMAP binding to proceed to completion, and then placed in an Envision multimode microplate reader (PerkinElmer, Shelton, Conn.) to measure the fluorescence polarization (Δmp).
[0632] A decrease in GMP concentration, measured as decreased Δmp, is indicative of inhibition of PDE activity. IC 50 values are determined by measuring enzyme activity in the presence of 8 to 16 concentrations of compound ranging from 0.0037 nM to 80,000 nM and then plotting drug concentration versus ΔmP, which allows IC 50 values to be estimated using nonlinear regression software (XLFit; IDBS, Cambridge, Mass.).
[0633] The Compounds of the Invention may be tested in an assay as described or similarly described herein for PDE1 inhibitory activity. The exemplified compounds generally have IC 50 values of less than 100 μM, some less than 10 μM, some less than 500 nM, some less than 10 nM, some against PDE1A.the Compounds of Examples 1, 3 and 5 generally have IC 50 values of about or less than 10 μM, some less than 500 nM, some less than 10 nM, particularly against PDE1A.
Example 17
PDE1 Inhibitor Effect on Sexual Response in Female Rats
[0634] The effect of PDE1 inhibitors on Lordosis Response in female rats may be measured as described in Mani, et al., Science (2000) 287: 1053. Ovariectomized and cannulated wild-type rats are primed with 2 μg estrogen followed 24 hours later by intracerebroventricular (icy) injection of progesterone (2 μg), PDE1 inhibitors of the present invention (0.1 mg, 1.0 mg or 2.5 mg) or sesame oil vehicle (control). The rats are tested for lordosis response in the presence of male rats. Lordosis response is quantified by the lordosis quotient (LQ=number of lordosis/10 mounts×100). | Optionally substituted 4,5,7,8-tetrahydro-(optionally 4-oxo, 4-thioxo or 4-imino)-2H-imidazo[1,2-a]pyrrolo[3,4-e]pyrimidine or 4,5,7,8,9-pentahydro-(optionally 4-oxo, 4-thioxo or 4-imino)-2H-pyrimido[1,2-a]pyrrolo[3,4-e]pyrimidine compounds or Compounds of Formula (I), processes for their production, their use as pharmaceuticals and pharmaceutical compositions comprising the same. | 0 |
BACKGROUND OF THE INVENTION
[0001] 1. Technical Field
[0002] The present invention relates to a position detection system for detecting a position of an object having a recess or a protrusion.
[0003] 2. Description of Related Art
[0004] As disclosed in Japanese Laid-open Patent Publication No. H05-241626, it has been common practice to determine an accurate position of an object by correcting detection data of the object acquired using a visual sensor or a camera. In Japanese Laid-open Patent Publication No. 2005-251086: an object is detected by a visual sensor provided on a robot; subsequently the visual sensor is moved by the robot; and an identical object is detected by the visual sensor thus moved. Further, in Japanese Laid-open Patent Publication No. 2005-251086, a determination is made as to whether the result of the detection by the visual sensor relates to an identical object.
[0005] However, when the object has a portion such for example as a recess or a protrusion that is difficult to detect by the visual sensor, an erroneous detection tends to occur. This may make it not possible to detect an accurate position of the object, thus lowering the operating efficiency.
[0006] The present invention has been made in view of such circumstances, and an object thereof is to provide a position detection system that is capable of accurately detecting a position of an object, even when the object has a recess or a protrusion.
SUMMARY OF THE INVENTION
[0007] In order to achieve the above object, according to a first aspect of the present invention, there is provided a position detection system for detecting a position of an object having a recess or a protrusion, the system including: a contactor including a tracing unit that traces and fits with the recess or the protrusion of the object; a slide member configured integrally with the contactor; a sliding unit that causes the slide member to slide in two directions perpendicular to each other; a moving unit that causes the contactor to move in a direction perpendicular to a plane defined between the two directions so as to cause the tracing unit of the contactor to trace and fit with the recess or the protrusion of the object; a contactor detecting unit that is in a fixed positional relationship with a base of the sliding unit and detects a position of the contactor in the plane; and an object position detecting unit that detects a position of the object based on the position of the contactor detected by the contactor detecting unit before and after the slide member slides on the sliding unit, when the tracing unit of the contactor traces the recess or the protrusion of the object.
[0008] According to a second aspect of the present invention, in the first aspect, when the moving unit causes the contactor to move in at least one direction of the two directions, the position of the object is detected based on the movement amount of the contactor by the moving unit and the movement amount of the contactor when the slide member slides on the sliding unit.
[0009] According to a third aspect of the present invention, in the first or second aspect, the contactor is a camera.
[0010] According to a fourth aspect of the present invention, in any one of the first to third aspects, the moving unit is a robot.
[0011] According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the object has a recess, and the contactor is a cone fittable with the recess.
[0012] According to a sixth aspect of the present invention, in any of the first to fourth aspects, the object has a conical protrusion, and the contactor has a cylindrical portion fittable with the protrusion.
[0013] These and other objects, features, and advantages of the present invention will become more apparent from a detailed description of exemplary embodiments of the present invention illustrated in the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1 is a perspective view illustrating a position detecting system based on the present invention.
[0015] FIG. 2 is a flow chart illustrating the operation of the position detection system illustrated in FIG. 1 .
[0016] FIG. 3A is a first perspective view for explaining the operation of the position detection system.
[0017] FIG. 3B is a second perspective view for explaining the operation of the position detection system.
[0018] FIG. 3C is a third perspective view for explaining the operation of the position detection system.
DETAILED DESCRIPTION
[0019] Embodiments of the present invention will now be described with reference to the accompanying drawings. Throughout the drawings, like reference numerals are assigned to like elements. In order to facilitate understanding, the scale of the drawings is appropriately changed.
[0020] FIG. 1 is a perspective view illustrating a position detection system based on the present invention. As illustrated in FIG. 1 , the position detection system 1 includes mainly a moving unit 11 , a contactor detecting unit 12 , and a control device 10 that controls the moving unit 11 and the contactor detecting unit 12 . Further, the control device 10 functions as an object position detecting unit that detects a position of an object as described hereinafter.
[0021] The moving unit 11 is a perpendicular articulated robot, for example, and instead may be another type of robot or another mechanism unit that can move in a vertical direction. Meanwhile, the contactor detecting unit 12 is a visual sensor or a camera. In the following, a description will be made on the assumption that the moving unit 11 is a robot and the contactor detecting unit 12 is a camera.
[0022] As illustrated, a base member 13 is attached to a distal end of the robot 11 . Further, the camera 12 is attached to a distal end of a bracket 14 fixed in such a manner as to extend substantially vertically with respect to the base member 13 .
[0023] Further, a sliding mechanism unit 20 is attached to the base member 13 . More specifically, mutually parallel two X-axis rails 21 of the sliding mechanism unit 20 are provided on the upper surface of the base member 13 . It is assumed that the positional relationship among the base member 13 , the bracket 14 , and the two X-axis rails 21 is such that they are fixed with respect to each other and are moved in unison when the robot 11 moves. Further, as illustrated, a first slider 23 of the sliding mechanism unit 20 is slidably located on the two X-axis rails 21 .
[0024] On the upper surface of the first slider 23 are provided mutually parallel two Y-axis rails 22 of the sliding mechanism unit 20 . These Y-axis rails 22 are perpendicular to the above-mentioned X-axis rails. A second slider 24 of the sliding mechanism unit 20 is slidably located on the two Y-axis rails 22 .
[0025] Further, a generally cylindrical contactor 30 is inserted and fixed in an opening provided at the center of the second slider 24 . Upper surface 31 of the contactor 30 is parallel with respect to the upper surface of the second slider 24 , and a target T is provided thereon. As can be seen from FIG. 1 , the target T is located below the camera 12 in the range of view of the camera 12 . Preferably, both the X-direction defined by the X-axis rails 21 and the Y-direction defined by the Y-axis rails 22 lie in a horizontal plane. Thus the upper surface of the second slider 24 lies in a horizontal plane.
[0026] As illustrated in FIG. 1 , the contactor 30 extends downwardly between the two Y-axis rails 22 and between the two X-axis rails 21 . An extension unit 32 extends from the lower surface of the contactor 30 , and a tracing unit 33 is provided on the distal end of the extension unit 32 . Preferably, the contactor 30 , the extension unit 32 , and the tracing unit 33 have a common center axis.
[0027] The extension unit 32 has a size greater than that of a recess formed on an object, which will be described hereinafter. The tracing unit 33 has a shape adapted to trace and fit with the recess of the object. In FIG. 1 , for example, the extension unit 32 is of a cylindrical shape having a diameter greater than that of the recess, and the tracing unit 33 is of a conical shape such for example as a cone provided on the distal end of the extension unit 32 .
[0028] FIG. 2 is a flow chart illustrating the operation of the position detection system illustrated in FIG. 1 . Further, FIGS. 3A through 3C are perspective views for explaining the operation of the position detection system. A description will now be made of the operation of the position detection system according to the present invention with reference to the drawings.
[0029] Prior to the operation of the position detection system 1 , the first slider 23 and the second slider 24 each are located at a predetermined initial position thereof. It is assumed, in this regard, that the first slider 23 and the second slider 24 will not be changed in position when the robot 11 is merely moved in the horizontal and/or vertical direction.
[0030] As illustrated in FIG. 3A , the object W is of a generally cubic shape in which an opening W 0 is formed in the top face. A cylindrical recess extends from the opening W 0 through the interior of the object W. It is assumed that the following description applies to an object W of another shape having a similar recess as well.
[0031] Firstly, at step S 11 of FIG. 2 , the control device 10 causes the robot 11 to move so that the base member 13 is made to approach above the object W. Since the robot 11 is operated in accordance with a simple program, in the present invention, the base member 13 can be made to approach above the object W easily and accurately.
[0032] As described above, the base member 13 , the bracket 14 , the camera 12 , and the two X-axis rails 21 are operated in unison so that when the base member 13 is moved, the camera 12 is also moved likewise. As such, as illustrated in FIG. 3A , the contactor 30 is located generally above the object W.
[0033] The movements of the base member 13 , etc. at step S 11 may include both horizontal and vertical movements. Preferably, the distance between the contactor 30 and the object W illustrated in FIG. 3A is in a predetermined range. When the contactor 30 is located generally above the object W, the camera 12 picks up an image of the target T of the contactor 30 , and the image is stored in the control device 10 .
[0034] At step S 12 , the base member 13 , etc. are moved only downwardly toward the object W by the robot 11 as illustrated by an arrow mark in FIG. 3A . In this manner, as illustrated in FIG. 3B , the distal end of the tracing unit 33 enters the opening W 0 so that a part of the side surface of the tracing unit 33 contacts a part of the opening W 0 .
[0035] As the base member 13 , etc. are moved further downwardly by the robot 11 , the tracing unit 33 descends while tracing the opening W 0 . In response to this descending operation, the contactor 30 and the second slider 24 are moved slightly in at least one of the X-direction and the Y-direction along the X-axis rail 21 and the Y-axis rail 22 . As illustrated in FIG. 3C , a part of the side surface of the tracing unit 33 fits with the opening W 0 over the entire circumference thereof. When the tracing unit 33 of the contactor 30 fits with the opening W 0 , the contactor 30 is prevented from moving any further in the X-direction and in the Y-direction. Then, the descending operation by the robot 11 is also ended.
[0036] Subsequently, at step S 13 , the target T of the contactor 30 is imaged by the camera 12 , and the image is stored in the control device 10 . Thereupon, the control device 10 compares the image imaged at step S 13 with the above-mentioned image and thus detects the movement amount of the contactor 30 in the X-direction and in the Y-direction. Finally, at step S 14 , the control device 10 detects a position of the object W in the X-Y plane based on the movement amount of the contactor 30 in the X-direction and in the Y-direction.
[0037] Alternatively, the control device 10 may process the image imaged at step S 13 , detect the movement amounts of the first slider 23 and the second slider 24 from their initial positions, and detect the position of the object W, with such movement amounts being the movement amounts of the contactor 30 . In such an instance, it is unnecessary for the camera 12 to pick up an image at step S 11 , and a single image processing suffices.
[0038] In this manner, in the present invention, the contactor 30 , which has traced and fitted with the object W, is detected, instead of the object W being detected directly by the camera 12 . When the tracing unit 33 of the contactor 30 fits with the opening W 0 of the object W, the contactor 30 is moved in the X-direction and in the Y-direction along the X-axis rail 21 and the Y-axis rail 22 . Thus, it is possible to indirectly grasp the position of the object W by detecting the movement amount of the contactor 30 using the camera 12 .
[0039] Consequently, in the present invention, it is possible to accurately detect the position of the object W even when the object W has a recess or a protrusion. In other words, in the present invention, it is possible to achieve a stable detection without being influenced by the feature of the object W, since the camera 12 does not detect the shape of the object W directly. As such, erroneous detection of the object W by the camera 12 decreases so that the operating efficiency is increased.
[0040] Meanwhile, at step S 11 , the robot 11 may move the base member 13 and the camera 12 , etc. in the horizontal direction. In this instance, the control device 10 stores the movement amount of the base member 13 , etc. moved in the X-direction and in the Y-direction by the robot 11 . Further, at step S 14 , the control device 10 detects the position of the object W using both the movement amount of the contactor 30 in the X-direction and in the Y-direction and the stored movement amount of the base member 13 , etc. in the X-direction and in the Y-direction. In such an instance, it will be appreciated that the object W can be detected over a wide range since the base member 13 , etc. are moved by the robot 11 .
[0041] In an unillustrated embodiment, the object has a protrusion, e.g., a conical protrusion. It is assumed, in this regard, that a recess, which is fittable with the protrusion and similar to that described above, is formed in the bottom surface of the extension unit 32 of the contactor 30 . In this instance, the shape of the recess is a shape corresponding to the bottom surface of the conical protrusion. Meanwhile, it is to be understood that the present invention encompasses a case in which the protrusion or the recess has a different cross-sectional shape and a case in which the recess or the protrusion is cylindrical.
[0042] Advantage of the Invention
[0043] In the first embodiment, the contactor is made to trace and fit with the object using the physical feature of the object. Then, the contactor detecting unit detects the contactor and indirectly grasps a position of the object. Thus, even with an object having a recess or a protrusion, it is possible to accurately detect a position of the object. Consequently, erroneous detection of the object by the contactor detecting unit decreases so that the operating rate is increased.
[0044] In the second embodiment, the object can be detected over a wide range when the contactor is moved by the moving unit.
[0045] In the third embodiment, the position of the contactor can be detected with ease via an analysis of an image acquired by imaging by the camera.
[0046] In the fourth embodiment, the object can be easily approached by operating the robot in accordance with a simple program.
[0047] In the fifth and sixth embodiments, it is possible, by a relatively simple structure, to cause the contactor to trace and fit with the object
[0048] While the present invention has been described using exemplary embodiments, those skilled in the art could understand that the above-described changes as well as various other changes, omissions, and additions are possible without departing from the scope of the present invention. | A position detection system includes: a contactor including a tracing unit that traces and fits with a recess or a protrusion of an object; a slide member; a sliding unit that causes the slide member to slide in two directions; a moving unit that causes the contactor to move in a direction perpendicular to a plane so as to cause the tracing unit of the contactor to trace and fit with the recess or the protrusion of the object; a contactor detecting unit that detects a position of the contactor in the plane; and an object position detecting unit that detects the position of the object based on movement amount of the contactor before and after the slide member slides on the sliding unit to slide, when the tracing unit traces the recess or the protrusion. | 1 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims the priority benefit of U.S. Provisional Application No. 61/739,283 entitled “Providing Premium Access to Aggregated Data Sets” and filed Dec. 19, 2012, the content of which is hereby incorporated by reference in its entirety.
FIELD OF THE INVENTION
[0002] This invention generally relates to providing access to aggregated data, and more particularly, to providing premium access channels to aggregated data available from a single source.
BACKGROUND OF THE INVENTION
[0003] Recently, access to shared data sets via data communications such as the Internet has increased greatly, providing access to this information to many people and organizations. For example, a collection of national provider identification (NPI) numbers is stored in the NPI database, which provides access to many individuals and organizations for verification of healthcare related information. For example, the NPI database may be used to: validate healthcare related correspondence; coordinate benefits between health plans; identify potential health care providers; verify healthcare providers on prescription information; and other related functions.
[0004] One drawback to shared data sets is the reliability of the data. Typically, when data is available for free, the data is of reasonable quality. However, the data is largely incomplete and may require multiple sources to verify the information. Conversely, commercially provided data typically has a high associated cost and is of questionable and varying quality. Additionally, data provided by multiple providers is typically in widely varying formats and is not easily imported into a single data set.
[0005] Varied reliability is especially common when reviewing health care provider/health care organization (HCP/HCO) information. As multiple providers sell, license, or otherwise provide access to the data, updates to the data provided by a first provider does not necessarily get reflected in another provider's data set. Thus, an individual or organization looking for reliable and updated information may have to access multiple providers, increasing the overall cost to the individual or organization.
SUMMARY
[0006] The present disclosure concerns methods and systems for providing premium access to aggregated data sets. For example, in one scenario, a method of providing access to aggregated data sets includes organizing a plurality of data sets into an aggregated data set, providing access to at least a portion of the aggregated data set based upon a subscription level associated with a user, receiving a search query from the user to search the aggregated data, determining which portions of the aggregated data set the user can access based upon the subscription level of the user, filtering a set of search results based upon the determination of which portions of the aggregated data set the user can access, and returning the filtered search results to the user.
[0007] In an alternative scenario, a system for providing access to aggregated data sets includes a non-transitory computer readable medium configured to store an aggregated data set and a processing device operably connected to the non-transitory computer readable medium. In the alternative scenario, processing device is configured to organize a plurality of data sets into an aggregated data set, provide access to at least a portion of the aggregated data set based upon a subscription level associated with a user, receive by the processing device, a search query from the user to search the aggregated data, determine which portions of the aggregated data set the user can access based upon the subscription level of the user, filter a set of search results based upon the determination of which portions of the aggregated data set the user can access, and return the filtered search results to the user.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 depicts a block diagram depicting a network used for accessing a data set stored on a central database according to an embodiment.
[0009] FIG. 2 depicts a block diagram of a customer computing device accessing a database according to an embodiment.
[0010] FIG. 3 depicts a flow chart of an example procedure for creating an aggregated database according to an embodiment.
[0011] FIG. 4 depicts a flow chart of an example procedure for accessing an aggregated database according to an embodiment.
[0012] FIG. 5 depicts various embodiments of a computing device for implementing the various methods and processes described herein.
DETAILED DESCRIPTION
[0013] It will be readily understood that the components of the embodiments as generally described herein and illustrated in the appended figures could be arranged and designed in a wide variety of different configurations. Thus, the following more detailed description of various embodiments, as represented in the figures, is not intended to limit the scope of the present disclosure, but is merely representative of various embodiments. While the various aspects of the embodiments are presented in drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
[0014] The present disclosure may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects only as illustrative and not restrictive. The scope of the disclosure is, therefore, indicated by the appended claims rather than by this detailed description. All changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
[0015] Reference throughout this specification to features, advantages, or similar language does not imply that all of the features and advantages that may be realized with the present disclosure should be or are in any single embodiment of the disclosure. Rather, language referring to the features and advantages is understood to mean that a specific feature, advantage, or characteristic described in connection with an embodiment is included in at least one embodiment of the present disclosure. Thus, discussions of the features and advantages, and similar language, throughout the specification may, but do not necessarily, refer to the same embodiment.
[0016] Furthermore, the described features, advantages and characteristics of the disclosure may be combined in any suitable manner in one or more embodiments. One skilled in the relevant art will recognize, in light of the description herein, that the teachings of the disclosure made herein can be practiced without one or more of the specific features or advantages of a particular embodiment. In other instances, additional features and advantages may be recognized in certain embodiments that may not be present in all embodiments of the disclosure.
[0017] As used in this document, the singular forms “a,” “an,” and “the” include plural references unless the context clearly dictates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art. As used in this document, the term “comprising” means “including, but not limited to.”
[0018] Reference throughout this specification to “one embodiment”, “an embodiment”, or similar language means that a particular feature, structure, or characteristic described in connection with the indicated embodiment is included in at least one embodiment of the present disclosure. Thus, the phrases “in one embodiment”, “in an embodiment”, and similar language throughout this specification may, but do not necessarily, all refer to the same embodiment.
[0019] An embodiment of the present invention advantageously provides for aggregating data from multiple customers (including individuals and organizations), public sources (e.g., state and federal government agencies), and commercial sources into a single database to enhance the quality and validity of the data, while increasing the convenience of customers accessing the data. Individual data sets received from a premium source (e.g., a data source that requires an additional fee or license to access its data) may be assigned to one or more premium access channels, each channel having an associated subscription requirement. Individual customers may be provided access to the one or more premium access channels, where the customer's access is to the aggregated data is determined based upon their subscription level.
[0020] As used herein, a subscriber refers to an organization or individual that contributes their privately collected data (customer master) on organizations and individuals (entities), and is licensed to use the database for their own purposes of referencing all those entities within the database as contributed/provided by all subscribers. Based upon their subscription level, an individual customer may have varying levels of access to one or more premium data sets contained within the aggregated data.
[0021] FIG. 1 is a block diagram depicting exemplary components of a system 100 employing the present invention. A web application platform such as a Microsoft SharePoint® Server 112 providing Microsoft SharePoint® Services may be operably connected to a database system server 114 . The SharePoint® Server may include a computer processor 102 , associated computer memory 104 , input/output interface 106 , a web services interface 108 and local data storage 110 . Either or both of the SharePoint® server 112 and the database system server 114 may include a computer memory configured with processor instructions and data which, when loaded into the processor, cause the processor to execute the methods of the invention. Either or both of the SharePoint® server 112 and the database system server 114 may alternatively include several processors with associated computer memory, as is well understood in the art.
[0022] The SharePoint server 112 may further be operably connected to a communication network such as the Internet 116 via the I/O interface 106 and the web services interface 108 , although alternatives to the Internet are envisioned, and even a stand-alone system may alternatively be deployed. A customer computing device such as tablet computer 118 may be operably connected to the SharePoint® server 112 via the Internet 116 . It should be noted that the tablet computer 118 is shown in FIG. 1 by way of example only, and additional computing devices such as a desktop computer, a notebook computer, a netbook computer, a smartphone, and other similar computing devices may be used to access the server 112 .
[0023] The I/O interface 106 may be the interface with which a human user of the system interacts, presented as a graphical user interface on the tablet computer and constructed by the SharePoint® server 112 as defined by a custom configuration by a software provider or management company. The web services interface 108 may be the computer interface through which the user's computing device (e.g., the tablet computer 118 ) interacts directly with the SharePoint® server 112 . Specifically, an application on the tablet computer 118 may be configured to connect to the SharePoint® server 112 via the web services interface 108 to access necessary back-end services running on the SharePoint® server 112 .
[0024] The SharePoint® server 112 as illustrated in FIG. 1 may be configured to run a specific application such as the RADS® system designed by R-Squared Services and Solutions, Inc. and described in application Ser. Nos. 12/699,398 and 12/952,296.
[0025] The database system server 114 may further include, or be operably connected to, a database 120 . The database 120 may incorporate the aggregating and premium access techniques described above, and described in more detail below.
[0026] An example of a database 120 may be the CIR 2 US® database designed by R-Squared Services and Solutions, Inc., for greater flexibility in storing HCP/HCO data. In summary, there is a master record that is used to aggregate a number of elements comprised of name, address, identifier, affiliation and professional details data. Multiple sources, such as the subscribers as discussed above, may contribute data elements to the aggregate such that the primary data constructed from a public source may be enlarged with specific client data. The flexible nature of the tables used to store the data may also contains keys to keep track of the elements contributed from single sources such that they may be updated in a manner similar to a single record containing the HCP/HCO data.
[0027] The data elements may be database normalized with auxiliary tables that constrain the types and sources to preset data. The data elements may be preprocessed such that components of the data are stored and are readily available. For example, in the case of addresses, the address may be geocoded and parsed into elements (number, pre-directional, street, suffix, post-directional, secondary-unit, and secondary-number). These components may be used on an item by item basis to match records using a chi-squared statistic target function. The location and address elements may then used to calculate the probability that two records are the same or strongly linked The data may be stored with permissions such that public data, client private data and licensed data may be housed together, but upon retrieval the data is filtered based on the subscriber's permissions, thereby ensuring the security of restricted or private data.
[0028] The name, address and identifier data may be treated as separate components for the search system build to provide fast approximate string searches. The database may support individual component searches as well as general searches in which the union of orthogonal searches is scored, ordered and returned to a requesting application. This is a unique approach for the database as well as searching as the typical approach is to have the name, address, identifier information in a single record that, by the nature of the table, limits the number of elements that may be grouped and/or aggregated together. An example of such is the NPI data base that uses a single key (NPI Number) to store a fixed number of elements tightly linked Associations between records or additions (noting source, time, and permissions) are not allowed in such a design. Since the components are separated into different tables and preprocessed with additional computational based information, the data is readily available for loading and searching in the database as taught herein. Like above, access permissions for the elements are controlled by the subscriber's permission in conjunction with the data type permissions. In this way, contributed license data as well as privileged firm data may be stored securely and accessed as a single data set.
[0029] For searching the database, an approximate string searching system may utilize string metric functions (e.g., edit distance norm/Levenstein, Jaccard, Dice and other similar functions) for comparisons to indexed data in an inverted list data structure to afford O(NlogN) search times on large (more than ten million string elements). The searching system may be parallelized to facilitate the search in which the data is first partitioned into sizes suitable based on the number of processors available on the machine. The system may separate the search and extraction subsystems such that search results may be supplemented with additional data and secondary searches can be constructed from preliminary results. The results may be scored using a chi-squared functional form utilizing the query elements on a pair-wise comparison. The confidence of the match may then have a robust statistic (chi-squared probability based on degrees of freedom) to measure the confidence in the match which in general will be comprised of elements of names, addresses and identifiers.
[0030] The CIR 2 US ® database as described herein is provided by way of example only. The data aggregation and premium access techniques as discussed herein may be applied to any database or data structure including data sets accessible by subscribers via public or private access.
[0031] Within the database, each entity may have a key master record that identifies and describes the entity, along with child records as contributed by each subscriber and source that further identifies various names, addresses, license data, credentials, specialties, and affiliations that are associated with the entity. As the number of subscribers and sources to the database increases, the quality and accuracy of the data may also increases. While any one subscriber's data may be questionable for a specific entity, the presence of the exact same data for that entity as provided by one or more other subscribers and sources may validate the accuracy of the data. In other words, the process validates the quality of the data through public input.
[0032] FIG. 2 illustrates a block diagram of a system 200 , the system including a server 202 (e.g., SharePoint® server 112 as shown in FIG. 1 ) accessing a database system 203 including a database 214 for providing access to an aggregated data set. A customer computing device, including a client application, may be operably connected to the server 202 , instructing the server to establish a connection with the database system 203 . The server 202 may initiate an instance of a server-side application 204 configured to establish an operable connection to and communicate with the database system 203 . It should be noted that while a direct connection is shown in FIG. 2 between the customer computing device 202 and the database system 203 , this is shown by way of example only. A direct connection (e.g., via a local intranet) or an indirect connection (e.g., the connection as shown in FIG. 1 via Internet 114 ) maybe used.
[0033] The server-side application 204 may access a local instance of a database application programming interface (API) 206 . For example, if the database 214 is a CIR 2 US® database as described above, the server-side application 204 may access a local instance of a CIR 2 US® API. Via the local instance of the database API 206 , the server-side application 204 may access a local instance of the database search service 208 . The local instance of the database search service 208 may have limited functionality and be configured to provide limited services such as general search (e.g., name, address, identifier searching) as well as access to the client's data.
[0034] In addition to the database 214 , the database system 203 may include an instance of the database API 210 as well as a database search application 212 . The database search application 212 may include additional functionality not available to the local instance of the database search service, such as access to master, inclusion and licensed data. In order to access this information, the client computing device 202 may require various credentials or authorization which is verified by the database search application prior to returning any private or licensed information.
[0035] The identity of each subscriber (i.e., each user of a client computing device operably connected to server 202 ) may be masked to other subscribers within the database so as to maintain the privacy of each subscriber, only the details of each entity are shared or used for validation. Other subscribers can see various levels of entity detail based on their subscription level, but cannot see which other subscriber(s) has provided the data.
[0036] FIG. 3 illustrates an example of a process for creating and updating the data stored within a database such as database 214 . Initially, the database may be created 302 to create each entity stored within the database. Each entity may have a master record that identifies and describes the entity, along with child records as contributed by each subscriber and source that further identifies various names, license data, credentials, specialties, and affiliations that are associated with the entity. The database may be created 302 as a combination of public available information as well as information available from private sources. The private sources may provide premium data that is integrated into the database such that it is available via a premium channel having a separate subscription level. The database system may be designed and engineered to accept the data from independent and distinct sources, and to provide varying security and subscription levels for the data.
[0037] Data provided by a subscriber, or received from a private or public data set, may be parsed 304 so that the data can be translated 306 into its native format and content. The translated data may then be mapped 308 into a proper database table and/or field.
[0038] Each of the data tables may be configured 310 to identify one or more premium data sources for accessing the data stored therein, as well as mapped 312 to licensing information and credentials for each customer/user in the system. As a user becomes licensed or subscribes to particular content, the mapping 312 information may be updated to reflect the changes, thereby providing the user with the appropriate access based upon their subscription level to one or more premium access channels, in which access to a higher number of premium channels may be available to customers having a higher subscription level. In particular, the database may be configured to recognize a user with a set of credentials along with a subscription level that is capable of relating what level or subscription data a customer is licensed for. Similarly, the data tables may include this security and licensing information such that, when a user connects to the database, only the data for which they are subscribed is available. Search results may be filtered or otherwise examined such that only appropriate data is delivered to a subscriber.
[0039] Various web services such as a database API may be created 314 for one or more subscribers, the APIs configured to provide customers access to the data from the customers' computing devices.
[0040] The process as shown in steps 304 - 314 may be repeated for each data source or subscriber. As each source is included in the database, the data is aggregated to improve the reliability of the data, thus increasing the ease of implementation of the database while maintaining a high level of data reliance. As additional data is integrated and aggregated into the database, the various premium access subscription channels may be updated accordingly to provide the appropriate customers with access to the newly aggregated data.
[0041] When data is entered into the system by a subscriber, it is tagged with attributes as to how the data is entered, for example, by form based input or by GPS location. Geo tagging the data may also help to increase the accuracy and validity of the data as it confirms an actual location for the entity.
[0042] Optionally, a subscriber may choose to participate at a private data level, whereby all of their data remains completely private and its presence is unknown to other subscribers in the system. A private subscriber may not see any data from any other subscriber and only has access to their data plus public data provided by the database system. Alternatively, a subscriber may opt to access varying levels of the data based upon a premium channel subscription service. For example, there may be various levels of subscription service, where the highest subscription level provides a customer with access to all of the premium channels, and lesser subscription levels results in access to a portion of the premium access channels.
[0043] FIG. 4 depicts a flow chart of an example procedure for accessing and searching a database by a customer. A customer's specific access to the data contained within the database is dependent upon the type of data licensed by the customer, along with their subscription level, i.e., private or public. The customer may access 402 the database system (for example, via server 202 as shown in FIG. 2 ) using their login credentials, e.g., a username and password combination. The database system verifies the customer's login credentials and, if correct, provides the customer access 402 to the system.
[0044] To initially access 402 the system, the user may obtain a license to at least a portion of the data as well as the associated security credentials. Once a customer has a license, a database deployment or development team may update or otherwise configure to the database with the proper credentials and enable the customer's subscriptions such that the customer can access the data they have licensed via a client application configured to connect to an instance of the database API. For example, if a customer licenses access to the CIR 2 US® database as discussed above, the customer's RADS® application may update to provide the customer access to their licensed data. The customer may then user their RADS® application to access the database.
[0045] After accessing 402 the database system, the customer may access and/or search 404 the data. The system may return and filter 406 the customer's search results according to the license and credentials associated with the customer. For example, the customer may have a private or public license. If the customer has a public credential, the database system may filter 406 the search results such that the customer receives a set of universal/public data. If the customer has a private credential, the database system may filter 406 the search results such that the customer receives their own private data. Additionally, the customer may have previously subscribed to one or more premium channels. During the filtering 406 , the database system may determine 408 which premium access channels the customer has access to and filter the search results accordingly.
[0046] After the data is filtered 406 appropriately for the requesting customer, the search results may be returned 410 to the customer for review.
[0047] FIG. 5 depicts a block diagram of internal hardware that may be used to contain or implement the various computer processes and systems as discussed above. An electrical bus 500 serves as the main information highway interconnecting the other illustrated components of the hardware. CPU 505 is the central processing unit of the system, performing calculations and logic operations required to execute a program. CPU 505 , alone or in conjunction with one or more of the other elements disclosed in FIG. 5 , is a processing device, computing device or processor as such terms are used within this disclosure. Read only memory (ROM) 510 and random access memory (RAM) 515 constitute examples of memory devices.
[0048] A controller 520 interfaces with one or more optional memory devices 525 to the system bus 500 . These memory devices 525 may include, for example, an external or internal DVD drive, a CD ROM drive, a hard drive, flash memory, a USB drive or the like. As indicated previously, these various drives and controllers are optional devices. Additionally, the memory devices 525 may be configured to include individual files for storing any software modules or instructions, auxiliary data, incident data, common files for storing groups of contingency tables and/or regression models, or one or more databases for storing the information as discussed above.
[0049] Program instructions, software or interactive modules for performing any of the functional steps associated with the processes as described above may be stored in the ROM 510 and/or the RAM 515 . Optionally, the program instructions may be stored on a tangible computer readable medium such as a compact disk, a digital disk, flash memory, a memory card, a USB drive, an optical disc storage medium, such as a Blu-ray™ disc, a distributed computer storage platform such as a cloud-based architecture, and/or other recording medium.
[0050] An optional display interface 530 may permit information from the bus 500 to be displayed on the display 535 in audio, visual, graphic or alphanumeric format. Communication with external devices may occur using various communication ports 540 . A communication port 540 may be attached to a communications network, such as the Internet or a local area network.
[0051] The hardware may also include an interface 545 which allows for receipt of data from input devices such as a keyboard 550 or other input device 555 such as a mouse, a joystick, a touch screen, a remote control, a pointing device, a video input device and/or an audio input device.
[0052] The present invention as discussed herein provides a single source data provider having a homogenized and blended data set created from data obtained from all providers, including premium data providers and sources, so as to be accessible in a common format and content while maintaining a high level of reliability. Flexible, source independent data tables and data structures, along with a powerful search engine that examines all data as a single data source for presentation to a customer, results in powerful and efficient flexible searching.
[0053] It should be noted the above examples and disclosure is directed to healthcare related data by way of example only and the ideas taught herein may be applied to any data sets. For example, data sets related to transportation, law, sports, and other similar topics may benefit from the aggregation and premium access techniques as taught herein to improve the reliability of the data.
[0054] Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It is therefore to be understood that numerous modifications may be made to the illustrative embodiments and that other arrangements may be devised without departing from the spirit and scope of the present invention as defined by the appended claims. | A method and system for providing access to aggregated data sets. The method includes organizing a plurality of data sets into an aggregated data set, providing access to at least a portion of the aggregated data set based upon a subscription level associated with a user, receiving a search query from the user to search the aggregated data, determining which portions of the aggregated data set the user can access based upon the subscription level of the user, filtering a set of search results based upon the determination of which portions of the aggregated data set the user can access, and returning the filtered search results to the user. The system includes various components for performing the method. | 6 |
REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of U.S. patent application Ser. No. 11/321,624, filed Dec. 29, 2005, which relies upon U.S. Provisional Application No. 60/642,057, filed Jan. 3, 2005, and is a continuation-in-part to U.S. patent application Ser. No. 10/810,751, filed Mar. 26, 2004, which is a continuation-in-part to U.S. patent application Ser. No. 10/603,006, filed Jun. 23, 2003, which is a continuation-in-part to U.S. patent application Ser. No. 10/348,231, filed Jan. 21, 2003, now U.S. Pat. No. 7,009,040 (including U.S. divisional application Ser. No. 10/891,866, filed Jul. 15, 2004), and is a continuation-in-part to U.S. patent application Ser. No. 09/727,361, filed Nov. 29, 2000, now U.S. Pat. No. 6,657,048 issued Dec. 2, 2003 (including U.S. divisional application Ser. No. 10/713,642, filed Nov. 13, 2003), the contents of each of which are herein incorporated by reference.
FIELD OF THE INVENTION
This invention relates to the diagnosis and treatment of cancerous diseases, particularly to the mediation of cytotoxicity of tumor cells; and most particularly to the use of cancerous disease modifying antibodies (CDMAB), optionally in combination with one or more chemotherapeutic agents, as a means for initiating the cytotoxic response. The invention further relates to binding assays, which utilize the CDMAB of the instant invention
BACKGROUND OF THE INVENTION
CD63 in Cancer: CD63 is a Type III membrane protein of the tetraspanin family whose 20 current members are characterized by the presence of four transmembrane segments. Several groups independently identified CD63, using antibodies raised to whole cell preparations of activated platelets, granulocytes, and melanoma cells. Cloning of the respective cDNAs of their cognate glycoprotein antigens led to the recognition that the different antigens were one and the same molecule. The Sixth International Workshop on Leukocyte Typing (1996) subsequently categorized these antibodies as CD63 antibodies. Prior to the 1996 Workshop, CD63 was known by multiple names (melanoma 1 antigen, ocular melanoma-associated antigen, melanoma associated antigen ME491, lysosome-associated membrane glycoprotein 3, granulophysin, melanoma-associated antigen MLA1), which were sometimes related to the antibodies that led to its partial characterization and identification. Thus, CD63 was also designated as antigen ME491 (MAb ME491), neuroglandular antigen (MAbs LS59, LS62, LS76, LS113, LS140 and LS152), Pltgp40 (MAbs H5C6, H4F8 and H5D2), human bone marrow stromal cell antigen (MAb 12F 12), osteoprogenitor-specific marker (MAb HOP-26), and integrin-associated protein (MAb 6H1). Other antibodies that were found to cross react with human CD63 were 8-1H, 8-2A (cross-reactivity with ME491), NKI/C-3 and NKI/black-13 (Vannegoor and Rumke, 1986; Demetrick et al., 1992; Wang et al., 1992).
CD63 was initially cloned from a melanoma cDNA library using MAb ME491, one of a number of antibodies raised against a preparation of human melanoma cells. It was shown that the reactivity of MAb ME491 appeared to be inversely correlated with melanoma progression in a study of human melanoma biopsies. The reactivity of the ME491 antibody was low in normal melanocytes, higher in the early stages of melanoma progression (dysplastic nevi and radial growth phase (RGP) tumors) and decreased or even absent in more advanced melanoma tumors such as those in the vertical growth phase (VGP) and in metastatic tumors.
CD63 was also found and partially characterized in human platelets using MAb 2.28 (raised against activated platelets) that detected an activation-dependent platelet membrane 53 kDa glycoprotein. This molecule was also associated with the membrane of internal granules in unstimulated platelets. In the same study MAb 2.28 also labelled internal granules in megakaryocytes and endothelial cells, where it co-localized with antibodies to the enzyme cathepsin D, a known marker of lysosomal compartments. Follow up studies with antibody clustering and expression cloning, led to the identification of the antigen recognized by this antibody as CD63, and further confirmed its presence in lysosomal compartments, where it co-localized with the compartment-specific markers LAMP-1 and LAMP-2. Cloning of this molecule identified it as CD63 and allowed its inclusion in the tetraspanin family.
Expression of CD63 was detected in many different tissues and cell types. At the cellular level it was found to be associated with the plasma membrane and also with intracellular late endosomal vesicular structures. Cell activation led, in certain cases, to increased surface expression by mobilization of intracellular stores of CD63. CD63 was also found to co-localize, and physically associate, with MHC class II in B-lymphocytes, particularly in endosomes, in exosomes involved in exporting MHC class II complexes to the surface, and in secreted vesicles. CD63 was found to interact with other members of the tetraspanin family, such as CD9, CD81, CD11 (integrin chain α M,L,X ), CD18 (integrin chain β 2 ), CD49c (VLA-3 or integrin chain α 3 ), CD49d (integrin chain α 4 ), CD49f (VLA-6 or integrin chain α 6 ) and CD29 (integrin chain β 1 ), in a variety of cell types including B- and T-lymphocytes, neutrophils, breast cancer and melanoma cells.
The role of CD63 in cancer has been unclear. Although CD63 was initially discovered by several independent groups to be involved in diverse events such as platelet and granulocyte activation, MHC class II-dependent antigen presentation, integrin-dependent cell adhesion and motility, and tumor progression in certain types of cancers, its function has yet to be fully elucidated. Even though current evidence supports its role in a variety of cellular physiological events, it is not clear if these functions are independent of each other or if there is an underlying common cellular mechanism in which CD63 is involved.
Several groups have investigated the association between CD63 and the progression of certain types of tumors, particularly melanomas. A number of other anti-CD63 monoclonal antibodies, in addition to Mab ME491, were developed for immunohistochemical (IHC) staining of cancer samples obtained from patients with tumors at various stages of progression. It was observed that decreased staining, interpreted by the authors as most likely reflecting decreased expression of CD63, correlated with advanced progression and with metastatic characteristics of the tumors. A more recent study, also described a significant correlation between the apparent decreased expression levels (after quantitation of mRNA) of several members of the tetraspanin protein family, including CD63, and the in vitro invasiveness of several mammary carcinoma-derived cell lines. Another study identified CD63, by differential display, in cultured breast cancer cells subjected to estrogen deprivation. This indicated that CD63 expression can be steroid-hormone regulated and that altered CD63 abundance and/or function might also be associated with breast tumor progression.
By contrast, work with anti-CD63 monoclonal antibody MAb FC-5.01 revealed that its reactive epitope was variably expressed in different normal tissues. Although this antibody was found to recognize CD63, it did not distinguish between early and more advanced stage melanomas, including metastatic melanomas (unlike MAb ME491), which suggested that the CD63 antigen was present in these more advanced tumors, but that some of its epitopes may have been masked in the cells from tumors at different stages. This might have been due to altered post-translational modifications of the core CD63 polypeptide, or to the interaction of CD63 with other molecules, which might have affected the availability of specific epitopes for antibody recognition and binding. These results supported the observation, described by Si and Hersey (1993), that staining with the anti-CD63 MAb NKI-C3, did not distinguish between tissue sections from melanomas at different stages of progression, such as primary, radial growth phase, vertical growth phase, and metastatic melanomas. Although in other studies (Adachi et al., 1998; Huang et al., 1998) analysis of mRNA from breast, and from non-small-cell lung cancers, by quantitative PCR, revealed that for two tetraspanin family members (CD9 and CD82) there was a significant correlation between their expression levels and tumor progression and patient prognosis, no such correlation was found for CD63, in that its expression was similar in all the samples. As a result of these, apparently conflicting, results, there is lack of strong and consistent data that would definitively demonstrate the association of CD63 with cancer.
To date very few in vivo studies have attempted to establish a link between CD63 and an eventual tumor suppressor function of this molecule. In one of these studies, human CD63-overexpressing H-ras-transformed NIH-3T3 cells, injected both subcutaneously and intraperitoneally into athymic mice, revealed a decreased malignant/tumorigenic phenotype, as indicated by decreased tumor size and metastatic potential as well as by increased survival time, when compared to the behavior of the parental non-CD63-overexpressing cells. This suggested that the presence of human CD63 in the transformed cells might suppress their malignant behavior. More recently, work with a transgenic mouse model expressing human CD63, and developed to induce tolerance to CD63, indicated that tumor growth of an injected human CD63-MHC class I (H-2K b ) co-transfected murine melanoma cell line could be inhibited, and survival increased, upon immunization with human CD63 fused to vaccinia virus. It was suggested by the authors that the therapeutic effect was T-lymphocyte dependent, and that endogenous anti-CD63 antibodies did not appear to be involved in this protective effect, since tumor growth inhibition only occurred when animals were injected with the CD63-MHC class I co-transfected cells and not with the CD63-only transfected cell line. This interpretation was supported by the fact that in wild type animals, pre-immunized with purified human CD63 and shown to have developed anti-human CD63 antibodies, there was no protective effect against tumor cell growth. Work described by Radford et al. (1995) using the KM3 cell line, initially thought to be of human origin but later characterized as being of rat lineage, transfected with human CD63, suggested that expression of this protein decreased the growth and metastastic potential of these cells, relative to that observed using the parental non-transfected KM3 cells, when injected intradermally into athymic mice, although there was no significant difference between the in vitro growth rates of the various transfected and non-transfected cell lines. These observations distinguished the potential effect of CD63 from that of other tumor suppressor genes known to affect both the in vivo and the in vitro growth rates of tumor cells. Furthermore, addition of the anti-CD63 monoclonal antibody ME491, which was found to have a functional effect on the same cells by decreasing their random motility in an in vitro assay (Radford et al., 1997), did not impact their in vitro growth rates.
This study also described the observation that CD63 may promote migration in response to extracellular matrix (ECM)-derived chemoattractants, such as laminin, fibronectin, collagen and vitronectin, and that this effect may be mediated by the functional involvement of β 1 -type integrins, although antibodies to the integrins were unable to block these effects. However, there appeared to be an antagonistic effect between the role of vitronectin-mediated signaling (a known ligand for the integrin α v β 5 ) and that of the signaling mediated by other ECM components such as fibronectin, laminin and collagen on CD63 transfected cells. This suggested that under specific conditions, in the presence of ECM components, expression of CD63 may lead to decreased migration, and that this may be dependent on a fine balance between adhesion and motility. In another study, an anti-CD63 monoclonal antibody (MAb 710F) enhanced the adhesion and spreading of PMA-treated HL-60 cells, while another anti-CD63 monoclonal antibody (MAb 2.28), promoted a similar effect, but only on a much smaller fraction of the cell population, and only when added in much larger amounts. These results showed that although many antibodies to CD63 have been developed, their functional effects can be quite different.
Tetraspanins may also be involved in cell proliferation. Oren et al. (1990) described anti-proliferative effects of the murine MAb 5A6, that recognizes CD81 (TAPA-1), on lymphoma cell lines. In another study, ligation of CD37 in human T-lymphocytes with antibodies blocked CD37-induced proliferation. More recently, a study with an animal model deficient in the expression of CD37 (CD37 knockout) revealed that T lymphocytes from this animal were hyperproliferative compared to those from wild type animals in response to concanavalin A activation and CD3/T cell receptor engagement. It was therefore proposed that a functional role in cell growth and proliferation might be a common feature of the tetraspanin family. Recent studies with hepatoblastoma and hepatocellular carcinoma cells revealed that engagement of these cells with anti-CD81 monoclonal antibodies led to activation of the Erk/MAP kinase pathway. This signaling pathway has been shown to be involved with cell growth and proliferation events. In parallel work, transfected cell lines overexpressing human CD81 displayed increased proliferation relative to the mock-transfected control cells. Therefore, available evidence has pointed to a role of the tetraspanins in general, and of CD63 in particular, in events associated with cell growth proliferation and with cell adhesion/motility. These two types of cellular events are currently the target of intense research as both play a central role in tumor progression and metastasis.
Until now, no anti-CD63 antibodies, or other reagents that specifically targeted CD63-expressing cells, were reported and shown to have a simultaneous impact on the in vitro and on the in vivo growth characteristics of tumor cells, and also on the survival time of animal models of tumor cell growth.
Amino acid sequence determination and analysis did not reveal homology between tetraspanins and other protein families, or with any previously characterized functional modules, nor has it suggested any previously known enzymatic activity. As a result it has been very difficult to investigate the role of this family of proteins in the modulation of signal transduction pathways. However, the evidence generated using tetraspanin-specific reagents that led to changes in cellular physiology, and which were intimately dependent on the modulation of signal transduction pathways, suggests that tetraspanins have signal transduction properties. CD63 was shown to associate, both physically and functionally, with a number of molecules that are themselves either enzymes involved in the generation of secondary messenger signals, or are associated physically and/or functionally with such enzymes.
Experiments designed to dissect the mechanism controlling the interaction of human neutrophils with endothelial cells, which is one of the initial steps of the inflammatory response, revealed that pre-treatment of neutrophils with several anti-CD63 monoclonal antibodies (AHN-16, AHN-16.1, AHN-16.2, AHN-16.3 and AHN-16-5) promoted their adhesion to cultured endothelial cell layers. Furthermore this effect was strongly dependent on the presence of calcium ion (Ca 2+ ), a well-known modulator of many intracellular signaling pathways and which was restricted to a specific period of time during which the cells were exposed to the stimulating antibodies. After longer exposure to the antibody, adhesion of the neutrophils to the endothelial cells became insensitive to the later addition of Ca 2+ , therefore implicating a dynamic and temporally regulated (transitory) event. In addition, CD63 was found to physically interact with the CD11/CD18 protein complex, and reagents that specifically targeted this complex mediated a modulatory signal. In this study CD63 was also found to be physically associated with, or to be part of, a complex that included the enzyme tyrosine kinases Lck and Hck. These enzymes are members of a class of proteins that play a central role in mediating intracellular regulatory signals upon activation of specific surface receptors and are part of cascades of signaling pathways that result in cell-specific physiological changes. Another study suggested that co-ligation of tetraspanins (including CD63) with monoclonal antibodies could enhance the phosphorylation or activity of the enzyme focal adhesion kinase (FAK) that was induced by adhesion of MDA-MB-231 breast cancer cells to collagen substrate. This pointed to a direct involvement of CD63 (and of other tetraspanin family members) in the modulation of integrin-mediated tyrosine kinase signaling pathways. Other signaling pathways that may functionally intersect with the presence and ligation of surface CD63 by the anti-CD63 monoclonal antibody MAb 710F appear to be those dependent on modulation of phosphorylation by the enzyme protein kinase C (PKC), another well known modulator of intracellular signaling pathways. In this context, enhancement of adhesion and of morphological changes in the myeloid cell line HL-60 by MAb 710F was dependent on pre-treatment of the cells with phorbol myristate acetate (PMA) although the temporal involvement of PKC was not conclusively demonstrated. However, later work by an independent group demonstrated that PMA-induced HL-60 differentiation was PKC-activity dependent since the molecule Ro31-8220, a specific inhibitor of this enzyme, blocked the effect of PMA.
Further evidence supporting the association of CD63, and other tetraspanin family members, with signal transduction pathways, arose from work that described a physical association, either direct or as part of a supramolecular complex, between CD63 (and also CD53) molecules with tyrosine phosphatase activity. In this study, immunoprecipitate complexes isolated with anti-CD63 antibodies were shown to be associated with tyrosine phosphatase activity, although unlike for CD53, which was shown to associate with the tyrosine phosphatase CD45, it was not possible to identify the CD63-associated phosphatase. More recently several members of the tetraspanin family were also found to be associated with a type II phosphatidylinositol 4-kinase (type II PI 4-K) (Berditchevski et al., 1997). This interaction appeared to be very specific since it was only identified for CD9, CD63, CD81, CD151 and A15/TALLA, and it was not observed to occur with CD37, CD52, CD82, or NAG-2. In addition, the association between tetraspanin family members and PI-4K was mutually exclusive since each PI-4 kinase-containing complex was limited to a single tetraspanin family member. CD63-PI-4 kinase complexes, in particular, were found, almost entirely, in intracellular compartments in lipid raft-like domains, unlike those formed with the other tetraspanin members. This observation suggested that this CD63 fraction, found to interact with the PI-4 kinase, might have been involved in specific intracellular events (Claas, C, et al., 2001) related to, or dependent from, phosphoinositide biosynthesis pathways, which are well known for their involvement in the regulation of membrane trafficking (endocytosis and exocytosis) and of cytoskeleton reorganization, in addition to their function as secondary messenger molecules (Martin, T., 1998).
The direct and important involvement of all the enzymes, that CD63 was found until now to be directly associated with, in the regulation of signaling pathways provided further evidence in support of the association of CD63 with the modulation of signal transduction pathways, either as a regulator or as an effector molecule downstream from the activity of these enzymes.
Elucidation of the mechanisms that lead to tumor progression is a very difficult and complex endeavor frequently marked by apparently contradictory observations and, as a result, it rare that those observations successfully translate into effective therapies. In view of what is currently known about the association of CD63 with tumor progression and metastasis and with signal transduction mechanisms, it is possible that its function may be altered, in tumor cells.
Development of antigen-specific reagents with cytotoxic effects on tumor cells, that bind cells expressing the recognized antigen(s) and which by themselves, or associated with other molecules, have cellular and in vivo physiological activity such that these reagents inhibit tumor cell growth, progression and metastasis, without significant deleterious effects on normal cell populations, would be extremely beneficial as a potential therapeutic and or diagnostic tool.
Monoclonal Antibodies as Cancer Therapy: Each individual who presents with cancer is unique and has a cancer that is as different from other cancers as that person's identity. Despite this, current therapy treats all patients with the same type of cancer, at the same stage, in the same way. At least 30% of these patients will fail the first line therapy, thus leading to further rounds of treatment and the increased probability of treatment failure, metastases, and ultimately, death. A superior approach to treatment would be the customization of therapy for the particular individual. The only current therapy which lends itself to customization is surgery. Chemotherapy and radiation treatment cannot be tailored to the patient, and surgery by itself, in most cases is inadequate for producing cures.
With the advent of monoclonal antibodies, the possibility of developing methods for customized therapy became more realistic since each antibody can be directed to a single epitope. Furthermore, it is possible to produce a combination of antibodies that are directed to the constellation of epitopes that uniquely define a particular individual's tumor.
Having recognized that a significant difference between cancerous and normal cells is that cancerous cells contain antigens that are specific to transformed cells, the scientific community has long held that monoclonal antibodies can be designed to specifically target transformed cells by binding specifically to these cancer antigens; thus giving rise to the belief that monoclonal antibodies can serve as “Magic Bullets” to eliminate cancer cells. However, it is now widely recognized that no single monoclonal antibody can serve in all instances of cancer, and that monoclonal antibodies can be deployed, as a class, as targeted cancer treatments. Monoclonal antibodies isolated in accordance with the teachings of the instantly disclosed invention have been shown to modify the cancerous disease process in a manner which is beneficial to the patient, for example by reducing the tumor burden, and will variously be referred to herein as cancerous disease modifying antibodies (CDMAB) or “anti-cancer” antibodies.
At the present time, the cancer patient usually has few options of treatment. The regimented approach to cancer therapy has produced improvements in global survival and morbidity rates. However, to the particular individual, these improved statistics do not necessarily correlate with an improvement in their personal situation.
Thus, if a methodology was put forth which enabled the practitioner to treat each tumor independently of other patients in the same cohort, this would permit the unique approach of tailoring therapy to just that one person. Such a course of therapy would, ideally, increase the rate of cures, and produce better outcomes, thereby satisfying a long-felt need.
Historically, the use of polyclonal antibodies has been used with limited success in the treatment of human cancers. Lymphomas and leukemias have been treated with human plasma, but there were few prolonged remission or responses. Furthermore, there was a lack of reproducibility and there was no additional benefit compared to chemotherapy. Solid tumors such as breast cancers, melanomas and renal cell carcinomas have also been treated with human blood, chimpanzee serum, human plasma and horse serum with correspondingly unpredictable and ineffective results.
There have been many clinical trials of monoclonal antibodies for solid tumors. In the 1980s there were at least four clinical trials for human breast cancer which produced only one responder from at least 47 patients using antibodies against specific antigens or based on tissue selectivity. It was not until 1998 that there was a successful clinical trial using a humanized anti-Her2/neu antibody (Herceptin®) in combination with Cisplatin. In this trial 37 patients were assessed for responses of which about a quarter had a partial response rate and an additional quarter had minor or stable disease progression. The median time to progression among the responders was 8.4 months with median response duration of 5.3 months.
Herceptin® was approved in 1998 for first line use in combination with Taxol®. Clinical study results showed an increase in the median time to disease progression for those who received antibody therapy plus Taxol® (6.9 months) in comparison to the group that received Taxol® alone (3.0 months). There was also a slight increase in median survival; 22 versus 18 months for the Herceptin® plus Taxol® treatment arm versus the Taxol® treatment alone arm. In addition, there was an increase in the number of both complete (8 versus 2 percent) and partial responders (34 versus 15 percent) in the antibody plus Taxol® combination group in comparison to Taxol® alone. However, treatment with Herceptin® and Taxol® led to a higher incidence of cardiotoxicity in comparison to Taxol® treatment alone (13 versus 1 percent respectively). Also, Herceptin® therapy was only effective for patients who over express (as determined through immunohistochemistry (IHC) analysis) the human epidermal growth factor receptor 2 (Her2/neu), a receptor, which currently has no known function or biologically important ligand; approximately 25 percent of patients who have metastatic breast cancer. Therefore, there is still a large unmet need for patients with breast cancer. Even those who can benefit from Herceptin® treatment would still require chemotherapy and consequently would still have to deal with, at least to some degree, the side effects of this kind of treatment.
The clinical trials investigating colorectal cancer involve antibodies against both glycoprotein and glycolipid targets. Antibodies such as 17-1A, which has some specificity for adenocarcinomas, has undergone Phase 2 clinical trials in over 60 patients with only 1 patient having a partial response. In other trials, use of 17-1A produced only 1 complete response and 2 minor responses among 52 patients in protocols using additional cyclophosphamide. To date, Phase III clinical trials of 17-1A have not demonstrated improved efficacy as adjuvant therapy for stage III colon cancer. The use of a humanized murine monoclonal antibody initially approved for imaging also did not produce tumor regression.
Only recently have there been any positive results from colorectal cancer clinical studies with the use of monoclonal antibodies. In 2004, ERBITUX® was approved for the second line treatment of patients with EGFR-expressing metastatic colorectal cancer who are refractory to irinotecan-based chemotherapy. Results from both a two-arm Phase II clinical study and a single arm study showed that ERBITUX® in combination with irinotecan had a response rate of 23 and 15 percent respectively with a median time to disease progression of 4.1 and 6.5 months respectively. Results from the same two-arm Phase II clinical study and another single arm study showed that treatment with ERBITUX® alone resulted in an 11 and 9 percent response rate respectively with a median time to disease progression of 1.5 and 4.2 months respectively.
Consequently in both Switzerland and the United States, ERBITUX® treatment in combination with irinotecan, and in the United States, ERBITUX® treatment alone, has been approved as a second line treatment of colon cancer patients who have failed first line irinotecan therapy. Therefore, like Herceptin®, treatment in Switzerland is only approved as a combination of monoclonal antibody and chemotherapy. In addition, treatment in both Switzerland and the US is only approved for patients as a second line therapy. Also, in 2004, AVASTIN® was approved for use in combination with intravenous 5-fluorouracil-based chemotherapy as a first line treatment of metastatic colorectal cancer. Phase III clinical study results demonstrated a prolongation in the median survival of patients treated with AVASTIN® plus 5-fluorouracil compared to patients treated with 5-fluourouracil alone (20 months versus 16 months respectively). However, again like Herceptin® and ERBITUX®, treatment is only approved as a combination of monoclonal antibody and chemotherapy.
There also continues to be poor results for lung, brain, ovarian, pancreatic, prostate, and stomach cancer. The most promising recent results for non-small cell lung cancer came from a Phase II clinical trial where treatment involved a monoclonal antibody (SGN-15; dox-BR96, anti-Sialyl-LeX) conjugated to the cell-killing drug doxorubicin in combination with the chemotherapeutic agent Taxotere. Taxotere is the only FDA approved chemotherapy for the second line treatment of lung cancer. Initial data indicate an improved overall survival compared to Taxotere alone. Out of the 62 patients who were recruited for the study, two-thirds received SGN-15 in combination with Taxotere while the remaining one-third received Taxotere alone. For the patients receiving SGN-15 in combination with Taxotere, median overall survival was 7.3 months in comparison to 5.9 months for patients receiving Taxotere alone. Overall survival at 1 year and 18 months was 29 and 18 percent respectively for patients receiving SNG-15 plus Taxotere compared to 24 and 8 percent respectively for patients receiving Taxotere alone. Further clinical trials are planned.
Preclinically, there has been some limited success in the use of monoclonal antibodies for melanoma. Very few of these antibodies have reached clinical trials and to date none have been approved or demonstrated favorable results in Phase III clinical trials.
The discovery of new drugs to treat disease is hindered by the lack of identification of relevant targets among the products of 30,000 known genes that unambiguously contribute to disease pathogenesis. In oncology research, potential drug targets are often selected simply due to the fact that they are over-expressed in tumor cells. Targets thus identified are then screened for interaction with a multitude of compounds. In the case of potential antibody therapies, these candidate compounds are usually derived from traditional methods of monoclonal antibody generation according to the fundamental principles laid down by Kohler and Milstein (1975, Nature, 256, 495-497, Kohler and Milstein). Spleen cells are collected from mice immunized with antigen (e.g. whole cells, cell fractions, purified antigen) and fused with immortalized hybridoma partners. The resulting hybridomas are screened and selected for secretion of antibodies which bind most avidly to the target. Many therapeutic and diagnostic antibodies directed against cancer cells, including Herceptin® and RITUXIMAB, have been produced using these methods and selected on the basis of their affinity. The flaws in this strategy are twofold. Firstly, the choice of appropriate targets for therapeutic or diagnostic antibody binding is limited by the paucity of knowledge surrounding tissue specific carcinogenic processes and the resulting simplistic methods, such as selection by overexpression, by which these targets are identified. Secondly, the assumption that the drug molecule that binds to the receptor with the greatest affinity usually has the highest probability for initiating or inhibiting a signal may not always be the case.
Despite some progress with the treatment of breast and colon cancer, the identification and development of efficacious antibody therapies, either as single agents or co-treatments, has been inadequate for all types of cancer.
Prior Patents:
US05296348 teaches methods for selecting monoclonal antibodies specific for cancer cell surface antigens that are internalizing, and for identifying monoclonal antibodies having anti-transcriptional and/or anti-replicational effects on cell metabolism. By way of example the ME491 antibody was shown to internalize in W9, WM35, WM983 melanoma cells, and SW948 colorectal carcinoma cells. In addition ME491 antibody was shown to decrease transcription and cell proliferation in SW948 cells. The patent application US20030211498A1 (and its related applications: WO0175177A3, WO0175177A2, AU0153140A5) allege a method of inhibiting the growth or metastasis of an ovarian tumor with an antibody that binds an ovarian tumor marker polypeptide encoded by an ovarian tumor marker gene selected from among a group that includes CD63 antigen. Serial analysis of gene expression using ovarian cancer was carried out to identify ovarian tumor marker genes which lead to the identification of CD63 as a candidate. The patent application WO02055551A1 (and its related application CN1364803A) alleges a new polypeptide-human CD63 antigen 56.87. The patent application CN1326962A alleges a new polypeptide-human CD63 antigen 14.63. The patent application CN1326951A alleges a new polypeptide-human CD63 antigen 15.07. The patent application CN1351054A alleges a new polypeptide-human CD63 antigen 11.11. These patents and patent applications identify CD63 antigens and antibodies but fail to disclose the isolated monoclonal antibody of the instant invention, or the utility of the isolated monoclonal antibody of the instant invention.
The gene encoding the ME491 polypeptide antigen was cloned and the sequence was received for publication on Feb. 24, 1988 (Can Res 48:2955, 1988, Jun. 1); the gene encoding CD63 was cloned and the sequence published in February 1991 (JBC 266(5):3239-3245, 1991) and the publication clearly indicated the identity of ME491 with CD63.
WO2004041170.89 (Sequence ID No.: 89, priority filing date: 29-Jun.-2004), WO2003068268-A2 (Sequence ID No.: 1, priority filing date: 13-Feb.-2003(2003WO-EP001461); other priority date: 14-Feb.-2002(2002GB-00003480)), WO2003057160-A29 (Sequence ID No.: 40, priority filing date: 30-Dec.-2002(2002WO-US041798); other priority date: 02-Jan.-2002(2002US-0345444P)) all allege polypeptides that have 100% sequence homology to CD63.
WO2003016475-A2(Sequence ID No.: 9787&12101, priority filing date: 14-Aug.-2002 (2002WO-US025765); other priority date: 14-Aug.-2001(2001 US-0312147P) allege polypeptides that have 100% sequence homology with 237 amino acids of 238 amino acids comprising CD63.
WO2003070902-A2(Sequence ID No.:27, priority filing date: 18-Feb.-2003(2003WO-US004902); other priority date: 20-Feb.-2002(2002US-0358279P)) allege polypeptides that have 94% sequence homology with 224 amino acids of 238 amino acids comprising CD63.
EP1033401-A2 (Sequence ID No.: 4168&4913, priority filing date: 21 Feb. 2000(2000EP-00200610); other priority date: 26 Feb. 1999(99US-0122487P)) allege polypeptides that have 100% sequence homology with 205 amino acids and with 94 amino acids of 238 amino acids comprising CD63, respectively.
WO200257303-A2 (Human prey protein for Shigella ospG#26, priority filing date: 11-Jan.-2002(2002WO-EP000777); other priority date: 12-Jan.-2001(2001US-0261130P)) allege polypeptides that have 100% sequence homology with 130 amino acids of 238 amino acids comprising CD63.
WO200055180-A2 (Sequence ID No.: 756, priority filing date: 08-Mar.-2000(2000WO-US005918); other priority date: 12-Mar.-1999(99US-0124270P)) allege polypeptides that have 99% sequence homology with 127 amino acids of 238 amino acids comprising CD63.
WO200200677-A1 (Sequence ID No.:3203, priority filing date: 07-Jun.-2001(2001WO-US018569); other priority date: 07-Jun.-2000(2000US-0209467P)) allege polypeptides that have 97% sequence homology with 132 amino acids of 238 amino acids comprising CD63.
WO9966027-A1 (Large extracellular loop sequence from human CD63 protein, priority filing date: 15-Jun.-1999(99WO-US013480); other priority date: 15-Jun.-1998(98US-0089226P)) allege polypeptides that have 100% sequence homology with 99 amino acids of 238 amino acids comprising CD63.
WO200270539-A2 (Sequence ID No.: 1207, priority filing date: 05-Mar.-2002(2002WO-US005095); other priority date: 05 Mar. 2001(2001US-00799451)) allege polypeptides that have 86% sequence homology with 102 amino acids of 238 amino acids comprising CD63.
EP1033401-A2 (Sequence ID No.: 4169, 21-Feb.-2000(2000EP-00200610); other priority date: 26-Feb.-1999(99US-0122487P)) allege polypeptides that have 100% sequence homology with 74 amino acids of 238 amino acids comprising CD63.
These patent applications identify polypeptides that have varying sequence homology to CD63 antigen. In most cases these application also allege antibodies and anitbody derivatives to the corresponding polypepide and their homologs but fail to disclose the isolated monoclonal antibody of the instant invention, or the utility of the applications monoclonal antibody of the instant invention. Importantly, all the above applications were filed after the publication of the sequence of the polynucleotide encoding CD63.
SUMMARY OF THE INVENTION
The instant inventors have previously been awarded U.S. Pat. No. 6,180,357, entitled “Individualized Patient Specific Anti-Cancer Antibodies” directed to a process for selecting individually customized anti-cancer antibodies which are useful in treating a cancerous disease. It is well recognized in the art that some amino acid sequence can be varied in a polypeptide without significant effect on the structure or function of the protein. In the molecular rearrangement of antibodies, modifications in the nucleic or amino acid sequence of the backbone region can generally be tolerated. These include, but are not limited to, substitutions (preferred are conservative substitutions), deletions or additions. Furthermore, it is within the purview of this invention to conjugate standard chemotherapeutic modalities, e.g. radionuclides, with the CDMAB of the instant invention, thereby focusing the use of said chemotherapeutics. The CDMAB can also be conjugated to toxins, cytotoxic moieties, enzymes e.g. biotin conjugated enzymes, or hematogenous cells, thereby forming an antibody conjugate.
This application utilizes the method for producing patient specific anti-cancer antibodies as taught in the '357 patent for isolating hybridoma cell lines which encode for cancerous disease modifying monoclonal antibodies. These antibodies can be made specifically for one tumor and thus make possible the customization of cancer therapy. Within the context of this application, anti-cancer antibodies having either cell-killing (cytotoxic) or cell-growth inhibiting (cytostatic) properties will hereafter be referred to as cytotoxic. These antibodies can be used in aid of staging and diagnosis of a cancer, and can be used to treat tumor metastases. These antibodies can also be used for the prevention of cancer by way of prophylactic treatment. Unlike antibodies generated according to traditional drug discovery paradigms, antibodies generated in this way may target molecules and pathways not previously shown to be integral to the growth and/or survival of malignant tissue. Furthermore, the binding affinity of these antibodies are suited to requirements for initiation of the cytotoxic events that may not be amenable to stronger affinity interactions.
The prospect of individualized anti-cancer treatment will bring about a change in the way a patient is managed. A likely clinical scenario is that a tumor sample is obtained at the time of presentation, and banked. From this sample, the tumor can be typed from a panel of pre-existing cancerous disease modifying antibodies. The patient will be conventionally staged but the available antibodies can be of use in further staging the patient. The patient can be treated immediately with the existing antibodies, and a panel of antibodies specific to the tumor can be produced either using the methods outlined herein or through the use of phage display libraries in conjunction with the screening methods herein disclosed. All the antibodies generated will be added to the library of anti-cancer antibodies since there is a possibility that other tumors can bear some of the same epitopes as the one that is being treated. The antibodies produced according to this method may be useful to treat cancerous disease in any number of patients who have cancers that bind to these antibodies.
In addition to anti-cancer antibodies, the patient can elect to receive the currently recommended therapies as part of a multi-modal regimen of treatment. The fact that the antibodies isolated via the present methodology are relatively non-toxic to non-cancerous cells allows for combinations of antibodies at high doses to be used, either alone, or in conjunction with conventional therapy. The high therapeutic index will also permit re-treatment on a short time scale that should decrease the likelihood of emergence of treatment resistant cells.
If the patient is refractory to the initial course of therapy or metastases develop, the process of generating specific antibodies to the tumor can be repeated for re-treatment. Furthermore, the anti-cancer antibodies can be conjugated to red blood cells obtained from that patient and re-infused for treatment of metastases. There have been few effective treatments for metastatic cancer and metastases usually portend a poor outcome resulting in death. However, metastatic cancers are usually well vascularized and the delivery of anti-cancer antibodies by red blood cells can have the effect of concentrating the antibodies at the site of the tumor. Even prior to metastases, most cancer cells are dependent on the host's blood supply for their survival and an anti-cancer antibody conjugated to red blood cells can be effective against in situ tumors as well. Alternatively, the antibodies may be conjugated to other hematogenous cells, e.g. lymphocytes, macrophages, monocytes, natural killer cells, etc.
There are five classes of antibodies and each is associated with a function that is conferred by its heavy chain. It is generally thought that cancer cell killing by naked antibodies are mediated either through antibody dependent cellular cytotoxicity or complement dependent cytotoxicity. For example murine IgM and IgG2a antibodies can activate human complement by binding the C1 component of the complement system thereby activating the classical pathway of complement activation which can lead to tumor lysis. For human antibodies the most effective complement activating antibodies are generally IgM and IgG1. Murine antibodies of the IgG2a and IgG3 isotype are effective at recruiting cytotoxic cells that have Fc receptors which will lead to cell killing by monocytes, macrophages, granulocytes and certain lymphocytes. Human antibodies of both the IgG1 and IgG3 isotype mediate ADCC.
Another possible mechanism of antibody mediated cancer killing may be through the use of antibodies that function to catalyze the hydrolysis of various chemical bonds in the cell membrane and its associated glycoproteins or glycolipids, so-called catalytic antibodies.
There are three additional mechanisms of antibody-mediated cancer cell killing. The first is the use of antibodies as a vaccine to induce the body to produce an immune response against the putative antigen that resides on the cancer cell. The second is the use of antibodies to target growth receptors and interfere with their function or to down regulate that receptor so that its function is effectively lost. The third is the effect of such antibodies on direct ligation of cell surface moieties that may lead to direct cell death, such as ligation of death receptors such as TRAIL R1 or TRAIL R2, or integrin molecules such as alpha V beta 3 and the like.
The clinical utility of a cancer drug is based on the benefit of the drug under an acceptable risk profile to the patient. In cancer therapy survival has generally been the most sought after benefit, however there are a number of other well-recognized benefits in addition to prolonging life. These other benefits, where treatment does not adversely affect survival, include symptom palliation, protection against adverse events, prolongation in time to recurrence or disease-free survival, and prolongation in time to progression. These criteria are generally accepted and regulatory bodies such as the U.S. Food and Drug Administration (F.D.A.) approve drugs that produce these benefits (Hirschfeld et al. Critical Reviews in Oncology/Hematolgy 42:137-143 2002). In addition to these criteria it is well recognized that there are other endpoints that may presage these types of benefits. In part, the accelerated approval process granted by the U.S. F.D.A. acknowledges that there are surrogates that will likely predict patient benefit. As of year-end (2003), there have been sixteen drugs approved under this process, and of these, four have gone on to full approval, i.e., follow-up studies have demonstrated direct patient benefit as predicted by surrogate endpoints. One important endpoint for determining drug effects in solid tumors is the assessment of tumor burden by measuring response to treatment (Therasse et al. Journal of the National Cancer Institute 92(3):205-216 2000). The clinical criteria (RECIST criteria) for such evaluation have been promulgated by Response Evaluation Criteria in Solid Tumors Working Group, a group of international experts in cancer. Drugs with a demonstrated effect on tumor burden, as shown by objective responses according to RECIST criteria, in comparison to the appropriate control group tend to, ultimately, produce direct patient benefit. In the pre-clinical setting tumor burden is generally more straightforward to assess and document. In that pre-clinical studies can be translated to the clinical setting, drugs that produce prolonged survival in pre-clinical models have the greatest anticipated clinical utility. Analogous to producing positive responses to clinical treatment, drugs that reduce tumor burden in the pre-clinical setting may also have significant direct impact on the disease. Although prolongation of survival is the most sought after clinical outcome from cancer drug treatment, there are other benefits that have clinical utility and it is clear that tumor burden reduction, which may correlate to a delay in disease progression, extended survival or both, can also lead to direct benefits and have clinical impact (Eckhardt et al. Developmental Therapeutics: Successes and Failures of Clinical Trial Designs of Targeted Compounds; ASCO Educational Book, 39 th Annual Meeting, 2003, pages 209-219).
Using substantially the process of U.S. Pat. No. 6,180,357, and as disclosed in U.S. Pat. No. 6,657,048 and in Ser. No. 10/348,231 and Ser. No. 60/642,057 the contents of each of which are herein incorporated by reference, the mouse monoclonal antibodies, 7BDI-58, 7BDI-60, H460-22-1, 1A245.6 and 7BD-33-11A were obtained following immunization of mice with cells from a patient's lung (H460-22-1) or breast (7BDI-58, 7BDI-60, 7BD-33-11A and 1A245.6) tumor biopsy. The H460-22-1, 1A245.6 and 7BD-33-11A antigen was expressed on the cell surface of a wide range of human cell lines from different tissue origins. The 7BDI-58 and the 7BDI-60 antigen was expressed on the cell surface of breast cancer cells. The breast cancer cell line MDA-MB-231 (MB-231) and the melanoma cell line A2058 were susceptible to the cytotoxic effect of H460-22-1 in vitro. The breast cancer cell line MCF-7 and prostate cancer cell line PC-3 were susceptible to the cytotoxic effects of 1A245.6 and 7BD-33-11A in vitro. The breast cancer cell line Hs574.T was susceptible to the cytotoxic effects of 7BDI-58 and 7BDI-60 in vitro.
The result of H460-22-1 cytotoxicity against breast cancer cells in culture was further extended by its anti-tumor activity towards this cancer indication in vivo (as disclosed in Ser. No. 11/321,624). In the preventative in vivo model of human breast cancer, H460-22-1 was given to mice one day prior to implantation of tumor cells followed by weekly injections for a period of 7 weeks. H460-22-1 treatment was significantly (p<0.0001) more effective in suppressing tumor growth during the treatment period than an isotype control antibody. At the end of the treatment phase, mice given H460-22-1 had tumors that grew to only 17.7 percent of the control group. During the post treatment follow-up period, the treatment effects of H460-22-1 were sustained and the mean tumor volume in the treated group continued to be significantly smaller than controls until the end of the measurement phase.
Using survival as a measure of antibody efficacy, the control group reached 50 percent mortality between day 74-81 post-implantation. In contrast, the H460-22-1 treated group had not reached 50 percent mortality at the time of termination of the study. This difference was significant between H460-22-1 and isotype control treated group (p<0.0015). These data demonstrated that H460-22-1 treatment conferred a survival benefit compared to the control-treated group. H460-22-1 treatment appeared safe, as it did not induce any signs of toxicity, including reduced body weight and clinical distress. Thus, H460-22-1 treatment was efficacious as it both delayed tumor growth and enhanced survival compared to the control-treated group in a well-established model of human breast cancer. These results were also reproducible as similar findings were observed in another study of this kind and suggest its relevance and benefit to treatment of people with cancer.
Besides the preventative in vivo tumor model of breast cancer, H460-22-1 demonstrated anti-tumor activity against MB-231 cells in an established in vivo tumor model (as disclosed in Ser. No. 11/321,624). In this xenograft tumor model, MB-231 breast cancer cells were transplanted subcutaneously into immunodeficient mice such that the tumor reached a critical size before antibody treatment. Treatment with H460-22-1 was compared to the standard chemotherapeutic drug, cisplatin, and it was shown that the cisplatin and H460-22-1 treatment groups had significantly (p<0.001) smaller mean tumor volumes compared with the group treated with isotype control antibody. H460-22-1 treatment mediated tumor suppression that was approximately two-thirds that of cisplatin chemotherapy but without the significant weight loss (p<0.003) and clinical distress observed with cisplatin. The anti-tumor activity of H460-22-1 and its minimal toxicity make it an attractive anti-cancer therapeutic agent.
In the post-treatment period, H460-22-1 maintained tumor suppression by delaying tumor growth compared to the isotype control antibody group. At 31 days post treatment, H460-22-1 limited tumor size by reducing tumor growth by 42 percent compared to the isotype control group, which is comparable to the 48 percent reduction observed at the end of the treatment. In the established tumor model of breast cancer, these results indicated the potential of H460-22-1 to maintain tumor suppression beyond the treatment phase and demonstrated the ability of the antibody to reduce the tumor burden and enhance survival in a mammal.
The result of 1A245.6 and 7BD-33-11A cytotoxicity against breast and prostate cancer cells in culture was further extended by its anti-tumor activity towards these cancer indications in vivo (as disclosed in Ser. Nos. 10/348,231, 10/891,866, 10/603,006 and 10/810,751).
7BD-33-11A and 1A245.6 prevented tumor growth and tumor burden in a MB-231 preventative in vivo model of human breast cancer. Monitoring continued past 300 days post-treatment. 7BD-33-11A never developed tumors and 87.5 percent of the 7BD-33-11A-treatment group was still alive at over 9 months post-implantation (one of the mice died from non-tumor related causes). Conversely, the isotype control group had 100 percent mortality by day 72 (23 days post-treatment). 1A245.6-treated mice reached 100 percent mortality by day 151 post-treatment, which is greater than 6 times longer than the isotype control treatment group. Therefore 1A245.6, and to a greater extent 7BD-33-11A enhanced survival and prevented tumor growth (thus delaying disease progression) in a breast cancer model.
7BD-33-11A and 1A245.6 also significantly suppressed tumor growth and decreased tumor burden in an established in vivo model of human breast cancer. By day 80 (23 days post-treatment), 7BD-33-11A treated mice had 83 percent lower mean tumor volumes in comparison to the isotype control group (p=0.001). 1A245.6 treatment reduced the mean tumor volumes on this day by 35 percent, however, the reduction did not reach significance in this experiment (p=0.135).
Using survival as a measure of antibody efficacy, it was estimated that the risk of dying in the 7BD-33-11A treatment group was about 16 percent of the isotype control group (p=0.0006) at around 60 days post-treatment. 100 percent of the isotype control group died by 50 days post-treatment. In comparison, 1A245.6-treated mice survived until 100 days post-treatment and 60 percent of the 7BD-33-11A treatment groups were still alive at 130 days post-treatment. This data demonstrated that both 1A245.6 and 7BD-33-11A treatment conferred a survival benefit and reduced tumor burden compared to the control treated group.
7BD-33-11A and 1A245.6 treatment appeared safe, as it did not induce any signs of toxicity, including reduced body weight and clinical distress. Thus, 7BD-33-11A and 1A245.6 treatment was efficacious as it both delayed tumor growth and enhanced survival compared to the control-treated group in a well-established model of human breast cancer.
In a study disclosed in Ser. No. 10/810,751, the contents of which are herein incorporated by reference, the effect of 7BD-33-11A compared to chemotherapeutic drug (Cisplatin) treatment alone or in combination was determined in two different established breast cancer xenograft models.
In the MB-231 model, at day 83 (20 days after treatment), 7BD-33-11A treatment resulted in an 83 percent reduction in tumor growth relative to the buffer control treated animals (p=0.002). Cisplatin treatment alone resulted in a 77 percent reduction in tumor size relative to the control, while Cisplatin in combination with 7BD-33-11A resulted in an 88 percent reduction in tumor size relative to the control (p=0.006).
In the MDA-MB-468 (MB-468) model, at day 62 (12 days after treatment) the greatest reduction in tumor growth (97 percent, p=0.001) was observed with Cisplatin treatment in combination with 7BD-33-11A. Cisplatin treatment alone produced a 95 percent decrease in tumor growth in comparison to the buffer control while 7BD-33-11A treatment alone showed a 37 percent (p=0.046) reduction.
In both the MB-231 and MB-468 model, treatment with 7BD-33-11A led to greater animal well-being in comparison to treatment with Cisplatin as measured by body weight. These results indicated that 7BD-33-11A treatment had greater efficacy in comparison with Cisplatin treatment alone in the MB-231 model and was better tolerated with fewer adverse effects, such as weight loss, than Cisplatin in both breast cancer models.
To determine the effects of 7BD-33-11A treatment at various doses, a dose response experiment was performed in a preventative breast cancer xenograft model (as disclosed in Ser. No. 10/810,751). At day 55 (5 days after treatment), the 0.2 mg/kg treatment group had reduced tumor growth by 85 percent relative to the isotype control treated group. Also at day 55, both the 2 and 20 mg/kg treatment groups had yet to develop tumors. Similar results were obtained past day 125 (75 days after treatment), where the 20 mg/kg treatment group had still not developed tumors and the 2 mg/kg treatment group had some initial tumor growth. 7BD-33-11A treatment also demonstrated a survival benefit. All of the mice in the isotype control group had died by day 104 (54 days after treatment) while the 0.2 mg/kg 7BD-33-11A treatment group survived until day 197 (147 days after treatment). Even greater survival benefits were observed with the 2.0 and 20 mg/kg 7BD-33-11A treatment groups; only 50 percent of the 2.0 mg/kg treatment group had died by day 290 (240 days after treatment) while none of the 20 mg/kg treatment group had died by day 290. Therefore, 7BD-33-11A treatment showed significant tumor growth reduction and increased survival with all three doses with the greatest degree of efficacy being exhibited by the highest dose.
In addition to the beneficial effects in the established in vivo tumor model of breast cancer, 7BD-33-11A and 1A245.6 treatment also had anti-tumor activity against PC-3 cells in a preventative in vivo prostate cancer model (disclosed in Ser. Nos. 10/603,006 and 10/810,751, the contents of each of which are herein incorporated by reference). 7BD-33-11A and 1A245.6 treatment was significantly (p=0.001 and 0.017 respectively) more effective in suppressing tumor growth shortly after the treatment period than an isotype control antibody. At the end of the treatment phase, mice given 7BD-33-11A or 1A245.6 had tumors that grew to only 31 and 50 percent of the isotype control group respectively.
For PC-3 SCID xenograft models, body weight can be used as a surrogate indicator of disease progression. On day 52, 7BD-33-11A and 1A245.6 treatment significantly (p=0.002 and 0.004 respectively) prevented the loss of body weight by 54 and 25 percent respectively in comparison to isotype control. Mice were monitored for survival post-treatment. At 11 days post-treatment, isotype and buffer control mice had reached 100 percent mortality. Conversely, 7BD-33-11A and 1A245.6 reached 100 percent mortality at day 38 post-treatment, 3 times longer than the control groups. Thus, 7BD-33-11A and 1A245.6 treatment was efficacious as it both delayed tumor growth, prevented body weight loss and extended survival compared to the isotype control treated group in a well-established model of human prostate cancer.
In addition to the preventative in vivo tumor model of prostate cancer, 7BD-33-11A demonstrated anti-tumor activity against PC-3 cells in an established in vivo tumor model (disclosed in Ser. Nos. 10/603,006 and 10/810,751, the contents of each of which are herein incorporated by reference). Treatment with 7BD-33-11A was again compared to isotype control. It was shown that the 7BD-33-11A treatment group had significantly (p<0.024) smaller mean tumor volumes compared with the isotype control treated group immediately following treatment. 7BD-33-11A treatment mediated tumor suppression by 36 percent compared to the isotype control group.
In addition to the beneficial effects in the in vivo tumor models of breast and prostate cancer, 7BD-33-11A treatment also had anti-tumor activity against BxPC-3 cells in a preventative in vivo pancreatic cancer model (as disclosed in Ser. No. 11/321,624). 7BD-33-11A treatment was significantly more effective in suppressing tumor growth (71 percent, p=0.0009) shortly after the treatment period than the buffer control. In addition, 7BD-33-11A treatment conferred a survival benefit in comparison to the buffer control treatment group. In the 7BD-33-11A treated group, 40 percent of the mice were still alive over 2 weeks after all of the buffer control group mice had died.
In addition to the beneficial effects in the in vivo tumor models of breast, prostate and pancreatic cancer, 7BD-33-11A treatment also had anti-tumor activity against A2058 and A375 cells in two separate preventative in vivo melanoma cancer models (as disclosed in Ser. No. 11/321,624). In both the A2058 and A375 model, 7BD-33-11A treatment was significantly more effective in suppressing tumor growth (72 percent, p=0.011 and 63 percent, p=0.0006 respectively) than the buffer control. The anti-tumor activities of 7BD-33-11A in melanoma as well as in breast, prostate and pancreatic cancer models make it an attractive anti-cancer therapeutic agent.
In addition to the beneficial effects demonstrated in the preventative in vivo model of human melanoma, 7BD-33-11A-treatment also had anti-tumor activity against A2058 and A375 cells in two separate established in vivo melanoma cancer models (as disclosed in Ser. No. 11/321,624). Tumor growth was significantly inhibited in the 7BD-33-11A-treatment and the 7BD-33-11A plus dacarbazine treatment group for the A2058 and A375 model respectively. In the A2058 model, the mean tumor volume was 30.87% (p<0443) of the control group measurement. In the A375 model, the 7BD-33-11A/dacarbazinbe combination treatment group resulted in a median TTE (time-to-endpoint) of 39.1 days, corresponding to a significant 147% delay in tumor growth (p<0.01). No toxic deaths were observed in either model. Therefore, 7BD-33-11A treatment appeared safe and has displayed efficacy in the treatment of breast and now melanoma in vivo models of established human cancer.
To determine if the efficacy demonstrated by 7BD-33-11A in vivo is due in whole or in part to ADCC activity, 7BD-33-11A anti-tumor activity was measured against MB-231 cells in an established tumor model in both NOD SCID and SCID mice. NOD SCID mice are functionally deficit in natural killer (NK) cells and lack circulating complement and a functionally immature macrophage population while SCID mice have both complement and robust NK cell activity. 7BD-33-11A is a murine IgG2a monoclonal antibody and is therefore capable of ADCC activity in vivo. The anti-tumor activity of 7BD-33-11A was compared to both a buffer control and H460-22-1, a murine IgG1 monoclonal antibody that should not exhibit its activity through ADCC based on its isotype. On day 54 (4 days after the last treatment), in the SCID treated group, 7BD-33-11A and H460-22-1 treated mice developed tumors that were only 1.9 and 3.6 percent respectively of the mean tumor volume of the buffer control treated mice. Conversely, in the NOD SCID treated group, again on day 54 (4 days after the last treatment), 7BD-33-11A treated mice had tumor growth that was 67 percent of the mean tumor volume of the buffer control treated mice. H460-22-1 treated mice exhibited a similar effect as in the SCID mice; tumor growth was 1.4 percent of the mean tumor volume of the buffer control treated mice. Consequently, 7BD-33-11A activity in vivo seems to be in-part due to ADCC activity while H460-22-1's anti-tumor effect appears to be independent of ADCC.
In order to validate the H460-22-1, 1A245.6 and 7BD-33-11A epitope as a drug target, the expression of their target antigens in normal human tissues was determined. As partially disclosed in Ser. Nos. 10/603,006 and 10/810,751, the contents of each of which are herein incorporated by reference, the binding of 7BD-33-11A, H460-22-1 and 1A245.6 towards normal human tissues was determined. By IHC staining, the majority of the tissues failed to express the 7BD-33-11A antigen, including the vital organs, such as the kidney, heart, and lung. 7BD-33-11A stained the salivary gland, liver, pancreas, stomach, prostate and duodenum, and strongly stained the tonsil. Results from tissue staining indicated that 7BD-33-11A showed restricted binding to various cell types but had binding to infiltrating macrophages, lymphocytes, and fibroblasts. For both H460-22-1 and 1A245.6, a wider range of tissues was positively stained. For the majority of cases, staining was restricted to the epithelium or infiltrating macrophages, lymphocytes, and fibroblasts. However, positive staining was seen on both cardiac muscle and hepatocytes. 7BD-33-11A, H460-22-1 and 1A245.6 displayed both membrane and cytoplasmic staining patterns.
As disclosed in Ser. No. 10/810,751, the contents of which are herein incorporated by reference, 7BD-33-11A was compared with commercially available anti-CD63 antibodies (RFAC4 and H5C6). Results from normal human tissue staining indicated that 7BD-33-11A again showed restricted binding to various cell types but had binding to infiltrating macrophages, lymphocytes, and fibroblasts. The RFAC4 and H5C6 antibodies showed a similar staining pattern in comparison to each other. However, the staining pattern of both RFAC4 and H5C6 was quite different than that observed with 7BD-33-11A. Specifically, both RFAC4 and H5C6 antibodies bound to a broader range of normal tissues, usually had higher staining intensity in tissues where 7BD-33-11A was also positive and bound not only to infiltrating macrophages, lymphocytes and fibroblasts but also to the epithelium in a majority of the tissues.
Localization of the H460-22-1, 1A245.6 and 7BD-33-11A antigen and determination of their prevalence within the population, such as among breast cancer patients, is important in assessing the therapeutic use of these antibodies and designing effective clinical trials. To address H460-22-1, 1A245.6 and 7BD-33-11A antigen expression in breast tumors from cancer patients, tumor tissue samples from 98 individual breast cancer patients were screened for expression of the 7BD-33-11A antigen (results from 50 patients have been previously described in Ser. Nos. 10/603,006 and 10/810,751, the contents of each of which are herein incorporated by reference) and tumor tissue samples from 50 patients were screened for 1A245.6 (disclosed in Ser. No. 10/603,006, the contents of which are herein incorporated by reference) and H460-22-1 antigen (disclosed in Ser. No. 11/321,624, the contents of which are herein incorporated by reference).
The results of these studies showed that 37 percent of tissue samples positively stained for the 7BD-33-11A antigen. Expression of 7BD-33-11A within patient samples appeared specific for cancer cells as staining was restricted to malignant cells. In addition, 7BD-33-11A stained 0 of 20 samples of normal tissue from breast cancer patients. On the other hand, H460-22-1 and 1A245.6 stained 92 percent and 98 percent of breast cancer tissue samples respectively. H460-22-1 and 1A245.6 also stained 9 out of 10 samples of normal tissue from breast cancer patients. However, this staining was generally much weaker than that observed with the breast cancer tissue samples and was generally restricted to infiltrating fibroblasts. Breast tumor expression of the 7BD-33-11A, H460-22-1 and 1A245.6 antigen appeared to be localized to the cell membrane and cytoplasm of malignant cells, making CD63 an attractive target for therapy.
As disclosed in Ser. No. 10/810,751, the contents of which are herein incorporated by reference, 7BD-33-11A was compared to RFAC4 and H5C6 and to an anti-Her2 antibody (c-erbB-2). The results of the current study were similar to previous results and showed that 36 percent of tumor tissue samples stained positive for the 7BD-33-11A antigen while 94 and 85 percent of breast tumor tissues were positive for the H5C6 and RFAC4 epitope respectively. Expression of 7BD-33-11A within patient samples appeared specific for cancer cells as staining was restricted to malignant cells. In addition, 7BD-33-11A stained 0 of 10 samples of normal tissue from breast cancer patients while both H5C6 and RFAC4 stained 7 of 8 samples of normal breast tissue. In comparison to c-erbB-2, 7BD-33-11A showed a completely different staining profile where half of the breast tumor tissue samples that were positive for the 7BD-33-11A antigen were negative for Her2 expression indicating that 7BD-33-11A targets a patient population that is not served by existing antibody therapies. There were also differences in the intensity of staining between the breast tumor tissue sections that were positive for both 7BD-33-11A and Her2. The c-erbB-2 antibody also positively stained one of the normal breast tissue sections.
As disclosed in Ser. Nos. 10/603,006, 10/810,751 and 11/321,624, the contents of each of which are herein incorporated by reference, 7BD-33-11A, H460-22-1 and 1A245.6 expression was further evaluated based on breast tumor expression of the receptors for the hormones estrogen and progesterone, which play an important role in the development, treatment, and prognosis of breast tumors. No correlation was apparent between expression of the 1A245.6 antigen and expression of the receptors for either estrogen or progesterone. There was a slight correlation between absence of estrogen receptors and presence of progesterone receptors and 7BD-33-11A antigen expression and presence of both estrogen and progesterone receptors and H460-22-1 antigen expression. When tumors were analyzed based on their stage, or degree to which the cancer advanced, results suggested a trend towards greater positive expression with higher tumor stage for both 7BD-33-11A and H460-22-1. Similar results were obtained with RFAC4. H5C6 also showed a very slight correlation with estrogen or progesterone receptor expression but there was no apparent correlation with tumor stage, however, conclusions were limited by the small sample size.
Localization of the 7BD-33-11A antigen and its prevalence within prostate cancer patients is important in assessing the benefits of 7BD-33-11A immunotherapy to patients with prostate cancer and designing effective clinical trials. To address 7BD-33-11A antigen expression in prostate tumors from cancer patients, tumor tissue samples from 51 individual prostate cancer patients were screened for expression of the 7BD-33-11A antigen (as disclosed in Ser. No. 10/810,751, the contents of which are herein incorporated by reference). The results of the study showed that 88 percent of tissue samples stained positive for the 7BD-33-11A antigen. Although 7BD-33-11A stained the normal tissue sections with high intensity as well, there was a higher degree of membranous staining in the tumor tissue samples in comparison to the normal samples. There was one embryonal rhabdomyosarcroma tissue sample that did not stain for the 7BD-33-11A antigen. In the small sample size tested there did not appear to be a direct correlation between tumor stage and presence of the 7BD-33-11A antigen.
Localization of the 7BD-33-11A antigen and its prevalence within melanoma cancer patients is important in assessing the benefits of 7BD-33-11A immunotherapy to patients with melanoma and designing effective clinical trials. To address 7BD-33-11A antigen expression in melanoma tumors from cancer patients, tumor tissue samples from 39 individual melanoma patients were screened for expression of the 7BD-33-11A antigen (as disclosed in Ser. No. 11/321,624). The results of the study showed that 90 percent of tissue samples stained positive for the 7BD-33-11A antigen. In this small sample, there also appeared to be no direct correlation between tumor stage and presence of the 7BD-33-11A antigen.
To further extend the potential therapeutic benefit of 7BD-33-11A, H460-22-1 and 1A245.6, the frequency and localization of the antigen within various human cancer tissues was also determined (disclosed in Ser. Nos. 10/603,006, 10/810,751 and 11/321,624, the contents of each of which are herein incorporated by reference). Several cancer types, in addition to breast and prostate cancer, expressed the 7BD-33-11A antigen. The positive human cancer types included skin (1/2), lung (3/4), liver (2/3), stomach (4/5), thyroid (2/2), uterus (4/4) and kidney (3/3). Some cancers did not express the antigen; these included ovary (0/3), testis (0/1), brain (0/2) and lymph node (0/2). For H460-22-1 and 1A245.6, as with the normal human tissue array, a multitude of cancers from various human tissue types were positively stained. Greater staining was seen on malignant cells of the skin, lung, liver, uterus, kidney, stomach and bladder. As with human breast, prostate and melanoma cancer tissue, localization of 7BD-33-11A, H460-22-1 and 1A245.6 occurred both on the membrane and within the cytoplasm of these tumor cells. Therefore, in addition to the H460-22-1, 1A245.6 and 7BD-33-11A antibody binding to cancer cell lines in vitro, there is evidence that the antigen is expressed in humans, and on multiple types of cancers.
As disclosed in Ser. No. 10/810,751, the contents of which are herein incorporated by reference, for 7BD-33-11A and in Ser. No. 11/321,624 for 1A245.6 and H460-22-1, biochemical data also indicate that the antigen recognized by H460-22-1, 1A245.6 and 7BD-33-11A is CD63. This is supported by studies showing that the monoclonal antibody RFAC4, reactive against CD63, identifies proteins that bound to 7BD-33-11A, H460-22-1 or 1A245.6 by immunoprecipitation. In addition, bacterial expression studies elucidated that H460-22-1, 1A245.6 and 7BD-33-11A bound to extracellular loop 2 of CD63. The 7BD-33-11A, H460-22-1 and 1A245.6 epitope was also distinguished by being conformation dependent. These IHC and biochemical results demonstrate that H460-22-1, 1A245.6 and 7BD-33-11A bind to the CD63 antigen. Thus, the preponderance of evidence shows that H460-22-1, 1A245.6 and 7BD-33-11A mediate anti-cancer effects through ligation of unique conformational epitope(s) present on CD63. For the purpose of this invention, said epitope is defined as a “CD63 antigenic moiety” characterized by its ability to bind with a monoclonal antibody encoded by the hybridoma cell line 7BD-33-11A, 1A245.6, H460-22-1, antigenic binding fragments thereof or antibody conjugates thereof.
In toto, this data demonstrates that the H460-22-1, 1A245.6 and 7BD-33-11A antigen is a cancer associated antigen and is expressed in humans, and is a pathologically relevant cancer target. Further, this data also demonstrates the binding of the H460-22-1, 1A245.6 and 7BD-33-11A antibody to human cancer tissues, and can be used appropriately for assays that can be diagnostic, predictive of therapy, or prognostic. In addition, the cell membrane localization of this antigen is indicative of the cancer status of the cell due to the relative infrequency of expression of the antigen in most non-malignant cells, and this observation permits the use of this antigen, its gene or derivatives, its protein or its variants to be used for assays that can be diagnostic, predictive of therapy, or prognostic.
The present invention describes the development and use of H460-22-1, 7BD-33-11A and 1A245.6, developed by the process described in U.S. Pat. No. 6,180,357 and identified by, its effect, in a cytotoxic assay, in non-established and established tumor growth in animal models and in prolonging survival time in those suffering from cancerous disease. In addition, the present invention discloses the development of two humanized versions of 7BD-33-11A, one of which displays similar cytotoxicity in a prophylatic animal model. The present invention also discloses the development and use of mouse monoclonal antibodies AR51A994.1, 7BDI-58 and 7BDI-60.
This invention represents an advance in the field of cancer treatment in that it describes reagents that bind specifically to an epitope or epitopes present on the target molecule, CD63, and that also have in vitro cytotoxic properties against malignant tumor cells but not normal cells, and which also directly mediate inhibition of tumor growth and extension of survival in in vivo models of human cancer. This is an advance in relation to any other previously described anti-CD63 antibody, since none have been shown to have similar properties. It also provides an advance in the field since it clearly demonstrates the direct involvement of CD63 in events associated with growth and development of certain types of tumors. It also represents an advance in cancer therapy since it has the potential to display similar anti-cancer properties in human patients. A further advance is that inclusion of these antibodies in a library of anti-cancer antibodies will enhance the possibility of targeting tumors expressing different antigen markers by determination of the appropriate combination of different anti-cancer antibodies, to find the most effective in targeting and inhibiting growth and development of the tumors.
In all, this invention teaches the use of the 7BD-33-11A antigen as a target for a therapeutic agent, that when administered can reduce the tumor burden of a cancer expressing the antigen in a mammal, and can also lead to a prolonged survival of the treated mammal.
Accordingly, it is an objective of the invention to utilize a method for producing cancerous disease modifying antibodies (CDMAB) raised against cancerous cells derived from a particular individual, or one or more particular cancer cell lines, which CDMAB are cytotoxic with respect to cancer cells while simultaneously being relatively non-toxic to non-cancerous cells, in order to isolate hybridoma cell lines and the corresponding isolated monoclonal antibodies and antigen binding fragments thereof for which said hybridoma cell lines are encoded.
It is an additional objective of the invention to teach cancerous disease modifying antibodies, ligands and antigen binding fragments thereof.
It is a further objective of the instant invention to produce cancerous disease modifying antibodies whose cytotoxicity is mediated through antibody dependent cellular toxicity.
It is yet an additional objective of the instant invention to produce cancerous disease modifying antibodies whose cytotoxicity is mediated through complement dependent cellular toxicity.
It is still a further objective of the instant invention to produce cancerous disease modifying antibodies whose cytotoxicity is a function of their ability to catalyze hydrolysis of cellular chemical bonds.
A still further objective of the instant invention is to produce cancerous disease modifying antibodies and ligands which are useful in a binding assay for diagnosis, prognosis, and monitoring of cancer.
Other objects and advantages of this invention will become apparent from the following description wherein are set forth, by way of illustration and example, certain embodiments of this invention.
BRIEF DESCRIPTION OF THE FIGURES
The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.
FIG. 1 compares the percentage cytotoxicity and binding levels of the hybridoma supernatants against cell lines OCC-1, OVAR-3 and CCD-27sk.
FIG. 2 is a comparison of AR51A994.1 versus positive and negative controls in a cytotoxicity assay.
FIG. 3 represents binding of AR51A994.1 and the anti-EGFR control to cancer and normal cell lines. The data is tabulated to present the mean fluorescence intensity as a fold increase above isotype control.
FIG. 4 includes representative FACS histograms of AR51A994.1 and anti-EGFR antibodies directed against several cancer and non-cancer cell lines.
FIG. 5 is a comparison of 7BDI-58 and 7BDI-60 versus positive and negative controls in a cytotoxicity assay.
FIG. 6 represents binding of 7BDI-58, 7BDI-60 and the anti-Her2 control to cancer and normal cell lines. The data is tabulated to present the mean fluorescence intensity as a fold increase above isotype control.
FIG. 7 includes representative FACS histograms of 7BDI-58, 7BDI-60 and anti-Her2 antibodies directed against several cancer and non-cancer cell lines.
FIG. 8 demonstrates the effect of 7BDI-58 on tumor growth in a prophylactic MDA-MB-231 breast cancer model. The vertical dashed lines indicate the period during which the antibody was administered. Data points represent the mean +/−SEM.
FIG. 9 demonstrates the effect of 7BDI-58 on body weight in a prophylactic MDA-MB-231 breast cancer model. Data points represent the mean +/−SEM.
FIG. 10 . Western blot of samples obtained from the total membrane fraction of MDA-MB-231 cells (lane 1) and from whole cell lysates of PC-3 (lane 2) and CCD-27sk (lane 3) cell lines. Blots were probed with 7BDI-58, 7BDI-60, AR51A994.1, 7BD-33-11A, 1A245.6 and H460-22-1 as described above.
FIG. 11 . Immunocomplex prepared by immunoprecipitation with 7BD-33-11A from the total membrane fraction of the MDA-MB-231 cell line. Individual lanes of the blot were probed with 7BDI-58 (lane 1), AR51A994.1 (lane 2), 7BD-33-11A (lane 3) and with isotype control antibodies (lanes 4 and 5).
FIG. 12 . Immunocomplex prepared by immunoprecipitation with 1A245.6 from the total membrane fraction of the ASPC-1 human pancreatic carcinoma cell line. Replicate lanes of the blot were probed with 7BDI-60 (lane 1), 1A245.6 (lane 2), anti-CD63 clone H5C6 (lane 3) and with an isotype control antibody (lane 4).
FIG. 13 . Western blot of human recombinant fusion construct GST-EC2 (CD63). Individual lanes of the blot were probed with 7BDI-58 (lane 1), 7BDI-60 (lane 2), AR51A994.1 (lane 3), 7BD-33-11A (lane 4), H460-22-1 (lane 5), 1A245.6 (lane 6) and with negative controls H460-16-2 (anti-CD44; lane 7) and isotype control antibodies (lanes 8 and 9).
FIG. 14 is a summary of 7BD-33-11A binding on a human pancreatic tumor and normal tissue microarray.
FIG. 15 . Representative micrographs showing the binding pattern on pancreatic tumor tissue obtained with 7BD-33-11A (A) or the isotype control antibody (B) and on non-neoplastic pancreatic tissue obtained with 7BD-33-11A (C) or the isotype control antibody (D) from a human tissue microarray. 7BD-33-11A displayed strong positive staining for the tumor cells and weak-moderate staining on the normal tissue. Magnification is 200×.
FIG. 16 . In vitro cytotoxic activity, of mouse effector cells against human breast cancer cells, elicited by 7BD-33-11A. 51 Cr-labelled MDA-MB-231 cells were incubated with non-adherent (a) and adherent (b) mouse splenic effector cells in the presence of varying concentrations of 7BD-33-11A or the isotype control.
FIG. 17 . Summary of the number of macrophages from MDA-MB-231 xenografts after various dosing regiments with 7BD-33-11A or buffer control.
FIG. 18 . Sequence of the N-terminal amino acids of 7BD-33-11A antibody.
FIG. 19 . cDNA sequence for the light chain variable region of the 7BD-33-11A antibody (SEQ ID NO:1). The deduced amino acid sequence is shown below the nucleotide sequence (SEQ ID NO:2). The signal peptide sequence is in italics. The CDRs (Kabat nomenclature) are underlined. The mature light chain begins with an asparagine residue (bold and double underlined).
FIG. 20 . cDNA sequence for the heavy chain variable region of the 7BD-33-11A antibody (SEQ ID NO:3). The deduced amino acid sequence is shown below the nucleotide sequence (SEQ ID NO:4). The signal peptide sequence is in italics. The CDRs (Kabat nomenclature) are underlined. The mature heavy chain begins with a glutamic acid residue (bold and double underlined).
FIG. 21 . Alignment of the V L region amino acid sequences. The amino acid sequences of the V L regions of 7BD-33-11A (Mu33-11A) and (hu)AR7BD-33-11A (Hu33-11A), and the human acceptor 1LVE and JK2 are shown in single letter code. The CDR sequences (Kabat nomenclature) are underlined in the 7BD-33-11A V L sequence. The CDR sequences in the human VL segment are omitted in the Figure. The single underlined amino acid in the (hu)AR7BD-33-11A V L sequence is predicted to contact the CDR sequences, and therefore has been substituted with the corresponding mouse residue. The sequences disclosed, as read from the top, are amino acid residues 21-50 of SEQ ID NO:2; amino acid residues 22-52 of SEQ ID NO:6; SEQ ID NO:62; amino acid residues 51-80 of SEQ ID NO:2; amino acid residues 53-82 of SEQ ID NO:6; amino acid residues 63-77 of SEQ ID NO:6; amino acid residues 81-110 of SEQ ID NO:2; amino acid residues 83-112 of SEQ ID NO:6; amino acid residues 85-112 of SEQ ID NO:6; amino acid residues 111-132 of SEQ ID NO:2; amino acid residues 113-134 of SEQ ID NO:6; amino acid residues 113-116 of SEQ ID NO:6 and amino acid residues 125-134 of SEQ ID NO:6.
FIG. 22 . Alignment of the V H region amino acid sequences. The amino acid sequences of the V H regions of 7BD-33-11A (Mu33-11A), (hu)AR7BD-33-11A (Hu33-11A), (hu)AR7BD-33-11A(V11L) and the human acceptor AAR32409 and JH6 are shown in single letter code. The CDR sequences (Kabat nomenclature) are underlined in the 7BD-33-11A V H sequence. The CDR sequences in the human V H segment are omitted in the Figure. The single underlined amino acids in the (hu)AR7BD-33-11A and (hu)AR7BD-33-11A(V11L) V H sequence are predicted to contact the CDR sequences, and therefore have been substituted with the corresponding mouse residues. The double underlined amino acids have been substituted with consensus human residues to reduce potential immunogenicity. The sequences disclosed, as read from the top are, amino acid residues 20-49 of SEQ ID NO:4; amino acid residues 20-49 of SEQ ID NO:8; amino acid residues 20-49 of SEQ ID NO:12; SEQ ID NO:63; amino acid residues 50-79 of SEQ ID NO:4; amino acid residues 50-79 of SEQ ID NO:8; amino acid residues 50-79 of SEQ ID NO:12; SEQ ID NO:64; amino acid residues 80-109 of SEQ ID NO:4; amino acid residues 80-109 of SEQ ID NO:8; amino acid residues 80-109 of SEQ ID NO:12; SEQ ID NO:65; amino acid residues 110-138 of SEQ ID NO:4; amino acid residues 110-138 of SEQ ID NO:8; amino acid residues 110-138 of SEQ ID NO: 12; SEQ ID NO:66 and amino acid resides 128-138 of SEQ ID NOS:8 and 12.
FIG. 23 . Nucleotide sequence (SEQ ID NO:5) and deduced amino acid sequence (SEQ ID NO:6) of the light chain variable region of (hu)AR7BD-33-11A in the mini exon. The signal peptide sequence is in italics. The CDRs (Kabat nomenclature) are underlined. The mature light chain begins with an aspartic acid residue (bold and double-underlined). The sequence is flanked by unique M1uI (ACGCGT) and XbaI (TCTAGA) sites.
FIG. 24 . Nucleotide sequence (SEQ ID NO:7) and deduced amino acid sequence (SEQ ID NO:8) of the heavy chain variable region of (hu)AR7BD-33-11A(V11L) in the mini exon. The signal peptide sequence is in italics. The CDRs (Kabat nomenclature) are underlined. The mature heavy chain begins with a glutamic acid residue (bold and double-underlined). The sequence shown is flanked by unique M1uI (ACGCGT) and XbaI (TCTAGA) sites.
FIG. 25 . Primers used for the construction of the 7BD-33-11A V L gene. The sequences disclosed, as read from the top, are SEQ ID NOS:21-39.
FIG. 26 . Primers used for the construction of the 7BD-33-11A V H gene. The sequences disclosed, as read from the top, are SEQ ID NOS:40-61.
FIG. 27 . Scheme for the synthesis of the (hu)AR7BD-33-11A V L or V H mini-exons. A series of 20 (for V L ) or 22 (for V H ; as illustrated in the Figure) overlapping oligonucleotides were used. Oligonucleotides 1-20 (for V L ) or 1-22 (for V H ) were annealed and extended with Pfu Turbo polymerase. The resulting assembled double stranded V gene was amplified by 5′ and 3′ flanking oligonucleotides to yield V L and V H gene fragments, which were gel purified, digested with M1uI and XbaI, and subcloned into the pVk and pVg1.D.Tt or pVg2M3.D.T vectors, respectively.
FIG. 28 . Summary of FACS competition experiments.
FIG. 29 . Scheme for generating single amino acid substitution V H mutants by site-directed mutagenesis. Two separate rounds of PCR were carried out. In the first round of PCR, two partial V H gene fragments were amplified. These two fragments were further amplified together in the second round of PCR, to generate a full length V H gene fragment with a single amino acid substitution. The V H gene with the desired mutation was subcloned into pVg1.D.Tt and pVg2M3.D.T using the flanking M1uI and XbaI sites.
FIG. 30 . Plasmid constructs for expression of (hu)AR7BD-33-11A(V11L) antibodies. The V L and V H genes were constructed as mini-exons flanked by M1ul and XbaI sites. The V regions were incorporated into the corresponding expression vectors.
FIG. 31 . (hu)AR7BD-33-11A kappa light chain cDNA (SEQ ID NO:9) and translated amino acid sequence (SEQ ID NO: 10). The amino acids are shown in single letter code; the dot (•) indicates the translation termination codon. The first amino acid of the mature light chain is double-underlined and bold, preceded by its signal peptide sequence.
FIG. 32 . (hu)AR7BD-33-11A(V11L)γ1 heavy chain cDNA (SEQ ID NO:11) and translated amino acid sequence (SEQ ID NO:12). The amino acids are shown in single letter code; the dot (•) indicates the translation termination codon. The first amino acid of the mature heavy chain is double-underlined and bold, preceded by its signal peptide sequence.
FIG. 33 . (hu)AR7BD-33-11A(V11L)γ2M3 heavy chain cDNA (SEQ ID NO:13) and translated amino acid sequence (SEQ ID NO:14). The amino acids are shown in single letter code; the dot (•) indicates the translation termination codon. The first amino acid of the mature heavy chain is double-underlined and bold, preceded by its signal peptide sequence.
FIG. 34 . SDS-PAGE analysis of 7BD-33-11A (Mu33-11A), (hu)AR7BD-33-11A-IgG1(V11L) and (hu)AR7BD-33-11A-IgG2M3(V11L) under non-reducing and reducing conditions as described in the text.
FIG. 35 . HPLC analysis of (A) (hu)AR7BD-33-11A-IgG1(V11L) and (B) (hu)AR7BD-33-11A-IgG2M3 (V11L) by size exclusion chromatography.
FIG. 36 . Summary of FACS competition experiments.
FIG. 37 . FACS competition to compare the relative binding affinity to human CD63 between 7BD-33-11A, (hu)AR7BD-33-11A-IgG1(V11L), and (hu)AR7BD-33-11A-IgG2M3(V11L). The binding of FITC-Iabeled 7BD-33-11A to human CD63 + PC-3 cells was analyzed in the presence of different amounts of competitor 7BD-33-11A, (hu)AR7BD-33-11A-IgG1(V11L) or (hu)AR7BD-33-11A-IgG2M3(V11L) as described in the text.
FIG. 38 demonstrates the effect of treatment with 7BD-33-11A, (hu)AR7BD-33-11A-IgG1, and (hu)AR7BD-33-11A-IgG2M3 on tumor growth in a mouse model of human melanoma. Tumor volume is presented as the group mean±SEM. Vertical dashed lines indicate the first and last day of dosing.
FIG. 39 demonstrates the effect of treatment with monoclonal antibodies on body weight over the duration of the study. Body weight is presented as the group mean±SEM.
FIG. 40 . Binding affinity of the anti-CD637BD-33-11A, H460-22-1, 1A245.6, and of the humanized antibodies (hu)AR7BD-33-11A-IgG1 and (hu)AR7BD-33-11A-IgG2M3. Dissociation constants for the binding of the antibodies to the purified recombinant GST fusion construct protein GST-EC2 (CD63) was assessed by surface plasmon resonance.
DETAILED DESCRIPTION OF THE INVENTION
In general, the following words or phrases have the indicated definition when used in the summary, description, examples, and claims.
The term “antibody” is used in the broadest sense and specifically covers, for example, single monoclonal antibodies (including agonist, antagonist, and neutralizing antibodies, de-immunized, murine, chimerized or humanized antibodies), antibody compositions with polyepitopic specificity, single chain antibodies, immunoconjugates and fragments of antibodies (see below).
The term “monoclonal antibody” as used herein refers to an antibody obtained from a population of substantially homogeneous antibodies, i.e., the individual antibodies comprising the population are identical except for possible naturally occurring mutations that may be present in minor amounts. Monoclonal antibodies are highly specific, being directed against a single antigenic site. Furthermore, in contrast to polyclonal antibody preparations which include different antibodies directed against different determinants (epitopes), each monoclonal antibody is directed against a single determinant on the antigen. In addition to their specificity, the monoclonal antibodies are advantageous in that they may be synthesized uncontaminated by other antibodies. The modifier “monoclonal” indicates the character of the antibody as being obtained from a substantially homogeneous population of antibodies, and is not to be construed as requiring production of the antibody by any particular method. For example, the monoclonal antibodies to be used in accordance with the present invention may be made by the hybridoma (murine or human) method first described by Kohler et al., Nature, 256:495 (1975), or may be made by recombinant DNA methods (see, e.g., U.S. Pat. No. 4,816,567). The “monoclonal antibodies” may also be isolated from phage antibody libraries using the techniques described in Clackson et al., Nature, 352:624-628 (1991) and Marks et al., J Mol. Biol., 222:581-597 (1991), for example.
“Antibody fragments” comprise a portion of an intact antibody, preferably comprising the antigen-binding or variable region thereof. Examples of antibody fragments include less than full length antibodies, Fab, Fab′, F(ab′) 2 , and Fv fragments; diabodies; linear antibodies; single-chain antibody molecules; single-chain antibodies, single domain antibody molecules, fusion proteins, recombinant proteins and multispecific antibodies formed from antibody fragment(s).
An “intact” antibody is one which comprises an antigen-binding variable region as well as a light chain constant domain (C L ) and heavy chain constant domains, C H 1, C H 2 and C H 3. The constant domains may be native sequence constant domains (e.g. human native sequence constant domains) or amino acid sequence variant thereof. Preferably, the intact antibody has one or more effector functions.
Depending on the amino acid sequence of the constant domain of their heavy chains, intact antibodies can be assigned to different “classes”. There are five-major classes of intact antibodies: IgA, IgD, IgE, IgG, and IgM, and several of these may be further divided into “subclasses” (isotypes), e.g., IgG1, IgG2, IgG3, IgG4, IgA, and IgA2. The heavy-chain constant domains that correspond to the different classes of antibodies are called a, d, e, ?, and μ, respectively. The subunit structures and three-dimensional configurations of different classes of immunoglobulins are well known.
Antibody “effector functions” refer to those biological activities attributable to the Fc region (a native sequence Fc region or amino acid sequence variant Fc region) of an antibody. Examples of antibody effector functions include C1q binding; complement dependent cytotoxicity; Fc receptor binding; antibody-dependent cell-mediated cytotoxicity (ADCC); phagocytosis; down regulation of cell surface receptors (e.g. B cell receptor; BCR), etc.
“Antibody-dependent cell-mediated cytotoxicity” and “ADCC” refer to a cell-mediated reaction in which nonspecific cytotoxic cells that express Fc receptors (FcRs)(e.g. Natural Killer (NK) cells, neutrophils, and macrophages) recognize bound antibody on a target cell and subsequently cause lysis of the target cell. The primary cells for mediating ADCC, NK cells, express Fc?RIII only, whereas monocytes express Fc?RI, Fc?RII and Fc?RIII. FcR expression on hematopoietic cells in summarized is Table 3 on page 464 of Ravetch and Kinet, Annu. Rev. Immunol 9:457-92 (1991). To assess ADCC activity of a molecule of interest, an in vitro ADCC assay, such as that described in U.S. Pat. No. 5,500,362 or 5,821,337 may be performed. Useful effector cells for such assays include peripheral blood mononuclear cells (PBMC) and Natural Killer (NK) cells. Alternatively, or additionally, ADCC activity of the molecule of interest may be assessed in vivo, e.g., in a animal model such as that disclosed in Clynes et al. PNAS (USA) 95:652-656 (1998).
“Effector cells” are leukocytes which express one or more FcRs and perform effector functions. Preferably, the cells express at least Fc?RIII and perform ADCC effector function. Examples of human leukocytes which mediate ADCC include peripheral blood mononuclear cells (PBMC), natural killer (NK) cells, monocytes, cytotoxic T cells and neutrophils; with PBMCs and NK cells being preferred. The effector cells may be isolated from a native source thereof, e.g. from blood or PBMCs as described herein.
The terms “Fc receptor” or “FcR” are used to describe a receptor that binds to the Fe region of an antibody. The preferred FcR is a native sequence human FcR. Moreover, a preferred FcR is one which binds an IgG antibody (a gamma receptor) and includes receptors of the Fc?RI, Fc?RII, and Fc? RIII subclasses, including allelic variants and alternatively spliced forms of these receptors. Fc?RII receptors include Fc?RIIA (an “activating receptor”) and Fc?RIIB (an “inhibiting receptor”), which have similar amino acid sequences that differ primarily in the cytoplasmic domains thereof. Activating receptor Fc?RIIA contains an immunoreceptor tyrosine-based activation motif (ITAM) in its cytoplasmic domain. Inhibiting receptor Fc?RIIB contains an immunoreceptor tyrosine-based inhibition motif (ITIM) in its cytoplasmic domain. (see review M. in Daëron, Annu. Rev. Immunol. 15:203-234 (1997)). FcRs are reviewed in Ravetch and Kinet, Annu. Rev. Immunol 9:457-92 (1991); Capel et al., Immunomethods 4:25-34 (1994); and de Haas et al., J Lab. Clin. Med. 126:330-41 (1995). Other FcRs, including those to be identified in the future, are encompassed by the term “FcR” herein. The term also includes the neonatal receptor, FcRn, which is responsible for the transfer of maternal IgGs to the fetus (Guyer et al., J Immunol. 117:587 (1976) and Kim et al., Eur. J. Immunol. 24:2429 (1994)).
“Complement dependent cytotoxicity” or “CDC” refers to the ability of a molecule to lyse a target in the presence of complement. The complement activation pathway is initiated by the binding of the first component of the complement system (C1q) to a molecule (e.g. an antibody) complexed with a cognate antigen. To assess complement activation, a CDC assay, e.g. as described in Gazzano-Santoro et al., J. Immunol. Methods 202:163 (1996), may be performed.
The term “variable” refers to the fact that certain portions of the variable domains differ extensively in sequence among antibodies and are used in the binding and specificity of each particular antibody for its particular antigen. However, the variability is not evenly distributed throughout the variable domains of antibodies. It is concentrated in three segments called hypervariable regions both in the light chain and the heavy chain variable domains. The more highly conserved portions of variable domains are called the framework regions (FRs). The variable domains of native heavy and light chains each comprise four FRs, largely adopting a β-sheet configuration, connected by three hypervariable regions, which form loops connecting, and in some cases forming part of, the >sheet structure. The hypervariable regions in each chain are held together in close proximity by the FRs and, with the hypervariable regions from the other chain, contribute to the formation of the antigen-binding site of antibodies (see Kabat et al., Sequences of Proteins of Immunological Interest, 5th Ed. Public Health Service, National Institutes of Health, Bethesda, Md. (1991)). The constant domains are not involved directly in binding an antibody to an antigen, but exhibit various effector functions, such as participation of the antibody in antibody dependent cellular cytotoxicity (ADCC).
The term “hypervariable region” when used herein refers to the amino acid residues of an antibody which are responsible for antigen-binding. The hypervariable region generally comprises amino acid residues from a “complementarity determining region” or “CDR” (e.g. residues 24-34 (L1), 50-56 (L2) and 89-97 (L3) in the light chain variable domain and 31-35 (H1), 50-65 (H2) and 95-102 (H3) in the heavy chain variable domain; Kabat et al., Sequences of proteins of Immunological Interest, 5th Ed. Public Health Service, National Institutes of Health, Bethesda, Md. (1991)) and/or those residues from a “hypervariable loop” (e.g. residues 2632 (L1), 50-52 (L2) and 91-96 (L3) in the light chain variable domain and 26-32 (H1), 53-55 (H2) and 96-101 (H3) in the heavy chain variable domain; Chothia and Lesk J. Mol. Biol. 196:901-917 (1987)). “Framework Region” or “FR” residues are those variable domain residues other than the hypervariable region residues as herein defined. Papain digestion of antibodies produces two identical antigen-binding fragments, called “Fab” fragments, each with a single antigen-binding site, and a residual “Fc” fragment, whose name reflects its ability to crystallize readily. Pepsin treatment yields an F(ab′) 2 fragment that has two antigen-binding sites and is still capable of cross-linking antigen.
“Fv” is the minimum antibody fragment which contains a complete antigen-recognition and antigen-binding site. This region consists of a dimer of one heavy chain and one light chain variable domain in tight, non-covalent association. It is in this configuration that the three hypervariable regions of each variable domain interact to define an antigen-binding site on the surface of the V H -V L dimer. Collectively, the six hypervariable regions confer antigen-binding specificity to the antibody. However, even a single variable domain (or half of an Fv comprising only three hypervariable regions specific for an antigen) has the ability to recognize and bind antigen, although at a lower affinity than the entire binding site. The Fab fragment also contains the constant domain of the light chain and the first constant domain (CH I) of the heavy chain. Fab′ fragments differ from Fab fragments by the addition of a few residues at the carboxy terminus of the heavy chain CH1 domain including one or more cysteines from the antibody hinge region. Fab′-SH is the designation herein for Fab′ in which the cysteine residue(s) of the constant domains bear at least one free thiol group. F(ab′) 2 antibody fragments originally were produced as pairs of Fab′ fragments which have hinge cysteines between them. Other chemical couplings of antibody fragments are also known.
The “light chains” of antibodies from any vertebrate species can be assigned to one of two clearly distinct types, called kappa (?) and lambda (?), based on the amino acid sequences of their constant domains.
“Single-chain Fv” or “scFv” antibody fragments comprise the V H and V L domains of antibody, wherein these domains are present in a single polypeptide chain. Preferably, the Fv polypeptide further comprises a polypeptide linker between the V H and V L domains which enables the scFv to form the desired structure for antigen binding. For a review of scFv see Plückthun in The Pharmacology of Monoclonal Antibodies , vol. 113, Rosenburg and Moore eds., Springer-Verlag, N.Y., pp. 269-315 (1994).
The term “diabodies” refers to small antibody fragments with two antigen-binding sites, which fragments comprise a variable heavy domain (V H ) connected to a variable light domain (V L ) in the same polypeptide chain (V H -V L ). By using a linker that is too short to allow pairing between the two domains on the same chain, the domains are forced to pair with the complementary domains of another chain and create two antigen-binding sites. Diabodies are described more fully in, for example, EP 404,097; WO 93/11161; and Hollinger et al., Proc. Natl. Acad. Sci. USA, 90:6444-6448 (1993).
An “isolated” antibody is one which has been identified and separated and/or recovered from a component of its natural environment. Contaminant components of its natural environment are materials which would interfere with diagnostic or therapeutic uses for the antibody, and may include enzymes, hormones, and other protcinaceous or nonproteinaceous solutes. Isolated antibody includes the antibody in situ within recombinant cells since at least one component of the antibody's natural environment will not be present. Ordinarily, however, isolated antibody will be prepared by at least one purification step.
An antibody “which binds” an antigen of interest, e.g. CD63 antigenic moiety, is one capable of binding that antigen with sufficient affinity such that the antibody is useful as a therapeutic or diagnostic agent in targeting a cell expressing the antigen. Where the antibody is one which binds CD63 antigenic moiety it will usually preferentially bind CD63 antigenic moiety as opposed to other receptors, and does not include incidental binding such as non-specific Fc contact, or binding to post-translational modifications common to other antigens and may be one which does not significantly cross-react with other proteins. Methods, for the detection of an antibody that binds an antigen of interest, are well known in the art and can include but are not limited to assays such as FACS, cell ELISA and Western blot.
As used herein, the expressions “cell”, “cell line”, and “cell culture” are used interchangeably, and all such designations include progeny. It is also understood that all progeny may not be precisely identical in DNA content, due to deliberate or inadvertent mutations. Mutant progeny that have the same function or biological activity as screened for in the originally transformed cell are included. It will be clear from the context where distinct designations are intended.
“Treatment” refers to both therapeutic treatment and prophylactic or preventative measures, wherein the object is to prevent or slow down (lessen) the targeted pathologic condition or disorder. Those in need of treatment include those already with the disorder as well as those prone to have the disorder or those in whom the disorder is to be prevented. Hence, the mammal to be treated herein may have been diagnosed as having the disorder or may be predisposed or susceptible to the disorder.
The terms “cancer” and “cancerous” refer to or describe the physiological condition in mammals that is typically characterized by unregulated cell growth or death. Examples of cancer include, but are not limited to, carcinoma, lymphoma, blastoma, sarcoma, and leukemia or lymphoid malignancies. More particular examples of such cancers include squamous cell cancer (e.g. epithelial squamous cell cancer), lung cancer including small-cell lung cancer, non-small cell lung cancer, adenocarcinoma of the lung and squamous carcinoma of the lung, cancer of the peritoneum, hepatocellular cancer, gastric or stomach cancer including gastrointestinal cancer, pancreatic cancer, glioblastoma, cervical cancer, ovarian cancer, liver cancer, bladder cancer, hepatoma, breast cancer, colon cancer, rectal cancer, colorectal cancer, endometrial or uterine carcinoma, salivary gland carcinoma, kidney or renal cancer, prostate cancer, vulval cancer, thyroid cancer, hepatic carcinoma, anal carcinoma, penile carcinoma, as well as head and neck cancer.
A “chemotherapeutic agent” is a chemical compound useful in the treatment of cancer. Examples of chemotherapeutic agents include alkylating agents such as thiotepa and cyclosphosphamide (CYTOXAN™); alkyl sulfonates such as busulfan, improsulfan and piposulfan; aziridines such as benzodopa, carboquone, meturedopa, and uredopa; ethylenimines and methylamelamines including altretamine, triethylenemelamine, trietylenephosphoramide, triethylenethiophosphaoramide and trimethylolomelamine; nitrogen mustards such as chlorambucil, chlomaphazine, cholophosphamide, estramustine, ifosfamide, mechlorethamine, mechlorethamine oxide hydrochloride, melphalan, novembichin, phenesterine, prednimustine, trofosfamide, uracil mustard; nitrosureas such as carmustine, chlorozotocin, fotemustine, lomustine, nimustine, ranimustine; antibiotics such as aclacinomysins, actinomycin, authramycin, azaserine, bleomycins, cactinomycin, calicheamicin, carabicin, camomycin, carzinophilin, chromomycins, dactinomycin, daunorubicin, detorubicin, 6-diazo-5-oxo-L-norleucine, doxorubicin, epirubicin, esorubicin, idarubicin, marcellomycin, mitomycins, mycophenolic acid, nogalamycin, olivomycins, peplomycin, potfiromycin, puromycin, quelamycin, rodorubicin, streptonigrin, streptozocin, tubercidin, ubenimex, zinostatin, zorubicin; anti-metabolites such as methotrexate and 5-fluorouracil (5-FU); folic acid analogues such as denopterin, methotrexate, pteropterin, trimetrexate; purine analogs such as fludarabine, 6-mercaptopurine, thiamiprine, thioguanine; pyrimidine analogs such as ancitabine, azacitidine, 6-azauridine, carmofur, cytarabine, dideoxyuridine, doxifluridine, enocitabine, floxuridine, 5-FU; androgens such as calusterone, dromostanolone propionate, epitiostanol, mepitiostane, testolactone; anti-adrenals such as aminoglutethimide, mitotane, trilostane; folic acid replenisher such as frolinic acid; aceglatone; aldophosphamide glycoside; aminolevulinic acid; amsacrine; bestrabucil; bisantrene; edatraxate; defofamine; demecolcine; diaziquone; elformithine; elliptinium acetate; etoglucid; gallium nitrate; hydroxyurea; lentinan; lonidamine; mitoguazone; mitoxantrone; mopidamol; nitracrine; pentostatin; phenamet; pirarubicin; podophyllinic acid; 2-ethylhydrazide; procarbazine; PSK®; razoxane; sizofiran; spirogermanium; tenuazonic acid; triaziquone; 2,2′,2?-trichlorotriethylamine; urethan; vindesine; dacarbazine; mannomustine; mitobronitol; mitolactol; pipobroman; gacytosine; arabinoside (“Ara-C”); cyclophosphamide; thiotepa; taxanes, e.g. paclitaxel (TAXOL®, Bristol-Myers Squibb Oncology, Princeton, N.J.) and docetaxel (TAXOTERE®, Aventis, Rhone-Poulenc Rorer, Antony, France); chlorambucil; gemcitabine; 6-thioguanine; mercaptopurine; methotrexate; platinum analogs such as cisplatin and carboplatin; vinblastine; platinum; etoposide (VP-16); ifosfamide; mitomycin C; mitoxantrone; vincristine; vinorelbine; navelbine; novantrone; teniposide; daunomycin; aminopterin; xeloda; ibandronate; CPT-11; topoisomerase inhibitor RFS 2000; difluoromethylomithine (DMFO); retinoic acid; esperamicins; capecitabine; and pharmaceutically acceptable salts, acids or derivatives of any of the above. Also included in this definition are anti-hormonal agents that act to regulate or inhibit hormone action on tumors such as anti-estrogens including for example tamoxifen, raloxifene, aromatase inhibiting 4(5)-imidazoles, 4-hydroxytamoxifen, trioxifene, keoxifene, LY117018, onapristone, and toremifene (Fareston); and anti-androgens such as flutamide, nilutamide, bicalutamide, leuprolide, and goserelin; and pharmaceutically acceptable salts, acids or derivatives of any of the above.
“Mammal” for purposes of treatment refers to any animal classified as a mammal, including humans, mice, SCID or nude mice or strains of mice, domestic and farm animals, and zoo, sports, or pet animals, such as sheep, dogs, horses, cats, cows, etc. Preferably, the mammal herein is human.
“Oligonucleotides” are short-length, single-or double-stranded polydeoxynucleotides that are chemically synthesized by known methods (such as phosphotriester, phosphite, or phosphoramidite chemistry, using solid phase techniques such as described in EP 266,032, published 4 May 1988, or via deoxynucleoside H-phosphonate intermediates as described by Froehler et al., Nucl. Acids Res., 14:5399-5407, 1986. They are then purified on polyacrylamide gels.
Unless indicated otherwise, the term “CD63 antigenic moiety” when used herein refers to the Type III membrane protein of the tetraspanin family also referred to as melanoma 1 antigen, ocular melanoma-associated antigen, melanoma associated antigen ME491, lysosome-associated membrane glycoprotein 3, granulophysin, melanoma-associated antigen MLA1.
“Chimeric” antibodies are immunoglobulins in which a portion of the heavy and/or light chain is identical with or homologous to corresponding sequences in antibodies derived from a particular species or belonging to a particular antibody class or subclass, while the remainder of the chain(s) is identical with or homologous to corresponding sequences in antibodies derived from another species or belonging to another antibody class or subclass, as well as fragments of such antibodies, so long as they exhibit the desired biological activity (U.S. Pat. No. 4,816,567 and Morrison et al, Proc. Natl. Acad. Sci. USA, 81:6851-6855 (1984)).
“Humanized” forms of non-human (e.g. murine) antibodies are specific chimeric immunoglobulins, immunoglobulin chains or fragments thereof (such as Fv, Fab, Fab′, F(ab) 2 or other antigen-binding subsequences of antibodies) which contain minimal sequence derived from non-human immunoglobulin. For the most part, humanized antibodies are human immunoglobulins (recipient antibody) in which residues from the complementarity determining regions (CDRs) of the recipient antibody are replaced by residues from the CDRs of a non-human species (donor antibody) such as mouse, rat or rabbit having the desired specificity, affinity and capacity. In some instances, Fv framework region (FR) residues of the human immunoglobulin are replaced by corresponding non-human FR residues. Furthermore, the humanized antibody may comprise residues which are found neither in the recipient antibody nor in the imported CDR or FR sequences. These modifications are made to further refine and optimize antibody performance. In general, the humanized antibody will comprise substantially all of at least one, and typically two, variable domains, in which all or substantially all of the CDR regions correspond to those of a non-human immunoglobulin and all or substantially all of the FR residues are those of a human immunoglobulin consensus sequence. The humanized antibody optimally also will comprise at least a portion of an immunoglobulin constant region (Fc), typically that of a human immunoglobulin.
“De-immunized” antibodies are immunoglobulins that are non-immunogenic, or less immunogenic, to a given species. De-immunization can be achieved through structural alterations to the antibody. Any de-immunization technique known to those skilled in the art can be employed. One suitable technique for de-immunizing antibodies is described, for example, in WO 00/34317 published Jun. 15, 2000.
“Homology” is defined as the percentage of residues in the amino acid sequence variant that are identical after aligning the sequences and introducing gaps, if necessary, to achieve the maximum percent homology. Methods and computer programs for the alignment are well known in the art.
Throughout the instant specification, hybridoma cell lines, as well as the isolated monoclonal antibodies which are produced therefrom, are alternatively referred to by their internal designation, 7BDI-58, 7BDI-60, 7BD-33-11A, 1A245.6, H460-22-1, or AR51A994.1 or Depository Designation, IDAC 141205-01, ATCC PTA-4623, ATCC PTA-4890, ATCC PTA-4889, ATCC PTA-4622, or IDAC 141205-06.
As used herein “ligand” includes a moiety which exhibits binding specificity for a target antigen, and which may be an intact antibody molecule and any molecule having at least an antigen-binding region or portion thereof (i.e., the variable portion of an antibody molecule), e.g., an Fv molecule, Fab molecule, Fab′ molecule, F(ab′).sub.2 molecule, a bispecific antibody, a fusion protein, or any genetically engineered molecule which specifically recognizes and binds the antigen bound by the isolated monoclonal antibody produced by the hybridoma cell line designated as, IDAC 141205-01, ATCC PTA-4623, ATCC PTA-4890, ATCC PTA-4889, ATCC PTA-4622, or IDAC 141205-06 (the IDAC 141205-01, ATCC PTA-4623, ATCC PTA-4890, ATCC PTA-4889, ATCC PTA-4622, or IDAC 141205-06 antigen).
As used herein “antigen-binding region” means a portion of the molecule which recognizes the target antigen.
As used herein “competitively inhibits” means being able to recognize and bind a determinant site to which the monoclonal antibody produced by the hybridoma cell line designated as IDAC 141205-01, ATCC PTA-4623, ATCC PTA-4890, ATCC PTA-4889, ATCC PTA-4622, or IDAC 141205-06, (the IDAC 141205-01, ATCC PTA-4623, ATCC PTA-4890, ATCC PTA-4889, ATCC PTA-4622, or IDAC 141205-06 antibody) is directed using conventional reciprocal antibody competition assays. (Belanger L., Sylvestre C. and Dufour D. (1973), Enzyme linked immunoassay for alpha fetoprotein by competitive and sandwich procedures. Clinica Chimica Acta 48, 15).
As used herein “target antigen” is the IDAC 141205-01, ATCC PTA-4623, ATCC PTA-4890, ATCC PTA-4889, ATCC PTA-4622, or IDAC 141205-06 antigen or portions thereof.
As used herein, an “immunoconjugate” means any molecule or ligand such as an antibody chemically or biologically linked to a cytotoxin, a radioactive agent, enzyme, toxin, an anti-tumor drug or a therapeutic agent. The antibody may be linked to the cytotoxin, radioactive agent, anti-tumor drug or therapeutic agent at any location along the molecule so long as it is able to bind its target. Examples of immunoconjugates include antibody toxin chemical conjugates and antibody-toxin fusion proteins.
As used herein, a “fusion protein” means any chimeric protein wherein an antigen binding region is connected to a biologically active molecule, e.g., toxin, enzyme, or protein drug.
In order that the invention herein described may be more fully understood, the following description is set forth.
The present invention provides ligands (i.e., IDAC 141205-01, ATCC PTA-4623, ATCC PTA-4890, ATCC PTA-4889, ATCC PTA-4622, or IDAC 141205-06 ligands) which specifically recognize and bind the IDAC 141205-01, ATCC PTA-4623, ATCC PTA-4890, ATCC PTA-4889, ATCC PTA-4622, or IDAC 141205-06 antigen.
The ligand of the invention may be in any form as long as it has an antigen-binding region which competitively inhibits the immunospecific binding of the monoclonal antibody produced by hybridoma IDAC 141205-01, ATCC PTA-4623, ATCC PTA-4890, ATCC PTA-4889, ATCC PTA-4622, or IDAC 141205-06 to its target antigen. Thus, any recombinant proteins (e.g., fusion proteins wherein the antibody is combined with a second protein such as a lymphokine or a tumor inhibitory growth factor) having the same binding specificity as the IDAC 141205-01, ATCC PTA-4623, ATCC PTA-4890, ATCC PTA-4889, ATCC PTA-4622, or IDAC 141205-06 antibody fall within the scope of this invention.
In one embodiment of the invention, the ligand is the IDAC 141205-01, ATCC PTA-4623, ATCC PTA-4890, ATCC PTA-4889, ATCC PTA-4622, or IDAC 141205-06 antibody.
In other embodiments, the ligand is an antigen binding fragment which may be a Fv molecule (such as a single chain Fv molecule), a Fab molecule, a Fab′ molecule, a F(ab′)2 molecule, a fusion protein, a bispecific antibody, a heteroantibody or any recombinant molecule having the antigen-binding region of the IDAC 141205-01, ATCC PTA-4623, ATCC PTA-4890, ATCC PTA-4889, ATCC PTA-4622, or IDAC 141205-06 antibody. The ligand of the invention is directed to the epitope to which the IDAC 141205-01, ATCC PTA-4623, ATCC PTA-4890, ATCC PTA-4889, ATCC PTA-4622, or IDAC 141205-06 monoclonal antibody is directed.
The ligand of the invention may be modified, i.e., by amino acid modifications within the molecule, so as to produce derivative molecules. Chemical modification may also be possible.
Derivative molecules would retain the functional property of the polypeptide, namely, the molecule having such substitutions will still permit the binding of the polypeptide to the IDAC 141205-01, ATCC PTA-4623, ATCC PTA-4890, ATCC PTA-4889, ATCC PTA-4622, or IDAC 141205-06 antigen or portions thereof.
These amino acid substitutions include, but are not necessarily limited to, amino acid substitutions known in the art as “conservative”.
For example, it is a well-established principle of protein chemistry that certain amino acid substitutions, entitled “conservative amino acid substitutions,” can frequently be made in a protein without altering either the conformation or the function of the protein.
Such changes include substituting any of isoleucine (I), valine (V), and leucine (L) for any other of these hydrophobic amino acids; aspartic acid (D) for glutamic acid (E) and vice versa; glutamine (Q) for asparagine (N) and vice versa; and serine (S) for threonine (T) and vice versa. Other substitutions can also be considered conservative, depending on the environment of the particular amino acid and its role in the three-dimensional structure of the protein. For example, glycine (G) and alanine (A) can frequently be interchangeable, as can alanine and valine (V). Methionine (M), which is relatively hydrophobic, can frequently be interchanged with leucine and isoleucine, and sometimes with valine. Lysine (K) and arginine (R) are frequently interchangeable in locations in which the significant feature of the amino acid residue is its charge and the differing pK's of these two amino acid residues are not significant. Still other changes can be considered “conservative” in particular environments.
Given an antibody, an individual ordinarily skilled in the art can generate a competitively inhibiting ligand, for example a competing antibody, which is one that recognizes the same epitope (Belanger et al., 1973). One method could entail immunizing with an immunogen that expresses the antigen recognized by the antibody. The sample may include but is not limited to tissue, isolated protein(s) or cell line(s). Resulting hybridomas could be screened using a competing assay, which is one that identifies antibodies that inhibit the binding of the test antibody, such as ELISA, FACS or immunoprecipiation. Another method could make use of phage display libraries and panning for antibodies that recognize said antigen (Rubinstein et al., 2003). In either case, hybridomas would be selected based on their ability to out-compete the binding of the original antibody to its target antigen. Such hybridomas would therefore possess the characteristic of recognizing the same antigen as the original antibody and more specifically would recognize the same epitope.
EXAMPLE 1
Hybridoma Production—Hybridoma Cell Line AR51A994.1 and 7BDI-58
The hybridoma cell lines 7BDI-58 and AR51A994.1 were deposited, in accordance with the Budapest Treaty, with the International Depository Authority of Canada (IDAC), Bureau of Microbiology, Health Canada, 1015 Arlington Street, Winnipeg, Manitoba, Canada, R3E 3R2, on Dec. 14, 2005, under Accession Numbers 141205-01 and 141205-06 respectively. In accordance with 37 CFR 1.808, the depositors assure that all restrictions imposed on the availability to the public of the deposited materials will be irrevocably removed upon the granting of a patent.
The hybridoma that produces the anti-cancer antibody 7BDI-58 was produced as disclosed in Ser. No. 10/713,642. To produce the hybridoma that produces the anti-cancer antibody AR51A994.1, a single cell suspension of frozen human ovarian endometroid adenocarcinoma tumor tissue (Genomics Collaborative, Cambridge, Mass.) was prepared in PBS. IMMUNEASY™ (Qiagen, Venlo, Netherlands) adjuvant was prepared for use by gentle mixing. Four to six week old BALB/c mice were immunized by injecting subcutaneously, 2 million cells in 50 microliters of the antigen-adjuvant. Recently prepared antigen-adjuvant was used to boost the immunized mice intraperitoneally, 2 and 5 weeks after the initial immunization, with approximately 2 million cells in 50-60 microliters. A spleen was used for fusion three days after the last immunization. The hybridomas were prepared by fusing the isolated splenocytes with NSO-1 myeloma partners. The supernatants from the fusions were tested from subclones of the hybridomas.
To determine whether the antibodies secreted by the hybridoma cells are of the IgG or IgM isotype, an ELISA assay was employed. 100 microliters/well of goat anti-mouse IgG+IgM (H+L) at a concentration of 2.4 micrograms/mL in coating buffer (0.1 M carbonate/bicarbonate buffer, pH 9.2-9.6) at 4° C. was added to the ELISA plates overnight. The plates were washed thrice in washing buffer (PBS+0.05% Tween). 100 microliters/well blocking buffer (5% milk in wash buffer) was added to the plate for 1 hour at room temperature and then washed thrice in washing buffer. 100 microliters/well of hybridoma supernatant was added and the plate incubated for 1 hour at room temperature. The plates were washed thrice with washing buffer and 1/100,000 dilution of either goat anti-mouse IgG or IgM horseradish peroxidase conjugate (diluted in PBS containing 5% milk), 100 microliters/well, was added. After incubating the plate for 1 hour. at room temperature the plate was washed thrice with washing buffer. 100 microliters/well of TMB solution was incubated for 1-3 minutes at room temperature. The color reaction was terminated by adding 50 microliters/well 2M H 2 SO 4 and the plate was read at 450 nm with a Perkin-Elmer HTS7000 plate reader. As indicated in FIG. 1 , the AR51A994.1 hybridoma secreted primarily antibodies of the IgG isotype.
To determine the subclass of antibody secreted by the hybridoma cells, an isotyping experiment was performed using a Mouse Monoclonal Antibody Isotyping Kit (HyCult Biotechnology, Frontstraat, Netherlands). 500 microliters of buffer solution was added to the test strip containing rat anti-mouse subclass specific antibodies. 500 microliters of hybridoma supernatant was added to the test tube, and submerged by gentle agitation. Captured mouse immunoglobulins were detected directly by a second rat monoclonal antibody which is coupled to colloid particles. The combination of these two proteins creates a visual signal used to analyse the isotype. The anti-cancer antibody AR51A994.1 is of the IgG1, kappa isotype.
After one round of limiting dilution, hybridoma supernatants were tested for antibodies that bound to target cells in a cell ELISA assay. Two human ovarian cancer cell lines, and 1 human normal skin cell line were tested: OCC-1, OVCAR-3 and CCD-27sk respectively. The plated cells were fixed prior to use. The plates were washed thrice with PBS containing MgCl 2 and CaCl 2 at room temperature. 100 microliters of 2% paraformaldehyde diluted in PBS was added to each well for 10 minutes at room temperature and then discarded. The plates were again washed with PBS containing MgCl 2 and CaCl 2 three times at room temperature. Blocking was done with 100 microliters/well of 5% milk in wash buffer (PBS+0.05% Tween) for 1 hour at room temperature. The plates were washed thrice with wash buffer and the hybridoma supernatant was added at 75 microliters/well for 1 hour at room temperature. The plates were washed 3 times with wash buffer and 100 microliters/well of 1/25,000 dilution of goat anti-mouse IgG antibody conjugated to horseradish peroxidase (diluted in PBS containing 5% milk) was added. After 1 hour incubation at room temperature the plates were washed 3 times with wash buffer and 100 microliters/well of TMB substrate was incubated for 1-3 minutes at room temperature. The reaction was terminated with 50 microliters/well 2M H 2 SO 4 and the plate read at 450 nm with a Perkin-Elmer HTS7000 plate reader. The results as tabulated in FIG. 1 were expressed as the number of folds above background compared to an in-house IgG isotype control that has previously been shown not to bind to the cell lines tested. The antibodies from the hybridoma AR51A994.1 showed binding to the ovarian cancer cell line OVCAR-3 and to the normal skin cell line CCD-27sk.
In conjunction with testing for antibody binding, the cytotoxic effect of the hybridoma supernatants was tested in the cell lines: OCC-1, OVCAR-3 and CCD-27sk. Calcein AM was obtained from Molecular Probes (Eugene, Oreg.). The assays were performed according to the manufacturer's instructions with the changes outlined below. Cells were plated before the assay at the predetermined appropriate density. After 2 days, 75 microliters of supernatant from the hybridoma microtitre plates were transferred to the cell plates and incubated in a 5 percent CO 2 incubator for 5 days. The wells that served as the positive controls were aspirated until empty and 100 microliters of sodium azide (NaN 3 ) or cycloheximide was added. After 5 days of treatment, the plates were then emptied by inverting and blotting dry. Room temperature DPBS (Dulbecco's phosphate buffered saline) containing MgCl 2 and CaCl 2 was dispensed into each well from a multichannel squeeze bottle, tapped 3 times, emptied by inversion and then blotted dry. 50 microliters of the fluorescent calcein dye diluted in DPBS containing MgCl 2 and CaCl 2 was added to each well and incubated at 37° C. in a 5% CO 2 incubator for 30 minutes. The plates were read in a Perkin-Elmer HTS7000 fluorescence plate reader and the data was analyzed in Microsoft Excel. The results are tabulated in FIG. 1 . Supernatant from the AR51A994.1 hybridoma produced specific cytotoxicity of 14 percent and 10 percent on the OCC-1 and OVCAR-3 cells respectively. On OCC-1, this was 16 and 15 percent of the cytotoxicity obtained with the positive controls sodium azide and cycloheximide, respectively. On OVCAR-3, this was 22 percent of the cytotoxicity obtained with the positive control cycloheximide. Results from FIG. 1 demonstrated that the cytotoxic effects of AR51A994.1 were not proportional to the binding levels on the cancer cell types. There was a greater level of cytotoxicity produced in the OCC-1 cells as compared to the OVCAR-3 cells, although the level of binding in the OVCAR-3 cells was higher. As tabulated in FIG. 1 , AR51A994.1 did not produce cytotoxicity in the CCD-27sk normal cell line. The known non-specific cytotoxic agents cycloheximide and NaN 3 generally produced cytotoxicity as expected.
EXAMPLE 2
Antibody Production:
The AR51A994.1, 7BDI-58 and 7BDI-60 monoclonal antibodies were produced by culturing the hybridomas in CL-1000 flasks (BD Biosciences, Oakville, ON) with collections and reseeding occurring twice/week. The antibody was purified according to standard antibody purification procedures with Protein G Sepharose 4 Fast Flow (Amersham Biosciences, Baie d'Urfé, QC). It is within the scope of this invention to utilize monoclonal antibodies that are de-immunized, humanized, chimerized or murine.
The AR51A994.1 antibody was compared to a number of both positive (anti-EGFR (C225, IgG1, kappa, 5 microgram/mL, Cedarlane, Hornby, ON), Cycloheximide (100 micromolar, Sigma, Oakville, ON), NaN 3 (0.1%, Sigma, Oakville, ON)) and negative (107.3 (anti-TNP, IgG1, kappa, 20 micrograms/mL, BD Biosciences, Oakville, ON), and 1B7.11 (anti-TNP), IgG1, kappa, 20 micrograms/mL purified in-house)), as well as a buffer diluent control in a cytotoxicity assay ( FIG. 2 ). Pancreatic cancer (BxPC-3), ovarian cancer (OCC-1 and OVCAR-3) and non-cancer (CCD-27sk, Hs888.Lu) cell lines were tested (all from the ATCC, Manassas, Va.). Calcein AM was obtained from Molecular Probes (Eugene,OR). The assays were performed according to the manufacturer's instructions with the changes outlined below. Cells were plated before the assay at the predetermined appropriate density. After 2 days, 100 microliters of purified antibody or controls were diluted into media, and then transferred to the cell plates and incubated in a 5 percent CO 2 incubator for 5 days. The plates were then emptied by inverting and blotted dry. Room temperature DPBS containing MgCl 2 and CaCl 2 was dispensed into each well from a multichannel squeeze bottle, tapped 3 times, emptied by inversion and then blotted dry. 50 μL of the fluorescent calcein dye diluted in DPBS containing MgCl 2 and CaCl 2 was added to each well and incubated at 37° C. in a 5 percent CO 2 incubator for 30 minutes. The plates were read in a Perkin-Elmer HTS7000 fluorescence plate reader and the data was analyzed in Microsoft Excel and the results were tabulated in FIG. 2 . Each antibody received a score between 5 and 50 based on the average cytotoxicity observed in four experiments tested in triplicate, and a score between 25 and 100 based on the variability observed between assays. The sum of these two scores (the cytotoxicity score) is presented in FIG. 2 . A cytotoxicity score of greater than or equal to 55 was considered to be positive on the cell line tested. The AR51A994.1 antibody produced specific cytotoxicity in the OVCAR-3 ovarian cancer cell line and the BxPC-3 pancreatic cancer cell line relative to both isotype and buffer negative controls. This is consistent with data from the hybridoma supernatant of the AR51A994.1 clone, which also showed specific cytotoxicity against the OVCAR-3 cell line (see Example 1). AR51A994.1 did not produce positive cytotoxicity scores in the OCC-1 ovarian cancer cell line. Importantly, AR51A994.1 did not produce significant cytotoxicity, compared to negative controls, against non-cancer cell lines such as CCD-27sk or Hs888.Lu, suggesting that the antibody is specifically cytotoxic towards cancer cells. The chemical cytotoxic agents induced their expected cytotoxicity against multiple cell lines.
Binding of AR51A994.1 to pancreatic cancer (BxPC-3), ovarian cancer (OCC-1 and OVCAR-3) and non-cancer (CCD-27sk, Hs888.Lu) cell lines was assessed by flow cytometry (FACS). Cells were prepared for FACS by initially washing the cell monolayer with DPBS (without Ca ++ and Mg ++ ). Cell dissociation buffer (INVITROGEN, Burlington, ON) was then used to dislodge the cells from their cell culture plates at 37° C. After centrifugation and collection, the cells were resuspended in DPBS containing MgCl 2 , CaCl 2 and 2 percent fetal bovine serum at 4° C. (staining media) and counted, aliquoted to appropriate cell density, spun down to pellet the cells and resuspended in staining media at 4° C. in the presence of test antibodies (AR51A994.1) or control antibodies (isotype control, anti-EGFR) at 20 μg/mL on ice for 30 minutes. Prior to the addition of Alexa Fluor 546-conjugated secondary antibody the cells were washed once with staining media. The Alexa Fluor 546-conjugated antibody in staining media was then added for 30 minutes at 4° C. The cells were then washed for the final time and resuspended in fixing media (staining media containing 1.5% paraformaldehyde). Flow cytometric acquisition of the cells was assessed by running samples on a FACSarray™ using the FACSarray™ System Software (BD Biosciences, Oakville, ON). The forward (FSC) and side scatter (SSC) of the cells were set by adjusting the voltage and amplitude gains on the FSC and SSC detectors. The detectors for the fluorescence (Alexa-546) channel was adjusted by running unstained cells such that cells had a uniform peak with a median fluorescent intensity of approximately 1-5 units. For each sample, approximately 10,000 gated events (stained fixed cells) were acquired for analysis and the results are presented in FIG. 3 .
FIG. 3 presents the mean fluorescence intensity fold increase above isotype control. Representative histograms of AR51A994.1 antibodies were compiled for FIG. 4 . AR51A994.1 showed strong binding to the ovarian cancer cell lines OCC-1 and OVCAR-3 (16 and 14.8 fold respectively) and the non-cancer lung cell line Hs888.Lu (24.6 fold) with weaker binding to the pancreatic cancer cell line BxPC-3 (8.6 fold) and the non-cancer skin cell line CCD-27sk (5.1 fold). These data demonstrate that AR51A994.1 exhibited functional specificity in that although there was clear binding to a number of cell lines tested, there was only associated cytotoxicity with OVCAR-3 ovarian and BxPC-3 pancreatic cancer in vitro.
To further the in vitro binding and cytotoxicity results from above, the AR51A994.1 antibody was tested with lung cancer (A549), additional pancreatic cancer (AsPC-1 and PL45) and ovarian cancer (C-13, ES-2, Hey, OV2008, OVCA-429 and OVCAR-3) cell lines (A549, AsPC-1, PL45 and OVCAR-3 were from ATCC, Manassas, Va. C-13, ES-2, Hey, OV2008 and OVCA-429 were obtained from the Ottawa Regional Cancer Center (Ottawa, Ontario)) along with the positive and negative controls as mentioned above, in a cytotoxicity assay. The Live/Dead cytotoxicity assay was performed as described above. The AR51A994.1 antibody produced specific cytotoxicity in the ES-2, OV2008 and OVCA-429 ovarian cancer cell lines and the A549 lung cancer cell line relative to both isotype and buffer negative controls ( FIG. 2 ). Also, the AR51A994.1 antibody produced specific cytotoxicity in the OVCAR-3 ovarian cancer cell line. This is consistent with the OVCAR-3 cytotoxicity data from above. AR51A994.1 did not produce positive cytotoxicity scores in the C-13 and Hey ovarian cancer cell lines or the AsPC-1 and PL45 pancreatic cell lines. The chemical cytotoxic agents induced their expected cytotoxicity against multiple cell lines.
Binding of AR51A994.1 to lung cancer (A549), additional pancreatic cancer (AsPC-1 and PL45) and ovarian cancer (C-13, ES-2, Hey, OV2008, OVCA-429 and OVCAR-3) cell lines was assessed by flow cytometry (FACS) as outlined above. FIG. 3 presents the mean fluorescence intensity fold increase above isotype control. Representative histograms of AR51A994.1 antibodies were compiled for FIG. 4 . AR51A994.1 showed greater binding to the ovarian cancer cell lines ES-2 and OV2008 (22.2 and 19.8 fold respectively) and weaker binding to the ovarian cancer cell lines C-13, Hey, OVCA-429 and OVCAR-3 (9.8, 4.4, 3.9 and 4.3 fold respectively), the pancreatic cell lines AsPC-1 and PL45 (4.1 and 2.4 fold respectively) and the lung cancer cell line A549 (4.6 fold). These data demonstrate that AR51A994.1 exhibited functional specificity in that although there was clear binding to all cell lines tested, there was only associated cytotoxicity with some of the cancer cell lines.
The 7BDI-58 and 7BDI-60 antibody was compared to a number of both positive (anti-Her2 (IgG1, kappa, 10 micrograms/mL, Inter Medico, Markham, ON), Cycloheximide (100 micromolar, Sigma, Oakville, ON)) and negative (107.3 (anti-TNP, IgG1, kappa, 20 micrograms/mL, BD Biosciences, Oakville, ON)), as well as a buffer diluent control in a cytotoxicity assay ( FIG. 5 ). Ovarian cancer (OVCAR-3) and breast cancer (MDA-MB-468 (MB-468)) and non-cancer (Bst549, CCD-27sk, Hs888.Lu) cell lines were tested (all from the ATCC, Manassas, Va.). The Live/Dead cytotoxicity assay was obtained from Molecular Probes (Eugene, Oreg.). The assays were performed according to the manufacturer's instructions with the changes outlined below. Cells were plated before the assay at the predetermined appropriate density. After 2 days, 100 microliters of purified antibody or controls were diluted into media, and then transferred to the cell plates and incubated in a 5 percent CO 2 incubator for 5 days. The plates were then emptied by inverting and blotted dry. Room temperature DPBS containing MgCl 2 and CaCl 2 was dispensed into each well from a multichannel squeeze bottle, tapped 3 times, emptied by inversion and then blotted dry. 50 microliters of the fluorescent calcein dye diluted in DPBS containing MgCl 2 and CaCl 2 was added to each well and incubated at 37° C. in a 5 percent CO 2 incubator for 30 minutes. The plates were read in a Perkin-Elmer HTS7000 fluorescence plate reader and the data was analyzed in Microsoft Excel and the results were tabulated in FIG. 5 . Each antibody received a score between 5 and 50 based on the average cytotoxicity observed in four experiments tested in triplicate, and a score between 25 and 100 based on the variability observed between assays. The sum of these two scores (the cytotoxicity score) is presented in FIG. 5 . A cytotoxicity score of greater than or equal to 55 was considered to be positive on the cell line tested. The 7BDI-58 antibody produced specific cytotoxicity in the OVCAR-3 ovarian cancer cell line relative to both isotype and buffer negative controls. 7BDI-58 did not produce positive cytotoxicity scores in the MB-468 breast cancer cell line. Importantly, 7BDI-58 did not produce significant cytotoxicity, compared to negative controls, against non-cancer cell lines such as Bst549, CCD-27sk or Hs888.Lu, suggesting that the antibody has specific cytotoxicity for cancer cells. The 7BDI-60 antibody produced specific cytotoxicity in the MB-468 breast cancer cell line relative to both isotype and buffer negative controls. 7BDI-60 did not produce positive cytotoxicity scores in the OVCAR-3 ovarian cancer cell line. Importantly, 7BDI-60 did not produce significant cytotoxicity, compared to negative controls, against non-cancer cell lines such as Bst549, CCD-27sk or Hs888.Lu, suggesting that the antibody has specific cytotoxicity for cancer cells. The chemical cytotoxic agent induced its expected cytotoxicity against multiple cell lines.
Binding of 7BDI-58 and 7BDI-60 to breast cancer (MB-468), ovarian cancer (OVCAR-3) and non-cancer (Bst549, CCD-27sk, Hs888.Lu) cell lines was assessed by flow cytometry (FACS). Cells were prepared for FACS by initially washing the cell monolayer with DPBS (without Ca ++ and Mg ++ ). Cell dissociation buffer (INVITROGEN, Burlington, ON) was then used to dislodge the cells from their cell culture plates at 37° C. After centrifugation and collection the cells were resuspended in Dulbecco's phosphate buffered saline containing MgCl 2 , CaCl 2 and 25% fetal bovine serum at 4° C. (wash media) and counted, aliquoted to appropriate cell density, spun down to pellet the cells and resuspended in staining media (DPBS containing MgCl 2 and CaCl 2 ) containing test antibodies (7BDI-58 or 7BDI-60) or control antibodies (isotype control or anti-EGFR) at 20 micrograms/mL on ice for 30 minutes. Prior to the addition of Alexa Fluor 488-conjugated secondary antibody the cells were washed once with wash media. The Alexa Fluor 488-conjugated antibody in staining media was then added for 20 minutes. The cells were then washed for the final time and resuspended in staining media containing 1 microgram/mL propidium iodide. Flow cytometric acquisition of the cells was assessed by running samples on a FACScan using the CellQuest software (BD Biosciences). The forward (FSC) and side scatter (SSC) of the cells were set by adjusting the voltage and amplitude gains on the FSC and SSC detectors. The detectors for the three fluorescence channels (FL1, FL2, and FL3) were adjusted by running cells stained with purified isotype control antibody followed by Alexa Fluor 488-conjugated secondary antibody such that cells had a uniform peak with a median fluorescent intensity of approximately 1-5 units. Live cells were acquired by gating for FSC and propidium iodide exclusion. For each sample, approximately 10,000 live cells were acquired for analysis and the results presented in FIG. 6 .
FIG. 6 presents the mean fluorescence intensity fold increase above isotype control for each antibody. Representative histograms of 7BDI-58 and 7BDI-60 antibodies were compiled for FIG. 7 . 7BDI-58 showed greater binding to the ovarian cancer cell line OVCAR-3 (13.8 fold), the non-cancer lung cell line Hs888.Lu (18.3 fold), the non-cancer breast cell line Bst549 (10.8 fold) and the non-cancer skin cell line CCD-27sk (22.5) with weaker binding to the breast cancer cell line MB-468 (3.8 fold). These data demonstrate that 7BDI-58 exhibited functional specificity in that although there was clear binding to a number of cell lines tested, there was only associated cytotoxicity with OVCAR-3 ovarian cancer. 7BDI-60 showed binding to the ovarian cancer cell line OVCAR-3 (5.7 fold), the breast cancer cell line MB-468 (5.1 fold), the non-cancer lung cell line Hs888.Lu (9.1 fold), the non-cancer breast cell line Bst549 (3.7 fold) and the non-cancer skin cell line CCD-27sk (8.1 fold). These data demonstrate that 7BDI-60 exhibited functional specificity in that although there was clear binding to a number of cell lines tested, there was only associated cytotoxicity with MB-468 breast cancer.
EXAMPLE 3
In vivo Tumor Experiments with MDA-MB-231 Cells
With reference to FIGS. 8 and 9 , 4 to 6 week old female SCID mice were implanted with 5 million human breast cancer cells (MDA-MB-231) in 100 microliters saline injected subcutaneously in the scruff of the neck. The mice were randomly divided into 2 treatment groups of 5. On the day after implantation, 20 mg/kg of 7BDI-58 test antibody or buffer control was administered intraperitoneally to each cohort in a volume of 300 microliters after dilution from the stock concentration with a diluent that contained 2.7 mM KCl, 1 mM KH 2 PO 4 , 137 mM NaCl and 20 mM Na 2 HPO 4 . The antibody and control samples were then administered once per week for the duration of the study, a total of 8 doses, in the same fashion. Tumor growth was measured about every seventh day with calipers. Body weights of the animals were recorded once per week for the duration of the study. At the end of the study all animals were euthanized according to CCAC guidelines.
7BDI-58 markedly reduced tumor growth in the MDA-MB-231 in vivo prophylactic model of human breast cancer. On day 55 post-implantation, 5 days after the last treatment dose, the mean tumor volume in the 7BDI-58 treated group was 91.2 percent lower than the tumor volume in the buffer control-treated group ( FIG. 8 ). The tumor volume at the end of the study was significantly different from that of the control (p=0.0105, t-test).
There were no clinical signs of toxicity throughout the study. Body weight measured at weekly intervals was a surrogate for well-being and failure to thrive. As seen in FIG. 9 , there were no significant differences in the body weights of the control or 7BDI-58-treated groups over the course of the study. There was also no significant difference in body weight between the two groups at the end of the treatment period.
In conclusion, 7BDI-58 was well-tolerated and decreased the tumor burden in this human breast cancer xenograft model.
EXAMPLE 4
Determination of Cross-reactivity Between the Monoclonal Antibodies 7BDI-58, 7BDI-60, AR55A994.1 and Anti-CD63 Antibodies
Results from Western blots of total membrane fractions and of whole cell lysates, when probed with the monoclonal antibodies 7BDI-58, 7BDI-60 and AR51A994.1 revealed a strong similarity with those obtained with ARIUS' anti-CD63 monoclonal antibodies 7BD-33-11A, 1A245.6 and H460-22-1 ( FIG. 10 ). In order to determine whether the former antibodies cross-reacted with CD63 they were used as probes on Western blots of immunoprecipitate complexes obtained with either 7BD-33-11A or with 1A245.6 from the total membrane fraction of cells grown in culture.
Briefly 300 micrograms of MDA-MB-231 total membrane fraction (1 mg/mL final protein concentration) was incubated with 7BD-33-11A-conjugated protein G Sepharose beads for 2 hours at 4° C. After washing the beads were boiled in 1× non-reducing SDS-PAGE sample buffer and the sample was analyzed by electrophoresis on a 10% polyacrylamide gel. After electrotransfer onto a PVDF membrane the blots were probed with the antibodies 7BDI-58, AR51A994.1, 7BD-33-11A and with IgG1 and IgG2a isotype controls according to standard Western blot procedure. All primary antibodies were used at a concentration of 5 micrograms/mL. The image of the resulting blots ( FIG. 11 ) shows that both the 7BDI-58 and AR51A994.1 cross-reacted with the same antigen as the 7BD-33-11A antibody, and therefore that they bind specifically with CD63.
To determine if the antibody 7BDI-60 cross-reacted with CD63, immunocomplexes of human CD63 and the antibody 1A245.5 were prepared from the total membrane fraction isolated from the ASPC-1 cell line. After analyzing the immunocomplexes by electrophoresis, under non-reducing conditions, on a 10% SDS-polyacrylamide gel, and after electrotransfer of the proteins onto a PVDF membrane, the blots were probed with the antibodies 7BDI-60, 1A245.6, anti-CD63 clone H5C6, and with an IgG1 isotype control. All primary antibodies were used at a concentration of 5 micrograms/mL. FIG. 12 demonstrates that all antibodies, with the exception of the isotype control, cross-reacted with the same antigen, CD63.
To further confirm the cross-reactivity between 7BDI-58, 7BDI-60 and AR51A994.1 against human CD63, the antibodies were used as probes on a Western blot of E.coli -expressed recombinant GST-fusion construct of the largest extracellular loop of human CD63. Briefly 5 micrograms of purified recombinant GST-fusion protein was analyzed by electrophoresis on a 10% preparative SDS-polyacrylamide gel. After transfer the blot was probed with the 7BDI-58, 7BDI-60 and AR51A994.1, and with the anti-CD63 antibodies 7BD-33-11A, 1A245.6 and H460-22-1, with an anti-CD44 antibody (clone H460-16-2) and with IgG1 and IgG2a isotype control antibodies, according to standard Western blot procedure. All primary antibodies were used at a concentartion of 5 micrograms/mL. The results from this experiment ( FIG. 13 ) revealed that all antibodies, with the exception of the isotype control, cross-reacted specifically with the recombinant GST-fusion construct of human CD63 largest extracellular loop, therefore demonstrating that 7BDI-58, 7BDI-60 and AR51A994.1 bind specifically with human CD63.
EXAMPLE 5
Human Pancreatic Tumor Tissue Staining
IHC studies were conducted to further (initial staining of pancreatic adenocarcinoma disclosed in Ser. No. 10/603,006) evaluate the binding of 7BD-33-11A to human pancreatic tumor tissue. IHC optimization studies were performed previously in order to determine the conditions for further experiments.
Tissue sections were deparaffinized by drying in an oven at 58° C. for 1 hour and dewaxed by immersing in xylene 5 times for 4 minutes each in Coplin jars. Following treatment through a series of graded ethanol washes (100%-75%) the sections were re-hydrated in water. The slides were immersed in 10 mM citrate buffer at pH 6 (Dako, Toronto, Ontario) then microwaved at high, medium, and low power settings for 5 minutes each and finally immersed in cold PBS. Slides were then immersed in 3% hydrogen peroxide solution for 6 minutes, washed with PBS three times for 5 minutes each, dried, incubated with Universal blocking solution (Dako, Toronto, Ontario) for 5 minutes at room temperature. 7BD-33-11A, monoclonal mouse anti-actin (Dako, Toronto, ON) or isotype control antibody (directed towards Aspergillus niger glucose oxidase, an enzyme which is neither present nor inducible in mammalian tissues; Dako, Toronto, Ontario) were diluted in antibody dilution buffer (Dako, Toronto, Ontario) to its working concentration (5 microgrnas/mL for each antibody except for anti-actin which was diluted to 2 micrograms/mL) and incubated for 1 hour at room temperature. The slides were washed with PBS 3 times for 5 minutes each. Immunoreactivity of the primary antibodies was detected/visualized with HRP conjugated secondary antibodies as supplied (Dako Envision System, Toronto, Ontario) for 30 minutes at room temperature. Following this step the slides were washed with PBS 3 times for 5 minutes each and a color reaction developed by adding DAB (3,3′-diaminobenzidine tetrahydrachloride, Dako, Toronto, Ontario) chromogen substrate solution for immunoperoxidase staining for 10 minutes at room temperature. Washing the slides in tap water terminated the chromogenic reaction. Following counterstaining with Meyer's Hematoxylin (Sigma Diagnostics, Oakville, ON), the slides were dehydrated with graded ethanols (75-100%) and cleared with xylene. Using mounting media (Dako Faramount, Toronto, Ontario) the slides were coverslipped. Slides were microscopically examined using an Axiovert 200 (Zeiss Canada, Toronto, ON) and digital images acquired and stored using Northern Eclipse Imaging Software (Mississauga, ON). Results were read, scored and interpreted by a histopathologist.
Testing for binding of antibodies to 32 human pancreatic tumor and 4 normal pancreatic tissues was performed using a human, pancreatic normal and tumor tissue microarray (Pentagen, Seoul, Korea). FIG. 14 presents a summary of the results of 7BD-33-11A staining of an array of human normal and tumor pancreatic tissues. Each tumor sample is represented by 2 spots to overcome tissue heterogeneity. The average score for the 2 spots was considered as the final section tumor. There was only one spot available for each of the four non-neoplastic tissues.
As shown in FIG. 14 , the total binding of 7BD-33-11A to pancreatic cancer tested on the microarray was 27/32 (84%). The antibody showed strong (+++) staining in 3/32, moderate (++) in 7/32, weak (+) in 9/32 and equivocal (+/−) in 8/32. The binding was restricted to tumor cells. The cellular localization was cytoplasmic and membranous with a granular staining pattern. The percentage of the stained cells showed heterogeneous binding to the tumor cells, ranging between <10 % to >50%. According to the histological type of the pancreatic tumors available on the tissue microarray, there was binding to 26/30 (87%) of ductal adenocarcinoma and to 1/2 (50%) of endocrine carcinomas. There was binding to 4/4 (100%) of non-neoplastic pancreatic tissues; the binding was to acinar epithelium and islets of langerhans ( FIG. 15 ).
According to the histological grade of the pancreatic tumors, there was binding of the antibody to 1/1 (100%), 2/3 (67%), 9/12 (75%), 2/2 (100%), 6/6 (100%), and 1/1 (100%) to sections graded as G1, G1-G2, G2, G2-G3, G3, G4, respectively. There was binding to 5/5 (100%) of the sections with unknown grade. In relation to tumor TNM stages of adenocarcinoma of the pancreas, there was binding of the antibody to 1/1 (100%), 14/17 (82%), 1/1 (100%) and 10/11 (91%) sections from stages I, II, III and IV, respectively. Therefore, no relation could be found between the antibody binding and various cancer parameters (histological tumor types, grades and TNM stages). This lack of correlation may be due to the small sample sizes representing some of the cancer stages.
The 7BD-33-11A antigen appears to be expressed on pancreatic tumor tissue. 7BD-33-11A therefore has potential as a therapeutic drug in the treatment of pancreatic cancer.
EXAMPLE 6
Demonstration of In vitro Antibody-Dependent Cellular Cytotoxicity (ADCC) Activity of the Antibody 7BD-33-11A
Previous evidence from in vivo therapeutic use of 7BD-33-11A on prophylactic human breast cancer models, obtained by comparing its efficacy in SCID versus NOD/SCID mice (as disclosed in Ser. No. 60/642,057), indicated that ADCC is a possible mechanism for the in vivo activity of this antibody in that animal model. Further demonstration of the ability of 7BD-33-11A to mediate antibody-dependent cellular cytotoxicity against the MDA-MB-231 breast cancer cell line was obtained by an in vitro cytotoxicity assay. Murine effector cells were obtained from the spleens of BALB/cAJcl − nu − mice and were stimulated with murine IL-2 (20 nM) for four days. Adherent and non-adherent effector cells were separated and used in the in vitro cytotoxicity assay. MDA-MB-231 target cells were dissociated from the cell culture plate and 10 million cells were labeled for 60 minutes with 40 μCi of Na 2 51 CrO 4 (GE Healthcare Amersham Biosciences) and 10 4 cells/well were added to 96-well plates. 7BD-33-11A or an IgG2a isotype-matched control were added to the 51 Cr-labeled target cells, at varying final concentrations immediately before adding the murine effector cells at effector: target (E:T) ratio of 25:1. After a 4 hour incubation at 37° C. the 51 Cr released from the lysed cells was measured. Each assay was carried out in triplicate and the results were expressed as the percentage of specific lysis which is defined as: (experimental cpm-spontaneous cpm)×100/(maximum cpm-spontaneous cpm).
The results from this experiment ( FIG. 16 ) clearly demonstrate that 7BD-33-11A induces a specific and dose-dependent MDA-MB-231 target cell lysis, both with adherent and non-adherent effector cells, that is not observed when the target cells are incubated in the presence of the isotype-matched control, at identical concentrations. Therefore, the data demonstrate that 7BD-33-11A is able to mediate ADCC by recruiting effector cell activity.
EXAMPLE 7
Macrophage Accumulation in MDA-MB-231 Xenografts
Additional demonstration of the ability of 7BD-33-11A in mediating antibody-dependent cellular cytotoxicity against the MDA-MB-231 breast cancer cell line was obtained from an in vivo study by immunohistochemistry.
Six to eight week old female SCID mice were implanted with 5 million human breast cancer cells (MDA-MB-231) in 100 microliters saline injected subcutaneously in the scruff of the neck. Tumor growth was measured with calipers every week. When the majority of the cohort reached an average tumor volume of 100 mm 3 (range 80-120 mm 3 ), 3 mice were sacrificed, and their tumors were harvested and portions were preserved in formalin and OCT. The remainder of the mice were assigned to treatment or control groups with 3 mice/group. The day after assignment, 7BD-33-11A test antibody or buffer control was administered intraperitoneally to each cohort, with dosing at 15 mg/kg of antibodies in a volume of 300 microliters after dilution from the stock concentration with a diluent that contained 2.7 mM KCl, 1 mM KH 2 PO 4 , 137 mM NaCl and 20 mM Na 2 HPO 4 . After 3, 6 or 10 doses of test antibody or control, given 3 times/week, mice were sacrificed and tumors were harvested and preserved in formalin and OCT. Tumor samples were transferred to the Pathology Research Lab in the Toronto General Hospital (Toronto, ON) for processing.
Tissue sections were deparaffinized by drying in an oven at 58° C. for 1 hour and dewaxed by immersing in xylene 5 times for 4 minutes each in Coplin jars. Following treatment through a series of graded ethanol washes (100%-75%) the sections were re-hydrated in water. The slides were immersed in 10 mM citrate buffer at pH 6 (Dako, Toronto, Ontario) then microwaved at high, medium, and low power settings for 5 minutes each and finally immersed in cold PBS. Slides were then immersed in 3% hydrogen peroxide solution for 6 minutes, washed with PBS three times for 5 minutes each, dried, incubated with Universal blocking solution (Dako, Toronto, Ontario) for 5 minutes at room temperature, Avidin D blocking solution (Vector Laboratories, Burlingame, Calif.) for 15 minutes at room temperature and Biotin blocking solution (Vector Laboratories, Burlingame, Calif.) for 15 minutes at room temperature. Anti-Mac-3 (BD Bioscience, Oakville, ON) was diluted in antibody dilution buffer (Dako, Toronto, Ontario) to its working concentration (0.75 micrograms/mL) and incubated for 1 hour at room temperature. Slides incubated with antibody dilution buffer alone were used as a negative control. The slides were washed with PBS 3 times for 5 minutes each. Immunoreactivity of the primary antibodies was detected/visualized with biotinylated anti-rat (BD Bioscience, Oakville, ON). The color reaction was detected with Vectastain EliteABC reagent (Vector Laboratories, Burlingame, Calif.). Washing the slides in tap water terminated the chromogenic reaction. Following counterstaining with Meyer's Hematoxylin (Sigma Diagnostics, Oakville, ON), the slides were dehydrated with graded ethanols (75-100%) and cleared with xylene. Using mounting media (Dako Faramount, Toronto, Ontario) the slides were coverslipped. Slides were microscopically examined using an Axiovert 200 (Zeiss Canada, Toronto, ON) and digital images acquired and stored using Northern Eclipse Imaging Software (Mississauga, ON). Results were read, scored and interpreted by a histopathologist. Scanning of the slides was done at 100× magnification power (Ziess Axiovert 200M). Macrophages (Mac-3 positive) were counted by randomly selecting 5 different hot spots. Intratumoral areas were selected for counting while avoiding the peripheral dense zones. After selecting the areas to be counted, magnification power was shifted to 400× and images were captured using a Qlmaging Retiga camera and Northern Eclipse software (Version 7.0). Manual counting of positive cells was done using the Northern Eclipse manual counting function. The necrotic areas and vascular spaces were avoided during counting.
Examination of tumor sections showed 3 distribution patterns of tumor associated macrophages. There was peripheral infiltration in a band like pattern between the periphery of tumor and the surrounding connective tissue. This pattern was obvious in all 7BD-33-11A treated tumors but only in some of buffer treated tumors. There was also aggregation in groups among the tumor cells, and lastly, there were sporadic single cells among or that encircled the tumor cells.
As displayed in FIG. 17 , 7BD-33-11A-treatrnent resulted in higher accumulation of macrophages compared to buffer treatment at all 3 doses. The highest accumulation was with the 6 dose samples, and was statistically significant (p=0.047). This correlated with the data illustrating that the greatest percentage tumor growth inhibition was seen after 6 doses of 7BD-33-11A. In addition, when taking into account the data from all 3 doses, the accumulation of macrophages in the 7BD-33-11A treated tumors was also significantly higher (p=0.037). All samples incubated with antibody dilution buffer alone were negative.
Therefore, in MDA-MB-231 xenografts, there was significant accumulation of tumor-associated macrophages in the 7BD-33-11A-treatment versus the buffer-treatment xenografts. This data supports the previous evidence of ADCC as a mechanism of action for 7BD-33-11A.
EXAMPLE 8
Humanization of 7BD-33-11A
Humanization of 7BD-33-11A was carried out essentially according to the procedure of Queen et al. (1989) by Protein Design Labs (PDL, Fremont, Calif.). First, human variable (V) regions, with high homology to the amino acid sequences of the variable regions of the heavy and light chains (V H and V L , respectively) of 7BD-33-11A, were identified. Next, the CDR sequences together with framework amino acids important for maintaining the structures of the CDRs were grafted into the selected human framework sequences. In addition, human framework amino acids that were found to be atypical in the corresponding human V region subgroup were substituted with consensus amino acids to reduce potential immunogenicity. The resulting humanized variable regions were expressed in the IgG1 and IgG2M3 forms ((hu)AR7BD-33-11A-IgG1(V11L) and (hu)AR7BD-33-11A-IgG2M3(V11L), respectively) in the mouse myeloma cell line Sp2/0.
The hybridoma cell line 7BD-33-11A, which produces mouse anti-human CD63 monoclonal antibody was cultured in DMEM (HyClone, Logan, Utah) containing 10% FBS (HyClone, Logan, Utah), 1% MEM-Non Essential Amino Acids (BioWhittaker, Walkersville, Md.), 0.1% 2-mercaptoethanol (Sigma, St. Louis, Mo.), 1% sodium pyruvate (Invitrogen, Carlsbad, Calif.), 1% L-glutamine (Invitrogen, Carlsbad, Calif.). Mouse myeloma cell line Sp2/0-Ag14 (ATCC, Manassus, Va.; referred to as Sp2/0 hereinafter) was maintained in DMEM containing 10% FBS. Mouse monoclonal antibody 7BD-33-11A was purified from culture supernatant by affinity chromatography using a Protein G Sepharose column. FITC-conjugated 7BD-33-11A was prepared using the FluoReporter Fluorescein-EX Protein Labeling Kit (Molecular Probes, Eugene, Oreg.). Human prostate cancer cell line PC-3, which was originally obtained from the National Cancer Institute, was maintained in RPMI-1640 (BioWhittaker, Walkersville, Md.) containing 10% FBS. All the cell lines were maintained at 37° C. in a 7.5% CO 2 incubator.
Sequencing of N-terminal amino acids of 7BD-33-11A was performed at Argo BioAnalytica, Inc. (Kenilworth, N.J.). The observed amino acid sequence shown in FIG. 18 was consistent with the sequence predicted from the mouse light chain and heavy light chain variable region genes.
Total RNA was extracted from approximately 10 7 7BD-33-11A hybridoma cells using TRIzol reagent (Invitrogen, Carlsbad, Calif., Burlington, ON) and poly (A) + RNA was isolated with the PolyATtract mRNA Isolation System (Promega Corporation, Madison, Wis.) according to the suppliers' protocols. Double-stranded cDNA was synthesized using the SMART RACE cDNA Amplification Kit (BD Biosciences Clontech, Palo Alto, Calif.) following the supplier's protocol. The variable region cDNAs for the heavy and light chains were amplified by polymerase chain reaction (PCR) using 3′ primers that anneal, respectively, to the mouse gamma and kappa chain C regions, and a 5′ universal primer provided in the SMART RACE cDNA Amplification Kit. For V H PCR, the 3′ primer had the sequence 5′-GCCAGTGGATAGACCGATGG-3′(SEQ ID NO:15). For V L PCR, the 3′ primer had the sequence 5′ -GATGGATACAGTTGGTGCAGC-3′ (SEQ ID NO:16). The V H and V L cDNAs were subcloned into the pCR4Blunt-TOPO vector (Invitrogen, Carlsbad, Calif.) for sequence determination. DNA sequencing was carried out by PCR cycle sequencing reactions with fluorescent dideoxy chain terminators (Applied Biosystems, Foster City, Calif.) according to the manufacturer's instructions. The sequencing reactions were analyzed on a Model 3100 Genetic Analyzer (Applied Biosystems, Foster City, Calif.). Unique sequences homologous to typical mouse light and heavy chain variable regions were identified. The V L and V H sequences were found to belong to subgroups I and IIA, respectively. The cDNA sequences encoding the light and heavy chain variable regions are shown in FIGS. 19 and 20, respectively. The deduced sequences of the N-terminal 20 amino acids from cDNA sequence analysis matched the corresponding sequences determined by amino acid sequencing for both the light and heavy chains.
Design of the humanized antibody V regions was carried out as disclosed by Queen et al. (1989). The human V region frameworks used as acceptors for the CDRs of 7BD-33-11A were chosen based on sequence homology. The computer programs ABMOD and ENCAD (Levitt, 1983) were used to construct a molecular model of the variable regions. Amino acids in the humanized V regions predicted to have contact with the CDRs were substituted with the corresponding residues of 7BD-33-11A. Amino acids in the humanized V region that were found to be atypical in the same V region subgroup were changed to consensus amino acids to eliminate potential immunogenicity. Based on a homology search against human V and J region sequences, the human V region AAR32409 (Huang et al., 1997) and J segment JH6 (Ravetch et al., 1981) were selected to provide the frameworks for the (hu)AR7BD-33-11A heavy chain variable region. For the (hu)AR7BD-33-11A light chain variable region, the human V region 1LVE (Miura et al. 2003) and J segment JK2 (Hieter et al., 1982) were used. The identity of the framework amino acids between 7BD-33-11A V H and the human acceptor AAR32409/JH6 was 77%, while the identity between 7BD-33-11A V L and the human acceptor 1L VE/JK2 was 88%.
At framework positions in which the computer model suggested significant contact with the CDRs, the amino acids from the V regions were substituted for the original human framework amino acids. This was done at residues 30, 48, 67, 68, 70, 72, 74, 97 and 98 of the heavy chain. For the light chain, replacement was made at residue 22. Framework residues that occurred only rarely at their respective positions in the corresponding human V region subgroups were replaced with human consensus amino acids at those positions. This was done at residues 38, 40 and 84 of the heavy chain. The alignments of 7BD-33-11A, designed (hu)AR7BD-33-11A and the acceptor human V region amino acid sequences for V L and V H are shown in FIGS. 21 and 22 , respectively.
The heavy and light chain variable region genes were constructed and amplified using 20 (for light chain) or 22 (for heavy chain) overlapping synthetic oligonucleotides approximately 40 base pairs in length (Stemmer et al., 1995). The oligonucleotides were annealed and extended with the Pfu Turbo Polymerase (Stratagene, La Jolla, Calif.), yielding an assembled double-stranded full-length V gene. The assembled heavy and light chain V gene fragments were amplified by PCR using Pfu Turbo Polymerase. The PCR-amplified fragments were gel-purified, digested with M1uI and XbaI, gel-purified, and subcloned, respectively, into pVg1.D.Tt or pVg2M3.D.Tt (Cole et al., 1997) and pVk (Co et al., 1992). Plasmid pVg1.D.Tt is similar to pVg2M3.D.Tt (Cole et al., 1997), but it contains a genomic fragment encoding the ?1 constant region instead of the ?2 constant region. Single amino acid substitutions were introduced by a PCR-based single step gene assembly method with 22 overlapping oligonucleotides (Stemmer et al., 1995) using Pfu Turbo Polymerase to generate a set of (hu)AR7BD-33-11A V H variants (V24A, R38K, and V24A,R38K). Site-directed mutagenesis was carried out by overlap-extension PCR using High Fidelity Expand Polymerase (Roche Diagnostics, Indianapolis, IN) to generate another set of (hu)AR7BD-33-11A V H variants (V11L, I20M, and Q111A). Genes encoding humanized V L or V H were designed as mini-exons ( FIGS. 23 and 24 ) including signal peptides, splice donor signals, and appropriate restriction enzyme sites for subsequent cloning into mammalian expression vectors. The splice donor signals in the V L and V H mini-exons were derived from the corresponding human germline JK and JH sequences, respectively. The signal peptide sequences in the humanized V L and V H mini-exons were derived from the mouse anti-E/P selectin monoclonal antibody EP5C7 V L and V H regions (He et al., 1998). The (hu)AR7BD-33-11A V L and V H genes were constructed by extension of 20 and 22 overlapping synthetic oligonucleotides ( FIGS. 25 and 26 ), respectively, and PCR amplification, as illustrated in FIG. 27 . Oligonucleotides 1-20 for V L and 1-22 for V H were mixed, annealed and extended by PCR with Pfu Turbo DNA polymerase. The resulting V gene double-stranded DNA assembly was amplified by PCR with primers 1 and 20 (for V L ) or 1 and 22 (for V H ) to incorporate the flanking Mlul and XbaI sites. The resulting V L gene fragment was cloned into the mammalian expression vector pVk (Co et al., 1992) to generate pVk-(hu)AR7BD-33-11A. The V H fragment was cloned into pVg1.D.Tt and pVg2M3.D.Tt (Cole et al., 1997) to generate pVgI-(hu)AR7BD-33-11A and pVg2M3-(hu)AR7BD-33-11A, respectively.
Transient transfection was done by co-transfection of pVg1-(hu)AR7BD-33-11A or pVg2M3-(hu)AR7BD-33-11A and pVk-(hu)AR7BD-33-11A into 293-H cells maintained in RPMI-1640 containing 2% low Ig FBS (HyClone, Logan, Utah) using the Lipofectamine method according to the supplier's recommendations. Approximately 7×10 6 cells were transfected with 15 micrograms each of light and heavy chain plasmids that had been allowed to form complexes with 70 microliters of Lipofectamine 2000 reagent. The cells were incubated for 5-7 days in a C02 incubator.
Purification of the transiently expressed (hu)AR7BD-33-11A.IgG 1 and (hu)AR7BD-33-11A.IgG2M3 antibodies was carried out by Protein A Sepharose column chromatography. The affinity of these two antibodies to human CD63 was analyzed in a FACS competition assay. 7BD-33-11A, (hu)AR7BD-33-11A.IgGI and (hu)AR7BD-33-11A.IgG2M3 antibodies competed with FITC-conjugated AR7BD-33-11A in a concentration-dependent manner. IC 50 values of the 7BD-33-11A, (hu)AR7BD-33-11A-IgG1 and (hu)AR7BD-33-11A-IgG2M3 antibodies, obtained using the computer software GraphPad Prism (GraphPad Software Inc., San Diego, Calif.), were 7.02 micrograms/mL, 25.3 micrograms/mL and 62.3 micrograms/mL, respectively ( FIG. 28 ). The affinity of (hu)AR7BD-33-11A-IgG1 was 3.6-fold lower than that of 7BD-33-11A.
To recover the antigen-binding affinity of 7BD-33-11A that was lost during humanization, several single amino acid substitutions from human residues to mouse residues were made in the V H by extension of 22 overlapping synthetic oligonucleotides and PCR amplification (V24A and R38K) and by site-directed mutagenesis (V11L, I20M and Q111A) as illustrated in FIG. 29 . For each mutant, the number in the middle denotes the location of the amino acid substitution, and the left and right letters denote amino acids before and after mutation in single letter code, respectively. The V24A and R38K mutants were combined to generate a double amino acid substitution mutant (V24A,R38K). The Six V H mutants were cloned into pVg1 as described above.
The six variant (hu)AR7BD-33-11A IgG 1 antibodies were expressed transiently in 293-H cells and purified by Protein A Sepharose column chromatography, and their affinity to human CD63 was analyzed by the FACS competition method. The six antibodies competed with FITC-conjugated 7BD-33-11A in a concentration-dependent manner. Their IC 50 values are shown in FIG. 28 . Among them, only the V11L variant showed higher binding to CD63 than the wild type and other variant antibodies. The affinity of the (hu)AR7BD-33-11A-IgG1 antibody carrying the V11L substitution in the V H ((hu)AR7BD-33-11A-IgG1(V11L)) was within 3-fold of that of 7BD-33-11A.
The heavy chain expression vector pVg1-(hu)AR7BD-33-11A carrying the V11L mutation (pVg1-(hu)AR7BD-33-11A(V11L) was generated as described above. For expression of (hu)AR7BD-33-11A-IgG2M3(V11L), the (hu)AR7BD-33-11A V H gene carrying the V11L mutation was cloned into pVg2M3.D.Tt (Cole et al., 1997) as described above, generating pVg2M3-(hu)AR7BD-33-11A.V11L. The light chain constant region was derived from the human germline κ fragment (Hieter et al., 1980), and the heavy chains were derived from the human germline γ1 (Ellison et al., 1982) and human γ2M3 (Cole et al., 1997) fragments, respectively. It should be noted that the penultimate residue of the γ2M3 heavy chain encoded in pVg2M3(hu)AR7BD-33-11A.V11L is glycine, a more typical residue than the serine used by Cole et al. (1997). The human cytomegalovirus major immediate early promoter and enhancer drive both the light and heavy chain genes. The selection marker, a gpt gene, is driven by the SV40 early promoter. The gross structures of the final plasmids, as shown in FIG. 30 , were verified by restriction mapping. The sequences of the variable and constant region exons of the light and heavy chain genes were verified by nucleotide sequencing.
To obtain cell lines stably producing (hu)AR7BD-33-11A-IgG1(V11L) and (hu)AR7BD-33-11A-IgG2M3(V11L), the corresponding heavy and light chain expression vectors were introduced into the chromosome of mouse myeloma cell line Sp2/0 by electroporation. Stable transfection into Sp2/0 was carried out by electroporation essentially as described by Co et al. (1992). Before transfection, the expression vectors were linearized using FspI. Approximately 10 7 cells were co-transfected with 25 micrograms and 50 micrograms of linearized light and heavy chain plasmids, respectively. The transfected cells were suspended in DMEM (BioWhittaker, Walkersville, Md.) containing 10% FBS (HyClone, Logan, Utah) and plated at 100 microliters/well into several 96-well plates. After 48 hours, 100 microliters of selection media (DMEM containing 10% FBS, HT media supplement (Sigma, St. Louis, Mo.), 0.5 mg/mL xanthine (Sigma, St. Louis, Mo.) and 2.4 micrograms/mL mycophenolic acid (Sigma, St. Louis, Mo.) was applied to each well. Approximately 10 days after initiation of selection, culture supernatants were assayed, by ELISA, for antibody production. Immulon 4 HBX immunoassay plates (ThermoLabsystems, Franklin, Mass.) were coated overnight at 4° C. with 100 microliters/well of 1 microgram/mL of AffiniPure goat anti-human IgG Fcγ-chain specific polyclonal antibodies (Jackson ImmunoResearch Laboratories, Inc., West Grove, Pa.) in 0.2M sodium carbonate-bicarbonate buffer, pH 9.4, washed with Wash Buffer (PBS containing 0.1 % Tween-20), and blocked for 30 minutes at room temperature with 300 microliters/well of SuperBlock Blocking Buffer in TBS (Pierce Biotechnology, Rockford, Ill.). After washing with Wash Buffer, samples containing (hu)AR7BD-33-11A were appropriately diluted in ELISA Buffer (PBS containing 1% BSA and 0.1 % Tween 20) and 100 microliters/well was applied to the ELISA plates. As standards, humanized IgG1, kappa antibody HuAIP12 (Protein Design Labs, Inc.; WO 2004/101511A2) and chimeric IgG2M3, kappa antibody OKT3 (Cole et al., 1997) were used. After incubating the plates for 1.5 hours at room temperature, and washing with Wash Buffer, bound antibodies were detected using 100 microliters/well of a 1:1000 dilution of HRP-conjugated AffiniPure goat anti-human IgG Fcγ-chain specific polyclonal antibodies (Jackson ImmunoResearch Laboratories, Inc., West Grove, Pa.). After incubating for 1 hour at room temperature, and washing with Wash Buffer, color development was performed by adding 100 microliters/well of ABTS Peroxidase Substrate/Peroxidase Solution B (KPL, Inc., Gaithersburg, Md.). After incubating for 4 minutes at room temperature, color development was stopped by adding 100 microliters/well of 2% oxalic acid. Absorbance was read at 415 nm using a VersaMax microplate reader (Molecular Devices Corporation, Sunnyvale, Calif.).
High-yielding Sp2/0 transfectants, Sp2/0-(hu)AR7BD-33-11A-IgG1(V11L)(clone #18) and Sp2/0-(hu)AR7BD-33-11A-IgG2M3(V11L)(clone #5), were expanded in DMEM containing 10% FBS, then adapted and expanded to growth in Protein-Free Basal Medium-2 (PFBM-2) (Protein Design Labs, Inc.; Sauer et al. (2000)) containing 1% low Ig FBS (HyClone, Logan, Utah), supplemented with Protein-Free Feed Medium-3 (PFFM-3) (Protein Design Labs, Inc.; Sauer et al. (2000)), and grown to exhaustion.
To confirm the light and heavy chain mRNA sequences, total RNA was isolated from Sp2/0(hu)AR7BD-33-11A-IgG1(V11L)(clone#18) and Sp2/0-(hu)AR7BD-33-11A-IgG2M3(V11L)(clone #5). First-strand cDNA was synthesized with the Superscript Preamplification System (Invitrogen, Carlsbad, Calif.) using total RNA as a template and random hexadeoxynucleotides as primers. The reaction was performed with SuperScript II reverse transcriptase according to the supplier's protocol. DNA fragments containing the entire coding region of the (hu)AR7BD-33-11A light or heavy chain were amplified by PCR using 5′ and 3′ primers which bind to the 5′ and 3′ non-coding regions, respectively. The primer sequences are shown below:
5′ primer for light chain and heavy chain: mbr3 5′-CCATAGAAGACACCGGGACC-3′ (SEQ ID NO:17) 3′ primer for light chain: mc121 5′-AGGTGCAAAGATTCACTT-3′ (SEQ ID NO:18) 3′ primer for heavy chain: mc124 5′-TCCCGTCGCGACCCACG-3′ (SEQ ID NO:19)
The amplified fragments were gel-purified and subjected to sequencing with appropriate primers. The determined sequences of the light and heavy chains agreed at every nucleotide position with the known coding sequences of (hu)AR7BD-33-11A-IgG1(V11L) and (hu)AR7BD-33-11A-IgG2M3(V11L)( FIGS. 31 , 32 and 33 ).
A seed bank of ten vials was made by freezing Sp2/0-(hu)AR7BD-33-11A.V11L.G1 (clone #18) and Sp2/0-(hu)AR7BD-33-11A.V11L.G2M3 (clone #5) transfectants in 90% FBS (HyClone, Logan, Utah), 10% DMSO (Sigma, St. Louis, Mo.). Each vial contained approximately 5×10 6 cells. One vial of each seed bank was thawed and grown in PFBM-2 and the cell culture was sent for mycoplasma testing (Bionique Testing Laboratories, Saranac Lake, N.Y.). The DNA-fluorochrome assay and direct culture methods were negative for mycoplasma contamination.
Hu)AR7BD-33-11A-IgG1(V11L) and (hu)AR7BD-33-11A-IgG2M3(V11L) antibodies were expressed transiently in 293-H cells or stably in Sp2/0 cells as described below. Sp2/0-(hu)AR7BD-33-11A-IgG1(V11L)(clone #18) and Sp2/0-(hu)AR7BD-33-11AIgG2M3(V11L)(clone #5) were expanded to 0.8 liters in PFBM-2 containing 1% low Ig FBS in roller bottles (400 mL per roller bottle). The (hu)AR7BD-33-11A-IgG1(V11L) and (hu)AR7BD-33-11A-IgG2M3(V11L) monoclonal antibodies were purified from spent culture supernatant by affiinity chromatography on Protein A Sepharose. After centrifugation and filtration, culture supernatant from transient or stable transfectants was loaded onto a HiTrap Protein A HP column (Amersham Biosciences, Piscataway, N.J.). The column was washed with 20 mM Na-Citrate buffer (pH 7.0) containing 150 mM NaCl before the antibody was eluted with 20 mM Na-Citrate buffer (pH 3.5). Eluted pooled fractions were neutralized with 1.5M Na-Citrate buffer (pH 6.5). The protein was dialyzed against PBS and then filtered through a 0.2 micrometer filter prior to storage at 4° C. Antibody concentration was determined by measuring the absorbance at 280 nm (1 mg/mL=1.4A 280 ). The yield was 50 mg for (hu)AR7BD-33-11A-IgG1(V11L) and 22 mg for (hu)AR7BD-33-11A-IgG2M3(V11L). Antibodies were then analyzed by SDS-PAGE that was performed according to standard procedures. 7BD-33-11A, (hu)AR7BD-33-11A-IgG1(V11L), and (hu)AR7BD-33-11A-IgG2M3(V11L) antibodies were heated at 70° C. for 10 minutes in the presence and absence of NuPAGE Sample Reducing Agent (Invitrogen, Carlsbad, Calif.) as per the supplier's recommendations for reducing and non-reducing conditions, respectively. Thereafter, antibodies were run on a 4-12% Bis-Tris NuPAGE gel (Invitrogen, Carlsbad, Calif.) for 20 minutes at 200 volts in NuPAGE MES SDS Running buffer (Invitrogen, Carlsbad, Calif.). As protein standards, Broad Range SDS-PAGE standard (BIO-RAD Laboratories, Hercules, Calif.) was run under reducing conditions. The gel was stained overnight at room temperature with SimplyBlue SafeStain (Invitrogen, Carlsbad, Calif.) and then destained overnight at room temperature with H 2 O. SDS-PAGE analysis ( FIG. 34 ) under nonreducing conditions indicated that the (hu)AR7BD-33-11A(V11L) antibodies have a molecular weight of about 150-160 kDa. Analysis under reducing conditions indicated that the (hu)AR7BD-33-11A(V11L) antibodies are comprised of a heavy chain with a molecular weight of about 50 kDa and a light chain with molecular weight of about 25 kDa. The purity was then analyzed by size exclusion chromatography. Size exclusion HPLC was performed using a Varion HPLC system consisting of a Rainin column heater model CH-1, a Dynamax solvent delivery system model SD200, and a Knaver variable wavelength monitor. Varian Prostar/Dynamax 0.24 system control version 5.51 software was used to control the autosampler, pump, and detector, and to acquire, store, and process the data. Separation was achieved using two TosoHaas TSK-GEL G3000SWXL size exclusion HPLC columns (7.8 mm×300 mm, 5 micrometer particle size, 250 Å pore size; TosoHaas, Montgomeryville, Md.) connected in series. The mobile phase was PBS, pH 7.4, and the flow rate was 1.5 mL/minute. The column eluate was monitored spectrophotometrically at 280 nm. The purity of the antibodies by size exclusion HPLC appeared to be greater than 95% pure ( FIG. 35 ).
The affinity to human CD63 of the (hu)AR7BD-33-11A (V11L) antibodies that had been purified from culture supernatants of stable transfectants was analyzed by the FACS competition method. PC-3 cells were washed three times with sterile PBS (BioWhittaker, Walkersville, Md.). The cells were incubated in HBSS (BioWhittaker, Walkersville, Md.) containing 2.5 mM EDTA media at 37° C. in a CO 2 incubator for 5-7 minutes to detach the cells. The cells were washed three times in FACS Staining Buffer (FSB)(PBS containing 0.5% BSA (Sigma, St. Louis, Mo.)) The final wash of the cells was carried out in V-bottom 96-well assay plates (Nalgene Nunc International, Rochester, N.Y.) and the supernatant was discarded. Each well contained 10 5 cells per test. A mixture of FITC-conjugated 7BD-33-11A (15 micrograms/mL final concentration) and competitor antibody (7BD-33-11A or (hu)AR7BD-33-11A starting at 400 micrograms/mL final concentration and serially diluted 3-fold) in 100 microliters/well was added to the cell pellet in the assay plate and incubated at 4° C. for 1 hour. The cells were washed three times in FSB, and then the pellet was resuspended in 200 microliters of 1% paraformaldehyde solution and analyzed by flow cytometry on a dual laser FACSCalibur flow cytometer (BD Biosciences Immunocytometry Systems, San Jose, Calif.). The 7BD-33-11A, (hu)AR7BD-33-11A-IgG1(V11L) and (hu)AR7BD-33-11A-IgG2M3(V11L) antibodies competed with FITC-conjugated 7BD-33-11A in a concentration-dependent manner. As shown in FIG. 36 , the mean IC 50 values of 7BD-33-11A, (hu)AR7BD-33-11A-IgG1(V11L) and (hu)AR7BD-33-11A-IgG2M3(V11L) obtained using the computer software GraphPad Prism were 6.83 micrograms/mL, 12.7 micrograms/mL and 38.8 micrograms/mL, respectively. A representative result of the FACS competition assay is shown in FIG. 37 . The relative binding of (hu)AR7BD-33-11A-IgG1(V11L) and (hu)AR7BD-33-11A-IgG2M3(V11L) to human CD63 was approximately 1.9- and 5.7-fold less than that of 7BD-33-11A. It has been shown previously that the avidity of IgG2 subclass antibodies is 2- to 3-fold lower than that of IgG1 subclass antibodies (Cole et al., 1997; Morelock et al., 1994) and here the same avidity difference was observed between the (hu)AR7BD-33-11A-IgG1(V11L) and (hu)AR7BD-33-11A-IgG2M3(V11L) antibodies. The humanized (hu)AR7BD-33-11A-IgG1(V11L) and (hu)AR7BD-33-11A-IgG2M3(V11L) antibodies are hereafter referred to as (hu)AR7BD-33-11A-IgG1 and (hu)AR7BD-33-11A-IgG2M3 respectively.
EXAMPLE 9
In vivo Tumor Experiments with A2058 Cells
With reference to FIGS. 38 and 39 , 4 to 6 week old female SCID mice were implanted with 500,000 human melanoma cells (A2058) in 100 microliters saline injected subcutaneously in the scruff of the neck. The mice were randomly divided into 4 treatment groups of 8 mice/group. On the day after implantation, 2 mg/kg of 7BD-33-11A, (hu)AR7BD-33-11A-IgG1, (hu)AR7BD-33-11A-IgG2M3 test antibodies or buffer control were administered intraperitoneally to each cohort in a volume of 300 microliters after dilution from the stock concentration with a diluent that contained 2.7 mM KCl, 1 mM KH 2 PO 4 , 137 mM NaCl and 20 mM Na 2 HPO 4 . The antibody and control samples were then administered once per week for the duration of the study in the same fashion. Tumor growth was measured about every seventh day with calipers. The group treated with (hu)AR7BD-33-11A-IgG2M3 received a total of 3 doses because of antibody availability. The study was terminated after 34 days, as the animals reached CCAC end-points due to large ulcerated lesions. At this point, the control, 7BD-33-11A, and (hu)AR7BD-33-11A-IgG1 treated groups had received 6 doses. Body weights of the animals were recorded once per week for the duration of the study. At the end of the study all animals were euthanized according to CCAC guidelines.
Both murine 7BD-33-11A and (hu)AR7BD-33-11A-IgG1 reduced tumor growth in an established A2058 in vivo model of human melanoma cancer. FIG. 38 shows the effect of the 3 antibodies on tumor growth at 2 mg/kg compared to the buffer control. On day 27, when all of the mice in the treatment groups were still alive, 7BD-33-11A decreased tumor growth by 56% (p=0.0086), (hu)AR7BD-33-11A-IgG1 decreased tumor growth by 63% (p=0.0016) and (hu)AR7BD-33-11A-IgG2M3 had no significant effect on tumor growth (10% tumor suppression). These results demonstrate that the humanized IgG1 retains the efficacy of the murine antibody, while the efficacy is markedly decreased in the IgG2M3 version. This observed decrease may be due, at least in part, to the lower number of doses received by the IgG2M3-treatment group, or the lower avidity of the isotype (see above).
There were no clinical signs of toxicity throughout the study. Body weight measured at weekly intervals was a surrogate for well-being and failure to thrive. FIG. 39 presents the results of the body weight of each of the treated groups over the course of the study. There were no significant changes in body weight in mice from any of the antibody-treated groups compared to the buffer control group, at day 27 or at the end of the study (day 34).
In summary, (hu)AR7BD-33-11A-IgG1 demonstrated the same or greater efficacy compared to the murine antibody in the A2058 melanoma model. By contrast, the (hu)AR7BD-33-11A-IgG2M3 chimeric antibody did not reduce tumor growth in this model of human A2058 melanoma. In addition, the murine and humanized antibodies appreared to be well-tolerated by the mice.
EXAMPLE 10
Determination of the Binding Affinity of the 7BD-33-11A, 1A245.6 H460-22-1, (hu)AR7BD-33-11A-IgG1 and (hu)AR7BD-33-11A-IgG2M3 to CD63
The binding affinity of 7BD-33-11A, 1A245.6, H460-22-1, and of (hu)AR7BD-33-11A-IgG1 and (hu)AR7BD-33-11A-IgG2M3, was compared by determination of the respective dissociation constants after binding to the bacteria-expressed and purified recombinant protein GST-fusion construct of the extracellular domain 2 (GST-EC2) of human CD63.
An anti-GST antibody was immobilized using the standard amine coupling procedure. The surface of a CM5 sensor chip (Biacore, Uppsala, Sweden) was activated by the injection of 35 mL of a mixture containing 0.05 M NHS and 0.2 M EDC in H 2 O. The anti-GST antibody was injected at a concentration of 30 mg/mL in 10 mM sodium acetate pH5.0 until 50,000 RU to 100,000 RU was captured. Finally, 35 mL of 1.0 M ethanolamine-HCl, pH 8.5, was injected to block any activated sites on the sensor chip surface. GST-EC2 (25 mL) was injected at 5 mg/mL followed by a 25-50 mL injection of the antibody. Regeneration of the sensor chip surface for subsequent injections was accomplished by application of two 10 mL pulses of 20 mM glycine pH 2.2. Antibodies were serially injected at concentration ranging from 12.5 to 200 nM. As a control, each antibody concentration was injected over a surface where GST, instead of GST-EC2, was captured. The affinity of the different antibodies for the EC2 was calculated from the measured steady state binding levels. For each sensorgram, a report point was taken 20 seconds before the end of the antibody injection (Req). For each antibody concentration, the Req obtained when antibody was injected over GST was subtracted from the Req obtained when the antibody was injected over the GST-EC2. The slope of a plot of Req/Conc vs. Req was determined and it represented the association constant (KA). The dissociation constant (KD) was calculated as the reciprocal of KA. The experiments were carried out using a Biacore 2000 system (Biacore, Uppsala, Sweden). This experiment yielded the values of 135 nM, 42 nM and 10 nM for 7BD-33-11A, H460-22-1 and 1A245.6, respectively ( FIG. 40 ), therefore indicating that 7BD-33-11A has the lowest affinity of those used in this study. It also indicates that the affinities of the humanized antibodies (hu)AR7BD-33-11A-IgG1 and (hu)AR7BD-33-11A-IgG2M3 are higher than that of the parental murine 7BD-33-11A. These results are different than those reported in Example 8. The differences in the results may be due, in part, to the following. First of all, different methodologies were used, FACS versus surface plasmon resonsance. Also, in Example 8, PC-3 cells were used whereas in Example 10, bacterially expressed recombinant CD63 was used. These two sources might represent slightly different conformational or glycosylated forms of CD63.
The preponderance of evidence shows that AR51A994.1, 7BDI-58, 7BDI-60, H460-22-1, 7BD-33-11A, (hu)AR7BD-33-11A-IgG1 and 1A245.6 mediate anti-cancer effects through ligation of epitopes present on CD63. It has been shown, in Example 4, AR51A994.1, 7BDI-58, 7BDI-60 and 7BD-33-11A antibody can be used to immunoprecipitate the cognate antigen from expressing cells such as MDA-MB-231 cells. Further it could be shown that the AR51A994.1, 7BDI-58, 7BDI-60, 7BD-33-11A, (hu)AR7BD-33-11A-IgG1 and (hu)AR7BD-33-11A-IgG2M3 antibody could be used in detection of cells and/or tissues which express a CD63 antigenic moiety which specifically binds thereto, utilizing techniques illustrated by, but not limited to FACS, cell ELISA or IHC.
Thus, it could be shown that the immunoprecipitated AR51A994.1, 7BDI-58, 7BDI-60 and 7BD-33-11A antigen can inhibit the binding of either antibody to such cells or tissues using FACS, cell ELISA or IHC assays. Further, as with the AR51A994.1, 7BDI-58, 7BDI-60 and 7BD-33-11A antibody, other anti-CD63 antibodies could be used to immunoprecipitate and isolate other forms of the CD63 antigen, and the antigen can also be used to inhibit the binding of those antibodies to the cells or tissues that express the antigen using the same types of assays.
All patents and publications mentioned in this specification are indicative of the levels of those skilled in the art to which the invention pertains. All patents and publications are herein incorporated by reference to the same extent as if each individual publication was specifically and individually indicated to be incorporated by reference.
It is to be understood that while a certain form of the invention is illustrated, it is not to be limited to the specific form or arrangement of parts herein described and shown. It will be apparent to those skilled in the art that various changes may be made without departing from the scope of the invention and the invention is not to be considered limited to what is shown and described in the specification. One skilled in the art will readily appreciate that the present invention is well adapted to carry out the objects and obtain the ends and advantages mentioned, as well as those inherent therein. Any oligonucleotides, peptides, polypeptides, biologically related compounds, methods, procedures and techniques described herein are presently representative of the preferred embodiments, are intended to be exemplary and are not intended as limitations on the scope. Changes therein and other uses will occur to those skilled in the art which are encompassed within the spirit of the invention and are defined by the scope of the appended claims. Although the invention has been described in connection with specific preferred embodiments, it should be understood that the invention as claimed should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention which are obvious to those skilled in the art are intended to be within the scope of the following claims. | This invention relates to the diagnosis and treatment of cancerous diseases, particularly to the mediation of cytotoxicity of tumor cells; and most particularly to the use of cancerous disease modifying antibodies (CDMAB), optionally in combination with one or more chemotherapeutic agents, as a means for initiating the cytotoxic response. The invention further relates to binding assays which utilize the CDMAB of the instant invention. | 0 |
PRIORITY CLAIM
[0001] This application claims the benefit of U.S. Provisional Patent Application Ser. No. 60/995,541, filed Sep. 27, 2007; the disclosure of which is incorporated herein by reference in its entirety.
GOVERNMENT INTEREST
[0002] This presently disclosed subject matter was made with U.S. Government support under Contract No. KT3408 awarded by the Defense Advanced Research Projects Agency (DARPA). Thus, the U.S. Government has certain rights in the presently disclosed subject matter.
TECHNICAL FIELD
[0003] The subject matter described herein relates to methods and systems for implementing pipelined processing. More particularly, the subject matter described herein relates to systems, methods, and computer readable media for counter-flow pipelining: preemption in asynchronous systems using anti-tokens.
BACKGROUND
[0004] As synchronous designs are increasingly facing challenges due to fundamental limitations of clocking, the VLSI design community has recently turned towards asynchronous logic to mitigate the challenges of global clock distribution in large complex high-speed systems. Asynchronous design offers several potential benefits, such as lower power consumption, higher performance, greater robustness, and significantly better modularity, all of which make asynchronous circuits a promising alternative to synchronous design.
[0005] When the problems that arise when using a global synchronous clock became apparent, the VLSI community started looking towards solving problems in asynchronous domain due to its inherent advantages. The main difference in the synchronous and asynchronous ideologies is the way timing between various modules is maintained. In a synchronous pipeline, for example, clocking gives a timing reference which dictates the completion of different stages. In asynchronous pipelines, timing is inferred by communication between the adjacent stages in the pipeline. This is referred to as handshaking. Handshaking protocols define the control behavior of asynchronous pipeline.
[0006] There are many areas where asynchronous circuits dominate their synchronous counterparts. Lower emissions of electromagnetic noise, no clock distribution (saving area and power), no clock skew, robustness to environmental variations (e.g. temperature and power supply) or transistor variations, better modularity and better security are just some of the properties for which most asynchronous designs have shown advantages over synchronous ones.
[0007] There are many different flavors of asynchronous design. However, the most commonly used approaches differ mainly in the following design choices.
Data signaling/encoding. In dual rail encoded data, each Boolean (i.e., two-valued signal) is implemented as two wires, typically a data signal and a clock signal. This allows the value and the timing information to be communicated for each data bit. Bundled data, on the other hand, has one wire for each data bit and a separate wire to indicate the timing. Control signaling/handshaking. Level sensitive circuits typically represent a logic one by a high voltage and a logic zero by a low voltage. Transition signaling uses a change in the signal level to convey information. Timing model. A speed independent design is tolerant to variations in gate speeds but not to propagation delays in wires while a delay insensitive circuit is tolerant to variations in wire delays as well.
[0011] The most popular form in recent years has been dual-rail encoding with level sensitive signaling. Full delay insensitivity is still achieved, but there must be a “return to zero” phase in each transaction, and therefore more power is dissipated than with transition signaling. The advantage of this approach over transition signaling is that the logic processing elements can be much simpler; familiar logic gates process levels whereas the circuits required to process transitions require state and are generally more complex.
[0012] FIG. 1 illustrates another conventional approach, which uses bundled data with a transition signaled handshake protocol to control data transfers. FIG. 1 shows the interface between a sender 100 and a receiver 102 . Sender 100 and receiver 102 may be two stages of a multi-stage pipeline, for example. A bundle of data, such as databus 104 , carries information, typically using one wire for each bit. A request signal (REQ) 106 is sent by the sender to the receiver and carries a transition when the data is valid. An acknowledge signal (ACK) 108 is sent from the receiver to the sender and carries a transition when the data has been used.
[0013] The protocol sequence is also shown as the timing diagram at the bottom of FIG. 1 . At time T 1 , sender 100 places valid data on databus 104 . At time T 2 , after some delay sufficient to allow the signals on databus 104 to stabilize, sender 100 causes a transition to occur on REQ 106 . Receiver 102 may use the transition of REQ 106 to internally capture (e.g., latch) the values on databus 104 . At time T 3 , after some delay sufficient to allow receiver 102 to guarantee that the data on databus 104 has been properly latched, receiver 102 may cause a transition to occur on ACK 108 , to indicate to sender 100 that the data has been successfully received by receiver 104 , after which time sender 100 may “release” the data, meaning that sender 100 need not maintain the valid data on databus 104 . In some cases, sender 100 may stop driving databus 104 , sometimes referred to as “tri-stating” the bus.
[0014] This approach has some disadvantages, however. Existing handshake protocols dictate a unidirectional flow of information. Given two adjacent stages, these protocols define one of the stages as active and the stage as passive. Only the active stage can initiate a communication with the passive stage. As used herein, the term “forward” refers to the direction that data is traveling as it passes through the pipeline, and the term “backward” refers to the opposite direction from forward. In conventional pipelines, initiation signals, such as REQ 106 can only travel forward, and response signals, such as ACK 108 , can only travel backward. Though these protocols have enabled building complex pipelines, their unidirectional nature has become a bottleneck in implementing certain useful architectural concepts, such as speculation, preemption, and eager evaluation. These concepts will now be described with reference to a simple example, described below and illustrated in FIG. 2 .
[0015] Consider the following example: a simple application consisting of an if-then-else statement.
[0000]
IF <CONDITION> THEN
<IF BRANCH>
ELSE
<ELSE BRANCH>
END IF
[0016] In the conventional control-driven approach, designing an asynchronous circuit for the above application would involve first computing the condition and then taking the if or else branch accordingly. The control is returned after the whole operation is completed. If a represents the time to compute the CONDITION, β represents the time to perform the operations within the IF block, and γ represents the time to perform the operations within the ELSE block, then the cycle time is α+β if the condition is TRUE and α+γ if the condition is FALSE. Where p is the probability that the condition will be TRUE, the average cycle time T AVG is given by the equation:
[0000] T AVG =α+p β+(1 −p )γ
[0000] As used herein, the term “speculation” refers to the execution of code or the performance of a process even though it is not known at the time whether the process is necessary or whether the results of the process will be used. Speculation may be performed by pipelines that have multiple parallel pipeline paths. Using the IF-THEN-ELSE example above, all the three operations—evaluating the condition, executing the IF branch, and executing the ELSE branch—can be performed in parallel using three separate, parallel pipelines. Since the branch outcome is not known until the condition is computed, both the IF and ELSE branches are speculatively executed and the appropriate result is selected based on the condition outcome.
[0017] As used herein, the term “preemption” refers to the cancelling of operations or a sequence of operations during execution of the operation or before the operation has been executed. In the IF-THEN-ELSE example, once the CONDITION has been evaluated, the unneeded branch may be preempted, e.g., the operations of the unneeded branch can be terminated if currently being executed or cancelled before execution has begun.
[0018] As used herein, the term “eager evaluation” refers to the evaluation of a CONDITION before all of its inputs are known. For example, if the CONDITION being evaluated includes an OR operation, and if one input to an OR operation is a logical 1, the output of the OR operation is known to be a logical 1 and thus the results of the OR operation can be forwarded to the next stage without waiting to receive the other input(s). Similarly, if one input to an AND operation is a logical 0, the output of the AND is known to be logical 0 regardless of the values of the other input(s). In either scenario, it would be unnecessary to evaluate, or wait for the completion of an ongoing evaluation of, the other terms of the OR/AND operation.
[0019] FIG. 2 is a block diagram illustrating a conventional transition signaling asynchronous pipeline implementation that does not support counterflow anti-tokens, which is disclosed in U.S. Pat. No. 6,958,627. Pipeline 200 consists of multiple stages 202 , two of which are shown in FIG. 2 as stage N−1 202 A and stage N 202 B. In one embodiment, each stage 202 includes a data latch 204 for latching incoming data 206 , and a latch controller 208 , which implements the latch enable logic. Latch controller 208 has 2 inputs, a request signal (REQ) 210 generated by the current stage and an acknowledgment signal (ACK) 212 from an adjacent stage, and outputs a latch enable signal 214 . The function of latch controller 208 is to disable latch 204 when the inputs of latch controller 208 don't match, e.g., when a request has not been acknowledged. In one embodiment, latch controller 208 may be implemented using a simple XNOR gate 216 .
[0020] In one embodiment, latch 204 remains transparent when its stage 202 is waiting for data. As soon as data enters the stage, the data is captured by closing the latch behind it. The latch reopens when the data held by the latch is captured by the subsequent stage. This allows requests (along with data) to flow in the forward direction and their acknowledgments in the backward direction.
[0021] In one embodiment, the request signal generated by one stage is also both the request signal sent to the next stage and the acknowledge signal sent to the previous stage. For example, in the embodiment illustrated in FIG. 2 , REQ 210 for stage N 204 is also both ACK for stage N−1 202 and REQ for stage N+1 (not shown). In conventional pipeline architectures, the signal wires are typically named based on the type of signal they carry. All the forward flowing signals carry requests and all the reverse flowing signals carry acknowledgments.
[0022] FIG. 3 illustrates an abstract picture of such a design that implements speculation but not preemption or early evaluation. The boxes represent operations performed by the circuit. Related operations are connected by lines, and connected boxes represent a sequence of operations. For pipelines, each operation may be performed by separate circuits. Thus, the boxes may represent separate hardware stages, such as sender 100 and receiver 102 , and the lines may represent the combination of REQ 106 , ACK 108 , and databus 104 as shown in FIG. 1 , above. For clarity, the boxes are hereinafter referred to generically as “stages”.
[0023] In the example shown in FIG. 3 , stage 300 represents the detection of an IF-THEN-ELSE construct and the subsequent creation of multiple, parallel operations. A stage that creates multiple, parallel operations is referred to as a “fork”. Line 302 represents the sequence of operations required to evaluate the CONDITION. Line 304 represents the sequence of operations performed by the IF branch. Line 306 represents the sequence of operations performed by the ELSE branch. Stage 308 represents the completion of the CONDITION evaluation and resulting selection of the results of one branch or the other, e.g., the results of sequence 304 or sequence 306 . A state that coalesces the results of multiple, parallel operations is referred to as a “join”. The abstract example illustrated in FIG. 3 is intended to show that each branch may involve different, and sometimes vastly different, numbers of operations.
[0024] During execution of the simple IF-THEN-ELSE example shown above, the pipeline will perform operations from each branch in parallel. For example, the first stages in sequences 302 , 304 , and 306 will be performed at the same time, the second stages in sequences 302 , 304 , and 306 will be performed at the same time, and so on.
[0025] Thus, the throughput of such a pipeline is limited by the mismatches in depths of the two branches. Let N IF be the number of stages in the IF branch and N ELSE be the number of stages in the ELSE branch. Assuming N IF ≦N ELSE , the cycle time of the given pipeline is given by the equation:
[0000] T CYCLE =( N ELSE /N IF )×(the cycle time of a given stage)
[0000] For example, if the IF and ELSE branches are perfectly matched, i.e., having the same number of stages, a pipeline having a 100 nS cycle time will produce a new output every (N/N)×100 nS=100 nS, i.e., every 1 cycle. However, if the IF branch has 4 stages and the ELSE branch has 5 stages, the pipeline will produce a new output every (5/4)×100 nS=125 nS, i.e., every 1.25 cycles. In other words, it can be said that the pipeline will produce a valid result during only 4 out of every 5 clock cycles. During the 1 out of every 5 clock cycles, the 4 stage pipe waits for the 5 stage pipe to finish; while it is waiting, it cannot accept as input the next operation.
[0026] The main drawback of the above design is that the final stage has to wait until all branches are computed even if some are not required. In part, this is due to the unidirectional nature of conventional pipeline designs, as illustrated in FIG. 1 . Even though stage 308 may quickly determine whether the CONDITION branch returns TRUE or FALSE, stage 308 cannot act on that information since all initiating signals may only travel forward, and stage 308 has no choice but to wait until it receives all REQ signals from the last blocks of stages 302 , 304 , and 306 , respectively. Furthermore, once the CONDITION has been evaluated, the operations of the non-selected branch are no longer needed, but stage 308 has no mechanism by which it can command the pipeline stages currently dedicated to performing those operations to discontinue processing of those operations. Thus, not only must stage 308 wait longer than necessary in some circumstances, the pipeline expends power to perform unnecessary operations.
[0027] Preemption is a technique that can overcome this disadvantage of conventional pipelines. One proposed method to implement preemption is to add the ability to send commands in the “backward” direction, referred to herein as “anti-tokens”. Referring again to the example illustrated in FIG. 3 , once stage 308 has evaluated the CONDITION, it knows whether to disregard the results of the IF branch 304 or the ELSE branch 306 . Stage 308 could then issue an anti-token backwards along the unneeded branch. Once the anti-token is received by a stage, the stage would cancel the operation and/or discard the result.
[0028] FIG. 4 compares the operation of a conventional pipeline 400 without anti-tokens to the operation of a conventional counterflow pipeline 402 which uses anti-tokens to implement preemption. The filled circles represent tokens, which flow in the forward direction through a pipeline, and empty circles represent anti-tokens, which flow in the backward direction through a pipeline. The flow of tokens and anti-tokens is represented as a sequence of views of the pipeline at various times T 1 through T 6 , arranged from top to bottom of FIG. 3 . The sequence of views illustrating the operation of pipeline 400 is on the left side of FIG. 3 , and the sequence of views illustrating the operation of counterflow pipeline 402 is on the right side of FIG. 3 . Within each single view, tokens flow from left to right and anti-tokens flow from right to left. The IF branch operations are represented by stages S 2 and S 3 , the CONDITION evaluation is represented by stage S 4 , and the ELSE branch operations are represented by stages S 5 ˜S 8 .
[0029] At time T 1 , stage S 1 has detected an IF-THEN-ELSE construct and prepares to perform the calculations of the CONDITION, IF branch, and ELSE branch in parallel. S 1 issues tokens to the first stage of each branch, namely stage S 2 of the IF branch, stage S 4 of the CONDITION branch, and stage S 5 of the ELSE branch. In this example, the operation of pipelines 400 and 402 are identical at time T 1 .
[0030] At time T 2 , stage S 2 has completed its operation and sends a token to stage S 3 . Stage S 4 has completed evaluation of the CONDITION, and sends a token to stage S 9 , indicating the results of the CONDITION. In this example, the result is TRUE, meaning that only the IF branch need be processed and the ELSE branch need not be performed. At time T 2 also the operation of pipelines 400 and 402 are identical.
[0031] At time T 3 , the operation of pipelines 400 and 402 begin to differ significantly. Pipeline 400 simply continues to wait for the completion of the IF and ELSE branches. The last stage of the IF branch, stage S 3 sends a token containing the result of the IF branch operations to stage S 9 , but stage S 9 cannot use that result, i.e., forward that result to the next stage, until it receives a token from the ELSE branch. Thus, pipeline 400 must wait during time T 4 and time T 5 while the ELSE branch completes its operation. Not until time T 6 can stage S 9 of pipeline 400 forward the results of the IF branch on to the next stage in the process.
[0032] In contrast, at time T 3 , stage S 9 of counterflow pipeline 402 has determined, based on the results of the CONDITION branch, that the ELSE branch is superfluous, and this issues an anti-token into last stage of the ELSE branch, stage S 8 . At time T 4 , stage S 9 of counterflow pipeline 402 may proceed to the next stage by forwarding the results of the IF branch on to the next stage in the process. Meanwhile, the anti-token passed backwards from stage S 8 to stage S 7 meets the token passed forwards from stage S 7 to stage S 8 , cancelling the operation that would have been performed by stage S 8 during time T 5 . Counterflow pipeline 402 performs the operation in less time and reduces power consumption by stage S 8 .
[0033] In another scenario, the each of the three branches may be split into two or more parallel sub-branches, each sub-branch calculating part of a logical CONDITION equation. In this scenario, if stage 308 has the ability to perform eager evaluation, additional time and/or power may be saved.
[0034] In this way, the use of anti-tokens provides the means by which pipelined systems can implement preemption, speculation, and eager evaluation. In general, the counterflow approach is useful for three key applications:
[0035] Pre-emption. An instruction that has received an exception can pass on information in a counterflow manner to any subsequently issued instructions to pre-maturely kill themselves before switching onto the exception handling routine.
[0036] Speculation. In general, control flow constructs, including conditional branches, switch and case statements, multiplexers with varying input delays, etc., are cases where speculation can improve throughput of an asynchronous pipeline.
[0037] Eager Evaluation. Applications range from a simple logic gate to a complex Boolean function. If the latencies of the input branches differ by a large amount, an anti-token can be propagated backward and the result validated immediately. Early output implementations allow logic to evaluate results before all inputs are presented. The results move to the next stage, but the current stage stalls while waiting for the late inputs to arrive simply to acknowledge them. This unnecessary wait can be removed by allowing backwards propagating anti-tokens to remove the late inputs. The use of anti-tokens and improved semi-decoupled latches allows the removal of many stalls due to unnecessary synchronizations, thus improving the performance of the circuit. Although the speed improvement might be sought after, the area and power consumption costs are high.
[0038] The idea of issuing an anti-token along the unwanted branch is useful in two ways. First, it aids in increasing the throughput by reducing the cycle time. Second, it aids in energy savings by preventing the unwanted requests flowing through the pipeline and hence preventing unwanted computations.
[0039] However, one disadvantage with conventional implementations of counterflow pipelines in general, and with conventional asynchronous counterflow pipelines in particular, is the problem of metastability.
[0040] As used herein, the term “metastability” refers to the transient, unstable but relatively long-lived state of a logic circuit (or any physical system). This occurs when a system that is designed to perform one action in response to one input and perform another action in response to another input is confronted with both inputs simultaneously, and must decide which action to perform. In logic circuits, metastability can cause unwanted glitches, which can lead to undesirable effects. Metastability is a characteristic of conventional asynchronous counterflow pipelines because each stage has to make a decision depending on whether it received a token or an anti-token. More specifically, the behavior of conventional counterflow pipelines will change depending on whether it received a token or an anti-token. In other words, conventional counterflow pipelines must choose between two possible actions to perform.
[0041] For example, referring again to FIG. 4 , pipeline 402 issues an anti-token during time T 3 and at time T 4 , the anti-token is traveling from stage S 8 to stage S 7 while at the same time the token is traveling from stage S 7 to stage S 8 . For conventional asynchronous counterflow pipeline designs, the relative timing of the token and anti-token is critical. If the token arrives at a stage before the anti-token arrives at the same stage, the data is sent forward. If the anti-token arrives at a stage before the token arrives at the same stage, incoming data from the previous stage is not accepted. If the token and anti-token arrive simultaneously, the stage must decide between two actions: whether to send the data forward or to reject the data. Furthermore, conventional asynchronous circuit implementations can glitch under certain timing scenarios, and rely on certain timing assumptions for correct behavior. Both mechanisms give rise to metastability.
[0042] One approach to solving the metastability problem involves maintaining two separate pipelines, one for tokens and the other for anti-tokens. However, this approach is expensive in terms of hardware complexity, chip area, and power consumption. Additional circuitry is required to ensure that the two pipelines are synchronized.
[0043] Another approach to solving the metastability problem involves adding arbitration logic to determine which signal arrived first. This approach also is expensive in terms of hardware complexity, chip area, and power consumption due to the requirement of an arbitration circuit at every stage.
[0044] Accordingly, in light of these disadvantages associated with conventional implementations of asynchronous counterflow pipelines, there exists a need for improved systems, methods, and computer readable media for preemption in asynchronous systems using anti-tokens.
SUMMARY
[0045] According to one aspect, configurable system for constructing asynchronous application specific integrated data pipeline circuits with preemption includes a plurality of modular circuit stages that are connectable with each other and with other circuit elements to form multi-stage asynchronous application specific integrated data pipeline circuits for asynchronously sending data and tokens in a forward direction through the pipeline and for asynchronously sending anti-tokens in a backward direction through the pipeline. Each stage is configured to perform a handshaking protocol with other pipeline stages, the protocol including receiving either a token from the previous stage or an anti-token from the next stage, and in response, sending both a token forward to the next stage and an anti-token backward to the previous stage.
[0046] According to another aspect, the subject matter described herein includes a for preemption in asynchronous systems using anti-tokens. The method includes, at an asynchronous pipeline stage for receiving tokens sent in a forward direction from a previous stage, receiving anti-tokens sent in a backward direction from a next stage, sending anti-tokens in a backward direction to the previous stage, and sending tokens in a forward direction to the next stage: receiving at least one of a token from the previous stage and an anti-token from the next stage; and in response to receiving the at least one of a token from the previous stage and an anti-token from the next stage, sending a token to the next stage and sending an anti-token to the previous stage.
[0047] The subject matter described herein for preemption in asynchronous systems using anti-tokens may be implemented in hardware, software, firmware, or any combination thereof. As such, the terms “function” or “module” as used herein refer to hardware, software, and/or firmware for implementing the feature being described. In one exemplary implementation, the subject matter described herein may be implemented using a computer readable medium having stored thereon computer executable instructions that when executed by the processor of a computer perform steps.
[0048] Exemplary computer readable media suitable for implementing the subject matter described herein include disk memory devices, chip memory devices, programmable logic devices, and application specific integrated circuits. In addition, a computer program product that implements the subject matter described herein may be located on a single device or computing platform or may be distributed across multiple devices or computing platforms.
BRIEF DESCRIPTION OF THE DRAWINGS
[0049] Preferred embodiments of the subject matter described herein will now be explained with reference to the accompanying drawings, wherein like reference numerals represent like parts, of which:
[0050] FIG. 1 is a block diagram illustrating a conventional pipeline that uses bundled data with a transition signaled handshake protocol to control data transfers;
[0051] FIG. 2 is a block diagram illustrating a conventional transition signaling asynchronous pipeline implementation;
[0052] FIG. 3 is a block diagram illustrating an abstract picture of a conventional design that implements speculation but not preemption or early evaluation;
[0053] FIG. 4 is a block diagram comparing the operation of a conventional pipeline without anti-tokens to the operation of a conventional counterflow pipeline which uses anti-tokens to implement preemption, illustrating the problem of metastability suffered by conventional counterflow pipeline designs;
[0054] FIG. 5 is a block diagram illustrating a portion of an asynchronous counterflow pipeline according to an embodiment of the subject matter described herein;
[0055] FIG. 6 is a Petri-net diagram (PND) illustrating an exemplary control protocol according to an embodiment of the subject matter describe herein;
[0056] FIG. 7 illustrates an exemplary asynchronous counterflow pipeline stage according to an embodiment of the subject matter described herein;
[0057] FIG. 8 illustrates an exemplary asynchronous counterflow pipeline fork stage according to an embodiment of the subject matter described herein;
[0058] FIG. 9 illustrates an exemplary asynchronous counterflow pipeline join stage according to an embodiment of the subject matter described herein;
[0059] FIG. 10 illustrates an exemplary asynchronous counterflow pipeline IF-THEN-ELSE join stage according to an embodiment of the subject matter described herein; and
[0060] FIG. 11 is a flow chart illustrating an exemplary process for preemption in asynchronous systems using anti-tokens according to an embodiment of the subject matter described herein.
DETAILED DESCRIPTION
[0061] In accordance with the subject matter disclosed herein, systems, methods, and computer program products are provided for preemption in asynchronous systems using anti-tokens. The subject matter disclosed herein includes a novel approach to asynchronous counterflow designs that addresses the metastability problem that can arise when two inputs arrive simultaneously and it must be decided which input arrived first. The metastability problem is solved by avoiding the decision making altogether. The approach described herein can be used to efficiently implement several useful architectural concepts, such as speculation, preemption, and eager evaluation, in asynchronous hardware systems.
[0062] In conventional pipelines, for any given pair of stages, only one stage can initiate communication with the other. By contrast, in counterflow pipelines each stage can initiate communication with the other stage. In other words, for any given pair of stages, each stage in the pair may issue a request to the other stage in the pair, and the other stage will issue an acknowledgement of the request back to the requesting stage.
[0063] In counterflow pipelining, special commands, called anti-tokens, can be propagated in a direction opposite to that of data, allowing certain computations to be killed before they are completed. The case during which both the stages initiate requests simultaneously is a special one and can be treated on an application-specific basis, as will be described below. Specific examples of how this kind of a counter flow nature will help in supporting speculation, preemption and eager evaluation paradigms in asynchronous circuits will also be described in more detail below.
[0064] To avoid confusion about which direction a signal is flowing, signals may be named using a notation that indicates the direction of a signal. Hereinafter, the following notation will be used: All the forward flowing signals are named F i and backward flowing signals are named B i . Data signals flow only in the forward direction. Data input to a stage is data i−1 , and its data output is data i . Specifically, the control signals controlled by stage i are F i and B i . In general, information flowing in the forward direction is called a token and information flowing in the reverse direction is called an anti-token.
[0065] FIG. 5 is a block diagram illustrating a portion of an asynchronous counterflow pipeline according to an embodiment of the subject matter described herein, with components labeled using the notation described above. A stage is said to be idle when no tokens or anti-tokens are being processed. For designs using transition signaling (2-phase), in one embodiment, the idle state may correspond to all the control signals being in the same state (either zero or one).
[0066] Using the notation convention described above, tokens and anti-tokens may be associated with the states of the control signals. In Table 1, below, a “0” indicates that a signal has not changed and a “1” indicates that a signal has changed, e.g., undergone a transition, changed logic state, etc.
[0000]
TABLE 1
Relationship Between Signal Inputs and State
F i−1
B i+1
STATE
0
0
Idle
1
0
Token received
0
1
Anti-token received
1
1
Both Token and Anti-token received
[0067] For a stage in the Idle state, a transition on input F i−1 , indicates that a token has been received. When this happens, the state of the input F i−1 , signal will be different from signals F i , B i , and B i+1 . The stage can then acknowledge the token by toggling B i , signal and send the token forward to the next stage by toggling the F i signal.
[0068] For a stage in the Idle state, a transition on input B i+1 , indicates that an anti-token has been received. When this happens, the state of the input B i+1 , signal will be different from signals F i−1 , F i , and B i . The stage can then acknowledge the anti-token by toggling F i signal and send the anti-token backward to the previous stage by toggling the B i signal.
[0069] It is important to note that toggling a signal wire may imply different actions. Specifically, when a stage toggles its F i signal, it either means sending a token or acknowledging an anti-token. When a stage toggles its B i signal, it either means sending an anti-token or acknowledging a token.
[0070] The protocol works as follows. In an idle state, a stage can receive either a token or an anti-token. If the stage receives a token, the stage sends an acknowledgment of the token backwards to the previous stage and simultaneously sends the token forward to the next stage. Similarly, if the stage receives an anti-token, the stage sends an acknowledgement of the anti-token forward to the next stage and simultaneously sends the anti-token backward to the previous stage. After sending a token forward or sending an anti-token backward, a stage cannot accept a new token or an anti-token until an acknowledgment, corresponding to the forwarded token or the anti-token, is received.
[0071] When a stage receives a token and an anti-token simultaneously, the stage may treat the received anti-token as the acknowledgment to the token that will be sent forward, or the stage may treat the received token as the acknowledgment to the anti-token that will be sent backward.
[0072] FIG. 6 is a Petri-net diagram (PND) illustrating an exemplary control protocol according to an embodiment of the subject matter describe herein. Circles represent places, boxes represent transitions, and arrows represent directed arcs. For simplicity, each “place” in the PND may be conceptually treated similarly to a “state” in a state machine diagram. Unlike a state machine diagram, however, where only one state may be active at a time, multiple places in a PND may be occupied simultaneously. A place is “occupied” when the place contains a token, which are conceptual markers to indicate control flow through the PND. This characteristic makes Petri-net diagrams useful to describe distributed systems or systems with parallelism.
[0073] Each transition has one or more inputs and one or more outputs. Transitions may “fire” only when all of its inputs are occupied by tokens. When a transition fires, all of its outputs become occupied by tokens and its inputs are cleared of tokens. Thus, a transition is suggestive of a token transitioning from one place to another; however, all outputs get a token, regardless of how many inputs a transition has. In other words, Petri-net tokens are markers or indicators only, and not an entity of which there is a finite supply. To avoid confusion between a Petri-net token and the token/anti-token concept used to describe information flowing in a forward/backward direction within an asynchronous counterflow pipeline, a place in a PND that is occupied by a Petri-net token is hereinafter referred to as “armed”. Thus, a transition cannot fire unless all of its input places are armed, and when a transition does fire, it arms all of its output places and disarms all of its input places.
[0074] By convention, all inputs to Petri-net transitions are places connected to the transition by directed arcs. For simplicity, however, some of the inputs to transitions in the PND illustrated in FIG. 6 are shown only as directed arcs, i.e., the place and trigger is not shown. These directed arcs are labeled with a description of an event that would have armed the un-shown place. Again, for simplicity, these directed arcs shown without places are herein referred to as “triggers”; thus, a transition will not fire unless it has been armed and triggered.
[0075] The PND illustrated in FIG. 6 includes the following restriction: a stage in a non-idle state cannot receive a new token or an anti-token until it has completely processed the existing token or anti-token. Completely processing a token/anti-token means sending the token/anti-token to the next/previous stage and receiving an acknowledgment. The inputs to the PND are signals indicating the receipt of a token and/or anti-token. The output of the PND is a latch control signal.
[0076] In the embodiment illustrated in FIG. 6 , PND 600 includes place P 0 , which corresponds to a stage in the IDLE state, in which the latch is open, allowing data and request signals to flow transparently through the stage. If P 0 is armed (i.e., the stage is in the IDLE state) receipt of a token by the stage, e.g., a transition on signal F i−1 in FIG. 5 , would cause transition T 1 to fire. As a result of transition T 1 firing, place P 0 would be disarmed and places P 1 and P 2 would be armed. Place P 1 corresponds to a state in which a stage has received a token but not an anti-token. Place P 2 corresponds to a state in which a stage has received either a token or an anti-token.
[0077] Since place P 2 is the only input to transition T 2 , transition T 2 fires, arming place P 3 and disarming place P 2 . Place P 3 represents a state in which the stage's latch is closed, capturing data, and where an acknowledgement is sent to the previous stage and a request is sent to the next stage, i.e., a transition on both F i and B i in FIG. 5 .
[0078] If place P 1 is armed, receipt of an anti-token by the stage, e.g., a transition on signal B i+1 in FIG. 5 , would cause transition T 3 to fire, arming place P 4 and disarming place P 1 . If place P 3 was previously armed, e.g., by receipt of a token prior to receipt of the anti-token, transition T 4 will fire, disarming places P 4 and P 5 and arming place P 0 , where the latch will again open.
[0079] Starting again with place P 0 in the armed state, if the stage receives an anti-token before receiving a token, transition T 5 will fire, arming places P 2 and P 5 , and disarming place P 0 . As described above, arming place P 2 causes a sequence of transitions leading to place P 3 being armed and the data latch being closed. Place P 5 corresponds to a state in which a stage has received an anti-token but not a token. Once place P 5 is armed, receipt of a token by the stage would cause transition T 6 to fire, arming place P 4 and disarming place P 5 . If place P 3 was previously armed, e.g., by receipt of an anti-token prior to receipt of the token, transition T 4 will fire, disarming places P 4 and P 5 and arming place P 0 , where the latch will again open.
[0080] Thus, from the IDLE state, whether the stage receives a token or anti-token first, the stage will respond by causing a transition on both the signal going to the next stage and the signal going to the previous stage, i.e., F i and B i in FIG. 5 .
[0081] FIG. 7 illustrates an exemplary asynchronous counterflow pipeline stage according to an embodiment of the subject matter described herein. In one embodiment, stage 700 consists of a controller 702 and data latch 704 . Controller 702 controls the outgoing requests and acknowledgments through which the stages communicate. It also controls the enable signal L to data latch 704 , controlling the data flow through the pipeline.
[0082] Controller 702 is implemented based on the Petri-net description of the protocol shown in FIG. 6 . Since PND 600 represents only the restricted version, in which a stage cannot receive a new token or anti-token until the existing token or anti-token has been processed, extra logic called the guarding C-Elements 706 and 708 are added to controller 702 to complete the counterflow protocol.
[0083] A C-Element operates according to the following description: if all of the C-Elements inputs are the same value, the output of the C-Element becomes that value. Thus, if all inputs are logic “1”, the output becomes logic “1”, and if all inputs are logic “0”, the output becomes logic “0”. For any other combination of inputs, the C-Element does not change output value but instead maintains the last value that was output by the C-Element. This behavior makes the C-Element very useful for transition-based logic. The C-element may be modeled by an unclocked set/reset flip-flop, where the set input signal is a logical AND of all inputs to the C-element and the reset input signal is a logical AND of all inverted inputs to the C-element.
[0084] The guarding C-Elements 706 and 708 are provided on all the control inputs to the controller. They ensure that a new incoming token or anti-token is not accepted until acknowledgment to the previously forwarded token or anti-token has been received. The control inputs F i−1 , and B i+1 are fed into their guarding C-Elements whose outputs, F and B respectively, are fed into the sub-circuit 710 , which itself contains C-element 712 for generating signal D, and C-element 714 for generating latch-control signal L. Sub-circuit 710 represents one implementation of PND 600 . Sub-circuit 710 can be generated either manually or using circuit generating tools. Table 2, below, contains equations to describe the function of sub-circuit 710 :
[0000]
TABLE 2
Boolean characteristic equations
Signal
Set
Reset
D
F × B × L
F × B × L
L
D × (F + B)
D × ( F + B )
[0000]
TABLE 3
States of a counterflow pipeline stage
F
B
L
D
Controller State
◯
◯
◯
◯
Idle
◯
◯
◯
Accepted a token
◯
◯
Waiting for token ACK
◯
◯
◯
Accepted an anti-token
◯
◯
Waiting for anti-token ACK
◯
◯
Token anti-token clashed
[0085] The states of these four signals indicate a specific state of the controller. In Table 3, above a signal has one value or another, arbitrarily indicated with either an open circle (∘) or a closed circle (). Because controller 702 implements a transition-based design rather than a level-based design, it is the relative, rather than absolute, logic level that is important. For example, in the Idle state, the signals F, B, L, and D all have the same value. This means that all of these signals may be at logic value “H” or that all of these signals may be at logic value “L”. When signal F is a different value than signals B, L, and D, this indicates that the stage has accepted a token from a previous stage. When both signals F and L both have the same value and that value is different from the value on both B and D, this indicates that the stage has closed the latch, has forwarded the token to the next stage, and is waiting to receive an acknowledgement to the token from the next stage. Similarly, when signal B is a different value than signals F, L, and D, this indicates that the stage has accepted an anti-token from the next stage. When both signals B and D both have the same value and that value is different from the value on both F and L, this indicates that the stage has closed the latch, has forwarded the anti-token to the previous stage, and is waiting to receive an acknowledgement to the anti-token from the previous stage. Finally, when signals F and B both have the same value and that value is different from the value on both L and D, this indicates that the stage has received both a token and an anti-token at the same time.
[0086] The flow of tokens through the pipeline will now be described conceptually. Initially, when the pipeline is empty, all the stages are in idle state and all the signals are the same value. For this example, the signals are all assumed to be low. When the first token (data item) flows through, all request lines will toggle from low to high as the first token flows through the pipeline from left to right. When the token is at some intermediate stage, all the signals associated with pipeline stages prior to this stage are high and all the signals associated with later stages are low. When the token arrives at the other end of the pipeline, all the stages are high. When a second token flows through, all the signals are toggled back to low again. When tokens are fed into the left end of the pipeline continuously, the signal values of the pipeline stages alternate along the pipeline.
[0087] The flow of anti-tokens will cause exactly the same kind of behavior as in the case of tokens but from the other end of the pipeline. If an anti-token is injected in an empty pipeline having all signals low, the anti-token toggles all the signal lines from low to high as the anti-token flows through the pipeline from right to left. Once the anti-token reaches the other end of the pipeline, all signals have been toggled from low to high. A second flowing anti-token will toggle all the signals back to low. Now consider injecting a token and an anti-token simultaneously into the right and the left end of the pipeline respectively. As the token and anti-token travel towards each other, they leave all the signals toggled in their trail. Finally as they clash (i.e., arrive at the same stage) at some intermediate stage, they cancel each other and all the signals will be at level one. Injecting a second token/anti-token pair will bring back all the signals to zero after they clash at some intermediate stage. When a token and an anti-token clash, the clash is treated exactly the same way as if the anti-token was an acknowledgment to the token. Because a clash is treated the same way as a normal acknowledgment, there is no need for a complex arbiter circuit, thus simplifying the design.
[0088] Tokens and anti-tokens may both carry information, and may or may not be associated with data traveling through the pipeline. For example, in one embodiment, tokens are considered as data-carrying requests and anti-tokens as request killers. In this embodiment, anti-tokens are not associated with any data; they merely kill the first token they encounter along their path, killing themselves in the process. Therefore, in these embodiments, the latch may be enabled when a token is passing through but not when an anti-token is passing through. In an alternative embodiment, the counterflow pipeline can be designed to support data flow in either direction.
[0089] Data flow through latch 704 is controlled by the enable signal L. In one embodiment, latch 704 is normally open, e.g., transparent, and close as soon as data passes through. The idea is to disable the latch until the stage receives an acknowledgment to a token that the stage had sent. The behavior of a high-active enable signal can be described by the following equation:
[0000] enable=( L XNOR B ).
[0090] However, keeping latches open all the time may allow any garbage (data with no associated request) to flow through the pipeline, wasting energy. The latches should then open only when there is an impending request (token). This behavior can be obtained using the following enable signal, designed to enable the latch only when there is an impending token and any previously sent token is acknowledged.
[0000] enable=( L XNOR B )AND( F XOR L )
[0091] However, the above condition does not cover the anti-token case. When a stage is processing an anti-token, there is no need to open the latch in any case. So, we need to make sure the latch is not opened when F toggles in response to a sent anti-token. The enable signal can be modified to include this case:
[0000] enable=( L XNOR B )AND( F XOR L )AND( D XNOR B )
[0092] In the embodiment illustrated in FIG. 7 , the latch control signal L will operate to open the latch only when a token arrives before an anti-token. Furthermore, the latch signal L feeds back into C-element 712 , with the result that latch control signal L operates as a one-shot, opening the latch briefly before closing it again. Complicating the enable logic could lead to glitches which may temporarily open the latch and contaminate its contents. However, the timing of the input signals ensures that glitches do not occur when the stage is processing tokens. In the case of anti-tokens however, there is the possibility that a glitch may occur. It is important to note that these glitches do not effect the control behavior of the pipeline, but would only effect the data path. The only concern is any energy wastage due to contents of latch switching unnecessarily.
[0093] However, these potential glitches are not a problem except at the stage where a token and a anti-token clash. When an anti-token alone flows through the pipeline, the inputs and outputs of the latch match since the input has not changed since the last token has passed through. (The values of the latch in particular stage are updated with the data associated with the token that passes through). Hence, even though a rare glitch may occur on the enable signal, this does not result in any changes in latch contents as the inputs and outputs are the same. This situation is different, however, at the token anti-token clash stage because the input data will be that which is associated with the token. A glitch may result in a change to some of the contents of the latch. This is of no consequence, however, since the arrival of an anti-token signifies that the operation currently being performed by the branch is to be terminated; thus, the potentially corrupted contents of the latch will be discarded in any case.
[0094] The asynchronous counterflow pipeline architecture described herein can be used to implement parallel pipeline designs. When an operation is split into multiple, parallel branches, the pipeline is said to “fork”. When the results of the parallel branches are merged, the pipeline is said to “join”. This is illustrated in FIG. 3 , which includes a fork stage 300 and a join stage 308 . In general, a fork is a stage which accepts a request and forwards it to two or more output stages, and a join is a stage which accepts request from two or more input stages and passes on a single request to the output stage.
[0095] A join stage that does not support eager evaluation will wait until it receives the request from all the input stages before forwarding the request to the next stage. In contrast, a join stage according to embodiment of the subject matter described herein will generate an output took as soon as there are a sufficient number of input tokens to determine the output.
[0096] A join stage that does not support preemption will not interrupt or terminate the processes that the join stage has determined are unneeded but are still being performed by a parallel input branch. In contrast, a join stage according to an embodiment of the subject matter described herein will also send anti-tokens down the join stage's unneeded input branches. In FIG. 3 , for example, join stage 308 may issue an anti-token into either IF branch 304 or ELSE branch 306 , depending on the result of the CONDITION branch 302 .
[0097] FIG. 8 illustrates an exemplary asynchronous counterflow pipeline fork stage according to an embodiment of the subject matter described herein. In one embodiment, a fork stage 800 may be very similar to the general pipeline stage 700 shown in FIG. 7 , but with additional circuitry, guarding C-elements 802 and 804 , to combine all incoming B signals. This ensures that when fork stage 800 forwards a token to multiple output stages, fork stage 800 will wait until all acknowledgements arrive before it can accept a new token. Similarly, when fork stage 800 receives an anti-token from one of its output stages, it waits until it receives anti-tokens from all of the output stages before fork stage 800 will send the anti-token backwards to its input stage(s).
[0098] FIG. 9 illustrates an exemplary asynchronous counterflow pipeline join stage according to an embodiment of the subject matter described herein. In one embodiment, a join stage 900 may be very similar to the general pipeline stage 700 shown in FIG. 7 , but with a join controller 902 that includes additional circuitry, guarding C-elements 904 and 906 , to combine all incoming F signals. However, in order to support eager evaluation and/or preemption, join stage 900 must also include a completion detection circuit CD 908 for determining whether the inputs received are sufficient to compute the output. The output of detection circuit CD 908 is signal S, indicating that the inputs are sufficient for the stage to take action. Table 4, below, contains equations to describe the function of join controller 902 .
[0000]
TABLE 4
Boolean characteristic equations
Signal
Set
Reset
D
F × B × L
F × B × L
L
D × (S + B)
D × ( S + B )
[0099] Once the input is determined to be sufficient to generate an output, join stage 900 may generate the outgoing token, acknowledgements down the input branches with valid inputs, and anti-tokens along the input branches with invalid inputs. The completion detector logic depends on the specific logic implemented by the join stage. One such example, and IF-THEN-ELSE join stage, will now be described.
[0100] FIG. 10 illustrates an exemplary asynchronous counterflow pipeline IF-THEN-ELSE join stage according to an embodiment of the subject matter described herein. In one embodiment, a join stage 1000 may be very similar to the general pipeline stage 700 shown in FIG. 7 , but with a join controller 1002 that implements an IF-THEN-ELSE construct where an extra optimization can be applied: the anti-token can be generated along an unwanted branch even before the token to the next stage is generated. This is possible because once the condition bit is evaluated, the join can immediately send an anti-token along the unwanted branch. In the embodiment illustrated in FIG. 10 , however, join controller 1002 must wait until the input on the desired branch has arrived before join controller 1002 can produce an outgoing token. While this optimization does not necessarily save time, it helps in killing computation along the unwanted branch by producing an early anti-token.
[0101] In the embodiment illustrated in FIG. 10 , some circuit details evident in the previously described general join stage are avoided for clarity. The if-then-else join has 3 input channels: the IF branch, with control signals F IF and B IF ; the ELSE branch, with control signals F ELSE and B ELSE ; and the CONDITION evaluation branch, with control signals F CN and B CN . Join controller 1002 also has the condition bit D CN as input, used in the completion detector logic. For this specific join, the completion detector can be implemented as follows.
[0102] First, a truth table specifying the output S (sufficiency signal) is drawn for a given set of inputs—F CN , D CN , F IF and F ELSE . Table 5, below, summarizes the different cases. The logic can be implemented using a C-Element with input set and ˜reset.
[0000]
TABLE 5
Determining the Completion Detector Logic
F CN
D CN
F IF
F ELSE
S
0
0
0
—
0
1
0
1
—
1
0
1
—
0
0
1
1
—
1
1
[0103] The same of approach described above can be used to generate logic that produce early anti-tokens. The Table 6, and Table 7, below, determine the logic required for the B IF and B el signals respectively.
[0000]
TABLE 6
Determining Logic to Compute B IF
D CN
F CN
I
B IF
1
1
—
1
1
0
—
0
0
—
1
1
0
—
0
0
[0000]
TABLE 7
Determining Logic to Compute B el
Table 5.3:
d cn
f cn
I
B el
0
1
—
1
0
0
—
0
1
—
1
1
1
—
0
0
[0104] FIG. 11 is a flow chart illustrating an exemplary process for preemption in asynchronous systems using anti-tokens according to an embodiment of the subject matter described herein. In block 1100 , at an arbiter-less asynchronous pipeline stage for receiving tokens sent in a forward direction from a previous stage, receiving anti-tokens sent in a backward direction from a next stage, sending anti-tokens in a backward direction to the previous stage, and sending tokens in a forward direction to the next stage, a token from the previous stage, an anti-token from the next stage, or both, is received. At block 1102 , in response to receiving the token, the anti-token, or both, a token is sent to the next stage and an anti-token is sent to the previous stage. In one embodiment, the simultaneous arrival of both a token from the previous stage and an anti-token from the next stage also causes a token to be sent to the next stage and an anti-token to be sent to the previous stage.
[0105] Architectural templates may be based on the counterflow idea to support speculation, preemption and eager evaluation in asynchronous pipelined systems. Adoption of the counterflow concepts can provide a significant improvement in the throughput of certain classes of systems, e.g., those involving conditional computation, where a bottleneck pipeline stage can often be preempted if its result is determined to be no longer required. Experimental results indicate that the counterflow approach can improve the system throughput by a factor of up to 2.2×, along with an energy savings of up to 27%.
[0106] A group of experiments were designed to determine the effectiveness of using anti-tokens with speculation and eager evaluation and to compare the performance of pipelines with and without those capabilities. To this end, a library of modules required for implementation of asynchronous counterflow pipelines was developed. These modules were designed at behavioral and structural level using Verilog language. A unit delay was assumed to be the latency of a two input C-Element. The energy consumption per toggle was assumed to be of 1 unit in a C-Element. The energy consumption per enable on a latch was assumed to be 32 units (considering a 32 bit latch). The experiments compared the throughput and power consumption of two asynchronous pipeline, one without preemption and early evaluation (pipeline 1 ) and one without (pipeline 2 ).
[0107] A simple IF-THEN-ELSE statement was rendered using the library of modules. The CONDITION evaluation operation consists of a single pipeline stage. The IF branch has 2 pipeline stages and the ELSE branch has 8 pipeline stages. The pipeline stages are assumed to be associated with logic of uniform delay of five units. The latches are enabled only when tokens pass through. The first set of experiments was intended to determine the effects, if any, that various probabilities of taking the IF branch had on throughput and energy savings. In each case, total time taken to complete 1000 simulations was observed.
[0108] Pipeline 1 took 3.2 microseconds to complete 1000 simulations. Because pipeline 1 does not support preemption or early evaluation, varying this probability of taking the IF branch does not affect the total time taken for the pipeline 1 because the join stage has to wait until it receives all inputs from both the if and else branches before generating the output.
[0109] Table 8, below, summarizes the results for pipeline 2 . The first column indicates R IF —probability that if branch is taken. The second column indicates the total time taken by pipeline 2 to run 1000 simulations. The third column lists the total energy consumed in each case. The fourth column shows the throughput improvement with respect to pipelines. The final column shows the energy savings with respect to pipeline 1 . Pipeline 1 consumed 33×10 4 units of energy for 1000 simulations.
[0000]
TABLE 8
Pipeline2 Performance Versus R IF
Time
Energy
Normalized
Energy
R if
(μsec)
(10 4 ) units
Throughput
Savings (%)
5
3.36
35.94
0.95
−8.90
10
3.29
35.30
0.98
−6.96
20
3.17
34.62
1.01
−4.92
30
3.05
33.91
1.05
−2.77
40
2.91
33.06
1.10
−0.17
50
2.72
31.88
1.18
3.40
60
2.49
30.52
1.29
7.51
70
2.26
29.15
1.42
11.66
80
1.97
27.32
1.63
17.21
90
1.67
25.45
1.93
22.87
95
1.45
24.10
2.22
26.98
[0110] At very low probabilities, e.g., around 5%, the extra overhead introduced in reverse latency may outweigh the possible benefits of using the counter-flowing anti-tokens. At probabilities around 20%, the throughput of both the protocols is almost the same. However, with the R IF equal to 50% and more, the savings in throughput increase significantly. When the smaller branch is taken with very high probability, the throughput of the counterflow pipeline more than doubles for this specific application. The energy savings also show a similar trend, with up to a 26% energy savings when the smaller branch is taken with high probability.
[0111] In another experiment, the effect of varying arrival times of the IF and ELSE branches was tested. This was done by varying the number of pipeline stages of the ELSE branch with respect to the number of stages of the IF branch. Table 9, below, summarizes the results of five cases with assumed R IF value 70%.
[0000]
TABLE 9
Effect of Varying Arrival Times
t ctrFlow
t MT
Normalized
N IF
N ELSE
(μsec)
(μsec)
Throughput
2
2
1.29
1.10
0.86
2
4
1.61
1.81
1.12
2
6
1.94
2.51
1.29
2
8
2.26
3.21
1.42
2
10
2.59
3.91
1.51
[0112] Columns N IF and N ELSE indicate the number of stages in the IF and the ELSE branches respectively. As expected, the relative effectiveness of pipeline 2 improves as the arrival times of the IF and ELSE branches differ more.
[0113] Often, there are high latency logic blocks in complex systems which cannot be pipelined. In these cases, a whole pipeline stage may be devoted for the computation of these high latency logic blocks. The performance of the asynchronous counterflow pipeline designs described herein was evaluated for use in these kinds of applications. A completion detector supporting eager evaluation was coupled with a two-input join which requires at least the input from the smaller branch (i.e., the branch with fewer computations or which otherwise completed its sequence of operations before the other branch) to compute the output. Sometimes, input form the smaller branch is alone sufficient to compute the output and sometimes both the inputs are required.
[0114] The chance of smaller branch being alone sufficient is represented by R SM . The smaller branch has 2 pipeline stages, the larger branch has 5 pipeline stages with one of the stages having a high latency logic block. In one experiment, the large block stage is in the middle of the slower branch. A latency of 40 units is assumed for the large block and 5 units for all the other stages. Also the energy consumed by the large block is assumed to be 100 units. The total time taken and the energy used by pipeline 2 in each case are compared to the performance of pipelines, which took 4 micro seconds to run 1000 simulations and consumed 30×10 4 units of energy in the process. The results are shown in Table 10, below.
[0000]
TABLE 10
Early Output Logic Using Counterflow Protocol
Time
Energy
Normalized
Energy
R sm
(μsec)
(10 4 units)
Throughput
Savings (%)
5
4.37
31.74
0.92
−6.17
10
4.31
31.41
0.93
−5.04
20
4.18
31.37
0.96
−4.93
30
4.03
30.10
1.00
−0.67
40
3.83
29.52
1.05
1.28
50
3.60
28.82
1.11
3.61
60
3.36
28.15
1.19
5.84
70
3.10
27.49
1.29
8.05
80
2.83
26.83
1.41
10.27
90
2.57
26.23
1.56
12.28
95
2.40
25.80
1.67
13.71
[0115] The results indicate a throughput improvement of 1.5× and a 13% improvement in energy usage for very high rates of R SM , i.e., only the smaller branch input is sufficient most of the time to compute the output. However, at low values of R SM , we see that the counterflow protocol is not effective in improving the throughput. This is largely because of the huge cycle time overhead introduced by the large block. This limits the rate at which anti-tokens (or tokens) can flow through the pipeline.
[0116] In addition, how the placement of the large block could affect the performance of the asynchronous counterflow protocol described herein was also tested. The same application above was taken and the large block in the slower branch was moved from one end to the other. It is assumed that the smaller branch results are sufficient to compute the output for 70% of the time. The results are summarized in Table 11, below. The first column indicates the placement of the large block in the slower branch. Position 1 indicates that the large block is the first stage (out of five) in the slower branch.
[0000]
TABLE 11
Effect of Placement of Large Block
Time
Energy
Normalized
Energy
Position
(μsec)
(10 4 units)
Throughput
Savings (%)
1
3.8056
23.57
1.05
21.16
2
3.0082
24.83
1.33
16.97
3
3.0966
27.49
1.29
8.05
4
3.0966
29.73
1.29
0.55
5
3.3124
32.00
1.21
−7.02
[0117] It can be seen that the throughput is best when the large block is at some intermediate stage. This is because the tokens and anti-tokens have some buffer to fill in before getting saturated with the cycle time of the large block. This helps in reducing the average cycle time to propagate anti-tokens. Considering energy savings, the case when the large block is far from the join stage gives the best energy savings because as this allows the least number of unwanted tokens to pass through the other four intermediate stages.
[0118] It will be understood that various details of the subject matter described herein may be changed without departing from the scope of the subject matter described herein. Furthermore, the foregoing description is for the purpose of illustration only, and not for the purpose of limitation. | Systems, methods, and computer program products for preemption in asynchronous systems using anti-tokens are disclosed. According to one aspect, configurable system for constructing asynchronous application specific integrated data pipeline circuits with preemption includes a plurality of modular circuit stages that are connectable with each other and with other circuit elements to form multi-stage asynchronous application specific integrated data pipeline circuits for asynchronously sending data and tokens in a forward direction through the pipeline and for asynchronously sending anti-tokens in a backward direction through the pipeline. Each stage is configured to perform a handshaking protocol with other pipeline stages, the protocol including receiving either a token from the previous stage or an anti-token from the next stage, and in response, sending both a token forward to the next stage and an anti-token backward to the previous stage. | 6 |
RELATED APPLICATION
This nonprovisional application claims the benefit of co-pending, provisional patent application U.S. Ser. No. 60/882,471, filed on Dec. 28, 2006, which is hereby incorporated by reference in its entirety.
TECHNICAL FIELD
The present invention relates generally to methods and systems for reservoir simulation and history matching, and more particularly, to methods and systems for calibrating reservoir models to conduct forecasts of future production from the reservoir models.
BACKGROUND OF THE INVENTION
One way to predict the flow performance of subsurface oil and gas reservoirs is to solve differential equations corresponding to the physical laws that govern the movement of fluids in the subsurface. Because of the nature of the problem, the differential equations are conventionally solved using numerical methods working in discrete representations in space and time. Solving such equations typically requires the use of three dimensional, discrete representations of the subsurface rock properties and the associated fluids in the rocks.
In the oil and gas industry, numerical methods to solve for the flow of fluids in the reservoir are called “Numerical Reservoir Simulation”, or simply “Flow Simulation”. Predictions of future performance of subsurface oil and gas reservoirs with models based on physical laws are considered the highest standard in current technology. The three dimensional, discrete models of the subsurface are constructed in such a way that the models are consistent with actual measurements taken from the reservoir. Some of these measurements can be included directly in the model at the time of the construction. Other measurements, such as ones that are related to the movement of fluids within the reservoir, are used in an indirect manner utilizing a model calibration process. The calibration process involves assigning properties to the model and then verifying that the solutions computed with a numerical reservoir simulator are consistent with the measurements of the fluids. This calibration process is iterative and stops when the reservoir model is able to replicate the observations within a predetermined tolerance. Once the model is appropriately calibrated, the model can be run in a flow simulator to forecast or predict future performance.
The process of calibrating numerical models of oil and gas reservoirs to measurements related to production and/or injection of fluids is usually referred to as history matching. The calibration problem described previously may be considered as being a particular case within the field of inverse problem theory in mathematics. While there exists a rigorous mathematical framework for the solution of model calibration problems, such a framework becomes impractical for dealing with complex problems such as large scale reservoir flow simulation. For a detailed explanation of such a framework, see A. Tarantola, Inverse Problem Theory—Methods for Data Fitting and Model Parameter Estimation , Elsevier, 1987, hereinafter referred to as “Tarantola”. This Tarantola reference is hereby incorporated by reference in its entirety into this specification.
There are numerous difficulties in calibrating numerical models of oil and gas reservoirs to data related to the movement of fluids within the reservoirs. First, numerical models based on laws of physics are usually complex and a significant amount of computational time is required to evaluate, i.e. run a simulation on, each numerical model. Data to calibrate the numerical models are often uncertain. Furthermore, data to calibrate numerical models are scarce, both in time and space dimensions. Finally, there is not a unique solution to the calibration problem. Rather, there are many ways to calibrate a numerical model that is still consistent with all the measurements. Thus, there is not a unique calibrated numerical model. Accordingly, a probability is associated with any combination of model parameters and this probability may be expressed such as by using a probability density function (PDF).
The mathematical inverse problem theory provides the framework to deal with the inverse problem presented by reservoir flow simulation. Tarantola describes the mathematical theory applicable to the problem of calibration and uncertainty estimation. The solution to the problem is based on application of techniques relying on Monte Carlo simulation. The general approach prescribed by the mathematical theory, as described by Tarantola, can be summarized with a high level of simplification as follows.
A parameterization system, comprising model parameters, is defined for a mathematical model. Initially, an “a priori” probabilistic description is defined for the model parameters describing the mathematical model. Next, a probabilistic model is defined for measured or observed data which is to be used for calibration. This probabilistic model is constructed by defining a measure of the discrepancy between actual observed measurements of parameters and corresponding calculated parameters predicted by using the mathematical model. This measure of discrepancy is associated with a “likelihood” function in a Bayesian approach to updating probabilities. Then an “a posteriori” probabilistic description of the model parameters is constructed by updating the “a priori” probabilistic model using the observed measurements. In the most general case, the model parameter space is sampled in such a way that the resulting probability density function provides the desired “a posteriori” probabilistic description of the model parameters. The sampling takes into account the “a priori” model description. A common approach for performing the sampling is the application of variants of the Metropolis algorithm for Monte Carlo sampling. This process also produces probability density functions that correspond to the predictions calculated with the reservoir model.
The step of sampling the model parameter space is the most computational demanding part of this process and limits the practical application of this rigorous mathematical approach to solving problems involving oil and gas reservoir models based on physical laws. Using terminology commonly associated with inverse problem theory, the process involves solving the “forward problem” (running the flow simulation) a very large number of times during the sampling of the parameter space. The “forward problem” refers to computing the model response to a given combination of input model parameters.
Tarantola describes the use of probability theory in inverse problems such as in history matching and production forecasting. Likelihood functions need to be computed in the applications described by Tarantola. A likelihood function is a measure of how good results from a simulation run on a proposed model are as compared to actual observed values. Computation of likelihood functions in conjunction with very large models, such as are used in reservoir simulations, are not practical due to great computational costs. Evaluation of a likelihood function requires a reservoir simulation run. Each run of a large reservoir simulation may require hours of time to complete. Furthermore, thousands of such simulations may be required to obtain valid results.
There is a need for a practical method for history matching and forecasting wherein the high computational costs associated with calculating likelihood functions are reduced to a manageable level. The present invention addresses this need.
SUMMARY OF THE INVENTION
A method, system and program storage device for history matching and forecasting of subterranean reservoirs is provided. Reservoir parameters and probability models associated with a reservoir model are defined. A likelihood function associated with observed data is also defined. A usable likelihood proxy for the likelihood function is constructed. Reservoir model parameters are sampled utilizing the usable proxy for the likelihood function and utilizing the probability models to determine a set of retained models. Forecasts are estimated for the retained models using a forecast proxy. Finally, computations are made on the parameters and forecasts associated with the retained models to obtain at least one of probability density functions, cumulative density functions and histograms for the reservoir model parameters and forecasts. The system carries out the above method and the program storage device carries instructions for carrying out the method.
It is an object of the present invention to substitute low computational cost, non-physics based likelihood proxies for likelihood functions while applying inverse problem theory to calibrate reservoir simulation models and to forecast production from such calibrated simulation models.
It is another object to create likelihood proxies for likelihood functions which are used in history matching of reservoir simulation models with actual production data.
It is yet another object to build a likelihood proxy for a likelihood function that optimizes the number of flow simulations required to achieve a predetermined level of accuracy in approximating the true likelihood function.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other objects, features and advantages of the present invention will become better understood with regard to the following description, pending claims and accompanying drawings where:
FIG. 1 is a flowchart of a preferred embodiment of a production forecasting method made in accordance with the present invention;
FIG. 2 is a flowchart of the construction of a usable likelihood proxy LP for a likelihood function L;
FIG. 3 is a flow chart describing steps in selecting sets or vectors a of model parameters m representative of reservoir models in constructing usable likelihood proxies LP;
FIG. 4 is a graph depicting how a likelihood proxy LP is constructed for an associated likelihood function L;
FIG. 5 is a flow chart describing steps taken in constructing a usable forecast proxy FP used to forecast results from selected reservoir models; and
FIG. 6 is a flow chart describing the process for generating forecasts and associated statistics using a generic Monte Carlo sampling.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a method to calibrate numerical models of subsurface oil and gas reservoirs to measurements related directly and indirectly to the production and/or injection of fluids from and/or into the reservoirs. Further, the present invention provides a method for estimating the uncertainty associated with future performance of the oil and gas reservoirs after the calibration of the numerical models.
Probabilistic descriptions can be obtained which are conditional to observed data related to the movement of fluids within the subsurface, for both the mathematical models used to represent actual oil and gas reservoirs and for the predictions of future performance computed using such models. Both model description and predictions are ideally conveyed by way of approximated probability density functions (PDF's) conditioned to the observed data. The probabilistic description of both the reservoir model and predictions (forecasts) are of significant importance to decision processes related to reservoir production based on risk analysis.
FIG. 1 is a flowchart of steps taken in a preferred embodiment of the present invention. High level steps will first be described. Then, these high level steps will be described in greater detail, often using other flow charts.
First, reservoir models, which include reservoir geologic models and reservoir flow simulation models, are defined in steps 50 and 70 , respectively, for one or more subterranean reservoirs. Reservoir model parameters, i.e., a set or vector a of parameters m i , characteristic of geologic and flow simulation properties, observed data d obs and probability models associated with the reservoir parameters m i and observed data d obs are defined in step 100 . A likelihood function L is then defined for flow simulation models in step 200 . A usable likelihood proxy LP is constructed in step 300 to approximate the likelihood function L. A usable forecast proxy FP is then constructed in step 400 . Next, a sampling is performed in step 500 on sets α of reservoir parameters m to obtain a set of retained reservoir models. A forecast is estimated in step 600 for each of the retained reservoir models using the usable forecast proxy FP. Finally, statistics, such as probability density functions (PDF's), cumulative density functions (CDF's) and histograms, are computed for the forecasts and for the sets a of reservoir parameters m.
One or more geologic models are created in step 50 in a process generally referred to as reservoir characterization. These geologic models are ideally three-dimensional, discrete representations of subsurface formations or reservoirs of interest which contain hydrocarbons such as oil and/or gas. Of course, the present invention could also be used with 2-D or even 1-D reservoir models. Examples of data used in constricting a geological model may include, by way of example and not limitation, seismic imaging, geological interpretation, analogs from other reservoirs and outcrops, geostatistics, well cores, well logs, etc. Data related to the flow of fluids in the reservoirs are typically not used in the construction of the geological models. Or if this data is used, it is generally only used in a minor way.
Reservoir flow simulation models are created in step 70 , generally one flow simulation model for each geologic model. These flow simulation models are to be run using a flow simulator program, such as Chears™, a proprietary software program of Chevron Corporation of San Ramon, Calif. or Eclipse™, a software program publicly available from Schlumberger Corporation of Houston, Tex. Those skilled in the art will appreciate that the present invention may also be practiced using many other simulator programs as well. These simulator programs numerically solve differential equations governing the flow of fluids within subsurface reservoirs and in wells that fluidly connect one or more subsurface reservoirs with the surface. Inputs for the flow simulation model typically include three dimensional, discrete representations of rock properties. These rock properties are obtained either directly from the geological model defined in step 50 or else through a coarsening process, commonly referred to as “scale-up”. Inputs for the flow simulation model typically also include the description of properties for fluids, the interaction between fluids and rocks (i.e. relative permeability, capillary pressure, etc), and boundary and initial conditions.
Reservoir models, i.e., vectors α of parameters m, observed data d obs and their associated probability models are defined in step 100 . The reservoir model, which includes the geologic and flow simulation models, is parameterized with a vector a of reservoir model parameters m. A non-limiting exemplary list of reservoir model parameters m includes:
(a) geological, geophysical, geostatistical parameters and, more generally, the same input parameters for algorithms invoked in the workflow used to construct the geological and/or flow simulation models, i.e., water-oil contacts, gas oil contacts, structure, porosity, permeability, fault transmissibility, histograms of these properties, variograms of these properties, etc. The reservoir model parameters m can be defined at different scales. For example, some parameters may affect the reservoir model at the scale used to construct a geological model, and others can affect a flow simulation model which results from the process of coarsening (scale-up). The coarsening process produces the flow simulation model used for computation of movement of fluids within the subsurface reservoir. For an example of a reservoir model parameterization system at the level of a Geological Model, see Jorge Landa, Technique to Integrate Production and Static Data in a Self - Consistent Way , SPE 71597 (2001) and Jorge Landa and Sebastien Strebelle, (2002), Sensitivity Analysis of Petrophysical Properties Spatial Distributions, and Floss Performance Forecasts to Geostatistical Parameters Using Derivative Coefficients , SPE 77430, 2002;
(b) parameters related to the description of the fluids properties in the reservoir (i.e. viscosity, saturation pressure, etc), parameters affecting the interaction between reservoir rock and reservoir fluids (i.e., relative permeability, etc), and well properties such as skin, non-darcy effects, etc.
A first “a priori” probabilistic model is defined for the vector α of reservoir model parameters m defined above. This probabilistic model could be as simple as a table defining the maximum and minimum values that each of the parameters m may take, or as complex as a joint probability density function (PDF) for all the reservoir model parameters m. The a priori probabilistic model defines the state of knowledge about the vector α reservoir model parameters m before taking into consideration data related to the movement of fluids in the reservoir or reservoirs.
A second probabilistic model is defined for observed data d obs . This observed data d obs will later be used to update the a priori probability reservoir model parameters m. The second probabilistic model for the observed data d obs ideally takes into consideration the errors in the measurements of the observed data d obs and the correlation between the measurements of the observed data d obs . The second probabilistic model may also include effects related to limitations due to approximations to the true physical laws governing the reservoir model.
A typical example for the second probabilistic model for the observed data d obs is a multi-Gaussian model with a covariance matrix C d . Of course, those skilled in the art of data analysis will appreciate that there are other possible data models which could be used as the second probabilistic model. In this preferred embodiment, the observed data d obs is data directly or indirectly related to the movement of fluids in the reservoir. Observed data d obs , by way of example and not limitation, may include: flowing and static pressure at wells, oil, gas and water production and injection rates at wells, production/injection profiles at wells and 4D seismic among others.
A likelihood function L is defined in step 200 for the reservoir models. Eqns (1), and (2) below represent non-limiting examples of likelihood functions L:
L ( α _ ) = k exp ( - 1 2 ( d _ obs - d _ calc ) T C d - 1 ( d _ obs - d _ calc ) ) ( 1 )
or alternatively
L ( α _ ) = k exp ( - ∑ i = 1 i = n_data d i obs - d i calc σ i ) ( 2 )
where
L=the likelihood function; k=is a constant of proportionality; {right arrow over (d)} obs =observed data; {right arrow over (d)} calc =calculated data; C d −1 =inverse of covariance matrix of observed data; n_data=number of observed data points; σ i =standard deviation for observation i; and i=index of data points in model parameter space.
For a more comprehensive list of approaches to define likelihood functions L, see Tarantola.
A likelihood proxy LP, preferably a “usable” likelihood proxy, for the likelihood function L is constructed in step 300 . A “usable” likelihood proxy is a proxy that provides an approximation to the mathematically exact likelihood function L within a predetermined criterion.
FIG. 2 is a flowchart describing exemplary steps comprising overall step 300 . A trial likelihood proxy LP is selected in step 310 . This trial likelihood proxy LP is ideally a low computational cost substitute for a computationally intensive model, such as is involved in computing an actual likelihood function L. The trial likelihood proxy LP need not be based on any physical laws. For example, it may be one of multi-dimensional data interpolation algorithms, such as kriging algorithms, which are commonly used in the field of geostatistics. In this exemplary embodiment, the preferred trial likelihood proxy LP for the estimation of the likelihood function L is a multi-dimensional data interpolator. The trial likelihood proxy LP uses, as part of its input, the reservoir model parameters m and produces an estimation of the likelihood function L that otherwise would practically have to be computed using a numerical flow simulator. Other non-limiting examples of trial likelihood proxies LP include other estimators such as, splines, Bezier curves, polynomials, etc.
A selected trial likelihood proxy LP may also require, as inputs, a secondary set of parameters β that can be used as tuning parameters. An approximation, P, to the likelihood function L, may be estimated as:
L (α)˜ P=f (α,β, s,ν ) (3)
where
f=trial likelihood proxy LP or the functional or algorithm to perform the estimation of L; α=a vector of reservoir model parameters m characterizing a reservoir model; s=a vector representing the locations in the reservoir model parameter space that has been previously sampled using a numerical flow simulator; ν=a vector corresponding to the values of L at the previously sampled locations s; and β=additional input parameters for f.
For example, if f is a kriging interpolation algorithm, then a variogram is a parameter for f.
If the full or partial gradients of L, with respect to the model parameters β, ∇L or grad(L), are available, then the definition of the proxy f is adjusted to take advantage of the gradient information, i.e., P=f(α, s, ν, ∇β, β).
The likelihood proxy LP, which is a low computational cost substitute for L, can be constructed to model L directly or indirectly, as in the case of constructing proxies for a function of L, for example log (L); or proxies for d calc which are used as input in the definition of L (Eqns. 1 and 2).
A proxy quality function index J 1 is defined in step 320 . This proxy quality function index J 1 is used to assess the quality of the output from the trial likelihood proxy LP relative to the output that would otherwise be obtained from a run of the numerical flow simulator. In this exemplary embodiment, a preferred mathematical form of the proxy quality function index J 1 may be expressed as:
J =(Σ( w i *|L i −P i | p ) 1/p ) (4)
where
w i =weighting factor for the sample i; L i =mathematically exact likelihood function for the sample i; P i =estimated likelihood function for the sample i; and p=power (usually 1 or 2).
A first set of vectors α of reservoir model parameters m are selected in step 330 . The reservoir models are constructed using reservoir model parameters m that are obtained from sampling the model parameter space within feasibility regions. Feasible models, located within the feasibility regions, are considered those which have a probability greater than zero in the a priori probability models. The sample locations are ideally determined using experimental design techniques. In this exemplary embodiment, the most preferred experimental design techniques are those which ensure that there is a good coverage of the sample space, such as using a uniform design sampling algorithm. Consequently, the sample vectors a are preferably more or less equidistantly distributed in the parameter space. Alternatively, sample locations might be determined using the experience of an expert practitioner. As a result of the above process, a geological model and a flow simulation model are obtained for each sample point.
Numerical flow simulations are run in step 340 on each of the flow simulation models constructed in step 330 to produce calculated data d calc . This calculated data d calc is required to calculate the likelihood function L defined in step 200 .
A likelihood threshold L thr is selected in step 350 . The value of likelihood threshold L thr is selected in such away that models that result in L less than the threshold L thr are considered very unlikely models. The threshold L thr will be used to guide the construction of the likelihood proxy LP in a step 390 , to be described below.
Likelihood functions L are computed in step 360 for the vector a of reservoir model parameters m of step 340 by combining the calculated data d calc , d obs , and the probability model for the observed data d obs defined in step 100 . This computation utilizes Eqns. (1) or (2) of step 200 . The results of the calculations are stored in step 365 in a flow simulation database which ideally stores (1) the vectors a of reservoir model parameters m used to create the flow simulation models, (2) the calculated data d calc and (3) the computed likelihood functions L.
An enhanced likelihood proxy LP is created in step 370 by optimizing the trial likelihood proxy LP utilizing the proxy quality function index J 1 . This step includes searching for a secondary set of parameters β, of step 310 , which results in a better proxy quality function J 1 , of step 320 . That is, the value of J 1 is minimized. In this exemplary embodiment, a preferred method of searching is based on gradients algorithms. Other non-limiting examples of applications might use commonly known optimizers, such as simulated annealing, genetic algorithms, polytopes, random search, trial and error.
The proxy quality function J 1 may be computed in several ways, depending on the particular type of trial likelihood proxy LP. For example, when using interpolation algorithms, such as kriging, there are numerous ways of calculating the proxy quality function index J 1 . As a first example, the database may contain n different sample points, i.e., 1000 points. A first set of 700 points may be selected to build a trial likelihood proxy LP. Then, the remaining points, i.e., i=300 points, are used to make comparisons such as described in equation (4). In the most preferred embodiment, one point is extracted from the set of 1000 points and a trial likelihood proxy LP is created from the remaining 999 points. The estimation error of this extracted point is then computed for this likelihood proxy LP. This process of removing one point, calculating the proxy for the remaining points, and then calculating the error between that trial likelihood proxy LP and the extracted point is used to create the proxy quality function index J 1 .
In step 380 , the enhanced likelihood proxy LP of step 370 is evaluated as to whether it meets a predetermined criterion. For example, the predetermined criterion might be checking whether the enhanced likelihood proxy LP is within 10% of the true value which is produced from a simulation run associated with the tested location, i.e. space vector s. If the predetermined criterion is met, then the enhanced proxy is considered to be a “usable” proxy. If the predetermined criterion is not met, then additional samplings are needed to improve the quality of the likelihood proxy LP. In the event a predetermined number of simulations or a time limit is reached without arriving at a “usable” likelihood proxy LP, and if a large number of sets or vector a of reservoir parameters m have been identified that produce reasonable matches to the observed data d obs , then the process is ended. These models a of reservoir parameters m are then used to estimate the range of variability of reservoir parameters and forecasts.
In step 390 , a new set or vector a of reservoir models is selected to generate new trial likelihood proxy LP candidates. Step 390 is further detailed out in steps 392 - 396 . Referring now to FIG. 3 , in step 392 , a first set of n f reservoir models is selected using the following process. The parameter space is sampled at the n f locations using the enhanced likelihood proxy LP from step 370 . In this process, the number n f of samples used is much greater than 1. This number n f is generally greater than 100, more preferably greater than 10,000, and most preferably will be on the order of a few million samples.
The process for obtaining the n f samples of locations is made in this example through the application of parallel or sequential sampling techniques such as experimental design, Monte Carlo, and/or deterministic search algorithms for finding locations in the parameter space that result in high values of estimated likelihood P. For example, the sampling technique could be random sampling, simulated annealing, uniform design, and/or gradient based optimization algorithms such as BFGS (Broyden, Fletcher, Golfarb and Shanno) formulation. Those skilled in art will appreciate that there are many other sampling techniques that will work with this invention. For example, see Tarantola and/or Philip E. Gill, Walter Murray, and Margaret H. Wright, Practical Optimization , Academic Press, (1992) for additional of these techniques.
The sampling may use one or a combination of several sampling and searching techniques. For example, if only one technique were used, then random sampling might be used. Or else, as a combination of techniques, random sampling, uniform design, random walks (such as Metropolis type algorithms) and gradient search algorithms might be used on each of a million sample points of the parameters to obtain the values of P for each of the sample points.
For each of the n f points selected, an estimated value of likelihood P is computed in step 394 .
It is generally not computationally practical to run numerical flow simulations on all n f sample points. Therefore, in step 396 a proper subset of n b sample points is preferably selected from the n f sample points. The size of this proper subset n b is related to the available computational power to run numerical flow simulations. For example, assume n f =1,000,000 and the proper subset n b =100. Ideally, the 100 sample points are chosen to equidistantly sample the parameter space. Further, the region in the parameter space to be improved is the region or regions that provide high values of P. However, some samples are required in regions of the parameter space that are highly uncertain. This sampling is performed through a combination of “exploration” and “refining.” “Exploration” refers to the sampling of regions of the parameter space with high uncertainty. “Refining” refers to the process of improving the quality of the proxy in regions that have already been identified as having high values of P. In the refining step, the selection is made such that the value of P is higher than the threshold value L thr determined in step 350 . From this proper subset n b . 100 sample points are selected which are generally equidistantly spaced, apart with respect to the previously locations that were sampled and used in flow simulations in step 340 and between the n b points. These n b points are used to create reservoir models to be processed in flow simulation in step 340 .
FIG. 4 depicts the evolution of likelihood proxy LP during the process of step 300 in constructing a usable likelihood. For the sake of simplicity a graph of likelihood L versus a particular reservoir parameter m is shown. The likelihood threshold L thr is shown by a dotted line. The true likelihood function L is shown by a solid line. This true likelihood function L is equivalent to sampling with an infinite number of numerical flow simulations. The purpose of step 300 is to find a likelihood proxy (or substitute) that provides a good estimation of the true likelihood L at a significantly lower computational cost. A line-dot curve is used to represent the computed value P (the estimated value of L using a likelihood proxy LP) for the case of a small number of samples, at the earlier stages of process 300 . This likelihood proxy LP does not generally provide a good approximation to L, and thus it is not generally usable proxy. A line-dot-dot curve represents a usable proxy LP, which provides a good approximation to L. This usable proxy LP is obtained after applying the process of taking addition samples during the refining and exploration stages in process 300 .
A usable forecast proxy FP is constructed in step 400 . Referring now to FIG. 5 , a trial forecast proxy FP is selected in step 410 . A proxy quality function index J 2 is defined in step 420 . The functional form for J 2 is similar to J 1 in Eqn. (4), but using forecasts instead of likelihood L. In step 430 , reservoir model parameters are selected which were stored in step 365 and which have a likelihood L greater than a predetermined threshold, i.e, L thr . In step 440 , reservoir simulations are run on the models selected in step 430 to create output forecast data d out . In step 450 , the trial forecast proxy FP of step 410 is optimized using the tuning parameters β to produce an optimized quality proxy index J 2 . In step 460 , a determination is made as to whether the enhanced forecast proxy FP meets a predetermined criterion of usability. If the criterion is not met, then a new trial forecast proxy FP is selected in step 410 and steps 450 - 460 are repeated. If after many trials no useable forecast proxy FP is found, then additional simulations are needed. However, if the criterion is met, then the enhanced forecast proxy FP is deemed usable.
At this point, two usable proxies have been created. The LP proxy for the likelihood function LP has been created in step 300 and the forecast proxy FP has been created in step 400 .
Reservoir model parameters are sampled in step 500 with Monte Carlo techniques utilizing the usable proxy LP for the likelihood function L, the forecast proxy FP, and utilizing the probability models to determine a set of retained models and their associated forecasts. In a preferred embodiment, the model parameter space is sampled using the well known Metropolis type algorithms that perform random walks in the reservoir model parameter space. Again, Tarantola can be consulted for a more detailed explanation.
Referring now to FIG. 6 , a reservoir model is proposed in step 510 from a random walk process that ensures the a priori probability models defined in step 100 . In step 520 , P, the estimated value for the likelihood function L, is computed using the usable likelihood proxy LP. The proposed model is tested based on an accept/reject basis in step 530 . If the estimated likelihood P for the proposed model is higher or equal than the estimated likelihood P of the previously accepted model, then the proposed model is accepted. If that is not the case, that is the estimated likelihood P for the proposed model is lower than the estimated likelihood P of the previously accepted model, then the proposed model is accepted randomly with a probability P proposed /P last — accepted .
If the reservoir model parameters in is rejected, then this reservoir model is ignored and another reservoir model will again be proposed in step 510 . If the reservoir model parameters are accepted, then an estimated forecast associated with the reservoir model parameters is computed in step 540 using the forecast proxy FP. The reservoir model parameters α and the associated forecast are stored for further use in step 550 .
In step 560 , a check is made to see if enough retained models have been accepted. If not, then another set a reservoir model parameter m is proposed in step 510 . When sufficient retained models and their associated forecast have been determined and stored, statistics are computed in step 610 . A first set of statistics can be generated for the sets α of reservoir model parameters m. This is commonly referred to as a “posterior probability” for the reservoir model parameters. A second set of statistics can be prepared for the forecast.
Ideally, these statistics are then displayed in step 620 in the form of a histogram, probability density function, probability cumulative density function (CDF), tables, etc.
Alternatively, by way of example and not limitation, step 500 could also be accomplished by direct application of Bayes Theorem (probability theory) using a large number of random sample points. See Eqn. (5) below:
p ( α _ ❘ d obs ) = p ( α _ ) p ( d obs ❘ α _ ) p ( d obs ) = k 1 p ( α _ ) L ( α _ ) p ( d obs ) ≅ k 1 p ( α _ ) P ( α _ ) p ( d obs ) = k 2 p ( α _ ) P ( α _ ) ( 5 )
where k 1 and k 2 are proportionality constants, p(α|d obs ) is the “posterior” probability of the reservoir model parameters (probability after adding the d obs information), p(α) is the “a priori” probability of the reservoir model parameters (probability before adding the d obs information); and P(a) is approximation to the Likelihood L computed using the usable proxy.
While in the foregoing specification this invention has been described in relation to certain preferred embodiments thereof, and many details have been set forth for purpose of illustration, it will be apparent to those skilled in the art that the invention is susceptible to alteration and that certain other details described herein can vary considerably without departing from the basic principles of the invention. | A method, system and program storage device for history matching and forecasting of subterranean reservoirs is provided. Reservoir parameters and probability models associated with a reservoir model are defined. A likelihood function associated with observed data is also defined. A usable likelihood proxy for the likelihood function is constructed. Reservoir model parameters are sampled utilizing the usable proxy for the likelihood function and utilizing the probability models to determine a set of retained models. Forecasts are estimated for the retained models using a forecast proxy. Finally, computations are made on the parameters and forecasts associated with the retained models to obtain at least one of probability density functions, cumulative density functions and histograms for the reservoir model parameters and forecasts. The system carries out the above method and the program storage device carries instructions for carrying out the method. | 4 |
CROSS-REFERENCES TO RELATED APPLICATIONS
This application is a continuation-in-part of application Ser. No. 09/842,274 filed Apr. 24, 2001, now U.S. Pat. No. 6,605,350, which is a continuation-in-part of application Ser. No. 09/574,538, filed May 18, 2000, now U.S. Pat. No. 6,331,354, which is a continuation-in-part of application Ser. No. 09/256,197, filed Feb. 24, 1999, now U.S. Pat. No. 6,210,801. All the above applications are herein fully incorporated by reference.
FIELD OF THE INVENTION
The present invention is directed to pulps useful for making lyocell-molded bodies, including films, fibers, and non-woven webs, and to methods of making such pulps useful for making the lyocell-molded bodies, to the lyocell-molded bodies made from the pulps and to the methods for making the lyocell-molded bodies. In particular, the present invention is directed to using “young” wood (often characterized as “core wood”, “juvenile wood”, “low specific gravity wood” or, in some cases as “thinnings”.).
BACKGROUND OF THE INVENTION
Cellulose is a polymer of D-glucose and is a structural component of plant cell walls. These cells are referred to as fibers. Cellulosic fibers are especially abundant in tree trunks from which they are extracted, converted into pulp, and thereafter utilized to manufacture a variety of products.
Rayon is the name given to a fibrous form of regenerated cellulose that is extensively used in the textile industry to manufacture articles of clothing. For over a century, strong fibers of rayon have been produced by the viscose and cuprammonium processes. The latter process was first patented in 1890 and the viscose process two years later. In the viscose process cellulose is first steeped in a mercerizing strength caustic soda solution to form an alkali cellulose. The cellulose is then reacted with carbon disulfide to form cellulose xanthate, which is then dissolved in dilute caustic soda solution. After filtration and deaeration, the xanthate solution is extruded from submerged spinnerets into a regenerating bath of sulfuric acid, sodium sulfate, and zinc sulfate to form continuous filaments. The resulting viscose rayon is presently used in textiles and was formerly widely used for reinforcing rubber articles such as tires and drive belts.
Cellulose is also soluble in a solution of ammonia copper oxide. This property forms the basis for production of cuprammonium rayon. The cellulose solution is forced through submerged spinnerets into a solution of 5% caustic soda or dilute sulfuric acid to form the fibers, which are then decoppered and washed. Cuprammonium rayon is available in fibers of very low deniers and is used almost exclusively in textiles.
The foregoing processes for preparing rayon both require that the cellulose be chemically derivatized or complexed in order to render it soluble and therefore capable of being spun into fibers. In the viscose process, the cellulose is derivatized, while in the cuprammonium rayon process, the cellulose is complexed. In either process, the derivatized or complexed cellulose must be regenerated and the reagents used to solubilize it must be removed. The derivatization and regeneration steps in the production of rayon significantly add to the cost of this form of cellulose fiber. Consequently, in recent years attempts have been made to identify solvents that are capable of dissolving underivatized cellulose to form a dope of underivatized cellulose from which fibers can be spun.
One class of organic solvents useful for dissolving cellulose are the amine N-oxides, in particular the tertiary amine N-oxides. For example, Graenacher, in U.S. Pat. No. 2,179,181, discloses a group of amine oxide materials suitable as solvents. Johnson, in U.S. Pat. No. 3,447,939, describes the use of anhydrous N-methylmorpholine-N-oxide (NMMO) and other amine N-oxides as solvents for cellulose and many other natural and synthetic polymers. Franks et al., in U.S. Pat. Nos. 4,145,532 and 4,196,282, deal with the difficulties of dissolving cellulose in amine oxide solvents and of achieving higher concentrations of cellulose.
Lyocell is an accepted generic term for a cellulose fiber precipitated from an organic solution in which no substitution of hydroxyl groups takes place and no chemical intermediates are formed. Several manufacturers presently produce lyocell fibers, principally for use in the textile industry. For example, Acordis, Ltd. presently manufactures and sells a lyocell fiber called Tencel® fiber.
Currently available lyocell fibers are produced from wood pulps that have been extensively processed to remove non-cellulose components, especially hemicellulose. These highly processed pulps are referred to as dissolving grade or high alpha (or high α) pulps, where the term alpha (or α) refers to the percentage of cellulose. Thus, a high alpha pulp contains a high percentage of cellulose, and a correspondingly low percentage of other components, especially hemicellulose. The processing required to generate a high alpha pulp significantly adds to the cost of lyocell fibers and products manufactured therefrom.
Since the conventional Kraft process stabilizes residual hemicelluloses against further alkaline attack, it is not possible to obtain acceptable high alpha pulps for lyocell products, through subsequent treatment of Kraft pulp in the conventional bleaching stages. In order to prepare high alpha pulps by the Kraft process, it is necessary to pretreat the wood chips in an acid phase before the alkaline pulping stage. A significant amount of material, primarily hemicellulose, on the order of 10% or greater of the original wood substance, is solubilized in this acid phase pretreatment and thus process yields drop. Under these conditions, the cellulose is largely resistant to attack, but the residual hemicelluloses are degraded to a much shorter chain length and are therefore removed to a large extent in the subsequent Kraft cook by a variety of hemicellulose hydrolysis reactions or by dissolution. The disadvantage of conventional high alpha pulps used for lyocell is the resulting loss of yield by having to eliminate hemicelluloses.
In view of the expense of producing commercial high alpha pulps, it would be desirable to have alternatives to conventional high alpha pulps for making lyocell products. In addition, manufacturers would like to minimize the capital investment necessary to produce such types of pulps by utilizing existing capital plants. Thus, there is a need for relatively inexpensive, low alpha (e.g., high yield, high hemicellulose) pulps that have attributes that render them useful in lyocell-molded body production.
In U.S. Pat. No. 6,210,801, fully incorporated herein by reference in its entirety, assigned to the assignee of the present application, low viscosity, high hemicellulose pulp is disclosed that is useful for lyocell-molded body production. The pulp is made by reducing the viscosity of the cellulose without substantially reducing the hemicellulose content. Such processes use an acid, or an acid substitute, or other methods therein described.
While the methods described in the '801 patent are effective at reducing the average degree of polymerization (D.P.) of cellulose without substantially decreasing the hemicellulose content, a further need existed for a process that did not require a separate copper number reducing step and which was readily adaptable to pulp mills that have oxygen reactors, multiple alkaline stages and/or alkaline conditions suitable for substantial D.P. reduction of bleached or semi-bleached pulp. Environmental concerns have also generated a great interest in using bleaching agents that reduce the use of chlorine compounds. In recent years, the use of oxygen as a delignifying agent has occurred on a commercial scale. Examples of equipment and apparatus useful for carrying out an oxygen stage delignification process are described in U.S. Pat. Nos. 4,295,927; 4,295,925; 4,298,426; and 4,295,926. In U.S. Pat. No. 6,331,554, assigned to the assignee of the present application, fully incorporated herein by reference in their entirety, a high hemicellulose, low viscosity pulp is disclosed that is useful for lyocell-molded body formation. The pulp is made from an alkaline pulp by treating the alkaline pulp with an oxidizing agent in a medium to high consistency reactor to reduce the D.P. of the cellulose, without substantially reducing the hemicellulose or increasing the copper number.
Further efforts to reduce the cost of making lyocell-molded bodies has resulted in U.S. application Ser. No. 09/842,274, now U.S. Pat. No. 6,605,350, fully incorporated by reference in its entirety. In the '274 application, the assignee of the present invention describes pulps made from sawdust and other low fiber length wood using a procedure similar to that of the '554 patent. These pulps are high in hemicellulose and low in viscosity, which makes them especially suitable for lyocell-molded body formation.
The forest industry continues to generate vast quantities of byproducts in the normal course of day-to-day forestry management and wood processing. These byproducts are for the most part underutilized. The need to conserve resources by utilizing wood byproducts in new ways presents a unique opportunity. It would be advantageous to develop a low cost pulp that is useful for making lyocell-molded bodies from all this underutilized wood, namely from the core wood or young or juvenile wood such as thinnings, hereafter referred to as low specific gravity wood. Thus, presenting a low cost alternative to the highly refined high-alpha pulps.
SUMMARY OF THE INVENTION
One embodiment of the invention is a pulp having at least 7% by weight hemicellulose; a viscosity of less than or about 32 cP; a copper number less than or about 2; a weighted average fiber length less than or about 2.7 mm; and a coarseness less than or about 23 mg/100 m. In another embodiment of the invention, a method for making lyocell-molded body is provided. The method includes dissolving a pulp in a solvent to form a cellulose solution; forming a lyocell-molded body from the solution; and regenerating the molded body, wherein the pulp has at least 7% by weight hemicellulose, a viscosity less than or about 32 cP; a copper number less than or about 2; a weighted average fiber length less than or about 2.7 mm; and a coarseness less than or about 23 mg/100 m. The method can use a meltblowing, centrifugal spinning, spun bonding, or dry-jet wet technique.
In another embodiment of the invention, a method of making a pulp is provided. The method includes pulping of wet material with a specific gravity less than or about 0.41 using an alkaline pulping process; and bleaching the pulp to reduce the viscosity of the pulp to or about 32 cP or lower. The bleached pulp has at least 7% hemicellulose by weight, a copper number less than or about 2, a weighted average fiber length less than or about 2.7 mm, and a coarseness less than or about 23 mg/100 m.
In another embodiment of the invention, a lyocell product is provided. The lyocell product has at least 7% hemicellulose by weight, and cellulose, wherein the pulp used to make the product has a viscosity less than or about 32 cP, a copper number less than or about 2, a weighted average fiber length less than or about 2.7 mm, and a coarseness less than or about 23 mg/100 m. Lyocell products can be fibers, films, or non-woven webs, for example.
The use of low specific gravity wood can produce a lower brownstock viscosity for a given kappa number target. Using wood with low specific gravity values reduce the bleach stage temperature and the chemical dose needed in the bleach plant to produce pulp having acceptable lyocell specifications. Low specific gravity wood results in very low viscosity levels without increasing the copper number of the pulp or the concentration of carbonyl in the pulp above acceptable levels. The process does not use an acid phase pretreatment prior to pulping, and the subsequent bleaching conditions do not result in a substantial decrease in hemicellulose content.
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 flowsheet illustrating one embodiment of a method of making a pulp according to the present invention; and
FIG. 2 is a flow sheet illustrating one embodiment of a method of making a lyocell-molded body according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIG. 1, a suitable method to produce a lyocell dissolving pulp from low specific gravity wood is illustrated. The method may be considered to include two broad processing areas, pulping depicted as block 126 and bleaching depicted as block 128 .
In block 100 , low specific gravity wood chips are loaded or fed into a digester. Specific gravity, according to The Handbook of Pulping and Papermaking , 2d ed., by Christopher J. Biermann, is the (unit less) ratio of the solid wood density to the density of water at the same temperature. As used herein, specific gravity is the average specific gravity of any population of wood feedstock material. The solid wood density may be determined using the green volume, the oven-dry volume, or intermediate volumes. The wood chips used in practicing the invention can be made from any cellulose source. Contrary to conventional thinking, low specific gravity wood has been found to be suitable for use as a source of cellulose for making lyocell-molded bodies. A suitable range of low specific gravity wood used for the present invention is any wood material having a specific gravity about equal or less than 0.41. Low specific gravity wood results in a lower brownstock pulp viscosity, which is believed to reduce the use of bleaching chemicals in the bleach plant. Representative sources of low specific gravity wood may be derived from “thinnings” and “juvenile” wood. Juvenile wood is defined as the first 10 growth rings surrounding the pith, according to Biermann. However, others define it as wood formed near the pith of the tree, often characterized by wide growth rings, lower density, and shorter fibers. However, in some instances the juvenile wood may extend to the 15-ring or more. Specific gravity increases with the increasing height of the tree, so specific gravity at 16 feet, 32 feet, or 48 feet is incrementally greater than at the butt of the tree. In some embodiments, the specific gravity will be less than 0.41, and could be less than 0.38, 0.36, 0.34, 0.32, or 0.30, or less.
Digesters for use in the present invention can include any digester suitable to pulp low specific gravity wood. One example of a suitable digester is a continuous digester that is often referred to as a “Kamyr” digester. (It should be noted that Kamyr is the name of a Company that designed and built such digesters and as such, the term Kamyr is loosely associated with a continuous digester. Kamyr no longer exists as a Company. Such continuous digesters are supplied by Kvaerner.) These digesters have been used in the pulp and paper industry for several years with the first one being installed in Sweden in 1950. Over the years, the modifications have been made to these digesters to improve their operation. The digester system may be either a single vessel or a two-vessel system.
“Kamyr” digesters are typically used in Kraft or alkaline wood pulping, but may also be used in semi-chemical pulping methods. Other continuous digesters, such as the M&D digester and the Pandia digester, are also suitable to use in the present invention. However, the present invention can also be practiced using any batch or other continuous digester.
Referring to FIG. 1, within the pulping process, block 126 , there are several operations, depicted as blocks 100 - 116 . Loading, or feeding chips as discussed above, occurs in block 100 . The wood chips may be presteamed prior to cooking, block 102 . Steam at atmospheric pressure preheats the chips and drives off air so that liquor penetration will be enhanced. After the pre-steaming operation is completed, cooking liquor, referred to as white liquor, containing the pulping chemicals may be added to the chips, block 104 . The white liquor and chips are then fed into the digester. In Kraft pulping, the active chemical compounds are NaOH and Na 2 S. Other chemicals may be added to influence or impart desirable effects on the pulping process. These additional chemicals are well known to those of skill in the art. The present invention provides a lower brownstock pulp viscosity from relatively lower specific gravity wood as composed with wood having a higher specific gravity, i.e., specific gravity is related to Kappa number.
Impregnation, block 106 , is the period during which the chemicals are allowed to impregnate the low specific gravity wood material. Good liquor penetration helps assure a uniform cooking of the chips.
“Cooking” occurs in blocks 108 and 110 . The co-current liquid contact operation, block 108 , is followed by the counter-current liquid contact operation, block 110 . Cooking of the low specific gravity wood occurs during these two operations. In either block 108 or 110 , the cooking liquor and chips can be brought to temperature.
Digester washing, block 112 , is accomplished by introducing wash liquor into the bottom of the digester and having it flow counter-current to the cooked pulp. Cooking for the most part ends when the pulp encounters the cooler wash liquor.
Upon completion of the cook operation, and digester washing, the digester contents are blown, block 112 . Digester blowing involves releasing the wood chips and liquor at atmospheric pressure. The release occurs with a sufficient amount of force to cause fiber separation. If desired, the blow tank may be equipped with heat recovery equipment to reduce operating expenses.
In block 114 , the pulp is sent from the blow tank to external brownstock pulp washers. The separation of black liquor from the pulp occurs at the brownstock washers.
In one embodiment of a method of making a pulp from low specific gravity wood to be used in the manufacture of lyocell-molded bodies, the time allowed for impregnation in block 106 is about 35 minutes. The initial percent effective alkali is about 8.5. The percent effective alkali at 5 minutes is about 1.6. The percent sulfidity is about 29. The liquor ratio is about 4. The initial temperature is about 110° C. The residual grams per liter of effective alkali is about 9.63. The residual percent effective alkali is about 3.85. The pH is about 12.77, and the H factor is about 2.
In one embodiment of the co-current operation, block 108 , the percent effective alkali is about 4.2. According to Biermann, the effective alkali is the ingredients that will actually produce alkali under pulping conditions. The percent sulfidity is about 29. According to Biermann, the sulfidity is the ratio of sodium sulfide to the active alkali, expressed as a percent. The liquor addition time is about 1 minute. The temperatures may be ramped to the final cooking temperature with a hold at one or more temperatures. The first temperature platform is about 154° C. The time to reach the temperature is about 9 minutes and the time at the temperature is about 5 minutes. A second and higher cooking temperature at the co-current operation is provided at 170° C. The time to reach the second temperature is about 51 minutes and the time at temperature is about 3 minutes. The effective alkali remaining after a cook operation is called the residual alkali. The residual grams per liter of effective alkali is about 9.42, following the co-current operation. The residual percent effective alkali is about 3.77. The pH is about 12.92, and the H factor is about 649.
In one embodiment of the counter-current operation, block 110 , the percent effective alkali is about 8. The percent sulfidity is about 29.2. Capability also exists for ramping to two different temperatures in the counter-current step. However, in one embodiment, the first and second cooking temperatures are both about 171° C. The time to reach temperature is about 54 minutes and the time at the temperature is about 162 minutes. The effective alkali grams per liter is about 16.0. The displacement rate is about 93 ml per minute. The displacement volume is about 20 liters. The volumes given here are relatively small, since the method was tested on a lab-scale bench reactor. However, with the parameters provided herein, and with no undue experimentation, the process can be scaled to any rate. The residual grams per liter of effective alkali is about 9.95. The residual percent effective alkali is about 3.98. The pH is about 12.74 and the H factor is about 3877. In one embodiment, the total time is about 319 minutes and the percent effective alkali for the total cook is about 22.3.
In one embodiment, after washing, the viscosity of the brownstock pulp is about 153 cP. The total yield on oven dried wood is about 41.04.
Following the pulping process, generally depicted as reference numeral 126 in FIG. 1, the brownstock pulp made from low specific gravity wood is bleached to reduce its viscosity. The bleaching process does not lead to a substantial reduction of the hemicellulose content of the pulp. The method according to the invention produces a bleached dissolving pulp that is suitable for lyocell-molded body production. Bleaching of chemical pulps involves the removal of lignin with an attendant decrease in the pulp fiber length and viscosity. However, the bleaching process does not cause a substantial reduction to the hemicellulose content of the pulp. Bleaching brownstock pulp made from low specific gravity wood may require fewer chemicals than the conventional highly refined, high-alpha pulps presently being used for lyocell.
In one embodiment, the low specific gravity brownstock pulp made according to the invention can be treated with various chemicals at different stages in the bleach plant. The stages are carried out in vessels or towers of conventional design. One representative bleaching sequence is ODE P D. The operations occurring in the bleaching plant are represented collectively by reference numeral 128 in FIG. 1 . Other embodiments of post bleaching the pulp after pulping are described in U.S. Pat. No. 6,331,354, and U.S. application Ser. No. 09/842,274, incorporated herein by reference in their entirety.
The first stage of bleaching is an O stage, block 116 . The O stage comprises bleaching with oxygen. However, according to Biermann, some consider oxygen bleaching to be an extension of the pulping process. Oxygen bleaching is the delignification of pulps using oxygen under pressure. The oxygen is considered to be less specific for the removal of lignin than the chlorine compounds. Oxygen bleaching takes place in an oxygen reactor. Suitable oxygen reactors capable of carrying out the method of the present invention are described in U.S. Pat. Nos. 4,295,925; 4,295,926; 4,298,426; and 4,295,927, fully incorporated herein by reference in their entirety. The reactor can operate at a high consistency, wherein the consistency of the feedstream to the reactor is greater than 20% or it can operate at medium consistency, where the medium consistency ranges between 8% up to 20%. Preferably, if a high consistency oxygen reactor is used, the oxygen pressure can reach the maximum pressure rating for the reactor, but more preferably is greater than 0 to about 85 psig. In medium consistency reactors, the oxygen can be present in an amount ranging from greater than 0 to about 100 pounds per ton of the pulp, but is more preferably about 50 to about 80 pounds per ton of pulp. The temperature of the O stage ranges from about 100° C. to about 140° C.
In one embodiment of the method to make a pulp suitable to be used in making lyocell-molded bodies, a D stage, block 118 follows the O stage, block 116 . The D stage comprises bleaching the pulp coming from the oxygen reactor with chlorine dioxide. Chlorine dioxide is more selective than oxygen for removing lignin. The amount of chlorine dioxide used in this stage ranges from about 20 to about 30 lb/ton, which may be lower than a conventional bleach plant that processes pulp from wood chips with a specific gravity not within the low specific gravity range of this invention. The temperature of the D stage ranges from about 50° C. to about 85° C.
In one embodiment of the method to make a pulp suitable to be used in making lyocell-molded bodies, an E p stage, block 120 , follows the D stage, block 118 . The E p stage is the hydrogen peroxide reinforced extraction stage where lignin is removed from the pulp using caustic in an amount ranging from about 20 to about 50 lb/ton. The amount of hydrogen peroxide ranges from about 20 to about 60 lb/ton, which may be lower than a conventional bleach plant that processes pulp from wood chips having a specific gravity not considered within the low specific gravity range of this invention. The temperature of the E p stage ranges from about 75 to about 95° C.
In one embodiment, a second D stage, block 122 , follows the E p stage, block 120 . The amount of chlorine dioxide used in this stage ranges from 10 to about 30 lb/ton, which may be lower than a conventional bleach plant that processes pulp from wood chips having a conventional specific gravity not considered to be within the low specific gravity range of this invention. The temperature of the D stage ranges from about 60° C. to about 90° C.
One embodiment of a pulp made from low specific gravity wood has a hemicellulose content of at least 7% hemicellulose, a pulp viscosity less than 32 cP, a copper number less than 2.0, and in some instances less than 1.3 (TAPPI T430), a weighted average fiber length less than 2.7 mm, and a coarseness less than 23 mg/100 m. Other embodiments of pulps made according to the present invention have a combined copper, manganese, and iron content less than 2 ppm, a total metal load less than 300 ppm, and a silicon content less than 50 ppm. Lyocell molded bodies made from the pulps of the invention will have a correspondingly high hemicellulose content of at least 7% by weight, and cellulose.
Hemicellulose is measured by a sugar content assay based on TAPPI standard T249 hm-85.
Methods for measuring pulp viscosity are well known in the art, such as TAPPI T230. Copper number is a measure of the carboxyl content of pulp. The copper number is an empirical test used to measure the reducing value of cellulose. The copper number is expressed in terms of the number of milligrams of metallic copper, which is reduced from cupric hydroxide to cuprous oxide in an alkaline medium by a specified weight of cellulosic material. The degree to which the copper number changes during the bleaching operation is determined by comparing the copper number of the brownstock pulp entering the bleaching plant and the copper number of the bleached pulp after the bleaching plant. A low copper number is desirable because it is generally believed that a high copper number causes cellulose and solvent degradation during and after dissolution of the bleached pulp to form a dope.
The weighted average fiber length (WAFL) is suitably measured by a FQA machine, model No. LDA93-R9704, with software version 2.0, made by the Optest Company of Hawkesbury, Ontario, Canada.
Coarseness is measured using Weyerhaeuser Standard Method WM W-FQA.
Transition metals are undesirable in pulp because they accelerate the degradation of cellulose and NMMO in the lyocell process. Examples of transition metals commonly found in bleached pulps include iron, copper, and manganese. Preferably, the combined metal content of these three metals in the pulps of the invention is less than about 20 ppm by Weyerhaeuser Test No. AM5-PULP-1/6010.
Additionally, pulps of the invention have a total metal load of less than 300 ppm by Weyerhaeuser Test No. AM5-PULP-1/6010. The total metal load refers to the combined amount, expressed in units of parts per million (ppm), of nickel, chromium, manganese, iron and copper.
Once the pulp has been bleached to reduce its viscosity without substantially increasing its copper number or decreasing the hemicellulose content, the pulp can either be washed in water and transferred to a bath of organic solvent, such as N-methyl-morpholine-N-oxide (NMMO), for dissolution prior to lyocell-molded body formation. Alternatively, the bleached washed pulp can be dried and broken into fragments for storage and/or shipping in a roll, sheet or bale, for example.
In order to make lyocell products from the low specific gravity wood pulps, the pulp is first dissolved in an amine oxide, preferably a tertiary amine oxide. Representative examples of amine oxide solvents useful in the practice of the present invention are set forth in U.S. Pat. No. 5,409,532, incorporated herein by reference in its entirety. The preferred amine oxide solvent is NMMO. Other representative examples of solvents useful in the practice of the present invention include dimethylsulfoxide (D.M.S.O.), dimethylacetamide (D.M.A.C.), dimethylformamide (D.M.F.) and caprolactan derivatives. The bleached pulp is dissolved in amine oxide solvent by any known means such as ones set forth in U.S. Pat. Nos. 5,534,113; 5,330,567; and 4,246,221, incorporated herein by reference in their entirety. The pulp solution is called dope. The dope is used to manufacture lyocell fibers, films, and nonwovens or other products, by a variety of techniques, including melt blowing, spunbonding, centrifugal spinning, dry-jet wet, or any other suitable method. Examples of some of these techniques are described in U.S. Pat. Nos. 6,235,392; 6,306,334; 6,210,802; and 6,331,354, incorporated herein by reference in their entirety. Examples of techniques for making films are set forth in U.S. Pat. Nos. 5,401,447; and 5,277,857, incorporated herein by reference in their entirety. Meltblowing, centrifugal spinning and spunbonding used to make lyocell fibers and nonwoven webs are described in U.S. Pat. Nos. 6,235,392 and 6,306,334, incorporated herein by reference in their entirety. Dry-jet wet techniques are more fully described in U.S. Pat. Nos. 6,235,392; 6,306,334; 6,210,802; 6,331,354; and 4,142,913; 4,144,080; 4,211,574; 4,246,221; incorporated herein by reference in their entirety.
One embodiment of a method for making lyocell products, including fibers, films, and nonwoven webs from dope derived from pulp is provided, wherein the pulp is made from low specific gravity wood, the pulp having at least 7% hemicellulose, a viscosity less than or about 32 cP, a copper number less than or about 2, a weighted average fiber length less than or about 2.7 mm, and a coarseness less than or about 23 mg/100 m. The method involves extruding the dope through a die to form a plurality of filaments, washing the filaments to remove the solvent, regenerating the filaments with a nonsolvent, including water or alcohol, and drying the filaments.
FIG. 2 shows a block diagram of one embodiment of a method for forming lyocell fibers from the pulps made from low specific gravity wood according to the present invention. Starting with low specific gravity wood pulp in block 200 , the pulp is physically broken down, for example by a shredder in block 202 . The pulp is dissolved with an amine oxide-water mixture to form a dope, block 204 . The pulp can be wetted with a nonsolvent mixture of about 40% NMMO and 60% water. The mixture can be mixed in a double arm sigma blade mixer and sufficient water distilled off to leave about 12-14% based on NMMO so that a cellulose solution is formed, block 208 . Alternatively, NMMO of appropriate water content may be used initially to eliminate the need for the vacuum distillation block 208 . This is a convenient way to prepare spinning dopes in the laboratory where commercially available NMMO of about 40-60% concentration can be mixed with laboratory reagent NMMO having only about 3% water to produce a cellulose solvent having 7-15% water. Moisture normally present in the pulp should be accounted for in adjusting the water present in the solvent. Reference is made to articles by Chanzy, H., and A. Peguy, Journal of Polymer Science, Polymer Physics Ed . 18:1137-1144 (1980), and Navard, P., and J. M. Haudin, British Polymer Journal , p. 174 (December 1980) for laboratory preparation of cellulose dopes in NMMO and water solvents.
The dissolved, bleached pulp (now called the dope) is forced through extrusion orifices in a process called spinning, block 210 , to produce cellulose filaments that are then regenerated with a non-solvent, block 202 . Spinning to form lyocell-molded bodies, including fibers, films, and nonwovens, may involve meltblowing, centrifugal spinning, spun bonding, and dry-jet wet techniques. Finally, the lyocell filaments or fibers are washed, block 214 .
The solvent can either be disposed of or reused. Due to its high costs, it is generally undesirable to dispose of the solvent. Regeneration of the solvent suffers from the drawback that the regeneration process involves dangerous, potentially explosive conditions.
The following examples merely illustrate the best mode now contemplated for practicing the invention, but should not be construed to limit the invention.
EXAMPLE 1
A commercial continuous extended delignification process was simulated in the laboratory utilizing a specially built reactor vessel with associated auxiliary equipment, including circulating pumps, accumulators, and direct heat exchangers, etc. Reactor temperatures were controlled by indirect heating and continuous circulation of cooking liquor. The reactor vessel was charged with a standard quantity of equivalent moisture free wood. An optional atmospheric pre-steaming step may be carried out prior to cooking. A quantity of cooking liquor, ranging from about 50% to 80% of the total, was then charged to the digester along with dilution water to achieve the target liquor to wood ratio. The reactor was then brought to impregnation temperature and pressure and allowed to remain for the target time. Following the impregnation period, an additional portion of the total cooking liquor was added to the reactor vessel, ranging from about 5% to 15% of the total. The reactor was then brought to cooking temperature and allowed to remain there for the target time period to simulate the co-current portion of the cook.
Following the co-current portion of the cook, the remainder of the cooking liquor was added to the reactor vessel at a fixed rate. The rate is dependent on the target time period and proportion of cooking liquor used for this step of the cook. The reactor was controlled at a target cooking temperature and allowed to remain there during the simulation of the counter-current portion of the cook. Spent cooking liquor was withdrawn from the reactor into an external collection container at the same fixed rate. At the end of the cook, the reactor vessel was slowly depressurized and allowed to cool below the flash point. The reactor vessel was opened and the cooked wood chips were collected, drained of liquor, washed, screened and made ready for testing. Three cooks of low specific gravity wood chips were prepared, along with three cooks of non-low specific gravity wood.
EXAMPLE 2
PULPING PROCESS PARAMETERS FOR LOW SPECIFIC GRAVITY WOOD
One cook for low specific gravity wood chips had the following parameters.
TABLE 1
Wood Chip S.G.
0.410
Pre-Steam @ 110 C., minutes
5
Impregnation:
Time, minutes
35
% Effective Alkali, initial
8.5
% EA, second @ 5 minutes
1.6
% sulfidity
29
Liquor ratio
4
Temperature - degrees C.
110
Residual, G/L EA
9.63
Residual, % EA
3.85
PH
12.77
H-factor
2
Pressure Relief Time, Minutes
3
Co-Current:
% Effective Alkali
4.2
% sulfidity
29
liquor addition time, minutes
1
temperature - degrees C.
154
time to, minutes
9
time at, minutes
5
temperature - degrees C.
170
time to, minutes
51
time at, minutes
3
residual, G/L EA
9.42
residual, % EA
3.77
PH
12.92
H-Factor
649
Counter-Current:
% effective alkali
8
% sulfidity
29.2
temperature - degrees C.
171
time to, minutes
54
time at, minutes
0
temperature - degrees C.
171
time to, minutes
0
time at, minutes
162
EA, G/L - strength
16.0
displacement rate, CC/M
93
displacement volume, liters
20.00
residual, G/L EA
9.95
residual, % EA
3.98
PH
12.74
H-factor
3877
Total Time, Minutes
319
% Effective Alkali - Total Cook
22.3
Accepts, % on O.D. Wood
41.01
Rejects, % on O.D. Wood
0.03
Total Yield, % on O.D. Wood
41.04
Kappa Number, 10 Minutes
16.80
EXAMPLE 3
BLEACHING PROCESS FOR LOW SPECIFIC GRAVITY WOOD
The pulp made by the process of Example 2 was bleached according to the following procedure.
O Stage
Inwoods low specific gravity wood chips were pulped into an alkaline Kraft pulp with a kappa number of 16.8 (TAPPI Standard T236 cm-85 and a viscosity of 239 cP (TAPPI T230). The brownstock pulp was treated with oxygen in a pressure vessel with high consistency mixing capabilities. The vessel was preheated to about 120° C. An amount of sodium hydroxide (NaOH) equivalent to 100 pounds per ton of pulp was added to the alkaline pulp. The reaction vessel was then closed and the pressure was increased to 60 psig by introducing oxygen into the pressure vessel. Water was present in the vessel in an amount sufficient to provide a 10% consistency.
After 45 minutes, the stirring was stopped and the pulp was removed from the pressure vessel and washed. The resulting washed pulp viscosity was 35.3 cP, and had a kappa number of 3.8.
D Stage
The D stage treated the pulp processed in the O stage by washing it three times with distilled water, pin fluffing the pulp, and then transferring the pulp to a polypropylene bag. The consistency of the pulp in the polypropylene bag was adjusted to 10% with the addition of water. Chlorine dioxide corresponding to an amount equivalent to 28.4 pounds per ton of pulp was introduced to the diluted pulp by dissolving the chlorine dioxide in the water used to adjust the consistency of the pulp in the bag. The bag was sealed and mixed and then held at 75° C. for 30 minutes in a water bath. The pulp was removed and washed with deionized water.
E p Stage
The washed pulp from the D stage was then placed in a fresh polypropylene bag and caustic was introduced with one-half of the amount of water necessary to provide a consistency of 10%. Hydrogen peroxide was mixed with the other one-half of the dilution water and added to the bag. The hydrogen peroxide charge was equivalent to 40 pounds per ton of pulp. The bag was sealed and mixed and held for 55 minutes at 88° C. in a water bath. After removing the pulp from the bag and washing it with water, the mat was filtered and then placed back into the polypropylene bag and broken up by hand.
D Stage Chlorine dioxide was introduced a second time to the pulp in an amount equivalent to 19 pounds per ton of pulp with the dilution water necessary to provide a consistency of 10%. The bag was sealed and mixed, and then held for 3 hours at 88° C. in a water bath. The treated pulp had a copper number of about 0.9 measured by TAPPI Standard T430 and had a hemicellulose (xylan and mannan) content of 12.7%.
EXAMPLE 4
Low specific gravity wood having a specific gravity of 0.410 was pulped using the Kraft process, and subsequently, bleached and treated with varying amounts of oxygen to reduce its viscosity. Components in the pulps made using Inwoods low specific gravity wood chips are 7.2% xylans and 5.5% mannans.
Table 2 shows the results for three different cooking conditions. While brownstock pulp WAFL is provided, it is apparent that bleaching the brownstock pulp to reduce its viscosity without substantially reducing the hemicellulose content, in accordance with the conditions of the present invention, will not result in any appreciable increase in the bleached pulp WAFL and may in fact be lower than the brownstock pulp WAFL.
TABLE 2
Inwoods
Inwoods
Inwoods
chips
chips
chips
Cook A
Cook B
Cook C
Chips Specific Gravity
0.410
0.410
0.410
Kappa of Brownstock
24.4
20.1
16.8
Yield %
43.2
41.4
41.0
Brownstock pulp viscosity
414
235
153
(cP) Falling Ball
Brownstock pulp WAFL
2.70
2.70
2.69
(mm)
Brownstock pulp Coarseness
18.3
17.9
17.6
(mg/100 m)
O2 pulp viscosity cP
55
34
28
(100 lbs/ton NaOH)
7.6 kappa
6.0 kappa
3.8 kappa
O2 pulp viscosity cP
80
63
49
(60 lbs/ton NaOH)
6.0 kappa
7.5 kappa
5.6 kappa
Bleached pulp coarseness
32.4
21.8
(mg/100 m)
Bleached pulp fibers/g × 10 6
4.8
4.6
Bleached pulp viscosity (cP)
31.8
29.5
Bleached pulp intrinsic
4.1
4.2
viscosity
Bleached pulp Cu (ppm)
0.6
<0.6
Bleached pulp Fe (ppm)
12
14.3
Bleached pulp Mn (ppm)
1.5
3.6
Bleached pulp Cr (ppm)
<0.4
<0.3
Bleached pulp Si (ppm)
41
31
COMPARATIVE EXAMPLE 5
Pulping Process Parameters for Non-Low Specific Gravity Wood
A conventional Tolleson wood chip made from wood having specific gravity of 0.495 was pulped using a Kraft process and subsequently treated with varying amounts of oxygen to reduce its viscosity. Table 3 shows the pulping conditions for one cook of Tolleson wood chips.
TABLE 3
Wood Chips S.G.
0.495
Pre-Steam @ 110 C., minutes
5
Impregnation:
time, minutes
35
% Effective Alkali, initial
8.5
% EA, second @ 5 minutes
1.6
% sulfidity
30.5
liquor ratio
4
temperature - degrees C.
110
residual, G/L EA
9.17
residual, % EA
3.67
PH
13.24
H-factor
2
Pressure Relief Time, Minutes
2
Co-Current:
% Effective Alkali
4.2
% sulfidity
30.5
liquor addition time, minutes
1
temperature - degrees C.
157
time to, minutes
14
time at, minutes
0
temperature - degrees C.
170
time to, minutes
54
time at, minutes
0
residual, G/L EA
8.31
residual, % EA
3.32
PH
13.07
H-Factor
680
Counter-Current:
% Effective Alkali
8
% sulfidity
30.0
Temperature - degrees C.
171
Time to, minutes
54
Time at, minutes
0
Temperature - degrees C.
171
Time to, minutes
0
Time at, minutes
162
EA, G/L - strength
20.4
Displacement rate, CC/M
73
Displacement volume, liters
15.87
Residual, G/L EA
9.72
residual, % EA
3.89
PH
13.18
H-factor
3975
Total Time, Minutes
319
% Effective Alkali - Total Cook
22.3
Accepts, % on O.D. Wood
44.23
Rejects, % on O.D. Wood
0.13
Total Yield, % on O.D. Wood
44.36
Kappa Number, 10 Minutes
17.75
Table 4 shows the results of three different cooks using a conventional Tolleson wood chip made from a non-low specific gravity wood. Components in the pulps made using Tolleson non-low specific gravity wood chips are 6.5% xylose; 6.6% mannose; 5.7% xylans; and 5.9% mannans.
TABLE 4
Tolleson
Tolleson
Tolleson
chips
chips
chips
Cook A
Cook B
Cook C
Chips Specific Gravity
0.495
0.495
0.495
Kappa of Brownstock
26.9
20.8
17.8
Yield %
46.6
46.1
44.4
Brownstock pulp
633
358
243
viscosity (cP) Falling
Ball
Brownstock pulp WAFL
4.13
4.14
4.19
(mm)
Brownstock pulp
26.1
24.4
24.3
Coarseness (mg/100 m)
O2 pulp viscosity cP
96
43
41
(100 lbs/ton NaOH)
6.4
6.9
4.7
kappa
kappa
kappa
O2 pulp viscosity cP
180
88
70
(60 lbs/ton NaOH)
8.3
5.5
6.2
kappa
kappa
kappa
Bleached pulp coarseness
24.9
27.5
(mg/100 m)
Bleached pulp
3.8
2.8
fibers/g × 10 6
Bleached pulp viscosity
28.5
24.2
(cP)
Bleached pulp intrinsic
4.3
4
viscosity
Bleached pulp Cu (ppm)
<0.6
<0.7
Bleached pulp Fe (ppm)
11.5
16
Bleached pulp Mn (ppm)
5
6
Bleached pulp Cr (ppm)
<0.4
0.3
Bleached pulp Si (ppm)
≧1
32
It can be seen that the viscosity of the pulps made from the Inwoods low specific gravity wood chips is lower than the viscosity of the pulps made from the Tolleson non-low specific gravity wood chips.
It can be seen that the viscosity of the pulps made from the Inwoods low specific gravity wood chips is lower than the viscosity of the pulps made from the Tolleson non-low specific gravity wood chips.
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. | The use of low specific gravity wood from thinning operations, for example, will produce a lower brownstock viscosity for a given kappa number target. A differential of 200-cP falling ball pulp viscosity has been detected from Kraft cooks of low and high specific gravity wood. Using low specific gravity wood can reduce the bleach stage temperature and the chemical dose needed in the bleach plant to produce lyocell pulp specifications. Low specific gravity wood also increases the ability to reduce pulp viscosity to very low levels without increasing the copper number of the pulp or the concentration of carbonyl in the pulp above acceptable levels. | 3 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention generally relates to an apparatus and method of recording data on and reproducing data from a recording medium and, more particularly, to recording medium recording and reproducing apparatus and method, by which the distance between an objective lens and an auxiliary lens is arbitrarily changed correspondingly to the thickness of a substrate of a recording medium.
2. Description of the Related Art
In recent years, techniques of recording information or data on a recording medium and of reproducing information or data therefrom by compressing video signals and audio signals at high densities in compliance with MPEG (Moving Picture Expert Group) system or the like have been being put into practical use. In the field of AV (audio visual) techniques, DVD (namely, a digital video disk (or disc)) attracts attention as a next-generation information recording medium of an optical disk unit. Further, in the field of computer technology, an optical disk of the magneto-optical recording type and an optical disk of the phase change type receive attention as such next-generation information recording media. Moreover, it has been proposed that video signals and audio signals are recorded on DVD in compliance with MPEG system and that mass data, which is an extremely large amount of data as never recorded on a single optical disk, is recorded on a recordable optical disk.
Thus, in the case of disk-like optical recording media, such as DVD, which aim at increasing storage capacity to an extremely large capacity, it is necessary to record digital data on the disk at high density to decrease the spot size of a light beam in such a manner as to be smaller than the spot size of a light beam used to record data or information on a conventional recording medium (for instance, CD (namely, Compact Disk)).
Here, let R, θ and λ denote the radius of a spot caused by a light beam, an angle of emission of an objective lens and the wavelength of the light beam, respectively. Generally, the radius of a spot of a light beam is given by the following equation (1):
R=0.32 λ/SINθ (1)
As is understood from the equation (1), it is sufficient for decreasing the (spot) size of the spot caused by the light beam to reduce the wavelength λ of the light beam and/or increase the numerical aperture NA (namely, SINθ(=n*SINθ (incidentally, a refractive index n is 1 in the air)) of the objective lens.
Further, it is sufficient for increasing the numerical aperture NA of the objective lens to increase the diameter of the objective lens. However, if the diameter of the objective lens is increased, not only the size but also the mass of an optical head, which is used for recording information on a disk and for reproducing information therefrom, should be increased. Consequently, it becomes difficult to perform a focus control operation and a tracking control operation.
Thus, there has been proposed a (conventional) system adapted to irradiate a disk with optical beams, which are used for recording or reproducing information, by utilizing a solid immersion lens (namely, what is called a hemispherical lens), as disclosed in U.S. Pat. No. 5,125,750.
In the case of the proposed system, light beams are converged by an objective lens L1 and are then incident on a solid immersion lens L2, which has an incidence surface formed as a spherical surface and further has an emission surface formed as a flat surface, as illustrated in FIG. 6. Incident light coming from the object lens L1 is incident on the solid immersion lens L2 in a direction perpendicular to the spherical surface of the solid immersion lens L2. Thus, the light beams are converged or focused on the center of the flat emission surface of the lens L2.
In the case that the refractive index of the solid immersion lens L2 is n, the numerical aperture is nSINθ. Thus, as compared with the case of a system which is not provided with the solid immersion lens L2, the numerical aperture of the objective lens of the proposed system is substantially n times that of an objective lens of the system which does not employ the solid immersion lens L2. Therefore, a high numerical aperture can be realized without increasing the diameter of an objective lens by using a two-group (namely, a doublet lens) composed of the objective lens L1 and a solid immersion lens L2. Namely, the radius of the spot obtained from the light beam is (1/n) the radius of a spot in the case of using the objective lens singly. Thus, information can be reproduced from a recording medium (namely, a disk) having recording density which is n 2 times the recording density in the case of using the objective lens singly.
Incidentally, actually, there is the necessity of converging light beams, which are emitted from the solid immersion lens L2, on a disk (not shown). Thus, the thickness of the solid immersion lens L2 is set at a value, which is smaller than an original value by the thickness of the disk substrate, so that an actual converging point is located on the disk.
Further, to obtain a further larger numerical aperture NA, it is devised that light beams emitted from the objective lens L1 are used in such a manner as to be somewhat refracted on the spherical surface of the solid immersion lens L2 as illustrated in FIG. 7.
Meanwhile, in the case of applying such a two-group lens to an optical head, for example, it is devised that the objective lens L1 and the solid immersion lens L2 are provided in such a way as to be integral with each other and are mounted on a floating head (namely, a flying head) and that the distance between the floating head and a disk is controlled according to a floating amount (of the disk). The floating amount is, however, controlled according to the linear velocity of the disk. Thus, the floating amount changes according to the linear velocity of the disk. It is, therefore, expected that a change in the distance between the disk and the solid immersion lens L2 causes spherical aberration which acts as a disturbance to reproduction (or reproducing) signals and that thus, it is difficult to obtain favorable reproduction signals.
Moreover, there are variations in the thickness of each of a light-transmissible substrate and a solid immersion lens, which compose a disk. The variations cause the spherical aberration. In this case, the conventional system has a problem that it is difficult to record information on or reproduce information from a recording medium.
The present invention is accomplished in view of such a situation or problem of the prior art.
SUMMARY OF THE INVENTION
Accordingly, an object of the present invention is to alleviate the spherical aberration caused owing to the variations in the thickness of each of a light-transmissible substrate and a solid immersion lens, which compose a disk, thereby accurately recording information on a recording medium and reproducing information therefrom.
To achieve the foregoing object, in accordance with the present invention, there is provided an optical recording medium recording and reproducing apparatus for recording information on an optical recording medium and/or reproducing information therefrom by irradiating the optical recording medium with laser light by the use of a two-group objective lens composed of at least first and second lenses. This apparatus is provided with: a light source for emitting laser light; a first lens for converging laser light emitted from the light source; a second lens interposed between the first lens and the optical recording medium; a detecting means for detecting a kind of the recording medium; and a movement means for changing the distance in the direction of an optical axis between the first and second lenses by causing a relative movement between the first and second lenses. Further, the distance between the first and second lenses is changed by the movement means, which causes the second lens to move, according to a result of a detection, which is performed by the detecting means.
Thus, in the case of the recording medium recording and reproducing apparatus of the present invention, the kind of a recording medium is detected by the detecting means. Further, the distance in the direction of the optical axis between the first and second lenses, which compose the objective lens, is changed according to a result of the detection performed by the detecting means. Consequently, favorable recording or reproduction signals can be obtained even when information is recorded on and is reproduced from a disk having a substrate, whose thickness is not uniform.
BRIEF DESCRIPTION OF THE DRAWINGS
Other features, objects and advantages of the present invention will become apparent from the following description of preferred embodiments with reference to the drawings in which like reference characters designate like or corresponding parts throughout several views, and in which:
FIG. 1 is a block diagram illustrating the configuration of a recording medium reproducing apparatus 1 (to be described later) embodying the present invention, to which a recording medium recording/reproducing apparatus of the present invention is applied;
FIG. 2 is a diagram illustrating the configuration of an example of an optical pickup 23 (to be described later);
FIG. 3 is a diagram illustrating the configuration of a first example of an actuator portion 42 (to be described later);
FIG. 4 is a graph illustrating a spherical aberration due to an error of thickness of a disk substrate;
FIG. 5 is a diagram illustrating the configuration of a second example of the actuator portion 42;
FIG. 6 is a diagram for illustrating the principle of a solid immersion lens; and
FIG. 7 is a diagram for illustrating how the solid immersion lens is actually used.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Hereinafter, preferred embodiments of the present invention will be described in detail by referring to the accompanying drawings.
FIG. 1 is a block diagram illustrating the configuration of a recording medium reproducing apparatus 1 employing a recording medium recording/reproducing apparatus of the present invention.
The spindle motor 21 is adapted to rotate a disk 2 in response to an instruction or a command issued from a rotation control circuit 22. The rotation control circuit 22 is adapted to drive the spindle motor 21 in accordance with an instruction or a command sent from a control circuit 28.
An optical pickup 23 is adapted to converge light beams on an information recording layer and further convert light, which is reflected from the information recording layer, into a reproduction signal and furthermore output a signal processing circuit 27.
A threading motor 24 is operative to move the optical pickup 23 to a target track position on the information recording layer of the disk 2. A threading motor control circuit 25 is adapted to drive the threading motor 24 according to an instruction or a command issued from the control circuit 28.
A pickup control circuit 26 is adapted to control focusing actuator and a tracking actuator in the optical pickup 23 in response to an instruction or command signal sent from the control circuit 28.
The signal processing circuit 27 is adapted to perform modulation processing, error processing and so forth on a reproduction signal sent from the optical pickup 23, and to detect, for example, the thickness of a substrate of the disk 2 (or a kind of the disk) from the signal level of an RF signal, and further to output a detection signal, which represents the detected kind of the disk, to the control circuit 28.
The control circuit 28 is adapted to output a command or instruction to each of the aforementioned circuits in response to an instruction signal inputted through an external interface 29. Further, the control circuit 28 is adapted to outputs reproduction signals, which are inputted from the signal processing circuit 27 through an external interface 29 to external equipment.
FIG. 2 is a diagram illustrating the configuration of an example of an optical pickup 23.
In the optical pickup 23, light beams emitted from a laser diode 31 are incident on a collimator (or collimating) lens 5 through a grating 32, a polarized light beam splitter 33 and a quarter wavelength plate 34. Further, the light beams, which are made by the collimator lens 35 to be parallel beams, are converged by the two-group lens, which consists of an objective lens 6 and an auxiliary lens 37, on the information recording face of the disk 2. The objective lens 36 and the auxiliary lens 37 are supported by a lens holder 59 which is held by a holding means (not shown) in such a manner as to be able to move with respect to a main base member 70.
Incidentally, a solid immersion lens, which is composed of a spherical surface and a flat surface, or an aspheric lens, which is composed of an aspheric curved surface and a flat surface, may be employed as this auxiliary lens 37.
Moreover, light reflected from the information recording face of the disk 2 is incident on the polarized light beam splitter 33 through the two-group lens (namely, the auxiliary lens 37 and the objective lens 36), the collimator lens 35 and the quarter wavelength plate 34. Furthermore, light beams reflected by the polarized light beam splitter 33 are converged on a photodetector 41, which is placed at a conjugate point, by a focusing lens 39 and a multi-lens 40. Namely, as a result of causing light beams reflected from the information recording face to impinge on the photodetector 41, digital data recorded on the information recording face of the disk 2 is converted into a reproduction signal.
When a predetermined amount of electric current is supplied, a tracking direction driving coil or a focusing direction driving coil of an actuator portion 42 is adapted to move the two-group lens in a direction corresponding to a tracking servo or to a focusing servo by utilizing a force acting between such a coil and a magnet 38.
FIG. 3 illustrates the configuration of a first example of an actuator portion 42 of the optical pickup 23 of FIG. 2. In FIG. 3, same reference characters designate corresponding parts of FIG. 2. Thus, the description of such parts is omitted herein.
When an electric current corresponding to a tracking error signal is supplied to a tracking direction driving coil 57, an electromagnetic force, which is generated between the coil 57 and the magnet 38, acts on the coil 57. This tracking direction driving coil 57 is fixed to a lens holder 59. The two-group lens (consisting of the objective lens 36 and the auxiliary lens 37) is supported on the lens holder 59, so that the movement of a base (namely, a lens holder 59) causes the two-group lens to move in a direction in which the two-group lens follows the center of a track (namely, a tracking control operation is performed).
Similarly, when an electric current corresponding to a focusing error signal is supplied to a focusing direction driving coil 58, an electromagnetic force, which is generated between the coil 58 and the magnet 38, acts on the coil 58. This focusing direction driving coil 57 is also fixed to the lens holder 59, so that the movement of the lens holder 59 causes the two-group lens to move in the direction of optical axis thereof (namely, a focusing control operation is performed).
Moreover, a stator 51 composing an ultrasonic motor 61 is attached to the lens holder 59, together with a rotator 52, feed screws 53 and 54, a pressure spring 55 and an encoder 56. This ultrasonic motor 61 is adapted to change the distance in the direction of the optical axis (namely, in the direction of arrows A and A' of FIG. 3) between the objective lens 36 and the auxiliary lens 37 in accordance with a control signal which is supplied from the pickup control circuit 26 and corresponds to the thickness of the substrate of the disk.
The stators 51 are made of PZT (lead zirconate titanate which is an electronic ceramic material) and have opposite electrode portions. Further, electrostriction (or electrostrictive) effects are produced by applying a predetermined voltage to the electrode portion. Standing waves can be generated in the stators 51 by utilizing such effects.
The rotator 52 is provided on the stators 51 and is adapted to rotate around the optical axis of the two-group lens in a horizontal plane, as viewed in this figure, by utilizing the standing waves generated in the stators 51 and a friction force that is present between the rotator 52 and each of the stators 51. Further, the rotating (or rotational) speed and the direction of rotation of the rotator 52 is changed by changing the signal level of a voltage signal supplied to the electrode portion of each of the stators 51.
The rotating speed and the position of the rotator 52 is detected by the encoder 56 attached to a peripheral portion of each of the stators 51 and the rotator 52. A result of a detection performed by the encoder 56 is outputted to the pickup control circuit 26. Thereby, an operation of the rotator 52 is monitored.
The feed screw 53 fixed to the rotator 52 has screw threads of predetermined pitch and diameter. Further, the feed screw 54 formed on the periphery of the holder 62, to the central portion of which the auxiliary lens 37 is fixed, has screw threads of predetermined pitch and diameter that correspond to the pitch and the diameter of the threads of the screw 54. The screw threads of the feed screw 54 are engaged with those of the feed screw 53. Namely, when the rotator 52 rotates in a predetermined manner, the feed screw 53 also rotates in conjunction with the rotator 52. As a result, the feed screw 54 engaged with the feed screw 53 is driven.
Incidentally, a detent 60 fixed to the lens holder 59 pierces through a hole 62a of the holder 62, so that the holder 62 is inhibited from rotating. As a result, when the rotator 52 rotates, the holder 62 does not rotate but moves upwardly or downwardly (namely, in the direction of the arrows A and A') as shown in FIG. 3.
The pressure spring 55 has an end portion fixed to the lens holder 59 and further has the other end portion which pushes down the holder 62 (namely, in the direction of the arrow A' in this figure). Thereby, the intimate contact between the stator 51 and the rotator 52 is enhanced. Moreover, the distance between the objective lens 36 and the auxiliary lens 37 is prevented from varying owing due to vibrations in the direction of the optical axis, which occur when the two-group lens follows the axial deflection of the disk 2. Therefore, even when the two-group lens is accelerated as a result of the movement of the base (namely, the lens holder) 59, the distance between the objective lens 36 and the auxiliary lens 37 is maintained at a constant value.
In this way, the distance between the objective lens 36 and the auxiliary lens 37 can be changed according to the distance between the disk 2 and the auxiliary lens 37 and the thickness of the substrate of the disk 2.
Next, the spherical aberration caused by the error of the thickness of the substrate of the disk 2 will be described hereinbelow by referring to FIG. 4.
Here, consider the case where information is reproduced from the disk 2, whose substrate thickness error (namely, the error of the thickness of the substrate) is Δd, by using the two-group lens consisting of the objective lens 36 and the auxiliary lens 37. Spherical aberration W40 occurring in this case is given by the following equation (2):
W40=(n.sup.2 -1)(NA.sup.4)Δd/(8n.sup.3) (2)
where n designates the refractive index of the disk 2; and NA the numerical aperture.
Meanwhile, as shown in FIG. 3, the spherical aberration W40 occurring in the case, in which the distance between the objective lens 36 and the auxiliary lens 37 is changed according to the error of the thickness of the substrate so as to reduce the spherical aberration, is obtained by the following equation (3):
W40=(n-1)(Δd).sup.2 ((SINθ).sup.4)/(8a) (3)
where a designates the radius of curvature of the auxiliary lens 37.
FIG. 4 illustrates a graph of the spherical aberration caused in these cases, which is plotted by using the equations (2) and (3), on condition that the numerical aperture NA, the refractive index n of the substrate and the radius of curvature of the auxiliary lens are 0.8, 1.5 and 1.25 mm, respectively.
In the graph of FIG. 4, the axis of abscissa represents the error of the thickness of the substrate; the axis of ordinates the caused spherical aberration. Further, in this figure, a dashed (or dotted) line indicates the spherical aberration caused in the case that the distance between the objective lens 36 and the auxiliary lens 37 is fixed; and a solid curve the spherical aberration caused in the case that the distance therebetween is variable. Furthermore, a unit of measure used to describe the abscissa values is μm, while a unit of measure to describe the ordinates is λrms (incidentally, "rms" is an abbreviation of "root-mean-square").
As is obvious from the equation (2), the spherical aberration in the case of fixing the distance between the objective lens 36 and the auxiliary lens 37 is proportional to the error Δd. The constant of proportion in this case is proportional to NA 4 . Thus, the graph shown by the dashed line in FIG. 4 is steep.
In contrast, the spherical aberration in the case, in which the distance between the objective lens 36 and the auxiliary lens 37 is variable, is proportional to (Δd) 2 , as is obvious from the equation (2). Further, in this case, the error Δd is a small quantity expressed in μm. Thus, the square of the error Δd has a further smaller value. Consequently, the graph shown by the solid curve in FIG. 4 is drawn like a gentle parabola.
As is understood from FIG. 4, in the case of suitably changing the distance between the objective lens 36 and the auxiliary lens 37, the spherical aberration caused due to the error of the thickness of the substrate can be suppressed, in comparison with the case that the distance therebetween is fixed.
Namely, in the case that the distance between the objective lens 36 and the auxiliary lens 37 is changed according to the error of the thickness of the substrate of the disk 2 as illustrated in FIG. 3, the spherical aberration occurring at that time can be suppressed, so that favorable reproduction signals can be obtained.
FIG. 5 is a diagram illustrating the configuration of a second example of the actuator portion 42. In FIG. 5, same reference characters designate corresponding parts of FIG. 3. Thus, the description of such parts is omitted herein.
In the case of this example, a stepping motor 71, which has stators 72 and a rotator 73, is used, instead of the ultrasonic motor 61. Moreover, the rotator 73 is driven by a predetermined amount in this example in accordance with a pulse signal corresponding to the thickness of the substrate of the disk 2, which is supplied from the pickup control circuit 26. An operation in this case is similar to that in the case of using the ultrasonic motor 61 and therefore, the description thereof is omitted herein.
Thus, the spherical aberration caused at the time of reproducing information can be reduced by changing the distance between the objective lens 36 and the auxiliary lens 37 according to the thickness of the substrate of the disk 2 as above described. Consequently, favorable reproduction signals can be obtained.
In the foregoing apparatuses of the present invention, the ultrasonic motor 61 or the stepping motor 71 is used. However, other motors, which have what is called holding (or retention) ability, may be employed. Namely, a motor may be employed as long as the rotational position thereof is not changed even when the supply of power is stopped and an external force having some strength is exerted thereon. Needless to say, theoretically, a motor having such holding ability may be employed. However, in such a case, it is inconvenient that the power should be supplied at all times. Additionally, the apparatus of the present invention may be adapted so that the kind of a disk is detected the control circuit 38 from a signal designated or inputted by a user.
Incidentally, the present invention can be applied not only to the case of recording information but also the case of recording information on or reproducing information from a recording medium other than a disk.
Although the preferred embodiments of the present invention have been described above, it should be understood that the present invention is not limited thereto and that other modifications will be apparent to those skilled in the art without departing from the spirit of the invention.
The scope of the present invention, therefore, should be determined solely by the appended claims. | An optical recording medium recording and reproducing apparatus for recording information on an optical recording medium and/or reproducing information therefrom by irradiating the optical recording medium with laser light by the use of a two-group objective lens composed of at least first and second lenses. This apparatus is provided with: a light source for emitting laser light; a first lens for converging laser light emitted from the light source; a second lens interposed between the first lens and the optical recording medium; a detecting unit for detecting a kind of the recording medium; and a movement unit for changing the distance in the direction of an optical axis between the first and second lenses by causing a relative movement between the first and second lenses. Further, the distance between the first and second lenses is changed by the movement unit, which causes the second lens to move, according to a result of a detection, which is performed by the detecting unit. Thereby, the numerical aperture NA of the objective lens is increased. Moreover, the influence of aberration is mitigated. Consequently, the high-density recording and reproducing of information signals can be achieved. | 6 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to British Patent Application No. 1004260.4, filed Mar. 15, 2010, which is incorporated herein by reference in its entirety.
TECHNICAL FIELD
[0002] The technical field relates to a method for diagnosing a fault in a fuel injection system of an internal combustion engine, typically a Diesel engine, of a motor vehicle.
BACKGROUND
[0003] In order to comply with tighter emission regulations, the motor vehicle must be provided with an On Board Diagnostic (OBD) system, for checking the proper operation of the vehicle sub-systems that can affect the polluting emissions. Since the polluting emissions strongly depend on the quality of the fuel combustion into the engine cylinders, the regulations generally require the OBD system to detect also the malfunctions of the engine fuel injection system.
[0004] The fuel injection system of modern Diesel engines comprises at least a fuel injector per engine cylinder, and a fuel pump that draws the fuel from a tank and delivers it in pressure to a fuel rail connected with all the fuel injectors. The fuel injectors are generally governed by an engine control unit (ECU) according to a multi-injection pattern, which provides for each fuel injector to perform a plurality of injection pulses per engine cycle.
[0005] Each injection pulse is characterized by an individual quantity of fuel to be injected, and by a timing at which said individual quantity of fuel must be injected. The injection timing depends on the instant at which the ECU commands the fuel injector to open, also referred as Start Of Injection (SOI), which can be expressed in temporal term as well as in term of angular position of the engine crankshaft. The individual fuel quantity depends on the opening time of the fuel injector, namely the time between the instant at which the ECU commands the fuel injector to open (SOI) and the instant at which the ECU commands the fuel injector to close, also referred as Energizing Time (ET). If a malfunction of the fuel injection system arises, the individual fuel quantity actually injected by each injection pulse may not correspond to that expected in response of the respective energizing time.
[0006] In order to overcome this drawback, most ECU implements a compensation strategy that automatically correct the energizing time of each injection pulse, in order to actually achieve a desired individual fuel quantity. Nevertheless, a malfunction of the fuel injection system may also cause the timing of each injection pulse to drift with respect to that expected.
[0007] This injection timing fault is particularly due to damages occurred by the mechanical devices driving the fuel injector, to errors of the ECU computing, or to injection drifts caused by production spread or aging of the fuel injectors. Since the injection timing has a very strict relationship with the quality of the combustion within the engine cylinders, wrong injection timing can cause the polluting emissions to exceed the maximum levels set by the regulation.
[0008] As a consequence, this regulation generally provides for the OBD system to detect a malfunction of the fuel injection system when the system is unable to deliver fuel at the proper crank angle/timing (e.g. injection timing too advanced or too retarded) necessary to maintain a vehicle's NMHC, CO, NOx, and PM emissions at, or below, an applicable emission level. In order to fulfill this requirement, a known solution uses the energizing time corrections that are determined by the above mentioned compensation strategy, and detects the malfunction of the fuel injection system when said energizing time corrections exceed a calibrated threshold.
[0009] In greater detail, the known solution provides for commanding an injection pulse to inject a desired fuel quantity, for monitoring the energizing time actually used for injecting said desired fuel quantity, and for generating an alert signal if the difference between the actual energizing time and the expected energizing time exceeds the above mentioned threshold. As a matter of fact, this known solution is based on the assumption that, when the energizing time corrections are too great, the fuel injection system is malfunctioning to the point that also the injection timing is suspected to drift.
[0010] However, this assumption represents the major deficiency of this known solution, because actually there is not an immediate and necessary relationship between energizing time, injection timing and combustion quality.
[0011] In view of the above, it is at least one object to provide an improved method for detecting injection timing faults of a fuel injection system. Another object of the present invention is to achieve the above mentioned goal with a simple, rational and rather inexpensive solution. In addition, other objects, desirable features and characteristics will become apparent from the subsequent summary and detailed description, and the appended claims, taken in conjunction with the accompanying drawings and this background.
SUMMARY
[0012] An embodiment provides a method to diagnose a fault in a fuel injection system of an internal combustion engine, comprising the steps of commanding an injection pulse for injecting a test quantity of fuel into an engine cylinder, of determining the torque released to an engine crankshaft due to a combustion of said injected fuel quantity, of calculating the difference between this torque and an expected value for said torque, and of diagnosing a fault in the fuel injection system if said difference exceeds a threshold value.
[0013] This strategy is based on the assumption that the torque released to the crankshaft is strongly affected by the quality of the combustion within the engine cylinders, which in turn has a very strict relationship with the injection timing, so that there is an immediate and necessary relationship also between the injection timing and the released torque. As a consequence, this new strategy provides a more reliable way to detect whether the fuel injection system is able to provide the desired injection timing.
[0014] According to an embodiment, the expected value is determined through an empirically determined map correlating the expected value with one or more engine operating parameters, such as for example engine speed, intake air mass flow, injected fuel quantity and other. This embodiment has at least the advantage that the map can be determined with an experimental activity and then stored in a data carrier, thereby simplifying the diagnosis of the injection system faults.
[0015] According to another embodiment, the test injection pulse is commanded during a fuel cut-off phase of the engine. This embodiment has the advantage that the diagnostic method does not affect the standard fuel injection strategy during the normal operation of the engine.
[0016] According to still another aspect of the invention, the test quantity of fuel is less than approximately 1 mm 3 . This small injected fuel quantity has the advantage of releasing to the crankshaft a torque that is generally not perceived by the driver.
[0017] According to an embodiment, the released torque is determined as a function of a rotational speed variation of the engine crankshaft due to said injection pulse. This embodiment is based on the assumption that there is a strict relationship between the torque released at the crankshaft and the rotational speed of the latter, so that is quite simple to calculate the released torque as a function of the rotational speed variation.
[0018] According to another embodiment, the rotational speed of the crankshaft is measured by means of an encoder associated to the crankshaft. As a matter of fact, the modern engines are always provided with an encoder associated to the crankshaft for other managing purposes, so that this solution allows a simple and economical way to monitor the crankshaft rotational speed also while performing the diagnostic method here concerned.
[0019] According to another embodiment, the diagnostic method comprises the further step of performing an emergency procedure when the released torque falls outside a torque range which comprises the expected value of said torque. This embodiment advantageously allows the diagnostic method to face up to an excessive drift of the injection timing, when this excessive drift is detected.
[0020] According to another embodiment, the emergency procedure provides for generating an alert signal. This aspect provides a simple and economic way to signal the malfunction of the fuel injection system.
[0021] The embodiments of the method described above may be carried out with the help of a computer program comprising a program code or computer readable instructions for carrying out all the method steps described above. The computer program can be stored on a data carrier or, in general, a computer readable medium or storage unit, to represent a computer program product. The storage unit may be a CD, DVD, a hard disk, a flash memory or the like. The computer program can be also embodied as an electromagnetic signal, the signal being modulated to carry a sequence of data bits which represent a computer program to carry out all steps of the methods.
[0022] The computer program may reside on or in a data carrier, e.g. a flash memory, which is data connected with a control apparatus for an internal combustion engine. The control apparatus has a microprocessor which receives computer readable instructions in form of parts of said computer program and executes them. Executing these instructions amounts to performing the steps of the method as described above, either wholly or in part.
[0023] The electronic control unit 60 or, in general, an ECA (Electronic Control Apparatus) can be a dedicated piece of hardware such as an ECU (Electronic Control Unit), which is commercially available and thus known in the art, or can be an apparatus different from such an ECU, e.g., an embedded controller. If the computer program is embodied as an electromagnetic signal as described above, then the electronic control apparatus, e.g. the ECU or ECA, has a receiver for receiving such a signal or is connected to such a receiver placed elsewhere. The signal may be transmitted by a programming robot in a manufacturing plant. The bit sequence carried by the signal is then extracted by a demodulator connected to the storage unit, after which the bit sequence is stored on or in said storage unit of the ECU or ECA.
[0024] Another embodiment relates to an apparatus for diagnosing a fault in a fuel injection system of an internal combustion engine. The apparatus comprises means for commanding an injection pulse for injecting a test quantity of fuel into an engine cylinder, means for determining the torque released to an engine crankshaft due to a combustion of said test quantity of fuel, means for calculating the difference between this torque and an expected value for said torque and means for diagnosing a fault if said difference exceeds a threshold value. This apparatus reliably detects whether the fuel injection system is able to provide the desired injection timing.
[0025] An embodiment of the apparatus has determination means for carrying out a determination through an empirically determined map correlating the expected value with one or more engine operating parameters, such as for example engine speed, intake air mass flow, injected fuel quantity and other. This embodiment has the advantage that the map can be determined with an experimental activity and then stored in a data carrier, thereby simplifying the diagnosis of the injection system faults.
[0026] Another embodiment of said apparatus has means for commanding configured to command during a fuel cut-off phase of the engine. This aspect of the invention has the advantage that the apparatus does not affect the standard fuel injection strategy during the normal operation of the engine. A further embodiment of the apparatus has means for commanding being configured to use a test quantity of fuel being less than 1 mm 3 . This small injected fuel quantity has the advantage of releasing to the crankshaft a torque that is generally not perceived by the driver.
[0027] Still another embodiment has determination means being configured to determine the released torque as a function of a rotational speed variation of the engine crankshaft due to said injection pulse. This embodiment of the invention is based on the assumption that there is a strict relationship between the torque released at the crankshaft and the rotational speed of the latter, so that is quite simple to calculate the released torque as a function of the rotational speed variation.
[0028] A further embodiment comprises an encoder for measuring the rotational speed of the crankshaft, said encoder being associated with the crankshaft. As a matter of fact, the modern engines are always provided with an encoder associated to the crankshaft for other managing purposes, so that this solution allows a simple and economic way to monitor the crankshaft rotational speed also while performing the diagnostic method here concerned.
[0029] Still another embodiment of the apparatus has means for performing an emergency procedure when the released torque falls outside a torque range which comprises the expected value of said torque. This embodiment advantageously allows the apparatus to face up to an excessive drift of the injection timing, when this excessive drift is detected. It is furthermore possible to choose an apparatus wherein said performing means are configured to provide an emergency procedure for generating an alert signal, for example by activating an indicator light on the dashboard of the vehicle.
BRIEF DESCRIPTION OF THE DRAWINGS
[0030] The present invention will hereinafter be described in conjunction with the following drawing figures, wherein like numerals denote like elements, and:
[0031] FIG. 1 is a schematic representation of a Diesel engine; and
[0032] FIG. 2 is a flowchart representing a diagnostic method according to an embodiment.
DETAILED DESCRIPTION
[0033] The following detailed description is merely exemplary in nature and is not intended to limit the application and uses. Furthermore, there is no intention to be bound by any theory presented in the preceding background or summary or the following detailed description.
[0034] An embodiment of the invention is hereinafter described with reference to a Diesel engine 10 of a motor vehicle. The Diesel engine 10 schematically comprises a plurality of cylinders 20 , in each of which a piston (not shown) reciprocates due to the fuel combustion, so as to rotate a crankshaft 30 . The fuel is supplied by means of a fuel injection system 40 arranged for injecting fuel directly into the engine cylinders 20 .
[0035] The fuel injection system 40 schematically comprises a fuel injector 41 per engine cylinder 20 , and a fuel pump 42 that draws the fuel from a tank 43 and delivers it under pressure into a fuel rail 44 connected to all fuel injectors 41 . Each fuel injector 41 is governed by an Engine Control Unit (ECU) 50 , which opens and closes the fuel injector 41 so as to perform single injections of fuel which are conventionally referred as injection pulses.
[0036] In greater detail, during normal operation of the Diesel engine 10 , namely when the accelerator pedal (non shown) is at least partially pushed, the ECU 50 carries out a standard injection strategy that provides for each fuel injector 41 to perform a plurality of injection pulses per engine cycle, according to a determined multi-injection pattern. Each injection pulse is conventionally controlled by the ECU 50 on the base of two key parameters, including the individual quantity of fuel to be injected, and the timing at which said individual quantity of fuel must be injected.
[0037] The injection timing is determined by the instant at which the ECU 50 commands the fuel injector 41 to open, also referred as Start Of Injection (SOI), which can be expressed either in temporal term or in term of angular position of the crankshaft 30 . The individual injected fuel quantity is determined by the opening time of the fuel injector 41 , namely the time between the instant at which the ECU 50 commands the fuel injector 41 to open and the instant at which the ECU 50 commands the fuel injector 41 to close, also referred as Energizing Time (ET). Both the SOI and the ET are determined by the ECU 50 taking into account a plurality of engine operating parameters, such as engine speed, engine load, coolant temperature, fuel rail internal pressure and other.
[0038] An embodiment provides a diagnostic test for detecting a malfunction of the fuel injection system 40 when the system is unable to deliver fuel at the proper timing. The diagnostic test is performed while the Diesel engine 10 is in a fuel cut-off phase, namely when the accelerator pedal is completely released and the standard injection strategy provides for maintaining the fuel injectors close. In this way, the diagnostic test does not affect the normal operation of the Diesel engine 10 .
[0039] Referring now to FIG. 2 , the diagnostic test firstly provides for commanding a fuel injector 41 to perform an injection pulse at a preset SOI, in order to inject a test quantity of fuel into the respective engine cylinder 20 . The test fuel quantity is a small quantity, typically not greater than 1 mm3, in order to have no effect on the torque perceived by the driver of the motor vehicle. The diagnostic test then provides for monitoring the torque TRa actually released to the crankshaft 30 due to the test fuel quantity injected by the injection pulse. The released torque TRa is determined as a function of the variation of the rotational speed of the crankshaft 30 , which is real time measured by means of an encoder 51 associated to the crankshaft 30 itself.
[0040] The relationship between the rotational speed variation of the crankshaft 30 and the released torque is well known to the skilled man, so that it is not described in further detail. The released torque TRa is then compared to an expected value TRe for said torque, which represent the torque that should be released to the crankshaft 30 if the injection pulse actually starts at the preset SOI. The expected value TRe can be determined through an empirically determined map correlating the expected value TRe with a plurality of engine operating parameters, such as engine speed, intake air mass flow and other. The expected value TRe is then sent to an adder that calculates the modulus E of the difference between the actual released torque TRa and the expected one TRe.
[0041] If the modulus E is equal or smaller than a threshold value E*, it means that the test injection pulse is actually started at the preset SOI, or at least with an allowable drift, and that the fuel injection system 40 works properly. If conversely the modulus E is greater that the threshold value E*, it means that the test injection pulse is actually started with an unallowable drift, and that a malfunction of the fuel injection system 40 is occurred. In the latter case, the diagnostic test provides for generating an alert signal, for example by activating an indicator light on the dashboard of the vehicle.
[0042] As a matter of fact, the threshold value E* defines an admissible torque range that is centered on the expected value TRe for the released torque, and that comprises the values of the released torque for which the drift between the preset SOI and the actual start of the injection pulse is allowable. If the actual released torque TRa falls outside of said admissible torque range, a malfunction of the fuel injection system is detected. The threshold value E* can be determined through an empirically determined map correlating the threshold value E* to a plurality of engine operating parameters, such as engine speed, intake air mass flow and other.
[0043] Since the injection timing drift is considered unallowable when it causes at least a vehicle's NMHC, CO, NOx or PM emission to exceed an applicable emission level specified by the antipollution regulation, the threshold value E* is calibrated accordingly. Notwithstanding the present embodiment discloses an admissible torque range centered on the expected value TRe, the invention does not exclude that the range could be asymmetrical with respect to the expected value TRe.
[0044] According to an embodiment, the diagnostic test can be performed on a fuel injector 41 only, or can be repeated on some or all the fuel injectors 41 . According to an embodiment, the diagnostic test can be performed with the help of a dedicated computer program comprising a program-code for carrying out all the steps of the method described above. The computer program is stored in a data carrier 52 associated to the engine control unit (ECU) 50 , which is in turn connected to the encoder 51 . In this way, when the ECU 50 executes the computer program, all the steps of the method described above are carried out.
[0045] While at least one exemplary embodiment has been presented in the foregoing summary or detailed description, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration in any way. Rather, the foregoing summary and detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment, it being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope as set forth in the appended claims and their legal equivalents. | A method is provided to diagnose a fault in a fuel injection system of an internal combustion engine. The method includes, but is not limited to commanding an injection pulse for injecting a test quantity of fuel into an engine cylinder, determining the torque released to an engine crankshaft due to the injection pulse, calculating the difference between this released torque and an expected value for the torque, and of detecting a fault in the fuel injection system if the difference exceeds a threshold. | 5 |
BACKGROUND OF THE INVENTION
Ceramic die nibs or inserts held within a steel casing for shaping of metal forced therethrough have been known for well over the past half-century. An early disclosure of such cased die nibs for wire drawing is in U.S. Pat. No. 1,096,688.
These ceramic die nibs have a propensity to suffer tensile stress failure in use. It was later found that this problem could be substantially alleviated by making the outside diameter of the nib very slightly larger than the inside diameter of the casing portion designed to surround the nib, then heating the casing to expand its noted inside diameter large enough to receive the nib (which is at room temperature), and lastly cooling the assembly to shrink-fit the casing onto and around the nib. Such shrink-fitted assembly placed the nib under sufficient compression to offset the tensile stress resulting from metal forced through a shaping aperture of the nib.
In order to avoid cracking of the nib during shrink-fitting into the casing, it became necessary to carefully grind and finish the outer circumferential surface of the nib to the same circumferential geometry as that of the surrounding inner circumferential surface of the casing, e.g. to concentricity between them. Otherwise, irregular or out-of-round mating between nib and casing caused uneven stresses in the nib that often produced early cracking of the nib (even during casing thereof).
However, the cost burden of such nib finishing work led to the discovery that such work could be substantially avoided by designing the assembly to accommodate a compressed intermediate layer of relatively low melting point glassy or resinous material between the shrink-fitted surfaces of the nib and casing as shown in U.S. Pat. No. 2,150,734. In addition to glassy or soft oxide material, U.S. Pat. No. 3,013,657 suggested the use of soft pure metal for the intermediate layer. U.S. Pat. No. 3,613,433 discloses relatively high-silica glaze or glassy materials which are incidentally shown between the shrink-fitted nib and casing. Because of their high SiO 2 content, the glassy materials in this latter patent are believed to have somewhat higher softening points than suggested by the other noted patents, e.g. that of Glaze 7 is estimated to be about 1050° C.±50° C. and the lowest of the disclosed glazes or vitreous coatings. In each of these cases, the assembly design involved an intermediate layer of material that could be heated to a liquid type of flowable condition or melted at a temperature well below the melting temperatures of the nib and casing, and during shrink-fitting the heated flowable or melted material could easily fill the shrinking space between nib and casing. Moreover, such material was of a relatively plastic and gradually hardening (thermoplastic) nature as it cooled with the nib and casing. While cooling glassy and resinous materials undergo substantially continuous increase in viscosity to a rigid state at room temperature, cooling metals solidify to a relatively plastic state (subject to creep under pressure) that continues to get stiffer and more rigid as cooling continues. Thus, these earlier designs were also apparently predicated on some plastic flow of the intermediate material during cooling of the shrink-fitted assembly so as to further accommodate any irregular or out-of-round, outer, circumferential surface of the nib and its mating with the casing.
In the U.S. Air Force sponsored report ML-TDR-64-295 (or AD 608497) by Hunt et al. and dated Nov. 25, 1964, it is also proposed to insert a relatively softer metal (e.g. copper or aluminum) sleeve cushion between the shrink-fitted nib and casing without melting this cushion.
Ceramic die nibs of particular interest today are those made essentially of zirconia like those disclosed in U.S. Pat. No. 3,365,317 and the July 1, 1965 issue of The Iron Age magazine at pages 58-59.
SUMMARY OF THE INVENTION
Our invention relates to an improved die assembly for shaping metal by extrusion, drawing, ironing and the like. It is especially useful in shaping hot metal, which can be of various kinds of ferrous and nonferrous metals. The assembly comprises: (1) a ceramic die having at least one aperture therein for passage of metal therethrough to work same whereby the shape and/or cross-section of the metal entering and exiting the nib is dissimilar, and (2) steel casing means to support the nib against axial displacement in the direction of the aperture and against tensile failure in use. The nib has an outer annular surface with a coating thereon, and the casing means has an inner annular surface shrink-fitted onto and around the coated outer annular surface of the nib.
We have discovered that greatly and reliably improved service life is attained in such die assembly by forming the coating, constituting the compressed interlayer between the nib and casing means, of all-crystalline ceramic material having a heating liquidus temperature within the range of 500°-570° C. (preferably 510°-530° C.). Such material can be applied as a coating on the outer annular surface of the nib before it is shrink-fitted into the casing. This coating readily melts upon insertion of the nib into the steel casing means heated to a temperature above the heating liquidus temperature of such coating, but not high enough to anneal the steel casing to an undesirable degree of softness. As the casing cools, this coating solidifies to the rigid state common of fully crystalline ceramics such that, when the die assembly becomes reheated in use for and by shaping hot metal, the coating or interlayer does not become softened or plastic (or subject to noticeable creep) and is not forced out from between the nib and casing since its temperature is well below the heating liquidus. Thus, this rigid coating or interlayer not only maintains its rigid integrity but also maintains its original, proper, shrink-fitted, circumferentially equalized compression on the nib to overcome or offset tensile stress resulting from metal forced through an aperture of the nib during usage of the assembly.
This invention, with its noted unique interlayer, makes it very easy to remove and replace the nib. The assembly is merely heated above the heating liquidus temperature of the interlayer or coating to a temperature as previously noted for casing, whereupon the interlayer becomes melted, and then the nib is easily pushed out of the casing to permit reuse of the casing.
Our invention is especially beneficial when the nib is formed of zirconia ceramic and the casing means is formed of case-hardened steel.
BRIEF DESCRIPTION OF DRAWING
The sole FIGURE is a diametral cross-section view of a preferred, illustrative embodiment of the die assembly according to the invention disclosed and claimed herein.
DETAILED DESCRIPTION
Steel casing 1 is formed with a centrally disposed orifice extending through the casing substantially along the axis of the casing. That orifice is of two axially adjacent and aligned portions defined by separate inner annular surfaces 2,4. The larger diameter portion or surface 2 opens at entrance face 3 of casing 1. That orifice portion 2 is of greater cross-sectional area transverse of the casing axis than that of the other orifice portion 4, which opens at the opposite, exit face 5 of casing 1. The two inner annular surfaces 2,4 are connected by inner supporting surface 6, which extends substantially transverse of the axis casing 1 (similar to entrance and exit faces 3,5). While casing 1 may be formed of any suitable steel, we prefer to make it of AISI Type H12 or H13 hardened tool steel and especially with such steel case-hardened to have a surface hardness of at least about Rockwell C-50 retained upon being tempered and reheated at temperatures up to about 593° C.
Ceramic die nib or insert 7 is formed with an outer annular surface 8 having the all-crystalline ceramic coating or interlayer 9 thereon, both of which axially extend from entrance face 3 to exit face 10 of nib 7. Centrally disposed within nib 7 is aperture 11 in axial alignment with the axis of casing 1 and extending from entrance face 3 to exit face 10 of the nib 7. In our best mode of the invention, the junction 12 of the entrance face 3 of the nib 7 with aperture 11 is formed by a rounded annular shoulder to facilitate passage of the metal to be worked into and through aperture 11. As is customary and known, the metal to be worked has an outer perimeter extending beyond the diametral space limitation of aperture 11 whereby passage of such metal into and through aperture 11 effects extrusion, drawing, ironing or the like of such metal. If desired, junction 12 may be squared-off or beveled. While nib 7 may be formed of any suitable ceramic, we prefer to make it of a zirconia ceramic (either partially or fully stabilized) and especially of a partially stabilized zirconia ceramic, e.g. like that disclosed in U.S. Pat. No. 3,365,317. In particular, we prefer to use such ceramic with either of the following two nominal compositions (analytically by weight):
______________________________________Composition: 1 2______________________________________MgO 3.3 3.1SiO.sub.2 0.2 0.8ZrO.sub.2 plus incidentalimpurities balance balance______________________________________
The coating 9 can be formed of any suitable fully crystalline ceramic material with the requisite heating liquidus temperature. However, in our best mode, we form it from devitrified lead-zinc-borate glass frit and especially with such frit consisting essentially, analytically by weight, of 70-82% PbO, 7-16% ZnO and 6.5-12% B 2 O 3 . That devitrified frit coating is made from undevitrified glass frit of the same composition and as set forth in British Pat. No. 863,500. Optionally, the frit can have a minor amount (up to 35 wt.% of mixture) of comminuted refractory material, such as oxide and/or silicate, added to and intimately mixed with it as disclosed in U.S. Pat. Nos. 3,250,631 and 3,258,350. In particular, we prefer to use a mixture of 98.75 wt.% glass frit (-100 mesh), 1.00 wt.% zircon (-325 mesh) and 0.25 wt.% silica (-200 mesh), in which the glass frit typically consists essentially (analytically by weight) of about 75.4% PbO, 12.15% ZnO, 8.4% B 2 O 3 , 2.05% SiO 2 , 1.9% BaO and 0.1% Al 2 O 3 . This glass frit has a devitrification temperature of about 435° C., above which it becomes all-crystalline as determined by X-ray diffraction analysis. The resultant devitrified frit has a heating liquidus (or crystalline remelt) temperature of about 515° C. The frit-zircon-silica mixture is dry blended by ball milling, and then it is mixed with a suitable vehicle for spraying, painting or otherwise coating it onto outer annular surface 8 of nib 7. We prefer to form a sprayable mixture of 100 grams of the frit-zircon-silica mixture blended with 60 cc of a vehicle solution consisting of 1.2 wt.% nitrocellulose in amyl acetate. Using a conventional commercially available spray gun, this sprayable mixture is sprayed onto surface 8 as it rotates at about 120 rpm and in several passes or layers thereof, with hot air drying of each pass or layer with a conventional, commercially available, electric heat gun or other hot air heating source. Optionally, drying can be done after completion of all spraying, either at room temperature or at slightly elevated temperature (e.g. 85° C.) in air.
The ultimate desired thickness of the frit coating determines the number of passes or layers sprayed onto surface 8. Such thickness can be varied as desired, depending upon the preferred diametral dimensions of the outer annular surface 8 and inner annular surface 2, to provide the desired diametral interference (i.e. difference in diametral dimensions) between the larger diameter of the devitrified coating or interlayer and the smaller diameter of surface 2. Such diametral interference determines the amount of shrink-fit compression on coating 9 and nib 7. Since the undevitrified frit mixture shrinks approximately 50% by volume upon being fired to devitrify and sinter it, the green or undevitrified thickness of coating 9 must be generally twice the desired fired or devitrified thickness of coating 9. Firing of the undevitrified coating to produce the devitrified and sintered coating is preferably done at about 450°-470° C. in a furnace for about one-half hour. By way of example, we have suitably employed fired coating thicknesses of about 2.5-10 mils (0.06-0.25 mm) on nibs with an outside diameter of about 2 inches (5 cm) to produce diametral interferences of about 5-15 mils (0.13-0.38 mm) with their casings, and we have suitably employed fired coating thicknesses of about 3.5-8 mils (0.09-0.20 mm) on nibs having an outer diameter of about 43/4 inches (12 cm) to provide diametral interferences of about 25-33 mils (0.63-0.84 mm).
For inserting a coated nib (at room temperature) into a casing, we prefer to heat the casing so as to expand its inner opening portion 2 to provide a diametral clearance of about 1-2 mils (0.03-0.05 mm) beyond the outer diameter 8 of the nib. Of course, it is also possible to chill the coated nib in liquid nitrogen to shrink its outer diameter 8 to provide similar insertion clearance into a casing at room temperature. However, heating of the casing seems more convenient, especially by doing so according to conventional induction heating procedures heretofore commercially employed. Generally for die assemblies made with out preferred materials for the casing and coating, heating the casing to temperatures above the heating liquidus temperature of the coating and in the range of about 550°-590° C. (preferably about 566° C.) is satisfactory. It is generally necessary to avoid heating such casings over about 590° C. so as not to reduce their case hardness to an unsatisfactory level for further use (without reheat-treatment to reharden them even if that might be possible).
After casing 1 has been properly heated for insertion of nib 7 and nib 7 has been placed into the opening portion 2 to rest against supporting surface 6, it is preferable to direct a source of heat (e.g. hot air from a heat gun) against the inside surface 11 of nib 7 to minimize temperature gradients in nib 7 as cooling and shrinking of casing 1 begins. We found that setting the heat gun to produce 700° C. temperature and applying that heat from it to surface 11 for about the initial 120 seconds of cooling of the casing 1 gave satisfactory results, including helping the onset of precompression (due to expansion of nib 7 until its temperature equalized with that of casing 1). Thereafter, the assembly is allowed to cool to room temperature and is ready for use in the desired metal working or shaping press.
Several optional modifications may be desirably employed in the assembly of our invention. First, the sharp edge 13 at the junction of aperture 11 and surface 10 can be rounded or beveled, either in a simply or compound manner to provide better service life to nib 7 or better surface finish on the worked/shaped metal passing through aperture 11. Similarly, edge 14 at the junction of opening portion 4 and exit face 5 can be rounded or beveled, also either in simple or compound manner and even extending up to about surface 6 to facilitate better service life and/or surface finish. Casing 1 may have an outer annular surface 15 that is conically tapered toward entrance face 3, either for part or all of the length of casing 1 between entrance face 3 and exit face 5. When such tapered surface is for only part of that length, it can be either intermediate such faces (without joining directly to them) or it can directly join one or the other of such faces. The particular choice depends on the design of the press into which the die assembly is to be mounted and the likely strength benefit thereby accorded to the die assembly. Of course, if desired, the outer annular surface 15 can be made parallel with the casing axis.
Uncasing of the nib 7 (i.e. removal of it from casing 1) is readily accomplished by reheating the casing 1 by the conventional induction heating to a temperature above the heating liquidus of interlayer 9. For our best mode interlayer 9, that means a temperature above about 515° C. and we prefer about 538° C. When casing 1 is adequately heated to such temperature, the nib 7 is easily pushed out of casing 1 with a simple hydraulic press ram exerting slight pressure on exit face 10 of nib 7. After so removing nib 7 from casing 1, the inner annular surface 2 and supporting surface 6 of the casing 1 is left clean and free of interlayer 9. We found that this beneficial result is consistently obtained with the interlayer formed of lead-zinc-borate devitrified glass frit. Apparently, such frit is relatively strongly bonded to the ceramic nib and not significantly bonded to the steel casing. Thus the emptied casing is left clean and ready for reuse. | A die assembly comprises a steel casing shrink-fitted onto and holding a ceramic die nib for extruding, drawing, ironing and the like of ferrous and nonferrous metal stock, especially in hot workable condition. The assembly includes an interlayer between the nib and casing to accommodate imperfect dimensional mating of adjacent shrink-fitted surfaces of the nib and casing. The interlayer is composed of all-crystalline ceramic material having a heating liquidus temperature within the range of 500°-570° C. Rigidity of solidified interlayer maintains uniform shrink-fitted compression on nib during usage of the assembly. Nib and preferred lead-zinc-borate devitrified glass interlayer are easily, jointly removable from casing and leave casing clean for reuse without affecting its case-hardening properties. | 1 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to the field of vehicle positioning systems that can be used to ascertain whether a vehicle is positioned within a lane on a roadway. More specifically, the present invention is directed to a vehicle positioning system that integrates global positioning system (GPS) data with other navigational data to determine in a real-time, robust and precise manner a lane position of the vehicle on a mapped roadway for lane departure detection.
[0003] 2. Description of the Related Art
[0004] Many different on-road vehicle systems exist or are being developed to address individual applications such as lane-keeping, lateral collision avoidance, intersection collisions, route planning, traffic management, collision notification, automated control, etc. Each of these systems varies in performance and implementation challenges. Both commercial and government activities continue to address the problem of combining systems designed for specific applications to provide low cost, integrated vehicle systems which can significantly increase driver and vehicle safety. GPS has significant potential for enabling a variety of transportation user services.
[0005] Prior art systems have used a variety of methods to determine and maintain the position of a vehicle with precision. One type, through the use of optical systems, uses cameras and visualization techniques to follow lane boundaries. The benefits of such optical systems are that they have a relatively low cost, are based on existing technology and use existing lane markers. Optical systems have problems related to reliability due to paint differences, weather, exit lanes, etc. Other methods to determine and maintain the position of a vehicle with precision are magnetic sensor systems. In such a system, the vehicle follows magnets or magnetic pavement marking tape along lane boundaries. Such systems have a relatively low cost since they use low cost magnetic sensors and electronics and are largely not adversely impacted by weather. However, such systems require a great deal of infrastructure and upkeep, have reliability issues due to missing sensors and are impacted by the presence of large metallic objects in the area, as well as by trucks and buildings.
[0006] Other prior art systems used to determine and maintain the position of a vehicle with precision utilize driver based sensors. Such systems detect drowsiness from driver characteristics such as eye movement and/or wheel motion. Such systems have the benefit in that they can often identify the state of the driver prior to lane departure but are hampered by reliability problems due to operator differences and false alarms and -do not benefit from an actual road position. RF systems are also used to detect lane position through the input of RF signals along lane/road boundaries. The RF systems are useful in all weather environments but require a great amount of infrastructure and upkeep required for the RF emitters along the road.
[0007] GPS and Differential GPS (DGPS) have also been used in prior art systems to determine and maintain the position of a vehicle with precision. In such prior art systems, the actual vehicle position is compared to surveyed lane boundaries through the use of GPS data. Such systems have the benefits of being useful in all weather, use existing lane markers and work with other systems that also use GPS data. However, in prior art systems, the survey of the roadway is still needed and more importantly there are reliability issues due to signal blockage. Additionally, the application of DGPS using a low cost GPS receiver can result in position accuracy on the order of 1-5 meters. While such a level of accuracy is adequate for many applications, in lane-keeping approaches and other applications that require greater precision, systems that rely only on GPS or DGPS are not adequate to prevent imminent lane departure.
SUMMARY OF THE INVENTION
[0008] Accordingly, for the above reasons, the present invention is directed to a real-time, high-precision, DGPS-based, robust (due to the use of other navigation aids in addition to DGPS), automotive navigation system that can support a wide range of highway traffic applications. Specifically, the GPS based system is used to precisely monitor a vehicle's location, in real time, relative to road lane boundaries. The present invention is directed to a GPS Roadside Integrated Precision Positioning System (GRIPPS).
[0009] A first embodiment of the present invention is directed to a real-time integrated navigation system for a vehicle. The system includes a GPS receiver, connected to a first antenna and receiving GPS data from satellites and outputting GPS position data, and a communications link, connected to a second antenna and to the GPS receiver, receiving range and carrier phase measurements from at least one base station. The system also includes navigation aids which provide relative position data of said vehicle, and a Kalman filter, connected to the output of the GPS receiver and the navigation aids, that integrates the GPS position data and the relative position data and outputs smoothed position data.
[0010] In the system of the first embodiment the smoothed position data compensates for degradation, blockages or communication dropouts of the GPS data from the satellites. The navigation aids of the system can include at least one, and, preferably, at least two or more, of a distance measurement, e.g., odometer measurements or anti-lock braking system (ABS) wheel turns, heading measurements, and tilt measurements. Distance and heading measurements are preferred if only two navigation aids are used. More specifically, the navigation aids can include at least one, and, preferably, at least two or more, of anti-lock braking system wheel turns, electronic compass heading and pitch, and map vertical height that provides for the generation of a high rate, robust reference relative position. The real-time integrated navigation system for a vehicle provides smoothed position data that has a 2-cm position accuracy when GPS updates from good phase measurements are available.
[0011] In addition, the system of the first embodiment can include a lane departure module that receives the smoothed position data and utilizes stored map data to output a signal that is related to imminent lane departures of the vehicle. The system may have a spread spectrum radio modem as a part of its communications link and the second antenna can be a 900 MHz communications antenna to facilitate communications with the ground stations; other, better communications systems are commercially available.
[0012] A second embodiment of the present invention is directed to a method of providing real-time navigation data to a vehicle, having the steps of: receiving GPS data from satellites via a first antenna connected to a GPS receiver located on the vehicle and then receiving range and carrier phase measurements from at least one base station via a communications link connected to a second antenna and sending the range and carrier phase measurements to the GPS receiver. The method further includes the steps of outputting GPS position data from said GPS receiver to a Kalman filter and querying navigation aids to provide relative position data of said vehicle and providing the relative position data to said Kalman filter. GPS position data and the relative position data are integrated, using said Kalman filter, and the smoothed position data for the vehicle is output.
[0013] The method compensates for degradation, blockages or communication dropouts of the GPS data from the satellites. In addition, the queried navigation aids can include components providing at least one, and, preferably, at least two or more, of a distance measurement, e.g., odometer measurements or ABS wheel turns, heading measurements, and tilt measurements. Distance and heading measurements are preferred if only two navigation aids are used. More specifically, the components can provide at least one, and, preferably, at least two or more, of anti-lock braking system wheel turns, electronic compass heading and pitch, and map vertical height that provides for the generation of a high rate, robust reference relative position.
[0014] The method may also include providing the smoothed position data to a lane departure module and computing imminent lane departures of the vehicle based on stored map data and the smoothed position data. Preferably, the smoothed position data has a 2-cm position accuracy.
[0015] The method is also applicable where the communications link receives range corrections via a spread spectrum radio modem and the second antenna is a 900 MHz communications antenna.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] The features of the disclosed method and system will become more readily apparent and may be better understood by referring to the following detailed description of illustrative embodiments of the present invention, taken in conjunction with the accompanying drawings. FIGS. 1 to 6 show embodiments of the present invention, wherein
[0017] [0017]FIG. 1 illustrates the overall configuration of the GPS Roadside Integrated Precision Positioning System (GRIPPS);
[0018] [0018]FIG. 2 illustrates an integrated system architecture for GRIPPS;
[0019] [0019]FIG. 3 illustrates a schematic showing the integration of data to determine lane departure of a vehicle;
[0020] [0020]FIG. 4 illustrates a schematic representation of navigational aids used in the system;
[0021] [0021]FIG. 5 illustrates a schematic representation of a specific embodiment of the system of the present invention; and
[0022] [0022]FIG. 6 illustrates experimental results of lane deviations of a vehicle as determined by the system of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0023] Embodiments of the present invention will now be described with reference to FIGS. 1 to 6 .
[0024] Standard commercial products for GPS support civilian Coarse/Acquisition (C/A) code GPS which provides position accuracy on the order of 30-50 meter Circular Error Probability (CAP), due primarily to Selective Availability (SA). The application of Differential GPS (DGPS) using a low cost GPS receiver can result in position accuracy on the order of 1-5 meters. DGPS involves the broadcasting of navigation data and measurements or corrections from a surveyed base station. This approach can mitigate the effect of common error sources.
[0025] Current efforts exist to provide an infrastructure (i.e. WAAS, WADGPS, US Coast Guard, Minnesota DOT, etc.) for the transmission of differential GPS corrections. In order to get high position accuracy (2-19 cm), a system based on good signal phase measurements and cycle ambiguity resolution is required to achieve positioning accuracy of a few centimeters. Furthermore, additional navigation data at a higher update rate must be provided; separation between surveyed ground stations must be minimized; and the GPS receiver would require the capability to minimize multipath and noise. However, in a dynamic environment, consistency of high accuracy GPS is dependent on many factors including: receiver quality, distance from base station, reliability of the communications RF link, satellite geometry, blockage of GPS signals, RF and GPS antenna placement/multipath, etc.
[0026] The potential ability to support multiple transportation applications, while taking advantage of existing infrastructure, makes precise vehicle positioning using GPS an important technology area to pursue. As noted above, however, prior art systems have been unable to take advantage of these benefits.
[0027] A wide range of transportation applications can be supported with a single, configurable on-board vehicle system. Some of the applications, such as route planning, collision notification, and traffic management require easily achieved position accuracies on the order of 10-30 meters. However, applications such as lane-keeping, collision avoidance, impaired driving detection, and automated vehicle control require real-time precise positioning and a precision reference map. For example, the lane-keeping application requires accuracy on the order of a few centimeters to identify imminent lane departures early enough such that the operator can take preventative measures. If multiple vehicles applied a precision positioning system with two-way communications, their positions could be broadcast to other vehicles in the immediate vicinity. These positions could be tracked by software on-board the vehicles to support warning the operators of potential collisions.
[0028] Monitoring accurate vehicle positions over time and comparing to nominal driver behavior could provide a measure of driver effectiveness (i.e. identify a drowsy or impaired driver). For real-time vehicle control, the precise position information could be used with surveyed map data and vehicle control actuators to support navigation and, hence, control of the vehicle. Even though the same accuracy is not required, the position information and two-way communications could be used to support route planning, collision notification and traffic management as well.
[0029] A properly designed, in-vehicle, GPS-based system can support all functions at a high level of accuracy and provide a robust, all weather alternative to other sensor systems being considered (magnetic, vision-based, radio frequency (RF) transponders). An integrated GPS system appears to offer the capability to support systems envisioned for “intelligent” vehicles of the future, —private automobiles, commercial and transit vehicles.
[0030] The development activities associated with the present invention concentrated on the real-time system instrumentation and software for an Instrumented Vehicle (IV). These activities can be broken up into system architecture, system development, Kalman filter, and software methodology.
[0031] The general architecture of the present invention is illustrated in FIG. 1. The IV is illustrated as a mobile unit 10, which contains a GPS unit and other processing portions of the system. The IV receives signals from GPS satellites 20 and communication relays 30 along the roadway. The signals sent to the communications relays are coordinated by base stations 40 that are also in communication with the GPS satellites 20 . Through the system, the position of the vehicle can be determined with a high degree or accuracy and departures from the lane of the roadway upon which the vehicle is traveling can be determined.
[0032] A specific embodiment of the present invention as it relates to determination of lane departure is illustrated generally in FIG. 2. The IV is illustrated as a ROVER portion 115 . The IV has a GPS receiver 100 and communication module 110 that provides data to the GPS receiver 100 . The communications module receives data from a base station that also has a GPS receiver 101 and a communication module 111 . The output of the GPS receiver 100 in the IV is sent to the Kalman filter 130 . The filter integrates data from other navigation aids 120 to determine an output that signals whether a lane departure has been determined by the lane departure module 140 .
[0033] An integrated system architecture, using DGPS 100 and navigation aids 120 to calculate real-time vehicle position, is illustrated in FIG. 3. The real-time data collection system was developed on the IV to acquire DGPS, odometer, heading, tilts, inertial navigation measurement, gyroscope, and video camera data. FIG. 3 also shows the outputs of the different portions of the system, that will be discussed in greater detail below.
[0034] The architecture developed for the system of the present example of the invention is based on convenience and utilization of existing hardware. A DGPS-based system was chosen over Optical, Magnetic, and RF systems for reasons mentioned in the previous section. First, the performance of several commercial GPS receivers were evaluated for ability to provide 2-cm accuracy. Examination of commercial GPS receiver performance showed that there are several receiver systems that offer differential position accuracy to a few centimeters. The GPS-based inertial navigation system of the present invention was designed around a DGPS system developed by ASHTECH, but other off-the-shelf DGPS systems can also be used.
[0035] In terms of communications options, for communicating between the vehicle and the base stations, options such as VHF/UHF radio, FM-subcarrier, cellular phone, Cellular switched-circuit data, Iridium, and Location and Monitoring Service (LMS) are all applicable to the present invention. The LMS communication link was selected in the preferred embodiment, despite the fact that cellular phone and VHF/UHF communications are proven technologies and are capable of transmitting data at greater distances. The reference stations used transmit L 1 and L 2 code and carrier phase data at a 2 Hz update rate to the mobile unit through a LMS 900 MHz RF antenna and communication modem. The Instrumented Vehicle (IV) was outfitted with two computers, inertial and vehicle sensors, and a differential GPS system.
[0036] In a preferred embodiment, the GPS system includes a GPS receiver, a choke ring antenna, a spread spectrum radio modem, and a 900 MHz antenna. In the preferred embodiment, an ASHTECH Z-12 GPS receiver served as the GPS receiver. The present invention finds utility with small, high-quality GPS antennas, which are generally available; however, choke ring antennas provide improved multipath mitigation, in the preferred embodiment.
[0037] The moving receiver uses navigation data and measurement data from the base station through the RF communications link, and data corrections for applicable satellites are computed by the receiver to accurately determine the vehicle position. High precision positioning is accomplished because the receiver employs sophisticated processing (which can include L 1 /L 2 codeless, narrow correlators, multipath/cycle slip mitigation, internal ambiguity fixing and differential carrier phase ranging techniques). Based on theoretical performance analysis, the highest accuracy is achieved when base to mobile separation is within a few kilometers.
[0038] In this implementation, the system directly applies the position information as provided by the receiver. As shown in FIG. 4, GPS position and velocity data, select navigation aids (odometers 201 , vehicle heading 202 , and vehicle tilts 203 ) and vertical map measurements (from the surveyed reference map 206 ) were integrated 204 using an Extended Kalman filter to smooth through GPS signal dropouts. This serves to enable vehicle navigation during GPS blockage with graceful performance degradation. Data from the navigation aids were analyzed to determine the optical configuration of sensors to smooth through data dropouts.
[0039] In testing, data was collected to evaluate several GPS hardware configurations to determine an initial system approach that would increase reliability of the position data. A video camera was also used to view the lane markings in order to provide an independent observation of the lane departures and to assist in mapping the road boundaries. A user interface for lane departure and warning capability was developed.
[0040] The data acquisition hardware will now be addressed. The Instrumented Vehicle (IV) data acquisition system is built around a processor equipped with several ports used to acquire serial and analog sensor outputs. This system is also equipped with a network interface to the Kalman Filter Processing System, which is run, preferably, on a separate processor. This processor accepts analog signals from the inertial measurement unit and a pulse train representing wheel turns from the Anti-Lock Braking System (ABS).
[0041] The Kalman filter utilizes software to process incoming signals. Upon receiving data, the Kalman filter software implements the filter on the real-time data and subsequently returns data indicating lane deviation, filter process status and whether the IV is in the reference map location.
[0042] An equipment stack contains navigation aids and the ABS interface. The wheel turns are sensed from the ABS, while heading and pitch data are measured from an electronic compass sensor module. The navigation aids also include an Inertial Measurement Unit, which provides linear accelerations and angular rates, and a fiber optic gyroscope.
[0043] In an exemplary embodiment, illustrated in FIG. 5, the GPS based inertial navigation system instrumentation installed in the Instrumented Vehicle is made up of the following:
[0044] Data Acquisition System Computer (PENTIUM 180 MHz computer), 401 ;
[0045] Kalman Filter Processor/Real Time video Computer (PENTIUM 180 MHz computer), 402 ;
[0046] CROSSBOW DU6 Inertial Measurement Unit, 403 ;
[0047] PRECISION NAVIGATION TCM2 Electronic Compass with tilt, 404 ;
[0048] ANDREW 225140 AUTOGYRO Fiber Optic Gyroscope, 405 ;
[0049] ASHTECH Z-12 DGPS Receiver, 406 ; and
[0050] ASHTECH Spread Spectrum Radio Modem, 407 .
[0051] The exemplary embodiment also includes interface modules that allow communication between the constituent parts. While the above constituent parts of the system have been used in a particular embodiment, the present invention is not so limited. The range of applicable components of the real-time integrate navigation system are discussed above.
[0052] The Kalman filter software will now be discussed. An eight-state Extended Kalman filter (E-KF) with GPS and navigation aids is used to estimate the vehicle position/velocity errors. An estimate and covariance propagation is performed every update time. A measurement update occurs when there is either GPS, height, or both measurements available. The state vector is:
δ x = [ δ N δ E δ D δ S F W δψ δ θ δ S F θ δ H ] { North vehicle position error ( m ) East vehicle position error ( m ) Down vehicle position error ( m ) Wheel turn scale factor error ( unitless ) Azimuth error ( deg ) Pitch error ( deg ) Pitch scale factor error ( unitless ) Height error ( m ) ( 1 )
[0053] where the vehicle position is in the North-East Down (NED) local frame defined by the reference (base station) position.
[0054] After each measurement update, the E-KF accumulates whole value estimates for position (r), navigation (α), and velocity (υ) by the following equations:
{circumflex over (r)}
i+
={circumflex over (r)}
i−
+δ{circumflex over (r)}
i+
{circumflex over (α)} i+ ={circumflex over (α)} i− +δ{circumflex over (α)} i+
υ i+ =υ i +δ{circumflex over (r)} i+ /Δt
δx= 0, (2)
[0055] where δr are the first three elements, and δα are the last five elements of the state vector, δx.
[0056] The transitions are defined by
[ δ r . δ α . ] = F * [ δ r δ α ] , w h e r e F = [ 0 F _ r a 0 0 ] ( 3 )
[0057] The transition matrix in the filter is approximated by:
Φ i , j - 1 = I + F * Δ t + 1 2 * F 2 * Δ t 2 ( 4 )
[0058] where
{overscore (F)} ra =[{dot over (d)} i *B 1 |−[{overscore (V)} x ]*A 3 |−[{overscore (V)} x ]*A 2 |−{overscore (θ)}*[{overscore (V)} x ]*A 2 |0],
T 1 =(−{overscore (ψ)}) 3 , T 2 =(−{overscore (θ)}) 2 , T NB2 =[T 1 *T 2 ] (5)
[0059] (A j , B j ) are the columns of (T 1 ,T NB2 ) and {dot over (d)} i is defined later in this section. Note that A 2 =B 2 and A 3 =[0, 0, 1] T . The diagonal process noise mat, which is based on judgement and testing, is Q=[q k 2 ], where the nominal
[0060] q k =[0.5, 0.5, 0.4, 10 −4, 0.5, 0.1, 0.0, 0.001]. The diagonal prior uncertainty matrix is P 0 =[p k 2 ], where P k =[10 +4 , 10 +4 , 10 +4 , 0.04, 20, 3, 10 −4 , 0.1].
[0061] The measurements are:
y * = [ North GPS position East GPS position Down GPS position Height map ] , a n d δ y = [ r G P S NED - r i - NED - δ d i - ] ( 6 )
[0062] where δd is the vehicle down position with respect to the map. The sensitivity matrix is
H = [ 1 0 0 | 0 0 0 0 0 0 1 0 | 0 0 0 0 0 0 0 1 | 0 0 0 0 0 0 0 1 | 0 0 0 0 - 1 ] ( 7 )
[0063] The noise matrix is
R = [ [ P G P S ] 0 0 ( 0.03 ) 2 ] ( 8 )
[0064] where P GPS is the position covariance from GPS or an override of P GPS =10 +4 * I 3 is used.
[0065] A survey approach and map representation were developed to provide both a height measurement and a lane departure and warning capability. The map is constructed to give the location of the GPS antenna when the passenger side, right wheel is on the right lane marker. The map frame is Along Track (a), Cross Track (c), and Down (d). The map is parameterized verses Along Track. The map frame has origin at R 0 (meters), and is rotated with respect to NED frame by azimuth from North in degrees (θ). To make the map, the GPS position points are put into the map frame. A cubic spline interpolation is used to get a map at uniform spacing for Along Path. The spline derivative, dc/da, is used to calculate φ(a), local line direction in the map frame. The map is in column format of a, c, d, φ, with a being uniformly spaced (nominally 2 meters). Because spline interpolation is used to produce the map on a defined grid, multiple vehicle tracks can be combined (averaged) to make a merged map.
[0066] To evaluate the vehicle position with respect to the map, the fixed NED to map transformation matrix, T MN =(θ) 3 , must be computed. This transformation matrix is based on a single rotation about the z-axis. The vehicle position is calculated in the map frame by
( a c d ) = r M a p = T M N ( r N E D - R 0 ) ( 9 )
[0067] where r NED is the estimated position in the NED frame.
[0068] The map is interpolated using a spline to generate the values {overscore (c)} (a), {overscore (d)} (a), and {overscore (φ)} (a). The vehicle position with respect to the map or right hand lane marker (delta lane, δl, and delta down, δd) is evaluated by
δc=c−{overscore (c)} ( a )
δl=δc * cos 436 ({overscore (φ)}( a ))
δd=d−{overscore (d)} ( a ) (10)
[0069] The delta lane measurement is the only desired output of the real time system.
[0070] Wheel turns from ABS with azimuth and pitch from the electronic compass are integrated to obtain the new navigated position, δ{circumflex over (r)} i− . Integration, and filter propagation and navigation aid updates occur whether there is a real-time DGPS measurement present or not. The distance traveled over the period of the update is computed by summing the incremental distances formed by products of wheel circumference (k), accumulated wheel scale factor estimate (1+{circumflex over (α)}(1)) and delta wheel counts (ΔWC). The wheel circumference is measured and variations due to temperature and pressure are accounted for.
[0071] The navigated position integration is performed using the following equations:
d j , j - 1 = k * ( 1 + α ^ ( 1 ) ) * Δ W C j , j - 1
ψ _ j = 1 2 * ( ψ j - 1 + ψ j ) + ψ B + ψ C + α ^ ( 2 )
θ _ j = 1 2 * ( 1 + α ^ ( 4 ) ) * ( θ j - 1 + θ j ) + θ B + α ^ ( 3 )
Δ r j , j - 1 = d j , j - 1 * [ cos θ _ j * cos ψ _ j cos θ _ j * sin ψ _ j - sin θ _ j ]
r j = r j - 1 + Δ r j , j - 1 ( 11 )
[0072] Then the following are computed at each update interval from the loop quantities above:
d . i = ∑ j = 1 m = 5 ( d j , j - 1 ) / t
r ^ i - = r ^ ( i - 1 ) + ∑ j = 1 m = 5 Δ r j , j - 1
v _ i = ( r ^ i - - r ^ ( i - 1 ) + ) / t
ψ _ = ∑ j = 0 m = 5 ψ j / ( m + 1 )
θ _ = ∑ j = 0 m = 5 θ j / ( m + 1 ) , ( 12 )
[0073] where
[0074] ψ=compass (magnetic) heading
[0075] θ=pitch (positive nose up)
[0076] WC=wheel counts or turns (fractional)
[0077] ψ B =prior heading bias (“magnetic true”, sensor mounting and sensor bias)
[0078] ψc(ψ)=calibration foe vehicle magnetic properties (deviation)
[0079] θ B =prior pitch bias (sensor mounting and sensor bias)
[0080] k=wheel circumference
[0081] Experimental results for the system of the present invention are shown in FIG. 6. The graph shows the output of the Kalman filter processor and lane deviations from the map during the drive. The test run also involved intentional lane departures, shown after 120 seconds on the graph.
[0082] Although the embodiments of the present invention have been described in detail, it will be understood that the present invention is not limited to the above-described embodiments, and various modifications in design may be made without departing from the spirit and scope of the invention defined in claims. | A real-time integrated navigation system for a vehicle includes a GPS receiver, connected to a first antenna, where the GPS receiver receives GPS data from satellites and outputs GPS position data. The system also includes a communications link, connected to a second antenna and to the GPS receiver, receiving range and carrier phase measurements from at least one base station. The system further includes navigation aids which provide relative position data of said vehicle and a Kalman filter, connected to the output of the GPS receiver and the navigation aids, that integrates the GPS position data and the relative position data and outputs smoothed position data. The smoothed position data is used in transportation applications, especially detection of lane departure. This GPS-based positioning system is suitable for highway speeds during all weather conditions. | 6 |
CROSS-REFERENCE TO RELEATED APPLICATIONS
This application is a continuation of application Ser. No. 10/310,059 filed on Dec. 5, 2002 now U.S. Pat. No. 7,050,504 which is divisional of application Ser. No. 10/300,849, filed Nov. 21, 2002 now U.S. Pat. No. 7,227,901, both of which are entirely incorporated herein by reference.
FIELD OF THE INVENTION
The present invention relates to the field of video coding, more particularly it relates to a method of reducing blocking artifacts inherent in hybrid block-based video coding.
BACKGROUND OF THE INVENTION
Video compression is used in many current and emerging products. It has found applications in video-conferencing, video streaming, serial storage media, high definition television (HDTV), and broadcast television. These applications benefit from video compression in the fact that they may require less storage space for archived video information, less bandwidth for the transmission of the video information from one point to another, or a combination of both.
Over the years, several standards for video compression have emerged, such as the Telecommunication Standardization Sector of the International Telecommunication Union (ITU-T) recommended video-coding standards: H.261, H.262, H.263 and the emerging H.264 standard and the International Standardization Organization and International Electrotechnical Commission (ISO/IEC) recommended standards MPEG-1, MPEG-2 and MPEG-4. These standards allow interoperability between systems designed by different manufacturers.
Video is composed of a stream of individual pictures (or frames) made up of discrete areas known as picture elements or pixels. The pixels are organised into lines for display on a CRT or the like. Each pixel is represented as a set of values corresponding to the intensity levels of the luminance and chrominance components of a particular area of the picture. Compression is based mainly on the recognition that much of the information in one frame is present in the next frame and, therefore, by providing a signal based on the changes from frame to frame a much reduced bandwidth is required. For the purpose of efficient coding of video, the pictures or frames can be partitioned into individual blocks of 16 by 16 luminance pixels called “macroblocks”. This practice simplifies the processing which needs to be done at each stage of the algorithm by an encoder or decoded. To encode a macroblock (or sub-macroblock partition) using motion-compensated prediction, an estimation is made of the amount of motion that is present in the block relative to the decoded pixel data in one or more reference frames, usually recently decoded frames, and the appropriate manner in which to convey the information from which the current frame may be reconstructed. The residual signal, which is the difference between the original pixel data for the macroblock and its prediction, is spatially transformed and the resulting transform coefficients are quantized before being entropy coded. The basic processing blocks of an encoder are a motion estimator/compensator/predictor, a transform, a quantizer and an entropy coder. Due to the quantization of the transformed coefficients of the residual signal, the reconstructed pixel values are generally not identical to those of the original frame. Since the coding is block-based, the errors that are introduced by the quantization process tend to produce artifacts in the form of sharp transitions in image intensity across transform block boundaries in the reconstructed frame. Such artifacts are referred to as “blocking artifacts”. The appearance of blocking significantly affects the natural smoothness seen in video images and leads to a degradation of the overall video image quality.
Blocking artifacts are inherent in hybrid block-based video coders, especially in low bit rate video applications. A number of solutions have been presented to alleviate the degradation in visual quality due to the presence of blocking artifacts. Two general approaches have been proposed to deal with blocking artifacts. The first approach is based on using a deblocking filter in the decoder only as a post-processing stage, and applying the deblocking filter on the decoded and reconstructed video frames before they are displayed. The purpose of the filter is to modify the sample values around the block boundaries in order to smooth unnatural sharp transitions that have been introduced by the block-based coding process Having a deblocking filter applied outside of the motion-compensation loop can be viewed as an optional process for the decoder, placing no requirements on the video encoder. However, this scheme has a disadvantage in that the reference frames that are used for generating predictions for the coding of subsequent frames will contain blocking artifacts. This can lead to reduced coding efficiency and degraded visual quality. The second approach to reduce the visibility of blocking artifacts is to apply a deblocking filter inside the motion-compensation loop. In this case, the reference frames that are used for generating predictions for subsequent encoded frames represent filtered reconstructed frames, generally providing improved predictions and improved compression and visual quality. In order to create identical predictions at both the encoder and decoder, the deblocking filter (sometimes referred to as a “loop filter” if it is inside the motion-compensation loop) must be applied in both the encoder and the decoder.
In order to reduce the appearance of blocking artifacts, a number of video coding standards, including H.263 version 2, and most recently the emerging H.264 video coding standard specify the use of a deblocking filter inside the motion-compensation loop. In particular, the H.264 video coding standard fully specifies a deblocking filter that is to be used inside the motion-compensation loop in both the encoder and decoder.
One of the known prior art methods is described in a document “Working Draft Number 2, Revision 2 (WD-2)” by the Joint Video Team (JVT) of ISO/IEC MPEG and ITU-T VCEG. In this prior art method, filtering occurs on the edges of 4×4 blocks in both the luminance and chrominance components of each reconstructed video frame. The filtering takes place on one 16×16 macroblock at a time, with macroblocks processed in raster-scan order throughout the frame. Within each macroblock, vertical edges are filtered first from left to right, followed by filtering of the horizontal edges, from top to bottom. The filtering of samples for one line-based filtering operation occurs along the boundary separating unfiltered samples p 0 , p 1 , p 2 , and p 3 on one side of the boundary, and unfiltered samples q 0 , q 1 , q 2 , and q 3 on the other side, as illustrated in FIG. 3 a . The block boundary lies between samples p 0 and q 0 . In some cases p 1 , p 2 may indicate samples that have been modified by filtering of a previous block edge. For each line-based filtering operation, unfiltered samples will be referred to with lower-case letters, and filtered samples with upper-case letters. For each block boundary segment (consisting of 4 rows or columns of samples), a “Boundary strength” parameter, referred to as “Bs”, is computed before filtering. The calculation of Bs is based on parameters that are used in encoding the bounding blocks of each segment. Each segment is assigned a Bs value from zero to four, with a value of zero indicating that no filtering will take place, and a value of 4 indicating that the strongest filtering mode will be used.
The process for determining Bs is as follows. For each boundary, a determination is made as to whether either one of the two blocks that neighbour the boundary is intra-coded. If either block is intra-coded, then a further determination is made as to whether the block boundary is also a macroblock boundary. If the block boundary is also a macroblock boundary, then Bs=4, else Bs=3.
Otherwise, if neither block is intra-coded then a further determination is made as to whether either block contains non-zero transform coefficients. If either block contains non-zero coefficients then Bs=2, otherwise if a prediction of the two blocks is formed using different reference frames or a different number of frames and if a pair of motion vectors from the two blocks reference the same frame and either component of this pair has a difference of more than one sample, then Bs=1, else Bs=0, in which case no filtering is performed on this boundary. The value of boundary strength, Bs, for a specific block boundary is determined by the encoding characteristics of the two 4×4 blocks along the boundary. Therefore, the control of the filtering process for each individual block boundary is well localized. The block boundary is filtered only when it is necessary, based on whether the coding modes used for the neighbouring blocks are likely to produce a visible blocking artifact.
The known filtering process starts with the step of filtering each 4×4 block edge in a reconstructed macroblock. The filtering “Boundary strength” parameter, Bs, is computed and assigned based on the coding parameters used for luma. Block boundaries of chroma blocks correspond to block boundaries of luma blocks, therefore, the corresponding Bs for luma is also used for chroma boundaries.
Filtering takes place in the order described above on all boundary segments with non-zero value for Bs. The following describes the process that takes place for each line-based filtering operation.
TABLE 1
QP av dependent activity threshold parameters α and β
QP av
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
α
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
β
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
QP av
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
α
0
4
4
5
6
7
9
10
12
14
17
20
24
28
33
39
46
55
65
β
0
3
3
3
4
4
4
6
6
7
7
8
8
9
9
10
10
11
11
QP av
38
39
40
41
42
43
44
45
46
47
48
49
50
51
α
76
90
106
126
148
175
207
245
255
255
255
255
255
255
β
12
12
13
13
14
14
15
15
16
16
17
17
18
18
A content activity check is performed. If the check is passed, filtering continues, otherwise, the sample values are not modified on this line of the boundary segment. The activity check makes use of a pair of activity threshold parameters, ALPHA (α) and BETA (β), whose particular values are selected from the above Table 1, based on the average quantization parameter (QP av ) used in coding each boundary segment. It is noted that QP av represents the average value of the quantization parameter values used in encoding the two blocks that neighbour the boundary, with rounding of the average by truncation of any fractional part. Accordingly, the content activity check is passed if
| p 0 −q 0 |<ALPHA (α) AND | p 1 −p 0 |<BETA (β) AND | q 1 −q 0 |<BETA (β).
Further, if this first content activity check is passed, and Bs is not equal to 4, default mode filtering is performed. Otherwise, if the check is passed and Bs is equal to 4, a second, stricter activity check is performed. This activity check involves the evaluation of the condition
1 <|p 0 −q 0 |<( QP av >>2) AND | p 2 −p 0 |<BETA (β) AND | q 2 −q 0 |<BETA (β).
If this second condition is true on a particular line of samples, a strong mode filtering is used on this line of samples. Otherwise, a default mode filtering is used on this line of samples. It should be noted the symbol “>>” is used to represent the operation of bit-wise shifting to the right.
Among the disadvantages of the above described known method is that it permits switching between two filtering modes with very different characteristics at the level of each line of samples within a boundary segment. This switching adds complexity to the filtering process and can significantly increase the worst-case critical path for processing on many architectures.
Further disadvantages include the particular values in the tables of filtering parameters, ALPHA (α) and BETA (β), which are not optimized to produce the best subjective viewing quality of reconstructed and filtered video. Further, the characteristics of the deblocking filter in terms of the threshold parameters used in the activity checks and equations used for generating filtered sample values are fixed in the known method, providing the encoder with little or no flexibility to control the properties of the deblocking filter. This hinders optimization of the subjective quality of the decoded video for different types of video content and displays.
In the default mode of the above identified filtering method, the value Δ, which represents the change from the unfiltered values of p 0 and q 0 to their respective filtered values is computed using:
Δ=Clip(− C, C , ((( q 0 −p 0 )<<2+( p 1 −q 1 )+4)>>3)),
where C is determined as specified below and the function “Clip” is defined as:
Clip (a, b, c)=IF (c<a) THEN a
ELSE IF (c>b) THEN b ELSE c
Further, the filtered values P 0 and Q 0 are computed where
P 0 =Clip(0, 255 , p 0 +Δ) and Q 0 =Clip(0, 255, q 0 −Δ).
In order to compute the clipping value, C, that is used to determine Δ, and also determine whether the values of p 1 and q 1 will be modified on this set of samples, two intermediate variables, a p and a q are computed, where:
α p , =|P 2 −P 0 | and α q =|q 2 −q 0 |.
If α p <β for a luminance edge, a filtered sample P 1 is produced as specified by:
P 1 =P 1 +Clip(− C 0 , C 0, ( p 2 +P 0 −( p 1 <<1))>>1).
If α q <β for a luminance edge, a filtered sample Q 1 is produced as specified by Q 1 =q 1 +Clip(−C0, C0, (q 2 +Q 0 −(q 1 <<1))>>1) where C0 is specified in Table 2 (see below), based on Bs and QP av for the block boundary. For both luma and chroma, C is determined by setting it equal to CO and then incrementing it by one if α p <β, and again by one if α q <β.
TABLE 2
Value of filter clipping parameter C0 as a function of QP av and Bs
QP av
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
Bs = 1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
Bs = 2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
1
Bs = 3
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
1
1
1
1
1
QP av
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
Bs = 1
1
1
1
1
1
1
1
2
2
2
2
3
3
3
4
4
4
5
6
6
7
8
9
10
11
13
Bs = 2
1
1
1
1
1
2
2
2
2
3
3
3
4
4
5
5
6
7
8
8
10
11
12
13
15
17
Bs = 3
1
2
2
2
2
3
3
3
4
4
4
5
6
6
7
8
9
10
11
13
14
16
18
20
23
25
It is important to note that the computation of the filtered values P 1 and Q 1 require as an input to the filtering equation the filtered values of P 0 and Q 0 from the current line of samples. This recursive filtering method presents a disadvantage as the values of P 0 and Q 0 must be computed before the computation of P 1 and Q 1 can begin. This design can impede parallel processing of the different samples and thereby increases the critical path for the default mode filtering on most hardware architectures.
An additional disadvantage in the default mode filtering process of the known method is that the calculation of the clipping parameter, C, for chroma samples is unnecessarily complex. The chroma samples p 1 and q 1 are never filtered in the default mode and, therefore, the computation of the variables a p and a q is only necessary to determine the C parameter that is used to clip the value of Δ. These computations could be avoided by specifying a simpler method to compute C for chroma filtering.
For strong mode filtering in the known method, the following equations are applied to calculate the filtered sample values:
P 0 =( p 2 +2* p 1 +2* p 0 +2* q 0 +q 1 +4)>>3,
P 1 =( p 3 +2* p 2 +2* p 1 +2* p 0 +q 0 +4)>>3,
Q 0 =( p 1 +2* p 0 +2* q 0 +2* q 1 +q 2 +4)>>3 and
Q 1 =( p 0 +2* q 0 +2* q 1 +2* q 2 +q 3 +4)>>3.
For the luminance component only, p 2 and q 2 are also filtered as specified by:
P 2 =(2* p 3 +3* p 2 +p 1 +p 0 +q 0 +4)>>3and
Q 2 =(2* q 3 +3* q 2 +q 1 +q 0 +p 0 +4)>>3.
Filtering with this set of equations can lead to insufficient reduction in the visibility of blocking artifacts It is therefore an object of the present invention to obviate or mitigate the above-mentioned disadvantages.
SUMMARY OF THE INVENTION
In accordance with one aspect of the present invention there is provided a method of filtering samples to minimise coding artifacts introduced at a block boundary in a block-based video encoder, the method having the steps of:
(a) calculating a pair of indices used to access a table of a pair of corresponding activity threshold values, the indices calculated using an average quantization parameter and an offset parameter, (b) determining the activity threshold values based on the pair of indicies; (c) confirming whether the filtering process will modify the sample values on every line of samples for the block boundary by checking a content activity for the every line of samples for the block boundary, the content activity based on the determined activity threshold values; and (d) filtering the confirmed samples when a block on either side of the block boundary was coded using inter prediction.
The determination of whether the filtering process will modify the sample values on each particular line is based on a content activity check which makes use of a set of adaptively selected thresholds whose values are determined using Variable-Shift Table Indexing (VSTI). The method is also operated on a system including tables for the various activity thresholds accessed through the calculated indicies,
In another aspect of the invention there is provided a method of controlling filter properties to adjust the properties of said filter at a block boundary, the method having the steps of:
(a) computing an average quantization parameter value (QP av ) at the block boundary; (b) adding offset values Filter_Offset_A and Filter_Offset_B to the average quantization parameter value QP av and clipping these values within a given range to determine table indices Index A and Index B ; and (c) accessing an ALPHA (α) table, a BETA (β) table, and a Clipping (C0) table using the indices computed based on the filter offsets and the average quantization parameter value such that:
ALPHA=ALPHA_TABLE[Index A ]
BETA=BETA_TABLE [Index B ]
C0=CLIP_TABLE[Bs][Index A ]
In a still further aspect of the invention there is provided a method of filtering samples to minimise coding artifacts introduced at a block boundary in a block-based video encoder, the method having the steps of checking content activity on every line of samples belonging to the boundary to be filtered and determining whether the filtering process will modify the sample values on said line of samples based on content activity thresholds that are dependent on a quantization parameter and determined using a filter offset parameter.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other features of the preferred embodiments of the invention will become more apparent in the following detailed description in which reference is made to the appended drawings wherein:
FIG. 1 is a schematic representation of a data transmission system;
FIG. 2 is a schematic representation of hierarchy of levels of an H.264 conformant bitstream,
FIG. 3 a is schematic representation of a macroblock and a block,
FIG. 3 b is a diagram showing relationship between unfiltered samples and activity thresholds;
FIG. 4 is a block diagram of a hybrid block-based video decoder including a deblocking filter inside the motion compensation loop of the system of FIG. 1 ;
FIG. 5 is a flowchart of the operation of the deblocking filter process for the decoder of FIG. 4 ;
FIG. 6 is the dependency graph for default mode filter for the decoder of FIG. 4 ; and
FIG. 7 is flowchart for the process of calculating the boundary strength for the decoder of FIG. 4 .
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1 , a video conferencing system 10 used as an example of a video transmission system has participants A and B that exchange video data 12 between monitors 13 , formatted as a compressed bit stream 15 over a network 14 (such as but not limited to the Internet), Each participant A, B has a video processor 16 having an encoder 18 for encoding transmitted video data 12 and a decoder 20 for decoding the received bit stream 15 . Each image frame 22 displayed on the monitors 13 is made of a series of macroblocks 24 , such as but not limited to a block of 16×16 pixels, representing (for example) an object 26 which moves over a background 28 (for example a person giving a presentation while standing in front of a backdrop). Accordingly, the processors 16 coordinate the display of successive frames 22 on the monitors 13 , as the video data 12 is communicated between the participants A, B. which can include applications such as video conferencing It will be appreciated recognised that the system 10 may also involve the exchange of video data 12 in the compressed bit stream 15 in either one direction or both and on peer-to-peer basis or broadcast.
The video data 12 is a temporal sequence of pictures, each referred to as a frame or field 22 . Each picture 22 is organized as a matrix of macroblocks 24 . Each macroblock 24 has a size of 16 by 16 pixels and the macroblocks 24 are stored from left to right and from top to bottom and groups of macroblocks 24 are combined in a slice 32 (see FIG. 2 ). Generally, a slice 32 contains macroblocks 24 and each macroblock 24 consists of blocks 25 (see FIG. 3 ). Generally, each macroblock 24 is composed of three images; one red (R), one green (G), and one blue (B). However, for compatibility with non-coloured media, the RGB model is represented as an equivalent YCbCr model, where Y is a luminance (luma) component, and Cb and Cr are chrominance (chroma) components, such that typically Y=0.299R+0.587G+0.114B, Cb=B−Y, and Cr=R−Y. Therefore, each frame 22 of the video data 12 is generically referred to as containing one luma image, one Cb chroma image, and one Cr chroma image. Standard formats have 8 bits per pixel to digitally represent each of the three components, where Cb and Cr images are typically downsampled by 2 in each dimension due to the sensitivity of human vision. Generally, each block 25 consists of four pixels for the luma components and one pixel for each chroma component of the 4:2:0 color data. The blocks 25 are processed and compressed for transmission as the bit stream 15 over the network 14 (see FIG. 1 ).
Generally, one of three fundamental coding modes can be selected for each macroblock 24 , with the choice of coding mode determining how the prediction of a macroblock 24 is formed. Intra-coded (I) macroblocks 24 make use of intra-prediction, in which the prediction is formed using only the current picture. In predictive (P), or inter-coded, macroblocks 24 the prediction of each sample is formed by referring to one block 25 in the set of previously decoded and stored reference pictures 22 . In bi-predictive (B) macroblocks 24 , predictions can be formed in this way, but can also be formed by computing a weighted average of two different blocks 25 in the set of previously decoded reference pictures 22 . It will be noted that some of the previously decoded pictures 22 are typically temporally subsequent to the current picture in terms of their intended display order when bi-predictive coding is used. Depending on the mode of each slice 32 , which is indicated in the slice header 27 , P- and B-macroblocks 24 may not be permitted within certain slices 32 .
Referring again to FIG. 2 , the bitstream 15 is organized into a hierarchy of syntax levels, with the 3 main levels being a sequence level 17 , a picture (or frame) level 19 , and slice level 21 . A concept know as “parameter sets” allows efficient transmission of infrequently changing data at the sequence 17 and picture level 19 in the H.264 standard. A sequence parameter set 29 in the first level 17 includes values of parameters that will remain unchanged for an entire video sequence, or from one instantaneous decoder refresh (IDR) picture to the next. (IDR pictures are used to provide points of random access into the bitstream). Examples of parameters in a sequence parameter set 29 include frame dimensions and the maximum number of reference frames. A unique ID number “N” identifies each sequence parameter set 29 .
A picture parameter set 31 in the second level 19 includes values of parameters that will remain unchanged within a coded representation of a picture (frame or field) 22 . Examples of parameters in the picture parameter set 31 include the entropy coding mode and a flag that specifies whether deblocking filter parameters will be transmitted in the slice headers 27 of the picture 22 (see FIG. 1 ). Each picture parameter set 31 , labeled as “M”, refers to the unique ID of a valid sequence parameter set 29 , which selects the active sequence parameters that are used when decoding coded pictures 22 that use the particular picture parameter set 31 . The unique ID number “M” identifies each picture parameter set 31 .
A slice 32 in the bit stream 15 contains a picture data 35 representing a sub-set of the macroblocks 24 of the complete picture 22 . The macroblocks 24 in a slice 32 are ordered contiguously in raster scan order. The coded slice 32 includes the slice header 27 and the slice data 35 (coded macroblocks 24 ). The slice header 27 contains a coded representation of data elements 35 that pertain to the decoding of the slice data that follow the slice header 27 . One of these data elements contains a reference to a valid picture parameter set 31 , which specifies the picture parameter values (and indirectly the sequence parameter values) to be used when decoding the slice data 35 . Each slice header 27 within the same picture 22 must refer to the same picture parameter set 31 . Other data elements in the slice header 27 include the initial quantization parameter for the first macroblock 24 in the slice 32 and deblocking filter offset parameters 39 (as further explained below), if the transmission of such offset parameters 39 is specified in the active picture parameter set.
Thus, the filter offsets 39 are transmitted in the slice header 27 , and therefore the offsets 39 can be different for each slice 32 within the picture 22 . However, depending on the value of a flag in the picture parameter set 31 (“filter_parameters_flag”), the transmission of these offsets 39 in the slice header 27 might be disabled. In the case that offsets 39 are not transmitted, a default value of zero is used for both filter offsets 39 for example. Further, each picture parameter set 31 contains parameter values that pertain to the decoding of the pictures 22 for which the particular parameter set 31 is active (i.e. selected in the slice headers 27 of the picture 22 ). The parameter sets 31 also contain a reference to the sequence parameter sets 29 , which are active for decoding of the pictures 22 . The choice of sequence parameter sets 29 and picture parameter sets 31 can be chosen by the encoder 18 (see FIG. 1 ), or set at the time of system 10 setup for sequential operation of the encoder 18 , decoder 20 pair.
Referring further to FIG. 2 , each of the pictures 22 can select individual picture parameter sets that specify the picture structure and the picture coding type. For exemplary purposes only, FIG. 3 a contains the macroblock 24 each consisting of a grouping of pixels, such as a 16×16 luma block 25 with the two associated 8×8 chroma blocks 25 . However, it is recognized that other sizes of blocks 24 could be used to represent the frames 22 , if desired. Each slice 32 of the frame 22 is encoded by the encoder 18 (see FIG. 1 ), independently from the other slices 32 in the frame 22 . Each of the slices 32 has the slice header 27 that provides information, such as but not limited to the position of the respective slice 32 in the frame 22 as well as the initial quantization parameter; and the slice data which provides information for reconstructing the macroblocks 24 of a slice 32 , such as but not limited to the prediction modes and quantised coefficients for each of the respective macroblocks 24 .
Referring to FIG. 4 , the decoder 20 processes the received bit stream 15 and then reconstructs the buffer 46 , using a stored copy of the reference frame(s) 48 , the transmitted motion vectors 23 , and the decompressed or reassembled prediction error 54 contained in the bit stream 15 .
The bit stream 15 generated by the encoder 18 is processed by the decoder 20 to produce the reconstructed video images 55 . Referring to FIG. 4 , the video decoder 20 is based on functional units or components similar to those found in other hybrid block-based video decoders. The functional units include a buffering unit 33 that receives the compressed bitstream 15 , an entropy decoder 34 which decodes the received bit stream 15 to produce syntax elements used in subsequent processing by the other decoder 20 components, a motion compensated prediction 36 to produce the predicted frame, an inverse scanning and quantization unit 38 , and inverse transform units 40 to reproduce the coded prediction error 54 . A reconstruction unit 42 adds the prediction error 54 to the predicted pixels 57 to produce the reconstructed frame 55 , and a deblocking filter 44 that smoothes the edges of sub-blocks within the reconstructed frame 55 to produce the filtered reconstructed frame 56 . Each of the above mentioned components is discussed in more detail in the following.
The incoming video bitstream 15 is stored in a buffer 33 at the input to the decoder 20 . The first stage in the decoding process includes the parsing and decoding of the entropy coded bitstream symbols that are stored in a buffer 46 to produce the syntax elements used by the other decoder 20 components.
The various syntax elements in the bitstream 15 are de-multiplexed for use in different processes within the decoder 20 . High-level syntax elements include temporal information for each frame, frame coding types and frame dimensions. The coding can be based primarily on macroblocks 24 consisting of 16×16 luminance-pixel blocks 25 and 2 8×8 chrominance pixel blocks 25 . On the macroblock 24 level, syntax elements include the coding mode of the macroblock 24 , information required for forming the prediction, such as motion vectors 23 and spatial prediction modes, and the coded information of the residual (difference) blocks, such as the coded block pattern (CBP) for each macroblock 24 and quantized transform coefficients for each of the underlying blocks 24 .
Depending on the coding mode of each macroblock 24 , the predicted macroblock 24 can be generated either temporally (inter prediction) or spatially (intra prediction). The prediction for an inter-coded macroblock 24 is specified by the motion vectors 23 that are associated with that macroblock 24 . The motion vectors 23 indicate the position within the set of previously decoded frames from which each block of pixels will be predicted. Each inter-coded macroblock 24 can be partitioned in a number of different ways, using blocks of seven different sizes, with luminance block sizes ranging from 16×16 pixels to 4×4 pixels. Also, a special SKIP mode exists in which no motion vector difference values 23 (or coded residual blocks) are transmitted and the prediction is taken from a location in the previous picture that is predicted by the values of previously decoded motion vectors 23 of macroblocks 24 neighbouring the current macroblock 24 . Thus, 0 to 16 motion vectors 23 can be transmitted for each inter-coded macroblock 24 . Additional predictive modes in which two different motion vectors 23 correspond to each pixel and the sample values are computed using a weighted average are supported when bi-predictive macroblock types are employed.
For each motion vector 23 , a predicted block 25 must be computed by the decoder 20 and then arranged with other blocks 24 to form the predicted macroblock 24 . Motion vectors 23 in H.264 are specified generally with quarter-pixel accuracy. Interpolation of the reference video frames is necessary to determine the predicted macroblock 24 using sub-pixel accurate motion vectors 23 .
Multiple (previous for P-pictures) reference pictures 22 can also be used for motion-compensated prediction. Selection of a particular reference pictures 22 is made on an 8×8 sub-macroblock 24 basis, or larger if a larger sub-macroblock partition size is used for generating the 18 motion-compensated prediction. This feature can improve coding efficiency by providing a larger set of options from which to generate a prediction signal.
Two different modes are supported in intra prediction and coding of macroblocks 24 . In the 4×4 Intra mode, each 4×4 block within a macroblock 24 can use a different prediction mode. In the 16×16 Intra mode, a single prediction mode is used for the entire macroblock 24 . The prediction of intra-coded blocks 25 is always based on neighboring pixel values that have already been decoded and reconstructed.
The decoding of a residual (difference) macroblock 24 requires that a number of transforms be performed on any blocks for which non-zero transform coefficients were transmitted in the bitstream, along with associated scanning and coefficient scaling operations. The transforms that are required for each macroblock 24 are determined based on the coding mode and the coded block pattern (CBP) of the macroblock 24 . The decoding of a difference macroblock 24 is based primarily on the transformation of 4×4 blocks 25 of both the luminance and chrominance pixels, although in some circumstances, a second-level transform must be performed on the DC coefficients of a group of 4×4 blocks 25 for macroblocks 24 that are coded in the 16×16 Intra prediction mode. Additionally, a special 2×2 transform is applied to the 4 DC coefficients of the chrominance residual blocks 25 of a macroblock 24 .
The values of the quantized coefficients are parsed and decoded by the entropy decoder 34 . These are put into their correct order based on the run values through the scanning process and then the levels, which represent quantized transform coefficients, are scaled via multiplication by a scaling factor. Finally, the necessary transform to reconstruct the coded residual signal for a block is performed on the scaled coefficients. The result of the transforms for each macroblock 24 is added to the predicted macroblock 24 and stored in the reconstructed frame buffer 48 .
In the final stage of the decoding process, the decoder 20 applies the normative de-blocking filtering process, which reduces blocking artifacts that are introduced by the coding process. The filter 44 is applied within the motion compensation loop, so both the encoder 18 and decoder 20 must perform this filtering. The filtering is performed on the 4×4 block edges of both luminance and chrominance components. The type of filter 44 used, the length of the filter and its strength are dependent on several coding parameters as well as picture content on both sides of each edge. A stronger filtering mode is used if the edge lies on a macroblock boundary 49 where the block on one or both sides of the edge is coded using intra prediction. The length of the filtering is also determined by the sample values over the edge, which determine the so-called “activity measures”. These activity measures determine whether 0, 1, or 2 samples on either side of the edge are modified by the filter,
Filtering is applied across the 4×4 block edges of both luminance and chrominance components. Looking at FIG. 3 a , the blocks 25 are separated by boundaries or block edges 47 , with unfiltered samples p 0 , p 1 , p 2 and p 3 on one side of the boundary 47 and unfiltered samples q 0 , q 1 , q 2 and q 3 on the other side, such that the boundary 47 lies between p 0 and q 0 . In some cases p 1 , p 2 may indicate samples that have been modified by filtering of the previous block edge 47 . The deblocking filter 44 (see FIG. 4 ) is applied on the block boundaries 47 of each reconstructed frame 56 , which helps to reduce the visibility of coding artifacts that can be introduced at those block boundaries 49 . The filter 44 includes a control function that determines the appropriate filtering to apply. The control algorithm is illustrated by FIG. 5 .
One of the parameters used to control the filtering process of all the block boundaries 47 is the boundary strength, Bs. The procedure for determining the boundary strength, Bs, for the block boundary 47 between two neighbouring blocks j and k is illustrated in FIG. 7 . For each edge 47 , a determination is made as to whether either one of the two blocks j and k across the boundary 47 is intra-coded, in step 140 . If either block j or k is intra-coded then a further determination is made as to whether the block boundary 47 is also a macroblock boundary 49 , in step 152 . If the block boundary 47 is also a macroblock boundary 49 , then Bs=4 (step 154 ), else Bs=3 (step 156 ).
Otherwise, if neither block j or k is intra-coded then a further determination is made as to whether either block 25 contains non-zero coefficients, in step 142 . If either block 25 contains non-zero coefficients then
Bs=2 (step 144 ), otherwise the following condition is applied:
R ( j ) ≠ R ( k ) or | V ( j, x )− V ( k, x ) |≧1 pixel or | V ( j, y )− V ( k, y ) |≧1pixel,
where R(j) is the reference picture 22 used for predicting block j, and V(j) is the motion vector 23 used for predicting block j, consisting of x and y (horizontal and vertical) components. Therefore, if a prediction of the two blocks 25 is formed using different reference frames 22 or a different number of frames 22 or if a pair of motion vectors 23 from the two blocks 25 reference the same frame and either component of this pair has a difference if more than one sample distance, then this condition holds true and
Bs=1 (step 148 );
else,
Bs=0 (step 150 ), in which case no filtering is performed.
The value of boundary strength, Bs, for a specific block boundary 47 is determined solely by characteristics of the two 4×4 blocks 24 across the boundary 47 . Therefore, the control of the filtering process for each individual block boundary 47 is well localized. A block boundary 47 is filtered only when it is necessary, so that unneeded computation and blurring can be effectively avoided.
The flowchart of FIG. 5 describes the filtering process starting with step 100 for the purposes of filtering each 4×4 block edge 47 in a reconstructed macroblock 24 . The filtering “Boundary strength” parameter, Bs, is computed ( 102 ) and assigned for luma. Block boundaries 47 of chroma blocks 25 always correspond to block boundaries 47 of luma blocks 25 , therefore, the corresponding Bs for luma is also used for chroma boundaries 47 . The boundary strength is based on the parameters that are used in encoding the bounding blocks 25 of each segment ( 104 ). Each segment is assigned a Bs value from 0 to 4, with a value of zero indicating that no filtering will take place ( 108 ), and a value of 4 indicating that the strongest filtering mode will be used.
In step 110 , the filtering process takes place for each line of samples on the block boundary 47 . The set of filtering operations that take place on one line of a block boundary is referred to as a line-based filtering operation. A content activity check at the boundary 47 between the two blocks 25 is performed in step 112 . The content activity measure is derived from the absolute value of the separation between sample values of p 0 , p 1 , q 0 , q 1 on either side of the boundary 47 . The activity check is based on two activity threshold parameters ALPHA (α) and BETA (β), whose particular values are selected based on the average quantization parameter (QP av ) used in coding each boundary segment, as well as upon a pair of encoder 18 selected parameter values, referred to as Filter_Offset_A and Filter_Offset_B (referred to as 39 in FIG. 2 ). QP av represents the average of the quantization parameter values used in coding the two blocks 25 that neighbour the boundary 47 , with rounding of the average by truncation of any fractional part. Thus, the content activity check is done by comparing difference in the unfiltered sample values p 0 and q 0 across the boundary 47 against the activity threshold ALPHA (α), and the difference in the unfiltered sample values p 0 and p 1 on one side of the boundary 47 and unfiltered sample values q 0 and q 1 on the other side of the boundary 47 against the activity threshold and BETA (β), as shown in FIG. 3 b . A determination is made to discover whether the activity on the line is above or below the activity threshold. If the activity is above the threshold, the sample values are not modified, otherwise filtering continues. The ALPHA (α) and BETA (β) values are considered as activity thresholds for the difference in magnitude between sample values along the line of samples being filtered.
Referring to FIG. 3 , the ALPHA (α) and BETA (β) parameters represent the activity thresholds for the difference in the values of unfiltered samples p 0 , p 1 , q 0 , q 1 across the boundary 47 . The content activity check is passed if:
p 0 −q 0 |<ALPHA (α) AND | p 1 −p 0 |<BETA (β) AND | q 1 −q 0 |<BETA(β)
The sets of samples p 0 , p 1 , q 0 , q 1 across this edge 46 are only filtered if Bs is not equal to zero and the content activity check expressed in the above condition is passed.
The values in the ALPHA (α)- and BETA (β)-tables used in the loop filter are optimal in terms of the resulting video visual quality and allow some flexibility in the encoder 18 in terms of adjusting the filter parameters, such as the activity threshold parameters and maximum change in a sample value produced by the default filter, through control of the indexing of these tables. The strength of the deblocking filter 44 refers to the magnitude of the change in sample intensities that is caused by the filtering process. Generally, the strength of the filter 44 varies with the coding mode, as well as the step-size used for quantization of the transform coefficients. Stronger filtering is applied when the quantization step-size (and its corresponding “quantization parameter”, QP) are larger, since it is more likely that large block artifacts are created when the quantization is coarse. Thus, flexibility in the properties of the loop filter 44 is provided by allowing the encoder 18 to select offsets 39 to the QP-based indices used to address these tables. This adds flexibility to the filter 44 , help making it more robust to different content, resolutions, display types, and other encoder 18 decision characteristics.
The α- and β-tables of the loop filter 44 are QP-dependent thresholds that define the maximum amount of activity at an edge for which the edge will still be filtered. The modified α-table of the preferred embodiment is based on the subjective evaluation of a number of sequences over the entire QP scale. In the preferred embodiment, the value of a doubles every 6 QP as it is related directly to the quantization step size, which also doubles every 6 QP in the H.264 standard.
A determination is made to find the QP value below which a should be zero, such that the filter is no longer used for values of a which equal zero. Looking at Table 1, in sequences with smooth areas, blocking artifacts are clearly visible using QP=19, which is the largest QP for which α is equal to zero. Based on Table 3, filtering will take place for QP values as low as 16, since blocking artifacts are still visible in smooth areas. The β-table is also extended at the low QP end in order to permit filtering at these lower QP values.
The content activity check ( 112 ) determines whether each sample line is to be filtered and uses the following specific values for α and β ( 114 ) as shown in Table 3 below, where the index used to access the tables is clipped to be within the range of valid QP values (0 to 51).
TABLE 3
Index A (for α) or Index B (for β)
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
α
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
4
4
5
β
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
2
2
Index A (for α) or Index B (for β)
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
α
6
7
8
9
10
12
13
15
17
20
22
25
28
32
36
40
45
50
56
β
3
3
3
3
4
4
4
6
6
7
7
8
8
9
9
10
10
11
11
Index A (for α) or Index B (for β)
38
39
40
41
42
43
44
45
46
47
48
49
50
51
α
63
71
80
90
101
113
127
144
162
182
203
226
255
255
β
12
12
13
13
14
14
15
15
16
16
17
17
18
18
Further, the particular values for α and β to be used on each block boundary 47 do not only depend on QP, but additionally upon a pair of parameter values, referred to as Filter_Offset_A and Filter_Offset_B, (referenced 39 in FIG. 2 ) that are transmitted in the higher-level syntax (sequence 17 , picture 19 , or preferably the slice level 21 ) within the video bitstream 15 . These offsets 39 are added to the average QP value between the blocks 24 in order to calculate the indices that are used to access the tables of ALPHA (α) and BETA (β) values ( 114 ), as well as the C0 table:
Index A =Clip( QP min , QP max , QP av +Filter_Offset_A)
Index B =Clip( QP min , QP max , QP av +Filter_Offset_B)
The variables QP min and QP max in the above equations represent the minimum and maximum permitted values, respectively, of the quantization parameter QP, and for example can be such that but not limited to the values 0 and 51, respectively.
However, because the values Index B and Index A are limited to lie in a predetermined interval, if any of the computed coefficients lie outside the interval, those values are limited to the permitted range by the “clip” function. The function “clip” is defined as:
clip (a, b, c)=IF (c<a) THEN a
ELSE IF (c>b) THEN b ELSE c
By default, Filter —Offset _A and Filter_Offset_B values 39 are both assumed to have a value of zero. Further, within the default filtering, Index A is also used to access the table of C0 values. Transmission of the Filter_Offset_A and Filter_Offset_B values 39 in the slice header 27 (see FIG. 2 ) provides a means of adapting the properties of the deblocking filter 44 in terms of the magnitude of the thresholds used in the activity checks and the maximum change in sample values that can be produced by the default filter 44 . This flexibility helps to allow the encoder to achieve the optimal visual quality of the decoded and filtered video. Typically, the semantic in the slice header 27 slice_alpha_c0_offset_div2 specifies the offset 39 used in accessing the ALPHA (α) and C0 deblocking filter tables for filtering operations controlled by the macroblocks 24 within the slice 32 . The decoded value of this parameter is in the range from +6 to −6, inclusive. From this value, the offset 39 that shall be applied when addressing these tables is computed as:
Filter_Offset_A=slice_alpha_c0_offset_div2 <<1
If this value is not present in the slice header 27 , then the value of this field shall be inferred to be zero.
Correspondingly, the semantic in the slice header 27 slice_beta_offset_div2 specifies the offset 39 used in accessing the BETA (β) deblocking filter tables for filtering operations controlled by the macroblocks 24 within the slice 32 . The decoded value of this parameter is in the range from +6 to −6, inclusive. From this value, the offset 39 that shall be applied when addressing these tables is computed as:
Filter_Offset_B=slice_beta_offset_div2 <<1.
If this value 39 is not present in the slice header 27 , then the value of this field shall be inferred to be zero. The resulting Variable-Shift Table Indexing (VSTI) method (using the offsets 39 to shift selection of the α-, β-, and clipping (C0) values) allows the decoder 20 to make use of the offset 39 that is specified on the individual slice 32 basis and that will be added to the QP value used in indexing the α-, β-, and clipping (C0) tables. Thus,
Alpha (α)=ALPHA_TABLE[Index A ]
Beta (β)=BETA_TABLE [Index B ]
C0=CLIP_TABLE [Bs][Index A ]
The offset 39 for indexing the clipping table is always the same as for the α-table. In general, it is desired have a and the clipping values remain in sync, although a different offset 39 for β can be beneficial. The implementation of this method can be simplified even further by applying the offset 39 to the base pointers that are used to access the tables. This way, the extra addition only occurs as often as the offset 39 can be changed (on a per-slice basis), not every time the table is accessed. Clipping of the index can be avoided by extending the tables with the last value in the valid range of indices at each end of the table.
A positive offset 39 results in more filtering by shifting a curve (of α, β, or C0 values) to the left on a horizontal QP scale, while a negative offset 39 results in less filtering by shifting a curve to the right. The range of permitted offsets 39 is −12 to +12, in increments of 2. This range is large enough to allow properties of the filter 44 to vary as widely, but is limited to limit additional memory requirements and/or added complexity. This variable-shift method provides both stronger and weaker filtering, and there is sufficient flexibility in the range of values, with reasonable constraints on the amount of variation permitted in the filtering, while maintaining the doubling rate of 6 QP's for α, consistent with the quantization step size. Also, the clipping (C0) and α values remain in sync with each other.
The specific decision on the choice of offsets 39 is varied, and dependent upon the content, resolution, and opinion of the viewer. Generally, less filtering is needed for slowly changing, detailed areas and for high-resolution pictures 22 , while more filtering (using positive offsets 39 ) is preferable for lower resolution pictures 22 , especially with smooth areas and human faces. More filtering can provide the viewer with a feeling of smoother motion.
Referring again to FIG. 5 , if the check is not passed in step 116 , the sample values are not modified on this line ( 118 ), otherwise filtering continues. The selection of the filtering mode occurs at the block boundary 47 level. More specifically, switching between the default-mode filtering and the strong-mode filtering does not occur on a line-to-line basis, and default-mode filtering is not used for intra-coded macroblock boundaries 47 . In step 120 , a further determination is made as to whether the macroblocks 24 are intra-coded. If the macroblocks 24 are not intracoded, then a default filter is applied in step 122 , in which the edges 47 with B s <4 are filtered by computing the filtered samples P 0 and Q 0 based on the DELTA (Δ). The variable Δ represents the difference the between the unfiltered samples p 0 and q 0 and their respective filtered samples, P 0 and Q 0 , according to the following relation:
Δ=Clip (− C,C ,((( q 0 −p 0 )<<2+( p 1 −q 1 )+4)>>3))
P 0 =Clip(0, 255 , p 0 +Δ)
Q 0 =Clip(0, 255 , q 0 −Δ)
The two intermediate threshold variables α p and α q are used to determine the clipping value for the default filtering of luminance samples, as well as the choice of one of the two sub-modes of the strong mode filter, where
a p =|p 2 −p 0 | and a q =|q 2 −q 0 |.
Thus, for default-mode filtering ( 122 ), the calculations of filtered samples P 1 and Q 1 are modified from the prior art to increase the parallelism of the filtering process. If a p <β for a luma edge, a filtered P 1 sample generated as specified by:
P 1 =p 1 +Clip(− C 0 , C 0, ( p 2 +( p 0 +q 0 )>>1−( p 1 <<1))>>1).
While if a q <β, for a luma edge, a filtered Q 1 sample generated as specified by:
Q 1 =q 1 +Clip(− C 0 , C 0, ( q 2 +( p 0 +q 0 )>>1−( q 1 <<1)) >>1)
where C0 is specified in Table 4. However, the adaptable parameter Index A is used to address the table, rather than QP av .
A dependency graph for the default mode filter with reduced critical path as shown in FIG. 6 shows that the complexity can be reduced significantly. By shortening the critical path, a reduced cost of default filtering can be achieved and opportunities for parallel processing can be substantially increased, leading to reduced computational requirements. Also, from this figure, the complexity of Bs=4 filtering is potentially reduced by not permitting the filter 44 to switch between default and strong filter modes on a line-by-line basis to help minimise branching stalls and control logic.
For luminance only, C, which represents the maximum change in the level of intensity that the default filter can apply to the p 0 and q 0 samples, is determined by setting it equal to C0 and then incrementing it by one if α p <β, and again by one if α q <β. In the default luma filtering, P 1 and Q 1 are filtered only if α p <β and α q <β, respectively, evaluate to true, while P 1 and Q 1 are never filtered for chroma. Therefore, for chrominance filtering, instead of doing these calculations, C can be defined with the basic relationship:
C=C 0 +1
Thus, there is a no need to perform the calculations of a p and a q for chrominance and therefore no need to load the sample values p 2 and q 2 . This can reduce the complexity of the default chroma filtering by approximately 20%. There is no reduction in quality, either objective or subjective, introduced by this simplification.
TABLE 4
Index A
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
Bs = 1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
Bs = 2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
1
Bs = 3
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
1
1
1
1
1
Index A
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
Bs = 1
1
1
1
1
1
1
1
2
2
2
2
3
3
3
4
4
4
5
6
6
7
8
9
10
11
13
Bs = 2
1
1
1
1
1
2
2
2
2
3
3
3
4
4
5
5
6
7
8
8
10
11
12
13
15
17
Bs = 3
1
2
2
2
2
3
3
3
4
4
4
5
6
6
7
8
9
10
11
13
14
16
18
20
23
25
For strong mode filtering where Bs=4 and the initial activity threshold check 112 has been passed, a further determination to check whether each side of the boundary 47 meets an additional smoothness criteria is performed in steps 124 and 126 . The smoothness criteria for the left/ upper side of the boundary 47 is checked in step 124 , while the smoothness criteria for the right/lower side is checked in step 126 . Thus, a choice between a 3-tap filter or a 5-tap filter for the left/upper (P) or the right/lower (Q) side of the boundary 47 is made. If the smoothness criterion is not met on a particular side, a 3-tap filter is used to filter only a single pixel on that side of the boundary 47 .
Specifically, for strong-mode filtering:
α p =|p 2 −p 0 |
α q =|q 2 −q 0 |
Therefore, in step 124 , for filtering of edges with Bs=4 if the following condition holds true
α p <BETA (β) AND | p 0 −q 0 |<((ALPHA (α)>>2) +2),
then filtering of the left/upper side of the block edge is specified by the equations ( 130 )
P 0 =( p 2 +2* p 1 +2* p 0 +2* q 0 +q 1 +4)>>3
P 1 =( p 2 +p 1 +p 0 +q 0 +2)>>2
In the case of luminance filtering, then ( 130 )
P 2 =(2* p 3 +3* p 2 +P 1 +p 0 +q 0 +4) >>3
Otherwise, if the above condition does not hold, then filter only P0 using the 3-tap filter ( 128 )
P 0 =(2* p 1 +p 0 +q 1 +2)>>2
Identical but mirrored filters are applied to the right/lower side of the boundary 47 , substituting q and Q for p and P, respectively, in the above description (and vice-versa) ( 132 , 134 ).
Therefore, if the following condition holds true ( 126 ):
α p <BETA (β) AND | p 0 −q 0 |<((ALPHA (α) >>2) +2)
filtering of the right/lower side of the block edge ( 134 ) is specified by the equations
Q 0 =( p 1 +2* p 0 +2* q 0 +2* q 1 +q 2 +4) >>3
Q 1 =( p 0 +q 0 +q 1 +q 2 +2)>>2
In the case of luminance filtering, then ( 134 )
Q 2 =(2* q 3 +3* q 2 +q 1 +q 0 +p 0 +4)>>3
Otherwise, if the above condition does not hold, then only P0 is filtered with the 3-tap filter ( 132 )
Q 0 =(2* q 1 +q 0 +p 1 +2) >>2
The system 10 thus includes a set of equations for the strong mode filtering to generate samples P 1 and Q 1 that can provide a greater reduction in the visibility of blocking artifacts than alternative equations that were used in the prior known method. Typically, the filters for samples P 1 and Q 1 consist of only 4 taps, as opposed to the 5 taps used for the other filtered samples in this strongest filtering mode. However, this is referred to as a 5-tap filter, since 5 taps is the maximum used for any sample. In addition to providing an improved reduction in blocking artifacts, these equations for filtering P 1 and Q 1 are simpler than those used in the prior art method, potentially reducing the complexity of the filter by a small amount.
The system 10 includes tables for ALPHA (α) and BETA (β) that can improve the subjective quality of the filtered video and can also specify an efficient method to allow the encoder 18 to control the characteristics of the deblocking filter 44 by transmitting variable offsets 39 that affect the QP-based indexing of these tables.
Although the invention has been described with reference to certain specific embodiments, various modifications thereof will be apparent to those skilled in the art without departing from the spirit and scope of the invention as outlined in the claims appended hereto | A method of filtering to remove coding artifacts introduced at block edges in a block-based video coder, the method having the steps of: checking the content activity on every line of samples belonging to a boundary to be filtered and where content activity is based on a set of adaptively selected thresholds determined using Variable-Shift Table Indexing (VSTI); determining whether the filtering process will modify the sample values on that particular line based on said content activity; and selecting a filtering mode between at least two filtering modes to apply on a block boundary basis, implying that there would be no switching between the two primary modes on a line by line basis along a given block boundary. The two filtering modes include a default mode based on a non-recursive filter, and a strong filtering mode which features two strong filtering sub-modes and a new selection criterion that is one-sided with respect to the block boundary to determine which of the two strong filtering sub-modes to use. The two strong filtering sub-modes include a new 3-tap filter sub-mode and a 5-tap filter sub-mode that permits a more efficient implementation of the filter. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates generally to a cleaning device for cleaning an article to be cleaned, such as a semiconductor wafer in a cleaning tub, and more particularly to such a cleaning device that can always keep clean atmosphere around the cleaning tub.
2. Description of the Related Art
A semiconductor wafer is subjected to various cleaning processes, such as a washing process, an ammonia process, fluoric acid process, and so forth. A device in which such processes are performed has a cleaning tub for a cleaning liquid, such as pure water. In the cleaning liquid contained in the cleaning tub, a semiconductor wafer is dipped and washed.
Some cleaning devices of this type have cleaning tubs in their chambers in order to prevent an cleaning liquids from being scattered on the outside of the chamber and prevent external fine particles, etc. from entering the chamber. A shutter which can be opened/closed is installed at the entrance portion of each chamber so that the semiconductor wafer can be taken in/out.
In this case, however, when the shutter is opened to take the wafer in/out of the chamber, an atmosphere can easily leak out of the chamber. In particular, in the case of using chemicals, as a cleaning liquid, heated at about 80° C., the vapor of the chemicals may cause environmental pollution. Moreover, fine particles are generated from a mechanical portion which carries the semiconductor wafer in the chamber and conveys it in/out of the cleaning tub, and an atmosphere containing the fine particles can easily enter in the chamber. As a result, many foreign objects are adhered on the semiconductor wafer and the yield of semiconductor products is decreased.
SUMMARY OF THE INVENTION
The object of the present invention is to provide a cleaning device which can always keep clean the circumference of a cleaning tub by using downflow of clean air.
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.
The above object will be achieved by the cleaning device in the present invention which comprises at least one cleaning tub containing a cleaning liquid; a chamber housing the cleaning tub; means for taking an article to be cleaned in/out of the cleaning liquid in the cleaning tub; a shutter for shutting out the chamber from the outside thereof, said shutter being opened when the cleaned material is taken in/out of the chamber, thereby passing the cleaned material there through; clean air supplying means for supplying clean air into the chamber and forming downflow of the clean air around the cleaning tub; and exhausting mean for sucking the clean air passing along the circumference of the cleaning tub and exhausting the air out of the chamber.
BRIEF DESCRIPTION OF THE DRAWINGS
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 plan view showing the internal structure of a cleaning device according to one embodiment of the present invention;
FIG. 2 is a perspective view showing a structure of each cleaning tub;
FIG. 3 is a partially sectional view of the entire structure of the above cleaning device;
FIG. 4 is a sectional view taken along line II-II of FIG. 3;
FIG. 5 is a sectional view of an aligning plate shown in FIG. 3;
FIG. 6 is a sectional view of a sealing structure of the portion where a liquid-supplying tube shown in FIG. 3 penetrates the chamber.
FIG. 7 is a sectional view of a sealing structure of the portion where the cleaning tub is connected with the liquid supplying device, shown in FIG. 3;
FIG. 8 is a perspective view of a partial section of the cleaning device described in a second embodiment of the present invention; and
FIG. 9 is a plan view of a partial section of the cleaning device of the second embodiment.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Embodiments of the present invention will now be described below with reference to the accompanying drawings.
The embodiments relate to a cleaning device used in a semiconductor wafer producing process.
As shown in FIG. 1, a cleaning device in one embodiment of the present invention consists of three cleaning process units 2, 4, and 6. Loading unit 8 is connected to wafer entrance-side cleaning unit 2, unloading unit10 to wafer exit-side cleaning unit 6, and further, transfer units 12 for combining three units are arranged between cleaning units 2 and 4 and alsobetween cleaning units 4 and 6 so as to combine these three units.
At the center position of wafer entrance-side cleaning unit 2, a first rotary convey arm 14 for taking out semiconductor wafer 20 is situated. One cleaning tub 18 is positioned in front of loading unit 8, and another cleaning tub 16 is positioned at the left side of rotary convey arm 14, sothat both tubs surround rotary convey arm 14.
In the present embodiment, cleaning tub 16 is used for a chemical-process tub in which an ammonia process is performed, and cleaning tub 18 is used for a quick dump rinse (QDR) tub in which a washing process is performed.
In central cleaning unit 4, transfer units 12 are arranged on the left and right sides of a second rotary convey arm 22. Two cleaning tubs 24 and 26 are arranged on the front and rear side of units 12 and arm 22. Cleaning tub 24 is used for a chemical-process tub in which a fluoric acid process is performed, and cleaning tub 26 is used for a washing overflow tub.
In wafer exit-side cleaning unit 6, cleaning tub 30 is situated in front ofunloading unit 10 and drying tub 32 is situated on the right side of a third rotary convey arm 28. Both tubs surround the third rotary convey armpositioned at the center of the wafer exit-side cleaning unit 6. In the present embodiment, cleaning tub 30 is used for a washing-final-rinse tub.
In the cleaning device having the above structure, when 25 pieces of semiconductor wafer 20 mounted on each of carriers 34 are taken in loadingunit 8, the orientation flat of semiconductor wafer 20 is positioned properly by means of an orientation-flat adjustable-unit (not shown in thedrawings) on the loading unit 8, the semiconductor wafer 20 is picked up bymeans of a pickup mechanism (not shown in the drawings), and the semiconductor wafer 20 is set on pick-up stage 36 by means of a robot arm (not shown in the drawings).
The first rotary convey arm 14 begins to take only semiconductor wafer 20 out from the upper side of loading unit 8, and then only the semiconductorwafer 20 is conveyed to the first cleaning tub 16. After a cleaning processis provided to the wafer 20 in the tub 16, the semiconductor wafer 20 is transferred from the first cleaning tub 16 to the second cleaning tub 18, and then to transfer unit 12, in each of which a cleaning process is performed.
Then, semiconductor wafer 20 is conveyed to a third cleaning tub 24, a fourth cleaning tub 26, and transfer unit 12 by the second rotary convey arm 22 of intermediate process unit 4 and to a fifth cleaning tub 30 and drying tub 32 by the third rotary convey arm 23 of wafer exit-side processunit 6. After wafer 20 is cleaned or dried in each tub, it is conveyed to unloading unit 10, in which the wafer is separated into two carriers 34 and conveyed out.
As shown in FIG. 2, in tubs 18, 26, and 30 for cleaning the wafers with pure water and tubs 16 and 24 for cleaning wafers with chemicals, 50 pieces of semiconductor wafers 20 are housed so as to put them on chemicalproof boat 40 at regular intervals, i.e. 1 cm or 6.35 mm. Processing-liquidsupplying tube 42 for supplying a cleaning liquid, such as pure water or chemicals, is disposed in the bottom portion of each tub. As wafers arranged on boat 40, a dummy wafer can be situated at least on the side onwhich a processed surface is exposed or a monitor wafer can be placed at the preferable position. Boat 40, as shown in FIG. 3, is installed in cylinder 44, by which boat 40 can move vertically.
Boat 40 comprises arm 40a and three claws 40b extending perpendicularly from the end portion of ar 40a, as shown in FIG. 2. Wafers 20 are kept upright by three claws 40b. Further, drain 62 is formed along with an outer peripheral surface of each of cleaning tubs 16 and 18 so as to receive a cleaning liquid supplied from process-liquid supplying entrance 42 and overflown from the tub.
Drain 62 is made of side walls higher than the peripheral walls of the cleaning tub, and is large enough to fully receive the overflown cleaning liquid when boat 40 in which semiconductor wafers 20 are fully housed is dipped in the cleaning tub. Further, drain 62 has exhaust port 64. The amount of a cleaning liquid exhaustable every second from this exhaust port 64 is more than the amount of a processing liquid overflown every second from the cleaning tub. In the present embodiment, the amount of theexhausted cleaning liquid is set at more than 20 l/sec.
The first cleaning tub 16 will no be described in greater detail.
As shown in FIG. 3, cleaning liquid L for cleaning an article, e.g. semiconductor wafer 20 is stored in cleaning tub 16, which is housed in chamber 50 in a sealing-up condition. Cleaning tub 16 is made of quartz glass so as not to elute impurities to the cleaning liquid, such as pure water or chemicals. Moreover, cleaning tub 16 is mounted on a supporting stage (not shown) which is set out at the bottom portion of chamber 50, and can be adjusted to the horizontal position by means of an adjusting mechanism (not shown).
As shown in FIGS. 3 and 4, chamber 50 surrounds cleaning tub 16, and at thetop portion of chamber 50, ULPA filter 52 for supplying clean air A into chamber 50 and air supply fan 54 are provided, and exhaust air duct 56 having an exhaust air fan (not shown in the drawings) for exhausting cleanair A in chamber 50 is connected to the side wall of the bottom portion of chamber 50.
At the upper side wall of chamber 50, semiconductor wafer entrance/exit opening 58 is provided. Opening 58 can be opened/closed by shutter 60 which is vertically slidable by means of a piston, etc. Shutter 60 is adjacent to the outside surface of chamber 50, with a seal made of fluororesin (hereinafter, referred to as "PFA") or polyvinyl chloride (hereinafter, referred to as "PVC") interposed therebetween. Moreover, shutter 60 is made of quartz glass or transparent PVC, and the inside of chamber 50 is kept airtight and can be seen through shutter 60. Shutter 60has a shutter cleaning mechanism (not shown).
Boat 40 is provided in chamber 50. The boat receives semiconductor wafer 20conveyed by conveying arm (not shown) and delivers a cleaned semiconductor wafer 20 to the conveying arm when shutter 60 is opened. As previously stated, this boat 40 mainly comprises arm 40a extending from the side wallof chamber 50 into cleaning tub 16, and forked claws 40b mounted in arm 40a. Arm 40a is lowered by means of cylinder 44 connected to arm 40a, so that semiconductor wafer 20 mounted on claw 40b is dipped in cleaning liquid L during a predetermined time period.
Drain 62, which receives cleaning liquid L overflown from a notch formed atthe upper end portion of cleaning tub 16, is formed at the upper outer peripheral surface of tub 16, as shown in FIGS. 3 and 4. Cleaning liquid Loverflown into drain 62 is exhausted out of chamber 50 through liquid-exhausting pipe 64, and compressed by bellows pump 66. The liquid Lbecomes free of pulsatile motion by damper 68. Thereafter, foreign material, impurity, etc. in the liquid L is eliminated by means of filter 70. Purified cleaning liquid L returns into cleaning tub 16 through supplying pipes 42. In such a manner, cleaning liquid L is always purifiedand circulated in cleaning tub 16. Exhaust pipe 74 for exhausting the liquid L and emptying cleaning tub 16, at the time of washing the tub, is installed in cleaning tub 16.
Each of liquid-exhausting pipe 64, liquid-supplying pipe 42, and exhaust pipe 74 is made of PFA, connected to cleaning tub 16, and disposed throughthe bottom wall of chamber 50. As an example, the sealing structures of liquid-supplying pipe 42, and chamber 50 and cleaning tub 16 will be described.
In the sealing structure for a through portion of chamber 50, as shown in FIG. 6, circular body 76 made of PVC is welded in the through hole portionof the bottom wall of chamber 50 into which liquid-supplying pipe 42 is penetrated. Each of rings 78 and 80 is fixed to circular body 76 by screw 82. In the inside of ring 78, a tubular portion is formed so as to fill upa gap formed between liquid-supplying pipe 42 and chamber 50, and O-rings 84 are provided respectively between ring 78 and circular body 76 and alsobetween ring 78 and liquid-supplying pipe 42. The through portion is kept fluid-tight by O-ring 84 tightened by screw 82. Therefore, if the liquid Lis scattered out of the tub and stored at the bottom of chamber 50, there is no possibility of leaking harmful liquid out of chamber 50. Rings 78 and 80 are made of PVC, screw 82 of polyether ether ketone, and O-ring of synthetic rubber.
In the sealing structure for the connecting portion of cleaning tub 16, as shown in FIG. 7, an annular groove is formed in quartz glass pipe 86 connected with the cleaning tub as one body. C-ring 88 is engaged in this groove, and nut 90 is tightened by C-ring 88 so as not to fall down, and moreover joint 92 into which liquid supplying pipe 42 is inserted is screwed with nut 90. O-ring 84 is provided at an annular groove formed at the inner peripheral surface of joint 92. Glass tube 86 and joint 92 are fluid-supplying sealed by this O-ring 84. Therefore, there is no possibility that cleaning liquid L leaks out of this connecting portion. Cring 88, nut 90, and joint 92 are made of PFA.
As shown in FIGS. 3 and 4, flow direction adjusting plate 94 is provided above cleaning tub 16 so as to cover the space between tub 16 and chamber 50. Adjusting plate 94 is disposed on the inside wall of chamber 50 and inclines downward toward the inside wall of chamber 50. In a proper portion of adjusting plate 94 near chamber 50, hole 96 for exhausting the liquid is formed, as shown in FIG. 5. It is preferable that the distance between the top surface of the fringe of cleaning tub 16 and adjusting plate 94 is set at 10-100 mm in the vertical direction. In the present embodiment, the distance is set at 30 mm.
Punched plate 98 is provided at the lower portion of chamber 50 for rectifying the flow of clean air A. Clean air A is sucked uniformly from the entire horizontal surface of the bottom of chamber 50 through this punched plate 98. In the present embodiment, there are a number of small holes each with a diameter of 10 mm, at its opening ratio of 10%. It is preferable that the diameter of each small hole is set at 5-20 mm.
On the bottom wall of chamber 50, waste water pipe 100 to eject cleaning liquid, etc. remaining at the bottom of chamber 50 is installed. Moreover,drainage-introducing pipe 102 is connected to waste pipe 100. Mist-phase cleaning liquid contained in clean air A exhausted through the exhaust duct 56 is trapped, and resultant drainage is introduced into waste pipe 100 through introducing pipe 102. This waste pipe 100 is used for exhausting the cleaning liquid overflown from cleaning tub 16 or exhausting water with which the inside of chamber 50 has been washed.
Duct 56 is connected to a butterfly-type exhaust pressure controller (not shown) with differential pressure gauge 104 interposed therebetween. In this embodiment, differential pressure gauge 104 is electrically connectedto supplying air fan 54, with fan controller 106 for controlling the amountof wind interposed. Therefore, a differential pressure signal detected by differential pressure gauge 104 is input in fan controller 106. A control signal is output to supplying air fan 54 from fan controller 106 in order to always maintain the pressure of -5 to -10 mm H 2 O in chamber 50 with respect to the outer air. The speed of exhausting air is adjusted to 0.2 to 0.5 m/s.
The function of the cleaning device relating to the first embodiment will now be described.
Air blown from supplying air fan 54 is cleaned through ULPA filter 52, and laminer-flow clean air A is flowed from the top portion of chamber 50. On the other hand, clean air A is exhausted out of chamber 50 from exhaust duct 56 of the bottom portion of chamber 50 by means of an exhaust fan. Inchamber 50, clean air A is flowed down. The surrounding portion of cleaningtub 16 is protected by the downflow of clean air A, and adhesion of foreignmaterials or impurities to the semiconductor wafer can be reduced, so that the yield of the semiconductor product is increased.
Further, the cleaning liquid etc. remaining at the bottom of chamber 50 is exhausted through waste pipe 100 soon, and cleaning liquid L in cleaning tub 16 is always kept clean as being purified by filter 70 and circulated;therefore, the inside of chamber 50 is kept clean. Moreover, in chamber 50,since the downflow of clean air A is always flowed and maintained at negative pressure, atmosphere of the inside of chamber 50 is difficult to leak out and contamination of the outer surrounding resulting from harmfulatmosphere can be reduced.
Since flow direction adjusting plate 94 is provided at the upper portion ofthe outer peripheral surface of cleaning tub 16, if the cleaning liquid is scattered out at the time of taking in/out of the semiconductor wafer, it can be received by adjusting plate 94, so that it is possible to prevent an impurity from entering cleaning tub 16. The cleaning liquid received atthe adjusting plate 94 is exhausted downward from hole 96. Moreover, since the flowing passage of the downflow is restricted by plate 94, the flow rate can be raised near cleaning tub 16, so that the steam of the liquid can be sucked and exhausted effectively.
In order to more effectively prevent entering of fine particles, etc. from the outside at the time of opening shutter 60, it is possible to provide an air-curtain on the outside of shutter 60. Moreover, if a number of holes, as well as hole 96, for passing the downflow of clean air A throughare formed at the outside portion of adjusting plate 94, i.e. the portion near the inside wall of chamber 50, it is possible to form an advantageousair-curtain also at the inside of shutter 60.
A cleaning device relating to the second embodiment of the present invention will now be described with reference to FIGS. 8 and 9. This cleaning device is a line-type, e.g. cleaning tubs are arranged side by side. The description relating to the same portion a that of the first embodiment will be omitted.
Cleaning device 110 comprises transverse body 112, in which the cleaning chamber is separated into four compartment 114a, 114b, 114c, and 114d by three shutters 116a, 116b, and 116c. The front surface of body 112 is covered with front panel 120 having transverse slit 118 which is formed along the convey passage for conveying a wafer in the chamber.
Robot arm 130 is formed in front of body 112. The arm has two arms 132 which are inserted into the chamber through said slit 118, and shifts horizontally.
The first compartment 114a has loading stage 115 for taking in/out wafers. A wafer holding portion and a wafer lifting mechanism (not shown in the drawings) are provided on this loading stage 115.
The second compartment 114b has three cleaning tubs 122a, 122b, and 122c; the first cleaning tub 122a is used as a chemical process tub in which an ammonia process is performed, and the second and third cleaning tubs 122b and 122c are used as quick dump rinse (QDR) process tubs in which washing is performed. Each tub has elevating mechanism 123 for holding and conveying wafers in/out of the tub.
The third compartment 114c also has three cleaning tubs 124a, 124b, and 124c; the fourth cleaning tub 124a is used as a chemical process tub in which a fluoric acid process is performed, the fifth cleaning tub 124b is used as a washing overflow processing tub, and the sixth cleaning tub 124cis used as a washing final rinse tub. Each tub has elevating mechanism 123 for holding and conveying wafers in/out of the tub.
The fourth compartment 114d has drying tub 126 and unloading stage 128. In drying stage 126, wafer holding mechanism 127 is provided, and in unloading stage 128, like loading stage 115, an wafer holding portion and an wafer lifting mechanism (not shown) are provided.
In the cleaning device disclosed in the present embodiment having such a structure as described above, the following processes are performed: about50 pieces of semiconductor wafers are conveyed in loading stage 115 by a loading robot (not shown in the drawings), the first shutter 116a is opened, the wafers are conveyed from loading stage 115 to the first cleaning tub 122a, and thereafter the shutter 116a is closed. After an alkali cleaning process, the wafers are conveyed orderly to, and cleaned in, the second cleaning tub 122b and the third cleaning tub 122c.
Thereafter, a second shutter 116b is opened, the wafers are conveyed to thefourth cleaning tub 124a by robot arm 130, and the shutter 116b is closed. After an acid cleaning process, the wafers are washed in the fifth and sixth cleaning tubs 124b and 124c. Finally, the wafers are conveyed to drying tub 126 in the same manner as the above second and third compartments.
After wafers 20 are dried in drying tub 126, the wafers are conveyed to unloading stage 128, and taken out by an unloading robot (not shown).
In the cleaning device of this embodiment, filter unit 134 having an air-supplying fan is provided on the upper portion of each compartment, and the downflow is formed in each of the compartments. Moreover, the sameexhaust duct (not shown) as disclosed in the first embodiment is provided on the lower portion of each compartment. Therefore, in each compartment, elimination of fine particles and suction or exhaustion of vapor of chemicals is performed.
Opening/closing door 140 is provided on the front surface of each of compartments 114a and 114d having loading stage 115 and unloading stage 128 and it is opened/closed when the wafers are taken in/out.
As stated above, the compartments are separated by shutters 116a, 116b, and116c. When conveying arm 130 horizontally moves between the compartments, the shutter by which the compartments are separated is opened, and the shutter is closed after arm 132 holding wafers 20 has passed through. Therefore, it is possible to suppress inflow of atmosphere of one compartment to another compartment.
As the above first and second embodiments, carrierless conveying and cleaning device of a semiconductor wafer has been described. The present invention can also be applicable to a cleaning device using a carrier.
Additional advantages and modifications will readily occur to those skilledin the art. Therefore, the invention in its broader aspects is not limited to the specific details, representative devices, and illustrated examples shown and described herein. Accordingly, various modifications may be madewithout departing from the spirit or scope of the general inventive conceptas defined by the appended claims and their equivalents. | A cleaning device comprises at least one cleaning tub containing a cleaning liquid, a chamber housing the cleaning tub, a mechanism for taking an article to be cleaned in/out of the cleaning liquid in the cleaning tub, and a shutter for shutting the inside of the chamber from the outside thereof. The shutter opens when a cleaned material is conveyed in/out of the chamber, thereby passing the cleaned material there through. A clean air supplying unit for forming downflow of clean air around the cleaning tub is provided on the upper portion of the chamber. A exhausting unit for sucking the clean air passing around the cleaning tub and exhausting the air out of the chamber is provided on the lower portion of the chamber. | 8 |
FIELD OF THE INVENTION
The present invention relates to a washing machine capable of washing, dewatering and drying a laundry article; and, more particularly, to a method for controlling a laundry dryer incorporated in the washing machine.
DESCRIPTION OF THE PRIOR ART
Generally, there are two categories of washing machines which are in practical use for the purpose of washing laundry articles such as clothes. A first category involves a vortex-type washer wherein the laundry articles are subjected to a washing action as a pulsator therein rotates to generate a vortex flow within a washer tub. Such a vortex-type washer may encompass, in a broad sense, a stirrer-type washer wherein the laundry items are made to undergo vigorous frictional movement in the washing fluid by means of a bladed stirrer. Normally, the conventional vortex-type washer is not equipped with a drying mechanism therein.
A second category involves a drum-type washer having a horizontal rotary drum partially submerged in a laundering water. With this type of washer, the laundry articles contained in the rotary drum are rubbed against each other as the drum rotates about its horizontal axis. U.S. Pat. No. 5,058,401 issued to Fumio Nakamura et al. illustrates one of the second-type washers that can wash, dehydrate and dry the laundry. During the drying process of the laundry articles dewatered at a preceding dewatering process, an inner tub containing the dewatered laundry articles is rotated about a horizontal axis, heated air is supplied to the inner tub, and the laundry subjects are uniformly exposed to the hot air to dry.
Conventionally, the heated air should be concentrated on a point of the dewatered laundry articles for at least 60 seconds in order to ensure them to dry. However, in the second-type washer, the hot air is distributed to the entire area of the inner tub due to its continuous revolution during the drying process, to thereby result in an extended drying time period and loss of power.
SUMMARY OF THE INVENTION
It is, therefore, an object of the invention to provide a vortex-type washing machine having a laundry dryer therein.
It is another object of the invention to provide a method for controlling the laundry dryer in the vortex-type washing machine during a drying process.
In accordance with the present invention, there is provided an improved method for controlling a drying process of a vortex-type washing machine which has a tub capable of accommodating a laundry article for drying therein, a heating means, a pulsator rotatably mounted on the bottom surface of the tub, a motor for rotating the pulsator, wherein the method comprises the steps of: (A) providing heated air to the tub by using the heating means; (B) driving the motor in a forward direction; (C) driving the motor in a backward direction; and (D) repeating the steps (B) and (C) until the laundry article becomes dried to a desired level. Further, each of the steps (B) and (C) includes the steps of: (a) turning on the motor to rotate the pulsator to spread the laundry article; (b) turning off the motor to pause the rotation of the pulsator to thereby help the settlement of the laundry article; and (c) repeating the steps (a) and (b) at least N number of times. The method further comprises, between the steps (B) and (C), a step of: (E) stopping the driving of the motor before the switching from the forward direction to the backward direction and vice versa for a predetermined period to expose the spread laundry article to the heated air.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other objects and features of the present invention will become apparent from the following description of preferred embodiments taken in conjunction with the accompanying drawings, in which:
FIG. 1 shows a schematic sectional view of the overall structure of a vortex-type washing machine equipped with a laundry dryer in accordance with the present invention;
FIG. 2 illustrates a schematic block diagram of a control device in accordance with the present invention;
FIG. 3 is a graph describing the relationship between the degree of drying and the drying efficiency; and
FIGS. 4A and 4B are flow charts explaining the control sequence executed by the control device shown in FIG. 2.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to FIG. 1, there is shown a washing machine equipped with a laundry dryer in accordance with the present invention. The washing machine 10 comprises a housing 12 and a stationary washer tub 14 fixedly mounted within the housing 12 for containing therein a level of washing fluid or detergent solution. Connected to the bottom of the stationary washer tub 14 are an electrical motor 30 and a clutch assembly 32 coupled to the electrical motor 30 by a belt-pulley assembly 34. As shown, the electrical motor 30 and the clutch assembly 32 are both secured to the stationary washer tub 14 by means of suitable fastener means, e.g., welding or threading. The electrical motor 30 is capable of rotating depending upon the drying process, in a clockwise or counterclockwise direction, and, the clutch assembly 32 serves to selectively couple the driving force generated by the electrical motor 30 with one of a first and a second driven shafts 36 and 38.
The first driven shaft 36 carries at its top end a rotatable washer tub 16 which is kept immovable during the washing process but is caused to rotate at a high speed during the dewatering process. The rotatable tub 16 is provided with, at its side wall, a plurality of washing fluid communication holes 40 permitting the washing fluid to flow into or out of the rotatable tub 16.
Rotatably mounted on the bottom surface of the rotatable tub 16 is a pulsator 20 carried by the second driven shaft 38. The pulsator 20 is rotatable in a forward or backward direction to create a vortex flow within the rotatable tub 16.
In a top portion of the housing 12, there is provided a heater 26 for heating ambient air and a fan 28 for blowing the heated air into the rotatable tub 16 under the control of a control device 100. The air blown by the fan 28 is entered into the rotatable tub 16 through an inlet 42 to circulate therein. After the completion of the circulation, a portion of the air is directly discharged via the top of the rotatable tub 16 through an outlet 46, and another portion of the air is discharged via the holes 40 and the passage between the top of the rotatable tub 16 and the lid of the stationary tub 14 through the outlet 46.
FIG. 2 shows a schematic diagram of the control device 100 for controlling the drying process of the washing machine 10. The control device 100 comprises a switch pad 50, a detection block 60, a microprocessor 70, and a load drive circuit 90. As shown in FIG. 2, the switch pad 50 and the detection block 60 are connected to the inputs of the microprocessor 70, and the load drive circuit 90 is connected to the outputs of the microprocessor 70.
The switch pad 50 includes a drying mode selection switch 52 and a drying time period selection switch 54 for manually selecting a drying time period. When the drying mode is selected by the drying mode selection switch 52 and the drying time period is set through the use of the drying time period selection switch 54, a drying mode selection signal indicative of the drying process for the laundry articles to dry is issued to the microprocessor 70. The microprocessor 70, in response to the drying mode selection signal, executes the drying process for the drying time period manually selected by the drying time period selection switch 54 or a predetermined drying time period which will be discussed hereinafter.
The detection block 60 includes a load sensor 62 for detecting the weight of the laundry articles in the rotatable tub 16 and a temperature sensor 64 for detecting the temperature in the rotatable tub 16. The load sensor 62 and the temperature sensor 64, as well known in the art, after detecting the weight and the temperature, issue a load signal indicative of the weight of laundry articles and a temperature signal indicative of the temperature to the microprocessor 70, respectively.
The microprocessor 70 may be of any type suitable for such control purpose, which has a storage region therein or a separate memory device. The storage region may contain a plurality of drying control programs stored in the form of instructions and data. Each drying control program may be selected with the load signal from the load sensor 62. The microprocessor 70 may execute and process a series of instructions and data in response to the load signal to provide control signals to the load drive circuit 90.
The load driving circuit 90 has a fan driving circuit 92 and a motor driving circuit 94. The fan driving circuit 92 is responsive to a fan control signal from the microprocessor 70 to enable the fan 28, shown in FIG. 1, to blow the heated air produced by the heater 26. The motor driving circuit 94 is responsive to a motor control signal from the microprocessor 70 to energize the motor 30 for the control of the pulsator 20. The motor control signal includes forward and reverse driving signals, which are repeatedly sent to the motor drive circuit 92 during the drying process. Accordingly, the motor 30 is alternately rotated in the forward and backward directions to cause forward and backward rotations of the pulsator 20.
In accordance with a preferred embodiment of the invention, in the course of each of the forward and reverse direction rotations, the motor 30 is repeatedly subjected to the ON/OFF control to cause the pulsator 20 to periodically rotate and pause in each direction.
The periodic repetition of the rotation and the pause states of the pulsator 20 is performed for N number of times whenever the rotation direction is reversely changed where N is a positive integer (N=1, 2, 3, . . . ). The number N is preferably from 2 to 4, as will be illustrated below.
The periodic repetition of rotation and pause of the pulsator 20 helps to untie or set loose the laundry items which may have been entangled during the dewatering process. It has been found that the laundry articles can be effectively untangled by rotating the pulsator 20 at an angle of not more than 180°, most preferably approximately 90°, from the pause state. The rotation of the pulsator 20 at the angle of 90° is achieved by turning the motor on for a time period "T 1 " of about 0.2 to 0.4 second.
The periodic pause state between rotations of the pulsator 20 is employed to settle down the laundry articles which have been agitated during the rotation of the pulsator 20; and may continue for a time period "T 2 " ranging from about 0.3 to 1 second, preferably, 0.6 second.
Further, the motor 30 may preferably be controlled to a stop to have the pulsator 20 in an idle state for a predetermined time period "T 3 " after the completion of the periodic repetition for the N number of times before turning from the forward direction to the backward direction and vice versa. The time period for the pause state permits the heated air to sufficiently concentrate on the exposed portion of the laundry load to thereby improve the drying efficiency. The stop state of the motor 30 can be made to continue in time intervals of, e.g., about 20 to 30 seconds, preferably, 20 seconds.
FIG. 3 is a graph showing the data for the different levels of dryness obtained by applying various conditions, which are empirically obtained by way of conducting the drying process with the N values of 2 and 3 and the intervals of 20 to 40 seconds. In this connection, it is assumed that the motor is rotated at the angle of 90° as set forth above.
As can be seen from the graph, the data exhibits a higher level of dryness when the number N is 3 and the time period is 20 seconds. In addition, although it is not shown herein, essentially same results are obtained even if the number N is 4, 5, or higher.
Referring now to FIGS. 4A and 4B, there is illustrated a flow diagram explaining the operation of the drying process, wherein the control operation begins at block 112 where the weight of the laundry articles is detected by the load sensor 62 when the drying mode selection switch 52 is depressed by the user. The detected weight by the load sensor 62 is signaled to the microprocessor 70.
In step 114, the microprocessor 70 automatically sets a drying time period "T D " with the detected weight as listed in Table 1.
TABLE 1______________________________________ Weight ofWeight of dewatereddried laundry laundry Timearticles(kg) articles(kg) period(min.)______________________________________1 1.82 602 3.7 1203 5.45 1804 7.27 240______________________________________
The time period for drying may be also set as the one selected by the drying time period selection switch 54.
In steps 116 and 118, the heater 26 and the fan 28 are driven under the control of the microprocessor 70 to heat ambient air and blow the heated air into the rotatable tub 16 through the inlet 42. And then the control process proceeds to step 120 where it is determined whether the temperature "H B " in the rotatable tub 16 reaches a predetermined temperature "H T " necessary to dry the laundry articles, e.g., a temperature of 30° C. If the temperature H B reaches the predetermined temperature H T , the control process flows to steps 122 and 124 where the pulsator 20 is rotated at an angle of 90° for the first predetermined time period "T 1 " and then paused for the second predetermined time period "T 2 ".
As in step 126, the repetitive rotation and pause states of the pulsator 20 are be repeated for the N number of times, e.g., 3. Thereafter, the control process goes to step 128 to make the pulsator 20 the idle state for the third predetermined time period "T 3 ".
After the lapse of the third time period T 3 , the rotation direction of the motor 30 is changed to the reverse direction in step 130 and the control process advances to step 132.
In step 132, it is checked whether the time period "T S " spent to dry the laundry articles reaches the predetermined drying time period T D as set forth in step 114. If the test result is NO, the control process returns to step 122 and the operation as mentioned above is continued therefrom until the time period T S lapses the predetermined time period T D . If, however, the test result is YES, the control process goes to step 134 and then step 136 where each of the heater 26 and the fan 28 is turned off to finish the drying process.
While the present invention has been shown and described with respect to the preferred embodiments, it will be apparent to those skilled in the art that many changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. | A method for controlling the drying process of a vortex-type washing machine capable of accommodating a laundry article for drying therein comprises the steps of (A) heating an ambient air by a heater, (B) driving a motor in a forward direction, (C) driving the motor in a reverse direction to the forward direction, and (D) repeating the steps (B) to (C) until the laundry article become dried to a desired dry level, wherein each of the steps (B) and (C) includes the steps of (a) turning on the motor to rotate the pulsator to spread the laundry article; (b) turning off the motor to pause the rotation of the pulsator to thereby help the settlement of the laundry article; and (c) repeating the steps (a) to (b) at least N number of times. | 3 |
BACKGROUND
The present invention generally relates to cable television (CATV) and consumer video communication systems. More particularly, the invention relates to a dual-conversion universal modulator having programmable synthesized phase-locked loop oscillators driving their respective mixers which select a specific HI-IF frequency depending upon what output frequencies or standards are desired. Such standards include NTSC, PAL, NICAM, DIN, SECAM and any other known standard.
To allow reception of more than the 12 VHF channels on an older television receiver, most CATV systems require a settop terminal at a subscriber's location. Today, settop terminals not only provide a means for accepting a plurality of channels broadcast with varying bandwidths and guardbands for forward and reverse frequencies, but they also secure pay television services from unauthorized viewing. Other functions include decoding digital video and audio, interactive services, creating personalized viewer channels and the like.
In addition to the conversion from a cable transmission to a standard output frequency, a variety of descrambling techniques are employed depending upon the techniques used at a system headend. CATV equipment manufacturers are developing more sophisticated scrambling techniques using complicated encryption methods and digital processing to thwart pirating.
Most settop terminals are tunable. A block diagram for a prior art settop terminal is shown in FIG. 1 . Incoming signals from a CATV transmission network are coupled to an input bandpass amplifier and up-converted to a high intermediate frequency (HI-IF). The up-conversion requires a tunable local oscillator which selects a desired channel and an associated mixer. The mixer is coupled to a bandpass filter and down-converted to an IF channel using a fixed-frequency local oscillator and mixer. The output channel is filtered and forwarded to a subscriber's television receiver. Prior art settop terminals use one down-converter mixer with an oscillator having slight frequency agility to provide an output at one or two preselected channel frequencies. The output frequencies and bandwidths depend upon the transmission standard used.
In the United States, the NTSC (National Television System Committee) is the standard for color television. Other countries have chosen different systems. SECAM (sequentiel couleur avec mémoire) is used by France and Russia. PAL A and PAL B (phase alternation line) are used by many European countries such as Germany and the United Kingdom. Accordingly, television receivers are typically manufactured for a specific transmission standard. For worldwide use, a settop terminal must be adapted to the established broadcast standards.
U.S. Pat. No. 5,640,697 teaches the use of two predetermined frequencies for each local oscillator, whereby the second oscillator frequency can be adjusted independently of the first oscillator frequency. Adjustment between the two frequencies is used to adapt to the different output frequencies, while eliminating noise caused by the local oscillators. Similar to U.S. Pat. No. 5,640,497, German Patent No. Application 4,306,578 adjusts the oscillator frequencies by a predetermined amount in order to eliminate noise. PCT International Patent Application No. 84/04637 employs two local oscillators that generate predetermined frequencies, in which the second oscillator is selected between one of two frequencies to eliminate this noise.
Accordingly, there exists a need for an inexpensive method to adapt the output of a settop terminal to a variety of television broadcast standards.
SUMMARY
The present invention is a universal modulator that accepts baseband audio and video inputs and modulated audio or data and converts the combined signal to one of a plurality of frequencies in dependence upon a desired output frequency and broadcast standard. The universal modulator is located between baseband video and audio outputs of a settop terminal demodulator/decoder and an antenna input of a television receiver or other audio/video component (such as a VCR). The universal modulator includes a dual conversion architecture using an up-converter mixer and a down-converter mixer. Each mixer receives an oscillator input from a corresponding addressable, programmable, PLL (phase-locked loop) frequency synthesizer. Each PLL frequency is controlled by firmware in the settop terminal. Configuration is performed via manual input using settop terminal controls, or interrogation directly by the CATV headend or by programmed settings. A communication bus coupled to the firmware distributes addressable instructions to selectively control each PLL frequency and obviate oscillator difference beat frequencies (ODBFs) that may be manifested.
Accordingly, it is an object of the present invention to provide a universal modulator within a settop terminal which is able to couple a CATV transmission network to a customer's television receiver notwithstanding the broadcast standard used to transmit the television programs.
Other objects and advantages will become apparent to those skilled in this art after reading the detailed description of the preferred embodiment.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram of a prior art CATV settop terminal.
FIG. 2 is a block diagram of a settop terminal incorporating the present invention.
FIG. 3 is a block diagram of the preferred embodiment of the universal modulator of the present invention for use in a settop terminal.
FIG. 4 is a block diagram of an addressable, programmable, phase-locked loop.
FIG. 5 is a flow chart of the universal modulator configuring process.
FIG. 6 is a flow chart of the ODBF translation process.
FIG. 7 is a block diagram of a prior art headend.
FIG. 8 is a block diagram of a headend made in accordance with the present invention.
FIGS. 9A and 9B are graphs of oscillator difference beat frequencies.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The preferred embodiment will be described with reference to the drawing figures where like numerals represent like elements throughout.
FIG. 2 is a block diagram of a settop terminal 17 with a universal modulator 19 shown coupled to the outputs 23 , 25 , 27 of a demodulator/decoder 21 . The demodulator/decoder 21 supplies a customer's channel selection to the universal modulator 19 as a baseband audio signal via the output 23 and as a baseband video signal via the output 25 . An alternate (second) audio signal, such as a NICAM carrier or modulated audio signal which differs from the baseband audio signal, may also be supplied to the universal modulator 19 via the output 27 of the demodulator/decoder 21 . A reference clock signal 37 originating from a master oscillator (not shown) and a common communication bus 39 are also coupled to the universal modulator 19 . The functional description of the demodulator/decoder 21 is beyond the scope of the present invention and shall not be described in further detail.
The higher quality baseband audio and video signals provided by outputs 23 and 25 of the demodulator/decoder 21 are made available as settop terminal outputs 31 , 33 , respectively, and may be coupled to television receivers that have baseband inputs. The alternate audio signal provided by output 27 may be made available as settop terminal output 29 . For television receivers that lack these features, the universal modulator 19 provides an up-conversion output 35 compatible with the television broadcast standard used, from baseband to VHF or UHF for coupling to an antenna input.
The universal modulator 19 is shown in more detail in FIG. 3 . The common communication bus 39 shown is an I 2 C interface from Phillips® Electronics. Other bus communication protocols may alternatively be used. The configuration for a settop terminal 17 may be downloaded from the CATV system headend via a dedicated channel, or inband on the VBI of a channel. One skilled in this art would appreciate that an advanced cable system can address and interrogate a specific settop terminal and alter its functionality. If the settop terminal has all configurations stored in firmware, the CATV system headend may simply instruct the settop terminal 17 of the standard being used. In this fashion, the settop terminal 17 does not require a technician to configure the unit but can auto-configure upon initial energization.
The communication bus protocol permits configuring component parameters to a particular broadcast standard using a unique addressing system within the settop terminal 17 . As shown in FIG. 3 , the I 2 C bus 39 communicates with: an addressable programmable PLL frequency synthesizer 41 for a baseband audio mixer 69 , a solid state switch 43 , adjustable amplifiers for the baseband video input 45 and baseband audio input 47 , an addressable programmable PLL frequency synthesizer 49 for an up-conversion mixer 91 and an addressable programmable PLL frequency synthesizer 51 for a down-conversion mixer 101 . Although the addressable programmable PLL frequency synthesizer 51 has been described as being coupled to a “down-conversion” mixer 101 , the down-conversion mixer 101 may in fact further up-convert a HI-IF signal 93 to a higher frequency signal. It should be noted that each PLL frequency synthesizer 41 , 49 , 51 has an associated oscillator driver L01, L02, L03 respectively (not shown). Each respective component has its own address to permit firmware contained parameters to be loaded for a given broadcast standard configuration.
An alternate (second) audio carrier 53 , provided by the output 27 of the demodulator/decoder 21 , is coupled to the solid state switch 43 . The output of the switch 43 is coupled to a first input 55 of a summing amplifier 57 . The baseband video input 59 is coupled to a clamp 61 which limits signal amplitude. The output from the clamp 61 is coupled to the video adjustable amplifier 45 where signal gain is increased or attenuated depending upon the broadcast standard. The output from the adjustable amplifier 45 is coupled to a hard limiter 63 which clips signal peaks. The output from the limiter 63 is coupled to a second input 65 of the summing amplifier 57 . The baseband audio input 67 is coupled to a baseband audio mixer 69 via an adjustable amplifier 68 . The baseband audio mixer 69 modulates the baseband to the broadcast standard. The baseband audio mixer 69 may be selectively activated or deactivated by the I 2 C bus as required to support the standard in use. The output from the baseband audio mixer 69 is coupled to a lowpass filter 71 to remove RF. A second input to the audio lowpass filter 71 is provided as a modulated audio input 72 . The audio lowpass filter 71 is coupled to an audio adjustable amplifier 47 where signal gain is increased or attenuated. The audio adjustable amplifier 47 output is coupled to a third input 73 of the summing amplifier 57 .
Each of the mixers mix a signal input with the outputs of the three addressable, programmable PLL frequency synthesizers 41 , 49 , 51 . The PLL output frequencies vary depending on the broadcast standard and the RF output frequency 105 desired. An addressable, programmable PLL frequency synthesizer 41 , 49 , 51 is shown in FIG. 4 .
The PLL 41 , 49 , 51 includes a phase detector 75 , a voltage-controlled oscillator (VCO) 77 and a loop filter 79 . The programmable PLL uses digital and analog techniques for frequency synthesis. The phase detector 75 compares two input frequencies 81 a , 81 b and generates an output 83 that is a measure of their phase difference. If both inputs 81 a , 81 b differ in frequency, the output is periodic at the difference frequency. If the frequency input does not equal the frequency output of the VCO 77 , the phase-error signal, after being filtered, causes the VCO frequency to deviate in the direction of the input frequency. When the frequencies match, the VCO 77 locks to the input frequency maintaining a fixed phase relationship with the input signal. The filtered output of the phase detector 75 is a dc signal. A modulo-n counter 87 is coupled between the VCO 77 output and the second input 81 a to the phase detector 75 to generate a multiple of the input reference frequency providing frequency synthesis.
Each PLL synthesizer 41 , 49 , 51 employed in the present invention 19 is addressable such that the input frequency can be adjusted by using an input modulo-n counter 89 or divide-by-n to adjust output frequency. Both the input frequency divide-by-n 89 and loop frequency divide-by-n 87 are addressable components. Each of the PLLs 41 , 49 , 51 are addressed and controlled in accordance with a predetermined settop terminal 17 configuration. The configuration determines both the output frequency and operating bandwidth of the settop terminal 17 and adjusts the up- and down-converter PLLs 49 , 51 accordingly.
Referring back to FIG. 3 , the summer amplifier 57 output is modulated with the frequency output from the second programmable PLL 49 to drive the up-conversion mixer 91 and translate the summed output to a high intermediate frequency (HI-IF) 93 . The HI-IF 93 is higher than the highest expected frequency in the summed amplifier 57 output bandwidth. In the present invention 19 , the input to the up-conversion mixer 91 is not bandwidth limited.
The summing amplifier 57 output frequencies are translated to a new bandwidth, starting at a low frequency of the second PLL 49 minus the highest input band frequency, and ending at a high frequency of the third PLL 51 minus the lowest input band frequency. The second PLL 49 frequency is selected to translate the summing amplifier 57 output to correspond to the passband of an intermediate lowpass filter 95 . The output from the lowpass filter 95 is coupled to a buffer amplifier 97 to restore gain losses. The output from the buffer amplifier 97 is input to a final lowpass filter 99 . The buffer amplifier 97 maintains the system noise figure by overcoming the losses in the up-conversion mixer 91 and first HI-IF filter 95 . The signal is filtered by a HI-IF filter 99 , with the output coupled to a down-conversion mixer 101 . The third PLL synthesizer 51 is coupled to the down-conversion mixer 101 . The difference between the HI-IF 93 and the third PLL 51 frequency is the desired output channel in the IF band. It should, however, be noted that the down-conversion mixer 101 may accept the HI-IF 93 and further up-convert the signal to a higher frequency RF signal. The output is then filtered via a low pass filter 103 , (or other appropriate filter if up-converted), and forwarded as an RF output frequency 105 for reception by a television receiver.
As discussed above, the second 49 and third 51 programmable PLLs are controlled by the common communication bus 39 . The bus 39 is coupled to a processor in the settop terminal demodulator/decoder 21 which receives instructions from the system headend or from the settop terminal's 17 keypad. The configuration takes place transparently upon initial energization of the unit 17 if the system headend is equipped to send broadcast configuration instructions to the settop terminal 17 . If the system headend does not have this capability, the settop terminal 17 is configured via the keypad and function display (not shown). The configuration request, whether from the headend or at a consumer location, outputs the predetermined parameters onto the I 2 C bus 39 for each of the addressable components. The predetermined parameters are related to the standard that is being employed by the CATV system on which the settop terminal 17 is located. These parameters will include the determination of whether a second audio carrier 53 exists, whether the baseband audio input 67 or the modulated audio input 72 are to be used and the frequency at which the RF output frequency 105 is desired. These parameters may also include any other configurable parameters which are employed by any of the addressable components coupled to the communication bus 39 . It should also be recognized that since many of the components are addressable by the communication bus 39 , a user may manually input and address a particular component and selectively configure that component if desired.
An undesirable artifact of dual conversion is the generation of harmonics based on the fundamental oscillator frequencies. The harmonics of the second and third PLL frequency synthesizers 49 , 51 mix with each other, thereby creating ODBFs. To obviate the intrusive effects of these PLL harmonics, the system and method of the present invention 119 eliminate this type of interference by translating the significant ODBFs out of the desired output channel.
A flowchart of the preferred method of the present invention 19 is shown in FIG. 5 . Upon making the necessary connections to the CATV cable 15 and subscriber's television receiver, the settop terminal 17 is energized (step 201 ) establishing communication with the system headend. If the cable system headend has forward communication ability (step 205 ), the settop terminal is instructed how to configure itself for the applicable broadcast standard by downloading the parameters for the regional standards being used and the channel broadcast maps (step 207 ). The predetermined PLL frequencies derived from the channel and broadcast maps in memory are converted into corresponding “divide-by” numbers for the PLL modulo-n, converters 87 , 89 and output to the second 49 and third 51 PLL frequency synthesizers. The settop terminal 17 acknowledges when configuration is complete. If the cable system does not have forward communication capability, the user will be prompted to enter the applicable information via a display and keypad, thereby manually loading the applicable broadcast configuration (step 209 ).
The settop terminal 19 reviews the loaded channel and broadcast maps. The predetermined frequencies are examined for potential ODBFs (step 211 ). If it is determined that ODBF's are likely (step 213 ), an ODBF translation is performed (step 215 ) as shown in FIG. 6 (which will be explained in greater detail hereafter). Otherwise, the original frequencies are maintained (step 217 ) ( FIG. 5 ) The frequencies are addressed to their respective PLL synthesizers as words over the I 2 C communication bus (step 219 ).
Referring to the flow diagram of FIG. 6 , the elimination of ODBFs is achieved by selectively adjusting the frequencies of the second 49 and third PLLs 51 to obtain the desired RF output frequency. For a typical NTSC signal, the up-converter mixer 91 modulates the input video 59 and audio signals 67 with the output 93 of the second PLL 49 to up-convert the input RF signal of the selected channel to the HI-IF 93 (step 301 ).
L01=audio carrier frequency (Equation 1)
L02=HI-IF (Equation 2)
The down-converter mixer mixes 101 the HI-IF 93 with the output of the third PLL synthesizer 51 (step 303 ) to down-convert, (or further up-convert if desired), to obtain the desired RF output frequency 105 .
L 03=( HI - IF )+ RF output (Equation 3)
Multiples of the second and third PLL synthesizer 49 , 51 fundamental frequencies define the even and odd harmonics,
m(L02) and m(L03), for m=1, 2, 3, 4, . . . ∞, (Equation 4)
which represent all possible harmonics (step 305 ). However, due to the high system frequencies involved, examination of frequencies beyond the 10th harmonic is unnecessary.
The existence of an interfering ODBF is determined by serially calculating the differences between two harmonics of the second 49 and 51 third PLL synthesizers that are separated by at least one degree until the absolute value of an ODBFm,n is within a given bandwidth or a predetermined number of ODBFm,n values are calculated. When an ODBFm,n absolute value is found within the RF channel bandwidth, it is designated as an interfering oscillator difference beat frequency (ODBF). The general equation for calculating ODBFs is:
OBDF m,n =( m+n ) ( L 02)−( m )( L 03), for m=1, 2, 3, 4, . . . 10, (Equation 5)
with n=1 for a first series, n=2 for a second series, n=3 for a third series, and so on up to n=8 for all previously calculated harmonics (step 305 ). The ODBFm,n calculated from the differing degrees of the second 49 and third PLL 51 harmonics are then examined (step 307 ). For example, if the ODBF lies outside of the desired RF output channel bandwidth, no adjustment of the second 49 and third 51 PLL frequency synthesizers is required.
For an ODBF which falls inband, the following equations can be used to determine which direction the second 49 and third 51 PLL frequencies should be adjusted to translate the ODBF out of band. In these equations, CLB is the channel low-band; CMB is the channel mid-band; and CHB is the channel high-band.
If −CHB≦ODBF<−CMB; then HI-IF is moved downward. (Equation 6A)
(If the result of Equation 5 is negative and the magnitude is greater than the mid-band of the desired RF output channel (step 309 ), the HI-IF is moved downward (step 311 )).
If −CMB≦ODBF<−CLB; then HI-IF is moved upward. (Equation 6B)
(If the result of Equation 5 is negative and the magnitude is less than or equal to the mid-band of the desired RF output channel (step 313 ), the HI-IF is moved upward (step 315 )).
If CLB≦ODBF≦CMB; then HI-IF is moved downward. (Equation 6C)
(If the result of Equation 5 is positive and the magnitude is less or equal to than the mid-band of the desired RF output channel (step 317 ), the HI-IF is moved downward (step 319 )).
If CMB<ODBF≦CHB; then HI-IF is moved upward. (Equation 6D)
(If the result of Equation 5 is positive and the magnitude is greater than the mid-band of the desired RF output channel (step 321 ), the HI-IF is moved upward (step 323 )).
The second 49 and third 51 PLLs are then adjusted (step 327 ) in accordance with the following: To translate the oscillator difference beats below or above the desired RF output channel, the following equation is used to determine the A in frequency for the second 49 and third 51 PLL frequency synthesizers.
Δ
=
CMB
-
[
(
m
+
n
)
(
LO2
)
-
m
(
LO3
)
]
(
m
+
n
)
-
m
(
Equation
7
)
The new second 49 and third 51 PLL frequencies (L02′ and L03′ respectively) are derived as shown in L02′ is calculated as shown in FIG. 6 .
The new PLL frequencies L02′ and L03′ translate the ODBFs above or below the desired RF output channel. The new PLL frequency values are used to program the second 49 and third 51 PLL frequency synthesizers (step 327 ).
In an alternative embodiment, a fixed value for Δ can be used to simplify the calculations and the operation of the system. For example, a value of 4 MHz for Δ will suffice for NTSC and PAL systems.
The present invention will now be explained with reference to several examples. In the first example, if the HI-IF is 960 MHz and the desired RF output channel has a picture carrier frequency of 319.25 MHz, we have the following:
L02=HI-IF=960 MHz; and (from Equation 2)
LO3
=
HI
-
IF
+
RF
output
=
960
+
319.25
=
1279.25
MHz
.
(
from
Equation
3
)
The graph for ODBFs versus the RF output frequencies for m=2 and n=1 is shown in FIG. 9A . If m=2 and n=1, then:
ODBF
2
,
1
(
960
)
=
(
m
+
n
)
(
LO2
)
-
m
(
LO3
)
=
3
(
960
)
-
2
(
1279.25
)
=
2880
-
2558.5
=
321.5
MHz
(
from
Equation
5
)
Since the desired RF output channel has a picture carrier frequency of 319.25 MHz (and assuming the bandwidth is 6 MHz for an NTSC channel), the ODBF is in-band for the desired RF output channel. From Equation 6D, since the ODBF is above the mid-band of the desired RF output channel, the HI-IF is moved upward. Assuming that Δ will be a fixed value of 4 MHz, L02′ will be 964 MHz and L03′ will be 1283.25 MHz.
Accordingly, from Equation 5:
ODBF
2
,
1
(
964
)
=
3
(
964
)
-
2
(
964
+
319.25
)
=
2892
-
2566.5
=
325.5
MHz
The ODBF is now out of band.
In the second example, if the HI-IF is 960 MHz and the desired RF output channel has a picture carrier frequency of 481.25 MHz, we then have the following:
L02=HI-IF=960 MHz; and (from Equation 2)
LO3
=
HI
-
IF
+
RF
output
=
960
+
481.25
=
1441.25
MHz
.
(
from
Equation
3
)
The graph for ODBFs versus the RF output frequencies for m=3 and n=1 is shown in FIG. 9B . If m=3 and n=1, the ODBF can be calculated as:
ODBF
3
,
1
(
960
)
=
4
(
960
)
-
3
(
1441.25
)
=
3840
-
4323.75
=
-
483.75
MHz
.
(
from
Equation
5
)
Since the selected channel is 481.25 MHz, (and assuming an NTSC channel), the ODBF is in-band and the HI-IF must be relocated. The result of Equation 5 for this example is negative and the magnitude is greater than the mid-band of the desired RF output channel (481.25 MHz). Accordingly, from Equation 6A, the HI-IF is moved lower. Assuming that A will be a fixed value of 4 MHz, L02′ will be 956 MHz and L03′ will be 1437.25 MHz. Recalculating the ODBF provides:
ODBF
3
,
1
(
956
)
=
4
(
956
)
-
3
(
956
+
481.25
)
=
3824
-
4311.75
=
-
487.75
MHz
.
(
from
Equation
5
)
The ODBF is now out of band.
Due to the simple design of the present invention and since there are no shielding requirements to avoid ODBFs, the universal modulator may be incorporated onto a single integrated circuit. This was not possible with prior art signs.
Although the present invention has been described with reference to a settop terminal, it should be understood by those of skill in the art that the invention is adaptable to other applications within the CATV environment, or even other communication applications which do not pertain to CATV systems.
For example, as shown in FIG. 7 , a prior art headend 700 generally includes two pieces of equipment; a baseband section 702 and an IF section 704 . These two sections 702 , 704 are typically designed to operate as “stand alone” units. Together, the two sections 702 , 704 output a single RF channel. The baseband section 702 generally comprises a video section 706 and an audio section 708 . These sections 706 , 708 receive audio and video baseband inputs and combine these inputs to an intermediate frequency for output to the IF section 704 . In the IF section 704 , the intermediate frequency is up-converted to the desired RF output channel. Since both sections 702 , 704 comprise units of equipment which are designed to work independently, this requires the duplication of many components between units 702 , 704 .
Referring to FIG. 8 , a headend 800 made in accordance with the present invention is shown. The headend 800 includes an audio pre-processing section 802 , a video pre-processing section 804 , the universal modulator 808 of the present invention (which is coupled to two filters 810 , 812 ), a transmitter 814 (if desired), and a microprocessor 806 , which controls all of the components of the headend 800 . As was previously described hereinbefore, since the universal modulator 808 can convert a baseband input signal to any desired RF output signal while avoiding ODBFs, the universal modulator 808 may be utilized to replace most of the components in the baseband section 702 and the IF section 704 . This significantly reduces the number of components required for a headend 800 . Accordingly, the cost and complexity are also thereby reduced.
It should be understood by those of skill in the art, with reference to FIG. 8 , that the universal modulator 808 of the present invention may also be used to accept a baseband digital VSB signal and remodulate the signal to a desired RF output signal for use with broadcast HDTV television receivers. The universal modulator 808 could also be used to transmit RF signals to devices which require high frequency RF signals, including wireless appliances such as a cordless telephone or a wireless LAN receiver. In such an application, the second mixer up-converts the HI-IF signal to a higher frequency RF signal, instead of down-converting the HI-IF as previously described. The desired RF output signal would be:
RF output ═(HI-IF)+L03 (Equation 10)
The RF output signal may then be transmitted directly to the wireless appliance. | A modulator generates a combined signal consisting of audio and video signals and converts the combined signal to one of a plurality of frequencies in dependence upon a desired output frequency and broadcast standard. The modulator includes a summing amplifier, a first frequency synthesizer and a second frequency synthesizer. The summing amplifier has a first input for receiving a video signal, a second input for receiving a first audio signal, a third input for receiving a second audio signal, and an output for outputting a modulated summed signal. The first frequency synthesizer generates a first frequency for mixing with the modulated summed signal to generate a high intermediate frequency (HI-IF) signal. The second frequency synthesizer generates a second frequency for mixing with said HI-IF signal to generate a desired RF output signal. | 7 |
BACKGROUND OF THE INVENTION
A need exists for a spare tire mounting or holding means within the cargo box of a pick-up truck. Some pick-up trucks have spare tire mounts at the rear of the cargo box and beneath the floor thereof. If an additional spare tire and wheel are carried, they are usually placed loosely in the cargo box and are subject to movement and are easily stolen.
The present invention, therefore, has for its objective the provision of a spare tire and wheel mount in a pick-up truck cargo box at a convenient and readily accessible location and out of the way of other cargo. The spare tire mount is sturdy and secure and features a clamping means which may grip any side wall portion of the cargo box around the perimeter of the box, thereby rendering the placement of the mount variable at the will of the user. The clamping means of the mount is padded to prevent damaging the painted wall of the truck cargo box. Advantage is taken of the existence of an upper marginal bead found on standard pick-up trucks in cooperating with mount clamping means so as to provide stability for the spare tire mount. The weight of the spare tire and wheel is borne by the cargo box floor. The mount may also be installed on the side wall of a tool box where such a box is employed.
Other features and advantages of the invention will become apparent during the course of the following description.
BRIEF DESCRIPTION OF DRAWING FIGURES
FIG. 1 is a fragmentary perspective view of a pick-up truck equipped with the spare tire mount embodying the invention.
FIG. 2 is an exploded perspective view of the elements forming the mount.
FIG. 3 is an enlarged vertical section taken on line 3--3 of FIG. 1.
FIG. 4 is a fragmentary horizontal section taken through a hasp guard and associated elements of the mount, on line 4--4 of FIG. 1.
FIG. 5 is a fragmentary section, similar to FIG. 4, showing a modification.
FIG. 6 is a fragmentary perspective view of portions of the invention in FIG. 5.
FIG. 7 is a fragmentary perspective view showing another modification.
DETAILED DESCRIPTION
Referring to the drawings in detail wherein like numerals designate like parts, and referring first to FIGS. 1 through 4, the numeral 10 designates a conventional pick-up truck whose cargo box 11 is provided around its top margin with a continuous bead 12 in the interest of strength and rigidity. This construction is standard on all pick-up trucks, although the cross sectional form of the bead 12 may vary from truck-to-truck.
The present invention comprises a primary mounting bracket 13, or holder, which is in the general form of an inverted U when in the installed position, FIG. 3. The bracket 13 has a top horizontal bar 14 and two spaced parallel depending arms or sections 15 and 16, the arm 16 being somewhat longer than the arm 15, as illustrated. The top bar 14 is preferably substantially at right angles to the parallel arms 15 and 16. The interior face of the arm 15 carries a pad 17 of rubber-like material for direct engagement with the opposing exterior surface of one cargo box vertical wall 18 to avoid scratching or marring this wall. The invention can be installed on any selected vertical wall of the cargo box and is therefore versatile.
A cooperating clamp plate 19 has its exterior face covered by a rubber-like pad 20 which engages the interior of the cargo box wall 18 when the device is installed. The plate 19 and its pad 20 are disposed immediately beneath the bead 12, FIG. 3, and thus are positively locked against upward displacement. The horizontal bar 14 is immediately above the bead 12 when the invention is installed and precludes downward movement of the mount on the vertical wall 18. Additionally, the spare tire 28 mounted on spare wheel 27 rests on the floor of cargo box 11 and bears its own weight and also prevents downward displacement of the invention. The invention merely holds the spare tire and wheel in the upright position and prevents removal thereof from the pick-up truck but does not support the weight of the tire and wheel.
A cooperating inclined stabilizing bar 21, preferably of channel cross-section, is welded to the plate 19 and projects upwardly and rearwardly therefrom at an angle near and below the horizontal bar 14 and between the arms 15 and 16. The bar 21 projects above the plate 19 and has a longitudinal adjustment slot 22 in its upper web, receiving a clamping bolt 23, or stud, carried by a triangular support element 24, rigidly secured by welding to the bottom of horizontal bar 14 substantially midway between the vertical arms 15 and 16. The inclination of the bottom wall of the support element 24 matches the degree of inclination of stabilizing bar 21. The bolt 23 receives a nut and washer indicated at 25 to complete the clamped installation of the mount on the cargo box wall 18 following proper adjustment. In connection with the arrangement of the elements 21, 23 and 24, it is to be noted that the bolt or stud 23, as well as the nut 25, are substantially enclosed between the side webs of stabilizing bar 21 and support element 24. Additionally, with the spare tire and wheel in place close to the vertical wall 18, it is impossible for a person to reach the elements 23 or 25 by hand or with a tool to separate them.
The vertical arm 16 spaced from the wall 18 has a bolt or stud 26 welded thereto near its lower end and projecting outwardly thereof to pass through the center opening 27' of spare wheel 27, as shown. A disc or plate 29 of flat configuration has a center opening 30 receiving the bolt 26, and this disc abuts the outer side of the wheel 27 and is clamped thereto firmly by a nut 31 applied to the bolt 26. Thus, the spare tire and wheel are securely anchored to the vertical arm 18 of bracket 13.
To prevent rotation of the disc 29 and possible loosening of nut 31, a rigid pin element 29' is secured by welding to the disc near one side thereof and extends forwardly of the disc, FIG. 4, and is received through one of the wheel openings 30'. The projecting pin element 29' extends near one vertical edge of the arm 16 so that this fixed arm will block and prevent rotation of the disc 29.
As a further anti-theft provision, a hasp guard 32 is hinged at 33 to the other side of disc 29 and is adapted to be positioned across and over the bolt 26 and nut 31 to guard these elements. The center offset portion of the hasp guard 32 which receives the nut 31 preferably is formed for close-fitting engagement over the nut so as to make it virtually impossible to disturb the nut with a tool. The hasp guard 32 has an end slot 34 receiving a U-shaped padlock anchor 35 on the disc 29 and projecting oppositely from pin element 29', FIG. 4. A padlock 36, FIG. 1, is employed to secure the hasp guard 32 in its protective position.
FIGS. 5 and 6 show a modification of the invention where, in lieu of the pin element 29', an equivalent pin element 37 is formed as an extension on one side or arm of the padlock anchor 38, the latter being turned 90° from the position of the anchor 35, previously described. Also, the slot 39 in hasp guard 40 is rotated 90°, FIG. 6, from the position of slot 34 in FIG. 2. The pin extension 37 functions in exactly the same manner as the pin element 29' to prevent rotation of disc 29 and consequent loosening of nut 31.
As an additional safety or anti-theft feature which is optional, FIGS. 5 and 6, a fixed sleeve 41 or guard element on the interior of hasp guard 40 may be provided to fit closely over the nut 31 and thereby substantially completely enclose the same. If desired, this feature may also be employed on the hasp guard 32, previously described in the embodiment of FIGS. 1 through 4.
FIG. 7 shows another modification of the invention wherein the pick-up truck is equipped with a tool box 42 in its cargo box 11, to which it is desired to attach a spare tire and wheel. In this case, the clamping components 19, 21, 24, etc. may be eliminated and the previously-described bracket 13 is bolted directly to the side wall of the tool box as at 43. The elements 26, 29, 31, 32, etc. shown in FIG. 3 are employed in the same manner to attach the spare tire and wheel to the mounting bracket 13 in FIG. 7. These elements are omitted in FIG. 7 for simplicity of illustration and to avoid duplication in the drawings.
It is to be understood that the forms of the invention herewith shown and described are to be taken as preferred examples of the same, and that various changes in the shape, size and arrangement of parts may be resorted to, without departing from the spirit of the invention or scope of the subjoined claims. | A mounting bracket and cooperating clamp grip the cargo box side wall of a pick-up truck beneath the customary bead at the top margin of the cargo box. The spare tire is bolted to a projecting arm of the mounting bracket and a lockable hasp device or guard encloses the bolting means for the spare tire and wheel. The mount is compact and stable and positions the spare tire conveniently. | 1 |
FIELD OF THE INVENTION
The present invention relates to the field of detecting changes to ambient conditions, for example by monitoring and assessing air flow conditions through Heating/Ventilation/Air-conditioning (HVAC)-type ducts and providing alarm indication when ambient conditions are compromised. More particularly, the present invention relates to a device with test features for assessing or directing sensor functions.
BACKGROUND OF THE INVENTION
Ambient condition detectors have been found to be useful in providing an indication of the presence or absence of the respective condition being detected. Smoke, gas, temperature, and relative humidity detectors, for example, have been found useful in providing early warnings of the presence of conditions such as, for example, mechanical malfunction and/or fire.
When used in Heating/Ventilation/Air-conditioning (HVAC) duct systems, ambient condition detectors are able to not only signal the presence of alarm conditions anywhere in the building, but also in the machinery of the HVAC ducts themselves. Generally, HVAC detectors have special requirements over conventional detectors. For example, HVAC detectors often sample airflow behind dust filters, which are required to prevent dirt or dust related false alarms. When clean, these filters serve to remove undesirable dust particles from activating the alarm, while still allowing a steady rate of air to flow through the detection mechanism. However, dust filters become clogged over time, compromising sensor function and necessitating periodic maintenance of the filter in addition to the operational checks of, for example, the power supply and detector operation.
Furthermore, HVAC detectors and sensors, particularly in industrial buildings, are often installed in remote locations and thus can be difficult to precisely locate when installed behind walls or within ducts, for example. Access to and disassembly of an installed smoke detector for mere checking the contamination level of a filter or activity of a sensor, for example, is undesirably cumbersome, undesirable, and uneconomical.
Therefore, there continues to be a need for an apparatus and method to test the functionality of a detector without necessary disassembly of an installed detector. It is also desirable to provide a means to test multiple functional parameters of a sensor with a single test feature that can optionally be actuated without necessary direct access to the detector.
SUMMARY OF THE INVENTION
The foregoing needs are met, at least in part, by the present invention wherein a device is provided with a switch that can perform multiple testing functions. The multi-test switch may be employed alone in an individual sensor of a ambient condition detector, or alone in a control unit coupled to multiple sensors, or in combination, with a respective switch being present on both the individual sensors and the control unit.
In one embodiment, a detector for detecting a condition is provided, comprising a first sensor that determines the presence of a first condition and provides a first alarm signal, a switch with a first engaged position for activating a first activity and a second engaged position for activating a second activity; and a control unit comprising a processor coupled to the sensor that provides a status message indicative of the state of the first alarm signal. In some embodiments, the detector may also comprise a second sensor to determine the presence of a second condition and provide a second alarm signal. The first sensor may be a photoelectric smoke sensor or an ionization-type smoke sensor. The first activity engaged by the switch may be an alarm test. In those embodiments wherein the sensor comprises an air filter, a filter test may also be engaged by the multi-test switch.
In other embodiments, the detector may comprise an air flow sensor and a processor to compare the air flow to a low air flow threshold, the processor providing an air flow alarm signal indicative of low air flow status when the air flow status is less than the low air flow threshold. The air flow threshold may be adjustable and/or set to ambient air flow.
In yet other embodiments, the detector may have a temperature sensor and a processor to compare the temperature to a high temperature threshold, the processor providing a temperature alarm signal indicative of high temperature when the temperature is greater than the temperature threshold. The temperature threshold may be adjustable and/or set to ambient air flow.
In yet still other embodiments, the detector may have a CO 2 sensor and a processor to compare the sensed CO 2 to a high CO 2 threshold, the processor providing a CO 2 alarm signal indicative of high CO 2 when the CO 2 present is greater than the CO 2 threshold. The CO 2 threshold may be adjustable and/or set to ambient air flow.
In yet still other embodiments, the detection device may comprise a second smoke sensor or a relative humidity sensor.
In other embodiments, a device is provided for detecting a condition, comprising a sensor that determines the presence of a condition and provides an alarm signal; a switch with a first engaged position for activating a first activity and a second engaged position for activating a second activity; and a processor for providing a status message indicative of the state of the alarm signal.
In other embodiments a device is provided for detecting a dangerous condition, comprising a first sensing means for determining a first ambient condition and for providing a first alarm signal, a switching means with a first engaged position for activating a first activity and a second engaged position for activating a second activity; and control means comprising a processing means coupled to the sensing means for providing a status message indicative of the state of the first alarm signal. The sensing means may be a photoelectric smoke sensor or an ionization smoke sensor in some embodiments.
There has thus been outlined, rather broadly, certain embodiments of the invention in order that the detailed description thereof herein may be better understood, and in order that the present contribution to the art may be better appreciated. There are, of course, additional embodiments of the invention that will be described below and which will form the subject matter of the claims appended hereto.
In this respect, before explaining at least one embodiment of the invention in detail, it is to be understood that the invention is not limited in its application to the details of construction and to the arrangements of the components set forth in the following description or illustrated in the drawings. The invention is capable of embodiments in addition to those described and of being practiced and carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein, as well as the abstract, are for the purpose of description and should not be regarded as limiting.
As such, those skilled in the art will appreciate that the conception upon which this disclosure is based may readily be utilized as a basis for the designing of other structures, methods and systems for carrying out the several purposes of the present invention. It is important, therefore, that the claims be regarded as including such equivalent constructions insofar as they do not depart from the spirit and scope of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram of a power supply and control unit, including an alarm detector and a trouble detector.
FIG. 2 is a block diagram of a sensor.
FIG. 3 is a flow chart of the logic operation of functions the detector will perform in one embodiment.
FIG. 4 is a flow chart of the logic operation of the test for filter contamination in one embodiment.
DETAILED DESCRIPTION
While this invention is susceptible of embodiment in many different forms, there are shown in the drawing figures and will be described herein in detail specific embodiments thereof with the understanding that the present disclosure is to be considered as an exemplification of the principles of the invention and is not intended to limit the invention to the specific embodiments illustrated.
The multi-test switch feature described herein can be used with a single sensor unit, or on a control unit of a detection system that is coupled to multiple individual sensors. Alternatively, multi-test switches of the present invention may also be installed in both the individual sensors and a control unit in combination. Switches of the present invention need not be limited to any particular sensor or detector. In fact, many types of ambient condition sensors are known in the art such as, for example, smoke, gas, temperature, and relative humidity detectors, and can be used in embodiments of the invention. In embodiments where smoke detectors are used, the sensors are preferably ionization-type or photoelectric. Switches described herein can be adapted for all known detectors in the art from the teachings described herein.
FIG. 1 illustrates one embodiment of the instant invention wherein the ambient condition detector 1 comprises multiple sensors 10 and 20 that are operationally coupled to a control unit 30 . Additional sensors may be integrated as desired with control unit 30 . The control unit 30 may comprise both a power supply 40 and an output control 50 as shown. Alternatively, in other embodiments, the power supply 40 may be coupled to the control unit 30 peripherally (not shown). In any case, the power supply 40 is powered by a power input 41 . A variety of power inputs 41 to power the power supply 40 are available and can be used, including 120V AC, 220V AC, and 24V AC/DC, and the power supply 40 may be equipped to receive the any one or all of the mentioned power inputs. The power supply 40 may power the control unit 30 and the sensors 10 and 20 , or alternatively, the sensors 10 and 20 may be independently powered. The power supply 40 transmits power through the power output bus 42 . The power output bus 42 may serve to power multiple devices within the detector 1 , including the output control 50 , the detectors 60 and 70 , and the individual sensors 10 and 20 , as is shown. The power output bus 42 may range from 12V to 24V DC, and preferably is 18V DC in some embodiments.
The power output bus 42 is coupled to the individual sensors 10 and 20 by means of a switch 80 . When in the “on” position, the switch 80 directs power from the power supply 40 to the sensors 10 and 20 via power output bus 42 . When the switch 80 is activated to the “off” position, however, transmission of power is interrupted to the sensors 10 and 20 . In the embodiment shown, activation of the switch 80 only terminates power to the sensors 10 and 20 , but not to the other devices, the output control 50 , the alarm detector 60 , and the trouble detector 70 . It will be understood from the description herein, however, that the switch 80 may be incorporated in other locations to operationally supply or interrupt power to any one or all of the devices.
Many known switching means are known to those skilled in the art and may be employed for the switch 80 . Preferably, in some embodiments, the switch 80 will be a multi-test switch. That is, one switch will embody multiple functions. As will be detailed below, switches of this invention will preferably have multiple engagable positions such that in one engaged position, the switch may signal one function or test, whereas in other engaged positions, the switch may signal a second function or test. In other embodiments, the switch may embody yet another engaged position so to signal yet a third function or test. In some embodiments, the switch may preferably be a single button, whereby multiple engaged positions may be indicated by the length of time the button remains depressed.
Turning to the coupling of the sensors 10 and 20 to the control unit 30 now, each sensor 10 and 20 is coupled to the control unit 30 of the detector 1 and may individually relay both an alarm signal and a trouble signal. The alarm sensor signal and trouble sensor signal from each of the sensors 10 and 20 are relayed via an alarm bus 12 and a trouble bus 22 , respectively. Information from the alarm bus 12 is synthesized in the alarm detector 60 and the alarm detector signal 61 is relayed to the output control 50 . Similarly, information from the trouble bus 22 is synthesized in the trouble detector 70 and the trouble detector signal 71 is relayed to the output control 50 . The output control 50 contains a microprocessor to evaluate and interpret the alarm detector signal 61 and the trouble detector signal 71 .
The control unit 30 assesses these signals along with other conditions such as power of the power source, and when a trouble condition is present, the control unit 30 sends a status message via the outputs 51 and 52 . The outputs 51 and 52 may be transmitted though any of multiple transmission methods, including radio frequency, electronic transmission, and/or fiber optics, and may optionally include an audio signal.
In the embodiment shown in FIG. 1 , the alarm detector 60 and the trouble detector 70 are individually coupled to the output control 50 . As shown, the alarm detector 60 and the trouble detector 70 , along with the switch 80 and the output control 50 are all installed as part of control unit 30 . However, each of the aforementioned devices may be installed peripheral to the control unit 30 , and not be encompassed in a single unit therein.
FIG. 2 shows a detail of the sensor unit 10 of the detector 1 in one embodiment of the instant invention. As mentioned above, one of ordinary skill in the art will appreciate from the teachings herein that the sensor may also be a stand-alone unit without the need for a separate control unit as shown in FIG. 2 . Such embodiments are within the scope of the instant invention. Also in the embodiment shown, the sensor 10 is a smoke sensor; however, as mentioned, the sensors of this invention are not limited to smoke sensors.
The sensor 10 includes a memory 90 , a clock 100 , a microprocessor 110 , status lights 120 , a power supply 130 , an amplifier 140 , and a smoke sensing chamber 150 . The smoke sensing chamber 150 comprises an infrared (IR) light-emitting diode (LED) transmitter 151 and a photo diode receiver 152 . The transmitter 151 and receiver 152 are generally positioned at 90-degree angles to one another. In the absence of smoke then, the light from transmitter 151 bypasses receiver 152 . When smoke enters the chamber 150 , however, the smoke particles scatter light from transmitter 151 and some amount of light is detected by receiver 152 . The signal 153 from the receiver diode 152 is further amplified by the amplifier 140 en route to the microprocessor 110 .
The microprocessor 110 may be calibrated to monitor changes in the signal 153 compared to a transmitter signal 154 that is relayed to IR LED transmitter 151 . The microprocessor clock 100 may be integral or peripheral to microprocessor chip 110 . As with the clock 100 , memory 90 may also be integral or peripheral to the microprocessor chip 110 . The status lights 120 may be LEDs to signal to the operator conditions such as, for example, trouble, alarm, and/or power status of the sensor 10 . In some embodiments, the status lights may be replaced by or combined with an audio annunciation. Likewise, if the sensor 10 is equipped with a filter to remove large particulate matter from the air flow though the smoke sensing chamber 80 , then an LED for the dirt level of the filter may also be included on the status light display 120 .
The status light display 120 may be comprised of a series of LEDs. The LEDs may signal proper function or the indication of an alarm condition when visible light is present. Alternatively, the detector may be designed such that proper function or indication of alarm condition is indicated by the lack of visible light. A combination of light signaling can also be implemented. In some preferred embodiments, a single light may be used to display multiple conditions. As will be explained in more detail below, for example, a single flash of the light may indicate a first status, a double flash of light may indicate a second status, so on and so forth. The same concept may be applied to audio annunciation.
The power source, alarm output, and trouble output, are each coupled to the power bus 42 , the alarm bus 12 , and the trouble bus 22 , respectively, and operably coupled to the microprocessor 110 . The microprocessor 110 is supplied power through a power supply 130 and may be equipped with a power monitor input 161 . In the event of inadvertent power failure, the power buffer 160 buffers the sudden drop in power or alternatively, buffers the sudden rise in power when power is once restored.
In some embodiments, the multiple testing features of the detectors of the instant invention are activated though intermittent cessation of power to the microprocessor. Such deliberate interruption of power by the operator is also buffered by the power buffer 160 . The microprocessor 110 then “reads” the interruption in power from the power input 161 and activates the appropriate test feature and/or response.
In some embodiments, the sensors and detectors of the instant invention may be equipped with a reed switch 170 . In this embodiment, instead of intermittently dropping the voltage from the outside of a cover of the detector or sensor, the reed switch 170 is turned on when a magnet is brought into proximity by an operator. Upon this turning-on of the reed switch 170 , a test signal 171 is relayed to the microprocessor 110 .
Here, in the above-described embodiment, in order to keep the reed switch 170 on continuously during test, the inspector must continuously hold a magnet in close proximity to the reed switch 170 . Where multiple tests may be signaled though a single reed switch 170 in some embodiments, different tests may be signaled by the duration of the reed switch 170 in the “on” position. That is, the length of time the magnet is placed in proximity to the reed switch 170 will indicate the time of engagement which may also indicate the type of test desired by the operator.
In addition, in the present invention, instead of the reed switch 170 and the magnet, an optical switch, such as an LED, or a wireless switch, such as infrared rays, or radio waves may be used as the test switch. Still alternatively, a test command, such as by intermittent changes in voltage, may be transmitted from a control panel to start test thereby effecting a remote test.
The microprocessors of this invention may be equipped to determine not only the presence or absence of the condition being sensed, but also the status level of the condition being sensed relative to a baseline or threshold value. In other words, a microprocessor of a temperature sensor in some embodiments may be calibrated to not only read the temperature level, but also be able to compare the temperature to a preset threshold. Such a threshold may be adjustable or may be set to ambient temperature. As the temperature of certain buildings may be preset to rise or fall at certain set cycles, so too are microprocessors of the present invention preferably embodied to take the ambient rise and fall in temperature into account when signaling an alarm condition. The same process described above for temperature sensors may also be similarly applied to CO 2 , smoke, and/or relative humidity sensors.
In some embodiments, an air flow sensor is also incorporated. Particularly with ambient air condition detectors where filters are placed internally to remove unwanted particulate matter from initiating false alarm signals, air flow can often become compromised when the filters get contaminated. Alternatively, where airflow is deliberately reduced at certain periods of the day, air flow through the sensor can also be reduced.
In either event, it is desirable to provide a microprocessor that is able to distinguish restrictions in air flow from air filter contamination from restrictions in air flow from preset reduction in air circulation through out the building. Many devices for detecting and comparing air flow are known and available in the art, including the use of thermistors.
One example of how a single switch may be used to activate multiple functions will now be described. Many permutations of the example given are possible and will be understood to one of ordinary skill in the art, and all such permutations are within the scope of the invention. In one embodiment, detectors of the instant invention are equipped with a multi-test button on both the control unit and on the individual sensors. Under conditions where an alarm has been activated, the button serves to reset the detector by virtue of dropping power to the sensors. The microprocessors of the sensors detect a temporary drop in voltage and shut down the alarm. The individual sensors 10 and 20 then sense whether or not the alarm condition is still present, and then reactivate the alarm or remain reset accordingly.
When no alarm condition is present and therefore no alarm has been activated, the same multi-test button, that functions to reset the sensors in an alarm condition, may serve as an alarm test or a test for filter contamination (“dirt test”) depending on the duration the button remains depressed on the control unit or sensor. FIG. 3 shows a flow chart of the logic operation of functions the detector will perform. When the button is depressed the mechanical switch is “active”. “Active” in this embodiment refers to the period of time power to the sensors is interrupted. The microprocessor 110 then assesses the length of time the switch is active. If the switch is active for less than 1 second, then no test is initiated. However, if the switch is active for 1 to 4 seconds, then the dirt test is initiated. Alternatively, if the switch is active for greater than 4 seconds, an alarm test is initiated. Upon completion of the dirt test or the alarm test, the mechanical switch is automatically reset to the inactive position.
In the embodiment described, a reed switch may also be incorporated on the individual sensors. The reed switch operationally functions similarly to the button switch on the control unit. For example, depressing the button switch is analogous to bringing a magnet into proximity to the reed switch. Moreover, depression of the button switch for 3 seconds is equivalent to holding a magnet to the reed switch for 3 seconds. Therefore, the magnet and reed switch combination can be operable in a manner similar to the button switch described above.
FIG. 4 shows a flow chart of the logic operation for the filter contamination (“dirt test”) in one embodiment of the present invention. Once the dirt test has been activated by one of several means mentioned above (e.g., activation of the reed switch 160 ), the microprocessor 110 first determines the dirt level by comparing the dirt present on the filter with that present when first installed. Once a percentage of dirtiness is calculated, the processor then computes which one of five dirt levels is present. As outlined in FIG. 4 dirt level 1 is indicative of 0%–25% contamination, dirt level 2 is indicative of 26%–50% contamination, dirt level 3 is indicative of 51%–75% contamination, dirt level 4 is indicative of 76%–99% contamination, and dirt level 5 is indicative of complete (100%) contamination. Depending on the dirt level, the microprocessor 110 then transmits the appropriate signal to an LED display which flashes once, twice, thrice, four times, or continuously to indicate dirt level 1 , 2 , 3 , 4 , or 5 , respectively.
The many features and advantages of the invention are apparent from the detailed specification, and thus, it is intended by the appended claims to cover all such features and advantages of the invention which fall within the true spirit and scope of the invention. Further, since numerous modifications and variations will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation illustrated and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention. | A device with a multi-function test feature for assessing or directing multiple sensor functions is provided for monitoring and interrogating air flow through Heating/Ventilation/Air-conditioning (HVAC)-type ducts for changes to ambient conditions such as smoke, heat, gas, and/or relative humidity. | 8 |
PRIORITY
[0001] The present application claims priority from a U.S. provisional application filed on Apr. 14, 2004 and assigned U.S. Provisional Application Ser. No. 60/562,200 and from a U.S. provisional application filed on Feb. 23, 2004 and assigned U.S. Provisional Application Ser. No. 60/546,789; the contents of both applications is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present disclosure relates generally to games, and more particularly, to a modified electronic video poker card game.
[0004] 2. Description of the Prior Art
[0005] The gaming industry, in particular, gambling casinos, has come to recognize that to sustain long term success it must be constantly innovative in introducing new games and new gambling concepts to the gaming public.
[0006] One game of interest over the years is poker. Table and video poker and other casino poker games are well known and enjoy substantial success. With reference to electronic video poker games, in a typical game a player makes a selected wager and initiates the play of the game. The processor of the video poker game is programmed to select from a suitable memory structure containing data representing 52 cards of a deck, data representative of a five card opening holding. These five cards are displayed face up for the player to see. The player can discard some or all of the cards whereupon the processor from the data structure replaces the discarded cards to define a final holding or hand. If the hand corresponds to a pre-determined schedule or table of poker holdings, e.g., a pair of Jacks or better, four-of a-kind, flush, the player is awarded a payoff.
[0007] Various attempts have been made to enhance play of poker over the years. There are video poker variations, such as deuces wild, where the deuces of the deck of cards are wild, Joker's wild where a Joker is included in the deck, which is wild as well as Joker/deuces wild games. Further variations have been made over the years. Examples of such attempts are described in U.S. Pat. No. 5,882,260, Marks et al. Marks et al. provides a number of examples of U.S. patent references:
[0008] U.S. Pat. No. 4,743,022, Wood, second chance poker method; U.S. Pat. No. 4,948,134, Suttle et al., electronic five card poker game where cards are given to the-players one at a time; U.S. Pat. No. 5,013,049, Tomaszewski, five card poker game where up to two cards are drawn; U.S. Pat. No. 5,118,109, Gumina, instant poker game card; U.S. Pat. No. 5,255,915, Miller, six card, two hand video poker game; U.S. Pat. No. 5,294,128, Marauez, six cards, three hand poker game; U.S. Pat. No. 5,382,025, Sklansky et al., three hands, two card poker game where each player chooses one hand and five communal cards are dealt face up; U.S. Pat. No. 5,407,199, Gumina, interactive video/casino poker game-drawpoker, hold'em poker; U.S. Pat. No. 5,415,404, Joshi et al., multiplay video poker game in which the player's sub-hands are compensated to increase the payoff level of the winning hands; and U.S. Pat. No. 5,431,407, Hofberg et al., casino poker game.
[0009] U.S. Pat. No. 5,437,451 to Fulton involves a modified poker game where the player is dealt pairs of cards, where one card is optional and the other mandatory. The player is permitted to exchange at each round the optional card until five cards are selected. The resulting five card hand is then evaluated for payoff against a fairly standard payoff table.
[0010] U.S. Pat. No. 5,314,194 to Wolf deals the player seven cards. The player then forms two hands: a five card hand (e.g., a front hand), and a two card hand (e.g., a back hand). The rules for playing this game are quite elaborate, including requiring each player to arrange the hand so that the rank of the back hand is greater than the rank of the front hand.
[0011] Each of the prior art attempts at making poker interesting and challenging have been successful to varying degrees. Each provides a poker game that combines the attributes of skill, luck, excitement and simplicity with rapid play.
[0012] It is an objective of the present disclosure to provide a modified poker game that combines the attributes of skill, luck, excitement and simplicity with rapid play that is both unique and innovative.
SUMMARY OF THE INVENTION
[0013] The present disclosure provides an embodiment for a computer readable medium comprising a set of computer readable instructions capable of being executed by at least one processor for playing an electronic video poker game in accordance with the present disclosure. The present embodiment provides a set of game icons, preferably representing cards from a standard deck of cards. The game icons are equally separated into a plurality of subsets, such as each subset representing a different suit of the standard deck of cards. A set of special icons is also included, for imparting predetermined benefits and detriments to a player. The special icons include: free spin, which provides at least one additional round in the current game; cherub, which increases the points assigned to each win condition by a given factor; and devil, which negates the current spin or round, resulting in a lost round.
[0014] A game board or matrix having a play region is provided for displaying the game icons in predetermined positions. The game board also includes a set of active play positions. In each round, a subset of icons is displayed in the active play positions. The player then moves the displayed icons in the play positions to their corresponding positions in the game board.
[0015] Additionally, the game includes a wild icon. The wild icon can be placed or positioned within any of the positions on the game board that are unoccupied at the end of the last round of the game. An interface is provided for enabling a player to select which position on the game board will be occupied by each acquired wild icon. Placement of the wild icons is performed with the goal of creating one or more winning conditions. The user interface further enables the player to interact with the game, e.g., initiating game play, indicating a wager amount, ending game play and cashing out any accumulated winnings and/or credits. A win condition is determined based on a predetermined set of possible winning game icon configurations modeled on standard poker hands. A score is calculated based on the determined win condition and points or winnings assigned based on a predetermined pay table.
[0016] In one embodiment of the present disclosure, all the special icons, when any are displayed, occupy one of the active play positions, while in an alternate embodiment, a special icon, such as a free spin, is overlaid on another game icon such that two game icons are displayed or represented by one active play position. Preferably, the game in accordance with both embodiments of the present disclosure is a bonus or secondary game which is initiated by a processor of a casino-type game machine (e.g., slot machine), a video poker game machine, etc. upon a player meeting predetermined criteria or a predetermined score in a primary game.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] These and other features, aspects, and advantages of the present disclosure will become better understood with regard to the following description, appended claims, and accompanying drawings wherein:
[0018] FIGS. 1-8 illustrate an embodiment of an electronic video poker game, in accordance with the present disclosure, in various stages of game play;
[0019] FIG. 9 is a pay table for the electronic video poker game shown in FIGS. 1-8 ;
[0020] FIGS. 10-25 illustrate an alternate embodiment of an electronic video poker game, in accordance with the present disclosure, in various stages of game play; and
[0021] FIG. 26 is a pay table for the electronic video poker game shown in FIGS. 10-26 .
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0022] The present disclosure provides a system and method for playing an electronic video poker card game in which the player has at least one turn or spin to get as many royal flushes, four-of-a-kinds, and three-of-a-kinds on a matrix of playing cards. Preferably, the player has four turns or spins. The present disclosure further provides a computer readable medium storing a set of computer readable instructions capable of being executed by at least one processor for playing then electronic video poker game in accordance with the present disclosure.
[0023] The electronic video poker card game is preferably provided in the form of a stand-alone or bonus casino-type machine, which accepts money or deducts money from a credit line. It is contemplated that the electronic video poker card game can also be provided as computer software for playing the game on a personal computer, a PDA, or other computing device. It is also contemplated that the software can be stored at a remote server which is accessible via a network, such as the Internet, for enabling players to play the game over a network connection without downloading the software.
[0024] Exemplary methods of playing two different embodiments of the video poker game of the present disclosure and preferred embodiments of the inventive system will now be described. Prior to beginning play of the game, a graphical user interface of the video poker game is displayed on a display of the casino-type machine. Exemplary graphical user interfaces are shown by FIGS. 1 and 10 and designated generally by reference numerals 100 and 200 , respectively. These are the main graphical user interfaces used throughout the duration of the game of a first embodiment and an alternate embodiment, respectively, as further described below and shown by the remaining figures.
[0025] In the first embodiment, the game is played with a 24-card deck of cards. The 24 cards contain cards from a standard deck of poker playing cards (four aces, four kings, four queens, four jacks, four tens, and one Joker) and three additional cards (one Free Spin card, one Devil card and one Cherub card). Each card of the four aces, four kings, four queens, four jacks, and four tens represents one of the four suits, i.e., diamonds, hearts, spades and clubs. These cards are displayed on a game board or matrix 102 of the graphical user interface 100 as shown by FIG. 1 . The matrix 102 has a plurality of windows 103 arranged as four columns 104 A-D and five rows 106 A-E. The aces are displayed by the first row 106 A of windows 103 , the kings are displayed by the second row 106 B of windows 103 , the queens are displayed by the third row 106 C of windows 103 , the jacks are displayed by the fourth row 106 D of windows 103 , and the tens are displayed by the fifth row 106 E of windows 103 .
[0026] In the alternate embodiment, the game is played with a 23-card deck of cards which include the same cards as the first embodiment except the Free Spin card. In this embodiment, one of the playing cards randomly has a free spin attached to it, which is graphically indicated to the player by overlaying the card, for example, with the words “FREE SPIN.” (See FIG. 11 ) When that card is matched with the corresponding card in the matrix 102 ′, the player is awarded the free spin.
[0027] The graphical user interface 100 further displays a window labeled “Winnings” 108 for displaying the player's winnings, a window labeled “Free Spin” 110 for indicating if a free spin has been awarded to the player, and a window labeled “Joker” 112 for indicating if the Joker card has been awarded to the player.
[0028] The graphical user interface 100 also displays four windows 114 A-D. Each window 114 is displayed below a corresponding column 104 of the matrix 102 . It is contemplated that the windows 114 A-D can be displayed at a different location of the graphical user interface 100 , such as above the matrix 102 , on the side of the matrix 102 , above the window 108 , etc.
[0029] After each spin, each of the windows 114 A-D displays one of the cards of the 24-card deck (or 23-card deck if playing the alternate embodiment) without any duplication. Without any duplication means that if, for example, the ten of hearts is displayed by window 114 A after a particular spin, this card cannot be displayed by windows 114 B-D after that same spin (also this card cannot be redisplayed by windows 114 A-D after any subsequent spin, since this card matches a card displayed by the matrix 102 as further described below).
[0030] If the cards displayed by the windows 114 A-D match a card displayed by the matrix 102 , those cards are removed from the 24-card deck (or 23-card deck if playing the alternate embodiment) and cannot be redisplayed after subsequent spins. Therefore, if after the first spin, the ten of hearts is displayed by window 114 A, the king of clubs is displayed by window 114 B, the Joker is displayed by window 114 C, and the queen of hearts is displayed by window 114 D, the ten of hearts, the king of clubs and the queen of hearts are removed from the deck, since these cards match a card displayed by the matrix 102 . Therefore, these cards, i.e., the ten of hearts, the king of clubs and the queen of hearts, cannot be redisplayed after the subsequent spins.
[0031] Also, the corresponding cards displayed by the matrix 102 , i.e., the ten of hearts, the king of clubs and the queen of hearts, are highlighted on the matrix 102 or some indication is made (e.g., blacked-out, overlaid with lines or some symbol (cross-hair, X), etc.) to indicate that the player has matched these cards. Preferably, the windows 103 of the matrix 102 at the start of the game are gray or shaded and the windows 103 are lit up or highlighted after their displayed card is matched with a card displayed by the windows 114 A-D.
[0032] Also, in the above example, since the Joker card is displayed by window 114 C, the Joker card is removed from the deck and the Joker window 112 indicates that the player has been awarded the Joker card. The Joker card is kept aside until all four spins have been played. Then the player can place the Joker card anywhere in the matrix 102 to fill in any possible royal flush, four-of-a-kind, and/or three-of-a-kind to meet the game's objective which is, as indicated above, to get as many royal flushes, four-of-a-kinds and three-of-a-kinds. In the alternate embodiment, the Joker card is not removed from the deck after first being obtained. In the alternate embodiment, the Joker card is removed from the deck after being obtained twice, such that in this embodiment the player can obtain the Joker card two times (see FIGS. 14 and 17 ).
[0033] If, in the above example, one of the windows 114 A-D displayed the Free Spin card, the Free Spin window 110 will indicate that the player has been awarded a free spin and the Free Spin card would be removed from the deck. The player would then be able to use the free spin after all four spins have been played.
[0034] If the Devil card is displayed by any of the windows 114 A-D after a spin, the Devil card negates the outcomes of that spin. Therefore, if the Devil card is displayed after a spin, the remaining cards displayed by the matrix 102 which match cards displayed by the windows 114 A-D are not highlighted and the cards displayed by the windows 114 A-D are removed from the deck.
[0035] This is also the case with the alternate embodiment (see FIG. 19 ); that is, if the Devil card is displayed after a spin, the remaining cards displayed by the matrix which match cards displayed by the windows are not highlighted and the cards displayed by the windows are removed from the deck (unless the Cherub card is also displayed, since the Cherub card negates the Devil card as further described below). It is also contemplated in a still alternate embodiment to remove the Joker card and the Free Spin card from the deck if they are concurrently displayed with the Devil card without awarding the Joker and free spin to the player (unless the Cherub card is also displayed).
[0036] If the Cherub card is displayed by any of the windows 114 A-D after a spin (see FIG. 11 indicative of the alternate embodiment), the Cherub card doubles the player's winnings for that spin only, if the player attains a round robin, a royal flush, a four-of-a-kind and/or a three-of-a-kind for that spin only.
[0037] Given the following winning payouts: royal flush, 50 points; four-of-a-kind, 25 points; three-of-a-kind, 10 points; and completing a round robin, 1,000 points plus awarding of a progressive jackpot, if, for example, a Cherub card is displayed by one of the windows 114 A-D after a spin and the player attains a royal flush after that spin, the player is awarded 100 points instead of 50 points.
[0038] In the alternate embodiment, the winning payout is preferably as follows: royal flush, 15 points; four-of-a-kind, 10 points; three-of-a-kind, 5 points; completing a round robin, 200 points; and highlighting the entire matrix 102 (cover all), 1135 points. It is contemplated that if the player highlights the entire matrix 102 , the player is also awarded a progressive jackpot where a plurality of gaming machines or computers are networked as known in the art. It is further contemplated that points for the above-described payouts can refer to dollars or other monetary units.
[0039] If the Devil card and the Cherub card are displayed after a spin, then the Cherub card negates the Devil card and the other two cards are in play for matching corresponding cards on the matrix 102 . If one of the other two cards, or both of the other two cards, correspond to the Free Spin card and/or the Joker card, the player is awarded the free spin and the Joker for use after the fourth spin. If the player has been awarded both, the free spin is played first prior to the Joker. However, it is contemplated that the game can be designed such that the Joker is played prior to the free spin.
[0040] An exemplary play of the game of the first embodiment of the present disclosure will now be described with reference to FIGS. 2-8 . To start playing the game, the player makes an initial wager by depositing coins, paper money, etc. into a slot or money receiving device of the casino-type machine. The player can then initiate the first spin by pressing a Spin button or pulling a lever of the casino-type machine.
[0041] FIG. 2 illustrates the graphical user interface 100 after the first spin where windows 114 A-D respectively display a ten of spades, an ace of clubs, a queen of spades, and a king of diamonds. The corresponding cards on the matrix 102 have been highlighted to indicate that the player has matched these cards. These cards are removed from the 24-card deck prior to the player initiating the second spin. Since none of the windows 114 A-D display the Free Spin card or the Joker card, windows 110 and 112 remain blank. Also, since the player has not attained a royal flush, a four-of-a-kind or a three-of-a-kind, the player is not awarded any points and the Winnings window 108 remains blank or displays a zero.
[0042] FIG. 3 illustrates the graphical user interface 100 after the second spin where windows 114 A-D respectively display a king of hearts, a king of spades, a jack of hearts, and the Free Spin card. The corresponding cards on the matrix 102 have been highlighted to indicate that the player has matched these cards. These cards are removed from the deck prior to the player initiating the third spin. Since window 114 D displays the Free Spin card, window 110 displays “FS” to indicate the player has been awarded a free spin. After this spin, the player has attained a three-of-a-kind (three kings) and the player is awarded ten points which are displayed by the Winnings window 108 .
[0043] FIG. 4 illustrates the graphical user interface 100 after the third spin where windows 114 A-D respectively display a jack of spades, a king of clubs, the Devil card, and an ace of hearts. The corresponding cards on the matrix 102 have not been highlighted, since the Devil card is displayed by window 114 C thereby negating the outcomes of the third spin. Accordingly, the matrix 102 is identical to the matrix 102 displayed after the second spin ( FIG. 2 ). The cards displayed by windows 114 A-D are removed from the deck.
[0044] FIG. 5 illustrates the graphical user interface 100 after the fourth spin where windows 114 A-D respectively display a jack of diamonds, a ten of diamonds, the Joker card, and a queen of diamonds. The corresponding cards on the matrix 102 have been highlighted to indicate that the player has matched these cards. These cards are removed from the deck prior to the player initiating the free spin awarded after the second spin. Since window 114 C displays the Joker card, window 112 displays “J” to indicate the player has been awarded the Joker card. After this spin, the player has not attained any additional points, and the Winnings window 108 continues to display 10 points.
[0045] FIG. 6 illustrates the graphical user interface 100 after the free spin where windows 114 A-D respectively display a jack of clubs, the Cherub card, an ace of diamonds, and a queen of hearts. The corresponding cards on the matrix 102 have been highlighted to indicate that the player has matched these cards. Since window 114 B displays the Cherub card, the points attained following the free spin due to attaining a royal flush and/or four-of-a-kind are doubled. After the free spin, the player has attained two three-of-a-kinds (three queens and three jacks) and the player is awarded twenty points; the player has also attained a royal flush and the player is awarded 50 points, which are doubled due to the Cherub card to 100 points. Therefore, the total points awarded to the player after the free spin is 120 points and hence, the Winnings window 108 displays 130 points.
[0046] FIG. 7 illustrates the graphical user interface 100 after the player has used the Joker card to black-out the queen of clubs on the matrix 102 to attain a four-of-a-kind and an additional 25 points to end up with a total of 155 points which are displayed by the Winnings window 108 .
[0047] FIG. 8 illustrates the graphical user interface 100 overlaid with a “GAME OVER” message to indicate the end of the game.
[0048] Even though the FIGS. 1-8 display or indicate the various cards of the deck by using abbreviations, it is desirable to implement the game by displaying the cards as they are generally illustrated or presented in a standard deck of poker playing cards and to use illustrations or icons for the Devil, Joker and Cherub (see FIGS. 9-26 ).
[0049] An exemplary play of the alternate embodiment of the present disclosure is shown by FIGS. 10-26 . FIG. 10 displays a graphical user interface 200 prior to initiation of the game. The graphical user interface 200 includes a matrix 202 having a plurality of windows 203 arranged as four columns 204 A-D and five rows 206 A-E. The aces are displayed by the first row 206 A of windows 203 , the kings are displayed by the second row 206 B of windows 203 , the queens are displayed by the third row 206 C of windows 203 , the jacks are displayed by the fourth row 206 D of windows 203 , and the tens are displayed by the fifth row 206 E of windows 203 .
[0050] The graphical user interface 200 further displays a window labeled “WINNINGS” 208 for displaying the player's winnings, a window labeled “START GAME” 209 , a window labeled “FREE SPIN” 210 (see FIG. 11 ) for indicating if one or more free spins have been awarded to the player, a window labeled “JOKER” 212 for indicating if the Joker card has been awarded to the player, and a window labeled “SPINS REMAINING” 215 for indicating how many spins are left.
[0051] The graphical user interface 200 also displays four windows 214 A-D. Each window 214 is displayed below a corresponding column 204 of the matrix 202 . It is contemplated that the windows 214 A-D can be displayed at a different location of the graphical user interface 200 , such as above the matrix 202 , on the side of the matrix 202 , above the window 208 , etc. A window labeled “PAYTABLE” 216 is also displayed by the graphical user interface 200 for accessing the pay table shown by FIG. 9 .
[0052] To start the game, the player clicks on the window labeled “START GAME” 209 or performs some other action (like pulling a lever on a gaming machine). After starting the game, the first spin of the four spins is played and the windows 214 A-D display one of the cards of the 23-card deck without any duplication as mentioned above. The only exception where a window 214 A-D displays more than one card is if the window displays the Free Spin card as shown by window 214 B in FIGS. 11-13 . Such a window displays a card from a standard deck of cards (in this case, an Ace of clubs) and the Free Spin card for a total of two cards.
[0053] With further reference to FIGS. 11-13 , after the first spin, the player attains a queen of hearts in window 214 A, an ace of clubs in window 214 B overlaid with the Free Spin card, an ace of diamonds in window 214 C and the Cherub card in window 214 D. The corresponding cards are blacked-out on the matrix 202 (see FIGS. 12 and 13 ) and removed from the 23-card deck (except the Free Spin card).
[0054] Since the Cherub card is attained after the first spin, the point value associated with any royal flush and/or four-of-a-kind attained after the first spin is doubled. An icon 218 (see FIG. 11 ) is displayed by the graphical user interface 200 indicating that the payout is doubled. Another icon 220 (see FIG. 12 ) is also displayed indicating that the Free Spin card has been revealed and the window labeled “FREE SPIN” 210 is incremented by one to show that the player has attained a free spin.
[0055] With reference to FIGS. 14 and 15 , after the second spin, the player attains a jack of hearts in window 214 A, the Joker card in window 214 B, a ten of clubs in window 214 C and a ten of diamonds in window 214 D. The corresponding cards are blacked-out on the matrix 202 and removed from the deck (except the Joker card).
[0056] Since the Joker card is attained after the second spin, an icon 222 (see FIG. 14 ) is displayed by the graphical user interface 200 indicating that the Joker card has been revealed and the window labeled “JOKER” 210 is incremented by one to show that the player has attained the Joker card.
[0057] With reference to FIG. 16 , after the third spin, the player attains a jack of diamonds in window 214 A, a jack of clubs in window 214 B, a queen of clubs in window 214 C and an ace of hearts in window 214 D. The corresponding cards are blacked-out on the matrix 202 and removed from the deck. After the third spin, the player also attains two three-of-a-kinds (three aces in row 206 A and three jacks in row 206 D) and is awarded ten points as indicated by the window labeled “WINNINGS” 208 .
[0058] With reference to FIGS. 17 and 18 , after the fourth spin, the player attains a king of hearts in window 214 A, a ten of spades in window 214 B, the Joker card in window 214 C and a king of diamonds in window 214 D. The corresponding cards are blacked-out on the matrix 202 and removed from the deck (including the Joker card).
[0059] Since the Joker card is attained after the fourth spin, the icon 222 (see FIG. 17 ) is redisplayed by the graphical user interface 200 indicating that the Joker card has been revealed once again and the window labeled “JOKER” 210 is incremented by one to show that the player has re-attained the Joker card. After the fourth spin, the player also attains one three-of-a-kind (three tens in row 206 E) and is awarded five points to bring the total number of points to fifteen as indicated by the window labeled “WINNINGS” 208 .
[0060] With reference to FIG. 19 , during play of the free spin, the Devil card is revealed in window 214 C and the spin is negated. An icon 224 is displayed by the graphical user interface 200 indicating that the Devil card has been revealed and that the spin is negated.
[0061] After the free spin is played, the player is then given the opportunity to place the first of the two Jokers on the matrix 202 (see FIG. 20 ). An icon 226 is displayed by the graphical user interface 200 notifying the player to place the Joker on the matrix 202 . After the Joker is placed on the matrix 202 (second window 103 from the left in row 206 E), the player attains a four-of-a-kind (four tens in row 206 E) and is awarded ten points to bring the total number of points awarded to twenty-five as shown by the window labeled “WINNINGS” 208 in FIG. 21 . The player also attains a royal flush (column 204 B) and is awarded fifteen points to bring the total number of points awarded to forty as shown by the window labeled “WINNINGS” 208 in FIG. 22 .
[0062] After the first Joker is placed on the matrix 202 , the player is then given the opportunity to place the second of the two Jokers on the matrix 202 (see FIG. 23 ). The icon 226 is redisplayed by the graphical user interface 200 notifying the player to place the Joker on the matrix 202 . After the second Joker is placed on the matrix 202 (leftmost window 103 in row 206 C), the player attains a three-of-a-kind (three queens in row 206 C) and is awarded five points to bring the total number of points awarded to forty-five as shown by the window labeled “WINNINGS” 208 in FIG. 24 . The player also attains a royal flush (column 204 A) and is awarded fifteen points to bring the total number of points awarded to sixty as shown by the window labeled “WINNINGS” 208 in FIG. 25 .
[0063] After placing the second Joker on the matrix 202 , the game is over and a GAME OVER icon 228 is displayed by the graphical user interface 200 as shown by FIG. 26 .
[0064] Preferably, the game in accordance with both embodiments of the present disclosure is a bonus or secondary game which is initiated by a processor of the casino-type game machine (e.g., slot machine), a video poker game machine, etc. upon a player meeting predetermined criteria or a predetermined score in a primary game.
[0065] The described embodiments of the present disclosure are intended to be illustrative rather than restrictive, and are not intended to represent every embodiment of the present disclosure. Various modifications and variations can be made without departing from the spirit or scope of the present disclosure as set forth in the following claims both literally and in equivalents recognized in law. | An electronic video game is provided which includes a display for displaying a set of game icons by a matrix, and at least one of an icon from a set of matching icons matching the set of game icons and an icon from a set of special icons during each round of the game. The special icons impart predetermined benefits and detriments to a player. At least one processor is provided for determining at least one of a matching condition and a special condition during play of each round. The matching condition is determined if the at least one displayed icon is an icon from the set of matching icons and the at least one displayed icon is matched with a corresponding icon of the set of game icons by the player. The special condition is determined if the at least one displayed icon is an icon from the set of special icons. The at least one processor determines a winning condition based on the matched set of game icons and calculates a score accordingly. | 6 |
BACKGROUND OF THE INVENTION
The present invention relates to a charged beam drawing method and a charged beam drawing apparatus for performing drawing on a mask or a wafer with use of a charged beam to manufacture a semiconductor device, and particularly, to a charged beam drawing method and a charged beam drawing apparatus which adopt a variable shape beam system in which a charged beam shaped and deflected into an arbitrary shape is irradiated on a sample.
Conventionally, to draw an arbitrary pattern on a sample such as a mask or a wafer used for manufacturing a semiconductor device, an electron beam drawing apparatus of a variable shape beam system is used in which an electron beam is shaped into a rectangular or a triangle shape of an arbitrary size, and the beam being focused and deflected is irradiated on the sample.
In this apparatus, due to limitations to the deflection amount with which an electron beam can be deflected, the fields where drawing is allowed without moving a sample are restricted. Therefore, drawing fields are divided into strips each of which has a Y-direction length equal to the maximum deflection amount and has an X-direction length equal to that of a drawing field, and drawing is performed on the entire drawing fields by combining a sequential movement of the sample in the X-direction and a stepped-movement of the sample in the Y-direction.
Further, a small sub-field is set in a maximum deflection field of a main deflector, and sub-deflection is performed at a high speed in the sub-field, thereby to achieve high-speed drawing.
Meanwhile, data which defines a pattern to be drawn is divided for every stripe in compliance with the drawing method system as described above. In addition, to compress the amount of stripe data, the stripe data is divided into small figure groups each being an aggregation of figures drawn by an equal main-deflection amount. In each of the small figure groups, positions of figures in each small figure groups are defined by coordinates relative to the origin of the small figure group.
In a conventional variable shape beam drawing apparatus, sub-fields are set so as to cover the small figure groups, and therefore, the positions of the sub-fields are controlled at random in accordance with the positions of the small figure groups.
In recent years, in accordance with down-sizing of semiconductor elements, it has been prolonged that positions and sizes of figures to be drawn are accurate and that connections at seams between figures are achieved without displacements. As a method of realizing such high accuracy, a multi-pass drawing system is adopted. This system improves the drawing accuracy by an effect of averaging attained by repeatedly drawing one same pattern.
In the multi-pass drawing system, if over-drawing is carried out under same conditions, white noise components are removed so that the drawing accuracy is increased. Further, if a drawing position in a sub-field and a drawing position in a stripe are changed, the drawing accuracy is much more increased since constant tendencies corresponding to the sub-field and the stripe are averaged. In particular, this effect is remarkable at boundaries of sub-fields and strips.
The sub-field multi-pass drawing in which sub-field boundaries are shifted in relation to a pattern figure and the stripe multi-pass drawing in which boundaries of strips are shifted in relation to a pattern figure are realized by preparing data corresponding to the number of times for which the pattern is multi-passed, while changing the data as to the manner of stripe division with respect to a pattern to be drawn and as to the manner of dividing a pattern part in a stripe, into small figure groups.
However, this kind of apparatus has a problem as follows. Specifically, in the system described above in which sub-fields are defined with respect to small figure groups constituting pattern data, there is a case that a sub-field is repeated, depending on the manner of defining the small figure groups.
This means, if pattern positions are adjacent to each other and are defined by different definitions as small figure groups, repetition of sub-field occurs. sub-fields which are regarded to be adjacent as pattern positions are defined by different definitions as small figure groups, repetition of sub-field occurs. Then, even a pattern which can originally be drawn by one sub-field is drawing by a plurality of sub-fields, resulting in a problem that the settling time of a deflector is excessively required and the drawing time is increase. This problem is not limited to a case where multi-pass drawing is carried out, but is common to a case where single drawing is carried out.
Further, to achieve sub-field multi-pass drawing and stripe multi-pass drawing in a charged beam drawing apparatus using a variable shape beam vector scanning system, as described above, different pattern data must be newly prepared for the number of times for which a pattern is multi-passed, changing the manner of stripe division and the manner of division of small figure groups with respect to a pattern to be drawn, so that burdens required for data processing and for data transmission are large. In addition, when the number of times for which a pattern is multi-passed is changed, all patterns to be multi-passed must be newly prepared.
Thus, in a conventional system in which sub-fields are defined for small figure groups constituting pattern data, there is a problem that repetition of sub-fields occurs and the settling time of a deflector is required excessively, so that the drawing time is increased. In addition, to perform sub-field multi-drawing and stripe multi-drawing, different pattern data must be newly prepared for the number of times for which a pattern is multi-passed.
The present invention has been made in view of the above situation, and has an object of providing a charged beam drawing method which realizes sub-field multi-drawing and stripe multi-drawing only with use of one piece of drawing pattern definition data, without involving large repetition of sub-fields and without preparing data in compliance with the number of times for which a pattern is multi-passed.
Further, the present invention has another object of providing a charged beam drawing apparatus which realizes sub-field multi-drawing and stripe multi-drawing only with use of one piece of drawing pattern definition data, without involving large repetition of sub-fields and without preparing data in compliance with the number of times for which a pattern is multi-passed.
BRIEF SUMMARY OF THE INVENTION
Therefore, according to the first aspect of the present invention, there is provided a charged beam drawing method comprising: a first step of setting a stripe field independent of drawing pattern definition data, and of determining the drawing pattern definition data which belongs to the stripe field set; a second step of setting a sub-field independent of the drawing pattern definition data, and of determining the drawing pattern definition data which belongs to the sub-field, among the drawing pattern definition data determined; a third step of drawing the drawing pattern definition data which belongs to the sub-field, onto an object to be subjected to drawing; a fourth step of shifting a position of the stripe field by a first predetermined value, and of shifting a position of the sub-field by a second predetermined value; and a fifth step of repeating the first to fourth steps for at least two times.
In the second aspect of the present invention according to the first aspect, the first predetermined amount is an amount obtained by dividing a height of the stripe field by a number of times for which drawing is repeatedly performed on the stripe field, and the second predetermined amount is an amount obtained by dividing a width of the sub-field by a number of times for which drawing is repeatedly performed on the sub-field.
In the third aspect of the present invention according to the first aspect, a width of a region occupied by a small figure group as a unit forming part of figure data included in the drawing pattern definition data is equal to or smaller than a between a maximum width which can be allowed by sub-deflection and a width of the sub-field, and determination obtained in the second step depends on whether or not coordinates closest to an origin of the sub-field among coordinates of small figure groups which constitute the drawing pattern definition data determined in the first belong to the sub-field.
Further, in the fourth aspect of the present invention according to the first aspect, the stripe field is a stripe-like field decided by a main-deflection width.
In the fifth aspect of the present invention according to the first aspect, the sub-field is a field smaller than a maximum field which can be allowed by sub-deflection.
According to the sixth aspect of the present invention, there is provided a charged beam drawing method comprising: a first step of setting a stripe field independent of drawing pattern definition data, and of determining the drawing pattern definition data which belongs to the stripe field set; a second step of setting a sub-field independent of the drawing pattern definition data, and of determining the drawing pattern definition data which belongs to the sub-field, among the drawing pattern definition data determined; and a third step of drawing the drawing pattern definition data which belongs to the sub-field, onto an object to be subjected to drawing.
In the seventh aspect of the present invention according to the sixth aspect, a width of a region occupied by a small figure group as a unit forming part of figure data included in the drawing pattern definition data is equal to or smaller than a difference between a maximum width which can be allowed by sub-deflection and a width of the sub-field, and determination obtained in the second step depends on whether or not coordinates closest to an origin of the sub-field among coordinates of small figure groups which constitute the drawing pattern definition data determined in the first step belong to the sub-field.
Further, in the eighth aspect of the present invention according to the sixth aspect, the stripe field is a stripe-like field decided by a main-deflection width.
Further, in the ninth aspect of the present invention according to the sixth aspect, the sub-field is a field smaller than a maximum field which can be allowed by sub-deflection.
According to the tenth aspect of the present invention, there is provided a charged beam drawing apparatus comprising: first determination means for setting a stripe field independent of drawing pattern definition data, and for determining the drawing pattern definition data which belongs to the stripe field set; second determination means for setting a sub-field independent of the drawing pattern definition data, and for determining the drawing pattern definition data which belongs to the sub-field, among the drawing pattern definition data determined; third drawing means for drawing the drawing pattern definition data determined by the second determination means, onto an object to be subjected to drawing; shift means for shifting a position of the stripe field by a first predetermined value, and for shifting a position of the sub-field by a second predetermined value; and repetition means for repeating operations of the first and second determination means, the third drawing means, and the shift means, for at least two times.
In the eleventh aspect of the present invention according to the tenth aspect, the first predetermined amount is an amount obtained by dividing a height of the stripe field by a number of times for which drawing is repeatedly performed on the stripe field, and the second predetermined amount is an amount obtained by dividing a width of the sub-field by a number of times for which drawing is repeatedly performed on the sub-field.
In the twelfth aspect of the present invention according to the tenth aspect, a width of a region occupied by a small figure group as a unit forming part of figure data included in the drawing pattern definition data is equal to or smaller than a difference between a maximum width which can be allowed by sub-deflection and a width of the sub-field, and determination obtained by the second determination means depends on whether or not coordinates closest to an origin of the sub-field among coordinates of small figure groups which constitute the drawing pattern definition data determined by the first determination means belong to the sub-field.
In the thirteenth aspect of the present invention according to the tenth aspect, the stripe field is a stripe-like field decided by a main-deflection width.
In the fourteenth aspect of the present invention according to the tenth aspect, the sub-field is a field smaller than a maximum field which can be allowed by sub-deflection.
According to fifteenth aspect of the present invention, there is provided a charged beam drawing apparatus comprising: first determination means for setting a stripe field independent of drawing pattern definition data, and for determining the drawing pattern definition data which belongs to the stripe field set;
second determination means for setting a sub-field independent of the drawing pattern definition data, and for determining the drawing pattern definition data which belongs to the sub-field, among the drawing pattern definition data determined; and third drawing means for drawing the drawing pattern definition data determined by the second determination means, onto an object to be subjected to drawing.
In the sixteenth aspect of the present invention according to the fifteenth aspect, a width of a region occupied by a small figure group as a unit forming part of figure data included in the drawing pattern definition data is equal to or smaller than a difference between a maximum width which can be allowed by sub-deflection and a width of the sub-field, and determination obtained by the second determination means depends on whether or not coordinates closest to an origin of the sub-field among coordinates of small figure groups which constitute the drawing pattern definition data determined by the first determination means belong to the sub-field.
In the seventeenth aspect of the present invention according to the fifteenth aspect, the stripe field is a stripe-like field decided by a main-deflection width.
In the eighteenth aspect of the present invention according to the fifteenth aspect, the sub-field is a field smaller than a maximum field which can be allowed by sub-deflection.
According to the nineteenth aspect of the present invention, there is provided an apparatus comprising: a memory device for storing drawing pattern definition data; a control calculator for reading the drawing pattern definition data stored in the memory device;
a pattern memory for temporarily storing the drawing pattern definition data read out from the control calculator; a pattern definition data developing unit for setting a stripe field independent of the drawing pattern definition data, for determining the drawing pattern definition data which belongs to the stripe field set, for setting a sub-field independent of the drawing pattern definition data, and for determining the drawing pattern definition data which belongs to the sub-field, among the drawing pattern definition data determined; drawing means for drawing the drawing pattern definition data determined by the drawing pattern definition data developing means, onto an object to be subjected to drawing; and shift means for shifting a position of the stripe field by a first predetermined value, and for shifting a position of the sub-field by a second predetermined value.
According to the present invention, sub-fields are set independently from drawing pattern definition data, and to which sub-fields figures belong are determined. Therefore, figures even defined as belonging to different small figure groups can be drawn together on one sub-field.
Further, the maximum size of the field which can be occupied by a small figure group as a unit constituting figure data defining a pattern is set to be equal to or less than the difference between the maximum width which can be allowed by sub-deflection and the grid cycle of the sub-field. Therefore, when performing drawing on one sub-field, a deflection amount larger than the maximum deflection amount which can be allowed by sub-deflection is not required.
Specifically, since the position of the sub-field to be set is shifted for each pass of multi-pass drawing, with respect to one piece of pattern data, one pattern figure is drawn at different positions in sub-fields, thus realizing sub-field multi-pass drawing.
Likewise, since the position of stripes to be set are shifted for each pass of multi-pass drawing, with respect to one piece of pattern data, one pattern figure is drawn at different positions in the main-deflection fields, so that stripe multi-pass drawing is realized.
Additional object 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 object 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 view showing a charged beam drawing apparatus according to an embodiment of the present invention.
FIG. 2 is a view showing a method of setting stripe fields.
FIG. 3 is a view showing a method of setting sub-fields.
FIG. 4 is a view for explaining the principle of multi-pass drawing according to the present invention.
FIG. 5 is a flow-chart for explaining the operation of the electric charge beam drawing apparatus according to an embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
In the following, an embodiment of the present invention will be explained with reference to the drawings.
FIG. 1 is a view showing a charged beam drawing apparatus according to an embodiment of the present invention.
In this figure, reference numeral 1 denotes a sample chamber, and a stage 3 on which a sample 2 such as a mask substrate or the like is contained in the sample chamber 1.
The stage 3 is driven in the X-direction (or the lateral direction of the figure) and Y-directions (or the direction vertical to the surface of the figure sheet). The moving position of the stage 3 is measured by a position circuit 5 using a laser length measurement device or the like.
Above the sample chamber 1, an electron beam optical system 10 is provided. This optical system 10 comprises an electron gun 6, various lenses 7, 8, 9, 11, and 12, a blanking deflector 13, a beam size shaping deflector 14, a main deflector 15 used for beam scanning, a sub-deflector 16 used for beam scanning, and two beam shaping apertures 17 and 18.
The main deflector 15 performs positioning with respect to a predetermined sub-deflection field (or sub-field) and the sub-deflector 16 performs positioning of a figure drawing position in the sub-field, while the beam shape is controlled by the beam size shaping deflector 14 and the beam shaping apertures 17 and 18. Drawing processing is performed on a sub-field while continuously moving the stage 3 in one direction. Upon completion of drawing on one sub-field in this manner, drawing on a next sub-field is started.
Further, upon completion of drawing on a stripe field as an aggregation of a plurality of sub-fields, the stage 3 is step-moved in the direction perpendicular to the continuous moving direction in which the stage has been moved, and then, the drawing processing as described above is repeated so that drawing processing is sequentially performed on each of stripe fields.
Here, a stripe field is a stripe-like drawing field decided by a deflection width of the main deflector 15. A sub-field is a unit drawing field decided by a deflection width of the sub-deflector 16.
Meanwhile, a control calculator 20 stores drawing pattern definition data of a mask in a magnetic disc 21 as a storage medium. Drawing pattern definition data read from the magnetic disc 21 is temporarily stored in a pattern memory 22.
The drawing pattern definition data stored in the pattern memory 22 is transmitted to a drawing pattern definition data developing unit 30 by the control calculator 20.
The drawing pattern definition data developing unit 30 determines whether or not data constituting a pattern belongs to a stripe field presently being drawn and determines where and in which sub-fields small figure groups constituting a pattern are positioned.
The drawing data obtained by the pattern data developing unit 30 is analyzed by a pattern data decoder 23 as a data analysis section and a drawing data decoder 24 and is transmitted to a blanking circuit 25, a beam shaper driver 26, a main deflector driver 27, and a sub-deflector driver 28.
Specifically, the pattern decoder 23 prepares blanking data on the basis of the above data, and the blanking data is transmitted to the blanking circuit 25.
Further, desired beam size data is prepared and is transmitted to the beam shaper driver 26. Further, a predetermined deflection signal is applied to the beam size shaping deflector 14 of the electronic optical system 10 described above, thereby to control the size of the electron beam.
In addition, in the drawing data decoder 24, sub-field positioning data is prepared on the basis of the data described above, and is transmitted to the main deflector 15. From the main deflector driver 27, a predetermined deflection signal is applied to the main deflector 15 of the electronic optical system 10, thereby to deflect the electron beam so as to scan a specified sub-field position.
Further, the drawing data decoder 24 generates a control signal for sub-deflector scanning, which is transmitted to the sub-deflector driver 28. From the sub-deflector driver 28, a predetermined sub-deflection signal is applied to the sub-deflector 16, thereby to perform drawing inside a sub-field.
In the next, the drawing method according to the present embodiment will be explained.
FIG. 2 is a view showing the manner of setting stripe shapes, and reference numeral 50 denotes drawing pattern definition data. The drawing pattern definition data is normally prepared and stored in form of frames having stripe shapes into which drawing pattern definition data is divided in compliance with a conventional drawing method. The frames are arranged as shown in FIG. 2.
Reference numerals 61 to 64 show setting states of strips when drawing is performed. Reference 61 indicates a drawing stripe setting state for first drawing of multi-pass drawing. References 62 indicates a drawing stripe setting state for second drawing thereof. Reference 63 denotes a drawing stripe setting state for third drawing. Reference 64 indicates a drawing stripe setting state for fourth drawing.
As shown in FIG. 2, the strips are shifted by a shift amount defined by dividing the height of the stripe-field by the number of times for which drawing is repeatedly performed.
By thus setting drawing stripe fields at positions gradually shifted on the drawing pattern definition data, one same pattern is drawn in different positions in a stripe field, drawing errors depending on positions in the stripe are averaged.
Although FIG. 2 is an example of four times multi-passing, the number of times for which drawing is repeatedly performed may be set to any times.
The pattern definition data developing unit 30 has a function of selecting and extracting what is included in the drawing stripe fields set, so that what is divided into two or more stripe fields in the data is drawn together in one stripe field.
The stripe drawing may be sequentially performed in the order from the stripe setting state 61 to the stripe setting state 62, or in the order of the lowest of the setting state 61, the second from the lowest of the setting state 62, to the second from the lowest of the setting state 63.
FIG. 3 is a view showing the manner of setting sub-fields and shows an example of four-times multi-passing, like in the case of FIG. 2. Reference numeral 71 indicates an arbitrary width equal to or less than the width which is allowed by the performance of a sub-deflection power source. Reference numeral 72 indicates the sub-field size when drawing is performed. Reference numerals 81 to 84 respectively indicate sub-field setting states for drawing stages of multi-passing drawing. Reference numeral 73 indicates the maximum size of a small figure group constituting the drawing pattern definition data.
The drawing pattern definition data developing unit 30 has a function of determining to which sub-field a small figure group belongs. In this determination, for example, to which sub-field coordinates of a left lower corner of a small figure group indicated by 73 belong is determined, i.e., to which sub-field coordinates closest to an origin of a sub-field among the coordinates indicating the small figure group belong is determined, to distribute small figure groups to sub-fields.
In this embodiment, the size of a small figure group is limited to the difference between the maximum width 71 which can be allowed by deflection and the sub-field width 72 set. Therefore, to perform drawing on one sub-field, a deflection amount larger than the maximum deflection amount which can be allowed by deflection is not required.
If the drawing pattern definition data is sorted with respect to lateral coordinates of FIG. 3, drawing can be performed on sub-fields having coordinates in the opposite side in the drawing proceeding direction with respect to the coordinate of data presently developed.
If the sub-fields are periodical grids which cover the entire fields, origins of grids are shifted by an arbitrary amount for each of multi-passing drawing in the two directions perpendicular to the sample plane. The shift amount is, for example, decided by dividing the drawing sub-field size (width) by the number of times for which drawing is repeatedly performed.
FIG. 4 is a view for explaining the principle of the multi-pass drawing of the present invention.
For convenience of explanation, the case of performing two-pass drawing is exemplified.
In this figure, reference numeral 91 indicates drawing pattern definition data, and this drawing pattern definition data 91 is divided into small regions (or small figures) indicated by broken lines. Here, one small figure group is constituted by 2×2 small regions.
In the first drawing, fields are set as indicated by reference numeral 92. In the second drawing, fields are set as indicated by reference numeral 93. Selected small regions are drawn, overlapped as indicated by reference numeral 94.
In the next, operation of a charged beam drawing apparatus according to embodiments of the present invention will be explained with reference to flow-charts shown in FIG. 5.
At first, position of stripe field is defined with respect to the mask surface, independently from drawing pattern definition data (in a step S1). Here, the position of stripe fields is set, shifted by a predetermined amount every time second or successive drawing is performed.
In the next, position of sub-field is defined with respect to the mask surface, independently from the drawing pattern definition data (in a step S2). Here, the position of the sub-field is shifted by a predetermined amount every time second or successive drawing is performed.
Subsequently, the drawing pattern definition data which overlaps the stripe fields defined in the step S1, i.e., the frame data which overlaps the stripe fields defined in the step S1 is developed (in a step S3).
Further, drawing pattern definition data which belongs to the sub-field defined is decided, and thereafter, the drawing pattern definition data is supplied to a pattern data decoder 23.
In the next, whether or not a next small figure group exists in the defined stripe field is determined (in a step S4). If a next small figure group does not exist in the step S4, the flow returns to the processing in the step S1.
Thus, multi-pass drawing is realized. For example, in case of two-pass drawing, the processing from the step S1 to S3 is repeatedly carried out twice.
If it is determined in the step S4 that a next small figure group exists, the small figure group is extracted (in a step S5). Subsequently, whether or not the origin of the extracted small figure group belongs to the stripe fields defined in the step S1 is determined (in a step S6).
If it is determined in the step S6 that the origin of the small figure group does not belong to the stripe field, the flow returns to the processing in the step S4.
Otherwise, if it is determined in the step S6 that the origin of the small figure group belongs to the stripe field, to which of the sub-field the small figure group belongs is determined (in a step S7).
Further, the position of the figure of the small figure group is obtained with respect to the origins of the sub-field. I.e., sub-deflection coordinates are calculated (in a step S8). Further, the calculated sub-deflection coordinates are stored into a memory or the like (in a step S9), the flow returns to the processing in the step S4.
Note that it is needless to say that the present invention is applicable to a case of single drawing, although the above embodiment has been explained with respect to a case of multi-pass drawing.
In this embodiment, the stripe field and sub-field has been explained as being set at the same time. However, only the sub-field may be shifted while the stripe field is fixed. Otherwise, the stripe field may be shifted while the sub-field is fixed.
Thus, according to this embodiment, sub-field is set independently from drawing pattern definition data, and to which sub-field figures belong are determined. Therefore, figures even defined as belonging to different small figure groups can be drawn together on one sub-field.
In addition, since positions of sub-field is shifted for each drawing stage of multi-pass drawing, one pattern figure is drawn at different positions in sub-field so that sub-field multi-pass drawing is realized.
Likewise, since positions of stripe set is shifted for each drawing stage of multi-pass drawing, one pattern figure is drawn at different positions in main-deflection field, so that stripe multi-pass drawing is realized.
Note that the present invention is not limited to the embodiment described above. The optical system structure of the drawing apparatus is not limited to the structure shown in FIG. 1, but may be variously modified in compliance with apparatus specifications.
Although the embodiment has been explained with reference to an example of an electron beam drawing apparatus, the present invention is also applicable to an ion beam drawing apparatus. Further, the present invention can be practiced in other modification forms than above, without deriving from the subject matter of the invention.
As has been explained above, according to the present invention, drawing pattern definition data of an efficient figure expression format can be directly used to perform drawing without repetition of sub-fields.
In addition, for one piece of drawing pattern definition data, multi-pass drawing can be performed for an arbitrary number of passes, without preparing drawing pattern definition data for each drawing pass of multi-pass drawing, by a calculator, or transmitting the data to a data developing circuit.
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 equivalent. | The present invention provides a charged beam drawing method comprising a first step of setting a stripe field independent of drawing pattern definition data and of determining the drawing pattern definition data which belongs to the stripe field set, a second step of setting a sub-field independent of the drawing pattern definition data and of determining the drawing pattern definition data which belongs to the sub-field, among the drawing pattern definition data determined, a third step of drawing the drawing pattern definition data which belongs to the sub-field onto an object to be subjected to drawing, a fourth step of shifting a position of the stripe field by a first predetermined value, and of shifting a position of the sub-field by a second predetermined value, and a fifth step of repeating the first to fourth steps for at least two times. | 8 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a plasma display panel (PDP) and, more particularly, to a composition of plasma display panel.
[0003] 2. Description of the Background Art
[0004] In general, a plasma display panel (PDP) device receives much attention as a next-generation display device together with a thin film transistor (TFT), a liquid crystal display (LCD), an EL (Electro-Luminescence) device, an FED (Field Emission Display) and the like.
[0005] The PDP is a display device which uses a luminescent phenomenon according to an energy difference made when red, green and blue fluorescent materials are changed from an excited state to a ground state after being excited by 147 nm of ultraviolet rays which are generated as a He+X3 gas or N3+X3 gas is discharged from a discharge cell isolated by a barrier rib.
[0006] Thanks to its properties of facilitation in manufacturing from a simple structure, a high luminance, a high light emitting efficiency, a memory function, a high non-linearity, a 160° or larger optical angular field and the like, the PDP display device is anticipated to occupy a 40″ or wider large-scale display device markets.
[0007] A structure of the conventional PDP will now be described with reference to FIG. 1 .
[0008] FIG. 1 is a sectional view showing a structure of a conventional PDP.
[0009] As shown in FIG. 1 , the conventional PDP includes: a lower insulation layer 20 formed on a lower glass substrate 21 ; an address electrode 22 formed at a predetermined portion on the lower insulation layer 20 ; a lower dielectric layer 19 formed on the address electrode 22 and the lower insulation layer 20 ; an isolation wall 17 defined in a predetermined portion on the lower dielectric layer 19 in order to divide each discharging cell; a black matrix layer 23 formed on the isolation wall 17 ; a fluorescent layer 18 formed with a predetermined thickness on the side of the black matrix layer 23 and the isolation wall 17 and on the lower dielectric layer 19 , and receiving ultraviolet ray and emitting each red, green and blue visible rays; a glass substrate 11 ; a sustain electrode 12 formed at a predetermined portion on the upper glass substrate 11 in a manner of vertically intersecting the address electrode 22 ; a bus electrode 12 formed on a predetermined portion on the sustain electrode 12 ; a first upper dielectric layer 14 formed on the bus electrode 13 , the sustain electrode 12 and the upper glass substrate 11 ; a second upper dielectric layer 15 formed on the first upper dielectric layer 14 ; and a protection layer (MgO) 16 formed on the second upper dielectric layer 15 in order to protect the second upper dielectric layer 15 .
[0010] The first and second upper dielectric layers 14 and 15 are called upper dielectric layers.
[0011] The operation of the conventional PDP will now be described.
[0012] First, as the upper glass substrate 11 and the lower glass substrate 21 of the conventional PDP, an SLS (Soda-Lime Silicate) glass substrate is used.
[0013] The lower insulation layer 20 is positioned on the lower glass substrate 21 , the SLS glass substrate, and the address electrode 22 is positioned on the lower insulation layer 20 .
[0014] The lower dielectric layer 19 positioned on the address electrode 22 and the lower insulation layer 20 blocks visible rays emitted toward the lower glass substrate 21 .
[0015] In order to increase the luminous efficacy, a dielectric layer having a high reflectance is used as the lower dielectric layer 19 . The lower dielectric layer 19 , a translucent dielectric layer with a reflectance of 60% or above, minimizes loss of light.
[0016] The fluorescent layer 18 is formed by laminating in a sequential order of red, green and blue fluorescent materials. A specific wavelength of visible ray is emitted depending on an intensity of an ultraviolet ray according to plasma generated between the isolation walls 17 .
[0017] Meanwhile, at a lower surface of the upper glass substrate 11 , the SLS glass substrate, there are formed the sustain electrode 12 positioned to vertically intersect the address electrode 22 and the bus electrode 13 positioned on the sustain electrode 12 . And upper dielectric layers 14 and 15 with an excellent light transmittance are positioned on the bus electrode 13 .
[0018] The protection layer 16 is positioned on the upper dielectric layer 15 in order to prevent the upper dielectric layer 15 from being damaged due to generation of plasma. Herein, since the first upper dielectric layer 14 is directly contacted with the sustain electrode 12 and the bus electrode 13 , it must have a high softening temperature in order to avoid a chemical reaction with the sustain electrode 12 and the bus electrode 13 . In addition, since the second upper dielectric layer 15 is expected to have a high smoothness because the protection layer 16 is formed thereon, its softening temperature must be lower by scores of ° C. than the first upper dielectric layer 14 .
[0019] Commonly, the PDP display device has a problem of jitter occurrence. The jitter phenomenon, which occurs as discharging is delayed for a certain time for a specific applied scan pulse, causes a mis-discharging and interferes a high speed driving.
[0020] The jitter phenomenon is affected mainly by a surface state of the protection layer (MgO) and a crystallinity, an electric permittivity (that is, a dielectric constant) and thickness of each layer, a structure and a gap of isolation walls and electrodes, a driving method, a type and a content of a discharging gas, and the like. Especially, Xe has a low diffusion rate in a discharging space, so if the Xe content is increased in order to obtain a high efficacy characteristics, there is higher probability that the jitter phenomenon occurs.
[0021] Therefore, in the conventional art, in order to solve the problem of the mis-discharging due to the jitter phenomenon, usually, an electric permittivity of the upper dielectric layer and the lower dielectric layer is increased or their thickness is reduced. In general, the upper dielectric layer and the lower dielectric layer of the PDP has an electric permittivity of about 12˜15 range, and especially, in case of the lower dielectric layer, because it contains TiO 2 powders for increasing the reflectance, it has a higher electric permittivity.
[0022] However, if the electric permittivity is increased by about twice, a discharge voltage is degraded due to the increase in the capacitance, and thus, about 20% of the overall jitter is reduced.
[0023] In addition, the jitter characteristics is also changed due to a change in the thickness of the upper dielectric layer and the lower dielectric layer of the PDP. For example, if the gap between the upper electrodes 12 and 13 and the lower electrode 22 narrows as the thickness of the upper dielectric layer and the lower dielectric layer of the PDP is reduced, the discharge voltage would be dropped and thus the jitter can be reduced.
[0024] The lower dielectric layer and the upper dielectric layer are made of a material having PbO as a principal component with an electric permittivity of about 12˜15, and the gap between the upper electrode and the lower electrode is maintained at about 100 μm.
[0025] The fabrication method of the lower dielectric layer 19 and the upper dielectric layers 14 and 15 will now be described in detail.
[0026] The lower dielectric layer is formed as follows: Mixed powders, in which scores of % of oxide in a powder state such as TiO 2 or Al 2 O 3 having a particle diameter of below 2 μm is mixed for improving reflection characteristics and controlling an electric permittivity, is mixed with an organic solvent to produce a paste with a viscosity of about 40000˜50000 cps, and the paste is printed/fired, thereby forming the lower dielectric layer. In this case, the firing temperature is usually at the range of 550˜600° C., and the thickness of the lower dielectric layer is about 20 μm.
[0027] The upper dielectric layer is formed as follows: a paste obtained by mixing an organic binder is coated to boro-silicate glass (BSG) powder with a size of a particle diameter of 1 μm˜2 μm and containing about 40% of Pb in a screen printing method, and then, the coated paste is fired at a temperature of 550° C.˜580° C.
[0028] Characteristics change in the jitter according to the change in the electric permittivity will now be described with reference to FIGS. 2A and 2B .
[0029] FIG. 2A shows jitter occurrence characteristics in case that a distance constant of the upper dielectric layer and the lower dielectric layer for a general PDP is 14, and FIG. 2B illustrates jitter occurrence characteristics in case that a distance constant of the upper dielectric layer and the lower dielectric layer for a general PDP is 25.
[0030] As shown in FIGS. 2A and 2B , if the electric permittivity is changed from 14 to 25, an operation speed is increased from 1.25 μs to 1.14 μs due to the increase in the capacitance, and according to which the overall jitter is reduced by about 11%.
[0031] However, since a withstand voltage is reduced according to the increase in the electric permittivity, there is a limitation in increasing the electric permittivity of the PbO-based dielectric material (the material of the upper dielectric layer and the lower dielectric layer).
[0032] In addition, in the case of increasing the capacitance by reducing the thickness of the material having the same electric permittivity, a problem arises that the conventional dielectric can not withstand the withstand voltage of about 560V.
[0033] To sum up, as stated above, the dielectric layer of the conventional PDP has the following problem.
[0034] That is, since the dielectric layer is made of the PbO-based dielectric material, if the electric permittivity of the dielectric is increased in order to reduce the jitter, the withstand voltage would be reduced. Thus, the electric permittivity of the dielectric can not be increased to its maximum.
[0035] In addition, if the thickness of the upper dielectric layer and the lower dielectric layer is reduced, the withstand voltage would be lowered down, causing the problem that jitter can not be effectively reduced, and thus, a high speed driving is hardly performed.
[0036] Other conventional PDPs and their fabrication methods are disclosed in the U.S. Pat. No. 5,838,106 issued on Nov. 17, 1998, a U.S. Pat. No. 6,242,859 issued on Jun. 5, 2001, and a U.S. Pat. No. 6,599,851 issued on Jul. 29, 2003.
SUMMARY OF THE INVENTION
[0037] Therefore, one object of the present invention is to provide a composition of a plasma display panel (PDP) capable of effectively reducing a jitter.
[0038] Another object of the present invention is to provide a composition of a PDP capable of preventing jitter occurrence and mis-discharging by increasing an electric permittivity of a dielectric to its maximum and increasing a capacitance.
[0039] Still another object of the present invention is to provide a composition of a PDP capable of heightening a luminance and an efficiency by reflecting a portion of a visible ray radiated from a fluorescent material.
[0040] To achieve these and other advantages and in accordance with the purpose of the present invention, as embodied and broadly described herein, there is provided a composition of a PDP containing a ferroelectric transparent ceramics material.
[0041] To achieve the above object, there is also provided a composition of a PDP, including: a lower dielectric layer containing a ferroelectric transparent ceramics material; an upper dielectric layer containing the ferroelectric transparent ceramics material; and a fluorescent material with the ferroelectric transparent ceramics material mixed therein or having a ferroelectric transparent ceramics thin film.
[0042] To achieve the above object, there is also provided a ferroelectric transparent ceramics material contained in a composition of a PDP is at least one of (Pb—La)(ZrTi)O 3 , (Pb,Bi)—(ZrTi)O 3 , (Pb,La)—(HfTi)O 3 , (Pb,Ba)—(ZrTi)O 3 , (Sr,Ca)—(LiNbTi)O 3 , LiTaO 3 , SrTiO 3 , La2Ti 2 O 7 , LiNbO 3 , (Pb,La)—(MgNbZtTi)O 3 , (Pb,Ba)—(LaNb)O 3 , (Sr,Ba)—Nb 2 O 3 , K(Ta,Nb)O 3 , (Sr,Ba,La)—(Nb 2 O 6 ), NaTiO 3 , MgTiO 3 , BaTiO 3 , SrZrO 3 or KnbO 3 .
[0043] The foregoing and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0044] The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention.
[0045] In the drawings:
[0046] FIG. 1 is a sectional view showing a structure of a PDP in accordance with a conventional art;
[0047] FIG. 2A shows jitter occurrence characteristics in case that a distance constant of the upper dielectric layer and the lower dielectric layer for a general PDP is 14;
[0048] FIG. 2B illustrates jitter occurrence characteristics in case that a distance constant of the upper dielectric layer and the lower dielectric layer for a general PDP is 25; and
[0049] FIG. 3 illustrates ferroelectric transparent ceramics materials applied in the present invention and their characteristics.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0050] Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the accompanying drawings.
[0051] A preferred embodiment of a composition of a PDP that is capable of effectively reducing a jitter by containing a ferroelectric transparent ceramics material thereto will now be described.
[0052] Namely, preferred embodiments of a composition of a PDP capable of increasing an electric permittivity of a dielectric of a PDP to its maximum by containing the ferroelectric transparent ceramics material, preventing a jitter occurrence and a mis-discharging by increasing a capacitance, and improving a luminance and an efficiency by reflecting a portion of a visible ray radiated from a fluorescent material, will now be described.
[0053] Herein, increase in the capacitance would lead to reduction of a jitter, which results in preventing of a mis-discharging generated when the PDP is at a low temperature or at a high temperature.
[0054] In addition, in the present invention, a ferroelectric transparent ceramics material having a high withstand voltage, a high electric permittivity (more than 1000), and a high dielectric strength is applied to the upper and lower dielectrics constituting the PDP device, to thereby increasing a capacitance and enhancing a resistance.
[0055] Moreover, the ferroelectric transparent ceramics material is also applied to a fluorescent material in order to increase the capacitance, and a visible ray reflection is induced to increase luminance and efficiency of the PDP.
[0056] FIG. 3 illustrates ferroelectric transparent ceramics materials applied in the present invention and their characteristics.
[0057] The materials as shown in FIG. 3 has a 1000 or higher electric permittivity, a 70% or higher visible ray transmittance, and a 10 6 /m or higher dielectric strength (not shown). Herein, since the electric permittivity, the ferroelectric transparent ceramics material applied in the present invention is higher than 1000, the jitter can be effectively reduced even with the less amount of ferroelectric transparent ceramics material.
[0058] Among the materials, (Pb, Bi)—(ZrTi)O 3 , (Pb, La)—(MgNbZrTi)O 3 , (Pb,Ba)—(LaNb)O 3 are transparent materials with a transmittance of almost 100% while having the high electric permittivity (higher than 1700), so they can be also applied to the upper dielectric of the PDP device.
[0059] Various embodiments in which the ferroelectric transparent ceramics material is applied to the PDP to reduce the jitter and thus prevent mis-discharging will now be described.
[heading-0060] First Embodiment
[0061] In the first embodiment, at least one of ferroelectric transparent ceramics materials of FIG. 3 is applied to the lower dielectric of the PDP. And the ferroelectric transparent ceramics powder is mixed in the conventional lower dielectric material or a ferroelectric transparent ceramics thin film is additionally formed on the conventional lower dielectric layer to increase a capacitance.
[0062] First, ferroelectric transparent ceramics powder is prepared and mixed to the lower dielectric material.
[0063] When the ferroelectric transparent ceramics powder is mixed in the lower dielectric material, the ferroelectric transparent ceramics powder with a particle diameter of a few μm is mixed in a range of 1 weight %˜20 weight % in parent glass powder. The ratio of the lower dielectric composition has been obtained by assuming the weight of the lower dielectric layer is 100 wt %.
[0064] Thereafter, the mixed powder is formed to a paste with a viscosity of about 40000˜50000, which is then printed and fired to form the lower dielectric layer.
[0065] When a ferroelectric transparent ceramics thin film is formed on the lower dielectric layer, a lower dielectric layer is formed thinner than the thickness of the conventional lower dielectric layer and the ferroelectric transparent ceramics material is coated with a thickness of thousands of Å at the surface of the thin lower dielectric layer or embedded in the lower dielectric layer by E-beam or sputtering.
[0066] Namely, by forming the ferroelectric transparent ceramics thin film on the lower dielectric layer, the electric permittivity of the lower dielectric can be improved.
[0067] In addition, by firing the ferroelectric transparent ceramics powder, the dielectric tissue can become denser, so that a life span of the device can be increased.
[heading-0068] Second Embodiment
[0069] In a second embodiment of the present invention, at least one of ferroelectric transparent ceramics materials shown in FIG. 3 is applied to the upper dielectric of the PDP. In addition, the ferroelectric transparent ceramics powder is mixed in the conventional upper dielectric material or a ferroelectric transparent ceramics thin film is additionally formed on the conventional upper dielectric layer in order to increase a capacitance.
[0070] First, ferroelectric transparent ceramics powder is prepared and mixed to the upper dielectric material.
[0071] When the ferroelectric transparent ceramics powder is mixed in the lower dielectric material, the ferroelectric transparent ceramics powder with a particle diameter of a few nm is mixed in a range of 1 wt %˜5 wt % in parent glass powder. The ratio of the upper dielectric composition has been obtained by assuming the weight of the upper dielectric layer is 100 wt %.
[0072] Thereafter, the mixed powder is formed to a paste with a viscosity of about 40000˜50000, which is then printed and fired to form the lower dielectric layer.
[0073] A ferroelectric transparent ceramics thin film is formed in the same manner as in the conventional art. That is, an upper dielectric layer is formed, on which the ferroelectric transparent ceramics material is coated with a thickness of scores of ˜hundreds of Å. Namely, by forming the ferroelectric transparent ceramics thin film on the upper dielectric layer, the electric permittivity of the upper dielectric can be improved.
[0074] Preferably, the ferroelectric transparent ceramics material used to heighten the electric permittivity of the upper dielectric is selected from the group consisting of (Pb,Bi)—(ZrTi)O 3 , (Pb,La)—(MgNbZrTi)O 3 , (Pb,Ba)—(LaNb)O 3 which have an extremely high transparent.
[heading-0075] Third Embodiment
[0076] In the third embodiment of the present invention, at least one of ferroelectric transparent ceramics material shown in FIG. 3 is applied to a fluorescent material of the PDP. The ferroelectric transparent ceramics material is mixed in power form to a conventional fluorescent material or a ferroelectric transparent ceramics thin film is additionally formed on the conventional fluorescent material, to thereby increasing a capacitance.
[0077] First, ferroelectric transparent ceramics powder is prepared and mixed to the fluorescent material.
[0078] When the ferroelectric transparent ceramics powder is mixed to the fluorescent material, the fine ferroelectric transparent ceramics powder with a particle diameter of a few nm is mixed in a range of 1 wt %˜10 wt % in the fluorescent material powder. The ratio of the fluorescent material composition has been obtained by assuming the weight of the fluorescent layer is 100 wt %.
[0079] When the ferroelectric transparent ceramics thin film is formed on the fluorescent layer, the ferroelectric transparent ceramics thin film is formed with a thickness of below 100 Å at the surface of the conventional fluorescent layer in an E-beam or a Sol-Gel method. That is, with the ferroelectric transparent ceramics thin film thereon, the fluorescent material can discharge a secondary electron and increase a surface charge, so that a mis-discharge occurrence can be reduced.
[0080] In this respect, if the ferroelectric transparent ceramics thin film is too thick, the ferroelectric transparent ceramics thin film is to absorb ultraviolet rays, reducing the luminance of the PDP. Thus, it is preferred that the ferroelectric transparent ceramics thin film has the thickness of below 100 Å.
[0081] In the present invention, by applying one of the first to third embodiment to the PDP, the electric permittivity of the PDP device can be increased, and accordingly, the capacitance can be also increased. In addition, because the ferroelectric transparent ceramics material used in the present invention has a high dielectric strength, a discharge withstand voltage can be heightened. Therefore, as the capacitance is increased, the jitter can be reduced, and thus, a mis-discharge occurrence rate can be reduced.
[0082] Moreover, because the ferroelectric transparent ceramics material can reflect a portion of the visible ray radiated from the fluorescent material, the strength of the discharged visible ray can be increased.
[0083] As so far described, by mixing the ferroelectric transparent ceramics powder to the upper dielectric or/and lower dielectric material or by forming the ferroelectric transparent ceramics thin film on the upper dielectric or/and lower dielectric, the electric permittivity of the upper and lower dielectric can be heightened.
[0084] In addition, because the electric permittivity of the upper and lower dielectric is heightened, the capacitance is increased, the jitter is reduced, and the mis-discharge occurrence rate can be considerably reduced.
[0085] Moreover, by mixing the ferroelectric transparent ceramics powder to the fluorescent material or by forming the ferroelectric transparent ceramics thin film on the fluorescent material, the visible ray radiated from the fluorescent material can be partially reflected, so that the luminance and efficiency of the PDP can be also enhanced.
[0086] As the present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, it should also be understood that the above-described embodiments are not limited by any of the details of the foregoing description, unless otherwise specified, but rather should be construed broadly within its spirit and scope as defined in the appended claims, and therefore all changes and modifications that fall within the metes and bounds of the claims, or equivalence of such metes and bounds are therefore intended to be embraced by the appended claims. | A composition of a plasma display panel (PDP) is disclosed. In order to effectively reduce a jitter, the composition contains a ferroelectric transparent ceramics material. | 7 |
BACKGROUND OF THE INVENTION
The present invention relates to waiting means for an embroidering machine, and more particularly to such waiting means wherein for example when the sewing operation is stopped, a needle, a nipple and a presser foot are lifted from the site where sewing operation is carried out to wait for the subsequent sewing operation.
SUMMARY OF THE INVENTION
According to the present invention, there is provided waiting means for use in an embroidering machine which has a head; a needle bar vertically movably carried in the forward end portion of the head and having a needle operatively connected thereto for forming embroidery stitches on a cloth; a nipple vertically movably carried in the forward end portion of the head in parallel relation with the needle bar, the nipple slidably receiving the needle bar therewithin and adapted to be lowered synchronously when the needle bar is lowered so as to press the cloth at the needle location where the needle passes through the cloth; and a presser foot vertically movably carried in the forward end portion of the head in parallel relation with the needle bar and the nipple, the presser foot, when the needle is raised, being adapted to be displaced horizontally so as to horizontally feed the cloth while pressing the cloth around the needle location. The waiting means comprises lifting means mechanically coupled to the top portion of the head and adapted to lift each of the needle bar, the nipple and the presser foot upwardly so as to bring each to a waiting position when the sewing operation is stopped. In a preferred embodiment of the present invention, the lifting means includes a needle waiting lever, a nipple waiting lever, and a presser foot waiting lever, each of which levers operatively engaging with a cam for raising the needle bar, the nipple and the pressor foot, respectively, when the sewing operation is stopped. In another embodiment, grooved cams are used to operatively engage with the waiting levers so that the fulcrum of swing of the respective levers is displaced to thereby adjust the upward movement from the top dead point of the needle, the nipple and the presser foot, respectively.
The present invention is directed to a modified mechanism for actuating the needle waiting lever, wherein the lifting means comprises a swing lever pivotally connected to the head for raising the needle bar when the sewing operation is stopped, the swing lever having a fulcrum of swing adapted for displacement; a main cam rotatably connected to the head and mechanically coupled to a source of rotational drive of the embroidering machine for normally reciprocating the needle bar; and an auxiliary cam rotatably connected to the head and mechanically coupled to a source of rotational drive of the embroidering machine for actuating the swing lever; the swing lever alternately engaging the main cam or the auxiliary cam to interlock solely therewith; whereby, when the fulcrum of the swing lever is displaced, the top dead point of the needle bar during normal vertical movement shifts up and down so as to adjust the length of stitch loops.
It is the primary object of the present invention to provide waiting means for an embroidering machine which, for example when cloths are changed or stitches are corrected, permits increased room above the sewing region to improve the accessibility for changing of cloths, inspection of stitches and others.
It is another object of the present invention to provide means for adjusting the length of a stitch loop in an embroidering machine, in which the loop length of the thread that forms stitches can be easily and positively changed.
The invention will become more apparent from the claims and the description as it proceeds in connection with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a front view of the essential parts of an embroidering machine incorporating a first embodiment of the present invention;
FIG. 2 is a side elevational view of FIG. 1;
FIG. 3 is a side elevational view of the nipple mechanism of FIG. 1;
FIG. 4 is a side elevational view of the cloth pressing mechanism of FIG. 1;
FIG. 5 is a top plan view of the waiting mechanism according to the first embodiment of the present invention;
FIG. 6 is a side elevational view of FIG. 5;
FIG. 7 is a top plan view of the waiting mechanism of a second embodiment of the present invention;
FIG. 8 is a view looking in the direction of arrows X--X of FIG. 7;
FIG. 9 is a view looking in the direction of arrows Y--Y of FIG. 7;
FIG. 10 is a view looking in the direction of arrows Z--Z of FIG. 7;
FIG. 11 is a diagrammatic side elevational view of the essential parts of a modified mechanism for raising the needle bar;
FIG. 12 is an enlarged side view of the mechanism of FIG. 11;
FIG. 13 is a view looking in the direction of arrows X--X of FIG. 12; and
FIG. 14 is a side view similar to FIG. 12 illustrating the swing lever being displaced.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Referring now to FIGS. 1 to 4 wherein the first embodiment of the present invention is shown, a support bracket 1 of recumbent U-shaped configuration in vertical section is provided at the forward end of a machine head H, and has upper and lower pieces 1a and 1b. A needle bar 2 is vertically movably supported by the upper and lower pieces 1a and 1b and has at the upper end portion thereof an engaging portion 2a having upper and lower flanges. A needle 3 is concentrically secured to the lower end of the needle bar 2. A bevel gear 4 is fitted on the mid portion of the needle bar 2. When the cloth to be embroidered is fed horizontally by a cloth feed mechanism (not shown), rotation of a driving motor (not shown) is transmitted through the bevel gear 4 to the needle bar 2 to rotate the same in the direction of cloth to be embroidered.
A holder 6 is disposed at the back of the upper end portion of the needle bar 2, and an elevating member 5 is vertically movably carried in the forward end of the holder 6. The elevating member 5 has a base 5a, a first engaging piece 5b extending sideways from the right (as viewed in FIG. 1) upper end of the base 5 and a forked nipping portion 5c projecting so as to nippingly engage with the engaging portion 2a of the needle bar 2. A main cam 8 is horizontally rotatably carried in the holder 6. A pin 7 is provided at the rear end of the base 5a projecting in such a way as to contact with the upper surface of the main cam 8. With this arrangement, the steady rotation of a main shaft 9 of the embroidering machine drives the main cam 8 for rotation which is converted through the pin 7 into vertical movement of the elevating member 5, and the needle bar 2 is vertically moved through the elevating member 5.
A nipple bar 10 is vertically movably carried by the upper and lower pieces 1a and 1b of the support bracket 1 in parallel relation to the needle bar 2 on the right hand (as viewed in FIG. 1). A second engaging piece 11 is secured to the upper end of the nipple bar 10. Numeral 13 designates a swing lever swingingly movable through rotation of a front cam 12A secured to the front end of the main shaft 9. A contact pin 14 transversely extends backwardly at the mid portion of the nipple bar 10 and is brought to bear on the swing lever 13 to vertically move the nipple bar 10 synchronously with the needle bar 2. A nipple holder 16 having a forked connecting portion 15 is secured to the lower end of the nipple bar 10.
A nipple 17 is fitted rotatably and vertically slidably on the lower portion of the needle bar 2, and is vertically movably carried by the lower piece 1b of the support bracket 1. The nipple 17 is of substantially cylindrical configuration and has at the upper end thereof an engaging portion 17a which is adapted to be engaged with the connecting portion 15 of the nipple holder 16 to connect the nipple 17 and the nipple bar 10 with each other so that the nipple 17 can be moved vertically together with the nipple bar 10. When the needle bar 2 is lowered, the needle 3 projects from under the lower end of the nipple 17 into the cloth and the nipple 17 is synchronously lowered to press the cloth, surrounding the needle location, against a feed plate 18. The feed plate 18 is disposed in contact with the lower surface of the cloth, being horizontally movable, and connected with the feed mechanism so as to feed the cloth around the needle location when the needle bar 2 moves upwardly.
A pressing bar 19 is vertically movably carried by the upper and lower pieces 1a and 1b of the support bracket 1 in parallel on the left hand (as viewed in FIG. 1) of the needle bar 2. A third engaging piece 20 is secured to the top end of the pressing bar 19. Numeral 21 designates a swing lever swingingly movable through rotation of a rear cam 12B provided in parallel at the back of the front cam 12A. A contact pin 22 transversely extends backwardly at the mid portion of the pressing bar 19 and is brought to bear on the swing lever 21 to vertically move the pressing bar 19 with the phase difference of 180 degrees in relation to the needle 3. There are provided, above and below the contact pin 22, upper and lower support pieces 23A and 23B transversely extending forwardly, respectively.
A universal joint 24 is movably fitted in the upper support piece 23A and also loosely received by the lower support piece 23B in such a manner as to be tilted relative to the support piece 23B. A resilient member 25 is connected to the lowermost end of the universal joint 24 and adapted to be resiliently transformed in the horizontal direction and restored centripetally through its resiliency. An annular presser foot 26 is connected through a connecting bar 26a to the lowermost end of the resilient member 25, and is placed in oppossed relation to the upper surface of the feed plate 18 in such a way that the center of the presser foot 26 is on the axis of rotation J of the needle 3. When the presser foot 26 is lowered through the universal joint 24 in connection with the pressing bar 19, the presser foot 26 presses the cloth around the needle location against the feed plate 18, and when the feed plate 18 moves horizontally, it is displaced in accordance with the movement of the feed plate 18 so as to feed the cloth around the needle location. When the presser foot 26 is moved upwardly in connection with the pressing bar 19, the presser foot 26 releases the cloth and is automatically restored centripetally to the axis of rotation J.
Now the waiting mechanism for the needle 3, the nipple 17 and the presser foot 26 will be described with reference to FIGS. 5 and 6. A shaft 28 is disposed transversely around the upper end portion of the machine head H, and a needle waiting lever 27 is pivotally carried by the shaft 28. The needle waiting lever 27 contacts with the elevating member 5 in such a way that a pin 29 provided at the forward end 27a of the needle waiting lever 27 will be brought to bear on the lower surface of the first engaging piece 5b of the elevating member 5 when it is at the most lowered position. The rearmost end 27b of the needle waiting lever 27 is connected through a support arm 36 to the shaft 28 and is in contact with a first waiting cam 31 which is fitted on a driving shaft 30 controlled for rotation of 180 degrees at a time by a motor (not shown) driven for rotation when the sewing operation is stopped. When the rearmost end 27b of the lever 27 is pressed down through the rotation of the first waiting cam 31, the elevating member 5 is pressed upwardly by the forward end 27a of the lever 27, and the needle bar 2 moves upwardly to be held at its elevated position, and the needle 3 is lifted upwardly from its normal position. When the first waiting cam 31 is further rotated 180 degrees, the rearmost end 27b of the lever 27 moves upwardly. As the forward end 27a is lowered, the elevating member 5 is lowered to its normal position, and consequently the needle bar 2 is lowered to restore the needle 3 to its normal position for the subsequent sewing operation.
A nipple waiting lever 32 is pivotally carried by the shaft 28 in parallel relation to the needle waiting lever 27. The nipple waiting lever 32 contacts with the nipple bar 10 in such a way that the forward end 32a of the nipple waiting lever 32 will be brought to bear on a pin 11a of the second engaging piece 11 which is secured to the upper end portion of the nipple bar 10 when it is at the most lowered position. The rearmost end 32b of the lever 32 is in contact with a second waiting cam 33 fitted on the driving shaft 30 on the right hand of the first waiting cam 31. When the rearmost end 32 of the nipple waiting lever 32 is pressed down through rotation of the second waiting cam 33, the nipple bar 10 is pressed upwardly by the forward end 32a to be held at its elevated position, and the nipple 17 is lifted upwardly from its normal position. When the second waiting cam 33 is further rotated 180 degrees, the rearmost end 32b of the lever 32 is moved upwardly, and as the forward end 32a is lowered, the nipple bar 10 is lowered to restore the nipple 17 to its normal position for the subsequent sewing operation.
A presser foot waiting lever 34 is pivotally carried by the shaft 28 in parallel relation to the needle waiting lever 27 and the nipple waiting lever 32. The presser foot waiting lever 34 contacts with the pressing bar 19 in such a way that the forward end 34a of the lever 34 will be brought to bear on a pin 20a of the third engaging piece 20 which is secured to the upper end portion of the pressing bar 19 when it is at the most lowered position. The rearmost end 34b is in contact with a third waiting cam 35 fitted on the driving shaft 30 at the left hand of the first waiting cam 31. When the rearmost end 34b of the lever 34 is pressed down through rotation of the third waiting cam 35, the pressing bar 19 is pressed upwardly by the forward end 34a to be held at its elevated position, and the presser foot 26 is lifted upwardly from its normal position. When the third waiting cam 35 is further rotated 180 degrees, the rearmost end 34b of the lever 34 is moved upwardly, and as the forward end 34a is lowered, the pressing bar 19 is lowered to restore the presser foot 26 to its normal position for the subsequent sewing operation.
Now, the operation of the first embodiment thus constructed will be described. When the sewing operation is stopped, the first, the second and the third waiting cams 31, 33 and 35 are controlled for rotation to pivotally move the needle waiting lever 27, the nipple waiting lever 32 and the presser foot waiting lever 34, respectively, and the needle 3, the nipple 17 and the presser foot 26 are lifted upwardly from their normal positions to be held at their elevated positions. With this arrangement, when the sewing operation is stopped, the needle 3, the nipple 17 and the presser foot 26 are brought apart from the upper surface of the cloth around the needle location. Thus, the sewing condition and the waiting condition can be easily shifted to each other, thereby greatly improving the efficiency of the operations incidental to the embroidery sewing such as setting the cloth in and out of a tambour, as is well known in the art, inspecting the stiches and correcting incorrect stitches.
Now the second embodiment of the present invention will be described with reference to FIGS. 7 and 10. Like parts are given like reference numerals having A affixed thereto. Three support arms 36A are pivotally connected to the head H, as seen in FIG. 7, each of which support arms 36A having a support pin 38 at the forward end thereof. A needle waiting lever 27A, a nipple waiting lever 32A and a presser foot waiting lever 34A are each pivotally carried by the support pin 38. Three circular adjusting cams 37 are rotatably carried on shaft 39 which is disposed generally above the support arms 36A. Each of the adjusting cams 37 has a groove with which each of the support pins 38 is operatively engaged. As may be seen in FIGS. 8, 9 and 10, each of the waiting levers 27A, 32A and 34A is pivotally moved through rotation of the first waiting cam 31A, the second waiting cam 33A and the third waiting cam 35A all fitted on the driving shaft 30A, respectively. Pivotal movement of each of the waiting levers 27A, 32A and 34A permits the first engaging piece 5bA connected to the needle bar, the second engaging piece 11A connected to the nipple bar and the third engaging piece 20A connected to the pressing bar to move vertically. When the fulcra S of swing of the waiting levers 27A, 32A and 34A are vertically adjusted through rotation of the adjusting cams 37, the levels of vertical movements of the forward ends of the waiting levers 27A, 32A and 34A or the contacting positions with the needle bar, nipple bar and pressing bar are vertically adjusted.
As the operation of the second embodiment is almost the same as that of the first embodiment, the explanation will be omitted.
Referring to FIGS. 11 to 14, shown therein is a modified mechanism for raising the needle bar. Numeral 51 designates a support bracket disposed at the forward end of the machine head H. A vertically movable needle bar 52 is rotatably carried by the support bracket 51. A needle 53 is secured to the lowermost end of the needle bar 52, and an interlocking piece 54 is attached to the top end of the needle bar 52.
A transversely extending shaft 55 is rotatably carried in the upper portion of the machine head H, and an upper interlocking gear 56 is fitted on the shaft 55. An eccentric collar 57 of eccentrically cylindrical configuration is fitted on the shaft 55, the center O 1 thereof being displaced from the axis O 2 of the shaft 55.
A swing lever 58 is pivotally carried on the shaft 55 through the eccentric collar 57, the swing lever 58 idly receiving the eccentric collar 57 to pivot about the center O 1 of the eccentric collar 57. The swing lever 58 is a three-pronged member having a front arm 58a, an upper arm 58b and a lower arm 58c. The front arm 58a contacts with the interlocking piece 54 of the needle bar 52 through a lock pin 59 provided at the front end of the front arm 58a, and thereby the needle bar 52 is vertically moved through swinging movement of the swing lever 58.
Numeral 61 designates a driving shaft rotatably carried by the head H and extending transversely above the shaft 55. The driving shaft 61 is driven for rotation through steady rotation of a main shaft (not shown) of the embroidering machine. A main cam 60 is fitted on the driving shaft 61 in opposed relation to the upper arm 58b of the swing lever 58, and has on the side surface thereof an annular cam groove 63 eccentrically provided to receive a guide pin 62 projecting from the extreme end of the upper arm 58b so as to impart steady swinging movement of the upper arm 58b. The cam groove 63 communicates with a clearance groove 64 which is provided at the most eccentric portion 63a corresponding to the top dead point of the needle bar 51 and is outwardly opening to allow the guide pin 62 to disengage from main cam 60 through the cam groove 63 when the guide pin 62 is guided to the most eccentric portion 63a. When the guide pin 62 is lifted outwardly from the clearance groove 64, the swing lever 58 is released to disengage from the main cam 60.
Numeral 65 designates an interlocking shaft 65 rotatably carried by the head H and extending transversely below the shaft 55. The interlocking shaft 65 is controlled for rotation by a control motor (not shown), such as a pulse motor, which is driven when the needle bar 52 moves upwardly to its top dead point.
A lower interlocking gear 66 is fitted on the interlocking shaft 65 in such a way as to mesh with the upper interlocking gear 56 to rotate the shaft 55. An auxiliary cam 67 is fitted on the interlocking shaft 65 in opposed relation to the lower arm 58c of the swing lever 58 and rotatable together with the lower interlocking gear 66. The auxiliary cam 67 has a convex portion 67a and a clearance portion 67b. When the main cam 60 is rotated until the most eccentric portion 63a of the cam groove 63 faces the guide pin 62 of the upper arm 58b, the lower arm 58c is pushed in the clockwise direction by the convex portion 67a through rotation of the control motor to withdraw the guide pin 62 outwardly from the main cam 60 through the clearance groove 64, and to thereby bring the swing lever 58 out of contact with the main cam 60. Thus, the top dead point of the swing lever 58 is displaced to thereby lift the needle bar 52 upwardly from its top dead point during normal vertical movement. The clearance portion 67b permits swinging movement of the lower arm 58c during the normal swinging movement of the swing lever 58 to release the swing lever 58 from the auxiliary cam 67. Thus, the swing lever 58 is brought to bear on the main cam 60 or the auxiliary cam 67 alternatively to be interlocked therewith. When the auxiliary cam 67 is rotated through rotation of the control motor to push the lower arm 58c by the convex portion 67a, the upper arm 58b is removed from the main cam 60 and subsequently the needle bar 52 is lifted upwardly. Further, when the clearance portion 67b faces the lower arm 58c, rotation of the lower interlocking gear 66 which is rotated together with the auxiliary cam 67 is transmitted through the upper interlocking gear 56 to the shaft 55. The shaft 55 is then rotated and at the same time, the center O 1 of swing of the swing lever 58 is displaced through the rotation of the eccentric collar 57 (See FIG. 14.), so that the top dead point and the bottom dead point of the needle bar 52 are vertically moved.
Thus, simple movement of the top dead point of the needle bar 52 allows ready change of the space relative to the lower sewing mechanism, such as a looper, disposed below in opposed relation to the needle 53 so as to adjust the loop length of the stitch formed by vertical movement of the needle 53.
When the cloth is fed horizontally for embroidering, travel of the cloth and loop length determined by the vertical movement of the needle 53 are adjusted, and horizontal feed of the cloth and the displacement of the top dead point of the needle bar 52 take place at the same time so as to eliminate improper tension applied on the thread when the stitch is formed, with the advantageous result of achievement of regular and accurate embroidering.
While the invention has been described with reference to a few preferred embodiments thereof, it is to be understood that modifications or variations may be easily made without departing from the scope of this invention which is defined by the appended claims. | Disclosed herein is waiting means for use in an embroidering machine which has a head; a needle bar vertically movably carried in the forward end portion of the head and having a needle operatively connected thereto for forming embroidery stitches on a cloth; a nipple vertically movably carried in the forward end portion of the head in parallel relation with the needle bar, the nipple slidably receiving the needle bar therewithin and adapted to be lowered synchronously when the needle bar is lowered so as to press the cloth at the needle location where the needle passes through the cloth; and a presser foot vertically movably carried in the forward end portion of the head in parallel relation with the needle bar and the nipple, the presser foot, when the needle is raised, being adapted to be displaced horizontally so as to horizontally feed the cloth while pressing the cloth around the needle location. The waiting means comprises lifting means mechanically coupled to the top portion of the head and adapted to lift each of the needle bar, the nipple and the presser foot upwardly so as to bring each to a waiting position when the sewing operation is stopped. | 3 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a U.S. national stage application of International Application No. PCT/EP2006/066128 filed Sep. 7, 2006, which designates the United States of America, and claims priority to German application number 10 2005 043 817.2 filed Sep. 13, 2005, the contents of which are hereby incorporated by reference in their entirety.
TECHNICAL FIELD
The subject matter of the invention is a method for operating a fuel pump in order to feed fuel from a fuel container to an internal combustion engine, in which method electrical energy in the form of pulses is fed to the fuel pump and the duty cycle is controlled as a function of the fuel requirement of the internal combustion engine. Such controlled fuel pumps are used, in particular, in fuel containers of motor vehicles.
BACKGROUND
A fuel pump which is controlled electronically as a function of the fuel requirement is known from DE 43 02 383 A1. Here, electrical energy is fed in a pulsed form to the fuel pump, wherein the duty cycle is changed as a direct function of a position output signal of an air mass flow rate sensor, wherein the sensor generates the signal as a function of the position of a throttle valve whose position is a measure of the fuel requirement of the internal combustion engine. This method of the regulated pulsed feeding of electrical energy is also known as pulse duration modulation. In particular, electric motors are composed of magnetic or magnetically permeable material which can have magnetostriction effects. Furthermore, they contain current-conducting electrical conductors in magnetic fields which experience a force which corresponds to electric current. If such an electric motor is regulated by means of pulse duration modulation, corresponding alternating forces act on the electrical conductors. In addition, the magnetostriction of the magnetic materials in the alternating magnetic field also brings about an alternating force effect and/or changes in dimensions of these components. Owing to the alternating force effects and the changes in dimensions, the electric motor may be mechanically excited so that sound waves are emitted into the surroundings. If the frequency of the sound waves is in the range of human hearing, the sound waves are perceived as noise. This is generally undesired.
It is therefore generally known to avoid sounds which can be heard by the human ear by selecting a frequency of the duty cycle of the pulse duration modulation outside the range of human hearing, preferably above 20 kHz.
The power loss of power switching transistors of corresponding control electronics is composed of conduction losses and switching losses. While the conduction losses are determined by the voltage drop across the component and the current, the switching losses are determined by the number of switching processes per time unit and the switched current. Depending on the operating parameters of the system to be controlled, the switching losses can significantly exceed the conduction losses. A further disadvantage is that the power loss leads to an increase in temperature of the switching electronics which is manifest as a reduction in the service life of the switching electronics.
SUMMARY
In a method for operating a fuel pump, on the one hand, noises which are disruptive to the user can be avoided and, on the other hand, the power loss of the control electronics may be reduced. According to an embodiment, a method for operating a fuel pump in order to feed fuel from a fuel container to an internal combustion engine, may comprise the steps of: feeding electrical energy in the form of pulses periodically to the fuel pump, controlling the duration of the pulses as a function of the fuel requirement of the internal combustion engine, and controlling the frequency of the pulses in such a way that a higher frequency is set when there is a low delivery rate of the fuel pump than when there is a relatively high delivery rate.
According to a further embodiment, a low delivery rate of the fuel pump may be less than 40% switch-on duration of the operating voltage, preferably less than 30% switch-on duration of the operating voltage, of the fuel pump. According to a further embodiment, when the delivery rate of the fuel pump is low, the frequency may be at least 10 kHz, preferably at least 20 kHz. According to a further embodiment, when the delivery rate is relatively high, the frequency of the pulses may be at a maximum of 50 Hz up to 10 kHz, preferably in the region of 1 kHz. According to a further embodiment, when there is a changeover between a relatively low delivery rate and a relatively high delivery rate of the fuel pump, the frequency may change continuously. According to a further embodiment, when there is a changeover between a relatively low delivery rate and a relatively high delivery rate of the fuel pump, the frequency may be changed suddenly or in a stepped fashion. According to a further embodiment, the current for the fuel pump may be used as a controlled variable for the changes in frequency. According to a further embodiment, the temperature of the control electronics may be used as a controlled variable for the changes in frequency. According to a further embodiment, a combination of the temperature of the control electronics and the current may be used as a controlled variable for the changes in frequency. According to a further embodiment, at least one integral controller can be used for the changes in frequency. According to a further embodiment, a method with generation of sliding mean values can be used for the changes in the frequency.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be explained in more detail with reference to an exemplary embodiment. In the drawings:
FIG. 1 shows a device which is operated with the method according to an embodiment, and
FIG. 2 is a current/time diagram according to the method.
DETAILED DESCRIPTION
The frequency of the pulses may be controlled in such a way that a higher frequency is set when there is a low delivery rate of the fuel pump than when there is a relatively high delivery rate.
While the delivery rate of the fuel pump is controlled by pulse duration modulation of the electrical energy supplied to the fuel pump, operating the fuel pump with different frequencies of the pulse-shaped energy supply permits the fuel pump to be adapted to various environmental conditions. Operating the fuel pump with a high frequency of the pulse duration modulation when the delivery rate is low causes the fuel pump to run particularly quietly in this operating state since it emits little solid-borne sound owing to magnetic effects. This is desired in particular if the low delivery rate of the fuel pump is accompanied by a low speed of the motor vehicle since, owing to the low travel speed, the travel noises are also low so that loud noises of the fuel pump are perceived as being disruptive.
In contrast, a relatively high delivery rate of the fuel pump occurs only when there is a relatively high fuel requirement of the internal combustion engine. This increased fuel requirement is accompanied by a relatively loud noise of the internal combustion engine, and by corresponding wind noises when the motor vehicle travels at a corresponding speed. Owing to these noises, the noises of the fuel pump are negligible to the effect that even relatively loud noises of the fuel pump can no longer be perceived. The fuel pump can therefore be operated at a relatively low frequency of pulse duration modulation. As a result, owing to the relatively small number of switching processes per time unit, the switching losses for the pulse duration modulation are minimized. As a result, the temperature loading of the control electronics is reduced owing to the lowering of the frequency, which has a positive effect on the service life of the control electronics. The method also has the advantage that it refers not only to a specific system but also can be used for fuel systems with fuel pumps of very different power classes and mechanical or electronic commutation.
A low delivery rate of the fuel pump is, according to this method, less than 40% switch-on duration of the operating voltage, preferably less than 30% switch-on duration of the operating voltage of the fuel pump.
In order to operate the fuel pump when the delivery rate is low, a frequency for pulse duration modulation of at least 10 kHz, preferably at least 20 kHz has proven advantageous. At these frequencies, the electromagnetic or magnetostrictive generation of audible solid-borne sound in the fuel pump is largely avoided so that the fuel pump can be operated so quietly that the noises which are generated in this way cannot be perceived acoustically even in relatively quiet surroundings.
By contrast, the method permits the frequency of the pulse duration modulation to be lowered to 50 Hz to 10 kHz, preferably in the region of 1 kHz, when the delivery rate is relatively high, in which case even 40% switch-on duration of the operating voltage of the fuel pump is considered to be a relatively high delivery rate.
When there is a changeover between a low delivery rate and a relatively high delivery rate of the fuel pump, the change in the frequency can easily take place continuously.
In another advantageous refinement, when there is a changeover between a low delivery rate and a relatively high delivery rate of the fuel pump, the frequency is changed suddenly or in a stepped fashion.
A particularly easy way of controlling the frequency is provided if the frequency is changed as a function of the current. Owing to the load-dependence of the current of the fuel pump, the current constitutes a good controlled variable.
Under certain driving conditions, load changes can occur at very short time intervals. When there is current-dependent frequency control, this can mean that there are equally frequent changes in frequency.
In order to avoid rapid changes in frequency it has proven advantageous to allow the rate of change of the frequency control to be carried out integrally as a function of the current in that at least one integral controller is provided. In particular, rapid changes in current are attenuated by the integral controller since as a result the change in frequency occurs more slowly than the change in current. Another way of controlling the frequency which is also suitable can be carried out by evaluating the temperature of the control electronics. The frequency is changed as a function of the measured temperature of particularly critical components. As a result, the integral controller can be dispensed with because the temperature constitutes the integration of past current loads and is the critical parameter for the control electronics.
If the temperature alone constitutes an excessively slow manipulated variable, a combination of temperature and current can also be used for frequency control.
FIG. 1 is a schematic illustration of the fuel container 1 of a motor vehicle (not illustrated in more detail). A fuel pump 2 which delivers fuel from the fuel container 1 to an internal combustion engine 4 of the motor vehicle via a forward flow line 3 is arranged in the fuel container 1 . An electrical signal 5 which is acquired in a known fashion and which constitutes a measure of the instantaneous fuel requirement of the internal combustion engine 4 is fed to control electronics 6 for the fuel pump 2 . The control electronics 6 comprise a pulse generator 7 which feeds the current for the fuel pump 2 in the form of pulses to the fuel pump 2 . The pulses are fed with constant amplitude, and the pulse duration here is a measure of the supplied electrical energy. In the illustration shown, the control electronics 6 are arranged outside the fuel container 1 , for example as a component of the engine controller. However, it is also conceivable to arrange the control electronics 6 on or in the fuel container 1 , for example on a flange or in the fuel pump 2 . Furthermore, the control electronics 6 comprise an integral controller 8 , which, in particular in the case of rapid load changes at the internal combustion engine 4 , permits changes in frequencies to occur more slowly than the changes in current.
The diagram in FIG. 2 shows, in region I, the current pulses which are generated by the pulse generator 7 for a signal 5 which corresponds to a full load operating mode, i.e. the internal combustion engine is operated with approximately maximum fuel consumption. The pulses are clocked with a relatively low frequency of 1 kHz. In such an operating mode of the internal combustion engine, the noise of the internal combustion engine and the corresponding travel noises are relatively loud so that noises of the fuel pump which are possibly generated by magnetostriction or magnetic forces at this frequency are not perceived.
The region II shows the operation of the internal combustion engine with approximately 60% power. Although the pulse duration of the pulses is correspondingly shorter, the frequency of the pulses is the same as that in region I. In this operating mode of the internal combustion engine, the noises of the internal combustion engine are also louder than the noises of the fuel pump so that in this power range of the internal combustion engine the pulses can also be clocked with a frequency of 1 kHz without the noises of the fuel pump being perceived.
The region III shows the operation of the internal combustion engine in the lower power range which corresponds, for example, to idling or to travel at low rotational speeds. When this travel behavior occurs, the noises of the internal combustion engine and the travel noises are significantly lower than when travel behavior as per region I or region II occurs. The pulses are therefore generated by the pulse generator with a frequency of 20 kHz. This frequency is so high that in the fuel pump no noises are generated in the range of human hearing, with the result that no noises from the fuel pump are perceived in this operating mode of the internal combustion engine either. | In a method for operating a fuel pump in order to guide fuel from the fuel container of an internal combustion engine, the electric energy, which is in the form of pulses, is periodically guided to the fuel pump and the duration of the pulses is controlled according to the fuel required by the internal combustion engine. The frequency of the pulses is controlled in such a manner that, in the event of low pump rate of the fuel pump, the frequency is controlled to a higher level than in the even of a high pump rate. | 5 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates to ink jet printing devices and more particularly to a thermal ink jet or Microelectromechanical Systems (MEMS) printhead having an array of coplanar nozzles in a nozzle face that are entirely surrounded by an insulative polymeric material, together with a method of fabrication thereof.
[0003] Thermal ink jet printing is a type of drop-on-demand ink jet system wherein an ink jet printhead expels ink droplets on demand by the selective application of a current pulse to a thermal energy generator, usually a resistor, located in capillary-filled parallel ink channels a predetermined distance upstream from the channel nozzles or orifices. The channels' ends opposite the nozzles are in communication with an ink reservoir to which an external ink supply is connected. The current pulses momentarily vaporize the ink and form bubbles on demand. Each temporary bubble expels an ink droplet and propels it towards a recording medium. The printing system may be incorporated in either a carriage-type printer or pagewidth type printer. A carriage-type printer generally has a relatively small printhead containing the ink channels and nozzles. The printhead is usually sealingly attached to a disposable ink supply cartridge in a combined printhead and cartridge assembly which is reciprocated to print one swath of information at a time on a stationarily held recording medium such as paper. After the swath is printed, the paper is stepped a distance equal to the height of the printed swath so that the next printed swath will be contiguous therewith. The procedure is repeated until the entire page is printed. In contrast, the pagewidth printer has a stationary printhead having a length equal to or greater than the width of the paper. The paper is continually moved past the printhead in a direction normal to the printhead length and at a constant speed during the printing process.
[0004] U.S. Pat. No. Re. 32,572 to Hawkins et al discloses a thermal ink jet printhead and method of fabrication. In this case, a plurality of printheads may be concurrently fabricated by forming a plurality of sets of heating elements with their individual addressing electrodes on one substrate, generally a silicon wafer, and etching corresponding sets of channel grooves with a common recess for each set of grooves in another silicon wafer. The wafer and substrate are aligned and bonded together so that each channel has a heating element. The individual printheads are obtained by milling away the unwanted silicon material to expose the addressing electrode terminals and then dicing the substrate to form separate printheads. This type of thermal ink jet printhead, where the direction of fluid ejection is substantially parallel to the plane of the wafer is sometimes called a sideshooter. A second generic type of ink jet printhead, called a roofshooter, has the direction of fluid ejection substantially perpendicular to the plane of the wafer. It is such roofshooter printheads that this invention applies to.
[0005] In microelectronics applications, there is a great need for low dielectric constant, high glass transition temperature, thermally stable, photopatternable polymers for use as interlayer dielectric layers which protect microelectronic circuitry. Poly(imides) are widely used to satisfy these needs; these materials, however, have disadvantageous characteristics such as relatively high water sorption and hydrolytic instability. There is thus a need for high performance polymers which can be effectively photopatterned and developed at high resolution.
[0006] Particular applications for such material include the fabrication of ink jet printheads as disclosed in related U.S. Pat. Nos. 5,762,812 and 6,260,956, the disclosures of which are incorporated herein. Ink jet printing systems generally are of two types: continuous stream and drop-on-demand. In continuous stream ink jet systems, ink is emitted in a continuous stream under pressure through at least one orifice or nozzle. The stream is perturbed, causing it to break up into droplets at a fixed distance from the orifice. At the break-up point, the droplets are charged in accordance with digital data signals and passed through an electrostatic field which adjusts the trajectory of each droplet in order to direct it to a gutter for recirculation or a specific location on a recording medium. In drop-on-demand systems, a droplet is expelled from an orifice directly to a position on a recording medium in accordance with digital data signals. A droplet is not formed or expelled unless it is to be placed on the recording medium.
[0007] Since drop-on-demand systems require no ink recovery, charging, or deflection, the system is much simpler than the continuous stream type. One type of drop-on-demand system is known as thermal ink jet, or bubble jet, and produces high velocity droplets and allows very close spacing of nozzles. The major components of this type of drop-on-demand system are an ink filled channel having a nozzle on one end and a heat generating resistor near the nozzle. Printing signals representing digital information originate an electric current pulse in a resistive layer within each ink passageway near the orifice or nozzle, causing the ink in the immediate vicinity to evaporate almost instantaneously and create a bubble. The ink at the orifice is forced out as a propelled droplet as the bubble expands. When the hydrodynamic motion of the ink stops, the process is ready to start all over again. With the introduction of a droplet ejection system based upon thermally generated bubbles, commonly referred to as the “bubble jet” system, the drop-on-demand ink jet printers provide simpler, lower cost devices than their continuous stream counterparts and yet have substantially the same high speed printing capability.
[0008] The operating sequence of the bubble jet system begins with a current pulse through the resistive layer in the ink filled channel, the resistive layer being in close proximity to the orifice or nozzle for that channel. Heat is transferred from the resistor to the ink. The ink becomes superheated far above its normal boiling point, and for water based ink, finally reaches the critical temperature for bubble formation or nucleation of around 280° C. Once nucleated, the bubble or water vapor thermally isolates the ink from the heater and no further heat can be applied to the ink. This bubble expands until all the heat stored in the ink in excess of the normal boiling point diffuses away or is used to convert liquid to vapor, which removes heat due to heat of vaporization. The expansion of the bubble forces a droplet of ink out of the nozzle, and once the excess heat is removed, the bubble collapses on the resistor. At this point, the resistor is no longer being heated because the current pulse has passed and, concurrently with the bubble collapse, the droplet is propelled at a high rate of speed in a direction towards a recording medium. The resistive layer encounters a severe cavitational force by the collapse of the bubble, which tends to erode it. Subsequently, the ink channel refills by capillary action. This entire bubble formation and collapse sequence occurs in about 10 microseconds. The channel can be refired after about 20 to 500 microseconds minimum dwell time to enable the channel to refilled and to enable the dynamic refilling factors to become somewhat dampened. Thermal ink jet processes are well known.
[0009] In ink jet printing, a printhead nozzleplate is provided having one or more ink-filled channels communicating with an ink supply chamber at one end and having an opening at the opposite end, referred to as a nozzle. These printheads form images on a recording medium such as paper by expelling droplets of ink from the nozzles onto the recording medium. The ink forms a meniscus at each nozzle prior to being expelled in the form of a droplet. After a droplet is expelled, additional ink surges to the nozzle to reform the meniscus.
[0010] Roofshooting ink jet printheads include a nozzleplate having an array of nozzles. This nozzle plate may be bonded to a silicon wafer, for example, which contains the bubble nucleating heater elements
[0011] In U.S. Pat. No. 6,260,956 it has been proposed to use a polyarylene ether precursor polymer, which is photopatternable, to form the insulating layer over the heater plate, followed by photopatterning to expose the heating elements. The channel plate is prepared from the same photopatternable polymer and is then bonded to the heater plate using a thin bonding layer of the same polymer. This may be accomplished by indirect means in order to prevent the bonding layer from flowing onto the channel walls and along the apex of each channel, causing formation of a thin film along the channel walls and a bead along each apex.
[0012] It is desirable to provide a method for forming thermal ink jet nozzleplates by which a photopatternable resist layer can be applied to the patterned surface of an activator wafer, without disturbing said surface, and can be photopatterned to form ink nozzles having shapes which produce improved ejection velocity.
[0013] It is also desirable to provide a method for forming nozzleplates containing an ink cavity gap over a MEMS structure surface containing topography
SUMMARY OF THE INVENTION
[0014] The present invention provides a novel lamination process for forming nozzle plates comprising fluidic ink passageways in actuator wafers, such as MEMS print heads containing silicon membranes which eject the ink through electrostatically-induced mechanical forces, without the need for planarization and sacrificial layers to prevent penetration of a fluid photoresist composition into the MEMS structure.
[0015] The present invention also enables the formation of an air gap separation between the MEMS surface and the nozzle layer, producing an ink reservoir to increase fluid flow and less flow resistance into the ink channels and nozzles.
[0016] This invention also enables the formation of novel nozzle geometries or cross-sections which are layered or constricted at the nozzle exit to provide increased ejection velocity.
[0017] According to the present invention novel nozzle plates are produced by spin coating a photopatternable curable resist layer of an epoxy novalak polymer onto an intermediate support having release properties; soft-baking the epoxy resist layer to a dry semi-solid adhesive condition; laminating the surface of the dry resist to the surface of a silicon wafer containing drop generating structures; separating the wafer from the coated intermediate support to cause the contacting portion of the adhesive resist layer to remain laminated to the wafer surface and transfer from the intermediate support while other portions of the resist layer, including peripheral edge bead portions thereof are retained on the intermediate support. The photoresist epoxy novolak polymer layer is photoexposed and patterned, either through the intermediate support if it is translucent, before lamination and transfer to the wafer surface, or after lamination and transfer onto the wafer surface.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] [0018]FIG. 1 is a cross-sectional view, to an enlarged scale, illustrating the lamination and transfer of a uniform thickness of a soft-baked, semi-solid photopatternable epoxy novolak polymer resist layer from an intermediate release film to the surface of an actuator wafer containing a plurality of actuator;
[0019] [0019]FIG. 2 is a face view of a photoexposed, processed resist layer as in FIG. 1 forming an ink nozzle layer over the drop generator surface of an actuator wafer. In this figure, each row of nozzles corresponds to a different one of the plurality of die on the wafer;
[0020] [0020]FIG. 3 is a cross-sectional view of FIG. 2 taken along the line 3 - 3 thereof, illustrating the constricted cross-sectional area of the ink-discharge nozzle;
[0021] [0021]FIG. 4 is a cross-sectional view, to an enlarged scale, illustrating the lamination and transfer of a soft-baked, semi-solid photopatternable epoxy novolak polymer resist layer from an intermediate resist film to the surface of a MEMS wafer containing topography, inherently producing an intermediate ink reservoir area, and
[0022] [0022]FIG. 5 is a cross-sectional view of the MEMS wafer formed according to claim 4 being photoexposed through a mask and developed to form an ink nozzle in the resist layer.
DETAILED DESCRIPTION
[0023] Referring to FIG. 1, a flexible, translucent release substrate, such as a 1-2 mil Mylar film disk 10 is spin coated on one surface with a layer 11 of a photopatternable epoxy novolak polymer composition and soft baked to a dry semi-solid adhesive condition.
[0024] Next, a silicon actuator wafer, having a smaller diameter than the resist-coated Mylar disk, is centered and laminated to the dry resist layer 11 under heat and pressure. After cooling the Mylar disk is peeled away, transferring a level portion 14 of the resist layer to the silicon wafer 12 while retaining peripheral bead portions 11 a of layer 11 on the Mylar disk, which portions are beyond the area against which the wafer surface was pressed. Thus, the undesirable edge bead 11 a is left on the Mylar substrate leaving a topographically perfect and level photoresist layer 14 on the silicon actuator wafer substrate 12 .
[0025] In the next step, the photoresist layer 14 is photoexposed and developed to convert it to an ink nozzle layer 17 , using a mask to form a desired plurality of clean, defect-free passages which are somewhat semi-parabolic in cross-sectional shape and have a narrower opening 18 at the surface of the layer 17 , tapering out to a wider opening 19 at the surface of the actuator wafer 12 , to form an integral actuator wafer 16 having discharge nozzles 20 which are constricted in diameter and provide increased ink-ejection velocity.
[0026] Referring to FIGS. 4 and 5, the silicon wafer thereof is a MEMS wafer 21 having a microelectromechanical surface area 22 surrounded by a peripheral topography wall 23 . It is not possible to coat a MEMS surface with a liquid resist layer since the liquid resist would flow into and contaminate the MEMS moving parts and/or fluidic passageways. The dry film resist layer is separated from the MEMS layer using elevated topography or peripheral walls 23 . The solid transfer of level resist layer 24 to the peripheral walls 23 of the MEMS wafer inherently produces an ink reservoir 25 over the MEMS layer 22 , as illustrated by FIG. 3.
[0027] Solid transfer of the level resist layer 24 is accomplished as discussed hereinbefore in connection with FIG. 1. Thus Mylar disk 10 is spin-coated with the photosensitive epoxy novolak resist composition and soft baked to a dry semi-solid composition. The MEMS wafer is pressed against a central area of the dry resist layer 11 and heated to laminate the peripheral MEMS walls 23 to the surface of the resist layer 11 . Next the Mylar disk is peeled away to release the level photoresist layer portion 24 to the walls 23 as a roof portion, forming an ink reservoir 25 spacing the MEMS layer 22 from the photoresist layer portion 24 .
[0028] As illustrated by FIG. 5, the photoresist layer portion 24 is aligned with a negative mask 26 and exposed to light of sufficient intensity to crosslink and cure the epoxy novolak polymer, after which the unexposed, uncured areas are developed with y-butyrolactone and rinsed with isopropyl alcohol to form nozzle areas 27 having a semi-parabolic cross-section.
[0029] A highly functionalized glycidylepoxy-derivatized bis phenol-A novolak resin compounded with a photoacid-generating catalyst is an ideal negative resist for fabrication of fluidic pathways in the present ink nozzle layers. This material can be spin cast onto a release surface such as a Mylar film 10 as in FIG. 1, and pre-baked in an oven to remove solvent and form a dry, semi-solid, adhesive resist layer 11 .
[0030] The preferred photoresist solution is made by addition of about 63 parts by weight of an epoxy polymer of the formula
[0031] wherein n has an average value of 3 to about 20 parts by weight of γ-butyrolactone containing about 13 or 14 parts by weight triphenylsulfonium hexafluoroantimonate solution (supplied commercially as CYRACURE® UVI- 6976 (obtained from Union Carbide) in a solution of 50 weight percent mixed triarylsulfonium hexafluoroantimonate in propylene carbonate). The resist-coated Mylar film is heated (soft baked) in an oven for between 15 and 25 minutes at 70° C. After cooling to 25° C. over 5 minutes, the soft baked resist layer 11 formed on the Mylar support film 10 was placed in surface contact with the surface of a channel wafer 12 , and heat and pressure are applied to laminate the photoresist layer 11 to the surface of the channel wafer 12 . Next, the Mylar support 10 is easily peeled away from the laminate to provide the resist-coated wafer 13 . Then the level resist coating 14 on the wafer 12 is covered with a filter-forming negative mask and exposed to the full arc of a super-high pressure mercury bulb, amounting to from about 25 to about 500 milliJoules per square centimeter as measured at 365 nanometers. The exposed wafer is then heated at from about 70 to about 95° C. for from about 10 to about 20 minutes post-exposure bake, followed by cooling to 25° C. over 5 minutes. The uncured areas of the resist coating are developed with γ-butyrolactone, washed with isopropanol, and then dried at about 70° C. for about 2 minutes to form the filter-coated wafer 16 shown in FIG. 3 having a channel/nozzle layer 17 , shown in FIG. 2, containing tapered, parabolic cross-section channels and nozzles 20 having narrow filter inlets 18 which exclude the entry of ink contaminants to the channels and nozzles on the surface of the channel wafer 12 .
[0032] Any suitable roofshooter printhead configuration comprising actuator wafers having ink-bearing passages terminating in nozzles on the printhead surface can be formed with the materials disclosed herein to form a printhead of the present invention. The printheads of the present invention are of ‘roofshooter’ configuration.
[0033] The present nozzleplate layer 17 is formed by crosslinking the precursor polymer which is a phenolic novolac resin having glycidyl ether functional groups on the monomer repeat units thereof, The glycidyl ether functional groups generally are situated at the locations of the former hydrogen atoms on the phenolic hydroxy groups, Examples of suitable backbone monomers for the phenolic novolac resin include phenol, of the formula
[0034] wherein the resulting glycidyl ether functionalized novolac resin includes structures of the formula
[0035] as well as branched structures thereof, o-cresol and p-cresol, of the formula
[0036] wherein the resulting glycidyl ether functionalized novolac resin includes structures of the formula
[0037] as well as branched structures thereof, bisphenol-A, of the formula
[0038] wherein the resulting glycidyl ether functionalized novolac resin includes structures of the formula
[0039] as well as randomized and branched structures thereof, and the like. The average number of repeat monomer units typically is from about 1 to about 20, and preferably is about 2, although the value of n can be outside of this range. One particularly preferred polymer is of the formula
[0040] wherein n is an integer representing the average number of repeating monomer units and typically is from about 2 to about 20, and preferably is about 3, although the value of n can be outside of this range. Another particularly preferred polymer is of the formula
[0041] wherein n is an integer representing the average number of repeating monomer units and typically is from about 1 to about 20, and preferably is about 2, although the value of n can be outside of this range. Polymers of the formula
[0042] wherein n has an average value of about 3 are commercially available from, for example, Shell Resins, Resolution Performance Products, Houston, Tex. as EPON® SU-8. Commercial photoresists containing this polymer, a solvent, and a cationic initiator are also available from MicroChem Corporation, Newton, Mass. and from Sotec Microsystems, Switzerland. This type of photoresist is also disclosed in, for example, U.S. Pat. Nos. 4,624,912 and 4,882,245, the disclosure of which is totally incorporated herein by reference. Polymers of the formula
[0043] wherein n has an average value of about 3 are commercially available from, for example, Shell Resins, Resolution Performance Products, Houston, Tex. as EPON® DPS-164. Suitable photoresists of the general formulae set forth hereinabove are also available from, for example, Dow Chemical Co., Midland, Mich.
[0044] The nozzleplate layer 17 containing the crosslinked epoxy polymer is prepared by applying to the intermediate film 10 a photoresist layer 11 containing the uncrosslinked precursor epoxy polymer, an optional solvent for the precursor polymer, a cationic photoinitiator, and an optional sensitizer. The solvent and precursor polymer typically are present in relative amounts of from 0 to about 99 percent by weight solvent and from about 1 to 100 percent precursor polymer, preferably are present in relative amounts of from about 5 to about 60 percent by weight solvent and from about 40 to about 95 percent by weight polymer, and more preferably are present in relative amounts of from about 5 to about 40 percent by weight solvent and from about 60 to about 95 percent by weight polymer, although the relative amounts can be outside these ranges. Examples of suitable solvents include γ-butyrolactone, propylene glycol methyl ether acetate, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, mixtures thereof, and the like.
[0045] Sensitizers absorb light energy and facilitate the transfer of energy to another compound, which can then form radical or ionic initiators to react to crosslink the precursor polymer. Sensitizers frequently expand the useful energy wavelength range for photoexposure, and typically are aromatic light absorbing chromophores. Sensitizers can also lead to the formation of photoinitiators, which can be free radical or ionic. When present, the optional sensitizer and the precursor polymer typically are present in relative amounts of from about 0.1 to about 20 percent by weight sensitizer and from about 80 to about 99.9 percent by weight precursor polymer, and preferably are present in relative amounts of from about 1 to about 20 percent by weight sensitizer and from about 80 to about 99 percent by weight precursor polymer. although the relative amounts can be outside these ranges.
[0046] Photoinitiators generally generate ions or free radicals which initiate polymerization upon exposure to actinic radiation. When present, the optional photoinitiator and the precursor polymer typically are present in relative amounts of from about 0.1 to about 20 percent by weight photoinitiator (in its pure form; not accounting for any solvent in which it may be commercially supplied) and from about 80 to about 99.9 percent by weight precursor polymer, and preferably are present in relative amounts of from about 1 to about 20 percent by weight photoinitiator and from about 80 to about 99 percent by weight precursor polymer, although the relative amounts can be outside these ranges.
[0047] A single material can also function as both a sensitizer and 25 a photoinitiator.
[0048] Further background material on initiators is disclosed in, for example, Ober et al., J. M. S.—Pure Appl. Chem ., A30 (12), 877-897 (1993); G. E. Green, B. P. Stark, and S. A. Zahir, “Photocrosslinkable Resin Systems,” J. Macro. Sci.—Revs, Macro. Chem ., C21(2), 187 (1981); H. F. Gruber, “Photoinitiators for Free Radical Polymerization-” Prog. Polym. Sci ., Vol. 17, 953 (1992); Johann G. Kloosterboer, “Network Formation by Chain Orosslinking PhotopolymerizatiOn and Its Applications in Electronics,” Advances in Polymer Science, 89, Springer-Verlag Berlin Heidelberg (1988); and “Diaryliodonium Salts as Thermal Initiators of Cationic Polymerization,” J. V. Crivello, T. P. Lockhart, and J. L. Lee, J, of Polymer Science. Polymer Chemistry Edition 21 97 (1983), the disclosures of each of which are totally incorporated herein by reference. Sensitizers are available from, for example, Aldrich Chemical Co., Milwaukee, Wis., First Chemical Corporation, Pascagoula, Miss., and Pfaltz and Bauer, Waterberry, Conn. Aromatic ketones, including benzophenone and its derivatives, thioxanthone, camphor quinone, and the like can function as photosensitizers. Additional examples of suitable photoinitiators include onium salts of Group VA elements, onium salts of Group VIA elements, such as sulfonium salts, and aromatic halonium salts, such as aromatic iodonium salts. Specific examples of sulfonium salts include triphenylsulfonium tetrafluoroborate, methyldiphenylsulfonium tetrafluoroborate, dimethylphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, diphenylnaphthylsulfonium hexafluoroarsenate, tritolysulfonium hexafluorophosphate, anisyldiphenylsulfonium hexafluoroantimonate, 4-butoxyphenyldiphenylsulfonium tetrafluoroborate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, tris(4-phenoxyphenyl)sulfonium hexafluorophosphate, di(4-ethoxyphenyl)methyulfonium hexafluoroarsenate, 4-acetoxy-phenyldiphenylsulfonium tetrafluoroborate, tris(4-thiomethoxyphenyl)Sulfonium hexafluorophosphate, di(methoxysulfonylphenyl)methylsulfonium hexafluoroantimonate, di(methoxynapththyl)methylSulfonium tetrafluoroborate,
[0049] di(carbomethoxyphenyl)methylsulfOnium hexafluorophosphate, 4-acetamidophenyldiphenylsulfOnium tetrafluoroborate, dimethylnaphthylsulfOnium hexafiuorophosphate, trifluoromethyldiphenylsulfOnium tetrafluoroborate,
[0050] methyl(n-methylphenothiazinyl)SulfOnium hexafluoroantimOnclte, phenylmethylbenzylsulfOniumhexafluorophosphate, and the like.
[0051] Specific examples of aromatic iodonium salts include diphenyliodonium tetrafluoroborate, di(4-methylphenyl)iodonium tetrafluoroborate, phenyl-4-methylphenyliodonium tetrafluoroborate di(4-heptylphenyl)iodonium tetrafluoroborate, di(3-nitrophenyl)iodOnium hexafluorophosphate, di(3-nitrophenyl)iodonium hexafluorophosphate, di(4-chlorophenyl)iodonium hexafluorophosphate, di(naphthyl)iodonium tetrafluroborate, di(4-trifluoromethylphenyl)iodonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, di(4-methylphenyl)iodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, di(4-phenoxyphenyl)iodonium tetrafluoroborate, phenyl-2-thienyliodonium hexafluorophosphate, 3,5-dimethylpyrazolyl-4-phenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, 2,2′-diphenyliodonium tetrafluoroborate, di(2,4-dichlorophenyl)iodonium hexafluorophosphate, di(4-bromophenyl)iodonium hexafluorophosphate, di(4-methoxyphenyl)iodonium hexafluorophosphate, di(3-carboxyphenyl)iodonium hexafluorophosphate, di(3-methoxycarbonylphenyl)iodonium hexafluorophosphate, di(3-methoxysulfonylphenyl)iodonium hexafluorophosphate, di(4-acetamidophenyl)iodonium hexafluorophosphate, di(2-benzoethienyl)iodonium hexafluorophosphate, and the like. Triarylsulfonium and diaryliodonium salts are examples of typical cationic photoinitiators. Aromatic onium salts of Group VIA elements, such as triarylsulfonium salts, are particularly preferred photoinitiators for the present invention; initiators of this type are disclosed in, for example, U.S. Pat. No. 4,058,401 and U.S. Pat. No. 4,245,029, the disclosures of each of which are totally incorporated herein by reference. Particularly preferred for the present invention are triphenylsulfonium hexafluoroantimonate and the like.
[0052] While the printheads of the present invention can be prepared with photoresist solutions containing only the precursor polymer, cationic initiator, and optional solvent, other optional ingredients can also be contained in the photoresist. For example, diluents can be employed if desired. Examples of suitable diluents include epoxy-substituted polyarylene ethers, such as those disclosed in U.S. Pat. No. 5,945,253, the disclosure of which is totally incorporated herein by reference, bisphenol-A epoxy materials, such as those disclosed as (nonpatternable) adhesives) in U.S. Pat. No. 5,762,812, the disclosure of which is totally incorporated herein by reference, having typical numbers of repeat monomer units of from about 1 to about 20, although the number of repeat monomer units can be outside of this range, and the like. Diluents can be present in the photoresist in any desired or effective amount, typically at least about 1 part by weight per 1 part by weight precursor polymer, and typically no more than about 70 parts by weight per one part by weight precursor polymer, preferably no more than about 10 parts by weight per one part by weight precursor polymer, and more preferably no more than about 5 parts by weight per one part by weight precursor polymer, although the relative amounts can be outside of these ranges.
[0053] The printheads of the present invention can be prepared with high aspect ratios and straight sidewalls. Nozzles as small as 5 microns wide can be easily resolved in 28 micron thick films exposed at, for example 200 to 500 millijoules per square centimeter (typically plus or minus about 50 millijoules per square centimeter, preferably plus or minus about 25 millijoules per square centimeter) (aspect ratio of 5.6). It is possible to develop processing conditions enabling a variety of shapes, angles or amounts of concavity. Preferred exposures can vary depending on the cationic initiator employed, the presence or absence of a diluent, relative humidity, and the like. These results easily enable high jet densities; jet densities typically are at least about 300 dots per inch, preferably at least about 600 dots per inch, and more preferably at least about 1,200 dots per inch, although the jet density can be outside of these ranges. Scanning electron microscopy micrographs indicate a topographically level surface devoid of detrimental lips or dips.
[0054] Specific embodiments of the invention will now be described in detail. These examples are intended to be illustrative, and the invention is not limited to the materials, conditions, or process parameters set forth in these embodiments. All parts and percentages are by weight unless otherwise indicated.
EXAMPLE I
Resist Solution Preparation
[0055] A resist solution was prepared by jar 33 grams of γ-butyrolactone (obtained from Aldrich Chemical Co., Milwaukee. Wisc.) and 23.3 CYRACURE® UVI-6976(containing 50 percent by weight triphenysulfonium hexafluoroantimonate in propylene carbonate, obtained from Union Carbide) Thereafter, 115 grams of EPON® SU-8 epoxy polymer of the formula
[0056] wherein n has an average value of 3 (obtained from Shell Resins) was added to the jar and the solution was mixed on a STONEWARE® roller for about one week prior to use.
[0057] A commercial resist solution of EPON SU-8 was also obtained from MicroChem Corporation Newton, Mass., and was used as received. This commercial solution is of similar composition to the one prepared as described, more specifically, accordingly to the MSDS sheet for this product, the commercial solution contained between 25 and 50 percent by weight y-butyrolactone, between 1 and 5 percent by weight of a mixed triarylsulfonium hexafluoroantimonate salt (sulfonium(thiodi-4,1-phenylene)bis(diphenylbis((OC-6-11)hexafluoroanti monate(1-)), CAS 89452-37-9, and p-thiophenoxyphenyldlphenysulfonium hexafluoroantimonate, CAS 71449-78-0) in propylene carbonate, and between 50 and 75 percent by weight of the epoxy resin.
Transfer Substrate Preparation
[0058] A thin transparent film, preferably a 1-2 mil film of Mylar (polyethylene terephthalate), has applied thereto 3 to 4 grams of the resist solution followed by spin coating on a Headway Research Inc. PWM 101 spin coater at 2000 to 4000 rpm for 20 seconds. The resulting film coating was soft baked in a circulating air oven at 70° for 20 minutes.
Laminate Preparation
[0059] Round blank silicon wafers, the top levels of which contained oxide or bare silicon were cleaned in a bath containing 75 percent by weight sulfuric acid and 25 percent by weight hydrogen peroxide at a temperature of 120° C. The wafers were heated on a hot plate at 70° C. for 2 minutes prior to lamination to the soft baked photoresist layer on the Mylar transfer substrate. Two methods were employed to increase contact between the dry resist layer on the Mylar disc and the silicon substrate. The first includes stacking 10 blank silicon wafers on top of the Mylar composite while in the oven. The second method includes rolling a steel mandrel back and forth over the Mylar surface before the composite has an opportunity to cool. The Mylar release layer can be removed easily after the composite has equilibrated to room temperature. Both released films and unreleased films were then photo-exposed and processed according to normal procedures where both types of films yielded clean defect free nozzle structures (FIG. 3). The cylindrical or conical structures are approximately 10-30 μm in width and are dependent upon the mask, film thickness, and processing conditions. It was also possible to photo-expose the resist using Mylar as the substrate and in this manner clean defect free nozzle features were also achieved. With appropriate release materials the resist can be separated free from the Mylar substrate yielding a freestanding plastic ink nozzle sheet.
Photoexposure and Processing
[0060] The wafers containing the soft-baked resist films laminated thereon were exposed through a chromium mask to the actinic radiation of an exposure aligner unit until the required dose had been delivered to the film. Exposure was effected with two different tools: (a) a CANON®PLA-501FA unit with a 250 Watt Ushio super-high pressure mercury lamp (model 250D) as the light source; (b) a KARL SUSS®MA 150 unit with a 350 Watt Ushio super high pressure mercury lamp (model 350DS) as the light source. The light intensity was about 6 to 10 milliwatts per square centimeter for each unit measured at 365 nonometers. Both exposure stations were operated on contact printing mode and the light intensity was measured at 365 nonometers. Light intensity for exposure with the CANON®PLA-501FA unit was performed using a UVP model UVX digital radiometer: the KARL SUSS® MA 150 unit had a built-in internal radiometer. All wafers were subjected to a post-exposure bake for 15 to 20 minutes at 70 to 95° C. in a circulating air oven directly after exposure. Subsequent to the post-exposure bake, the latent images were exposed to development with γ-butyrolactone (obtained from Aldrich Chemical Co.), followed by rinsing with isopropanol.
Results
[0061] Overall, clean, well-resolved nozzleplates with passages of parabolic cross-section, with diameters between about 15 and 20 microns at the exposed surface and between 20 and 25 microns at the wafer surface and film thicknesses of about 30 microns were resolved. Nearly identical results were obtained with the resist solution mixed as indicated above and the commercial resist solution obtained from MicroChem Corporation.
[0062] Other embodiments and modifications of the present invention may occur to those of ordinary skill in the art subsequent to a review of the information presented herein; these embodiments and modifications, as well as equivalents thereof, are also included within the scope of this invention. | Disclosed is a process for forming a novel ink jet printhead which comprises: (a) providing a lower substrate in which one surface thereof has an array of drop generating elements and addressing electrodes formed thereon; (b) depositing onto the release surface of an intermediate film support a photopatternable layer comprising a precursor polymer which is a phenolic novolac resin having glycidyl ether functional groups; (c) prebaking the photopatternable layer to dry, semi-solid condition; (d) laminating the dry, semi-solid layer to the surface of the lower substrate under heat and pressure and separating it from the release surface of the intermediate film support; (e) exposing the photopatternable layer to actinic radiation in an imagewise pattern corresponding to ink nozzles and developing to form a nozzle plate section, and (f) removing the precursor polymer from the unexposed areas, thereby forming ink nozzle recesses which are aligned to communicate with the drop generating elements and terminal ends of the electrodes of the lower substrate laminated thereto. Step (e) may be carried out either before or after step (d). | 1 |
CROSS REFERENCE TO RELATED APPLICATION
This application is related to an application in the names of Clark and Goldstein, Ser. No. 878,814 filed Feb. 17, 1978 entitled "Motor Transmission Construction".
BRIEF SUMMARY OF THE INVENTION
In said copending application there is taught a transmission which can replace the conventional connecting rod and double universal joint, where it is necessary to transmit the torque from an element which gyrates about an axis while rotating, to an element which rotates on true centers. That transmission is particularly useful in connection with progressing cavity type pumps or motors, based on principles first disclosed by R. J. L. Moineau in his early patent, e.g. U.S. Pat. No. 1,892,217 of Dec. 27, 1932.
A forerunner of said copending Clark and Goldstein application involved a radial arm non-rotatably secured at one of its ends to the inner member of a helical gear pair, and fixed means to limit the other end of the radial arm to reciprocatory and oscillatory motion. Reference may be had to U.S. Pat. No. 3,932,072 issued Jan. 13, 1976 in the name of Wallace Clark. A later U.S. Pat. No. 3,951,097, dated Apr. 20, 1976 in the name of Wallace Clark, made use of the ball and tube disclosed in U.S. Pat. No. 3,932,072 in connection with water swivels. The principles disclosed in the above mentioned patents were carried forward in U.S. Pat. No. 4,059,165 dated Nov. 22, 1977 in the name of Wallace Clark. Among other things, the last mentioned patent disclosed the substitution of a pair of parallel axial cheeks for the radial tube, so that the various elements could be disassembled axially which was impossible with the ball and tube construction.
The present invention makes use of a ball and half-tube as disclosed in said copending application in the names of Clark and Goldstein, and provides additionally a plate secured to the tail end of the inner helical gear member to bear against the end of the outer member, and thus allow the drill string to be raised an amount sufficient to withdraw the ball from between the cheeks or from the half-tube. The plate at the tail end of the inner helical member prevents it from falling down, and causes it to be withdrawn with the drill string. Then the circulating fluid (which may be drilling mud) can continue to drive the helical gear motor freely (in neutral, so to speak) while the drill bit and its associated parts rest on the bottom of the bore, or suspended anywhere, without rotating. When the drill string is raised as above outlined it may be caused to interlock with the drill shaft so that by rotating the drill string by means of the rotary table at the top of the hole the bit may be caused to rotate in order to free it from an obstruction with which it may have become engaged in the hole, without driving the motor by means of drilling mud.
BRIEF DESCRIPTION OF THE FIGURES OF THE DRAWINGS
FIG. 1 is a longitudinal cross sectional view through a drilling motor, shortened in length by breaking out non-essential portions, in the drilling mode.
FIG. 2 is a view similar to FIG. 1 showing the device in free circulation mode.
FIG. 3 is a view similar to FIG. 1 showing a slightly different embodiment.
FIG. 4 is a view similar to FIG. 3 showing the device of FIG. 3 in the free circulation mode.
FIG. 5 is a cross sectional view through the helical gear pair showing the stator cross section of the helical gear pair and the rotor cross section in its two extreme positions as well as its center position, at that particular cross section.
FIG. 6 is a diagrammatic representation of the relationship between the rotor cross section and the rotor head and showing the path of the rotor head and its relationship to the cheeks against which it exerts a driving force. The diagram of FIG. 6 relates to the embodiment of FIGS. 1 and 2.
FIG. 7 is a diagrammatic representation of the relationship of the various parts in the embodiment of FIGS. 3 and 4.
FIG. 8 is a fragmentary cross sectional view taken on the line 8--8 of FIG. 1; and
FIG. 9 is a fragmentary cross sectional view taken on the line 9--9 of FIG. 2.
DETAILED DESCRIPTION
Referring to FIG. 1, the down-hole motor is generally indicated at 10. It will be understood that it is very much longer than shown in the drawings but since the motor, per se, does not form any part of the invention, it has been shortened by breaking out a large portion thereof. The outer helical gear element is indicated at 11 and is secured inside the drill pipe 12. The inner helical gear member 13 is provided with the extension 14 and ball 15 disposed on the lathe axis of the member 13 as disclosed in said copending application. The ball 15 engages between a pair of parallel cheeks 16 and thereby when the motor 10 is operating, produces rotation of the hollow shaft 17 to which the drill bit is ultimately secured at the bit box 18. The shaft 17 is provided with the bearings at 19 and 20 which serve as both radial and thrust bearings, and which comprise a water swivel.
Between the bearings 19 and 20 there is provided a slidable sleeve 30; and between the sleeve 30 and a slidable sleeve 31 there may be provided a rubber radial bearing 34 with housing 32, similar to a conventional marine bearing. An annulus 33 serves as a flow restrictor and the amount of restriction is determined by the inside diameter of the member 33. The clearance should be such as to allow for small flow (say 5% to 15% of the total down-hole flow) for lubrication of the bearings. It should be noted that the sleeve 31 must not fill the entire space between the bearings 19 and 20, because room must be allowed for these bearings to approach each other as they wear.
Secured to the tail end of the inner helical gear member 13 is a support plate 21.
It will be observed that there are passages, one of which is indicated at 22, through which drilling mud may pass from the motor 10 through the hollow shaft 17 to provide drilling mud for the bit which is secured at 18.
If it is desired for any reason to clean out the bore, add to the density of the mud in it, or flush the hole while remaining in the hole, it is possible to declutch (so to speak) the motor from the drill bit as follows. The drill string 12 is withdrawn upwardly until the member 21 abuts the end of the outer helical gear member 11 and thereby withdraws the inner member 13 and the ball 15 to the point where the ball 15 no longer engages between the cheeks 16.
In this state, the motor can continue to run but the shaft 17 and drill bit will simply rest motionless on the bottom, or anywhere, being supported by the bearings, thereby saving wear and tear on the drill bit as well as on the bearings and associated parts.
Comparing FIGS. 1 and 2, it will be seen that the gap 35 in the drilling mode of FIG. 1, is relatively large, and that there is a small gap 38 between the members 36 and 37 of about the amount of ball and race wear which reasonably can be tolerated. In the idling mode of FIG. 2, the gap 35 is reduced in size, and a greater gap 38 now appears between the members 36 and 37. The member 37b may have a well known brake lining 37 secured on top of it and, with the bit box 18 serves as a brake in cooperation with the retaining nut 36. Ratchet-like teeth may be provided on the opposed faces of the members 18 and 37b, or any other well known means may be provided to keep these two metal parts from sliding on each other, such as countersunk bolts passing through 37 and 37b into 18. The main force in holding these members against relative rotation will be the weight of the drill stem which is transmitted to the retaining nut 36 and thence to the members 37, 37b and 18.
The member 37b with lining 37 may be referred to as a brake, and it is spaced from the retaining nut (in the drilling mode) by an amount of bearing wear which the operator wishes to tolerate. By virtue of this structure, the operator will receive a signal while drilling, by virtue of a pressure rise at the mudpump. This pressure rise gives the operator sufficient notice of bearing wear so that he can stop the operation. If drilling continues after this warning signal, the digging into each other of the retaining nut 36 and brake lining 37 will cause the motor to stall, so that the bearings will not be worn out beyond a safe point. If at this point the operator raises the assembly out of the hole and renews the races and balls, he avoids having the bearing come apart and being lost in the hole, which would necessitate an expensive job of fishing out the parts before drilling could be restarted.
It will be noted that the driving member 17a which is secured to the shaft 17 is provided with one or more lugs 17b and that the member 12 is provided with a like number of lugs 12a. The space between these lugs is such that when the drill string is raised to the position of FIG. 2, the lugs 12a and 17a will interengage. Thus, the drill will no longer be driven by the motor 10 but at the same time if the drill bit is stuck or wedged under an overhanging ledge or the like, the drill string may be rotated by means of the conventional rotary table at the top of the hole whereby the operator can drill his way out or roll the bit out from under a ledge from which it might be caught. This situation is shown in FIG. 2. FIG. 5 may be thought of as looking in the direction of the arrows 5--5 in FIG. 1.
The relationship of the parts in cross section through the motor is shown best in FIG. 5. In this Figure, the drill pipe is indicated at 12 and the outer helical gear member at 11. The elongated oval on the vertical axis represents the bore in a particular cross section of the outer helical gear member and three positions of the inner member are indicated at 13a, 13b and 13c. The positions 13a and 13b indicate the two extreme positions of the inner helical gear member in a particular cross section and the circle 13c indicates the central position.
The embodiments disclosed in FIGS. 3 and 4 differs from that of FIGS. 1 and 2 only in the location of the ball which in FIGS. 3 and 4 is designated at 15a. Whereas in the embodiment of FIGS. 1 and 2 the ball is on the lathe axis of the inner member 13, in FIGS. 3 and 4 the ball is offset from the lathe axis and is therefore at a greater eccentricity. The operation of the arrangement is the same in both cases, however, except that the ball does not rotate but oscillates with relation to the half tube or cheeks, and also reciprocates. Other parts of the embodiment of FIGS. 3 and 4 which are the same as those of FIGS. 1 and 2, have been designated by the same reference numerals. The rotor head which is indicated at 14 in FIGS. 1 and 2 has been indicated at 14a in FIGS. 3 and 4. In each case the rotor head may be provided with the wrench flats 23 to facilitate assembly.
It may also be pointed out that the hanger plate bearing 21 is preferably mounted in the center of the inner member cross section rather than on the lathe center, thereby making it possible for the member 21 mounting hole in the inner member to be considerably larger than it could be if it were mounted on the lathe center of the inner member, due to the gear shape of the inner one of the gear pair. By being mounted on the center of the inner member cross section, there is provided a substantial amount of over-hang on the end of the outer member.
It should be noted that by virtue of the peculiar motion of the inner helical gear member with respect to the outer helical gear member, the ball in FIGS. 3 and 4 never crosses the centerline of the half-tube or cheeks, if its arm length perpendicular to the motor axis is equal to or greater than the eccentricity of the rotor, as will be described in connection with FIG. 7. It is also true of the embodiment of FIGS. 1 and 2 as to not crossing the center, which will be described in connection with FIG. 6. When the ball is withdrawn from between the cheeks or from the half-tube, and is later caused to re-enter the half-tube or cheeks, there is a fifty percent chance of changing the location of the ball to the other half of the half-tube or cheeks. In this way, wear on the half-tube or cheeks is effectively halved.
FIG. 6 diagrammatically illustrates the relationship of parts and their relative movement during operation in the embodiment of FIGS. 1 and 2. It may be considered as viewed in the direction of the arrows 6--6 in FIG. 1. The rotor cross section is indicated at 13a, 13b and 13c just at it was in FIG. 5. The rotor head is indicated at 14 and the ball head is indicated at 15. The center of the rotor head path, and also incidentally of the ball path, is indicated by the broken line circle 13d. The arrows indicate the direction of rotation of the various parts. Thus, the rotor head and ball center rotate in a clockwise direction while the rotor head itself and the ball rotate in a counterclockwise direction during the clockwise rotation of their center. The cheeks against which the ball drives are indicated in one position at 16, 16 and in broken lines by the same reference numerals.
It should be noted that the rotor diameter is slightly larger than two times the eccentricity which is the radius of the circular path 13d.
From a study of FIG. 6, it will be clear that the center of the ball will never cross the centerline of the cheeks but will travel entirely on one side of the cheeks. Thus, when the unit is uncoupled as described above and later recoupled, the chances are 50/50 that the ball will be on the other side of the cheeks and thus the wear of the cheeks is distributed more evenly.
Turning now to FIG. 7, this diagram represents the relationship and rotational directions of the various parts in the embodiment of FIGS. 3 and 4. It will be recalled that in the embodiment of FIGS. 3 and 4 the ball is offset from the rotor head. In this Figure the ball is shown in four positions and bears the reference numeral 15a as it does in FIGS. 3 and 4. The broken line ellipse shows the path of the center of the ball. Again, the rotor eccentricity is indicated by the radius of the small broken line circle 13c which describes the center of the path of the rotor head. Four positions of the rotor head are indicated at 14a. It will be noted that the rotor head center path moves counterclockwise while the rotor head itself rotates clockwise. The heavy line 15d represents the ball offset at the twelve o'clock position. The heavy line 15e represents that same offset in the three o'clock position. The heavy line 15f represents the offset at approximately the 4:30 position. It will be noted that because of the elliptical path there will be variations in speed and torque and also because of this elliptical path the ball will oscillate somewhat in the position between twelve and three o'clock, three and six o'clock, six and nine o'clock, nine and twelve o'clock. In the 15f position, it will be observed that the angles θ and π are unequal and the perpendicular to the arm 15f indicated at 15g is skewed. In other words, the arm oscillates somewhat at the four positions between the twelve, three, six and nine o'clock positions.
This rocking and the variation in torque and speed can be reduced by lengthening the arm as can be accomplished among other ways by truncating the ball at 15b. It will be clear that the centerline of the ball 15a cannot cross the centerline of the cheeks 16 so long as the ball offset from the rotor head is equal to, or greater than the eccentricity of the rotor head and preferably greater than twice the eccentricity thereof. This assists in smoothing out the variations in torque and speed which have been described above.
Referring to FIGS. 6 and 7, it will be seen that the inner member head 14 is turning to the left, and the inner member head 14a is turning to the right. The gear pair of the FIG. 6 type motor would preferably have right-hand threads, while the FIG. 7 type motor would preferably have left-hand threads. This would produce a right-hand eccentricity of the inner member in FIG. 6, and left-hand eccentricity of the inner member in FIG. 7, as indicated by the broken line circles 13d and 13c, respectively.
Assuming that the Figures represent the situation looking down the hole, the ball 15 will revolve to the left, but the ball 15a will only reciprocate and oscillate as it moves around its elliptical path to the right, as shown by the arrows. FIG. 7 therefore depicts a motor accommodating the right-hand turning direction of a conventional bit (as viewed down hole). However, the ball 15, as stated above, will revolve to the left, while its circular path will be to the right as shown on the broken line circle 13d of FIG. 6. This revolution of the ball 15 involves no reciprocation or oscillation. The arrangement of FIG. 6 thus also accommodates the conventional bit rotation to the right, and without variation in speed and torque.
It will be understood that in order to keep threads tight, the ball 15 would be attached to the inner member head by means of left-hand threads, while the ball 15a would be attached by means of right-hand threads. Also the plate 21 would be attached to the inner member with right-hand threading in FIGS. 1 and 2, and with left-hand threading in FIGS. 3 and 4, for the same reason.
In order to reduce the shock on the system when the ball is caused to re-enter between the cheeks, it is desirable that while the cheek against which the ball presses be vertical, the cheek following behind the ball against which the ball is not bearing, may be sloped so that the shock of the ball entering the cheeks is reduced.
It will be understood that modifications may be made without departing from the spirit of the invention and no limitation which is not expressly set forth in the claims should be implied and no such limitation is intended. | There is disclosed a down-hole drilling motor having a connection to the drill bit, such that, when desirable or necessary, fluid may be circulated in the bore by means of the motor to clean out undue accumulation of cuttings, or for other reasons, while at the same time the bit is stopped, thereby saving wear on the bit and bit drive parts. When the motor is disconnected from the drill shaft, the drill shaft may be locked to the drill pipe so that the bit may be rotated by turning the drill pipe from the top of the bore with the conventional rotary table to permit the operator to drill his way out if the drill is stuck or to roll the bit out from under a ledge under which it might be caught during drilling. | 5 |
This is a continuation of international application Ser. No. PCT/ES93/00078, filed Sep. 22, 1993.
This is a continuation of international application Ser. No. PCT/ES93/00078, filed Sep. 22, 1993.
TECHNICAL FIELD OF THE INVENTION
The present invention is comprised in the technical field of the production of compounds with antitumoral activity.
Specifically, the present invention refers to the obtainment of new areno indols, useful in the synthesis of hexahydroareno[e]cidopropa[c]indol-4-ones with antitumoral properties.
PRIOR ART OF THE INVENTION
Obtaining phenantrenes by oxidative photochemical cycling of stilbenes is a synthetic method largely used as can be seen in the review of F. B. Mallory and C. W. Mallory in Organic Reactions, Wiley: New York, 1984; Vol. 30, page 1. The analogous reaction of oxidative photocycling of 1-aryl-2-pyrrilethylenes (II) to produce areno[e]indols (III) is less described in the bibliography, in spite of its unquestionable potential. The reason is that this reaction tends to give very small yields and is highly dependent on the substrate. This small yield is often due to the oxidative decomposition in the reaction medium of the 1-aryl-2-pyrrilethylenes (II) as starting products. A solution to this problem consists of the use of carefully studied reaction conditions to give the best yields in a given substrate. Hence, for example, M. P. Cava et al. in J. Org. Chem., 56, 2240 (1991) and cited references have carried out these oxidative cyclings on some 1-aryl-2-pyrrilethylenes (II), irradiating them with ultraviolet light in the presence of palladium on carbon, silica-gel, triethylamine and p-nitrobenzoic acid in acetonitrile to reflux and an inert atmosphere, with very good yields. These good yields are obtained however as a result of a laborious search for reaction conditions which end up being little versatile; furthermore, these conditions may end up to be technically complex to use. ##STR1##
On the other hand, the areno[e]indols (III) are intermediates useful for preparing hexahydroareno[e]cyclopropa[c]indol-4-ones (IV.) These indolones have a great pharmaceutical interest as they contain the structural unity of cyclopropa[c]indol-4-one which, among others D. L. Boger et al. in J. Am. Chem. Soc., 113, 2779 (1991) have proven that it is responsible for the antitumoral activity of the CC-1065 agent (V) and synthesis analogues of the same. ##STR2##
The object of the present invention is to solve the problem raised in the preparation of areno[e]indols (III) by photochemical irradiation in the presence of 1-aryl-2-pyrrilethylene oxidants (II.)
The problems associated with the photochemical cycling of 1-aryl-2-pyrrilethylenes (II) are solved in this invention by preparing compounds of general structure (II) wherein the double central bond is substituted by an arylsulfonyl group. This group acts by drawing out charge and therefore stabilizing the 1-aryl-2-pyrrilethylene to which it is linked against undesired oxidations, which allows easy photocycling thereof leading to an areno[e]indol substituted with an arylsulfonyl group, that can be easily eliminated, if desired, by using a reducing agent capable of breaking the carbon sulfur bond.
DETAILED DESCRIPTION OF THE INVENTION
Just as is stated in the title hereof, the present invention refers to new areno[e]indols, preparation method and application thereof as intermediates in the synthesis of products with antitumoral activity. Said new areno[e]indols have the general formula (I): ##STR3## wherein --Ar represents phenyl or substituted phenyl, Ar' represents a condensed radical of formula: ##STR4## wherein R, R 1 , R 2 , R 3 may represent hydrogen, halogen, a linear or branched alkyl, alkenyl or alkynyl radical, a formyl, acyl, carboxy, akoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, cyano, hydroxy, alkoxy, amino, alkylamino, dialkylamino, acylamino or nitro radical and X represents oxygen, sulfur or a substituted or unsubstituted nitrogen and --R represents an acyl group with 2 to 5 linear or branched chain carbon atoms.
In order to obtain the compounds of formula (I) one starts with a methyl 2-arylsulfinylmethyl-N-methoxymethyl-4-pyrrolcarboxylate of general formula (VI): ##STR5## wherein Ar has the meaning given above.
These compounds of formula (VI) can be prepared, in turn, starting with methyl 2-formyl-pyrrolcarboxylate, a compound that is easily obtained by using the process described by H. J. Anderson, C. E. Loader and A. Foster in Cam. J. Chem., 58, 2527 (1980.)
The treatment of methyl 2-formyl-4-pyrrolcarboylate with chloromethyl ethyl ether in the presence of a base and an adequate organic solvent results in methyl 2-formyl-N-methoxymethyl-4-pyrrolcarboxylate. The base used is an alkoxide, a tertiary amine, an alkaline amide or an organolytic compound; the organic solvent is an aprotic dipolar solvent, an ether or a hydrocarboned solvent; the reaction time is between 1 and 40 hours and the temperature between -10° and 50° C.
The reduction of methyl 2-formyl-N-methoxymethyl-4-pyrrolcarboxylate with a metal hydride in an organic solvent leads to the formation of methyl 2-hydroxymethyl-N-methoxymethyl-4-pyrrolcarboxylate. Normally the preferred metal hydride is boron hydride and the organic solvent is an alcohol with a low molecular weight such as methanol or ethanol. The reaction temperature is generally between 0° and 40° C. and the time between 0.5 and 3 hours.
The treatment of methyl 2-hydroxymethyl-N-methoxymethylpyrrol4-carboxylate with a substituted or unsubstituted benzenesulfinate in an acid medium gives rise to methyl 2-aryl-sulfinylmetho-N-methoxymethyl-4-pyrrolcarboxylate of general formula (VI) indicated above. In the same manner as the benzenesulfinate, 1-toluenesulfinate can be used its counter-ion ion being a metallic cation, usually a sodium cation. The acid medium tends to be determined by an organic acid that is normally used as the solvent, for example, formic acid. The reaction temperature is normally between 0° and 50° C. and the time between 0.5 and 3 days.
The first step of the process of the invention includes reacting methyl 2-arylsulfinilmetyl-N-methoxymethyl-4-pyrrolcarboxylate (VI) with a strong base in an inert solvent and then with an aromatic aldehyde, obtaining as a product of the reaction the compounds methyl 2-(2-aryl-1-arylsulfonil-2-hydroxyethyl)-N-methoxymethylpyrrol-4-carboxylate compounds of general formula: ##STR6## wherein Ar" represents an aryl, phenyl, pyrrolyl, furyl or thiophenyl group substituted up to three times by any of the above mentioned radicals R, R 1 , R 2 and R 3 and Ar has the meaning given above.
The strong base used to obtain the compound of formula (VII) can be alkaline amide, an alkyl-lithium or an aryl-lithium, preferably lithium diisopropylamide; the solvent has to be an inert solvent such as dialkyl ether, 1,4-dioxane or tetrahydrofuran, preferably tetrahydrofuran, and the aldehyde an aromatic aldehyde, such as methyl 2-formyl-N-methoxymethylpyrrol-4-carboxylate, 4-methoxybenzaldehyde or 3,4,5-trimethoxybenzaldehyde.
The compounds of formula (VII) obtained are oxidized in an inert solvent to give the corresponding ketone of general formula: ##STR7## wherein --Ar and --Ar" have the above cited meaning.
The oxidant used is 2,3-dicyano-5,6-dichloro-p-benzoquinone and the inert solvent benzene, toluene, xylene, 1,4-dioxane or chlorobenzene.
The ketone of general formula (VIII) is subjected to acylation by treating it with a suitable base in an inert solvent and then with an acyl chloride as an acylating agent, obtaining the acylated derivate of general formula: ##STR8## wherein Ar, Ar" and R have the meaning given above.
The base used can be an amine, an alkaline amide, an alkyl-lithium or an aryl-lithium, preferably triethylamine; the inert solvent may be chloroform, dichloromethane or 1,2-dichloroethane and the acylating agent a chloride of an acid having 2 to 5 linear or branched chain carbon atoms, preferably acetyl chloride.
The compound of formula (IX) is subjected to a photochemical cycling process in an organic solvent, preferably an alcohol with a low molecular weight such as methanol or ethanol, in the presence of an oxidant, such as oxygen associated catalytic iodine, and under ultraviolet irradiation.
The compound obtained by this photochemical cycling process from the acylated derivative of formula (IX) is a compound of general formula (I), an intermediary product in the synthesis of compounds with antitumoral activity.
EMBODIMENTS OF THE INVENTION
The present invention is illustrated with the following example, that are not intended to limit at all the scope of the applicability thereof.
In order to describe the physical data of the synthesized compounds the following abbreviations are used:
m.p.: melting point
IR: infrared
UV: ultraviolet
1 H--NMR: nuclear magnetic resonance
S: singlet
d: doblet
t: triplet
m: multiplet
J: coupling constant
MS: mass spectrum
ei: electronic impact
FAB: fast atom bombardment
M + : molecular ion
.O slashed.: diameter
TS: tosyl=p-toluenesulfonyl
EXAMPLE OF PREPARATION
Preparation of methyl N-methoxymethyl-2-tosylmethyl-4-pyrrolcarboxylate
Step 1: Preparation of methyl 2-formyl-N-methoxymethyl-4-pyrrolcarboxylate
A solution of 5.995 g of methyl 2-formyl-4-pyrrolcarboxylate is prepared in 60 mL of dry N,N-dimethylformamide, in a flask provided with a calcium chloride tube. To this solution magnetically stirred and cooled in an ice/water bath 7.323 g. of potassium tertbutoxide were added. When the addition was ended, the reaction is left to room temperature and the stirring is maintained for 1.75 hours, after which the reaction is cooled again in an ice/water bath and 6 mL of chloromethyl ethyl they are added slowly. After the addition is finished the reaction is left to room temperature and the stirring is maintained for 18 hours. Thereafter, by fine layer chromatography analysis the existence of the starting product is tested, so that, by repeating the same process used above, 1.864 g. of potassium tert-butoxide and 1.5 mL of chloromethyl methyl ether were added, leaving the stirring at room temperature for 16 more hours.
The preparation is carried out by adding water and extraction with ethyl acetate, followed by drying the organic phase with sodium sulfate and elimination of the solvent in a steam rotator, resulting in an oil that is purified by silica gel column chromatography (25×3 cm .O slashed.), by elution with dichloromethanol/ethyl acetate (20:1.) 6.817 g. of protected pyrrol are obtained.
Yield: 88% m.p.: 65°-66° C. (petroleum ether:diethyl ether) IR(KBr, maximum γ): 1670, 1705, 2950, 3115 cm -1 UV (ethanol, maximum λ): 220, 278 nm.
1 H--NMR (CDCl 3 ): 3.34 (s, 3H, ArCH 2 OCH 3 ), 3.85 (s, 3H, ArCO 2 CH 3 ), 5.67 (s, 2H, ArCH 2 OCH 3 ), 7.39 (d. 1H, J=1.6 Hz, ArH), 7.69 (s wide, 1H, ArH), 9.62 (d, 1H, J=0.8 Hz, ArCHO) ppm.
MS (e.i., m/e, %): 197 (M + , 29) 182 (M + . --CH 3 , 100), 166 (M + . --OCH 3 , 28), 154 (M + . --CH 3 CO, 23.)
Elemental analysis for C 9 H 11 NO 4 : Calculated: % C=54.77: % H=5.62; % N=7.10 Found: % C=55.04: % H=5.65; % N=6.95
Step 2: Preparation of methyl 2-hydroxymethyl-N-methoxymethyl-4-pyrrolcarboxylate 165 mg. NaBH 4 are added to a magnetically stirred solution cooled in an ice/water bath of 515 mg. of methyl 2-formyl-N-methoxymethyl-4-pyrrolcarboxylate in 8 mL of dry methanol, in a flask provided with a calcium chloride tube. After the addition has been ended, stirring is maintaining for 1.5 hours.
Addition of water to the reaction mixture followed by elimination of the methanol in the steam rotor, extraction with ethyl acetate, drying the organic phase with sodium sulfate and elimination of the solvent in the steam rotor, gives rise to an oil, which is purified by silica gel column chromatography (15×2 cm .O slashed.), by elution with dichloromethane/ethyl acetate (5:1), whereby 507 mg of the desired alcohol are obtained.
Yield: 98% m.p.: 56°-57° C. (ethyl acetate:hexane) IR (KRr, maximum γ): 1710, 2950, 3120, 3400 wide cm -1 UV ethanol maximum λ): 208 225 260 shoulder nm 1 H--NMR (CDCl 3 ): 3.29 (s, 3H, ArCH 2 OCH 3 ), 3.80 (s, 3H, ArCO 2 CH 3 ), 4.61 (s, 2H, ArCH 2 OH). 5.28 (s, 2H, ArCH 2 OCH 3 ), 6.60 (d, 1H, J=1.6 Hz, ArH), 7.40 (d, 1H, J=1.7 Hz, ArH) ppm
MS (e.i., m/s, %): 199 (M + ., 182 (M + . --OH, 3) 168 (M + . --OCH 3 , 13) 45 (CH 3 OCH 2 +, 100).
Elementary analysis for C 9 H 13 NO 4 : Calculated: % C=54.26: % H=6.57: % N=7.03 Found: % C=53.91: % H=6.82: % N=6.95
Step 3: Preparation of methyl N-methoxymethyl-2-tosylmethyl-4-pyrrolcarboxylate
A solution of 438 mg. methyl 2-hydroxymethyl-N-methoxymethyl-4-pyrrolcarboxylate and 1.881 g. of sodium p-toluenesulfinate in 5 mL of aqueous 85% formic acid is stirred at room temperature for 23 hours.
Addition of water to the reaction mixture, followed by extraction with dichloromethane, drying of the organic phase with sodium sulfate and elimination of the solvent in the steam rotator, leads to a solid that is purified by means of a silica gel column (15×1.5 cm, .O slashed.), elution with dichloromethane:ethyl acetate (20:1), whereby 702 mg. of sulfone are obtained.
Yield: 95% m.p.: 104°-105° C. (ethyl acetate: petroleum ether) IR (KBR, maximum γ): 1705. 2940, 3120 cm -1 IV ethanol, maximum λ): 202, 208, 226 nm
1 H--NMR (CDCl 3 ): 2.44 (s, 3H, ArCH 3 ), 3.17 (s, 3H, ArCH 2 OCH 3 ), 3.77 (s. 3H, ArCO 2 CH 3 ), 4.42 (s, 2H, ArCH 2 Ts), 5.27 (s, 2H, ArCH 2 OCH 3 ). 6.30 (d, 1H, J=1.3 Hz, ArH), 7.30 (d, 2H, J=8.2 Hz, ArH), 7.38 (d, 1H, J=1.7 Hz, ArH), 7.57 (d, 2H, J=8.2 Hz, ArH) ppm.
MS (e.i., m/s, %), 337 (M + ., 0.3) 306 (M + . --OCH 3 , 3), 1.82 (M + . --SO 2 (C 6 H 4 )CH 3 , 100).
Elementary analysis for C 16 H 19 MO 5 S: Calculated: % C=56.96; % H=5.67; % N=4.15 Found: % C=56.83; % H=5.80; % N=3.86
EXAMPLE 1
1) Methyl 2-[2-hydroxy-2-(4-methoxycarbonyl-N-methoxymethyl-2-pyrryl)-1-tosylethyl]-N-methoxymethyl-4-pyrrolcarboxylate
A solution of lithium diisoproplyamide is prepared by adding 0.8 mL of a 2.7M solution of n-butyl-lithium in hexane on a solution of 0.31 mL of diisopropylamine in 20 mL of tetrahydrofuran. 600 mg. of methyl N-methoxymethyl-2-tosylmethyl-4-pyrrolcarboxylate are added to the solution of lithium diisopropylamide stirred magnetically and cooled to -75° C. The temperature of the resulting suspension is left to rise to -40° C. for 1.25 hours and on the generated red soluion 351 mg. of methyl 2-formyl-N-methoxymethyl-4-pyrrolcarboxylate are added. The temperature of the reaction mixture is left to rise to -15° C. for 2 hours and 5 mL of hydrochloric acid 10% are added.
Addition of 20 mL of brine, followed by extraction with diethyl ether, drying of the organic phase with sodium sulfate and elimination of the solvent in a steam rotator, leads to a solid residue that is purified on silica gel column chromatography (18×2 cm .O slashed.), using an elution gradient of dichloromethane/ethyl acetate increasing the proportion of ethyl acetate from 15 to 25%. 921 mg. of the condensation product is obtained as a sole diastereoisomer.
Yield: 97% m.p.: 180°-181° C. (ethyl acetate) IR (KBr, maximum γ: 1688, 1715, 2950, 3120, 3460 cm -1 UV (ethanol maximum): 205, 225 shoulder , 255 shoulder nm
1 H--NMR (CDCl 3 ): 2.40 (S, 3H, ArCH 3 ), 3.08 (s, 3H, ArCH 2 OCH 3 ), 3.17 (s, 3H, ArCH 2 OCH 3 ), 3.67 (s, 3H, ArCO 2 CH 3 ) 3.71 (s, 3H, ArCO 2 CH 3 ), 4.06 (d, 1H, J=3.7 Hz, ArCH(R)OH) 4.70 (d, 1H, J=11.4 Hz, ArCH 2 OCH 3 ), 5.09 (m, 2H, ArCH 2 OCH 3 and ArCH(Ts)R) 5.36 (d, 1H J=11.5 Hz ArCH 2 OCH 3 ), 5.37 (d, 1H, J=10.7 Hz, ArCH 2 OCH 3 ), 5.54 (dd, 1H, J=2.6 and 10.4 Hz, ArCH(OH)R), 6.42 (d, 1H, J=1.3 Hz, ArH), 6.49 (d, 1H, J=1.5 Hz, ArH), 7.18 (m, 2H, ArH), 7.25 (d, 2H, J=7.9 Hz, ArH) 7.57 (d, 2H, J=8.3 Hz, ArH) ppm.
MS (FAB, m/s, %): 535 (M+1H 2 O, 29), 503 (M+1--CH 3 OH, 28), 489 (M+1--CH 3 OCH 3 ,6), 379 (M+1--CH 3 (C 6 H 4 )SO 2 H, 4), 362 M+1+H 2 O--CH 3 (C 6 H 4 )SO 2 ,100), 348 (M+1--CH 3 (C 6 H 4 )SO 2 H--OCH 3 , 21), 333 (M+1--CH 3 (C 6 H 4 )SO 2 H--CH 3 OCH 3 , 9) 315 (M+1--CH 3 (C 6 H 4 )SO 2 H--CH 3 OCH 3 --H 2 O, 61) 182 (ArCH 2 A, 83).
Elementary analysis for C 25 H 30 N 2 O 9 S: Calculated: % C=56.17; % H=5.66; % N=5.24% S=6.00 Found: % C=55.92; 4 H=5.58; % N=5.22; % S=6,36
2) Methyl 2-[2-hydroxy-2-(4-methoxyphenyl)-1-tosylethyl]-N-methoxymethyl-4-pyrrolcarboxylate
A solution of lithium diisopropylamide is prepared by adding 4.21 mL of a 2.4M solution of -n-butyl-lithium in hexanes on a 1.5 mL solution of diisopropylaminde in 100 mL of tetrahydrofuran. 2.9 g. of methyl N-methoxy-2-tosylmethyl-4-pyrrolcarboxylate are added to a solution of lithium diisopropylamide stirred magnetically and cooled to -50° C. 2 hours later 1.06 mL of methoxybenzaldehyde are added on the cenerated red solution. 1 hour later HCl 10% is added.
Addition of brine, followed by extraction with diethyl ether, drying the organic phase with sodium sulfate and elimination of the solvent in a steam rotator, leads to a dry residue that is purified by silica gel column chromatography (27×3.5 cm .O slashed.), by elution with dichloromethane/ethyl acetate (3:1.) 3.58 g. of the condensation product are obtained as two diasteroeoisomers in the ratio of 3:1.
Yield: 88% IR (film, maximum γ): 1560, 1610, 1710, 2960, 3480 cm -1 UV (ethanol, maximum λ): 204, 328 nm
1 H--NMR (CDCl 3 ): 2.37 (s, ArCH 3 , minority), 2.40 (s, CH 2 OCH 3 , minority), 2.42 (s, ArCH 3 , majority), 2.50 (s, CH 2 OCH 3 , majority), 3.70 (s, CO 2 CH 3 , majority+minority), 3.79 (s, ArOCH 3 , majority+minority), 4.05 (d, J=11.3 Hz, NCH 2 OCH 3 , minority), 4.39 (d, J=11.13 Hz, NCH 2 OCH 3 , minority). 4.39 (d, J=11.3 Hz, NCH 2 OCH 3 majority), 4.48 (d, J=11.3 Hz, NCH 2 OCH 3 , minority) 4.56 (d, J=1.9 Hz, HCOH, minority), 4.75 (d, J=9.8 Hz, HCOH, majority), 4.78 (d, J=11.3 Hz, NCH 2 OCH 3 , majority), 5.33 (d, J=9.8 Hz, CHTs, majority), 5.80 (d, J=1.9 Hz, CHTs, minority), 6.61 (d, J=1.4 Hz, ArH, majority), 6.68 (d, J=8.7 Hz, ArH, majority), 6.71 (d, J=8.6 Hz, ArH, minority), 7.00 (d, J=1.4 Hz, ArH, majority+minority), 7.02 (d, J=8.6 Hz, ArH, minority), 7.14 (d, J=8.7 Hz, ArH. majority), 7.27 (d, J=8.3 Hz, ArH, majority), 7.37 (d, J=1.4 Hz, ArH, minority), 7.57 (d, J=8.3 Hz, ArH, majority+minority), 7.64 (d, J=8.3 Hz, ArH, minority)
MS (FAB, m/s, %): 474 (M+1.7), 476 (M+1--H 2 O, 63) 442 (M+1--HOCH 3 , 3) 318 (M+1--TsH,24), 301 (M+1--H 2 O--TsH, 70 ), 286 (M+1--HOCH 3 --TsH, 67) 258 (M+1--HOCH 3 --TsH--CO, 23. )
Elementary analysis for C 24 H 27 NO 7 S: Calculated: % C=60.87; % H--5.75; % N=2.96 Found: % C=61.32; % H=5.96: % N=2.72
3) Methyl 2-[2-hydroxy-2-(3,4,5-trimethoxyphenyl)-1-tosylethyl]-N-methoxymethyl-4-pyrrolcarboxylate
A solution of lithium diisoproplylamide is prepared by adding 4.8 mL of a solution of 2.44M n-butyl-lithium in hexanes on a solution of 1.9 Ml of diisopropylamine in 70 mL of tetrahydrofuran. 3.0 g. of methyl N-methoxymethyl-2-tosylmethyl-4-pyrrolcarboxylate are added to the solution of lithium diisopropylamide stirred magnetically and cooled to -80° C. The resulting suspension is left stirring at -50° C. for 2.3 hours and 1.75 g. of 3,4,5-trimethoxybenzaldehyde are added to the generated red solution. After 1.5 hours of stirring at -50° C. the reaction is cooled to -70° C. and 100 ml. of hydrochloric acid 10% are added.
Extraction with diethyl ether, followed by drying of the organic phase with sodium sulfate and elimination of the solvent in the steam rotator, leads to a solid residue that is purified by recrystallization of dichloromethanecyclohexane, giving a first fraction that is mixed with a second fraction of product, result of concentrating the mother liquors, dissolving the residue in methanol, adding cyclohexane and filtering the resulting precipitate. 3,15 g. of the condensation product are obtained as two two diasteroisomers in the ratio of 3:1.
Yield: 66% m.p. 80°-90° C. IR (film, maximum γ): 1590, 1710, 2950, 3000. 3470 cm -1 UV (ethanol maximum λ): 282 nm
1 H--NMR (CDCl 3 ): 2.34 (d, J=1.3 Hz, ArCH 3 minority), 2.40 (t, J=1.5 Hz, ArCH 3 majority), 3.85-3.65 (m, ArOCH 3 +CO 2 CH 3 +CH 2 OCH 3 , majority+minority), 3.98 (d, J=1.7 Hz, NCH 2 OCH 3 minoirty). 4.43 (d, J=10.8 Hz, NCH 2 OCH 3 majority), 4.45 (d, J=1.7 Hz, NCH 2 OCH 3 minority),
4.76-4.62 (m, HCOH+HCTs, majority+minority), 5.32 (d, J=9.5 Hz, NCH 2 OCH 3 majority), 5.85 (s, OH) 633 (d, J=1.1 Hz, ArH minority), 6.44 (d, J=1.3 Hz, ArH majority), 6.73 (s, ArH majority), 6.98 (t, J=1.6 Hz, ArH majority), 7.08 (t, J=1.6 Hz, ArH minority), 7.24 (d, ArH minoirty), 7.25 (dd, ArH majority), 7.34 (s, ArH minority), 7.57 (dd, J=1.5 and 8.4 Hz, ArH majority), 7.61 (d, J=6.9 Hz, ArH minority) ppm.
EXAMPLE 2
1) Methyl 2-[2-(4-methoxycarbonyl-N-methoxymethyl-2-pirryl)-2-oxo-1-tosylethyl]-N-,ethoxymethyl-4-pyrrolcarboxylate
A mixture of 2.35 g. of methyl 2-[2-hydroxy-2-(4-methoxycarbonyl-N-methoxymethyl-2-pyrril)-1-tosylethyl]-N-methoxymethyl-pyrrolcarboxylate and 2.51 g. of 2,3-dicyano-5,6-dichloro-p-benzoquinone in 25 mL of dry benzene is heated to reflux under argon for 24 hours.
Addition of 100 mL of a saturated solution of Na 2 S 2 O 5 , followed by extraction with dichloromethane, washing the organic solution with a saturated Na 2 S 2 O 5 solution, drying with sodium sulfate and concentration of the same, gives rise to an oil that is purified by silica gel column chromatography (20×2 cm .O slashed.), by elution with ethyl acetate/hexane (1:1) to give rise to 2.20 g. of the desired ketone.
Yield: 92% m.p.: 58°-60° C. (ethyl acetate-hexane) IR (KBr, maximum γ): 1670, 1718, 2950, 3120 cm -1 UV (ethanol, maximum λ): 208, 222 shoulder , 293 nm
1 H--NMR (CDCl 3 ): 2.39 (s, 3H, ArCH 3 ); 3.27 (s, 6H, ArCH 2 OCH 3 ), 3.71 (s, 3H, ArCO 2 CH 3 ), 3.79 (s, 3H, ArCO 2 CH 3 ), 4.92 (d, 1H, J=11.1 Hz, ArCH 2 OCH 3 ), 5.58 (d, 1H, J=10.2 Hz, ArCH 2 OCH 3 ), 5.61 (d, 1H, J=10.2 Hz, ArCH 2 OCH 3 ), 6.04 (d, 1H, J=11.1 Hz, ArCH 2 OCH 3 ), 6.27 (s, 1H, ArCH (Ts)R), 6.47 (d, 1H, J=1.7 Hz, ArH), 7.22 (d, 2H, J=8.2 Hz, ArH), 7.42 (d, 1H, J=1.8 Hz, ArH), 7.50 (d, 2H, J=8.3 Hz, ArH), 7.59 (d, 1H, J=1.7 Hz, ArH), 7.64 (d, 1H, J=117 Hz, ArH) ppm.
MS (e.i., m/s %): 532 (M + ., 1) 501 (M + . --CH30.8) 377 (M + . --CH 3 (C 6 H 4 )SO 2 , 94), 395 (M + . --CH 3 O--CH 3 (C 6 H 4 )SO 2 H. 99) 317 (M + . --CH 3 O--CH 3 (C 6 H 4 )SO 2 H--CO, 100), 196 (ArCO + , 44), 182 (ArCH 2 +, 22), 139 (CH 3 (C 6 H 4 )SO + ., 11) 91 (CH 3 (C 6 H 4 ) + , 16).
Elementary analysis for C 25 H 28 N 2 O 9 S: Calculated: % C=56.38; % H=5.30: % N=5.26: S=6.02 Found: % C=56.08; % H=5.45; N=5.13: % S=5.98
2) Methyl 2-[2-(4-methoxyphenl)-2-oxo-tosylethyl]-N-methoxymethyl-4-pyrrolcarboxylate
A mixture of 1.42 g. of methyl 2-[2-hydroxy-2-(4-methoxyphenyl)-1-tosylethyl]-N-methoxymethyl-4-pyrrolcarboxylate and 1.7 g. of 2,3-dicyano-5,6-dichloro-p-benzoquinone in 70 mL of dry toluene is heated to reflux under argon for 12 hours.
Addition of a saturated solution of Na 2 S 2 O 5 , followed by extraction dichloromethane, washing the organic solution with a saturated solution of Na 2 S 2 O 5 , drying with sodium sulfate and concentrating the same, gives rise to an oil that can be purified by silica gel column chromatography (35×3 cm .O slashed.), by elution with ethyl acetate/hexane (1:1) to give rise to 1,27 g. of the desired ketone.
Yield: 90% m.p.: 108°-109° C. IR (film, maximum γ): 1570, 1600, 1680. 1715 cm -1 UV (ethanol, maximum λ): 294, 222 nm)
1 H--NMR (CDCl 3 ): 2.44 (s, 3H, ArCH 3 ), 3.26 (s, 3H, NCH 2 OCH 3 ), 3.73 (s, 3H, CO 2 CH 3 ), 3.85 (s, 3H, ArOCH 3 ), 4.97 (d, 1H, J=11.1 Hz, NCH 2 OCH 3 ), 6.24 (d, 1H, J=11.1 Hz, NCH 2 OCH 3 ), 6.39 (d, 1H, J=1.8 Hz, ArH), 6.54 (s, 1H, HCTs), 6.89 (d, 2H, J=9.0 Hz, ArH), 7.26 (d, 2H, J=8.3 Hz, ArH), 7.46 (d, 1 H, J=1.8 Hz, ArH), 7.52 (d, 2H, J=8.3 Hz, ArH), 7.96 (d, 2H, J=9.0 Hz, ArH) ppm.
MS (e.i., m/s, %) 471 (M + ., 3), 316 (M + . --TsH 100) 135 (CH 3 O(C 6 H 4 )CO + , 49) 91 (CH 3 C 6 H 4 +, 19).
3) Methyl 2-[2-(3,4,5-trimethoxyphenyl)-2-oxo-1-tosylethyl]-N-methoxymethyl-4-pyrrolcarboxylate
A mixture of 2.65 g. of methyl 2-[2-hydroxy-2-(3,4,5-trimethoxyphenyl)-1-tosylethyl]-N-methoxymethyl-4-pyrrolcarboxylate and 3,95 g. of 2.3-dicyano-5,6-dichloro-p-benzoquinone in 90 mL of dry toluene is dried to reflux under argon for 9 hours.
The elimination of toluene gives rise to a dark residue that is dissolved in dichloromethane. The resulting solution is filtered, washed with an aqueous saturated Na 2 SO3 solution and concentrated, yielding a residue that is purified by silica gel column chromatography, by elution with dichloromethane-ethyl acetate (9:1), giving rise to 1.63 g. of the desired ketone.
Yield: 62% 1 H--NMR (CDCl 3 ): 2.46 (s, 3H, ArCH 3 ), 3.27 (s, 3H, NCH 2 OCH 3 ), 3.75 (s, 3H, CO 2 CH 3 ), 3.84 (s, 6H, ArOCH 3 ), 3.94 (2, 3H, ArOCH 3 ), 5.00 (d, 1H, J=11 Hz, NCH 2 OCH 3 ), 6.26 (d, 1H, J=11 Hz, NCH 2 OCH 3 ), 6.36 (d, 1H, J=1.7 Hz, ArH), 6.54 (s, 1H, HCTs), 7.27 (s, 2H, ArH), 7.28 (d, 2H, J=8.4 Hz, ArH), 7.48 (d, 1H, J=1 Hz, ArH), 7.5 (d, 2H, J=8.4 Hz, ArH) ppm.
EXAMPLE 3
1) Methyl 2-[2-acetoxy-2-(4-methoxycarbonyl-N-methoxymethyl-2-pyrril)-1-tosylethenyl]-N-methoxymethyl-4-pyrrolcarboxylate
4.4 mL of acetyl chloride are slowly added to a solution, magnetically stirred and kept at -40° C. under argon, of 4.67 g. of methyl 2-[2-(4-methoxycarbonyl-N-methoxymethyl-2-pirryl)-2-oxo-1-tosylethyl]-N-methoxymethyl-4-pyrrolcarboxylate and 12.1 mL of triethylamine in 60 mL of dry dichloromethane.
After 2.25 hours, 100 mL of hydrochloric acid 10% are added and extracted with dichloromethane. Drying with sodium sulfate and concentrating the organic phase yields an oil that is purified by silica gel column chromatography (18×3 cm .O slashed.), by elution with a hexane-ethyl acetate gradient of 40 to 60% in ethyl acetate. 4.96 g. of enol acetate.
Yield: 98% m.p. 59°-61° C. (Dichloromethane-ethyl acetate) IR (film, maximum γ): 1720, 1785, 2880, 2960 cm -1 UV (ethanol, maximum λ): 205, 302, 315 shoulder nm
1 H--MMR (CDCl 3 ): 2.32 (s, 3H, ArOCOCH 3 ), 2.42 (s, 3H, ArCH 3 ), 2.99 (s, 3H, NCH 2 OCH 3 ), 3.20 (s, 3H, NCH 2 OCH 3 ) 3.69 (s, 3H, ArCO 2 CH 3 ), 3.76 (s, 3H, ArCO 2 CH 3 ), 4.82 (d, 1H, J=10.6 Hz, ArCH 2 OCH 3 ), 4.99 (d, 1H, J=10.6 Hz, ArCH 2 OCH 3 ), 5.13 (d, 1H, J=10.6 Hz, ArCH 2 OCH 3 ), 5.23 (d, 1H, J=10.6, ArCH 2 OCH 3 ), 6.26 (d, 1H, J=1.8 Hz, ArH), 6.47 (d, 1H, J=1.8 Hz, ArH), 7.27 (d, 2H, J=8.1 Hz, ArH), 7.31 (d, 1H, J=1.7 Hz, ArH), 7.40 (d, 1H, J=1.8 Hz, ArH), 7.62 (d, 2H, J=8.3 Hz, ArH) ppm.
MS (e.i., m/s, %): 574 (M + ., 4), 543 (M + . --CH 3 O, 7) 532 (M + . --CH 2 CO, 75) 500 (M + . --CH 3 OH----CH 2 CO, 20), 377 (M + . --CH 2 CO--CH 3 (C 6 H 4 )SO 2 , 32), 345 (M + . --CH 3 OH--CH 2 CO--CH 3 (C 6 H 4 ) SO 2 , 90), 317 (M + . --CH 3 OH--CH 2 CO--CH 3 (C 6 H 4 )SO 2 --CO, 54), 196 (ArCO + , 41) 182 (ArCH 2 +100), 139 (CH 3 (C 6 H 4 )SO + ., 24) 91 (CH 3 (C 6 H 4 )+, 18.)
2) Methyl 2-[2-acetoxy-2- (4-methoxyphenyl)-1-tosylethenyl]-N-methoxymethyl-4-pyrrolcarboxylate
1.34 mL of acetyl chloride are slowly added on a solution, magnetically stirred and kept at -40° C. under argon, of 1.27 g. of methyl 2-[2-(4-methoxyphenyl)-2-oxo-1-tosylethyla-N-methoxymethyl-4-pyrrolcarboxylate and 3.76 mL of triethylamine in 60 mL of dry dichloromethane.
After 2 hours 20 mL of hydrochloric acid 10% are added and extracted with dichloromethane. Drying with sodium sulfate and concentration of the organic phase gives an oil that is purified by silica gel column chromatography (30×3 cm .O slashed.), by elution with hexane-ethyl acetate (1:1). 1.34 g. of enol acetate are obtained as the sole isomer.
Yield: 97% m.p. 152.5°-153.5° C. IR (film, maximum γ): 1510, 1550, 1595, 1780, 2955 cm -1 UV (ethanol, maximum λ): 298, 212 nm
1 H--NMR (CDCl 3 ): 2.42 abd 2,43 (s, 3H, ArCH 3 and ArOCOCH 3 ), 3.00 (s, 3H, NCH 2 OCH 3 ), 3.74 (s, 3H, ArCO 2 CH 3 ), 3.79 (s, 3H, ArOCH 3 ), 4.64 (d, 1H, J=10.3 Hz, NCH 2 OCH 3 ), 5.00 (d, 1H, J=10.3 Hz, NCH 2 OCH 3 ), 6.44 (d, 1H, J=1.7 Hz, ArH), 6.69 (d, 2H, J=9.0 Hz, ArH), 7.12 (d, 2H, J=9.0 Hz, ArH), 7.28 (d, 2H, J=8.3 Hz, ArH), 7.54 (d, 1H, J=1.7 Hz, ArH), 7.68 (d, 1H, J=8.3 Hz, ArH)
MS (FAB, m/s, %): 514 (M+, 9), 471 (M+1--CH 2 CO, 37) 440 (M+1--CH 2 CO--CH 2 OCH 3 , 30) 135 (CH 3 O(C 6 H 4 ) + , 100) 284 (M+1--CH 2 CO--CH 2 OCH 3 --TsH, 33).
3) Methyl 2-[2-acetoxy-2-(3,4,5-trimethoxyphenyl)-1-tosylethenyl]-N-methoxymethyl-4-pyrrolcarboxilate
0.24 mL of acetyl chloride are slowly added to a solution, magnetically stirred and kept at -40° C. under argon, of 99 mg. of methyl 2-[2-(3,4,5-trimethoxyphenyl)-2-oxo-1-tosylethyl]-N-methoxymethyl-4-pyrrolcarboxylate and 0.24 mL of triethylamine in 5 mL of dry dichloromethane.
After 5.7 hours 5 mL of hydrochloric acid 10% are added and extracted with dichloromethane. Drying with sodium sulfate and concentration of the organic phase gives rise to an oil that is purified by silica gel column chromatography (15×1 cm .O slashed.), by elution with hexane-ethyl acetate (1:1). 101 mg. of enol acetate are obtained as a mixture of isomers in a ratio of 5:1.
Yield: 95% IR (film, maximum γ): 1580. 1715, 1775. 2740, 2945, 2955, 3055, 3120 cm -1 UV (ethanol, maximum λ): 304 nm.
1 H--NMR (CDCl 3 ) (majority isomer) 2.43 and 2.42 (s, 3H, ArCH 3 and ArOCOCH 3 ), 3.12 (s, 3H, NCH 2 OCH 3 ), 3.79-374 (singlets, 6H, ArOCH 3 and ArOCH 3 ), 4.94 (d, 1H, J=10.1 Hz, NCH 2 OCH 3 ), 5.12 (d, 1H, J=10.5 Hz, NCH 2 OCH 3 ), 6.39 (d, 1H, J=1.7 Hz, ArH), 7.27 (s, 2H, ArH), 7.32 (d, 2H, J=8.4 Hz, ArH), 7.48 (d, 1H, J=1.8 Hz, ArH), 7.70 (d, 2H, J=8.3 Hz, ArH) ppm.
EXAMPLE 4
1) Dimethyl 5-acetoxy-3,6-bis(methoxymethyl)-4-tosyl-3,6-dihydropyrrol[3,2-e]indol-1,8-dicarboxylate
An aerated solution of 2.30 g. of methyl 2-[2-acetoxy-2-(4-methoxycarbonyl-N-methoxymethyl-2-pirryl)-1-tosylethenyl]-N-methoxymethyl-4-pyrrolcarboxylate and 160 mg. of iodine in 225 mL of ethanol, introduced in a photochemical Pyrex glass reactor is irradiated for 3.5 hours with ultraviolet light produced by a Hanowia 400 W lamp.
Addition of an aqueous saturated solution of Na 2 S 2 O 5 until the color due to the iodine disappears, followed by elimination of the ethanol under reduced pressure, extraction with dichloromethane, drying of the organic phase with sodium sulfate and elimination of the solvent, gives rise to a residue that is purified by silica gel column chromatography (19×2 cm .O slashed.), by elution with hexane-ethyl acetate (1:1) to give 2.18 g. of the desired pyrrolindol.
Yield: 95% m.p.: 128°-130° C. (hexane-ethyl acetate) IR (film, maximum γ): 1720, 1790, 2950 cm -1 UV (ethanol, maximum λ): 202, 215, 237, 264, 326 nm
1 H--NMR (CDCl 3 ): 2.26 (s, 3H, ArOCOCH 3 ), 2.35 (s, 3H, ArCH 3 ). 2.96 (s, 3H, NCH 2 OCH 3 ), 3.14 (s, 3H, NCH 2 OCH 3 ), 3.82 (s, 3H, ArCO 2 CH 3 ), 3.83 (s, 3H, ArCO 2 CH 3 ), 4.97 (d, 1H, J=10.9 Hz, NCH 2 OCH 3 ), 5.79 (m, 3H, NCH 2 OCH 3 ), 7.18 (d, 2H, J=8.1 Hz, ArH), 7.55 (d, 2H, J=8.3 Hz, ArH), (s, 1H, ArH), 7.96 (s, 1H, ArH) ppm.
MS (e.i., m/s, %): 572 (M + . --CH 2 O, 100), 498 (M + . --CH 2 O--CH 3 OH, 49), 433 (M + . --CH 3 (C 6 H 4 )SO, 33) 402 (M + . --CH 3 (C 6 H 4 )SO--CH 3 O, 67), 375 (M + . --CH 2 CO--CH 3 (C 6 H 4 )SO 2 , 67), 343 (M + . CH 2 CO--CH 3 (C 6 H 4 )SO 2 --CH 3 OH. 38), 139 (CH 3 (C 6 H 4 )SO + , 29) 91 (CH 3 (C 6 H 4 ) + , 23).
Elementary analysis for C 27 H 28 N 2 O 10 S: Calculated: % C=56.64, % H=4.93; % H=4.89; % S=5.60 Found: % C=56.89; % H=5.05; % N=5.01; % S=5.66
2) Methyl 5-acetoxy-8-methoxy-N-methoxymethyl-4-tosylbenzo[e]indol-1-carboxylate
An aerated solution of 560 mg. of methyl 2-[2-acetoxy-2-(4-methoxyphenyl)-1-tosylethenyl]-N-methoxymethyl-4-pyrrolcarboxylate and 40 mg. of iodine in 100 mL of ethanol introduced in a photochemical Pyrex glass reactor, is irradiated for 17 hours with ultraviolet light produced by a Hanowia 400 W lamp.
Addition of an aqueous saturated solution of Na 2 S 2 O 5 until the color due to the iodine disappears, followed by elimination of the ethanol under reduced pressure, extraction with dichloromethane, drying of the organic phase with sodium sulfate and elimination of the solvent gives rise to a residue that is purified by silica gel Column chromatography (23×1 cm .O slashed.), by elution with hexane-ethyl acetate (1:1) to give 457 mg. of the desired pyrrolindol.
Yield: 82% m.p.: 163°-164° C. IR (KBr, maximum): 1510, 1620, 1710, 1780, 2950, 3120 cm -1 UV (ethanol, maximum γ): 216, 272, 326 nm
1 H--NMR(CDCl 3 ): 2.37 (s, 3H, ArCH 3 ), 2.39 (s, 3H, ArOCOCH 3 ), 2.95 (s, 3H, ArCH 2 OCH 3 ), 3.95 (s, 3H, ArCO 2 CH 3 ), 4.06 (s, 3H, ArCO 2 CH 3 ) 5.86 (s, 2H, ArCH 2 OCH 3 ), 7.13 (dd, 1 H, J=2.5 and 9.2 Hz, ArH), 7.2 (d, 2H, J=8.2 Hz, ArH), 7.59 (d, 2H, J=8.2 Hz, ArH), 7.60 (s, 1H, ArH), 8,24 (s, 1H, ArH), 9.42 (d, 1H, J=2.5 Hz, ArH) ppm
MS (e.i., m/s, %): 511 (M + ., 11), 469 (M + . --CH 2 CO, 100), 437 (M + . --CH 2 CO--CH 3 OH, 35), 315 (M + . --CH 2 CO--Ts. 40), 139 (CH 3 (C 6 H 4 )SO + ., 26), 91 (CH 3 (C 6 H 4 ) + ., 12).
3) Methyl 5-acetoxy-7,8,9-trimethoxy-N-methoxymethyl-4-tosylbenzo[3]indol-1-carboxylate
An aerated solution of 101 mg. of methyl 2-[2-acetoxy-2-(3,4,5-trimethoxyphenyl)-1-tosylethenyl]-N-methoxymethyl-4-pyrrolcarboxylate and 9 mg. of iodine in 30 mL of ethanol, introduced in a photochemical Pyrex glass reaction, is irradiated for 2.6 hours with ultraviolet light produced by a Hanowia 400 W lamp.
Addition of an aqueous saturated solution of Na 2 S 2 O 5 until the color due to the iodine disappears, followed by elimination of the ethanol under reduced pressure, extraction with dichloromethane, drying of the organic phase with sodium sulfate and elimination of the solvent, gives rise to a residue that is purified by silica gel column chromatography, by elution with a dichloromethane-ethyl acetate gradient, increasing the proportion of ethyl acetate from 0 to 10%, to give 32 mg. of the desired pyrrolindol.
Yield: 32% UV (ethanol, maximum γ): 228, 256, 336 nm.
1 H--NMR (CDCl 3 ): 2.39 (s, 6H, NCH 2 OCH 3 and ArCH 3 ), 2.95 (s, 3H, ArOCOCH 3 ), 3.73 (s, 3H, ArOCH 3 ), 3.84 (s, 3H, ArOCH 3 ), 3.90 (s, 3H, ArCO 2 CH 3 ), 4.06 (s, 3H, ArOCH 3 ), 5.84 (s, 2H, NCH 2 OCH 3 ), 6.79 (s, 1H, ArH), 7.25 (d, 2H, J=8.5 Hz, ArH), 7.67 (d, 2H, J=8.4 Hz, ArH), 7.74 (s, 1H, ArH) ppm. | The areno[e]indols have the formula (I). The methods comprises: (a) reacting (VI) with an aldehyde Ar"--CHO to obtain (VII); (b) oxidizing (VII) to yield the cetone (VIII); (c) reating (VIII) with a strong base and thereafter with an acycle chloride ClCOR, to produce (IX); (d) subjecting to a photochemical cyclization (IX) to produce (I). In said formulas Ar is phenyl or substituted phenyl; Ar' is radical (i) or (ii); R is an acyle group, Ar" is a phenyl, pyrolyl, furanyl or thiophenyl group substituted up to three times by any of the radials R, R 1 , R 2 , or R 3 . The compounds (I) are useful as intermediates in the synthesis of hexahydroareno(e)cyclopropa(c)indol-4-ones with antitumoral activity. | 2 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The invention concerns a method for contact-free monitoring of the fill state of liquids in an unpressurized liquid reservoir and a device for detection of fill states and/or fill state changes in an unpressurized liquid reservoir for acceptance of a liquid.
[0003] 2. Description of the Prior Art
[0004] Sensor systems for larger fill volumes and container (reservoir) sizes are generally known. These sensor systems operate with contacting or non-contacting measurement principles that are based on many different physical effects.
[0005] Examples of such different contacting measurement principles are mechanical fill state sensors operating according to the Schwimmer principle, capacitive fill state sensors, hydrostatic fill state sensors, vibration limit sensors and directed microwave fill state sensors. One significant property of the contacting measurement principles is that they can significantly influence the measurement subject in the determination of the state of the measurement value with a measurement sensor. A measurement sensor that is immersed in a liquid, or that accepts a liquid volume, exhibits an increased influence on the measured fill state as the ratio of total liquid volume to measurement sensor volume decreases. These sensor systems therefore are well-suited for large liquid volumes, but rapidly reach their limits given small liquid volumes.
[0006] Examples of non-contacting measurement principles are optical sensors, and ultrasound or radar sensors. Optical fill state sensors operate either according to the light barrier principle in transparent tubes or as immersion probes with prisms for directing radiation that either reflect the light totally or refract the light given contact with liquid. These optical sensors supply a switching level given the presence of liquid and are in principle not suitable for continuous monitoring of fill states. Ultrasound and radar fill state sensors can be used for large measurement intervals in large reservoirs.
[0007] Given small reservoirs, the fill state can be indirectly determined without influencing the liquid by the gravimetric measurement of the fill volume. This procedure requires a highly-sensitive force measurement that incurs high costs in the process environment of an automated production. Furthermore, manufacturing tolerances of the container geometry have a significant effect on the actual fill state in the container. Gravimetric measurements therefore are best suited for production on the laboratory scale.
[0008] In automated production small liquid volumes are normally output with automated dispensers that determine a volume by a monitored ejection or discharge in closed systems. This is a controlled volume emission. When the liquid is emitted into an unpressurized reservoir, no monitoring of the actual fill state achieved normally ensues. When partial volumes are extracted from the container in further process steps, the fill state generally cannot be determined without a gravimetric measurement.
[0009] Optical measurement systems are known that can measure through transparent surfaces (so as to monitor the fill state of a liquid in a container) by means of interferometric measurement principles. Due to the high costs, however, these can normally not be used in a production environment, but rather are used for research and development and statistical quality assurance. Such a measurement method is particularly relevant given under-filling of attached micro-components or upon filling of gaps between micro-components, for which it must be ensured that filling material is actually filled into the existing gap, such as by monitoring and how long the filling process takes or how far the filling process has proceeded. An exemplary special application is the design of detector components for electromagnetic radiation as used, for example, in computed tomography.
SUMMARY OF THE INVENTION
[0010] An object of the present invention is to provide a cost-effective and simple method and a device for influence-free fill state monitoring in small open containers, wherein the monitoring does not significantly influence the filling.
[0011] The invention is based on the recognition that fill states and their state changes given small volumes in small containers can be detected very easily by the effect of different fill state-dependent light reflections in the surroundings (environment) of boundary surfaces between the liquid and an abutting wall. In this region a significant change of the orientation of the liquid surface is associated with the varying fill state If these surfaces are irradiated with light and the reflected light is measured, slight fill state changes thus can be simply detected by changes in the reflected light.
[0012] If a thin light beam is used for this purpose, a fill state change can be concluded from a varying angle of incidence. Making a precise measurement of the angle of incidence of the light beam is, however, relatively elaborate. If a light beam is used with a greater diameter, a light reflection arises with a spatial intensity that likewise changes with the change of the fill state of the liquid. It is thus sufficient to measure the intensity of the reflected light at a single location in order to detect fill state changes or previously-calibrated fill states.
[0013] Based on this recognition, the above object is achieved in accordance with the invention by a method for non-contacting monitoring of the fill state of liquids in a as unpressurized liquid reservoir, wherein the fill state and/or the fill state change is determined by radiating light onto the boundary region of the liquid at which a fill state-dependent surface curvature (meniscus) arises due to adhesion forces of the liquid at the reservoir wall and surface tension, and the intensity of the reflected light is measured at a predetermined location.
[0014] The reservoir in which the liquid quantity for under-filling of a previously-attached micro-component is located can be used as a liquid container.
[0015] The variation of the intensity of the reflected light for monitoring of an automatic dosing process can be used, with the liquid reservoir having a connection to a gap to be filled at a micro-component via a capillary and the start, the course and the end of the filling of the gap are detected by the intensity change of the reflected light
[0016] The start of the filling can be detected by a first intensity change of the reflected light and the running process of the filling can be detected by a continuous intensity change of the reflected light. The end of the filling process can be detected by the cessation of the intensity change following a previously-detected intensity change of the reflected lights or by reaching a predetermined intensity value of the reflected light.
[0017] Furthermore, the current fill level can also be determined (after previous calibration) by the current intensity of the reflected light.
[0018] A laser (preferably a laser diode) can be used as a preferred light source.
[0019] Corresponding to the basic ideas described above, the above object also is achieved in accordance with the present invention by a method for non-contacting monitoring of the fill state of liquids in an unpressurized liquid reservoir in which the fill state and/or the fill state change is determined, by radiating a light beam onto the boundary region of the liquid at which a fill state-dependent surface curvature arises due to adhesion forces of the liquid at the reservoir wall and surface tension, and the reflection angle of the reflected light beam is measured. The reflection angle can be measured, for example, using a photodetector array
[0020] If this embodiment of the method for monitoring of an automatic dosing process is used, the liquid reservoir can exhibit a connection (via a capillary) to a gap to be filled at a micro-component and the start, the course and the end of the filling of the gap are detected by the angle change of the reflected light beam. The start of the filling can be detected by a first angle change of the reflected light beam; the running procedure of the filling can be detected by a continuous angle change of the reflected light beam. The end of the filling process can be detected by the cessation of the angle change following a previously-detected angle change of the reflected light beam, or by reaching a predetermined angle of the reflected light beam.
[0021] Corresponding to the method variants described above, the above object also is achieved in accordance with the invention by a device for detection of fill states and/or fill state changes in an unpressurized reservoir for acceptance of a liquid, having a light source with a directed emission that irradiates the boundary region of the liquid in the reservoir at which a fill state-dependent surface curvature arises via adhesion forces of the liquid at the reservoir wall and surface tension, and having a detector for measurement of the reflection angle of the reflected light beam.
[0022] For example, for measurement of the reflection angle a photodetector array can be arranged in the reflection region of the light beam.
[0023] Corresponding to the basic inventive ideas, an improved device for filling of air gaps at micro-components has a reservoir for acceptance of a filling liquid, a discharge arrangement for filling the reservoir with a predetermined quantity of fluid, and a transfer arrangement for direct transfer of the liquid from the reservoir into the gap to be filled with the aid of surface tension and adhesion forces between the fluid and walls. According to the invention this device is improved by using one of the devices described above for detection of fill states and/or fill state changes.
[0024] The reservoir can thereby exhibit a connection (via a capillary) to a gap to be filled at a micro-component and/or a laser (preferably a laser diode) can be used as a light source.
[0025] This device can be connected with a computer or processor in which a computer program is stored or accessed that is executed to implement the method steps described above.
DESCRIPTION OF THE DRAWINGS
[0026] FIG. 1 illustrates a small reservoir with varying fill states.
[0027] FIG. 2 illustrates the basic principle of light reflection at different liquid levels.
[0028] FIG. 3 schematically illustrates an embodiment of a measurement system with inventive reflection measurement.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0029] In the following figures, only features necessary for understanding of the invention are shown, and the following reference characters are used: 1 : reservoir; 2 : liquid; 3 : contact point; 4 : container wall; 5 : liquid surface; 5 ′, 5 ″, 5 ″: liquid level; 6 : normal; 7 : incidence point; 8 : light beam; 8 . 1 , 8 . 2 : edge rays of the light beam; 8 . 1 ′, 8 . 2 ′: reflected edge rays of the light beam; 8 . 1 ″, 8 . 2 ″: reflected edge rays given the liquid level 5 ″; 8 . 1 ″′, 8 . 2 ″′: reflected edge rays given the liquid level 5 ″′; 9 : laser diode; 10 : photodiode; 11 : control and evaluation computer; 12 : horizontal; α: angle of incidence; β: light angle of incidence; γ: vertical [plumb] angle; φ′, φ″, φ″′: reflection angles; Θ: wetting angle; h; fill height; Prgx: computer programs; x, z: coordinates.
[0030] The continuous monitoring of the fill state of liquids in small reservoirs is inventively determined without contact by detecting the reflection ratio of a light ray or of a light beam to the surface curvature of the liquid that arises at the reservoir wall. In principle three states for the formation of the surface curvature occur dependent on the fill state of the liquid in the container. These three states I-III are schematically shown in FIG. 1 in a perpendicular x-z section plane through a reservoir 1 .
[0031] In the state I a free surface to be wetted is made available to the liquid 2 . The contact point 3 between the reservoir wall 4 and the liquid surface 5 freely shifts in the z-direction at the reservoir wall depending on the liquid volume. The wetting angle Θ and the surface curvature thereby remain constant. The wetting angle Θ depends on the wetting properties between the reservoir wall and the liquid. A concave surface curvature results given a good wetting of the reservoir surface. The surface curvature thereby significantly depends on the surface tension and the density of the liquid.
[0032] In the state II the contact point 3 between the reservoir wall 4 and the liquid surface 5 do not shift further since, given z=a, it meets the upper edge of the reservoir. With increasing liquid volume the wetting angle Θ tends towards 90° and the surface curvature tends towards 0° or, respectively, the curvature radius tend towards∞. At the end of the state II the liquid surface forms a plane at z=a.
[0033] In a state III the surface develops a convex curvature with further increasing liquid volume.
[0034] In this state the liquid volume is greater than the reservoir volume. The wetting angle exceeds 90° as long as the liquid does not wet the reservoir edge. The state III can be viewed as an unstable fill state of the reservoir since the smallest disruptions can lead to deformation of the surface curvature to the point of leakage of the excess volume In a production process this state is normally to be avoided or to be monitored within predetermined limits, which is also possible with the proposed fill state monitoring method.
[0035] Reproducible analog signal curves can be generated for the three described states with the system design shown in FIG. 2 . A light ray or a light beam is directed form a light source at a defined constant light angle of incidence β onto the reservoir wall 4 . Depending on the fill state, the light strikes on the liquid surface at a specific point or, respectively, region of the surface curvature. The angle γ occurring at this point of the curvature between its normal 6 and the horizontal 12 is dependent on the fill height in the reservoir in the z-direction. The vertical angle γ and therewith also the angle of incidence a can be represented as a function of the fill level over the surface curvature. In the present case of the transition of the light into an optically-denser medium a portion of the light is always refracted in the medium at the incidence point 7 and a portion is reflected on the surface. A measurement signal dependent on the fill level is obtained via the measurement of the power of the reflected light in relation to the incident light power at a specific point or via the measurement of the light angle of incidence.
[0036] By suitable geometric parameters of the system design a steady and reproducible signal curve over the three described states can be generated A monitoring of the fill state (such as, for example, failing or rising fill states, fill state differences and phase transitions) is possible via specific features such as slope and reversal points of the non-linear signal curve. The fill level h in a reservoir can be determined from the measurement signal via a calibration.
[0037] The design of a measurement system with a laser diode 9 generating a relatively broad light beam and a photodiode 10 is exemplarily shown in FIG. 3 . The broad light beam 8 of the laser diode 9 with the edge rays 8 . 1 and 8 . 2 is directed onto the boundary region of the reservoir 1 (open as above) in which the liquid 2 is located. Shown are three different liquid levels with the surfaces 5 ′, 5 ″, 5 ″′, whereby the edge rays ( 8 . 1 ′ with 8 . 2 ′, 8 . 1 ″ with 8 . 2 ″ and 8 . 1 ″′ with 8 . 2 ″′) reflected on the respective liquid surfaces are drawn for each liquid level. Since the surface continuously, progressively develops with regard to its tangential direction between the points of incidence of the edge rays 8 . 1 and 8 . 2 , the shown angle ranges φ′, φ″ and φ″′ describe the spatial angles in which the primary light intensity is radiated with different angle-dependent intensity. The light intensity at this location can be measured via the arrangement of a light-sensitive sensor 10 and its variation can be used as a measure for fill state change.
[0038] To control the system, in particular the laser diode 9 , a control and evaluation computer 11 is connected with the light sensor 10 . The information regarding the fill state or regarding the current fill state change can hereby be used in a production process likewise controlled by the computer 11 .
[0039] Although modifications and changes may be suggested by those skilled in the art, it is the intention of the inventors to embody within the patent warranted hereon all changes and modifications as reasonably and properly come within the scope of their contribution to the art. | In a method and a device for non-contacting monitoring of the fill state of liquids in an unpressurized liquid container, the fill state and/or the fill state change is determined by radiating light onto the boundary region of the liquid at which a fill state-dependent curvature arises due to adhesion forces of the liquid at the reservoir wall and surface tension, and the intensity of the reflected light or the reflection angle is measured at a predetermined location. | 6 |
This application is a continuation of application Ser. No. 719,332, filed Jun. 21, 1991, now abandoned.
FIELD OF THE INVENTION
Background of the Invention
The invention relates to a clamping system for an annular-saw blade, in which the saw blade is held at its outer margin by means of a holding ring, connected via holding elements to a machine rotary part, and is tensioned by a clamping ring, which is integrated into the holding ring and can be pressed into a recess in the machine rotary part by means of clamping elements distributed over the periphery of the holding ring. It relates, furthermore, to the use of the clamping system in the sawing of bars, in particular of semiconductor material, into wafers.
Annular saws are used primarily in cases for cutting wafers off workpieces in bar form in which extreme accuracy is required in the cutting operation. The main area of application is therefore semiconductor technology, in which the wafers, thin slices of typically 0.1 to 1 mm thickness, are cut off usually monocrystalline bars of the semiconductor material, generally elemental semiconductors such as silicon or germanium, or compound semiconductors such as gallium arsenide or indium phosphide. In addition, annular saws are also used, for example, in the sawing of oxidic materials, such as gallium-gadolinium garnet or quartz or quartz glass, into wafers, allowing minimal tolerances.
In particular for the reason of high accuracy, it must be accomplished with such annular saws that the saw blade is held at its outer margin and is tensioned tightly in the manner of the skin of a drum, as a result of which the cutting edge of the saw blade, which is set with cutting grain and surrounds the centerhole, is guided during the cutting operation more stably with respect to deflections in comparison with externally cutting saws. However, it is accordingly important that the saw blade, as a rule made from rolled steel, is fitted accurately. Compensations have to be made in this operation for variations in the material characteristics, e.g. the deformability, caused for example by the rolling operation, and a central running of the saw blade, and in particular of the cutting edge, free from radial and axial unbalances, must be set, in order finally to be able to achieve good sawing results. It is also important here that, as far as possible, this setting does not change during the sawing operation under the influence of the forces acting on the saw blade.
With clamping systems of the type mentioned at the beginning, such as are known for instance from German Patent Specification 2,841,653 or U.S. Pat. Specification 4,498,449, annular-saw blades can be fitted with an accuracy which, when sawing semiconductor bars, in particular silicon bars of up to about 10 cm diameter, permits satisfactory yields of wafers within the usual tolerances with respect to the geometrical parameters specified by the component manufacturers. However, in cases of greater bar diameters, as in cases of more stringent specifications with respect to the wafer geometry, the proportion of the sawed wafers which no longer meet the requirements for geometrical precision, and therefore have to be discarded, increases.
SUMMARY OF THE INVENTION
The object of the invention was therefore to provide a clamping system which permits annular-saw blades to be fitted more reliably in comparison and with which even stringent geometrical requirements can be met with good yields when cutting semiconductor bars up into wafers.
The object is achieved by a clamping system of the type mentioned at the beginning wherein the axially adjustable clamping elements are releasably connected to the machine rotary part.
BRIEF DESCRIPTION OF THE DRAWING
The invention is explained in greater detail below with reference to FIGS. 1 to 3. In these figures, analogous components are provided with the same reference numerals.
FIG. 1 is an elevational view in partial section showing machine rotary part usual in the case of annular saws, with annular-saw blade fitted by means of a known clamping system.
FIG. 2a is a sectional view of an embodiment of the clamping system according to the invention in an untensioned state.
FIG. 2b is a sectional view of the embodiment shown in FIG. 2a in a tension state.
FIG. 3a is a sectional view of another embodiment of the clamping system according to the invention in an untensioned state which provides for the accurate fitting of the saw blade and a correction of running inaccuracies in the axial direction.
FIG. 3b is a sectional view of the embodiment shown in FIG. 3a in a tension state.
FIG. 4 is an elevational view in partial section showing a saw with a saw blade mounted according to FIG. 2(a) and 2b).
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 shows the machine rotary part 1, which widens in a cup-like manner and to the end face of which the clamping system 2 is fastened, as a rule by screwing. With the aid of the clamping system 2, the annular-saw blade 3 is tensioned tightly from its outer margin, so that the cutting edge 4, usually exhibiting a drop-shaped cross-section, provided with diamond cutting grains embedded in a nickel coating and surrounding the central bore of the saw blade displays a concentricity free as far as possible from radial and axial disparities. The rotary part runs in a bearing 5 and is brought to the desired rotational speed by a drive 6, as a rule an electric motor. The frame 7 holding the arrangement is shown only diagrammatically here; in principle, with the various known types of device either a vertical position or a horizontal position of the axis of rotation is maintained.
In the sawing operation, the workpiece to be sawed, for example a semiconductor bar, is introduced by the intended amount into the centerhole with the aid of the workpiece infeed, not shown here for reasons of clarity. By means of an advancing device, a relative movement between workpiece and saw blade is then executed, during the course of which the cutting edge works through the workpiece and finally cuts off the desired wafer. After its removal, the workpiece and saw blade are once again brought back into cutting position, and the next wafer can be cut off.
FIGS. 2a and 2b and FIG. 4 show an embodiment of the clamping system according to the invention, in the untensioned state and, in the tensioned state respectively. In the right-hand representation. In this arrangement, the saw blade 3 rests with its outer margin on the end part 8 of the machine rotary part 1. The saw blade is clamped in place with the aid of a holding ring 9, which is laid on the saw blade and connected, preferably screwed, to the end part initially with the aid of suitable holding elements, preferably holding screws 10, distributed over its entire periphery, by means of dimensionally appropriately predetermined fixtures, preferably threaded bores 11. As a result, the saw blade is initially fixed between the end part and holding ring at its outer margin, but is still in the untensioned state.
In this state, the clamping ring 12, integrated into the holding ring and displaceable in the axial direction, is not pressed by means of the clamping elements provided, in particular clamping screws 13, against the saw blade; said clamping elements engage only loosely in the receptacles predetermined dimensionally appropriately in the end part, which are configured in particular as threaded bores 14. Consequently, the saw blade also does not as yet experience any deforming force which deflects it out of the untensioned starting position in the direction of the clearance provided in the end part for its reception, advantageously an annular groove 15, which is expediently shaped dimensionally appropriately with respect to the surface of the clamping ring acting on the saw blade.
In the clamping operation, the clamping elements, in particular clamping screws 13, distributed over the periphery of the clamping ring, are progressively tightened. As a result, the clamping ring 12 is drawn increasingly against the saw blade 3 and presses the latter into the annular groove 15. Depending on the intensity of this deformation, i.e. with the clamping screws being screwed in further or less far, a more or less strong tensile stress can be applied to the saw blade, distributed around the periphery, so that it is ultimately possible to give the saw blade the uniform and tight tensioning required for an accurate sawing operation. At the same time, the clamping operation allows compensation for. radial irregularities in the running of the cutting edge, by the centerhole periphery being drawn outward to a greater or lesser extent by corresponding adaptation of the tensioning of the saw blade. In this case, an all the more finely graduated setting is possible the smaller the thread pitch, although the usual thread pitches of 0.5 to 1.5 mm as a rule permit an adequately accurate clamping operation.
As shown in FIG. 4, the clamping screws, the corresponding leadthrough openings for them in the clamping ring and the corresponding threaded bores in the annular groove are advantageously distributed uniformly over the periphery of the clamping ring and are preferably arranged at the same intervals from one another. In this way it is ensured that the tensioning forces acting on the saw blade are distributed uniformly over its periphery and unbalances in the machine rotary part/clamping system/saw blade system caused by uneven mass distribution are avoided during the rotation. At the same time, it is not compulsory for the number of clamping screws to be the same or half the number of holding screws, although such embodiments with the same or half the number have proved to be particularly successful, since they are the simplest way of ensuring a mass distribution which is as rotationally symmetrical as possible and consequently free from unbalances. In this preferred case, arrangements in which clamping and holding screws are in each case provided one after the other on a line pointing radially to the axis of rotation, or as shown in FIG. 4 in a position centrally offset in each case in comparison with the above, have proved successful. As shown in FIG. 4, the number of clamping screws distributed over the periphery of the clamping ring is expediently chosen such that the angles α between successive clamping screws, measured from the axis of rotation of the system, lie in the range from 5° to 30°, preferably 10° to 20°, these angles advantageously having the same value. Arrangements in which the distances of the clamping screws from one another, measured in each case from screw center to screw center and along the curved center line of the clamping ring, lie in the range from 50 to 100 mm and are preferably the same have proved to be particularly stable.
The advantage of the clamping system according to the invention is that the clamping forces holding the saw blade, exerted by the holding ring, and the tensioning forces act in the same sense and, as a result, both an improved clamping and a more reliable tensioning of the saw blade is achieved. Surprisingly, it was also found that the necessary additional bores in the saw blade do not have as a consequence any increased susceptibility to deformation or cracking or instabilities in the sawing operation. On the other hand, in the case of the known clamping systems, the tensioning forces exerted by the clamping screws act against the clamping forces and cause a deformation of the holding ring and, ultimately, a reduced retention of the saw blade, caused by the widening of the clamping surfaces. The effects in practice are poor concentricity and saw blades "drawn out of the ring", i.e. excessively deformed during tensioning and no longer seated satisfactorily in the holding ring.
A further development of the invention, which permits not only the fitting of the saw blade and the correction of radial running irregularities but also a correction of axial running irregularities of the saw blade, is shown in FIGS. 3a and 3b clamping ring 12 in this case merges at its inner periphery into a bridge part 16, which juts out into the free region 17 of the saw blade and has a preferably bead-like projection 18, and to which a deflection in the axial direction can be imparted with the aid of adjusting devices, preferably setscrews 19.
When tensioning the saw blade, in analogy with the method described in conjunction with FIGS. 2a and 2b, the saw blade is pressed into the annular groove 15 by the clamping ring. In addition, by tightening the setscrews 19 to a greater or lesser extent, the saw blade can then be deflected in the axial direction out of the standard position predetermined by the inner edge 20 of the end part. Consequently, it is possible to compensate the deviations of the saw blade in the axial direction from its ideal, undisturbed running, the so-called "axial runout", which as a rule can reach values of up to about 100 μm.
As a rule, the setscrews are provided in the same number and in an analogous arrangement as the clamping screws. Just as important is a rotationally symmetrical, uniform distribution over the periphery of the bridge part, in order to avoid mass-related unbalances. Sometimes, however, an increased number may be necessary in order to be able to set the deflection of the projection 18 with sufficient accuracy, which may be the case for example with large clamping ring diameters. However, experience shows that even such arrangements run most steadily when they are rotationally symmetrical with respect to the holding screws, clamping screws and setscrews.
In the clamping operation, axial and radial runout of the saw blade can be determined in each case location-dependently in trial rotations of the saw blade with the aid of suitable measuring instruments and sensors, for example commercially available optical concentricity measuring devices or mechanical feelers. This then determines the position of the clamping screws and, in the case of the embodiment of the invention according to FIGS. 3a and 3b, also of the setscrews, which require a readjustment, and whether they have to be tightened to a greater or lesser extent in order to achieve an optimum adjustment of the saw blade. In most cases, after a few preliminary trials, it can even be concluded from the measured deviation how many turns of the clamping screws, and if appropriate setscrews, in the suitable position, are necessary for their correction.
With the aid of the clamping systems according to the invention, annular-saw blades can be fitted into the machine rotary parts provided for their reception with high precision remaining constant over long operating times of the saw blade and it also being possible to achieve higher saw blade tensionings. Accordingly, on the one hand the cutting precision in the actual sawing operation increases, on the other hand the service life of the saw blades also increases, which is reflected in turn in shorter setting-up times and higher sawing output. Therefore, the clamping system is used with particular advantage in the case of sawing operations in which extreme precision matters. Consequently, a preferred area of application is the annular sawing of crystal bars, in particular semiconductor bars, to be precise preferably bars of monocrystalline silicon.
The invention is explained in greater detail below with reference to an illustrative embodiment: Example:
In the case of a commercially available arrangement for the annular sawing of monocrystalline silicon bars, which was constructed analogously to the apparatus represented in FIG. 1, the machine rotary part (outside diameter about 690 mm) had been converted for use of the clamping system according to the invention. For this purpose, a total of 30 threaded bores (thread pitch 1 mm) had been additionally made at 12° intervals on its end face in the concentrically running annular groove, milled in concavely about 3.5 mm, in order to be able then to screw the clamping screws into the machine rotary part during the actual clamping operation. The distance from screw to screw was consequently about 65.5 mm.
Correspondingly positioned and dimensioned bores had also been made in the circular clamping ring (diameter about 645 mm, cross-section as shown in FIGS. 2a and 2b) as well as in the circular saw blade provided for fitting (centerhole diameter about 235 mm, nickel/diamond-set cutting edge) of rolled stainless steel (thickness about 0.15 mm).
Then, the saw blade was initially laid on the end part in the starting position, in the usual way with the aid of positioning pins provided on the machine rotary part, and the holding ring with the axially movable clamping ring integrated therein was laid on top. Thereafter, the 60 holding screws, distributed at 6° angular intervals over the holding ring, were screwed in and tightened, so that finally the saw blade was clamped in firmly at its outer margin between holding ring and machine rotary part, but was still not under tension.
Next, the 30 clamping screws were then introduced into the bores provided for their reception--these did not in each case lie in line with the holding screws but centrally offset, in relation to the axis of rotation of the system--and were tightened to such an extent that the clamping ring was in contact with the saw blade around its entire periphery. Thereafter, a basic tension was applied to the saw blade by each screw being tightened one full turn. Subsequently, a revolution of the machine rotary part was performed and, during this revolution, the radial deviation of the cutting edge of the saw blade from ideally circular running was determined location-dependently with the aid of commercially available measuring optics. Depending on the extent of the deviation, the clamping screws in the respective regions were then further tightened to a greater or lesser extent and, as a result, the centerhole of the saw blade was stretched outward with changing intensity, in order to compensate for its "radial run-out". The tensioning step was followed by a further saw blade rotation and location-dependent measurement of the still remaining "radial run-out". According to the measured, already distinctly smaller deviations, the clamping screws were then tightened again in the regions stretched too little, the centerhole stretching resulting from a certain number of turns of the clamping screws being roughly known from preliminary trials and it thus being possible to estimate the required turning of the screws. In a final saw blade rotation, it was found that the "radial run-out" had been reduced to a deviation of less than 20 μm from the ideal circular path of the centerhole and consequently of the cutting edge.
The saw blade fitted in the clamping system in such a manner was then used to saw in the usual way monocrystalline silicon bars (bar diameter about 150 mm) into wafers of about 850 μm thickness.
In a control test, the saw blade in an annular saw of the same type was fitted in a conventional clamping system according to German Patent Specification 2,841,653, in which there was no screw connection of the clamping screws to the machine rotary part. Otherwise, the fitting was carried out by the method given above until the radial run-out had been suppressed to a value below 20 μm. With the saw blade fitted in such a manner, monocrystalline silicon bars (diameter about 150 mm) were likewise sawed into wafers of about 850 μm thickness at the same time under otherwise identical process conditions.
The evaluation of the two sawing operations revealed that, compared with the control test, it was possible in the case of the clamping system according to the invention to reduce distinctly the number of sharpening interventions necessary for resharpening the saw blade; it was about one third of the number of sharpening interventions necessary in the case of the conventional clamping system. The number of wafers sawed within an eight-hour shift in the case of the saw equipped with the clamping system according to the invention was about 18% above the saw with the conventionally fitted saw blade. Moreover, it was possible to achieve a 70% longer saw blade service life. | In the annular sawing of bars, in particular of semiconductor material, theccurate fitting of the saw blade is of great importance. In the case of the conventional clamping systems, in which the saw blade is held on the machine rotary part by clamping forces exerted by means of a holding ring and is subjected to tension by means of an additional clamping ring, inadequate tensioning constancy is usually caused by the tensioning forces acting against the clamping forces. A tensioning behavior which is better in comparison can be achieved according to the invention by the tensioning forces being applied to the clamping ring by clamping elements releasably connected to the machine rotary part and consequently clamping forces and tensioning forces no longer being directed against one another. By the use of such clamping systems, longer saw blade service lives and higher sawing outputs can be achieved. | 1 |
Subsets and Splits
No community queries yet
The top public SQL queries from the community will appear here once available.