Patent Grant
7371712
This invention relates to conveyor lubricants and to a method for conveying articles. The invention also relates to conveyor systems and containers wholly or partially coated with such lubricant compositions.
In commercial container filling or packaging operations, the containers typically are moved by a conveying system at very high rates of speed. Copious amounts of aqueous dilute lubricant solutions (usually based on fatty acid amines) are typically applied to the conveyor or containers using spray or pumping equipment. These lubricant solutions permit high-speed operation of the conveyor and limit marring of the containers or labels, but also have some disadvantages. For example, aqueous conveyor lubricants based on fatty amines typically contain ingredients that can react with spilled carbonated beverages or other food or liquid components to form solid deposits. Formation of such deposits on a conveyor can change the lubricity of the conveyor and require shutdown to permit cleanup. Some aqueous conveyor lubricants are incompatible with thermoplastic beverage containers made of polyethylene terephthalate (PET) and other plastics, and can cause environmental stress cracking (crazing and cracking that occurs when the plastic polymer is under tension) in plastic containers. Dilute aqueous lubricants typically require use of large amounts of water on the conveying line, which must then be disposed of or recycled, and which causes an unduly wet environment near the conveyor line. Moreover, some aqueous lubricants can promote the growth of microbes.
The present invention provides, in one aspect, a method for lubricating the passage of a container along a conveyor comprising applying a mixture of a water-miscible silicone material and a water-miscible lubricant to at least a portion of the container-contacting surface of the conveyor or to at least a portion of the conveyor-contacting surface of the container.
The present invention provides, in another aspect, a lubricated conveyor or container, having a lubricant coating on a container-contacting surface of the conveyor or on a conveyor-contacting surface of the container, wherein the coating comprises a mixture of a water-miscible silicone material and a water-miscible lubricant.
The invention also provides conveyor lubricant compositions comprising a mixture of a water-miscible silicone material and a water-miscible lubricant.
The compositions used in the invention can be applied in relatively low amounts and do not require in-line dilution with significant amounts of water. The compositions of the invention provide thin, substantially non-dripping lubricating films. In contrast to dilute aqueous lubricants, the lubricants of the invention provide drier lubrication of the conveyors and containers, a cleaner and drier conveyor line and working area, and reduced lubricant usage, thereby reducing waste, cleanup and disposal problems.
The invention provides a lubricant coating that reduces the coefficient of friction of coated conveyor parts and containers and thereby facilitates movement of containers along a conveyor line. The lubricant compositions used in the invention can optionally contain water or a hydrophilic diluent, as a component or components in the lubricant composition as sold or added just prior to use. The lubricant composition does not require in-line dilution with significant amounts of water, that is, it can be applied undiluted or with relatively modest dilution, e.g., at a water:lubricant ratio of about 1:1 to 5:1. In contrast, conventional dilute aqueous lubricants are applied using significant amounts of water, at dilution ratios of about 100:1 to 500:1. The lubricant compositions preferably provide a renewable coating that can be reapplied, if desired, to offset the effects of coating wear. They preferably can be applied while the conveyor is at rest or while it is moving, e.g., at the conveyor's normal operating speed. Preferably the lubricant coating is water-based cleaning agent-removable, that is, it preferably is sufficiently soluble or dispersible in water so that the coating can be removed from the container or conveyor using conventional aqueous cleaners, without the need for high pressure, mechanical abrasion or the use of aggressive cleaning chemicals. The lubricant coating preferably is substantially non-dripping, that is, preferably the majority of the lubricant remains on the container or conveyor following application until such time as the lubricant may be deliberately washed away.
The invention is further illustrated in
The silicone material and hydrophilic lubricant are “water-miscible”, that is, they are sufficiently water-soluble or water-dispersible so that when added to water at the desired use level they form a stable solution, emulsion or suspension. The desired use level will vary according to the particular conveyor or container application, and according to the type of silicone and hydrophilic lubricant employed.
A variety of water-miscible silicone materials can be employed in the lubricant compositions, including silicone emulsions (such as emulsions formed from methyl(dimethyl), higher alkyl and aryl silicones; functionalized silicones such as chlorosilanes; amino-, methoxy-, epoxy- and vinyl-substituted siloxanes; and silanols). Suitable silicone emulsions include E2175 high viscosity polydimethylsiloxane (a 60% siloxane emulsion commercially available from Lambent Technologies, Inc.), E21456 FG food grade intermediate viscosity polydimethylsiloxane (a 35% siloxane emulsion commercially available from Lambent Technologies, Inc.), HV490 high molecular weight hydroxy-terminated dimethyl silicone (an anionic 30-60% siloxane emulsion commercially available from Dow Corning Corporation), SM2135 polydimethylsiloxane (a nonionic 50% siloxane emulsion commercially available from GE Silicones) and SM2167 polydimethylsiloxane (a cationic 50% siloxane emulsion commercially available from GE Silicones. Other water-miscible silicone materials include finely divided silicone powders such as the TOSPEARL™ series (commercially available from Toshiba Silicone Co. Ltd.); and silicone surfactants such as SWP30 anionic silicone surfactant, WAXWS-P nonionic silicone surfactant, QUATQ-400M cationic silicone surfactant and 703 specialty silicone surfactant (all commercially available from Lambent Technologies, Inc.). Preferred silicone emulsions typically contain from about 30 wt. % to about 70 wt. % water. Non-water-miscible silicone materials (e.g., non-water-soluble silicone fluids and non-water-dispersible silicone powders) can also be employed in the lubricant if combined with a suitable emulsifier (e.g., nonionic, anionic or cationic emulsifiers). For applications involving plastic containers (e.g., PET beverage bottles), care should be taken to avoid the use of emulsifiers or other surfactants that promote environmental stress cracking in plastic containers when evaluated using the PET Stress Crack Test set out below. Polydimethylsiloxane emulsions are preferred silicone materials. Preferably the lubricant composition is substantially free of surfactants aside from those that may be required to emulsify the silicone compound sufficiently to form the silicone emulsion.
A variety of water-miscible lubricants can be employed in the lubricant compositions, including hydroxy-containing compounds such as polyols (e.g., glycerol and propylene glycol); polyalkylene glycols (e.g., the CARBOWAX™ series of polyethylene and methoxypolyethylene glycols, commercially available from Union Carbide Corp.); linear copolymers of ethylene and propylene oxides (e.g., UCON™ 50-HB-100 water-soluble ethylene oxide:propylene oxide copolymer, commercially available from Union Carbide Corp.); and sorbitan esters (e.g., TWEEN™ series 20, 40, 60, 80 and 85 polyoxyethylene sorbitan monooleates and SPAN™ series 20, 80, 83 and 85 sorbitan esters, commercially available from ICI Surfactants). Other suitable water-miscible lubricants include phosphate esters, amines and their derivatives, and other commercially available water-miscible lubricants that will be familiar to those skilled in the art. Derivatives (e.g., partial esters or ethoxylates) of the above lubricants can also be employed. For applications involving plastic containers, care should be taken to avoid the use of water-miscible lubricants that might promote environmental stress cracking in plastic containers when evaluated using the PET Stress Crack Test set out below. Preferably the water-miscible lubricant is a polyol such as glycerol.
If water is employed in the lubricant compositions, preferably it is deionized water. Suitable hydrophilic diluents include alcohols such as isopropyl alcohol. For applications involving plastic containers, care should be taken to avoid the use of water or hydrophilic diluents containing contaminants that might promote environmental stress cracking in plastic containers when evaluated using the PET Stress Crack Test set out below.
Preferred amounts for the silicone material, hydrophilic lubricant and optional water or hydrophilic diluent are about 0.05 to about 12 wt. % of the silicone material (exclusive of any water or other hydrophilic diluent that may be present if the silicone material is, for example, a silicone emulsion), about 30 to about 99.95 wt. % of the hydrophilic lubricant, and 0 to about 69.95 wt. % of water or hydrophilic diluent. More preferably, the lubricant composition contains about 0.5 to about 8 wt. % of the silicone material, about 50 to about 90 wt. % of the hydrophilic lubricant, and about 2 to about 49.5 wt. % of water or hydrophilic diluent. Most preferably, the lubricant composition contains about 0.8 to about 4 wt. % of the silicone material, about 65 to about 85 wt. % of the hydrophilic lubricant, and about 11 to about 34.2 wt. % of water or hydrophilic diluent.
The lubricant compositions can contain additional components if desired. For example, the compositions can contain adjuvants such as conventional waterborne conveyor lubricants (e.g., fatty acid lubricants), antimicrobial agents, colorants, foam inhibitors or foam generators, cracking inhibitors (e.g., PET stress cracking inhibitors), viscosity modifiers, film forming materials, antioxidants or antistatic agents. The amounts and types of such additional components will be apparent to those skilled in the art.
For applications involving plastic containers, the lubricant compositions preferably have a total alkalinity equivalent to less than about 100 ppm CaCO3, more preferably less than about 50 ppm CaCO3, and most preferably less than about 30 ppm CaCO3, as measured in accordance with Standard Methods for the Examination of Water and Wastewater, 18th Edition, Section 2320, Alkalinity.
The lubricant compositions preferably have a coefficient of friction (COF) that is less than about 0.14, more preferably less than about 0.1, when evaluated using the Short Track Conveyor Test described below.
A variety of kinds of conveyors and conveyor parts can be coated with the lubricant composition. Parts of the conveyor that support or guide or move the containers and thus are preferably coated with the lubricant composition include belts, chains, gates, chutes, sensors, and ramps having surfaces made of fabrics, metals, plastics, composites, or combinations of these materials.
The lubricant composition can also be applied to a wide variety of containers including beverage containers; food containers; household or commercial cleaning product containers; and containers for oils, antifreeze or other industrial fluids. The containers can be made of a wide variety of materials including glasses; plastics (e.g., polyolefins such as polyethylene and polypropylene; polystyrenes; polyesters such as PET and polyethylene naphthalate (PEN); polyamides, polycarbonates; and mixtures or copolymers thereof); metals (e.g., aluminum, tin or steel); papers (e.g., untreated, treated, waxed or other coated papers); ceramics; and laminates or composites of two or more of these materials (e.g., laminates of PET, PEN or mixtures thereof with another plastic material). The containers can have a variety of sizes and forms, including cartons (e.g., waxed cartons or TETRAPACK™ boxes), cans, bottles and the like. Although any desired portion of the container can be coated with the lubricant composition, the lubricant composition preferably is applied only to parts of the container that will come into contact with the conveyor or with other containers. Preferably, the lubricant composition is not applied to portions of thermoplastic containers that are prone to stress cracking. In a preferred embodiment of the invention, the lubricant composition is applied to the crystalline foot portion of a blow-molded, footed PET container (or to one or more portions of a conveyor that will contact such foot portion) without applying significant quantities of lubricant composition to the amorphous center base portion of the container. Also, the lubricant composition preferably is not applied to portions of a container that might later be gripped by a user holding the container, or, if so applied, is preferably removed from such portion prior to shipment and sale of the container. For some such applications the lubricant composition preferably is applied to the conveyor rather than to the container, in order to limit the extent to which the container might later become slippery in actual use.
The lubricant composition can be a liquid or semi-solid at the time of application. Preferably the lubricant composition is a liquid having a viscosity that will permit it to be pumped and readily applied to a conveyor or containers, and that will facilitate rapid film formation whether or not the conveyor is in motion. The lubricant composition can be formulated so that it exhibits shear thinning or other pseudo-plastic behavior, manifested by a higher viscosity (e.g., non-dripping behavior) when at rest, and a much lower viscosity when subjected to shear stresses such as those provided by pumping, spraying or brushing the lubricant composition. This behavior can be brought about by, for example, including appropriate types and amounts of thixotropic fillers (e.g., treated or untreated fumed silicas) or other rheology modifiers in the lubricant composition. The lubricant coating can be applied in a constant or intermittent fashion. Preferably, the lubricant coating is applied in an intermittent fashion in order to minimize the amount of applied lubricant composition. For example, the lubricant composition can be applied for a period of time during which at least one complete revolution of the conveyor takes place. Application of the lubricant composition can then be halted for a period of time (e.g., minutes or hours) and then resumed for a further period of time (e.g., one or more further conveyor revolutions). The lubricant coating should be sufficiently thick to provide the desired degree of lubrication, and sufficiently thin to permit economical operation and to discourage drip formation. The lubricant coating thickness preferably is maintained at at least about 0.0001 mm, more preferably about 0.001 to about 2 mm, and most preferably about 0.005 to about 0.5 mm.
Application of the lubricant composition can be carried out using any suitable technique including spraying, wiping, brushing, drip coating, roll coating, and other methods for application of a thin film. If desired, the lubricant composition can be applied using spray equipment designed for the application of conventional aqueous conveyor lubricants, modified as need be to suit the substantially lower application rates and preferred non-dripping coating characteristics of the lubricant compositions used in the invention. For example, the spray nozzles of a conventional beverage container lube line can be replaced with smaller spray nozzles or with brushes, or the metering pump can be altered to reduce the metering rate.
The lubricant compositions can if desired be evaluated using a Short Track Conveyor Test and a PET Stress Crack Test.
A conveyor system employing a motor-driven 83 mm wide by 6.1 meter long REXNORD™ LF polyacetal thermoplastic conveyor belt is operated at a belt speed of 30.48 meters/minute. Six 2-liter filled PET beverage bottles are stacked in an open-bottomed rack and allowed to rest on the moving belt. The total weight of the rack and bottles is 16.15 Kg. The rack is held in position on the belt by a wire affixed to a stationary strain gauge. The force exerted on the strain gauge during belt operation is recorded using a computer. A thin, even coat of the lubricant composition is applied to the surface of the belt using an applicator made from a conventional bottle wash brush. The belt is allowed to run for 25 to 90 minutes during which time a consistently low COF is observed. The COF is calculated on the basis of the measured force and the mass of the bottles, averaged over the run duration.
Standard 2-liter PET beverage bottles (commercially available from Constar International) are charged with 1850 g of chilled water, 31.0 g of sodium bicarbonate and 31.0 g of citric acid. The charged bottle is capped, rinsed with deionized water and set on clean paper towels overnight. The bottoms of 12 bottles are dipped in a 200 g sample of the undiluted lube in a 125×65 mm crystal dish, then placed in a bin and stored in an environmental chamber at 37.8° C., 90% relative humidity for 14 days. The bottles are removed from the chamber, observed for crazes, creases and crack patterns on the bottom. The aged bottles are compared with 12 control bottles that were exposed to a standard dilute aqueous lubricant (LUBODRIVE™ RX, commercially available from Ecolab) prepared as follows. A 1.7 wt. % solution of the LUBODRIVE lubricant (in water containing 43 ppm alkalinity as CaCO3) was foamed for several minutes using a mixer. The foam was transferred to a lined bin and the control bottles were dipped in the foam. The bottles were then aged in the environmental chamber as outlined above.
The invention can be better understood by reviewing the following examples. The examples are for illustration purposes only, and do not limit the scope of the invention.
77.2 parts of a 96 wt. % glycerol solution, 20.7 parts deionized water, and 2.1 parts E2175 high viscosity polydimethylsiloxane (60% siloxane emulsion commercially available from Lambent Technologies, Inc.) were combined with stirring until a uniform mixture was obtained. The resulting lubricant composition was slippery to the touch and readily could be rinsed from surfaces using a plain water wash. Using the Short Track Conveyor Test, about 20 g of the lubricant composition was applied to the moving belt over a 90 minute period. The observed COF was 0.062. In a comparison Short Track Conveyor test performed using a dilute aqueous solution of a standard conveyor lubricant (LUBODRIVE™ RX, commercially available from Ecolab, applied using a 0.5% dilution in water and about an 8 liter/hour spray application rate), the observed COF was 0.126, thus indicating that the lubricant composition of the invention provided reduced sliding friction.
The lubricant composition of Example 1 was also evaluated using the PET Stress Crack Test. The aged bottles exhibited infrequent small, shallow crazing marks. For the comparison dilute aqueous lubricant, frequent medium depth crazing marks and infrequent deeper crazing marks were observed. No bottles leaked or burst for either lubricant, but the bottoms of bottles lubricated with a lubricant composition of the invention had a better visual appearance after aging.
Using the method of Example 1, 77.2 parts of a 96 wt. % glycerol solution, 20.7 parts deionized water, and 2.1 parts HV490 high molecular weight hydroxy-terminated dimethyl silicone (anionic 30-60% siloxane emulsion commercially available from Dow Corning Corporation) were combined with stirring until a uniform mixture was obtained. The resulting lubricant composition was slippery to the touch and readily could be rinsed from surfaces using a plain water wash. Using the Short Track Conveyor Test, about 20 g of the lubricant composition was applied to the moving belt over a 15 minute period. The observed COF was 0.058.
Using the method of Example 1, 75.7 parts of a 96 wt. % glycerol solution, 20.3 parts deionized water, 2.0 parts HV490 high molecular weight hydroxy-terminated dimethyl silicone (anionic 30-60% siloxane emulsion commercially available from Dow Corning Corporation) and 2.0 parts GLUCOPON™ 220 alkyl polyglycoside surfactant (commercially available from Henkel Corporation) were combined with stirring until a uniform mixture was obtained. The resulting lubricant composition was slippery to the touch and readily could be rinsed from surfaces using a plain water wash. Using the Short Track Conveyor Test, about 20 g of the lubricant composition was applied to the moving belt over a 15 minute period. The observed COF was 0.071.
Using the method of Example 1, 72.7 parts of a 99.5 wt. % glycerol solution, 23.3 parts deionized water, 2 parts HV495 silicone emulsion (commercially available from Dow Corning Corporation) and 2 parts GLUCOPON™ 220 alkyl polyglycoside surfactant (commercially available from Henkel Corporation) were combined with stirring until a uniform mixture was obtained. The resulting lubricant composition was slippery to the touch and readily could be rinsed from surfaces using a plain water wash. However, the presence of the surfactant caused an increase in stress cracking in the PET Stress Crack Test.
Various modifications and alterations of this invention will be apparent to those skilled in the art without departing from the scope and spirit of the invention, and are intended to be within the scope of the following claims.
This application is a continuation of application Ser. No. 10/287,559 filed Nov. 1, 2002 now U.S. Pat. No. 6,743,758 B1, which is in turn a continuation of application Ser. No. 09/596,599 filed Jun. 16, 2000, now U.S. Pat. No. 6,495,494 B1.
| Number | Name | Date | Kind |
|---|---|---|---|
| 3011975 | Nitzsche et al. | Dec 1961 | A |
| 3213024 | Blake et al. | Oct 1965 | A |
| 3664956 | Messina et al. | May 1972 | A |
| 3853607 | Iyengar et al. | Dec 1974 | A |
| 3981812 | Zletz | Sep 1976 | A |
| 4062785 | Nibert | Dec 1977 | A |
| 4065590 | Salensky | Dec 1977 | A |
| 4069933 | Newing | Jan 1978 | A |
| 4149624 | Douty et al. | Apr 1979 | A |
| 4162347 | Montgomery | Jul 1979 | A |
| 4248724 | MacIntosh | Feb 1981 | A |
| 4252528 | Decker et al. | Feb 1981 | A |
| 4262776 | Wilson et al. | Apr 1981 | A |
| 4274973 | Stanton et al. | Jun 1981 | A |
| 4289671 | Hernandez | Sep 1981 | A |
| 4324671 | Christian et al. | Apr 1982 | A |
| 4343616 | Decker et al. | Aug 1982 | A |
| 4375444 | Deeken | Mar 1983 | A |
| 4420578 | Hagens et al. | Dec 1983 | A |
| 4436200 | Hodlewski et al. | Mar 1984 | A |
| 4478889 | Maruhashi et al. | Oct 1984 | A |
| 4486378 | Hirata et al. | Dec 1984 | A |
| 4515836 | Cobbs, Jr. et al. | May 1985 | A |
| 4525377 | Nickel et al. | Jun 1985 | A |
| 4534995 | Pocock et al. | Aug 1985 | A |
| 4538542 | Kennon et al. | Sep 1985 | A |
| 4543909 | Sharpless | Oct 1985 | A |
| 4569869 | Kushida et al. | Feb 1986 | A |
| 4573429 | Cobbs, Jr. et al. | Mar 1986 | A |
| 4604220 | Stanton | Aug 1986 | A |
| 4627457 | Bird et al. | Dec 1986 | A |
| 4632053 | Villanueva et al. | Dec 1986 | A |
| 4652386 | Alberts et al. | Mar 1987 | A |
| 4690299 | Cannon | Sep 1987 | A |
| 4709806 | Candle | Dec 1987 | A |
| 4713266 | Hasegawa et al. | Dec 1987 | A |
| 4714580 | Maruhashi et al. | Dec 1987 | A |
| 4719022 | Hyde | Jan 1988 | A |
| 4769162 | Remus | Sep 1988 | A |
| 4828727 | McAninch | May 1989 | A |
| 4851287 | Hartsing, Jr. | Jul 1989 | A |
| 4874647 | Yatsu et al. | Oct 1989 | A |
| 4919984 | Maruhashi et al. | Apr 1990 | A |
| 4929375 | Rossio et al. | May 1990 | A |
| 4980211 | Kushida et al. | Dec 1990 | A |
| 5001935 | Tekkanat et al. | Mar 1991 | A |
| 5009801 | Wider et al. | Apr 1991 | A |
| 5043380 | Cole | Aug 1991 | A |
| 5062979 | Scharf et al. | Nov 1991 | A |
| 5073280 | Rossio et al. | Dec 1991 | A |
| 5115047 | Hashimoto et al. | May 1992 | A |
| 5139834 | Cole | Aug 1992 | A |
| 5160646 | Scheld | Nov 1992 | A |
| 5174914 | Gutzmann | Dec 1992 | A |
| 5182035 | Schmidt et al. | Jan 1993 | A |
| 5191779 | Imaiu et al. | Mar 1993 | A |
| 5202037 | LaVelle et al. | Apr 1993 | A |
| 5238718 | Yano et al. | Aug 1993 | A |
| 5244589 | Lin et al. | Sep 1993 | A |
| 5320132 | Weisse | Jun 1994 | A |
| 5334322 | Williams, Jr. | Aug 1994 | A |
| RE34742 | Maier et al. | Sep 1994 | E |
| 5352376 | Gutzmann | Oct 1994 | A |
| 5371112 | Sayre et al. | Dec 1994 | A |
| 5391308 | Despo | Feb 1995 | A |
| 5427258 | Krishnakumar et al. | Jun 1995 | A |
| 5474692 | Laufenberg et al. | Dec 1995 | A |
| 5486316 | Bershas et al. | Jan 1996 | A |
| 5509965 | Harry et al. | Apr 1996 | A |
| 5534172 | Perry et al. | Jul 1996 | A |
| 5549836 | Moses | Aug 1996 | A |
| 5559087 | Halsrud et al. | Sep 1996 | A |
| 5565127 | Laufenberg et al. | Oct 1996 | A |
| 5573819 | Nugent, Jr. et al. | Nov 1996 | A |
| 5652034 | Seiner | Jul 1997 | A |
| 5658619 | Kirschner et al. | Aug 1997 | A |
| 5663131 | Winicov et al. | Sep 1997 | A |
| 5672401 | Anglin et al. | Sep 1997 | A |
| 5681628 | Niederst et al. | Oct 1997 | A |
| 5688747 | Khan et al. | Nov 1997 | A |
| 5698269 | Carlblom et al. | Dec 1997 | A |
| 5698498 | Luciani et al. | Dec 1997 | A |
| 5721023 | Ostapchenko | Feb 1998 | A |
| 5723418 | Person Hei et al. | Mar 1998 | A |
| 5728770 | Yamamoto et al. | Mar 1998 | A |
| 5747430 | Matsushita et al. | May 1998 | A |
| 5747431 | Taylour et al. | May 1998 | A |
| 5783303 | Tsuei | Jul 1998 | A |
| 5789459 | Inagaki et al. | Aug 1998 | A |
| 5863874 | Person Hei et al. | Jan 1999 | A |
| 5869436 | Lindman | Feb 1999 | A |
| 5871590 | Hei et al. | Feb 1999 | A |
| 5876812 | Frisk et al. | Mar 1999 | A |
| 5925601 | McSherry | Jul 1999 | A |
| 5935914 | Theyssen et al. | Aug 1999 | A |
| 5952601 | Sanford et al. | Sep 1999 | A |
| 6060444 | Schulz et al. | May 2000 | A |
| 6087308 | Butler et al. | Jul 2000 | A |
| 6207622 | Li et al. | Mar 2001 | B1 |
| 6214777 | Li et al. | Apr 2001 | B1 |
| 6288012 | Li et al. | Sep 2001 | B1 |
| 6302263 | Bennett et al. | Oct 2001 | B1 |
| 6310013 | Lokkesmoe et al. | Oct 2001 | B1 |
| 6423303 | Ryklin et al. | Jul 2002 | B1 |
| 6427826 | Li et al. | Aug 2002 | B1 |
| 6485794 | Li et al. | Nov 2002 | B1 |
| 6495494 | Li et al. | Dec 2002 | B1 |
| 6576298 | Bennett et al. | Jun 2003 | B2 |
| 6653263 | Kupper et al. | Nov 2003 | B1 |
| 6677280 | Kupper et al. | Jan 2004 | B2 |
| 6780823 | Li et al. | Aug 2004 | B2 |
| 6806240 | Hei et al. | Oct 2004 | B1 |
| 6809068 | Kupper et al. | Oct 2004 | B1 |
| 6962897 | Kupper et al. | Nov 2005 | B2 |
| 7067182 | Li et al. | Jun 2006 | B2 |
| 7091162 | Lewis et al. | Aug 2006 | B2 |
| 7109152 | Corby et al. | Sep 2006 | B1 |
| Number | Date | Country |
|---|---|---|
| 1157456 | Nov 1983 | CA |
| 0 359 330 | Mar 1990 | EP |
| 0 844 299 | May 1998 | EP |
| 99305796.7 | Jul 1999 | EP |
| 1564128 | Apr 1980 | GB |
| 57-003892 | Jan 1982 | JP |
| 06-136377 | May 1994 | JP |
| 07247293 | Sep 1995 | JP |
| 07268380 | Oct 1995 | JP |
| 10-053679 | Aug 1996 | JP |
| 10-059523 | Mar 1998 | JP |
| 9300742 | May 1993 | NL |
| WO 9608601 | Mar 1996 | WO |
| WO 9851746 | Nov 1998 | WO |
| WO 0107554 | Feb 2001 | WO |
| WO 0112759 | Feb 2001 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20040102337 A1 | May 2004 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 10287559 | Nov 2002 | US |
| Child | 10715692 | US | |
| Parent | 09596599 | Jun 2000 | US |
| Child | 10287559 | US |
