The present invention relates to systems and methods useful for treating a fabric article with a composition comprising polyol-based fabric care materials and a dispersing medium. The dispersing medium is a liquid at room temperature and has a flash point of greater than about 65° C. Specifically, the composition may be dispensed to treat fabric articles in an appliance during the fabric article drying process.
Fabric article treating methods and/or apparatuses have been evolving over the past 20 years. For example, technologies relating to fabric treatment compositions and/or dispensing devices suitable for use in a tumble dryer are disclosed in U.S. Pat. No. 4,207,683; U.S. Patent Publications 2003/0200674A1; 2003/0213145A1; and PCT Publication WO 03/087286A1.
There exists a continuing need to develop a fabric article treating methods and/or systems, especially for in-home fabric article treating applications in the drying cycle that improves and/or enhances the deposition of fabric article actives onto fabric articles being treated. There also exists a continuing need to develop fabric treatment compositions having characteristics (such as viscosity-temperature profile, flash point, odor) suitable for use in those fabric article treating method and/or systems. Moreover there exists a continuing need to develop fabric treatment compositions that are comfortable against the skin and that does not yellow with repeated use.
One aspect of the present invention relates to a fabric article treating system comprising:
In another aspect of the invention, methods for treating a fabric article with a composition comprising polyol-based fabric care materials in a fabric article drying appliance are also provided.
The accompanying drawings incorporated in and forming a part of the specification illustrate several aspects of the present invention, and together with the description and claims serve to explain the principles of the invention. In the drawings:
Definitions
As used herein, “fabric article” means an article composed of fabrics and/or fibers. Such articles include, but are not limited to, clothing, towels and other bath linens, bed linens, table cloths, carpets, curtains, upholstery coverings, sleeping bags, tents, shoes, and car interior (such as car seat covers, car floor mats).
As used herein, “during a drying cycle” means while the dryer is operating.
As used herein, “fabric care material” means a material or combination of materials that can deliver one or more of the following benefits to a fabric article; softening, crispness, water and/or stain repellency, refreshing, antistatic, anti-shrinkage, anti-microbial, durable press, wrinkle resistance, odor resistance, abrasion resistance, anti-felting, anti-pilling, appearance enhancement, and mixtures thereof.
As used herein, “fabric treatment composition” means a composition that comprises one or more fabric care materials, or one or more perfume materials, or combinations thereof. Suitable forms of treatment compositions include, but are not limited to, fluidic substances, such as liquids or gases, and solid compounds, such particles or powders.
As used herein, the terms “treatment composition”, “fabric treatment composition” and “benefit composition” are synonymous.
As used herein, the articles “a” and “an”, when used in a claim, are understood to mean one or more of the material that is claimed or described.
Unless otherwise noted, all component or composition levels are in reference to the active level of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources.
Unless otherwise indicated, all percentages and ratios are calculated based on weight of the total composition.
Treating System and Delivery Method
In one aspect of Applicants' invention, a fabric treatment composition that is applied by processes including, but not limited to, spraying, to a fabric article, wherein the treatment composition comprises one or more polyol-based fabric care materials.
In another aspect of Applicants' invention, the treatment composition that is applied by processes including, but not limited to, spraying, to a fabric article can be a composition comprising a polyol-based fabric care material, a dispersing medium, and optionally, one or more adjunct materials, such as fabric care materials or other adjuncts.
In a further aspect of Applicants' invention, the treatment composition is applied to a fabric article by a treating system that is configured to deliver, such as spraying, or otherwise release the treatment composition into a receiving volume, which could be the drum (or other chamber) of a clothes drying appliance, within which a fabric article is treated.
The treating system would typically comprise: a drying appliance comprising a drum in which the fabric article is deposited and treated; a housing or enclosure, such as a reservoir, that contains a source of the fabric treatment composition, or is in communication with an external source of the fabric treatment composition; a dispensing device that provides the means for releasing or dispensing the fabric treatment composition, such as a nozzle; a controller, such as an electronic control device with a processing circuit, and input and output circuits; one or more sensors, such as a temperature sensor or a vapor and/or gas sensor; one or more input devices, such as a start switch and/or a keypad; one or more indicating devices, such as color lights or LED's; and optionally, a charging system, if the fabric treatment composition is to be electrostatically charged before (or while) being delivered. Details of the electrostatically charged spraying apparatus and method are disclosed in U.S. Patent Publication No. 2004/0025368A1 filed Apr. 17, 2003.
Reference will now be made in detail to suitable non-limiting embodiments of the treating system for delivering a fabric treatment, an example of which is illustrated in the accompanying drawings, wherein like numerals indicate the same elements throughout the views. Other treating systems suitable for use herein are disclosed in U.S. Pat. No. 4,207,683; U.S. Patent Publications Nos. 2003/0200674A1; 2003/0213145A1; 2004/0025368A1; and U.S. patent application Ser. Nos. 10/697,685 and 10/697,736.
Referring now to the embodiment of
Enclosure 50 may be permanently mounted to the exterior surface, or preferably releasably attached to the exterior surface. Likewise, enclosure 20 may be permanently mounted to the interior surface, or releasably attached to the interior surface. One configuration for such an attachment is illustrated in
When mounted on the interior surface of the door, for example, the enclosure 20 may be constructed so as to have the appearance of being “permanently” mounted, such that it seems to be “built into” the door of a dryer unit (or other type of fabric article drying appliance), without it actually being truly constructed as part of the fabric article drying appliance. On the other hand, enclosure 20 perhaps may be more loosely mounted near the door, or along side the interior surface of the door, much like one of the embodiments 10 as depicted in
It should be noted that the treating apparatus 10 may be grounded by way of being in contact with a grounded part of the fabric article drying appliance such as by a spring, patch, magnet, screw, or other attaching means, and/or by arc corona discharge, or by way of dissipating residual charge. Non-limiting examples of suitable methods for dissipating charge are disclosed in U.S. Patent Publication No. 2004/0025368.
In
A spray nozzle or a fluid atomizing nozzle typically provides an average droplet size that is less than about 1000 microns, typically from about 100 to about 1000 microns, or from about 120 to about 500 microns, or from about 150 to about 300 microns. This average droplet size is measured by a Malvern particle analyzer. When a spray nozzle is covered with a fine grid or a membrane to produce a finer mist of droplets with an average particle size of less than 100 microns.
Nebulizers, atomizers and like devices are well known to those skilled in the art. A suitable device for use herein is a nebulizer that has at least one ultrasonic sonotrode, or ultrasonic vibrating cell. Typical of such nebulizer is commercially available under the tradename Acu Mist® from Sono Tek Corporation, Milton, N.Y. Still other examples of such devices are available from Omron Health Care, GmbH, Germany; and from Flaem Nuove, S.P.A, Italy. Likewise, aerosol delivery systems, which are well known to the art, can be used to deliver the detergent and/or finishing compositions. The benefit composition can comprise a fluidic substance, such as a liquid or a gaseous compound, or it can comprise a solid compound in the form of particles, such as a powder, or solid particles in solution with a liquid.
Reservoir 26 can be of essentially any size and shape, and could take the form, for example, of a pouch or a cartridge; or perhaps the reservoir could be connected to a source of dispersing medium (for example, a household water line for situations in which the benefit composition comprises potable water) such that the benefit composition in the reservoir can be diluted to the desired viscosity and/or surface tension.
The inner housing 20 and outer housing 50 are typically in electrical communication. In the embodiment of
Referring now to
Referring now to
The flat cable 40 will bring certain command signals and electrical power into the inner housing 20, and will also receive electrical signals from sensors mounted in the inner housing 20 and communicate those sensor signals back to the outer housing 50. A power supply control signal follows a wire 70 through the quick disconnect switch 34 to the high voltage power supply 28. This signal can comprise a constant DC voltage, a constant AC voltage, a variable DC voltage, a variable AC voltage, or some type of pulse voltage, depending on the type of control methodology selected by the designer of the fabric article treating apparatus 10.
In one embodiment, the signal at 70 is a variable DC voltage, and as this voltage increases, the output of the high voltage power supply 28 will also increase in voltage magnitude, along a conductor 39 (e.g., a wire) that is attached to an electrode 38 that carries the high voltage to the nozzle 24, or into the reservoir 26. The voltage impressed onto the electrode 38 will then be transferred into the benefit composition. A constant output voltage DC high voltage power supply could optionally be used instead of the variable output voltage power supply 28 of the exemplary embodiment.
Once the benefit composition is charged within the reservoir 26 it will travel through a tube or channel 42 to the inlet of the pump 30, after which the composition will be pressurized and travel through the outlet of the pump along another tube (or channel) 44 to the discharge nozzle 24. For use in the present invention, the actual details of the type of tubing used, the type of pump 30, and the type of electric motor 32 that drives the pump, can be readily configured for almost any type of pressure and flow requirements. The electrical voltage and current requirements of the electric motor 32 to provide the desired pressure and flow on the outlet of the pump 30 can also be readily configured for use in the present invention. Virtually any type of pump and electric motor combination can be utilized in some form or another to create a useful device that falls within the teachings of the present invention, or a stand-alone pump can be used (i.e., without an associated electric motor), as discussed below.
It should be noted that some types of pumps do not require separate input and output lines or tubes to be connected thereto, such as peristaltic pumps, in which the pump acts upon a continuous tube that extends through an inlet opening and continues through a discharge opening of the pump. This arrangement is particularly beneficial for use with electrostatically charged fluids or particles that are being pumped toward the discharge nozzle 24, because the tubing can electrically insulate the pump from the charged benefit composition. It should also be noted that an alternative pumping device could be used, if desired, such as a spring-actuated pumping mechanism. A non-limiting example of a suitable peristaltic pump is the Model 10/30 peristaltic pump, which may be obtained from Thomas Industries of Louisville, Ky.
The types of control signals used to control the electric motor 32 can vary according to the design requirements of the apparatus 10, and such signals will travel along an electrical conductor 72 to control motor 32, via the flat cable 40. If the motor 32 is a DC variable-speed motor, then a variable “steady” DC voltage can be applied, in which the greater the voltage magnitude, the greater the rotational speed of the motor. In one embodiment, the electrical signal traveling along conductor 72 can be a pulse-width modulated (PWM) signal, that is controlled by a microprocessor or a microcontroller. Of course, such a pulse-width modulated signal can also be controlled by discrete logic, including analog electronic components.
The fabric article treating apparatus 10 can be enhanced by use of certain sensors, examples of which include but are not limited to a door (or lid) sensor 22, a motion sensor 36, a humidity sensor 46, and/or a temperature sensor 48. An analog output temperature sensor can be used to provide an analog signal along the electrical conductor 86 that leads back to the controller in the outer housing 50.
The major components of the exterior housing 50 typically comprise the electronics 54 and the power source 52. For example, if power source 52 comprises four D-cell batteries connected in series, a +6 volt DC voltage will be provided to a set of DC power supplies generally designated by the reference numeral 58. It will be presumed that more than one DC power supply voltage will be required by the control circuit in the outer housing 50. One of the DC power supply voltages provides energy for the high voltage power supply 28, via the electrical conductor 70 that runs through the flat cable 40. Another output voltage is provided to a microcontroller 60, which in an exemplary embodiment requires a +3.3 volt DC power supply. In an exemplary embodiment, a digital-to-analog converter (DAC) 62 is used, and the device provided by Analog Devices of Norwood, Mass. (Part No. AD 5301), requires a +5 volt DC power supply. All of these power supplies are provided by the “set” of DC power supplies 58.
Part of the external housing 50 includes inputs to the microcontroller 60. One important element that could be used as a user interface to the microcontroller 60 would be a keypad 66, such as a set of bubble or membrane switches that have the numbers 0-9, as well as an “ENTER” key. Other keys could be included as part of keypad 66, including a “CANCEL” key, or perhaps a decimal point key.
Contained within the inner housing 20 are the reservoir 26, pump 30, electric motor 32, optional high voltage power supply 28, discharge nozzle 24, and various sensors that may or may not be included for a particular version of the treating apparatus 10. The electrical conductor 39 is depicted, which carries the high voltage to the nozzle 24, and this is one configuration that could be alternatively used instead of carrying the high voltage to the reservoir 26. The tubing 42 to the inlet of the pump is illustrated, as well as the tubing 44 from the outlet of the pump that provides the benefit composition to the nozzle 24. It should be noted that the high voltage power supply 28 is strictly optional within the teachings of the present invention; if spray droplets/particles emitted from the nozzle 24 are not to be electrostatically charged, then there is no need for a high voltage power supply within the inner housing 20.
In
As illustrated in
The enclosure 1150 comprises a main body 1151 having a back wall 1151a, a first inner compartment 1151b, see
Extending through corresponding openings in the face plate 1162 are an ON-OFF switch 1266c, a “refluff” key or switch 266d, and a dial 266a, which may comprise a potentiometer, which a user rotates to dial in a desired one of a strong, regular or light setting corresponding to a strong, regular or light benefit level to be provided by a benefit composition during the drying process.
The cable 1140 is coupled to and extends between the enclosures 1120 and 1150. The cable 1140 may run along the inner surface of the fabric enhancement apparatus door, over the top of the door, and down the exterior surface of the door. Any unused length of the cable 1140 can be manually inserted into the first compartment 1151b for storage.
The cable 1140 carries benefit composition from the fluid pump 1130 in the outer enclosure 1150 to the nozzle 24 in the inner enclosure 1120, see
A first fitment 1172 is mounted to the main body 1151 via first and second mounting shelves 1155a and 1155b, see
The types of control signals used to control the electric motor 1132 can vary according to the design requirements of the apparatus 1100, and such signals will travel to the motor 1132 via an electrical conductor 1172. In the illustrated embodiment, the electrical signal traveling along conductor 1172 comprises a pulse-width modulated (PWM) signal controlled by the microcontroller 1160. Of course, such a pulse-width modulated signal can also be generated by any appropriate controller or processor, or appropriate discrete logic.
As noted above, the enclosure 1150 comprises a second compartment 1151c for storing batteries 52, which may comprise two AA batteries.
A suitable microcontroller 1160 is a microprocessor manufactured by Atmel Corporation and sold under the product designation Atmega48-16AI. Alternatively, the microcontroller 1160 may comprise a microprocessor manufactured by Atmel Corporation and sold under the product designation Atmega48-16AJ. Of course, other microcontrollers, microprocessors, controllers, or processors made by different manufacturers, or discrete digital logic could alternatively be used.
The microcontroller 1160 includes on-board memory and input and output lines for analog and digital signals. The microcontroller 1160 also has a serial port that can be interfaced to an optional programmer interface using an RS-232 communications link. As noted above, the ON-OFF switch 1266c, and the refluff key 266d are coupled to the microcontroller 1160, see
Further coupled to the microcontroller 1160 are first, second, third, fourth and fifth light emitting diodes 1400a-1400e, see
It is further contemplated that a benefit composition dispensing apparatus constructed in accordance with the present invention may comprise a “single-housing” stand-alone unit similar to the one disclosed in U.S. patent application Ser. No. 10/762,152, entitled “Volatile Material Delivery Method.” In such an embodiment, the apparatus comprises a single housing in which all electrical, electronic and mechanical components are housed. For example, such a single-housing stand-alone unit may comprise the components illustrated in
In most conventional dryers, whether for home use or commercial use, the heating element will be a binary device, such that it is always ON at full power or is completely OFF at zero power. A more expensive dryer apparatus could use a proportional controller to control an electrical heating element, for example, although the typical result of proportional control would nevertheless exhibit undershoots and overshoots about the setpoint temperature. The principles of the present invention could be used in such a proportional controller.
Assuming for this example that the heating element is a binary device, then while it is energized, the temperature will tend to continually increase within the drying chamber. Once the heating element is turned off, then the temperature will begin to decrease (although there could be some overshoot). During a single drying cycle, the heating element may be turned on and off several times, in which case a temperature versus time graph would have the appearance of a sawtooth waveform, in which an increasing slope (assuming temperature is the Y-axis and time is the X-axis) would occur when the heating element is turned on, and a decreasing slope when the heating element is turned off. During this sawtooth waveform interval, the overall temperature versus time chart will have the appearance of a plateau, in which the chart exhibits a relatively long increasing slope during the beginning of the drying cycle, then it reaches the plateau region (exhibiting the sawtooth waveform), and at the end of the drying cycle the slope will continually decrease on the “far” side of the plateau.
If the fabric treatment composition contains a volatile material (such as certain perfumes), then it normally would be better to not release such volatile materials into the drying chamber until the temperature of that drying chamber is below a certain level, which might not occur until after the heating cycle has been completed. One way to detect this is to know when the heating element is actually energized or not, and an integral control device that is mated into the dryer's heating element controller would have knowledge of that status for the heating element, and thus could easily prevent any dispensing or application of the fabric treatment composition until after the heating element had been de-energized at the end of a heating cycle (as opposed to during the plateau region of the heating cycle, when the heating element could turn off, but also could later turn back on).
Assuming, however, that the heating element control status is not known to the fabric treatment composition dispensing controller, which would be the case if the dispensing apparatus was a self-contained unit that is not in communication with the dryer's controller, then another means of determining the end of the heating cycle would be required. One way of determining the end of a heating cycle (or “heating event”) would be to determine the maximum and minimum temperatures that occur during the sawtooth waveform portion of the heating cycle, also referred to above as the “plateau region.” If, for example, the internal temperature of the dryer's chamber will rise to a maximum temperature TMAX, and then fall to a momentary “minimum” temperature that is about 10-15° C. lower than TMAX, then the controller for the dispensing apparatus could determine when to begin applying the fabric treatment composition, which is after the dryer's internal temperature falls below maximum temperature TMAX, less the 10-15° C. “minimum” temperature. These sawtooth minimum and maximum temperature values can be considered a single differential temperature value, and that type of differential temperature will be referred to herein by a variable “TDIFF”. Some extra tolerance could be built in to the TDIFF value, so that, for example, if most home dryers rise and fall by approximately 15° C. during the plateau region of the drying cycle, then the value for TDIFF could be set to 20° C.
One optional aspect of the present invention is to provide the fabric treatment composition at two different time intervals during the drying cycle such as described in commonly assigned co-pending U.S. application Ser. No. 10/762,152, filed Jan. 21, 2004.
Fabric Treatment Composition
One aspect of Applicants' invention is a fabric treatment composition that can comprise a polyol-based fabric care material, a dispersing medium, and optionally, one or more adjunct materials.
In one embodiment, the fabric treatment composition comprises a polyol-based fabric care material, such as sucrose esters; a dispersing medium, such as water, alcohols, diols; and optionally, one or more adjunct materials (such as fabric care agents and adjunct materials) selected from the group consisting of softening agents, perfumes, wetting agents, emulsifiers, emulsion stabilizing agents, viscosity modifiers, pH buffers, antibacterial agents, antioxidants, radical scavengers, chelants, antifoaming agents, and mixtures thereof.
In another embodiment, the fabric treatment composition comprises from about 0.1% to about 95% by weight of the treatment composition of a polyol-based fabric care material and from about 1% to about 99% by weight of the treatment composition of a dispersing medium.
In another embodiment, the fabric treatment composition comprises a polyol-based fabric care material and a dispersing medium having the weight ratio ranging from about 1:1000 to about 90:1, or from about 1:40 to about 1:4.
In another embodiment, the fabric treatment composition comprises from about 0.1% to about 95% by weight of the treatment composition of a polyol-based fabric care material, from about 1% to about 99% by weight of the treatment composition of a dispersing medium, and the balance of one or more adjunct materials.
In another aspect of the invention, the treatment composition that is applied to the fabric article comprises a polyol-based fabric care material that has a boiling point of less than or equal to 250° C. at 1 atmosphere. Suitable polyol-based fabric care materials and sources for obtaining such materials are described herein below.
In another aspect of the invention, the treatment composition that is applied to the fabric article comprises a dispersing medium that has a flash point, as measured according to American Society for Testing and Materials (ASTM) method D93-02a, of at least about 65° C., or at least about 75° C., or at least about 95° C., or from about 65° C. to about 400° C., or from about 80° C. to about 300° C., or from about 90° C. to about 232° C.
In another aspect of the invention, the treatment composition suitable for use in the treatment system of the present invention has a viscosity of from about 1 to about 200 cps (0.001 to 0.20 Pa·s), or from about 5 to about 150 cps (0.002 to 0.15 Pa·s), or from about 10 to about 100 cps (0.01 to 0.1 Pa·s), as measured by a Brookfield viscometer model # LVDVII+ at 20° C. The spindle used for these measurements is LV1 with the appropriate rotational speed to measure compositions of different viscosities, e.g., 30 rpm to measure compositions with viscosities between about 500 cps (0.5 Pa·s) and about 1000 cps (1 Pa·s); 60 rpm to measure compositions with viscosities less than about 500 cps (0.5 Pa·s).
In another aspect of the invention, the treatment composition suitable for use in the treatment system of the present invention has a static surface tension of from about 3 to about 70 dynes/cm, or from about 5 to about 50 dynes/cm, or from about 10 to about 40 dynes/cm, at room temperature, as measured by a Kruss K12 Processor Tensiometer using the Wilhemy test method at room temperature.
Polyol-Based Fabric Care Materials
“Polyol”, as used herein, means any aliphatic or aromatic compound containing at least two free hydroxyl groups. In practicing the processes disclosed herein, the selection of a suitable polyol is simply a matter of choice. For example, suitable polyols may have a backbone chain selected from the following classes: saturated or unsaturated, linear or branched or cyclic (including heterocyclic), aliphatic or aromatic (including mononuclear or polynuclear aromatics). Exemplary polyols include carbohydrates (such as saccharides), glycols (such as glycerin), and derivatives thereof (such as sugar alcohols). Monosaccharides suitable for use herein include, but are not limited to, mannose, galactose, arabinose, xylose, ribose, apiose, rhamnose, psicose, fructose, sorbose, tagitose, ribulose, xylulose, glucose, and erythrulose. Oligosaccharides suitable for use herein include, but are not limited to, maltose, kojibiose, nigerose, cellobiose, lactose, melibiose, gentiobiose, turanose, rutinose, trehalose, sucrose and raffinose. Polysaccharides suitable for use herein include, but are not limited to, amylose, glycogen, cellulose, chitin, inulin, agarose, xylans, mannan and galactans. The sugar alcohols suitable for use herein include, but are not limited to, sorbitol, erythritol, arabitol, xylitol, threitol, pentaerythritol, mannitol and galactitol.
Also suitable for use herein are other classes of polyol-based materials include sugar ethers, alkoxylated polyols, such as polyethoxy glycerol, pentaerythritol and other polyols containing amines such as glucosamine.
These polyol-based materials have the ability to modify a fabric surface to provide fabric care benefits. The derivatization or functionalization of the polyol is designed to be effective for different fabric care applications. Examples of functionalization approaches may include, but not limited to, esterification, etherification, alkylation, amidation, amination and other linking chemistries.
Typical fabric care benefits may include, but are not limited to: enhancement of fabric feel such as softness, hand and comfort; reduce or resist wrinkling; ease of ironing; enhancement of fabric color; abrasion resistance; fabric shape retention (elasticity, non-shrinkage, non-elongation); static reduction; lint reduction; faster drying; whitening; stain repellency.
Polyol-based materials suitable for use herein may have the following general formula:
P(OH)w-s(OC(O)R1)x(OR2)yR3z(LR4)uXv
In one embodiment, the polyol-based fabric care material is a sucrose derivatized by esterification and has the following formula
P(OH)8-x(OC(O)R1)x
In one embodiment, some of the R1 moieties may comprise linear alkyl or alkoxy moieties comprising varying chain length. For example, R1 may comprise a mixture of linear alkyl or alkoxy moieties wherein greater than about 20% of the linear chains are C18, or greater than about 50% of the linear chains are C18, or greater than about 80% of the linear chains are C18.
In another embodiment, some of the R1 moieties may comprise a mixture of saturate and unsaturated alkyl or alkoxy moieties; the degree of unsaturation can be measured by “Iodine Value” (hereinafter referred as “IV”, as measured by the standard AOCS method). The IV of the polyol-based fabric care material suitable for use herein ranges from about 1 to about 150, or from about 2 to about 100, or from about 5 to about 85. The R1 moieties may be hydrogenated to reduce the degree of unsaturation.
In a further embodiment, some of the R1 moieties may comprise unsaturated alkyl or alkoxy moieties, wherein the unsaturated moieties may comprise a mixture of “cis” and “trans” forms about the unsaturated sites. The “cis”/“trans” ratios may range from about 1:1 to about 50:1, or from about 2:1 to about 40:1, or from about 3:1 to about 30:1, or from about 4:1 to about 20:1.
The polyol-based fabric care materials are present in the treatment composition of the present invention at levels from about 0.1% to about 95%, or from about 1% to about 50%, or from about 2% to about 30%, by weight of the composition.
Dispersing Medium
The fabric treatment composition of the present invention also comprises a dispersing medium. Suitable dispersing medium include, but are not limited to, water, water soluble solvents selected from the group consisting of C4 to C10 glycol ethers, C2 to C7 glycols, polyethers, such as glycerin, and mixtures thereof.
The treatment composition may comprise, based on weight percent of the treatment composition, from about 1 wt % to about 99 wt %, from about 10 wt % to about 95 wt %, or from about 30 wt % to about 90 wt % of the dispersing medium. Typically, water comprises greater than about 40 wt %, or greater than about 60 wt %, or greater than about 80%, or greater than about 90 wt % of the treatment composition; the balance of the dispersing medium comprises water soluble solvents.
When fabric treatment composition comprises water, the pH of said composition may be in the range of from about 2 to about 10, from about 3 to about 9, from about 4 to about 8, or from about 5.5 to about 7.5. Commonly known pH buffers, such as those disclosed below in the “Adjunct materials”, can be used to adjust and/or control the pH of the composition.
Adjunct Materials
The treatment composition may also comprise optional adjunct materials. Adjunct materials include, but are not limited to, wetting agents, emulsifiers, emulsion stabilizing agents, viscosity modifiers, pH buffers, antibacterial agents, antioxidants, radical scavengers, chelants, antifoaming agents, fabric care agents such as softening agents, perfumes, and mixtures thereof.
When present, each adjunct material is present, based on total composition weight, at one of the following levels, at least about 0.5 wt %, at least about 2 wt %, from about 4 wt % to about 90 wt %, from about 4 wt % to about 50 wt %, or from about 4 wt % to about 10 wt %.
The composition of the present invention may optionally comprise one or more fabric care materials. These fabric care material provides one or more fabric benefits including, but not limited to, softness, odor, anti-soil re-deposition, stain or water repellency, color or whiteness enhancement, enhanced absorbency, anti-static, anti-bacterial, or fabric abrasion resistance. Some representative, but nonlimiting examples of fabric care materials, such as softening agnets, are described below.
Exemplary softening agents include, but are not limited to, diester quaternary ammonium compounds (DEQA); polyquaternary ammonium compounds; triethanolamine esterified with carboxylic acid and quaternized (so called “esterquat”); amino esterquats; cationic diesters; betaine esters; betaines; silicone or silicone emulsions comprising aminosilicones, cationic silicones, quat/silicone mixtures; functionalized PDMS; amine oxides; and mixtures thereof.
Nonlimiting examples of quaternaty ammonium type softeners may be selected from the group consisting of: N,N-dimethyl-N,N-di(tallowyloxyethyl) ammonium methylsulfate, N-methyl-N-hydroxyethyl-N,N-di(canoyloxyethyl) ammonium methylsulfate, N,N-ditallow N,N-dimethyl ammonium chloride, N,N-ditallowylethanol N,N-dimethyl ammonium chloride, and mixtures thereof.
Additional examples of non-silicone fabric softening agents and deposition aids are described in EP 902 009; WO 99/58492; U.S. Pat. No. 4,137,180; WO 97/08284; WO 00/70004; WO 00/70005; WO 01/46361; WO 01/46363; WO 99/64661; WO 99/64660; JP 11-350349; JP11-081134; and JP 11-043863. Additional examples of silicone fabric softening agents and deposition aids are described in U.S. Pat. Nos. 4,448,810; 4,800,026; 4,891,166; 5,593,611; EP 459 821; EP 530 974; WO 92/01773; WO 97/32917; WO 00/71806; WO 00/71807; WO 01/07546; WO 01/23394; JP 2000-64180; JP 2000-144199; JP 2000-178583; and JP 2000-192075.
Some of the softening agents are described in details below. Suitable protonatable amines include, protonatable amines having Formula I below:
wherein the index m=0, 1, 2 or 3; the index n=1, 2, 3 or 4, preferably n is 2 or 3, more preferably n is 2, each R is independently selected from C1-C22 alkyl, C1-C22 hydroxyalkyl or a benzyl group; each R1 is independently selected from C11-C22 linear alkyl, C11-C22 branched alkyl, C11-C22 linear alkenyl, or C11-C22 branched alkenyl; and each Q may comprise a carbonyl, carboxyl, or amide moiety.
Suitable alkylated quaternary ammonium compounds (quats), include mono-alkyl quats, di-alkyl, tri-alkyl quats and tetra-alkyl quats and certain cationic surfactants. Suitable mono-alkyl quats, di-alkyl, tri-alkyl quats and tetra-alkyl quats typically have Formula II below:
wherein the index m=0, 1, 2, 3 or 4; the index n=1, 2, 3 or 4, preferably n is 2 or 3, more preferably n is 2, each R is independently selected from C1-C22 alkyl, C1-C22 hydroxyalkyl, or a benzyl group; each R1 is independently selected from C11-C22 linear alkyl, C11-C22 branched alkyl, C11-C22 linear alkenyl, or C11-C22 branched alkenyl; X− is a water soluble anionic species such as chloride, bromide or methyl sulfate, and Q may comprise a carbonyl, carboxyl, or amide moiety.
Suitable cationic surfactants include quaternary ammonium surfactants selected from the group consisting of mono C6-C16, preferably C6-C10 N-alkyl or alkenyl ammonium surfactants, wherein the remaining N positions are substituted by methyl, hydroxyehthyl or hydroxypropyl groups. Another preferred cationic surfactant is C6-C18 alkyl or alkenyl ester of an quaternary ammonium alcohol, such as quaternary choline esters. More preferably, the cationic surfactants have Formula III below:
wherein R1 is a C8-C18 hydrocarbyl, preferably C8-14 alkyl, more preferably C8, C10 or C12 alkyl, and X− is a water soluble anionic species such as chloride, bromide or methyl sulfate.
Suitable cationic silicones include silicones functionalized by amine derived compounds and cationic silicone polymers. Suitable silicones functionalized by amine derived compounds include amino silicones having Formula IV below:
(R1R2R3SiO1/2)p(R4R4SiO2/2)m[R4Si(L-NR5R6)O2/2]a[Si(K-NR7R8)O3/2]b[R4SiO3/2]c Formula IV
wherein m, a, b, and c are independently selected from integers between 0 and 6000; p=2+b+c; R1, R2, R3, R4, R5, R6, R7 R8, L, K are various side chains attached to the silicone or nitrogen atoms within the molecule. In Formula IV above, R1, R2, R3, R4 are independently selected from:
Suitable cationic silicone polymers include cationic silicone polymers having Formula V below:
[CAP]-Zm-[CAP] Formula V
wherein [CAP] is a backbone termination or truncation unit; m is an integer from 1 to 50 and each Z unit has Formula VI below:
—(R)x—W—(R)x— Formula VI
wherein for Formula VI:
Other suitable fabric materials may be polymeric materials such as polyacrylates, polyvinylalcohols, polyethyleneglycols, and derivatives or copolymers of the aforementioned materials.
Non-limiting examples of suitable silicone copolyols are silicone copolyols having Formula X below:
R1—(CH3)2SiO—[(CH3)2SiO]a—[(CH3)(R1)SiO]b—Si(CH3)2—R1 Formula X
wherein for Formula X above, a+b is an integer from 1 to about 50, preferably a+b is an integer from about 3 to about 30, more preferably a+b is an integer from about 10 to about 25; and at least one R1 is a poly(ethyleneoxy/propyleneoxy) copolymer group having Formula XI below and the remaining R1 moieties are independently selected from the group consisting of methyl and the poly(ethyleneoxide/propyleneoxide) copolymer group having Formula XI below:
—(CH2)nO(C2H4O)c(C3H6O)dR2 Formula XI
wherein for Formula XI above, n is 3 or 4, preferably n is 3; c is an integer from 1 to about 100, preferably c is an integer from about 6 to about 100; d is an integer from 1 to about 14, and preferably d is an integer from 1 to about 3; the total of c+d is an integer of from about 5 to about 150, preferably the total of c+d is an integer from about 9 to about 100; and each R2 is independently selected from the group consisting of hydrogen, an alkyl moiety comprising up to 4 carbon atoms, or an acetyl group.
Nonlimiting examples of emulsifiers include amine oxides, alkyl polyglucosides, cetyltrimethyl ammonium chloride, alkyl sulfates, alkyl sulfonates, alkyl ethoxylates, alkyl ethoxy sulfates, and mixtures thereof.
Nonlimiting examples of emulsion stabilizing agent is selected from the group consisting of ethoxylated terepthalate, arabinogalactan, ethoxylated polyethylene imines, and mixtures thereof.
Nonlimiting examples of viscosity modifiers include salts, such as CaCl2, MgCl2, NaCl, guar gum, polysaccharides, and mixtures thereof. Other salts containing and other alkali or alkaline earth metal cations and halide anions, and the like, are also suitable.
Nonlimiting examples of pH buffers include citric acid, lactic acid, succinic acid, phosphoric acid, sodium bicarbonate, and mixtures thereof.
The antibacterial agents include didecyl dimethyl ammonium chloride, which is available under the tradename Uniquat® (from Lonza), 1,2-benzisothiozolin-3-one, which is available under the tradename Proxel® (from Zeneca Inc.), dimethylol-5,5-dimethylhydantoin, which is available under the tradename Dantoguard® (from Lonza) and 5-Chloro-2-methyl-4-isothiazolin-3-one/2-methyl-4-isothiazolin-3-one, which is available under the tradename Kathon® (from Rohm and Haas).
The antioxidants include, but are not limited to tocopherol acetates, quinines, polyphenols, and mixtures thereof.
The radical scavengers include, but are not limited to propyl gallate, polyimines, trimethoxy benzoic acid and mixtures thereof.
The chelants include, but are not limited to diethylene triamine pentaacetic acid, ethylene diamine teraacetic acid, diethylene triamine pentamethylethylene phosphomic acid, citric acid and mixtures thereof.
The antifoaming agent include, but are not limited to silicone oils, ethoxylated surfactants, Tetronics® (available from BASF), and mixtures thereof.
Other examples of ethoxylated surfactant include, but are not limited to, carboxylated alcohol ethoxylates; ethoxylated quaternary ammonium surfactants; and ethoxylated alkyl amines. Nonlimiting examples of ethoxylated surfactants are provided:
Other examples of ethoxylated surfactant include carboxylated alcohol ethoxylates; ethoxylated quaternary ammonium surfactants; and ethoxylated alkyl amines.
Suitable nonionic materials include certain surfactants produced by the condensation of alkylene oxide groups with an organic hydrophobic moiety, said moiety can be aliphatic or alkyl aromatic in nature; silicone copolyols; and mixtures thereof. Examples of suitable nonionic surfactants include, but are not limited to alkyl phenol ethoxylates, polyethylene glycol/polypropylene glycol block copolymers, fatty alcohol and fatty acid ethoxylates, long chain tertiary amine oxides, alkyl polysaccharide, polyethylene glycol (PEG) glyceryl fatty esters and mixtures thereof.
The perfume materials may be obtained from one or more of the following perfume material suppliers Firmenich (Geneva, Switzerland), Givaudan (Argenteuil, France), IFF (Hazlet, N.J.), Quest (Mount Olive, N.J.), Bedoukian (Danbury, Conn.), Sigma Aldrich (St. Louis, Mo.), Millennium Specialty Chemicals (Olympia Fields, Ill.), Polarone International (Jersey City, N.J.), Fragrance Resources (Keyport, N.J.), and Aroma & Flavor Specialties (Danbury, Conn.).
Suitable particulate materials include inorganic or organic particulates such as polymeric particles, clays, talcs, zeolites and mixtures thereof. Suitable polymeric particles typically have an average particle size less than about 10 microns, preferably less than 5 microns, more preferably less than about 1 micron. Such particles may comprise polyethylene, polystyrene, polypropylene and mixtures thereof. Suitable clay materials include phyllosilicate clays with a 2:1 layer structure, such as smectite clays for example pyrophyllite, montmorillonite, hectorite, saponite and vermiculite, and micas. Particularly suitable clay materials include smectite clays described in U.S. Pat. No. 4,062,647. Other disclosures of suitable clay materials for fabric softening purposes include European patent specification EP 26528-A1, U.S. Pat. Nos. 3,959,155 and 3,936,537.
Other suitable adjunct materials include, but are note limited to, preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidazolidinyl urea; suspending agents such as magnesium/aluminum silicate; sequestering agents such as disodium ethylenediamine tetraacetate; and certain synthetic or naturally-derived oils and/or fats, such as certain triglycerides, mineral oils, and mixtures thereof. Specific examples of oils or fats suitable for use herein as adjunct materials include but are not limited to; triglycerides from beef tallow, palm oil, cottonseed oil, canola oil, and soybean oil, all with varying levels of hydrogenation; paraffin oils, and mixtures thereof.
Additional adjunct materials further include, but are not limited to, wrinkle releasing/prevention agent, anti-static agent, crystal modifier, soil release/prevention agent, colorant, brightener, odor reducer/eliminator, deodorizer/refresher agent, stain repellent, color enhancer, perfume release and/or delivery agent, shape retention agent, fiber rebuild agent, fiber repair agent, and mixtures thereof.
Additional examples of suitable adjuncts and levels of use are found in U.S. Pat. No. 6,653,275.
Suitable adjunct materials are commercially available from Mazer Chemicals (Gurnee, Ill., USA), Clariant Corporation (Glattbrugg, Switzerland), Rhodia Incorporated (Cranbury, N.J., USA), Scher Chemicals, Inc. (Clifton, N.J., USA), Dow Corning Corporation (Midland, Mich., USA) and General Electric Company (Fairfield, Conn., USA), Witco Corporation (Middlebury, Conn., USA), Degussa-Huls (Marl, Germany), BASF (Mount Olive, N.J., USA), Sigma-Aldrich (St. Louis, Mo., USA), 20 Microns Ltd. (Baroda, India), and Twin Rivers Technologies (Quincy, Mass., USA).
Processes of Making Fabric Treatment Compositions
The fabric treatment compositions of the present invention can be formulated into any suitable form and prepared by any process chosen by the formulator, non-limiting examples of which are described in U.S. Pat. No. 6,653,275.
The following compositions are examples of fabric treatment compositions useful in the present invention:
a DTDMAC = Di-Tallow Di-methyl Ammonium Chloride
b DTDMAMS = Di-Tallow Di-methyl Ammonium Methyl Sulfateb.
c DEEHMAMS = Di-(Tallow oxyethyl) Hydroxy Ethyl Methyl Ammonium Methyl Sulfate
d CTMAC = Cetyl Trimethyl Ammonium Chloride
e Proxel ® = 1,2-Benzisothiozolin-3-one
f Dantoguard ® = Dimethylol-5,5-Dimethylhydantoin
g TMBA = Trimethoxy Benzoic Acid
h DTPA = Sodium Diethylene Triamine Pentaacetate
It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.
All documents cited are, in relevant part, incorporated herein by reference; the citation of any document is not to be construed as an admission that it is prior art with respect to the present invention.
While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
This application is a continuation of U.S. Ser. No. 10/842,926, entitled “Fabric Article Treating System and Method”, filed on May 11, 2004 now U.S. Pat. No. 7,047,663; which claims the benefit of U.S. Provisional Application Ser. No. 60/568,771 entitled “Uniform Delivery of Compositions”, filed on May 6, 2004 and is a continuation-in-part of U.S. Ser. No. 10/839,549 entitled “Processes and Apparatuses for Applying a Benefit Composition to One or More Fabric Articles During a Fabric Enhancement Operation”, filed on May 5, 2004; which is a continuation-in-part of U.S. Ser. No. 10/762,152, entitled “Volatile Material Delivery Method”, filed on Jan. 21, 2004; which is a continuation-in-part of U.S. Ser. No. 10/697,736, entitled “Fabric Article Treating Method and Device Comprising a Heating Means”, filed on Oct. 29, 2003; U.S. Ser. No. 10/697,734, entitled “Thermal Protection of Fabric Article Treating Device”, filed on Oct. 29, 2003; U.S. Ser. No. 10/697,685, entitled “Fabric Article Treating Device Comprising More Than One Housing”, filed on Oct. 29, 2003 now U.S. Pat. No. 7,043,855; and U.S. Ser. No. 10/697,735, entitled “Fabric Article Treating Apparatus with Safety Device and Controller”, filed Oct. 29, 2003 now U.S. Pat. No. 7,146,749; each of which is a continuation-in-part of U.S. Ser. No. 10/418,595, entitled “Fabric Article Treating Method and Apparatus”, filed on Apr. 17, 2003 now U.S. Pat. No. 7,059,065, which claims the benefit of U.S. Provisional Application Ser. No. 60/374,601, filed Apr. 22, 2002 and U.S. Provisional Application Ser. No. 60/426,438, filed Nov. 14, 2002.
Number | Name | Date | Kind |
---|---|---|---|
2079280 | Couch | May 1937 | A |
2807893 | Morey | Oct 1957 | A |
2812593 | Olthuis | Nov 1957 | A |
2846776 | Clark | Aug 1958 | A |
2851791 | Olthuis | Sep 1958 | A |
2873539 | Morey | Feb 1959 | A |
2941309 | Cobb | Jun 1960 | A |
2958954 | Longenecker | Nov 1960 | A |
3002288 | Conlee | Oct 1961 | A |
3022580 | Doty | Feb 1962 | A |
3103450 | Janson | Sep 1963 | A |
3114653 | Kruzan | Dec 1963 | A |
3172604 | Brock | Mar 1965 | A |
3180037 | Kenreich et al. | Apr 1965 | A |
3239947 | Kenreich et al. | Mar 1966 | A |
3267701 | Mandarino | Aug 1966 | A |
3364585 | Fish | Jan 1968 | A |
3583180 | Arbogast | Jun 1971 | A |
3595036 | Laddle | Jul 1971 | A |
3634947 | Furgal | Jan 1972 | A |
3816070 | Candor et al. | Jun 1974 | A |
3872604 | Keller | Mar 1975 | A |
4009598 | Bernard et al. | Mar 1977 | A |
4014105 | Furgal et al. | Mar 1977 | A |
4022938 | Zaki et al. | May 1977 | A |
4098937 | Mizuno et al. | Jul 1978 | A |
4161283 | Hyman | Jul 1979 | A |
4207683 | Horton | Jun 1980 | A |
4236320 | Schwadike et al. | Dec 1980 | A |
4242377 | Roberts et al. | Dec 1980 | A |
4341347 | DeVittorio | Jul 1982 | A |
4501682 | Goodman et al. | Feb 1985 | A |
4511495 | Melville | Apr 1985 | A |
4532722 | Sax | Aug 1985 | A |
4567675 | Rennie | Feb 1986 | A |
4579279 | Marchant | Apr 1986 | A |
4618099 | Nagao et al. | Oct 1986 | A |
4642908 | Brenner | Feb 1987 | A |
4806254 | Church | Feb 1989 | A |
4891890 | Church | Jan 1990 | A |
5040311 | Roy | Aug 1991 | A |
5234610 | Gardlik et al. | Aug 1993 | A |
5438773 | Chaffee | Aug 1995 | A |
5442938 | Kislyuk | Aug 1995 | A |
5445747 | Kvietok et al. | Aug 1995 | A |
5461742 | Pasad et al. | Oct 1995 | A |
5595071 | Pasad et al. | Jan 1997 | A |
5749163 | Staub et al. | May 1998 | A |
5771604 | Wunderlich et al. | Jun 1998 | A |
5789368 | You et al. | Aug 1998 | A |
5810265 | Cornelius et al. | Sep 1998 | A |
5884418 | McNally | Mar 1999 | A |
5912408 | Trinh et al. | Jun 1999 | A |
5930909 | McNally | Aug 1999 | A |
5945111 | Esser | Aug 1999 | A |
5965517 | Mooney | Oct 1999 | A |
5966831 | Anderson | Oct 1999 | A |
5968404 | Trinh et al. | Oct 1999 | A |
5980583 | Staub et al. | Nov 1999 | A |
5997759 | Trinh et al. | Dec 1999 | A |
6001343 | Trinh et al. | Dec 1999 | A |
6067723 | Lafrenz | May 2000 | A |
6103678 | Masschelein et al. | Aug 2000 | A |
6160110 | Thomaides et al. | Dec 2000 | A |
6277810 | Baines et al. | Aug 2001 | B2 |
6279834 | Fox et al. | Aug 2001 | B1 |
6315800 | Gomes et al. | Nov 2001 | B1 |
6376455 | Friedi et al. | Apr 2002 | B1 |
6474563 | Pletcher et al. | Nov 2002 | B2 |
6491840 | Frankenbach et al. | Dec 2002 | B1 |
6495058 | Frankenbach et al. | Dec 2002 | B1 |
6503413 | Uchiyama et al. | Jan 2003 | B2 |
6571993 | Rodd et al. | Jun 2003 | B2 |
6574883 | Giblin et al. | Jun 2003 | B2 |
6604297 | Hagemann et al. | Aug 2003 | B2 |
6609311 | Hagemann et al. | Aug 2003 | B2 |
6696405 | Mooney | Feb 2004 | B2 |
6792695 | Fry et al. | Sep 2004 | B2 |
6883723 | Griese et al. | Apr 2005 | B2 |
6889399 | Steiner et al. | May 2005 | B2 |
7059065 | Gerlach et al. | Jun 2006 | B2 |
7146749 | Barron et al. | Dec 2006 | B2 |
20010036909 | Levinson | Nov 2001 | A1 |
20010044399 | Keppie et al. | Nov 2001 | A1 |
20010052551 | Pletcher et al. | Dec 2001 | A1 |
20010052552 | Hamaguchi et al. | Dec 2001 | A1 |
20020050073 | Hagemann et al. | May 2002 | A1 |
20020069465 | Chute et al. | Jun 2002 | A1 |
20020078589 | Hagemann et al. | Jun 2002 | A1 |
20020083615 | Giblin et al. | Jul 2002 | A1 |
20020100122 | Rodrigues et al. | Aug 2002 | A1 |
20020112293 | Trinh et al. | Aug 2002 | A1 |
20030035748 | Trinh et al. | Feb 2003 | A1 |
20030091749 | France et al. | May 2003 | A1 |
20030196348 | Hagemann et al. | Oct 2003 | A1 |
20030199416 | Fry et al. | Oct 2003 | A1 |
20030199417 | Fry et al. | Oct 2003 | A1 |
20030200674 | Fry et al. | Oct 2003 | A1 |
20030213145 | Hagemann et al. | Nov 2003 | A1 |
20030224965 | Conley et al. | Dec 2003 | A1 |
20040064970 | Hagemann et al. | Apr 2004 | A1 |
20040118014 | Burgess et al. | Jun 2004 | A1 |
20040123489 | Pancheri et al. | Jul 2004 | A1 |
20040123490 | Pancheri et al. | Jul 2004 | A1 |
20040134090 | Heilman et al. | Jul 2004 | A1 |
20040134094 | Hahn et al. | Jul 2004 | A1 |
20040221476 | Jones et al. | Nov 2004 | A1 |
20040253376 | Parker | Dec 2004 | A1 |
20040259750 | DuVal et al. | Dec 2004 | A1 |
20050020478 | Cooke et al. | Jan 2005 | A1 |
20050022311 | Zhang et al. | Feb 2005 | A1 |
20050076453 | Lucas et al. | Apr 2005 | A1 |
20050076532 | Ward et al. | Apr 2005 | A1 |
20050076533 | Huston et al. | Apr 2005 | A1 |
20050076534 | Ofosu-Asante et al. | Apr 2005 | A1 |
20050120584 | DuVal et al. | Jun 2005 | A1 |
20050251924 | DuVal et al. | Nov 2005 | A1 |
20060080860 | Clark et al. | Apr 2006 | A1 |
20060162180 | Heilman et al. | Jul 2006 | A1 |
20060191157 | Gerlach et al. | Aug 2006 | A1 |
20070000068 | France et al. | Jan 2007 | A1 |
20070000291 | France et al. | Jan 2007 | A1 |
Number | Date | Country |
---|---|---|
23 18 596 | Apr 1980 | DE |
0 130 682 | Jan 1985 | EP |
0 118 313 | May 1987 | EP |
0 315 879 | May 1989 | EP |
0 204 484 | Mar 1992 | EP |
0 594 154 | Apr 1994 | EP |
0 848 999 | Jun 1998 | EP |
0 676 497 | Sep 1999 | EP |
0 953 669 | Nov 1999 | EP |
1 479 757 | Nov 2004 | EP |
2 066 309 | Jul 1981 | GB |
2 231 944 | Nov 1990 | GB |
2 354 006 | Mar 2001 | GB |
2 366 568 | Mar 2002 | GB |
2 346 678 | Oct 2002 | GB |
02-302300 | Dec 1990 | JP |
06-015090 | Jan 1994 | JP |
1995068094 | Mar 1995 | JP |
08-150293 | Jun 1996 | JP |
1996215488 | Aug 1996 | JP |
09-267000 | Oct 1997 | JP |
10-290898 | Nov 1998 | JP |
2002069832 | Mar 2002 | JP |
2002115182 | Apr 2002 | JP |
WO 9609430 | Mar 1996 | WO |
WO 9955952 | Nov 1999 | WO |
WO 9955953 | Nov 1999 | WO |
WO 0001421 | Jan 2000 | WO |
WO 0001422 | Jan 2000 | WO |
WO 0001493 | Jan 2000 | WO |
WO 0011133 | Mar 2000 | WO |
WO 0024851 | May 2000 | WO |
WO 0024856 | May 2000 | WO |
WO 0024858 | May 2000 | WO |
WO 0038512 | Jul 2000 | WO |
WO 0055292 | Sep 2000 | WO |
WO 0058428 | Oct 2000 | WO |
WO 0107710 | Feb 2001 | WO |
WO 0118145 | Mar 2001 | WO |
WO 0166264 | Sep 2001 | WO |
WO 0208510 | Jan 2002 | WO |
WO 0112423 | Feb 2002 | WO |
WO 0233161 | Apr 2002 | WO |
WO 0240623 | May 2002 | WO |
WO 03004170 | Jan 2003 | WO |
WO 03008528 | Jan 2003 | WO |
WO 03087286 | Oct 2003 | WO |
WO 03087461 | Oct 2003 | WO |
WO 03102289 | Dec 2003 | WO |
WO 2004099489 | Nov 2004 | WO |
WO 2006006016 | Jan 2006 | WO |
Number | Date | Country | |
---|---|---|---|
20060123654 A1 | Jun 2006 | US |
Number | Date | Country | |
---|---|---|---|
60374601 | Apr 2002 | US | |
60568771 | May 2004 | US | |
60426438 | Nov 2002 | US |
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