EP1599569B1 - Foam-generating kit containing a foam-generating dispenser and a high viscosity composition - Google Patents
Foam-generating kit containing a foam-generating dispenser and a high viscosity composition Download PDFInfo
- Publication number
- EP1599569B1 EP1599569B1 EP04716083A EP04716083A EP1599569B1 EP 1599569 B1 EP1599569 B1 EP 1599569B1 EP 04716083 A EP04716083 A EP 04716083A EP 04716083 A EP04716083 A EP 04716083A EP 1599569 B1 EP1599569 B1 EP 1599569B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- foam
- generating
- high viscosity
- composition
- dispenser
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 119
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0017—Multi-phase liquid compositions
- C11D17/0021—Aqueous microemulsions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B11/00—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use
- B05B11/01—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use characterised by the means producing the flow
- B05B11/10—Pump arrangements for transferring the contents from the container to a pump chamber by a sucking effect and forcing the contents out through the dispensing nozzle
- B05B11/1087—Combination of liquid and air pumps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
- B05B7/0018—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas with devices for making foam
- B05B7/0025—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas with devices for making foam with a compressed gas supply
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
- B05B7/0018—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas with devices for making foam
- B05B7/0025—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas with devices for making foam with a compressed gas supply
- B05B7/0031—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas with devices for making foam with a compressed gas supply with disturbing means promoting mixing, e.g. balls, crowns
- B05B7/0037—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas with devices for making foam with a compressed gas supply with disturbing means promoting mixing, e.g. balls, crowns including sieves, porous members or the like
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/049—Cleaning or scouring pads; Wipes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0094—High foaming compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/18—Hydrocarbons
- C11D3/188—Terpenes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
- C11D3/2037—Terpenes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2068—Ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
Definitions
- the present invention relates to compositions and containers therefor. Specifically, the present invention relates to high viscosity compositions, especially high viscosity cleaning compositions, and containers therefor. The present invention also generally relates to foam-generating dispensers.
- High viscosity compositions such as dish washing compositions, hand soap compositions, hair conditioner compositions, fabric conditioner compositions, scrubbing compositions, etc. are well known and have typically provided in a liquid, a gel or a paste. While liquids and pastes may be useful in a variety of situations, such physical forms are no longer considered new and exciting. Also, while it is desirable to provide new and interesting physical forms, the use of the above compositions has typically been limited to application or pre-application of such liquids, gels and pastes into a substrate, and then the additional step of direct application to the desired surface.
- the need exists for a foam-generating dispenser which is able to produce foam from a high viscosity composition.
- the need further exists for a foam-generating dispenser which may produce such a foam, without the need for excessive physical exertion, and/or the need to use an aerosol propellant.
- the present invention relates to foam-generating kit containing a non-aerosol container with a foam-generating dispenser and a high viscosity dishwashing microemulsion composition, preferably within the container.
- the high viscosity composition has a viscosity of at least about 0.05 Pa*s.
- the foam-generating dispenser When the foam-generating dispenser is employed with the high viscosity composition, the foam-generating dispenser generates a foam having a foam (i.e., volume) to weight ratio of greater than about 2 mL/g.
- a foam-generating dispenser and a high viscosity composition can simultaneously provide acceptable foaming without excessive physical exertion and without employing an aerosol propellant. Without intending to be limited by theory, it is believed that when an increasingly turbulent flow path is produced, even a high viscosity composition having a viscosity of at least about 0.050 Pa*s can be made to produce an acceptable foam.
- the term “comprising” means that other steps, ingredients, elements, etc. which do not affect the end result can be added. This term encompasses the terms “consisting of” and “consisting essentially of”.
- the term “dish” means any dishware, tableware, cookware, glassware, cutlery, cutting board, food preparation equipment, etc. which is washed prior to or after contacting food, being used in a food preparation process and/or in the serving of food.
- the terms "foam” and “suds” are used interchangeably and indicate discrete bubbles of gas bounded by and suspended in a liquid phase.
- microemulsion means a oil-in-water emulsion which has the ability to emulsify oil into non-visible droplets.
- non-visible droplets typically have maximum diameter of less than about 100 angstroms ( ⁇ ), preferably less than 50 ⁇ as measured by methods known in the art, such as ISO 7027 which measures turbidity at a wavelength of 880 nm. Turbidity measuring equipment is easily available from, for example, Omega Engineering, Inc., Stamford, Connecticut, U.S.A.
- the container useful herein is a non-aerosol container and typically has a hollow body for holding a high viscosity dishwashing composition, and is typically a bottle or canister formed of plastic, glass, and/or metal, preferably a polymer or resin such as polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, polystyrene, ethyl vinyl alcohol, polyvinyl alcohol, thermoplastic elastomer, and combinations thereof, although other materials known in the art may also be used.
- Such containers will typically hold from about 100 mL to about 2 L of liquid, preferably from about 150 mL to about 1.2 L of liquid, and more preferably from about 200 mL to about 1 L of liquid, and are well known for holding liquid consumer products.
- Such containers are widely available from many packaging suppliers.
- a foam-generating dispenser for generating a foam.
- the foam-generating dispenser When activated, the foam-generating dispenser generates foam and concurrently dispenses the foamed composition from the container.
- the foam-generating dispenser may be formed as either integral with, or separate from the container. If formed separately, the foam-generating dispenser may attach to the container via methods known in the art such as by employing a transition piece, corresponding threaded male and female members, pressurized and non-pressurized seals, locking and snap-on parts, and/or other methods known in the art.
- the foam-generating dispenser is attached to the container via a transition piece and/or with corresponding threaded male and female members which allow easy refilling.
- the foam-generating dispenser may interact with the high viscosity composition via any method so as to generate a foam, such as a chemical reaction, an enzymatic reaction, and/or a mechanical action.
- a mechanical action is preferred herein, and typically involves a mechanism which imparts or mixes a gas, such as air, nitrogen, carbon dioxide, etc., directly into the dishwashing composition in a turbulent manner as it dispenses, so as to physically form the foam.
- the foam-generating dispenser includes a gas imparting mechanism to form the foam from air via an air injection piston, foam-generating aperture, an impinging surface, a mesh or net, a pump, and/or a sprayer, more preferably, an air injection piston, a pump, an impinging surface, a plurality of meshes or nets, and/or a sprayer which injects or imparts air from the atmosphere into the dishwashing composition.
- the foam-generating dispenser employs at least three, preferably from three to five, meshes wherein the high viscosity composition flows through these meshes in series so as to generate the foam.
- the high viscosity composition is repeatedly turbulently mixed with air, thereby multiplying the foam-generating effect beyond that of any single mesh.
- additional meshes may be added to provide the desired level of foaming and/or quality of foam.
- the foam-generating dispenser also typically includes an activator, preferably a manual activator such as, for example, a trigger, a pressure-activated pumping mechanism, a button, and/or a slider, more preferably a button and/or a pressure-activated pumping mechanism which can be activated with a single finger.
- an activator preferably a manual activator such as, for example, a trigger, a pressure-activated pumping mechanism, a button, and/or a slider, more preferably a button and/or a pressure-activated pumping mechanism which can be activated with a single finger.
- the activator be designed such that a consumer may easily activate it when their hands are wet and/or slippery, such as when in the middle of a manual dishwashing process.
- Such an activator should allow the user to easily and conveniently control both the speed of dispensing and the volume dispensed.
- the foam-generating dispenser useful herein generates a foam having a foam to weight ratio of greater than about 2 mL/g, more preferably from about 3 mL/g to about 10 mL/g, and even more preferably from about 4 mL/g to about 8 mL/g.
- the foam-generating dispenser useful herein generates at least about 2 mL foam, preferably from about 3 mL to about 10 mL, and more preferably from about 4 mL to about 8 mL, per mL of dishwashing composition.
- "Creamy” and “smooth” foams having fine bubbles dispersed relatively evenly throughout may be especially preferred for their aesthetic and/or performance characteristics.
- preferred foams are those which do not significantly degrade into liquid over a period of 3 minutes are especially preferred.
- a clean glass surface e.g., a PYREX TM plate
- liquid i.e., non-foam
- this liquid permeates into the applicator (e.g., a sponge), and further extends the mileage of the high viscosity composition when it is used for, example, cleaning dishes.
- Fig. 1 is a cut-away view of a preferred embodiment of the foam-generating dispenser, 10, with a nozzle, 12, from which the foamed dishwashing composition is dispensed.
- the dishwashing composition enters the foam-generating dispenser via a dip tube, 14, and flows past a ball, 16, and into a cylinder, 18.
- a plug, 20, prevents the ball, 16, from escaping, and also supports a coil spring, 22, and a inner rod, 24.
- a liquid piston, 26, creates a suction which draws the dishwashing composition past the ball, 16 and the plug, 20, into a liquid chamber, 28, and thereby primes the foam-generating dispenser, 10.
- an air chamber, 30, and an air piston, 31 are also primed, and when the activator, 32, is depressed, both the air from the air chamber, 30, and the dishwashing composition from the liquid chamber, 28, are turbulently forced into the mixing chamber, 34, and past a first mesh, 36 and a second mesh, 38, which are both kept in place by a mesh holder, 40.
- a first mesh, 36 and a second mesh, 38 which are both kept in place by a mesh holder, 40.
- a first, rough foam is generated, which becomes more fine and even after passing through the second mesh, 38, and the third mesh, 41.
- These meshes may have the same, or different pore sizes. Also, additional meshes may also be employed, as desired.
- the foam-generating dispenser contains a sponge therein or attached thereto, either in place of, or in addition to one or more meshes.
- a sponge also produces foam as the high viscosity composition is turbulently forced through its, open-celled structure.
- Such a sponge may be contained within the interior of the foam-generating dispenser and/or may also be located at the end of the nozzle, as desired. Without intending to be limited by theory, it has been found that additional meshes and/or a sponge located slightly within, and/or at the tip of the nozzle are especially useful herein, as they serve to generate the foam immediately prior to dispensing. Therefore, the user sees the desired foam as, or immediately after, it passes through the last turbulent flow area, while the foam quality is at its best and before it noticeably degrades and/or otherwise changes in quality.
- Fig. 1 also shows a base cap, 42, which secures the foaming dispenser to a container, 44, which holds the high viscosity composition.
- Preferred foam-generating dispensers useful herein include: T8900, OpAd FO, 8203, and 7512 series foamers from Afa-Polytek, Helmond, The Netherlands; T1, F2, and WR-F3 series foamers from Airspray International, Inc., Alkmaar, The Netherlands or North Pompano Beach, Florida, U.S.A.; TS-800 and Mixor series foamers from Saint-Gobain Calmar, Inc., City of Industry, California, U.S.A.; pump foamers and squeeze foamers from Daiwa Can Company, Tokyo, Japan; TS1 and TS2 series foamers from Guala Dispensing USA, Inc., Hillsborough, New Jersey, U.S.A.; and YT-87L-FP, YT-87L-FX, and YT-97 series foamers from Yoshino Kogyosho Co., Ltd., Tokyo, Japan.
- foam-generating dispensers discussed in the Japanese-language publications Food & Package, (2001) vol. 42, no. 10, pp 609-13 ; Food & Package, (2001) vol. 42, no. 11, pp 676-79 ; and Food & Package, (2001) vol. 42, no. 12, pp 732-35 .
- Variations and modifications of existing foam-generating dispensers are especially useful herein, especially by modifying air piston:product piston volume ratio, mesh/net sizes, impinging angle, etc., as well as optimization of the sizes and dimensions of the cylinder, rod, dip tube, nozzle, etc.
- a finger and/or palm-activated type pump (see, e.g., Fig. 1 ) is often preferred for aesthetic reasons. This is especially the case where the foam-generating kit is to be distinguished from the "harsh" image of typical hard-surface cleaners and similar heavy-duty products.
- the high viscosity composition herein is ,a dishwashing composition, and preferably a hand dishwashing composition.
- a high viscosity composition may therefore typically include a surfactant system, a solvent, and one or more optional ingredients known in the art of cleaning such as a dye, an enzyme, a perfume, a thickener, a pH controlling agent, a reducing or oxidizing bleach, an odor control agent, antioxidants and free radical inhibitors, and a mixture thereof.
- the surfactant system herein typically includes an anionic surfactant, an amphoteric surfactant, a cationic surfactant, a nonionic surfactant, a zwitterionic surfactant, or a mixture thereof, preferably an alkyl sulfate, an alkoxy sulfate, an alkyl sulfonate, an alkoxy sulfonate, an alkyl aryl sulfonate, an amine oxide, a betaine or a derivative of aliphatic or heterocyclic secondary and ternary amine, a quaternary ammonium surfactant, an amine, a singly or multiply alkoxylated alcohol, an alkyl polyglycoside, a fatty acid amide surfactant, a C 8 -C 20 ammonia amide, a monoethanolamide, a diethanolamide, an isopropanolamide, a polyhydroxy fatty acid amide and a mixture thereof.
- the solvent useful herein is typically selected from the group consisting of water, alcohols, glycols, ether alcohols, and a mixture thereof, more preferably the group consisting of water, glycol, ethanol, glycol ethers, water, and a mixture thereof, even more preferably the group consisting of propylene carbonate, propylene glycol, tripropyleneglycol n-propyl ether, diethylene glycol n-butyl ether, water, and a mixture thereof.
- the solvent herein preferably has a solubility in water of at least about 12%, more preferably of at least about 50%, by weight of the solution.
- Solvents which are capable of decreasing the product viscosity and/or imparting a shear-thinning or non-Newtonian rheology profile to the compositions may be present, but are not preferred herein, as such solvents are typically expensive, and do not provide significant non-shear related benefits. Accordingly, in a preferred embodiment, the high viscosity composition herein acts as a Newtonian Fluid throughout the relevant shear-range during use in the foam-generating dispenser.
- Preferred solvents useful herein which impart a Newtonian behavior include mono, di and poly hydroxy alcohols, ethers, and mixtures thereof.
- Alkyl carbonates such as propylene carbonate are also preferred.
- the enzyme useful herein includes a cellulase, a hemicellulase, a peroxidase, a protease, a gluco-amylase, an amylase, a lipase, a cutinase, a pectinase, a xylanase, a reductase, an oxidase, a phenoloxidase, a lipoxygenase, a ligninase, a pullulanase, a tannase, a pentosanase, a malanase, a ⁇ -glucanase, an arabinosidase and a mixture thereof.
- a preferred combination is a detergent composition having a cocktail of conventional applicable enzymes such as protease, amylase, lipase, cutinase and/or cellulase.
- An enzyme is typically present at from about 0.0001% to about 5% of active enzyme, by weight.
- Preferred proteolytic enzymes are selected from the group consisting of ALCALASE ® (Novo Industri A/S), BPN', Protease A and Protease B (Genencor), and mixtures thereof. Protease B is more preferred.
- Preferred amylase enzymes include TERMAMYL ® , DURAMYL ® and the amylase enzymes described in WO 94/18314 A1 to Antrim, et al., published on August 18, 1994 (assigned to Genencor International) and WO 94/02597 A1 to Svendsen and Bisgard-Frantzen, published on February 3, 1994 (assigned to Novo Nordisk A/S). Further non-limiting examples of preferred enzymes are disclosed in WO 99/63034 A1 to Vinson, et al., published on December 9, 1999 .
- a microemulsion dishwashing composition typically also contains a low water-soluble oil having a solubility in water of less than 5,000 ppm, preferably from 0 parts per million (ppm) to 1,500 ppm, by weight of the low water-soluble oil, and more preferably from about 1 part per trillion to about 100 ppm.
- a low water-soluble oil having a solubility in water of less than 5,000 ppm, preferably from 0 parts per million (ppm) to 1,500 ppm, by weight of the low water-soluble oil, and more preferably from about 1 part per trillion to about 100 ppm.
- Preferred low water-soluble oils useful herein include terpenes, isoparaffins, other oils having the above solubility, and a mixture thereof.
- the dishwashing composition In the absence of a foam-generating dispenser, the dishwashing composition here typically has an effective foaming dilution range of less than about 50%, preferably from about 0% to about 40%, and more preferably from about 0% to about 35% of the dilution range.
- the dishwashing composition when used with the foam-generating dispenser, has an effective foaming dilution range of at least about 50%, preferably from about 50% to about 100%, more preferably from about 75% to about 100%, and even more preferably from about 85% to about 100% of the dilution range.
- the effective foaming dilution range is calculated as follows:
- the suds generation curves of Graph I are generated by testing various dilutions of a dishwashing composition via the suds cylinder test herein. Such a curve can be generated either with or without dispensing from a foam-generating dispenser into the cylinders.
- "Effective foam” is defmed herein as foam which is at least half (50%) the maximum volume of foam generated for a given dishwashing composition according to the suds generation curve. Accordingly, in Graph I for when the foam-generating dispenser is not employed, effective foam is formed from about 28% to about 2% product concentration, which translates into an effective foaming dilution range of 26% (i.e., 28% - 2%).
- the same dishwashing composition is employed with (i.e., dispensed from) the foam-generating dispenser, it can be seen that effective foam is generated from the point of dispensing (100% product concentration) until a product concentration of about 3% is reached.
- the dishwashing kit generates foam at a substantially different dishwashing composition to water dilution than the dilution at which the maximum volume of foam is formed according to the suds cylinder test.
- the effective foaming dilution range when the dishwashing composition in Graph I is dispensed from a foaming dispenser is 97% (i.e., 100% - 3%).
- the dishwashing composition useful herein has an oil solubilization curve which is generated by the oil solubilization test defined herein.
- Effective oil solubilization is defined herein as oil solubilization which is at least 20% of the maximum amount of oil solubilized for a given dishwashing composition according to the oil solubilization curve which is plotted as a function of product concentration (i.e., dilution). Accordingly, in Graph I, the maximum amount of oil solubilized is about 4.7 at a 70% product concentration, and thus the effective oil solubilization is an amount of at least about 0.94.
- the effective oil solubilization occurs from dilution ranges of about 96% to about 42%, which translates into an effective oil solubilization dilution range of about 54%.
- the effective foaming dilution range overlaps the effective oil solubilization dilution range, preferably the effective foaming dilution range overlaps the effective oil solubilization dilution range by at least about 10%, more preferably by from about 25% to about 100%, and even more preferably from about 50% to about 100%, especially in the case of a microemulsion or a protomicroemulsion. Furthermore, it is highly preferred that the effective foaming dilution range overlaps the point in the oil solubilization curve where the oil solubilization is at a maximum. Thus, the present invention encourages a user to use the product at a concentration/product dilution which more effectively solubilizes oil, and thereby optimizes cleaning.
- the present invention has recognized that such microemulsion dishwashing compositions require the container and foam-generating dispenser herein to achieve consumer-acceptable foaming at a dilution where the oil solubilization curve is more effective, and preferably maximized. Accordingly, it is preferred that when the dishwashing composition is employed with the container and foam-generating dispenser, an effective foam is generated at a dilution factor significantly different from the suds generation curve when the container and foam-generating dispenser is not employed.
- Hand dishwashing compositions, cleaning compositions, protomicroemulsion compositions and microemulsion compositions useful in the present invention are known in the art, as described in, for example, WO 96/01305 A1 to Farnworth and Martin, published on January 18, 1996 ; US Patent No. 5,854,187 to Blum, et al., issued on Dec. 29, 1998 ; U.S. Patent No. 6,147,047 to Robbins, et al., issued on November 14, 2000 ; WO 99/58631 A1 to Robbins, et al., published on November 18, 1999 ; U.S. Patent No. 4,511,488 to Matta, issued on April 16, 1985 ; U.S. Patent No.
- the high viscosity composition herein typically has a viscosity of at least about 0.05 Pa*s, preferably from about 0.05 Pa*s to about 10 Pa*s, more preferably from about 0.1 Pa*s to about 7 Pa*s, even more preferably from about 0.2 Pa*s to about 5 Pa*s, and yet even more preferably from about 0.3 Pa*s to about 4 Pa*s.
- a foam is produced.
- the high viscosity composition is preferably sold within the container as a single item, this is not necessary, as refills, and separate components within the same kit are contemplated herein.
- a shaped applicator can surprisingly provide significantly improved results and ease of use as compared to a normal applicator.
- the shaped applicator is designed and sized to be easily held in the hand and is used to apply the foamed dishwashing composition to the surface to be cleaned, i.e., the dish. It has been found that if the foamed dishwashing composition is applied to a flat applicator, then the foamed dishwashing composition is quickly wiped onto the first dish contacted, but that little foamed dishwashing composition will remain on the flat applicator, for cleaning subsequent dishes.
- the shaped applicator will often be used for scrubbing, it is preferred that at least one surface thereof contain an abrasive surface.
- the shaped applicator is typically selected from a porous material such as a natural or artificial sponge, a brush, a metal scouring device, a woven material, a nonwoven material, an abrasive material, a plastic material, a cloth material, a microfiber cleaning material, a polymeric material, a resin material, a rubber material, or a mixture thereof, preferably a natural or artificial sponge, a brush, a metal scouring device, an abrasive material, a foam rubber material, a functional absorbent material (FAM), a polyurethane foam, and a mixture thereof, and more preferably a natural or artificial sponge, a brush, an abrasive material, a foam rubber material, and a mixture thereof, with all types of open-celled structures being highly preferred.
- a porous material such as a natural or artificial sponge,
- Such shaped applicators are available from a variety of commercial sources, such as Minnesota Mining and Manufacturing Company (3M), St. Paul, Minnesota, U.S.A. If the shaped applicator is formed from a relatively delicate material, or a material which is easily torn, then it is preferable that this material be covered, partially or completely, with a water-permeable, more robust material, such as a nonwoven material. Also useful are surfaces formed from plastic or polymeric materials such as available from, for example, Minnesota Mining and Manufacturing Company (3M), St. Paul, Minnesota, U.S.A., and found on, for example, Scotch-BriteTM General Purpose Scrubbing Pads.
- the FAM useful herein has an absorbent ability of more than about 20 g H 2 O/g, more preferably, 40 g H 2 O/g by weight of FAM.
- a preferred FAM is described in U.S. Pat. No. 5,260,345 to DesMarais, et al., issued on November 9, 1993 or U.S. Pat. No. 5,889,893 to Dyer, et al., issued on May 4, 1999 .
- Examples of a preferred polyurethane is described in U.S. Pat. No. 5,089,534 to Thoen, et al., issued on February 18, 1992 ; U.S. Pat. No.
- the shaped applicator is not hard, but instead has at least one resilient portion, preferably a resilient portion which is covered by an abrasive surface.
- a resilient portion which is covered by an abrasive surface.
- Such an optional resilient portion allows the user to vary the amount of contact, pressure, etc., between the scrubbing surface and the dish.
- the foamed dishwashing composition is thus preferably applied into or onto the shaped applicator directly from the foam-generating dispenser.
- FIG. 2 which shows a top perspective, cut-away view of a preferred embodiment of the shaped applicator, 12, herein, a sponge-type shaped applicator, 12, contains a receiving area, 50, to which the foamed dishwashing composition is applied for use.
- the receiving area, 50 is therefore typically bounded by a wall, 52, which protects the foamed composition from being quickly rubbed off of the shaped applicator, 12.
- the receiving area is preferably a concave indentation in the shaped applicator which may be of any shape and design which keeps the foamed dishwashing composition in contact with the shaped applicator.
- the receiving area contains a relatively steep concave wall or other structure which effectively keeps the foamed detergent in the receiving area and dispenses it over time during typical use.
- the receiving area holds from about 1 mL to about 200 mL, preferably from about 2 mL to about 150 mL, and more preferably from about 5 mL to about 100 mL of foamed dishwashing composition.
- the shaped applicator, 12, further contains a plurality of abrasive surfaces, 54, for scrubbing a dish. It is highly preferred that at least one abrasive surface be provided on the shaped applicator.
- Fig. 3 shows a perspective, cut-away view of a preferred embodiment of the shaped applicator, 12, which is formed as a sponge-type shaped applicator, 12, having a pocket-like receiving area, 50, whose internal dimensions are indicated by dashed lines.
- the foamed dishwashing composition is added to the receiving area, 50, via a mouth, 56, which may be permanently open, or may be closeable, as desired.
- An abrasive surface, 54 substantially covers the entire exterior of the shaped applicator, 12, to assist in removing stains from a dish.
- the viscosity herein is measured on a Brookfield viscometer model # LVDVII+ at 20 °C.
- the spindle used for these measurements is a S31 spindle with the appropriate speed to measure products of different viscosities; e.g., 12 rpm to measure products of viscosity greater than 1 Pa*s; 30 rpm to measure products with viscosities between 0.5 Pa*s - 1 Pa*s; 60 rpm to measure products with viscosities less than 0.5 Pa*s.
- the ISO 7027 method measures turbidity at a wavelength of 880 nm with turbidity measuring equipment such as that available from Omega Engineering, Inc., Stamford, Connecticut, U.S.A. If the vial becomes clear, then more oil is added, in increments of 0.1 g, until the vial fails to become clear within the prescribed time. The % oil dissolution is recorded as the maximum amount of oil which was successfully solubilized (i.e., the vial is clear) by 10.0 g of product.
- the dishwashing composition herein solubilizes at least about 1 g of dyed canola oil, more preferably at least about 3 g of dyed canola oil, and even more preferably at least about 4 g of dyed canola oil when tested at a 75% product concentration.
- the sudsing profile can be measured by employing a suds cylinder tester (SCT), and using the data to plot a suds generation curve.
- SCT suds cylinder tester
- the SCT has a set of 4 cylinders. Each cylinder is typically 30 cm long, and 10 cm in diameter. The cylinder walls are 0.5 cm thick, and the cylinder bottom is 1 cm thick.
- the SCT rotates a test solution in a closed cylinder, typically a plurality of clear plastic cylinders, at a rate of about 21 revolutions per minute, for 2 minutes, after which the suds height is measured. Soil may then be added to the test solution, agitated again, and the resulting suds height measured, again.
- Such a test may be used to simulate the initial sudsing profile of a composition, as well as its sudsing profile during use, as more soils are introduced from the surface being washed.
- the sudsing profile test is as follows:
- compositions according to the invention preferably have a sudsing profile maxima of at least about 2 cm, more preferably at least about 3 cm, and even more preferably about 4 cm.
- Foam to weight ratio is a measurement of the mL of foam generated per gram of product. Foam to weight ratio is measured as follows: a volumetric measuring device, such as a graduated cylinder is weighed to get a tare weight. Then, the product is dispensed, using the foam-generating dispenser, if appropriate, into a graduated cylinder a set number of strokes for non-continuous dispensing devices or for a set time period for continuous dispensing devices. 10 strokes for non-continuous devices (pumps, sprayers) or 10 seconds for continuous devices is the suggested duration. The dispensing rate in the test should be consistent with the dispensing rate during normal usage scenarios. For example, 120 strokes per minute for trigger sprayers, or 45 strokes per minute for palm pumps.
- the volume of foam generated is measured in mL using the volumetric measuring device.
- the volumetric measuring device containing the dispensed product is weighed in grams.
- the tare weight of the volumetric measuring device is subtracted from this weight. The result is the grams of the product dispensed.
- the foam to weight ratio in mL/g is calculated by dividing the volume of foam generated (in mL) by the weight product dispensed (in g).
- the foam to weight ratio of mL/g is easily converted to mL foam per mL of product by multiplying by the density of the high viscosity composition.
- a foam-generating kit contains a 300 mL hollow plastic container filled with a microemulsion dishwashing composition, and an attached T1 series foamer from Airspray, similar to that shown in Fig. 1 .
- the T1 foamer is modified to include a third mesh, as seen in Fig. 1 , at 41, at the tip of the nozzle.
- a shaped applicator according to Fig. 3 is also included.
- the foamed dishwashing composition has a foam to weight ratio of about 3 mL/g, and the foam has a creamy, even look and feel.
- the foamed dishwashing composition is dispensed from the foaming dispenser into a pocket-type shaped applicator by sticking the nozzle of the foam-generating dispenser into the mouth of the shaped applicator, and pressing down on the activator.
- the dishwashing kit provides good mileage, and a foam which lasts throughout the normal use to clean dishes.
- the foam-generating dispenser is not used (i.e., the dishwashing composition is merely poured out of the container), the effective foaming dilution range does not significantly overlap the effective oil solubilization dilution range.
- An ionic-based microemulsion is provided, packaged with the foam-generating dispenser of Example 1.
- a foam-generating kit according to Example 1 is prepared, except that the T1 foamer is modified with a sponge at the tip, instead of a third mesh.
- the sponge is an artificial sponge which is cut into shape and is securely affixed immediately inside of the nozzle. The foam generated is creamy and aesthetically pleasing.
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Abstract
Description
- The present invention relates to compositions and containers therefor. Specifically, the present invention relates to high viscosity compositions, especially high viscosity cleaning compositions, and containers therefor. The present invention also generally relates to foam-generating dispensers.
- High viscosity compositions, such as dish washing compositions, hand soap compositions, hair conditioner compositions, fabric conditioner compositions, scrubbing compositions, etc. are well known and have typically provided in a liquid, a gel or a paste. While liquids and pastes may be useful in a variety of situations, such physical forms are no longer considered new and exciting. Also, while it is desirable to provide new and interesting physical forms, the use of the above compositions has typically been limited to application or pre-application of such liquids, gels and pastes into a substrate, and then the additional step of direct application to the desired surface.
- While it is known to employ a foam-generating dispenser to make low-viscosity compositions foam, this approach has not to date succeeded for high viscosity compositions. Specifically, the rheology of high viscosity compositions makes it difficult to achieve an acceptable foam without extremely turbulent and violent flow characteristics. As such turbulent flow characteristics often require excessive physical exertion or a highly-pressurized container, the practical result is that formulators are often required to lower the viscosity of their products so as to match the limitations of the foam-generating dispensers currently on the market. Therefore, this approach imparts an artificial, physical constraint upon formulators' freedom to achieve the best performing and/or lowest cost composition.
- Accordingly, the need exists for a foam-generating dispenser which is able to produce foam from a high viscosity composition. The need further exists for a foam-generating dispenser which may produce such a foam, without the need for excessive physical exertion, and/or the need to use an aerosol propellant.
- The present invention relates to foam-generating kit containing a non-aerosol container with a foam-generating dispenser and a high viscosity dishwashing microemulsion composition, preferably within the container. The high viscosity composition has a viscosity of at least about 0.05 Pa*s. When the foam-generating dispenser is employed with the high viscosity composition, the foam-generating dispenser generates a foam having a foam (i.e., volume) to weight ratio of greater than about 2 mL/g.
- It has now been found that the combination of a foam-generating dispenser and a high viscosity composition can simultaneously provide acceptable foaming without excessive physical exertion and without employing an aerosol propellant. Without intending to be limited by theory, it is believed that when an increasingly turbulent flow path is produced, even a high viscosity composition having a viscosity of at least about 0.050 Pa*s can be made to produce an acceptable foam.
- These and other features, aspects, advantages, and variations of the present invention, and the embodiments described herein, will become evident to those skilled in the art from a reading of the present disclosure with the appended claims, and are covered within the scope of these claims.
- While the specification concludes with claims particularly pointing out and distinctly claiming the invention, it is believed that the invention will be better understood from the following description of the accompanying figures in which like reference numerals identify like elements, and wherein:
-
Fig. 1 is a cut-away view of a preferred embodiment of the foam-generating dispenser; -
Fig. 2 is a top perspective, cut-away view of a preferred embodiment of the shaped applicator; and -
Fig. 3 is a perspective, cut-away view of a preferred embodiment of the shaped applicator. - The figures herein are not necessarily drawn to scale.
- All percentages, ratios and proportions herein are by weight of the final high viscosity composition, unless otherwise specified. All temperatures are in degrees Celsius (°C) unless otherwise specified.
- As used herein, the term "comprising" means that other steps, ingredients, elements, etc. which do not affect the end result can be added. This term encompasses the terms "consisting of" and "consisting essentially of".
- As used herein, the term "dish" means any dishware, tableware, cookware, glassware, cutlery, cutting board, food preparation equipment, etc. which is washed prior to or after contacting food, being used in a food preparation process and/or in the serving of food.
- As used herein, the terms "foam" and "suds" are used interchangeably and indicate discrete bubbles of gas bounded by and suspended in a liquid phase.
- As used herein, the term "microemulsion" means a oil-in-water emulsion which has the ability to emulsify oil into non-visible droplets. Such non-visible droplets typically have maximum diameter of less than about 100 angstroms (Å), preferably less than 50 Å as measured by methods known in the art, such as ISO 7027 which measures turbidity at a wavelength of 880 nm. Turbidity measuring equipment is easily available from, for example, Omega Engineering, Inc., Stamford, Connecticut, U.S.A.
- The container useful herein is a non-aerosol container and typically has a hollow body for holding a high viscosity dishwashing composition, and is typically a bottle or canister formed of plastic, glass, and/or metal, preferably a polymer or resin such as polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, polystyrene, ethyl vinyl alcohol, polyvinyl alcohol, thermoplastic elastomer, and combinations thereof, although other materials known in the art may also be used. Such containers will typically hold from about 100 mL to about 2 L of liquid, preferably from about 150 mL to about 1.2 L of liquid, and more preferably from about 200 mL to about 1 L of liquid, and are well known for holding liquid consumer products. Such containers are widely available from many packaging suppliers.
- Operatively attached to the container either directly or indirectly is a foam-generating dispenser for generating a foam. When activated, the foam-generating dispenser generates foam and concurrently dispenses the foamed composition from the container. The foam-generating dispenser may be formed as either integral with, or separate from the container. If formed separately, the foam-generating dispenser may attach to the container via methods known in the art such as by employing a transition piece, corresponding threaded male and female members, pressurized and non-pressurized seals, locking and snap-on parts, and/or other methods known in the art. Preferably, the foam-generating dispenser is attached to the container via a transition piece and/or with corresponding threaded male and female members which allow easy refilling.
- The foam-generating dispenser may interact with the high viscosity composition via any method so as to generate a foam, such as a chemical reaction, an enzymatic reaction, and/or a mechanical action. However, a mechanical action is preferred herein, and typically involves a mechanism which imparts or mixes a gas, such as air, nitrogen, carbon dioxide, etc., directly into the dishwashing composition in a turbulent manner as it dispenses, so as to physically form the foam. Preferably, the foam-generating dispenser includes a gas imparting mechanism to form the foam from air via an air injection piston, foam-generating aperture, an impinging surface, a mesh or net, a pump, and/or a sprayer, more preferably, an air injection piston, a pump, an impinging surface, a plurality of meshes or nets, and/or a sprayer which injects or imparts air from the atmosphere into the dishwashing composition. In a highly preferred embodiment, the foam-generating dispenser employs at least three, preferably from three to five, meshes wherein the high viscosity composition flows through these meshes in series so as to generate the foam. Without intending to be limited by theory, it is believed that by flowing through the above meshes in series, the high viscosity composition is repeatedly turbulently mixed with air, thereby multiplying the foam-generating effect beyond that of any single mesh. As the viscosity of the high viscosity composition increases, additional meshes may be added to provide the desired level of foaming and/or quality of foam.
- The foam-generating dispenser also typically includes an activator, preferably a manual activator such as, for example, a trigger, a pressure-activated pumping mechanism, a button, and/or a slider, more preferably a button and/or a pressure-activated pumping mechanism which can be activated with a single finger. It is highly preferred that the activator be designed such that a consumer may easily activate it when their hands are wet and/or slippery, such as when in the middle of a manual dishwashing process. Such an activator should allow the user to easily and conveniently control both the speed of dispensing and the volume dispensed. For certain applications, such as in industry or in public facilities, other activators may be useful, such as an electronic activator, a computer-controlled activator, an electric eye or an infrared detection activator, a manual lever-assist activator, etc. The foam-generating dispenser useful herein generates a foam having a foam to weight ratio of greater than about 2 mL/g, more preferably from about 3 mL/g to about 10 mL/g, and even more preferably from about 4 mL/g to about 8 mL/g. Furthermore, the foam-generating dispenser useful herein generates at least about 2 mL foam, preferably from about 3 mL to about 10 mL, and more preferably from about 4 mL to about 8 mL, per mL of dishwashing composition. "Creamy" and "smooth" foams having fine bubbles dispersed relatively evenly throughout may be especially preferred for their aesthetic and/or performance characteristics. In certain cases, preferred foams are those which do not significantly degrade into liquid over a period of 3 minutes are especially preferred. Specifically, when the foam is dispensed onto a clean glass surface (e.g., a PYREX™ plate) and let sit for 3 minutes at 25°C, less than 1 mm of liquid should be apparent. Preferably, no liquid is visible at the edge of the foam after 3 minutes. However, on other cases, it has also been found that a certain amount of liquid (i.e., non-foam) is also preferable, as this liquid then permeates into the applicator (e.g., a sponge), and further extends the mileage of the high viscosity composition when it is used for, example, cleaning dishes.
-
Fig. 1 is a cut-away view of a preferred embodiment of the foam-generating dispenser, 10, with a nozzle, 12, from which the foamed dishwashing composition is dispensed. The dishwashing composition enters the foam-generating dispenser via a dip tube, 14, and flows past a ball, 16, and into a cylinder, 18. A plug, 20, prevents the ball, 16, from escaping, and also supports a coil spring, 22, and a inner rod, 24. A liquid piston, 26, creates a suction which draws the dishwashing composition past the ball, 16 and the plug, 20, into a liquid chamber, 28, and thereby primes the foam-generating dispenser, 10. Meanwhile, an air chamber, 30, and an air piston, 31 are also primed, and when the activator, 32, is depressed, both the air from the air chamber, 30, and the dishwashing composition from the liquid chamber, 28, are turbulently forced into the mixing chamber, 34, and past a first mesh, 36 and a second mesh, 38, which are both kept in place by a mesh holder, 40. As the turbulent air/dishwashing composition mixture is forced past the first mesh, 36, a first, rough foam is generated, which becomes more fine and even after passing through the second mesh, 38, and the third mesh, 41. These meshes may have the same, or different pore sizes. Also, additional meshes may also be employed, as desired. - In a preferred embodiment, the foam-generating dispenser contains a sponge therein or attached thereto, either in place of, or in addition to one or more meshes. A sponge also produces foam as the high viscosity composition is turbulently forced through its, open-celled structure. Such a sponge may be contained within the interior of the foam-generating dispenser and/or may also be located at the end of the nozzle, as desired. Without intending to be limited by theory, it has been found that additional meshes and/or a sponge located slightly within, and/or at the tip of the nozzle are especially useful herein, as they serve to generate the foam immediately prior to dispensing. Therefore, the user sees the desired foam as, or immediately after, it passes through the last turbulent flow area, while the foam quality is at its best and before it noticeably degrades and/or otherwise changes in quality.
-
Fig. 1 also shows a base cap, 42, which secures the foaming dispenser to a container, 44, which holds the high viscosity composition. - Preferred foam-generating dispensers useful herein include: T8900, OpAd FO, 8203, and 7512 series foamers from Afa-Polytek, Helmond, The Netherlands; T1, F2, and WR-F3 series foamers from Airspray International, Inc., Alkmaar, The Netherlands or North Pompano Beach, Florida, U.S.A.; TS-800 and Mixor series foamers from Saint-Gobain Calmar, Inc., City of Industry, California, U.S.A.; pump foamers and squeeze foamers from Daiwa Can Company, Tokyo, Japan; TS1 and TS2 series foamers from Guala Dispensing USA, Inc., Hillsborough, New Jersey, U.S.A.; and YT-87L-FP, YT-87L-FX, and YT-97 series foamers from Yoshino Kogyosho Co., Ltd., Tokyo, Japan. Also see the foam-generating dispensers discussed in the Japanese-language publications Food & Package, (2001) vol. 42, no. 10, pp 609-13; Food & Package, (2001) vol. 42, no. 11, pp 676-79; and Food & Package, (2001) vol. 42, no. 12, pp 732-35. Variations and modifications of existing foam-generating dispensers are especially useful herein, especially by modifying air piston:product piston volume ratio, mesh/net sizes, impinging angle, etc., as well as optimization of the sizes and dimensions of the cylinder, rod, dip tube, nozzle, etc.
- While trigger-type foam-generating dispensers may be preferred for certain embodiments herein, a finger and/or palm-activated type pump (see, e.g.,
Fig. 1 ) is often preferred for aesthetic reasons. This is especially the case where the foam-generating kit is to be distinguished from the "harsh" image of typical hard-surface cleaners and similar heavy-duty products. - The high viscosity composition herein is ,a dishwashing composition, and preferably a hand dishwashing composition. Such a high viscosity composition may therefore typically include a surfactant system, a solvent, and one or more optional ingredients known in the art of cleaning such as a dye, an enzyme, a perfume, a thickener, a pH controlling agent, a reducing or oxidizing bleach, an odor control agent, antioxidants and free radical inhibitors, and a mixture thereof.
- The surfactant system herein typically includes an anionic surfactant, an amphoteric surfactant, a cationic surfactant, a nonionic surfactant, a zwitterionic surfactant, or a mixture thereof, preferably an alkyl sulfate, an alkoxy sulfate, an alkyl sulfonate, an alkoxy sulfonate, an alkyl aryl sulfonate, an amine oxide, a betaine or a derivative of aliphatic or heterocyclic secondary and ternary amine, a quaternary ammonium surfactant, an amine, a singly or multiply alkoxylated alcohol, an alkyl polyglycoside, a fatty acid amide surfactant, a C8-C20 ammonia amide, a monoethanolamide, a diethanolamide, an isopropanolamide, a polyhydroxy fatty acid amide and a mixture thereof. The surfactants useful herein may be further be branched and/or linear, substituted or unsubstituted, as desired. See also "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch).
- The solvent useful herein is typically selected from the group consisting of water, alcohols, glycols, ether alcohols, and a mixture thereof, more preferably the group consisting of water, glycol, ethanol, glycol ethers, water, and a mixture thereof, even more preferably the group consisting of propylene carbonate, propylene glycol, tripropyleneglycol n-propyl ether, diethylene glycol n-butyl ether, water, and a mixture thereof. The solvent herein preferably has a solubility in water of at least about 12%, more preferably of at least about 50%, by weight of the solution.
- Solvents which are capable of decreasing the product viscosity and/or imparting a shear-thinning or non-Newtonian rheology profile to the compositions may be present, but are not preferred herein, as such solvents are typically expensive, and do not provide significant non-shear related benefits. Accordingly, in a preferred embodiment, the high viscosity composition herein acts as a Newtonian Fluid throughout the relevant shear-range during use in the foam-generating dispenser.
- Preferred solvents useful herein which impart a Newtonian behavior include mono, di and poly hydroxy alcohols, ethers, and mixtures thereof. Alkyl carbonates such as propylene carbonate are also preferred.
- The enzyme useful herein includes a cellulase, a hemicellulase, a peroxidase, a protease, a gluco-amylase, an amylase, a lipase, a cutinase, a pectinase, a xylanase, a reductase, an oxidase, a phenoloxidase, a lipoxygenase, a ligninase, a pullulanase, a tannase, a pentosanase, a malanase, a β-glucanase, an arabinosidase and a mixture thereof. A preferred combination is a detergent composition having a cocktail of conventional applicable enzymes such as protease, amylase, lipase, cutinase and/or cellulase. An enzyme is typically present at from about 0.0001% to about 5% of active enzyme, by weight. Preferred proteolytic enzymes are selected from the group consisting of ALCALASE ® (Novo Industri A/S), BPN', Protease A and Protease B (Genencor), and mixtures thereof. Protease B is more preferred. Preferred amylase enzymes include TERMAMYL®, DURAMYL® and the amylase enzymes described in
WO 94/18314 A1 to Antrim, et al., published on August 18, 1994 WO 94/02597 A1 to Svendsen and Bisgard-Frantzen, published on February 3, 1994 WO 99/63034 A1 to Vinson, et al., published on December 9, 1999 - A microemulsion dishwashing composition typically also contains a low water-soluble oil having a solubility in water of less than 5,000 ppm, preferably from 0 parts per million (ppm) to 1,500 ppm, by weight of the low water-soluble oil, and more preferably from about 1 part per trillion to about 100 ppm. Preferred low water-soluble oils useful herein include terpenes, isoparaffins, other oils having the above solubility, and a mixture thereof.
- In the absence of a foam-generating dispenser, the dishwashing composition here typically has an effective foaming dilution range of less than about 50%, preferably from about 0% to about 40%, and more preferably from about 0% to about 35% of the dilution range. However, in an embodiment of the invention herein, the dishwashing composition, when used with the foam-generating dispenser, has an effective foaming dilution range of at least about 50%, preferably from about 50% to about 100%, more preferably from about 75% to about 100%, and even more preferably from about 85% to about 100% of the dilution range. The effective foaming dilution range is calculated as follows: The suds generation curves of Graph I are generated by testing various dilutions of a dishwashing composition via the suds cylinder test herein. Such a curve can be generated either with or without dispensing from a foam-generating dispenser into the cylinders. "Effective foam" is defmed herein as foam which is at least half (50%) the maximum volume of foam generated for a given dishwashing composition according to the suds generation curve. Accordingly, in Graph I for when the foam-generating dispenser is not employed, effective foam is formed from about 28% to about 2% product concentration, which translates into an effective foaming dilution range of 26% (i.e., 28% - 2%). However, when the same dishwashing composition is employed with (i.e., dispensed from) the foam-generating dispenser, it can be seen that effective foam is generated from the point of dispensing (100% product concentration) until a product concentration of about 3% is reached. This is because the dishwashing kit generates foam at a substantially different dishwashing composition to water dilution than the dilution at which the maximum volume of foam is formed according to the suds cylinder test. Thus, the effective foaming dilution range when the dishwashing composition in Graph I is dispensed from a foaming dispenser is 97% (i.e., 100% - 3%).
- The dishwashing composition useful herein has an oil solubilization curve which is generated by the oil solubilization test defined herein. "Effective oil solubilization" is defined herein as oil solubilization which is at least 20% of the maximum amount of oil solubilized for a given dishwashing composition according to the oil solubilization curve which is plotted as a function of product concentration (i.e., dilution). Accordingly, in Graph I, the maximum amount of oil solubilized is about 4.7 at a 70% product concentration, and thus the effective oil solubilization is an amount of at least about 0.94. The effective oil solubilization occurs from dilution ranges of about 96% to about 42%, which translates into an effective oil solubilization dilution range of about 54%.
- As it can be seen in Graph I, there is virtually no overlap between the suds generation curve without a foam-generating dispenser and the effective oil solubilization dilution range. Similarly, it can be seen that absent a foam-generating dispenser, there is no overlap between the effective foaming dilution range (28% to 2%) and the effective oil solubilization dilution range (from 42% to 96%). In contrast, when a foam-generating dispenser is employed, the effective foaming dilution range (from 3% to 100%) completely (100%) overlaps the entire effective oil solubilization dilution range (from 42% to 96%). In a preferred embodiment, the effective foaming dilution range overlaps the effective oil solubilization dilution range, preferably the effective foaming dilution range overlaps the effective oil solubilization dilution range by at least about 10%, more preferably by from about 25% to about 100%, and even more preferably from about 50% to about 100%, especially in the case of a microemulsion or a protomicroemulsion. Furthermore, it is highly preferred that the effective foaming dilution range overlaps the point in the oil solubilization curve where the oil solubilization is at a maximum. Thus, the present invention encourages a user to use the product at a concentration/product dilution which more effectively solubilizes oil, and thereby optimizes cleaning.
- The present invention has recognized that such microemulsion dishwashing compositions require the container and foam-generating dispenser herein to achieve consumer-acceptable foaming at a dilution where the oil solubilization curve is more effective, and preferably maximized. Accordingly, it is preferred that when the dishwashing composition is employed with the container and foam-generating dispenser, an effective foam is generated at a dilution factor significantly different from the suds generation curve when the container and foam-generating dispenser is not employed.
- Hand dishwashing compositions, cleaning compositions, protomicroemulsion compositions and microemulsion compositions useful in the present invention are known in the art, as described in, for example,
WO 96/01305 A1 to Farnworth and Martin, published on January 18, 1996 US Patent No. 5,854,187 to Blum, et al., issued on Dec. 29, 1998 ;U.S. Patent No. 6,147,047 to Robbins, et al., issued on November 14, 2000 ;WO 99/58631 A1 to Robbins, et al., published on November 18, 1999 U.S. Patent No. 4,511,488 to Matta, issued on April 16, 1985 ;U.S. Patent No. 5,075,026 to Loth, et al., issued on Dec. 24, 1991 ;U.S. Patent No. 5,076,954 to Loth, et al., issued on December 31, 1991 ;U.S. Patent No. US05082584 to Loth, et al., issued on January 21, 1992 ;U.S. Patent No. 5,108,643 to Loth, et al., issued on April 28, 1992 ; co-pendingUS Patent Application No. 60/451064 US Patent Application No. 60/472941 - The high viscosity composition herein typically has a viscosity of at least about 0.05 Pa*s, preferably from about 0.05 Pa*s to about 10 Pa*s, more preferably from about 0.1 Pa*s to about 7 Pa*s, even more preferably from about 0.2 Pa*s to about 5 Pa*s, and yet even more preferably from about 0.3 Pa*s to about 4 Pa*s. When the high viscosity composition is dispensed from the foam-generating dispenser, a foam is produced.
- While the high viscosity composition is preferably sold within the container as a single item, this is not necessary, as refills, and separate components within the same kit are contemplated herein.
- It has further been discovered that a shaped applicator can surprisingly provide significantly improved results and ease of use as compared to a normal applicator. The shaped applicator is designed and sized to be easily held in the hand and is used to apply the foamed dishwashing composition to the surface to be cleaned, i.e., the dish. It has been found that if the foamed dishwashing composition is applied to a flat applicator, then the foamed dishwashing composition is quickly wiped onto the first dish contacted, but that little foamed dishwashing composition will remain on the flat applicator, for cleaning subsequent dishes. This makes the use of a foamed dishwashing composition both expensive, as composition mileage is significantly decreased, and tiresome, as new foamed dishwashing composition constantly needs to be applied to the flat applicator. In contrast, a shaped applicator which contains a receiving area, such as a protected indentation and/or a pocket, for the foamed dishwashing composition will more effectively hold and mete out the foamed dishwashing composition over time.
- As the shaped applicator will often be used for scrubbing, it is preferred that at least one surface thereof contain an abrasive surface. The shaped applicator is typically selected from a porous material such as a natural or artificial sponge, a brush, a metal scouring device, a woven material, a nonwoven material, an abrasive material, a plastic material, a cloth material, a microfiber cleaning material, a polymeric material, a resin material, a rubber material, or a mixture thereof, preferably a natural or artificial sponge, a brush, a metal scouring device, an abrasive material, a foam rubber material, a functional absorbent material (FAM), a polyurethane foam, and a mixture thereof, and more preferably a natural or artificial sponge, a brush, an abrasive material, a foam rubber material, and a mixture thereof, with all types of open-celled structures being highly preferred. Such shaped applicators are available from a variety of commercial sources, such as Minnesota Mining and Manufacturing Company (3M), St. Paul, Minnesota, U.S.A. If the shaped applicator is formed from a relatively delicate material, or a material which is easily torn, then it is preferable that this material be covered, partially or completely, with a water-permeable, more robust material, such as a nonwoven material. Also useful are surfaces formed from plastic or polymeric materials such as available from, for example, Minnesota Mining and Manufacturing Company (3M), St. Paul, Minnesota, U.S.A., and found on, for example, Scotch-Brite™ General Purpose Scrubbing Pads.
- Preferably, the FAM useful herein has an absorbent ability of more than about 20 g H2O/g, more preferably, 40 g H2O/g by weight of FAM. Such a preferred FAM is described in
U.S. Pat. No. 5,260,345 to DesMarais, et al., issued on November 9, 1993 orU.S. Pat. No. 5,889,893 to Dyer, et al., issued on May 4, 1999 . Examples of a preferred polyurethane is described inU.S. Pat. No. 5,089,534 to Thoen, et al., issued on February 18, 1992 ;U.S. Pat. No. 4,789,690 to Milovanovic-Lerik, et al., issued on December 6, 1988 ; Japanese Patent Publication No.10-182780 9-30215 to Yokohama Gum, published on February 4, 1997 5-70544 10-176073 - Preferably, the shaped applicator is not hard, but instead has at least one resilient portion, preferably a resilient portion which is covered by an abrasive surface. Such an optional resilient portion allows the user to vary the amount of contact, pressure, etc., between the scrubbing surface and the dish. The foamed dishwashing composition is thus preferably applied into or onto the shaped applicator directly from the foam-generating dispenser.
- Turning to
Fig. 2 , which shows a top perspective, cut-away view of a preferred embodiment of the shaped applicator, 12, herein, a sponge-type shaped applicator, 12, contains a receiving area, 50, to which the foamed dishwashing composition is applied for use. The receiving area, 50, is therefore typically bounded by a wall, 52, which protects the foamed composition from being quickly rubbed off of the shaped applicator, 12. The receiving area is preferably a concave indentation in the shaped applicator which may be of any shape and design which keeps the foamed dishwashing composition in contact with the shaped applicator. In a preferred embodiment, the receiving area contains a relatively steep concave wall or other structure which effectively keeps the foamed detergent in the receiving area and dispenses it over time during typical use. Typically the receiving area holds from about 1 mL to about 200 mL, preferably from about 2 mL to about 150 mL, and more preferably from about 5 mL to about 100 mL of foamed dishwashing composition. - In
Fig. 2 , the shaped applicator, 12, further contains a plurality of abrasive surfaces, 54, for scrubbing a dish. It is highly preferred that at least one abrasive surface be provided on the shaped applicator. -
Fig. 3 shows a perspective, cut-away view of a preferred embodiment of the shaped applicator, 12, which is formed as a sponge-type shaped applicator, 12, having a pocket-like receiving area, 50, whose internal dimensions are indicated by dashed lines. The foamed dishwashing composition is added to the receiving area, 50, via a mouth, 56, which may be permanently open, or may be closeable, as desired. An abrasive surface, 54, substantially covers the entire exterior of the shaped applicator, 12, to assist in removing stains from a dish. - The viscosity herein is measured on a Brookfield viscometer model # LVDVII+ at 20 °C. The spindle used for these measurements is a S31 spindle with the appropriate speed to measure products of different viscosities; e.g., 12 rpm to measure products of viscosity greater than 1 Pa*s; 30 rpm to measure products with viscosities between 0.5 Pa*s - 1 Pa*s; 60 rpm to measure products with viscosities less than 0.5 Pa*s.
- To measure the solubilization capacity, 10.0 g of product (this amount includes water, if testing at a specific dilution) to be tested is placed in a 25 mL scintillation vial. To this, 0.1 g food grade canola oil dyed with 0.045% of Pylakrome RED - LX1903 (a mixture of
SOLVENT RED 24 CAS# 85-83-6 andSOLVENT RED 26 CAS# 4477-79-6, available from Pylam Products, Tempe, Arizona, U.S.A.) dye is added, and the vial capped. The vial is shaken vigorously by hand for 5 seconds, and allowed to stand until it becomes clear via the ISO 7027 turbidity measuring procedure, or until 5 minutes has passed, whichever comes first. The ISO 7027 method measures turbidity at a wavelength of 880 nm with turbidity measuring equipment such as that available from Omega Engineering, Inc., Stamford, Connecticut, U.S.A. If the vial becomes clear, then more oil is added, in increments of 0.1 g, until the vial fails to become clear within the prescribed time. The % oil dissolution is recorded as the maximum amount of oil which was successfully solubilized (i.e., the vial is clear) by 10.0 g of product. Preferably, the dishwashing composition herein solubilizes at least about 1 g of dyed canola oil, more preferably at least about 3 g of dyed canola oil, and even more preferably at least about 4 g of dyed canola oil when tested at a 75% product concentration. - The sudsing profile can be measured by employing a suds cylinder tester (SCT), and using the data to plot a suds generation curve. The SCT has a set of 4 cylinders. Each cylinder is typically 30 cm long, and 10 cm in diameter. The cylinder walls are 0.5 cm thick, and the cylinder bottom is 1 cm thick. The SCT rotates a test solution in a closed cylinder, typically a plurality of clear plastic cylinders, at a rate of about 21 revolutions per minute, for 2 minutes, after which the suds height is measured. Soil may then be added to the test solution, agitated again, and the resulting suds height measured, again. Such a test may be used to simulate the initial sudsing profile of a composition, as well as its sudsing profile during use, as more soils are introduced from the surface being washed.
- The sudsing profile test is as follows:
- 1. Prepare a set of clean, dry, calibrated cylinders, and water having a water hardness of 136.8 parts per million (2.1 grains per liter), and having a temperature of 25 °C.
- 2. Add the appropriate amount of test composition to each cylinder and add water to make a total 500 mL of composition + water in each cylinder.
- 3. Seal the cylinders and place them in the SCT.
- 4. Turn on the SCT and rotate the cylinders for 2 minutes.
- 5. Within 1 minute, measure the height of the suds in centimeters.
- 6. The sudsing profile is the average level of suds, in cm, generated by the composition.
- The compositions according to the invention preferably have a sudsing profile maxima of at least about 2 cm, more preferably at least about 3 cm, and even more preferably about 4 cm.
- Foam to weight ratio is a measurement of the mL of foam generated per gram of product. Foam to weight ratio is measured as follows: a volumetric measuring device, such as a graduated cylinder is weighed to get a tare weight. Then, the product is dispensed, using the foam-generating dispenser, if appropriate, into a graduated cylinder a set number of strokes for non-continuous dispensing devices or for a set time period for continuous dispensing devices. 10 strokes for non-continuous devices (pumps, sprayers) or 10 seconds for continuous devices is the suggested duration. The dispensing rate in the test should be consistent with the dispensing rate during normal usage scenarios. For example, 120 strokes per minute for trigger sprayers, or 45 strokes per minute for palm pumps.
- The volume of foam generated is measured in mL using the volumetric measuring device.
- The volumetric measuring device containing the dispensed product is weighed in grams. The tare weight of the volumetric measuring device is subtracted from this weight. The result is the grams of the product dispensed. Finally, the foam to weight ratio in mL/g is calculated by dividing the volume of foam generated (in mL) by the weight product dispensed (in g).
- The foam to weight ratio of mL/g is easily converted to mL foam per mL of product by multiplying by the density of the high viscosity composition.
- Examples of the invention are set forth hereinafter by way of illustration and are not intended to be in any way limiting of the invention. The examples are not to be construed as limitations of the present invention since many variations thereof are possible without departing from its spirit and scope.
- A foam-generating kit contains a 300 mL hollow plastic container filled with a microemulsion dishwashing composition, and an attached T1 series foamer from Airspray, similar to that shown in
Fig. 1 . The T1 foamer is modified to include a third mesh, as seen inFig. 1 , at 41, at the tip of the nozzle. A shaped applicator according toFig. 3 is also included. When dispensed, the foamed dishwashing composition has a foam to weight ratio of about 3 mL/g, and the foam has a creamy, even look and feel. The foamed dishwashing composition is dispensed from the foaming dispenser into a pocket-type shaped applicator by sticking the nozzle of the foam-generating dispenser into the mouth of the shaped applicator, and pressing down on the activator. When used as described above, the dishwashing kit provides good mileage, and a foam which lasts throughout the normal use to clean dishes. However, if the foam-generating dispenser is not used (i.e., the dishwashing composition is merely poured out of the container), the effective foaming dilution range does not significantly overlap the effective oil solubilization dilution range. - An ionic-based microemulsion is provided, packaged with the foam-generating dispenser of Example 1.
- A foam-generating kit according to Example 1 is prepared, except that the T1 foamer is modified with a sponge at the tip, instead of a third mesh. The sponge is an artificial sponge which is cut into shape and is securely affixed immediately inside of the nozzle. The foam generated is creamy and aesthetically pleasing.
Claims (7)
- A foam-generating kit comprising:A. a non-aerosol container comprising a foam-generating dispenser for generating a foam; andB. a high viscosity dishwashing microemulsion composition having a viscosity of at least 0.05 Pa*s,wherein when employed with the high viscosity composition, the foam-generating dispenser generates a foam having a foam to weight ratio of greater than about 2 mL/g.
- The foam-generating kit according to Claim 1, wherein the high viscosity composition has a viscosity of from 0.05 Pa*s to 10 Pa*s.
- The foam-generating kit according to Claim 1, wherein the foam-generating dispenser comprises at least three meshes, wherein the high viscosity composition flows through the three meshes in series so as to generate the foam.
- The foam-generating kit according to Claim 1, wherein the high viscosity composition is a Newtonian Fluid.
- The foam-generating kit according to Claim 1, wherein the high viscosity composition further comprises an enzyme.
- The foam-generating kit according to Claim 1, further comprising a shaped applicator.
- The foam-generating kit of Claim 1, wherein the foam-generating dispenser comprises a sponge.
Applications Claiming Priority (10)
Application Number | Priority Date | Filing Date | Title |
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US45106403P | 2003-02-28 | 2003-02-28 | |
US45106303P | 2003-02-28 | 2003-02-28 | |
US451063P | 2003-02-28 | ||
US47294103P | 2003-05-23 | 2003-05-23 | |
US47295403P | 2003-05-23 | 2003-05-23 | |
US472954P | 2003-05-23 | ||
US50266803P | 2003-09-12 | 2003-09-12 | |
US50267303P | 2003-09-12 | 2003-09-12 | |
US502668P | 2003-09-12 | ||
PCT/US2004/005998 WO2004078901A1 (en) | 2003-02-28 | 2004-03-01 | Foam-generating kit containing a foam-generating dispenser and a high viscosity composition |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1599569A1 EP1599569A1 (en) | 2005-11-30 |
EP1599569B1 true EP1599569B1 (en) | 2009-04-22 |
EP1599569B2 EP1599569B2 (en) | 2012-04-11 |
Family
ID=43971306
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06111776A Withdrawn EP1826261A3 (en) | 2003-02-28 | 2004-03-01 | Foam-generating kit containing a foam-generating dispenser and a composition containing a high level of surfactant |
EP06111774A Withdrawn EP1862521A3 (en) | 2003-02-28 | 2004-03-01 | Foam-generating kit containing a foam-generating dispensor and a composition containing a high level of surfactant |
EP04716084A Expired - Lifetime EP1507845B1 (en) | 2003-02-28 | 2004-03-01 | Foam-generating kit containing a foam-generating dispenser and a composition containing a high level of surfactant |
EP04716083A Expired - Lifetime EP1599569B2 (en) | 2003-02-28 | 2004-03-01 | Foam-generating kit containing a foam-generating dispenser and a high viscosity composition |
Family Applications Before (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06111776A Withdrawn EP1826261A3 (en) | 2003-02-28 | 2004-03-01 | Foam-generating kit containing a foam-generating dispenser and a composition containing a high level of surfactant |
EP06111774A Withdrawn EP1862521A3 (en) | 2003-02-28 | 2004-03-01 | Foam-generating kit containing a foam-generating dispensor and a composition containing a high level of surfactant |
EP04716084A Expired - Lifetime EP1507845B1 (en) | 2003-02-28 | 2004-03-01 | Foam-generating kit containing a foam-generating dispenser and a composition containing a high level of surfactant |
Country Status (11)
Country | Link |
---|---|
EP (4) | EP1826261A3 (en) |
JP (4) | JP2006515380A (en) |
KR (2) | KR20050106051A (en) |
CN (1) | CN100519725C (en) |
AT (2) | ATE429481T1 (en) |
BR (2) | BRPI0407890A (en) |
CA (2) | CA2516744A1 (en) |
DE (2) | DE602004020745D1 (en) |
ES (2) | ES2279353T3 (en) |
MX (2) | MXPA05009196A (en) |
WO (2) | WO2004078901A1 (en) |
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- 2004-03-01 DE DE602004020745T patent/DE602004020745D1/en not_active Expired - Fee Related
- 2004-03-01 EP EP06111776A patent/EP1826261A3/en not_active Withdrawn
- 2004-03-01 WO PCT/US2004/005998 patent/WO2004078901A1/en active Application Filing
- 2004-03-01 AT AT04716083T patent/ATE429481T1/en not_active IP Right Cessation
- 2004-03-01 ES ES04716084T patent/ES2279353T3/en not_active Expired - Lifetime
- 2004-03-01 CA CA002516740A patent/CA2516740A1/en not_active Abandoned
- 2004-03-01 MX MXPA05009196A patent/MXPA05009196A/en active IP Right Grant
- 2004-03-01 WO PCT/US2004/005999 patent/WO2004078902A1/en active IP Right Grant
- 2004-03-01 JP JP2005518146A patent/JP2006515380A/en active Pending
- 2004-03-01 EP EP06111774A patent/EP1862521A3/en not_active Withdrawn
- 2004-03-01 CN CNB2004800051760A patent/CN100519725C/en not_active Expired - Fee Related
- 2004-03-01 ES ES04716083T patent/ES2324474T5/en not_active Expired - Lifetime
- 2004-03-01 EP EP04716084A patent/EP1507845B1/en not_active Expired - Lifetime
- 2004-03-01 MX MXPA05009194A patent/MXPA05009194A/en unknown
- 2004-03-01 DE DE602004004013T patent/DE602004004013T2/en not_active Expired - Lifetime
- 2004-03-01 BR BRPI0407890-0A patent/BRPI0407890A/en not_active Application Discontinuation
- 2004-03-01 EP EP04716083A patent/EP1599569B2/en not_active Expired - Lifetime
- 2004-03-01 BR BRPI0407843-8A patent/BRPI0407843A/en not_active Application Discontinuation
- 2004-03-01 JP JP2005518147A patent/JP2006513312A/en active Pending
- 2004-03-01 KR KR1020057016017A patent/KR20050106052A/en not_active Application Discontinuation
- 2004-03-01 AT AT04716084T patent/ATE350459T1/en not_active IP Right Cessation
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2009
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Also Published As
Publication number | Publication date |
---|---|
EP1826261A2 (en) | 2007-08-29 |
ES2279353T3 (en) | 2007-08-16 |
ES2324474T3 (en) | 2009-08-07 |
MXPA05009196A (en) | 2005-10-18 |
KR20050106051A (en) | 2005-11-08 |
EP1826261A3 (en) | 2010-05-26 |
WO2004078902A1 (en) | 2004-09-16 |
JP2010018805A (en) | 2010-01-28 |
CA2516744A1 (en) | 2004-09-16 |
JP2006515380A (en) | 2006-05-25 |
ES2324474T5 (en) | 2012-07-26 |
ATE350459T1 (en) | 2007-01-15 |
DE602004004013T2 (en) | 2007-10-04 |
BRPI0407890A (en) | 2006-03-01 |
EP1862521A2 (en) | 2007-12-05 |
EP1599569B2 (en) | 2012-04-11 |
CN100519725C (en) | 2009-07-29 |
JP2010018806A (en) | 2010-01-28 |
EP1507845B1 (en) | 2007-01-03 |
BRPI0407843A (en) | 2006-02-14 |
DE602004020745D1 (en) | 2009-06-04 |
CA2516740A1 (en) | 2004-09-16 |
WO2004078901A1 (en) | 2004-09-16 |
JP2006513312A (en) | 2006-04-20 |
EP1862521A3 (en) | 2010-05-26 |
CN1753986A (en) | 2006-03-29 |
EP1507845A1 (en) | 2005-02-23 |
KR20050106052A (en) | 2005-11-08 |
ATE429481T1 (en) | 2009-05-15 |
MXPA05009194A (en) | 2005-10-18 |
DE602004004013D1 (en) | 2007-02-15 |
EP1599569A1 (en) | 2005-11-30 |
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