[go: up one dir, main page]

EP2004785B1 - Liquid laundry detergents containing cationic hydroxyethyl cellulose polymer - Google Patents

Liquid laundry detergents containing cationic hydroxyethyl cellulose polymer Download PDF

Info

Publication number
EP2004785B1
EP2004785B1 EP07754834A EP07754834A EP2004785B1 EP 2004785 B1 EP2004785 B1 EP 2004785B1 EP 07754834 A EP07754834 A EP 07754834A EP 07754834 A EP07754834 A EP 07754834A EP 2004785 B1 EP2004785 B1 EP 2004785B1
Authority
EP
European Patent Office
Prior art keywords
aqueous liquid
liquid laundry
laundry detergent
detergent composition
composition according
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.)
Revoked
Application number
EP07754834A
Other languages
German (de)
French (fr)
Other versions
EP2004785A1 (en
Inventor
Peter Gerard Gray
Karel Jozef Maria Depoot
Luc Marie Willy Lievens
Falke Elisabeth Vanneste
Serge Omer Alfons Jean Thooft
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=38458031&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2004785(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP2004785A1 publication Critical patent/EP2004785A1/en
Application granted granted Critical
Publication of EP2004785B1 publication Critical patent/EP2004785B1/en
Revoked legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2079—Monocarboxylic acids-salts thereof
    • 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
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups

Definitions

  • the present invention relates to the use of cationic hydroxyethyl celluloses in liquid laundry detergent compositions for the laundering of textiles (e.g. clothing, linens, fabric).
  • a large number of liquid laundry detergents are available to today's consumers. While many of the detergents adequately remove dirt, soil and odors, effectively cleaning textiles (for example, clothing items) very well in traditional horizontal axis and/or vertical access washing machines, there is an ongoing desire to provide consumers with additional fabric care benefits resulting from their laundry detergent and through the wash cycle, such as softening, color protection, protection from fabric wear, and gentle treatment of fine textiles (such as wool and silk).
  • Cationic polymers such as cationic hydroxyethyl cellulose polymers are traditionally commercially supplied for inclusion in detergent compositions, particularly hair products such as shampoos. More recently, such cationic polymers have been experimented with in heavy duty liquid laundry detergents to enhance deposition of other known materials that provide softening benefits to laundered textiles but do not deposit well during traditional washing machine cycles. Cationic celluloses are known from WO 2004022686 A1 and WO 2004113484 A1 .
  • cationic polymers may in combination with surfactant and fatty acid provide fabric care benefits to laundered textiles, when included in selected aqueous liquid laundry detergent compositions.
  • the present invention relates to aqueous liquid laundry detergent compositions useful for cleaning delicate fabrics comprising from 0.05% to 0.4%, by weight of the composition, of a cationic hydroxyethyl cellulose polymer having a degree of substitution of the cationic charge of from 0.01 to 0.20; from 5% to 30%, by weight of the composition, of a surfactant comprising at least one anionic surfactant and at least one nonionic surfactant; and from 2.5% to 7%, by weight of the composition, of fatty acid.
  • the present invention further relates to aqueous liquid laundry detergent compositions useful for cleaning delicate fabrics, comprising from 0.15% to 0.2%, by weight of the composition, of a cationic hydroxyethyl cellulose polymer having a molecular weight of from 200,000 to 800,000 and a degree of substitution of the cationic charge of from 0.01 to 0.20; from 7% to about 15%, by weight of the composition, of a surfactant comprising an alkyl ethoxylate sulfate surfactant and at least one nonionic surfactant; from 2.5 % to 7%, by weight of the composition, of fatty acid; wherein the composition is substantially free of optical brightener; and wherein the composition is substantially free of enzymes having cellulytic activity.
  • the present invention also relates to the above compositions wherein the cationic hydroxyethyl cellulose polymer has a degree of substitution of the cationic charge of from 0.01 to 0.1.
  • the present invention also relates to the above compositions wherein the cationic hydroxyethyl cellulose polymer has a degree of substitution of the cationic charge of from 0.01. to less than 0.1.
  • the present invention also relates to the above compositions wherein the cationic hydroxyethyl cellulose polymer has a molecular weight of from about 200,000 to 800,000.
  • the present invention also relates to the above compositions wherein the composition is substantially free of enzymes having cellulytic activity.
  • the present invention also relates to the above compositions wherein the composition is substantially free of optical brightener.
  • the present invention also relates to the above compositions wherein the composition comprises from 0.1% to 0.3%, by weight of the composition, of the cationic hydroxyethyl cellulose polymer.
  • the present invention also relates to the above compositions wherein the composition comprises from 0.15% to 0.2%, by weight of the composition, of the cationic hydroxyethyl cellulose polymer.
  • the present invention also relates to the above compositions wherein the composition comprises from 7% to 15%, by weight of the composition, of the surfactant.
  • the present invention also relates to the above compositions wherein the composition comprises from 2.5% 7%, by weight of the composition, of the fatty acid.
  • the present invention also relates to the above compositions wherein the composition further comprises an opacifying agent.
  • the present invention also relates to the above compositions wherein the anionic surfactant is selected from alkyl ethoxylate sulfates and linear alkyl benzene sulfonates.
  • the present invention also relates to the above compositions wherein the anionic surfactant is selected from alkyl ethoxylate sulfates having a chain length of from 12 to 14 and a degree of ethoxylation of from 1 to 8.
  • the present invention also relates to the above compositions wherein the composition further comprises a suds suppressor.
  • the present invention also relates to the above compositions wherein the composition is substantially free of enzymes.
  • the present invention also relates to the above compositions wherein the composition further comprises a laundry adjunct ingredient selected from soil release polymers, dye transfer inhibiting polymers, chelants, performance boosting polymers, preservatives, stabilizers, structurants, viscosity modifiers, and citric acid.
  • a laundry adjunct ingredient selected from soil release polymers, dye transfer inhibiting polymers, chelants, performance boosting polymers, preservatives, stabilizers, structurants, viscosity modifiers, and citric acid.
  • the present invention also relates to the above compositions wherein the composition further comprises from 0.01 to 1% of a structurant that is selected from hydrogenated castor oil.
  • the present invention further relates to use of the above compositions for handwashing delicate fabrics.
  • the present invention further relates to use of the above compositions for machine washing of delicate fabrics, wherein the machine washing occurs at a delicate machine setting.
  • the present invention relates to aqueous liquid laundry detergent compositions comprising a surfactant containing at least an anionic and an nonionic surfactant, fatty acid, and a cationic hydroxyethyl cellulose polymer having a degree of substitution of the cationic charge of from 0.01 to 0.20 and a molecular weight of from 200,000 to 800,000.
  • the lower charge density of the cationic hydroxyethyl cellulose polymer is important in providing a liquid laundry detergent product containing relatively low levels of surfactant (at least an anionic surfactant and a nonionic surfactant) that is capable of offering both fabric care benefits and good cleaning to laundered textiles.
  • compositions and methods of the present invention are advantageous in providing low cost liquid laundry detergents compositions offering good cleaning along with softening benefits through the wash to textiles such as clothing and fabrics. Additional objects and advantages will be apparent in view of the detailed description of the invention.
  • the aqueous liquid laundry detergent compositions of the present invention contain from 0.05% to 0.4%, by weight of the composition, of a cationic hydroxyethyl cellulose polymer. In one embodiment, the composition contains from 0.1% to 0.3%, by weight of the composition, alternatively from 0.15% to 0.2%, of the cationic hydroxyethyl cellulose polymer.
  • the cationic hydroxyethyl cellulose polymers useful herein have a degree of substitution of the cationic charge of from 0.01 (one cationic charge per 100 polymer repeating units) to 0.20 (two cationic charges per 10 polymer repeating units).
  • the cationic hydroxyethyl cellulose polymers useful herein have a degree of substitution of the cationic charge of from 0.01 to 0.1, more preferably a degree of substitution of the cationic charge of less than 0.1, in one embodiment from 0.01 to less than 0.1.
  • the positive charges could be on the backbone of the polymers or the side chains of polymers.
  • Cationic hydroxyethyl cellulose polymers useful include those which may or may not be hydrophobically-modified and have a molecular weight of from 200,000 to 800,000. These cationic materials have repeating substituted anhydroglucose units that correspond to the general Structural Formula I as follows:
  • Water-soluble anions useful herein include C8-C24 alkyl sulfates, C8-C24 alkyl alkoxy sulfates, preferably alkyl ethoxy sulfates, C8-C24 alkyl sulfonates, C8-C16 alkyl benzene sulfonates, xylene sulfonates, toluene sulfonates, cumene sulfonates, fatty alkyl carboxylates, chlorine ions, bromine ions, or mixtures thereof, while chlorine and/or bromine ions are preferred.
  • the cationic hydroxyethyl cellulose may have alkyl substitution on the anhydroglucose rings of the polymer ranges. When such alkyl substitution is present, it may be from 0% to 5% per glucose unit, more preferably from 0% to 2% per glucose unit, of the polymeric material.
  • the cationic cellulose may lightly cross-linked with a dialdehyde such as glyoxyl to prevent forming lumps, nodules or other agglomerations when added to water at ambient temperatures.
  • a dialdehyde such as glyoxyl
  • the cationic hydroxyethyl cellulose ethers of Structural Formula I likewise include those which are commercially available and further include materials which can be prepared by conventional chemical modification of commercially available materials.
  • Commercially available cellulose ethers of the Structural Formula I type useful herein include the LR 400 and LK 400 polymers, preferably the LK 400 polymers, which are marketed by Dow Chemical.
  • the aqueous liquid laundry detergent products of the present invention comprise from 5% to 30%, by weight of the composition, of surfactant. In one embodiment, the aqueous liquid laundry detergent products of the present invention comprise from about 5% to 20%, alternatively from 7% to 15%, by weight of the composition, of surfactant.
  • the surfactant of the detergent products of the present invention includes at least one anionic surfactant and at least one nonionic surfactant.
  • the detergent products of the present invention may also include other surfactants such as zwitterionic, ampholytic or cationic type or can comprise compatible mixtures of these types in conjunction with the anionic surfactant and nonionic surfactant.
  • the anionic surfactant is selected from alkyl ethoxylate sulfates and linear alkyl benzene sulfonates. In another embodiment, the anionic surfactant is selected from alkyl ethoxylate- sulfates having a chain length of from 12 to 14 and a degree of ethoxylation of from 1 to 8.
  • Detergent surfactants useful herein include those described in U.S. Patent 3,664,961, Norris, issued May 23, 1972 , U.S. Patent 3,919;678, Laughlin et al., issued December 30, 1975 , U.S. Patent 4,222,905, Cockrell, issued September 16, 1980 , and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980 .
  • Anionic surfactants which are suitable for use herein include the water-soluble salts, preferably the alkali metal, and ammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from 10 to 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyl is the alkyl portion of acyl groups.
  • this group of synthetic surfactants are a) the sodium, potassium and ammonium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 8 -C 18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; b) the sodium, potassium and ammonium alkyl polyethoxylate sulfates, particularly those in which the alkyl group contains from 10 to 22, preferably from 12 to 18 carbon atoms, and wherein the polyethoxylate chain contains from 1 to 15, preferably 1 to 6 ethoxylate moieties; and c) the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from 9 to 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S.
  • Patents 2,220,099 and 2,477,383 are also useful.
  • linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from 11 to 13, abbreviated as C 11-13 LAS.
  • nonionic surfactants useful herein include those of the formula R 1 (OC 2 H 4 ) n OH, wherein R 1 is a C 10 -C 16 alkyl group or a C 8 -C 12 alkyl phenyl group, and n is from 3 to 80.
  • the nonionic surfactants are condensation products of C 12 -C 15 alcohols with from 5 to 20 moles of ethylene oxide per mole of alcohol, e.g., C 12 -C 13 alcohol condensed with 6.5 moles of ethylene oxide per mole of alcohol.
  • Nonionic surfactants include polyhydroxy fatty acid amides of the formula: wherein R is a C 9-17 alkyl or alkenyl, R 1 is a methyl group and Z is glycidyl derived from a reduced sugar or alkoxylated derivative thereof. Examples are N-methyl N-1-deoxyglucityl cocoamide and N-methyl N-1-deoxyglucityl oleamide. Processes for making polyhydroxy fatty acid amides are known and can be found in Wilson, U.S. Patent 2,965,576 and Schwartz, U.S. Patent 2,703,798
  • aqueous liquid detergent compositions of the present invention contain from 2.5% to 7%, by weight of the composition, of fatty acid.
  • fatty acids refers to a range of fatty acids including those that contain from 8 to 24 carbon atoms, alternatively from 12 to 18 carbon atoms.
  • the fatty acids useful herein include those that are both saturated and unsaturated, as well as mixtures thereof.
  • the aqueous liquid detergent compositions of the present invention are substantially free of optical brightener.
  • substantially free of optical brightener means that the aqueous liquid detergent composition contains less than 0.0001% of optical brightener, preferably no detectable amount of optical brightener.
  • the aqueous liquid detergent compositions of the present invention are substantially free of enzymes containing cellulytic activity.
  • the aqueous liquid detergent compositions of the present invention may comprise an enzyme that is free of cellulytic activity.
  • substantially free of enzymes containing cellulytic activity means that the aqueous liquid detergent composition contains less than 0.001% of an enzyme containing cellulytic activity, preferably no detectable amount of enzyme containing cellulytic activity.
  • cellulase present in certain enzymes will hydrolyze the cationic hydroxyethyl cellulose polymer molecule, thereby destroying the fabric care benefits otherwise associated with the cationic hydroxyethyl cellulose polymer.
  • aqueous liquid detergent compositions of the present invention that do contain enzymes having cellulytic activity as long as the composition also contains an effective amount of a cellulase inhibitor.
  • the aqueous liquid detergent compositions of the present invention may contain up to 5 mg by weight, more typically from 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically comprise from 0.001% to 5%, preferably from 0.01% to 1% by weight of the composition, of a commercial enzyme preparation. Protease enzymes are preferably present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. Higher active levels may be desirable in highly concentrated detergent formulations.
  • AU Anson units
  • Selected proteases which are useful herein include the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis.
  • a preferred protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo.
  • Other suitable proteases include ALCALASE® and SAVINASE® from Novo and MAXATASE® from International Bio-Synthetics, Inc., The Netherlands.
  • a protease having decreased adsorption and increased hydrolysis may be included in the compositions herein, as described in WO 9507791 to Procter & Gamble.
  • Another recombinant trypsin-like protease for detergents suitable herein is described in WO 9425583 to Novo.
  • amylase Any known amylase may be included in the compositions of the present invention.
  • Suitable lipase enzymes for use herein include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1,372,034 . See also lipases in Japanese Patent Application 53,20487, laid open Feb. 24, 1978 . This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," or "Amano-P.” Other suitable commercial lipases include Amano-CBS, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • LEPOLASE® enzyme derived from Humicola lanuginosa and commercially available from Novo, see also EP 341,947 is a preferred lipase for use herein.
  • compositions of the present invention contain a compatible enzyme
  • the compositions preferably also contain an effective enzyme stabilizing system.
  • the enzymecontaining aqueous liquid laundry detergent compositions herein may therefore optionally also comprise from 0.001% to 10%, preferably from 0.005% to 8%, most preferably from 0.01% to 6%, by weight of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the enzymes useful herein. Such a system may be inherently provided by other formulation actives, or be added separately, e.g., by the formulator or by a manufacturer of enzymes.
  • Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, or mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.
  • the enzyme stabilizing system should also include the cellulase inhibitor.
  • compositions may also comprise from 0.1% to 80% by weight of a builder.
  • compositions of the present invention contain from 1% to 20% by weight of the builder component.
  • Detergent builders are well known in the art and can comprise, for example, phosphate salts as well as various organic and inorganic nonphosphorus builders.
  • Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates.
  • polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
  • Other suitable polycarboxylates for use herein are the polyacetal carboxylates described in U.S.
  • Polycarboxylate builders useful herein include the oxydisuccinates and the ether carboxylate builder compositions comprising a combination of tartrate monosuccinate and tartrate disuccinate described in U.S. Patent 4.663.071, Bush et al., issued May 5, 1987 .
  • nonphosphorus, inorganic builders examples include the silicates, aluminosilicates, borates and carbonates.
  • aqueous liquid detergent compositions of the present invention may be made by any known process, including those processes disclosed in U.S. Patent Nos. 6,274,540 and 6,306,817 ; WIPO Publication Nos. WO 01/16237 published March 8, 2001 ; and WO 01/16263 published on March 8, 2001 .
  • the laundry detergent compositions herein are formulated as aqueous liquid laundry detergents.
  • the detergent compositions herein therefore comprise from 3% to 98%, alternatively from 5% to 95%, by weight of the liquid detergent composition, of an aqueous liquid carrier which is preferably water.
  • the liquid laundry compositions according to the present invention should provide a wash solution pH from 6 to 10, more preferably from 7 to 9, in order to maintain a preferred cleaning and fabric care performance by the aqueous liquid detergents according to the present invention.
  • the cleaning compositions may contain alkalinizing agents, pH control agents and/or buffering agents.
  • the laundry detergents herein may further comprise a laundry adjunct ingredient.
  • Suitable laundry adjuncts are known in the art and include soil release polymers, dye transfer inhibiting polymers, chelants, performance boosting polymers, preservatives, stabilizers, structurants, viscosity modifiers, citric acid, and benefit agent containing delivery particles.
  • Benefit agent containing delivery particles useful herein comprise a core material and a wall material that at least partially surrounds said core material.
  • the phrase "benefit agent containing delivery particle” encompasses microcapsules, including perfume microcapsules (where the core material includes perfume).
  • the terms "particle”, “benefit agent containing delivery particle”, “capsule” and “microcapsule” are synonymous.
  • aqueous liquid detergent formulations may be made by traditional methods and means as known to one of ordinary skill in the art.
  • Ingredient 1 2 3 4 Wt.% Wt% Wt% Wt%
  • Anionic surfactant 7.0 3.0 8.0 3.0 Citric Acid 2.0 3.0 2.5 3.0 Fatty acid 4.5 3.0 6.0 3.0 PVPVI 0.02 0.03 0.05 0.03

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Molecular Biology (AREA)
  • Detergent Compositions (AREA)

Abstract

Aqueous liquid laundry detergent compositions useful for cleaning fabrics wherein the compositions contain from about 0.05% to about 0.4%, by weight of the composition, of a cationic hydroxyethyl cellulose polymer having a degree of substitution of the cationic charge of from about 0.01 to about 0.20; from about 5% to about 30%, by weight of the composition, of a surfactant comprising at least one anionic surfactant and at least one nonionic surfactant; and from about 2% to about 15%, by weight of the composition, of fatty acid. Use of such aqueous liquid laundry detergent compositions for handwashing delicate fabrics. Use of such aqueous liquid laundry detergent compositions for machine washing of delicate fabrics, wherein the machine washing occurs at a delicate machine setting.

Description

    FIELD OF THE INVENTION
  • The present invention relates to the use of cationic hydroxyethyl celluloses in liquid laundry detergent compositions for the laundering of textiles (e.g. clothing, linens, fabric).
    • BACKGROUND OF THE INVENTION
  • A large number of liquid laundry detergents are available to today's consumers. While many of the detergents adequately remove dirt, soil and odors, effectively cleaning textiles (for example, clothing items) very well in traditional horizontal axis and/or vertical access washing machines, there is an ongoing desire to provide consumers with additional fabric care benefits resulting from their laundry detergent and through the wash cycle, such as softening, color protection, protection from fabric wear, and gentle treatment of fine textiles (such as wool and silk).
  • Cationic polymers such as cationic hydroxyethyl cellulose polymers are traditionally commercially supplied for inclusion in detergent compositions, particularly hair products such as shampoos. More recently, such cationic polymers have been experimented with in heavy duty liquid laundry detergents to enhance deposition of other known materials that provide softening benefits to laundered textiles but do not deposit well during traditional washing machine cycles. Cationic celluloses are known from WO 2004022686 A1 and WO 2004113484 A1 .
  • It has now been surprisingly discovered that such cationic polymers may in combination with surfactant and fatty acid provide fabric care benefits to laundered textiles, when included in selected aqueous liquid laundry detergent compositions.
    • SUMMARY OF THE INVENTION
  • The present invention relates to aqueous liquid laundry detergent compositions useful for cleaning delicate fabrics comprising from 0.05% to 0.4%, by weight of the composition, of a cationic hydroxyethyl cellulose polymer having a degree of substitution of the cationic charge of from 0.01 to 0.20; from 5% to 30%, by weight of the composition, of a surfactant comprising at least one anionic surfactant and at least one nonionic surfactant; and from 2.5% to 7%, by weight of the composition, of fatty acid.
  • The present invention further relates to aqueous liquid laundry detergent compositions useful for cleaning delicate fabrics, comprising from 0.15% to 0.2%, by weight of the composition, of a cationic hydroxyethyl cellulose polymer having a molecular weight of from 200,000 to 800,000 and a degree of substitution of the cationic charge of from 0.01 to 0.20; from 7% to about 15%, by weight of the composition, of a surfactant comprising an alkyl ethoxylate sulfate surfactant and at least one nonionic surfactant; from 2.5 % to 7%, by weight of the composition, of fatty acid; wherein the composition is substantially free of optical brightener; and wherein the composition is substantially free of enzymes having cellulytic activity.
  • The present invention also relates to the above compositions wherein the cationic hydroxyethyl cellulose polymer has a degree of substitution of the cationic charge of from 0.01 to 0.1.
  • The present invention also relates to the above compositions wherein the cationic hydroxyethyl cellulose polymer has a degree of substitution of the cationic charge of from 0.01. to less than 0.1.
  • The present invention also relates to the above compositions wherein the cationic hydroxyethyl cellulose polymer has a molecular weight of from about 200,000 to 800,000.
  • The present invention also relates to the above compositions wherein the composition is substantially free of enzymes having cellulytic activity.
  • The present invention also relates to the above compositions wherein the composition is substantially free of optical brightener.
  • The present invention also relates to the above compositions wherein the composition comprises from 0.1% to 0.3%, by weight of the composition, of the cationic hydroxyethyl cellulose polymer.
  • The present invention also relates to the above compositions wherein the composition comprises from 0.15% to 0.2%, by weight of the composition, of the cationic hydroxyethyl cellulose polymer.
  • The present invention also relates to the above compositions wherein the composition comprises from 7% to 15%, by weight of the composition, of the surfactant.
  • The present invention also relates to the above compositions wherein the composition comprises from 2.5% 7%, by weight of the composition, of the fatty acid.
  • The present invention also relates to the above compositions wherein the composition further comprises an opacifying agent.
  • The present invention also relates to the above compositions wherein the anionic surfactant is selected from alkyl ethoxylate sulfates and linear alkyl benzene sulfonates.
  • The present invention also relates to the above compositions wherein the anionic surfactant is selected from alkyl ethoxylate sulfates having a chain length of from 12 to 14 and a degree of ethoxylation of from 1 to 8.
  • The present invention also relates to the above compositions wherein the composition further comprises a suds suppressor.
  • The present invention also relates to the above compositions wherein the composition is substantially free of enzymes.
  • The present invention also relates to the above compositions wherein the composition further comprises a laundry adjunct ingredient selected from soil release polymers, dye transfer inhibiting polymers, chelants, performance boosting polymers, preservatives, stabilizers, structurants, viscosity modifiers, and citric acid.
  • The present invention also relates to the above compositions wherein the composition further comprises from 0.01 to 1% of a structurant that is selected from hydrogenated castor oil.
  • The present invention further relates to use of the above compositions for handwashing delicate fabrics.
  • The present invention further relates to use of the above compositions for machine washing of delicate fabrics, wherein the machine washing occurs at a delicate machine setting.
    • DETAILED DESCRIPTION OF THE INVENTION
  • All percentages, ratios and proportions herein are on a weight basis unless otherwise indicated.
  • The present invention relates to aqueous liquid laundry detergent compositions comprising a surfactant containing at least an anionic and an nonionic surfactant, fatty acid, and a cationic hydroxyethyl cellulose polymer having a degree of substitution of the cationic charge of from 0.01 to 0.20 and a molecular weight of from 200,000 to 800,000.
  • Without being limited by theory, it is now believed that the lower charge density of the cationic hydroxyethyl cellulose polymer is important in providing a liquid laundry detergent product containing relatively low levels of surfactant (at least an anionic surfactant and a nonionic surfactant) that is capable of offering both fabric care benefits and good cleaning to laundered textiles.
  • The compositions and methods of the present invention are advantageous in providing low cost liquid laundry detergents compositions offering good cleaning along with softening benefits through the wash to textiles such as clothing and fabrics. Additional objects and advantages will be apparent in view of the detailed description of the invention.
    • Cationic Hydroxyethyl Cellulose Polymers
  • The aqueous liquid laundry detergent compositions of the present invention contain from 0.05% to 0.4%, by weight of the composition, of a cationic hydroxyethyl cellulose polymer. In one embodiment, the composition contains from 0.1% to 0.3%, by weight of the composition, alternatively from 0.15% to 0.2%, of the cationic hydroxyethyl cellulose polymer.
  • The cationic hydroxyethyl cellulose polymers useful herein have a degree of substitution of the cationic charge of from 0.01 (one cationic charge per 100 polymer repeating units) to 0.20 (two cationic charges per 10 polymer repeating units). Preferably, the cationic hydroxyethyl cellulose polymers useful herein have a degree of substitution of the cationic charge of from 0.01 to 0.1, more preferably a degree of substitution of the cationic charge of less than 0.1, in one embodiment from 0.01 to less than 0.1. The positive charges could be on the backbone of the polymers or the side chains of polymers.
  • Cationic hydroxyethyl cellulose polymers useful include those which may or may not be hydrophobically-modified and have a molecular weight of from 200,000 to 800,000. These cationic materials have repeating substituted anhydroglucose units that correspond to the general Structural Formula I as follows:
    Figure imgb0001
    • STRUCTURAL FORMULA I
  • Wherein R1, R2, R3 are each independently H, CH3, C8-24 alkyl (linear or branched),
    Figure imgb0002
    or mixtures thereof; wherein n is from about 1 to about 10; Rx is H, CH3,
    C8-24 alkyl (linear or branched),
    Figure imgb0003
    or mixtures thereof, wherein Z is a water soluble anion, preferably a chlorine ion and/or a bromine ion; R5 is H, CH3, CH2CH3, or mixtures thereof; R7 is CH3, CH2CH3, a phenyl group, a C8-24 alkyl group (linear or branched), or mixture thereof; and
    R8 and R9 are each independently CH3, CH2CH3, phenyl, or mixtures thereof:
    R4 is H,
    Figure imgb0004
    or mixtures thereof wherein P is a repeat unit of an addition polymer formed by radical polymerization of a cationic monomer such as
    Figure imgb0005
    wherein Z' is a water-soluble anion, preferably chlorine ion, bromine ion or mixtures thereof and q is from 1 to 10.
  • Water-soluble anions useful herein include C8-C24 alkyl sulfates, C8-C24 alkyl alkoxy sulfates, preferably alkyl ethoxy sulfates, C8-C24 alkyl sulfonates, C8-C16 alkyl benzene sulfonates, xylene sulfonates, toluene sulfonates, cumene sulfonates, fatty alkyl carboxylates, chlorine ions, bromine ions, or mixtures thereof, while chlorine and/or bromine ions are preferred.
  • The cationic hydroxyethyl cellulose may have alkyl substitution on the anhydroglucose rings of the polymer ranges. When such alkyl substitution is present, it may be from 0% to 5% per glucose unit, more preferably from 0% to 2% per glucose unit, of the polymeric material.
  • The cationic cellulose may lightly cross-linked with a dialdehyde such as glyoxyl to prevent forming lumps, nodules or other agglomerations when added to water at ambient temperatures.
  • The cationic hydroxyethyl cellulose ethers of Structural Formula I likewise include those which are commercially available and further include materials which can be prepared by conventional chemical modification of commercially available materials. Commercially available cellulose ethers of the Structural Formula I type useful herein include the LR 400 and LK 400 polymers, preferably the LK 400 polymers, which are marketed by Dow Chemical.
    • Surfactant
  • The aqueous liquid laundry detergent products of the present invention comprise from 5% to 30%, by weight of the composition, of surfactant. In one embodiment, the aqueous liquid laundry detergent products of the present invention comprise from about 5% to 20%, alternatively from 7% to 15%, by weight of the composition, of surfactant.
  • The surfactant of the detergent products of the present invention includes at least one anionic surfactant and at least one nonionic surfactant. The detergent products of the present invention may also include other surfactants such as zwitterionic, ampholytic or cationic type or can comprise compatible mixtures of these types in conjunction with the anionic surfactant and nonionic surfactant.
  • In one embodiment, the anionic surfactant is selected from alkyl ethoxylate sulfates and linear alkyl benzene sulfonates. In another embodiment, the anionic surfactant is selected from alkyl ethoxylate- sulfates having a chain length of from 12 to 14 and a degree of ethoxylation of from 1 to 8.
  • Anionic surfactants which are suitable for use herein include the water-soluble salts, preferably the alkali metal, and ammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from 10 to 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups.) Examples of this group of synthetic surfactants are a) the sodium, potassium and ammonium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8-C18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; b) the sodium, potassium and ammonium alkyl polyethoxylate sulfates, particularly those in which the alkyl group contains from 10 to 22, preferably from 12 to 18 carbon atoms, and wherein the polyethoxylate chain contains from 1 to 15, preferably 1 to 6 ethoxylate moieties; and c) the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from 9 to 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383 . Also useful are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from 11 to 13, abbreviated as C11-13 LAS.
  • In one embodiment, nonionic surfactants useful herein include those of the formula R1(OC2H4)nOH, wherein R1 is a C10-C16 alkyl group or a C8-C12 alkyl phenyl group, and n is from 3 to 80. In one embodiment, the nonionic surfactants are condensation products of C12-C15 alcohols with from 5 to 20 moles of ethylene oxide per mole of alcohol, e.g., C12-C13 alcohol condensed with 6.5 moles of ethylene oxide per mole of alcohol.
  • Additional suitable nonionic surfactants include polyhydroxy fatty acid amides of the formula:
    Figure imgb0006
     wherein R is a C9-17 alkyl or alkenyl, R1 is a methyl group and Z is glycidyl derived from a reduced sugar or alkoxylated derivative thereof. Examples are N-methyl N-1-deoxyglucityl cocoamide and N-methyl N-1-deoxyglucityl oleamide. Processes for making polyhydroxy fatty acid amides are known and can be found in Wilson, U.S. Patent 2,965,576 and Schwartz, U.S. Patent 2,703,798
    • Fatty Acid
  • The aqueous liquid detergent compositions of the present invention contain from 2.5% to 7%, by weight of the composition, of fatty acid.
  • As used herein, "fatty acids" refers to a range of fatty acids including those that contain from 8 to 24 carbon atoms, alternatively from 12 to 18 carbon atoms. The fatty acids useful herein include those that are both saturated and unsaturated, as well as mixtures thereof.
    • Free of Optical Brightener
  • In one embodiment, the aqueous liquid detergent compositions of the present invention are substantially free of optical brightener. As used herein, "substantially free of optical brightener" means that the aqueous liquid detergent composition contains less than 0.0001% of optical brightener, preferably no detectable amount of optical brightener.
    • Enzymes having Cellulytic Activity
  • In one embodiment, the aqueous liquid detergent compositions of the present invention are substantially free of enzymes containing cellulytic activity. The aqueous liquid detergent compositions of the present invention may comprise an enzyme that is free of cellulytic activity. As used herein, "substantially free of enzymes containing cellulytic activity" means that the aqueous liquid detergent composition contains less than 0.001% of an enzyme containing cellulytic activity, preferably no detectable amount of enzyme containing cellulytic activity.
  • Without being limited by theory, it is believed that the cellulase present in certain enzymes will hydrolyze the cationic hydroxyethyl cellulose polymer molecule, thereby destroying the fabric care benefits otherwise associated with the cationic hydroxyethyl cellulose polymer.
  • However, where desirable, it is possible to formulate aqueous liquid detergent compositions of the present invention that do contain enzymes having cellulytic activity as long as the composition also contains an effective amount of a cellulase inhibitor.
    • Enzymes
  • When incorporated into the formulations of the present invention, enzymes are included at levels sufficient to provide a "cleaning-effective amount". The term "cleaning-effective amount" refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on substrates such as fabrics. In one embodiment, the aqueous liquid detergent compositions of the present invention may contain up to 5 mg by weight, more typically from 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically comprise from 0.001% to 5%, preferably from 0.01% to 1% by weight of the composition, of a commercial enzyme preparation. Protease enzymes are preferably present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. Higher active levels may be desirable in highly concentrated detergent formulations.
  • Selected proteases which are useful herein include the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis. A preferred protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include ALCALASE® and SAVINASE® from Novo and MAXATASE® from International Bio-Synthetics, Inc., The Netherlands. When desired, a protease having decreased adsorption and increased hydrolysis may be included in the compositions herein, as described in WO 9507791 to Procter & Gamble. Another recombinant trypsin-like protease for detergents suitable herein is described in WO 9425583 to Novo.
  • Any known amylase may be included in the compositions of the present invention.
  • Suitable lipase enzymes for use herein include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1,372,034 . See also lipases in Japanese Patent Application 53,20487, laid open Feb. 24, 1978 . This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," or "Amano-P." Other suitable commercial lipases include Amano-CBS, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. LEPOLASE® enzyme derived from Humicola lanuginosa and commercially available from Novo, see also EP 341,947 , is a preferred lipase for use herein.
  • When the compositions of the present invention contain a compatible enzyme, the compositions preferably also contain an effective enzyme stabilizing system. The enzymecontaining aqueous liquid laundry detergent compositions herein may therefore optionally also comprise from 0.001% to 10%, preferably from 0.005% to 8%, most preferably from 0.01% to 6%, by weight of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is compatible with the enzymes useful herein. Such a system may be inherently provided by other formulation actives, or be added separately, e.g., by the formulator or by a manufacturer of enzymes. Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, or mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition. Where enzymes having cellulytic activity are included into the aqueous liquid laundry detergent compositions herein, the enzyme stabilizing system should also include the cellulase inhibitor.
    • Builder
  • The compositions may also comprise from 0.1% to 80% by weight of a builder. In one embodiment, the compositions of the present invention contain from 1% to 20% by weight of the builder component. Detergent builders are well known in the art and can comprise, for example, phosphate salts as well as various organic and inorganic nonphosphorus builders.
  • Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates. Examples of polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid. Other suitable polycarboxylates for use herein are the polyacetal carboxylates described in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al , and U.S. Patent 4,246,495, issued March 27, 1979 to Crutchfield et al. Polycarboxylate builders useful herein include the oxydisuccinates and the ether carboxylate builder compositions comprising a combination of tartrate monosuccinate and tartrate disuccinate described in U.S. Patent 4.663.071, Bush et al., issued May 5, 1987 .
  • Examples of suitable nonphosphorus, inorganic builders include the silicates, aluminosilicates, borates and carbonates.
    • Aqueous liquid laundry detergents
  • The aqueous liquid detergent compositions of the present invention may be made by any known process, including those processes disclosed in U.S. Patent Nos. 6,274,540 and 6,306,817 ; WIPO Publication Nos. WO 01/16237 published March 8, 2001 ; and WO 01/16263 published on March 8, 2001 .
  • The laundry detergent compositions herein are formulated as aqueous liquid laundry detergents. The detergent compositions herein therefore comprise from 3% to 98%, alternatively from 5% to 95%, by weight of the liquid detergent composition, of an aqueous liquid carrier which is preferably water. Preferably, the liquid laundry compositions according to the present invention should provide a wash solution pH from 6 to 10, more preferably from 7 to 9, in order to maintain a preferred cleaning and fabric care performance by the aqueous liquid detergents according to the present invention. If needed, the cleaning compositions may contain alkalinizing agents, pH control agents and/or buffering agents.
  • Laundry Adjunct Ingredients
  • The laundry detergents herein may further comprise a laundry adjunct ingredient. Suitable laundry adjuncts are known in the art and include soil release polymers, dye transfer inhibiting polymers, chelants, performance boosting polymers, preservatives, stabilizers, structurants, viscosity modifiers, citric acid, and benefit agent containing delivery particles.
  • Benefit agent containing delivery particles useful herein comprise a core material and a wall material that at least partially surrounds said core material. As used herein, the phrase "benefit agent containing delivery particle" encompasses microcapsules, including perfume microcapsules (where the core material includes perfume). As used herein, the terms "particle", "benefit agent containing delivery particle", "capsule" and "microcapsule" are synonymous.
    • EXAMPLES 1-4
  • The following example aqueous liquid detergent formulations may be made by traditional methods and means as known to one of ordinary skill in the art.
    Ingredient 1 2 3 4
    Wt.% Wt% Wt% Wt%
    Nonionic surfactant 4.0 4.0 7.0 4.0
    Anionic surfactant 7.0 3.0 8.0 3.0
    Citric Acid 2.0 3.0 2.5 3.0
    Fatty acid 4.5 3.0 6.0 3.0
    PVPVI 0.02 0.03 0.05 0.03
    Performance Boosters 0.3 0.5
    Cationic hydroxyl ethyl
    cellulose    		 0.18 0.15 0.25 0.15
    Ethanol 0.85 1.00 1.2 1.00
    Boric acid 1.2 0.85 1.00 0.85
    DB110A 0.0025 0.0025 0.0025 0.0025
    Sodium hydroxide 3.0 3.0 3.5 3.0
    Perfumes and Dyes 0.6 0.5 0.7 0.5
    Opacifier 0.100 0.040 0.040
    Preservative 0.002 0.001 0.0018 0.001
    Perfume Microcapsules 1.3
    Water Remainder Remainder Remainder Remainder

Claims (11)

  1. An aqueous liquid laundry detergent composition useful for cleaning fabrics wherein the composition comprises:
    a) from 0.05% to 0.4%, preferably from 0.1% to 0.3%, more preferably from 0.15% to 0.2%, by weight of the composition, of a cationic hydroxyethyl cellulose polymer having a degree of substitution of the cationic charge of from 0.01 to 0.20, preferably from 0.01 to 0.1, more preferably from 0.01 to Less than 0.1:
    b) from 5% to 30%, preferably from 7% to 15%, by weight of the composition, of a surfactant comprising at least one anionic surfactants and at least one nonionic surfactant; and
    c) from 2.5% to 7%, by weight of the composition, of fatty acid.
  2. An aqueous liquid laundry detergent composition according to Claim 1 wherein the carionic hydroxyethyl cellulose polymer has a molecular weight of from 200,000 to 800,000.
  3. An aqueous liquid laundry detergent composition according to Claim 1 or 2 wherein the composition is substantially free of enzymes having cellulytic activity and is preferably substantially free of optical brightener.
  4. An aqueous liquid laundry detergent composition according to any one of the preceding claims wherein the composition further comprises an opacifying agent.
  5. An aqueous liquid laundry detergent composition according to any one of the preceding claims wherein the anionic surfactant is selected from alkyl ethoxylate sulfates and linear alkyl benzene sulfonates, preferably from alkyl ethoxylate sulfates having a chain length of from 12 to 14 and a degree of ethoxylation of from 1 to 8.
  6. An aqueous liquid laundry detergent composition according to any one of the preceding claims wherein the composition further comprises a suds suppressor and is substantially free of enzymes.
  7. An aqueous liquid laundry detergent composition according to any one of the preceding claims wherein the composition further comprises a laundry adjunct ingredient selected from soil release polymers, dye transfer inhibiting polymers, chelants, performance boosting polymers, preservatives, stabilizers, structurants, viscosity modifiers, benefit agent containing delivery particles, and citric acid.
  8. An aqueous liquid laundry detergent composition according to Claim 1 wherein the composition further comprises from 0.01 to 1% of a structurant that is selected from hydrogenated castor oil.
  9. An aqueous liquid laundry detergent composition according to any one of the preceding claims, wherein the composition further comprises a benefit agent containing delivery particle, wherein the benefit agent containing delivery particle is preferably a perfume microcapsule.
  10. Use of an aqueous liquid laundry detergent composition according to any one of the preceding claims for handwashing delicate fabrics.
  11. Use of an aqueous liquid laundry detergent composition according to any one of claims 1 through 9 for machine washing of delicate fabrics, wherein the machine washing occurs at a delicate machine setting.
EP07754834A 2006-04-13 2007-04-05 Liquid laundry detergents containing cationic hydroxyethyl cellulose polymer Revoked EP2004785B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US79164706P 2006-04-13 2006-04-13
PCT/US2007/008376 WO2007120547A1 (en) 2006-04-13 2007-04-05 Liquid laundry detergents containing cationic hydroxyethyl cellulose polymer

Publications (2)

Publication Number Publication Date
EP2004785A1 EP2004785A1 (en) 2008-12-24
EP2004785B1 true EP2004785B1 (en) 2011-08-17

Family

ID=38458031

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07754834A Revoked EP2004785B1 (en) 2006-04-13 2007-04-05 Liquid laundry detergents containing cationic hydroxyethyl cellulose polymer

Country Status (11)

Country Link
EP (1) EP2004785B1 (en)
JP (1) JP2009532566A (en)
CN (1) CN101415809A (en)
AR (1) AR060456A1 (en)
AT (1) ATE520764T1 (en)
BR (1) BRPI0710140A2 (en)
CA (1) CA2645374C (en)
MX (1) MX2008013243A (en)
RU (1) RU2421506C2 (en)
WO (1) WO2007120547A1 (en)
ZA (1) ZA200808541B (en)

Families Citing this family (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX2010012962A (en) 2008-05-28 2011-04-05 Procter & Gamble Fabric softening laundry detergents with good stability.
JP2011521083A (en) * 2008-05-28 2011-07-21 ザ プロクター アンド ギャンブル カンパニー Fabric softening laundry detergent with good stability
JP2012503082A (en) * 2008-09-19 2012-02-02 ザ プロクター アンド ギャンブル カンパニー Detergent composition containing modified biopolymer for foam enhancement and stabilization
EP2302026A1 (en) * 2009-09-15 2011-03-30 The Procter & Gamble Company Detergent composition comprising surfactant boosting polymers
AR078890A1 (en) 2009-11-06 2011-12-07 Procter & Gamble SUPPLY PARTICLE IN COMPOSITIONS WITH A BENEFIT AGENT
EP2399978B2 (en) 2010-06-24 2020-11-25 The Procter and Gamble Company Stable non-aqueous liquid compositions comprising a cationic polymer in particulate form
ES2394066T3 (en) 2010-06-24 2013-01-16 The Procter & Gamble Company Stable compositions comprising cationic cellulose polymer and cellulase
EP2399979B2 (en) * 2010-06-24 2021-12-29 The Procter & Gamble Company Soluble unit dose articles comprising a cationic polymer
WO2012081722A1 (en) 2010-12-17 2012-06-21 学校法人神奈川大学 Protective structure of substance to be protected, method of protecting substance to be protected, enzymatic reaction method, method of producing reaction product, method for adjusting the speed of enzymatic reaction, and enzyme material use kit
JP6817065B2 (en) * 2014-02-25 2021-01-20 エルジー ハウスホールド アンド ヘルスケア リミテッド Fiber softener composition
EP2982738B2 (en) 2014-08-07 2022-06-29 The Procter & Gamble Company Laundry detergent composition
PL2982735T5 (en) * 2014-08-07 2021-09-27 The Procter & Gamble Company Laundry detergent composition
US10604723B2 (en) 2014-11-11 2020-03-31 Rohm And Haas Company Cationic carbohydrate polymers for fabric care
CN105779157A (en) * 2014-12-24 2016-07-20 阎珊珊 Preparation of lavender liquid laundry detergent
CN106821995B (en) * 2017-02-22 2020-08-21 佛山市南海东方澳龙制药有限公司 Triclabendazole preparation and preparation method and application thereof
WO2018231751A1 (en) * 2017-06-13 2018-12-20 The Procter & Gamble Company Consumer product
EP3415602A1 (en) * 2017-06-13 2018-12-19 The Procter & Gamble Company Consumer product
EP3415603A1 (en) * 2017-06-13 2018-12-19 The Procter & Gamble Company Consumer product
WO2018231750A1 (en) 2017-06-13 2018-12-20 The Procter & Gamble Company Process for treating at least one garment
EP3441449A1 (en) * 2017-08-11 2019-02-13 The Procter & Gamble Company Use of the combination of a cationic polysaccharide polymer and an anionic non-soap surfactant
EP3441448A1 (en) * 2017-08-11 2019-02-13 The Procter & Gamble Company Method of laundering fabrics
MX2020005976A (en) 2017-12-06 2020-08-24 Kao Corp Fabric treatment composition.
AU2018381369B2 (en) 2017-12-06 2023-11-30 Kao Corporation Composition
WO2019111948A1 (en) * 2017-12-06 2019-06-13 花王株式会社 Soil release agent
EP3722329B1 (en) 2017-12-06 2024-10-16 Kao Corporation Polysaccharide derivative
WO2019111936A1 (en) * 2017-12-06 2019-06-13 花王株式会社 Liquid washing agent composition for textile products
US11662182B2 (en) 2018-11-13 2023-05-30 David Daniel Rankin, Sr. Non-lethal defensive fluid composition and pressurized delivery system
US11320245B2 (en) 2018-11-13 2022-05-03 David Daniel Rankin, Sr. Non-lethal defensive fluid composition and pressurized delivery system
US20200148965A1 (en) * 2018-11-13 2020-05-14 David Daniel Rankin, Sr. Non-lethal defensive fluid composition and pressurized delivery system
US11499120B2 (en) * 2020-01-30 2022-11-15 Henkel Ag & Co. Kgaa Three polymer blend to achieve fabric care in laundry
CA3100416C (en) * 2020-03-26 2024-04-09 David Daniel Rankin, Sr. Non-lethal defensive fluid composition and pressurized delivery system
WO2021247339A1 (en) 2020-06-02 2021-12-09 Dow Global Technologies Llc Aqueous liquid laundry formulation

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2220099A (en) 1934-01-10 1940-11-05 Gen Aniline & Flim Corp Sulphonic acids
US2477383A (en) 1946-12-26 1949-07-26 California Research Corp Sulfonated detergent and its method of preparation
GB1234445A (en) 1967-10-03 1971-06-03
US3664961A (en) 1970-03-31 1972-05-23 Procter & Gamble Enzyme detergent composition containing coagglomerated perborate bleaching agent
GB1372034A (en) 1970-12-31 1974-10-30 Unilever Ltd Detergent compositions
US3919678A (en) 1974-04-01 1975-11-11 Telic Corp Magnetic field generation apparatus
JPS5837833B2 (en) 1976-08-11 1983-08-18 天野製薬株式会社 Method for purifying microbial lipoprotein lipase
US4222905A (en) 1978-06-26 1980-09-16 The Procter & Gamble Company Laundry detergent compositions having enhanced particulate soil removal performance
US4144226A (en) 1977-08-22 1979-03-13 Monsanto Company Polymeric acetal carboxylates
US4246495A (en) 1978-10-05 1981-01-20 Jerome Pressman Television monitor and control
US4239659A (en) 1978-12-15 1980-12-16 The Procter & Gamble Company Detergent compositions containing nonionic and cationic surfactants, the cationic surfactant having a long alkyl chain of from about 20 to about 30 carbon atoms
US4663071A (en) 1986-01-30 1987-05-05 The Procter & Gamble Company Ether carboxylate detergent builders and process for their preparation
GB8810954D0 (en) 1988-05-09 1988-06-15 Unilever Plc Enzymatic detergent & bleaching composition
US4946624A (en) * 1989-02-27 1990-08-07 The Procter & Gamble Company Microcapsules containing hydrophobic liquid core
US5234611A (en) * 1991-08-28 1993-08-10 The Procter & Gamble Company Fabric softener, preferably liquid, with protected, dryer-activated, cyclodextrin/perfume complex
JPH05310542A (en) * 1992-05-14 1993-11-22 Kao Corp Cleaning composition
DK52393D0 (en) 1993-05-05 1993-05-05 Novo Nordisk As
WO1995007791A1 (en) 1993-09-14 1995-03-23 Rego-Fix Ag Clamping device for machine tools
CA2297161C (en) 1997-07-21 2003-12-23 The Procter & Gamble Company Detergent compositions containing mixtures of crystallinity-disrupted surfactants
PH11998001775B1 (en) 1997-07-21 2004-02-11 Procter & Gamble Improved alkyl aryl sulfonate surfactants
WO2001016263A2 (en) 1999-08-27 2001-03-08 The Procter & Gamble Company Controlled availability of formulation components, compositions and laundry methods employing same
DE19941132A1 (en) 1999-08-30 2001-03-01 Basf Ag Process for the continuous production of glutaraldehyde
GB9930433D0 (en) * 1999-12-22 2000-02-16 Unilever Plc Use of fabric conditioning compositions for ironing benefits
BR0314147A (en) * 2002-09-09 2005-07-12 Procter & Gamble Laundry Product Composition
EP1462512B1 (en) * 2003-03-24 2007-08-01 The Procter & Gamble Company Compositions comprising complexes of cyclodextrin and at least one laundry treatment active
US7226900B2 (en) * 2003-06-16 2007-06-05 The Proctor & Gamble Company Liquid laundry detergent composition containing boron-compatible cationic deposition aids
CA2590707A1 (en) * 2004-12-06 2006-06-15 The Procter & Gamble Company Fabric enhancing composition
GB0514147D0 (en) * 2005-07-11 2005-08-17 Unilever Plc Laundry treatment compositions

Also Published As

Publication number Publication date
EP2004785A1 (en) 2008-12-24
MX2008013243A (en) 2008-10-21
ATE520764T1 (en) 2011-09-15
CA2645374C (en) 2011-11-29
JP2009532566A (en) 2009-09-10
RU2008138401A (en) 2010-05-20
CA2645374A1 (en) 2007-10-25
AR060456A1 (en) 2008-06-18
BRPI0710140A2 (en) 2011-08-02
RU2421506C2 (en) 2011-06-20
ZA200808541B (en) 2009-11-25
CN101415809A (en) 2009-04-22
WO2007120547A1 (en) 2007-10-25

Similar Documents

Publication Publication Date Title
EP2004785B1 (en) Liquid laundry detergents containing cationic hydroxyethyl cellulose polymer
US7576048B2 (en) Liquid laundry detergents containing cationic hydroxyethyl cellulose polymer
US7056880B2 (en) Using cationic celluloses to enhance delivery of fabric care benefit agents
US7056879B2 (en) Using cationic celluloses to enhance delivery of fabric care benefit agents
EP1224253B1 (en) Laundry detergent compositions with fabric care
EP1317524B2 (en) Laundry articles and methods for combined cleaning and care of fabrics
EP1773974B1 (en) Softening laundry detergent
CZ2000964A3 (en) Laundry detergent compositions with cellulose-based polymers beneficial to the appearance and integrity of fabrics laundered therein
EP1440141A2 (en) Detergent or cleanser that can be dispersed in an essentially sediment-free manner
US6156722A (en) Laundry detergent compositions comprising dye fixatives
EP3655462B1 (en) Functionalized siloxane polymers and compositions comprising same
EP1537197B1 (en) Using cationic celluloses to enhance delivery of fabric care benefit agents
WO2008017668A1 (en) Washing and cleaning agent containing oxidoreductases and bleach activators
WO2009027247A1 (en) Laundry pretreatment agent and method
MXPA99006226A (en) Laundry detergent compositions comprising dye fixatives

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20081002

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20090525

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602007016598

Country of ref document: DE

Effective date: 20111013

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20110817

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111219

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110817

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110817

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111217

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110817

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 520764

Country of ref document: AT

Kind code of ref document: T

Effective date: 20110817

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110817

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110817

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110817

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110817

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111118

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110817

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110817

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110817

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110817

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110817

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110817

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110817

26 Opposition filed

Opponent name: HENKEL AG & CO. KGAA

Effective date: 20120516

Opponent name: UNILEVER PLC / UNILEVER N.V.

Effective date: 20120515

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110817

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602007016598

Country of ref document: DE

Effective date: 20120516

PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

Free format text: ORIGINAL CODE: EPIDOSCOBS2

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120430

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20121228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120430

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120430

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120405

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111128

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111117

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110817

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110817

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120405

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070405

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

APBQ Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3O

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20170329

Year of fee payment: 11

REG Reference to a national code

Ref country code: DE

Ref legal event code: R064

Ref document number: 602007016598

Country of ref document: DE

Ref country code: DE

Ref legal event code: R103

Ref document number: 602007016598

Country of ref document: DE

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20180329

Year of fee payment: 12

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 20180108

GBPR Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state

Effective date: 20180108

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20180412

Year of fee payment: 12