WO1996025477A1 - Compositions detersives comprenant des ethers de polysaccharide non ioniques et des lipases - Google Patents

Compositions detersives comprenant des ethers de polysaccharide non ioniques et des lipases Download PDF

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Publication number
WO1996025477A1
WO1996025477A1 PCT/US1996/001644 US9601644W WO9625477A1 WO 1996025477 A1 WO1996025477 A1 WO 1996025477A1 US 9601644 W US9601644 W US 9601644W WO 9625477 A1 WO9625477 A1 WO 9625477A1
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WO
WIPO (PCT)
Prior art keywords
detergent composition
ether
composition according
lipase
nonionic
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PCT/US1996/001644
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English (en)
Inventor
Gerard Marcel Baillely
Nour-Eddine Guedira
Robin Gibson Hall
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The Procter & Gamble Company
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Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to JP8525003A priority Critical patent/JPH11501958A/ja
Priority to EP96904584A priority patent/EP0820502A4/fr
Priority to BR9607507A priority patent/BR9607507A/pt
Publication of WO1996025477A1 publication Critical patent/WO1996025477A1/fr
Priority to MXPA/A/1997/006228A priority patent/MXPA97006228A/xx

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    • 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
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
    • 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
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC

Definitions

  • the present invention relates to detergent composition comprising lipase enzymes and nonionic polysaccharide ethers providing improved stain removal.
  • lipase enzymes incorporated into detergent compositions to aid the removal of triglyceride or fatty ester based stains is well known.
  • WO 92/05249 discloses certain lipase enzyme variants for improved properties and methods of their production.
  • W094/25577 discloses novel lipase enzyme variants and detergent compositions comprising 0.02 to 200mg per gram of detergent additive of said lipase enzymes.
  • the stain removal performance of lipase enzymes is directly related to their concentration in the detergent composition, so that an increase in the amount of lipase enzyme increases the stain removal performance. It has however been observed that under stressed conditions, such as the use of short washing machine cycles, or at low temperatures or in the presence of highly stained substrates, the optimum performance of the lipase enzyme is achieved at a certain level. Increasing the level of lipase enzyme beyond this amount does not result in increased stain removal performance benefits. Furthermore another disadvantage of increasing the amount of lipase enzyme present in a detergent composition is the resulting increase of the known malodour problem on the washed fabrics.
  • a further advantage of the present invention is that the stai removal benefits are observed after the completion of only one was cycle. This is in contrast to the soil release and or anti redepositio benefits associated with nonionic polysaccharide ethers and also lipas enzymes which require multicycle application in order for these benefit to be observed.
  • Another advantage of the present invention is that there are no associated malodour problems.
  • nonionic polysaccharide ethers as soil release agents have been described in the art.
  • US 4 740 326 discloses a laundry product comprising a substrate material coated with a soil release polymer for improved cleaning performance of hydrophobic soils on synthetic and synthetic natural blend fabrics.
  • the soil release polymers include alkyl or hydroxyalkyl cellulose ethers having a molar degree o substitution (ds) of from 1.5 to 2.7 and an average molecular weight of from 2000 to 100000, preferably 10000 to 30000. Enzymes are disclosed, but lipase is not specifically mentioned.
  • US 4 174 305 discloses detergent compositions comprising LAS and etherified cellulose soil release agents having a ds of up to 3 and a dp of from 100 to 10000. Enzymes are disclosed, specifically proteolytic and lipolytic enzymes, although not their levels. Lipases are not included in the examples.
  • US 4 136 038 discloses fabric conditioning compositions containing cellulose ethers having a molecular weight of 3000 to 10000 and ds of 1.8 to 2.7 and from 0.05% to 2% of detergency enzymes selected from protease, lipase, amylase and mixtures thereof. There are no exemplified compositions comprising lipase and cellulose ethers.
  • EPO 495 257 discloses a compact detergent composition comprising high activity cellulase.
  • Anti-redeposition agents such as cellulose derivatives are disclosed, in particular methyl cellulose, carboxymethylcellulose (CMC) and hydroxyethyl cellulose. Their dp and ds values are not disclosed.
  • Other enzymes including lipase are disclosed, but not the levels.
  • a detergent composition comprising a lipase enzyme which provides improved triglycerid and fatty ester based stain removal performance, particularly under stressed conditions.
  • None of the identified prior art documents disclose the performance benefits of the combination of lipase enzymes and nonionic poly saccharide ethers as is the present invention.
  • the present invention relates to a detergent composition
  • a detergent composition comprising at least 1 % of a surfactant characterised in that said detergent composition comprises the combination of an lipase enzyme with a nonionic polysaccharide ether having a molecular weight of more than 10000, said lipase enzyme having an activity such that said detergent composition has an activity of at least 0.001 LU per milligram.
  • the detergent composition comprises as an essential component a lipase enzyme in combination with a nonionic polysaccharide ether.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P. " Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • lipolyticum NRRLB 3673 commerciall available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • the LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo is a preferred lipase for use herein.
  • Another preferred lipase for use herein is D96L lipolytic enzyme variant of the native lipase derived from Humicola lanuginosa. Most preferably the Humicola lanuginosa strain DSM 4106 is used.
  • D96L lipolytic enzyme variant is meant the lipase variant as described in patent application WO 92/05249 viz. wherein the native lipase ex Humicola lanuginosa aspartic acid (D) residue at position 96 is changed to Leucine (L). According to this nomenclature said substitution of aspartic acid to Leucine in position 96 is shown as : D96L.
  • D96L the standard LU assay was used (Analytical method, internal Novo Nordisk number AF 95/6-GB 1991.02.07).
  • a substrate for D96L was prepared by emulsifying glycerine tributyrate (Merck) using gum-arabic as emulsifier. Lipase activity was assayed at pH 7 using pH stat. method.
  • the lipase enzyme is incorporated into the composition in accordance with the invention at a level of from 0.001LU to 100LU per milligram of detergent composition, preferably from 0.005LU to 10LU per milligram of detergent composition. More preferably at a level of from 0.01LU to 5LU per milligram of detergent composition.
  • another essential component of the detergent composition is a nonionic polysaccharide ether having a molecular weight of more than 10000.
  • the polysaccharides are composed of pentoses or hexoses.
  • Suitable polysaccharide ethers for use herein are selected from cellulose ethers, starch ethers, dextran ethers and mixtures thereof.
  • Preferably said nonionic polysaccharide ether is a cellulose ether.
  • Cellulose ethers are generally obtained from vegetable tissues and fibres, including cotton and wood pulp.
  • the hydroxy group of the anhydro glucose unit of cellulose can be reacted with various reagents thereby replacing the hydrogen of the hydroxy 1 group with other chemical groups.
  • Various alkylating and hydroxyalkylating agents can be reacted with cellulose ethers to produce either alkyl-, hydroxyalkyl- or alkylhydroxyalkyl-cellulose ethers or mixtures thereof.
  • the most preferred for use in the present invention are C1-C4 alkyl cellulose ether or a C1-C4 hydroxyalkyl cellulose ether or a C1-C4 alkylhydroxy alkyl cellulose ether or mixtures thereof.
  • the polysaccharides of the present invention have a degree of substitution of from 0.5 to 2.8, preferably from 1 to 2.5, most preferably from 1.5 to 2 inclusive.
  • Suitable nonionic cellulose ethers include methylcellulose ether, hydroxypropyl methylcellulose ether, hydroxyethyl methylcellulose ether, hydroxypropyl cellulose ether, hydroxybutyl methylcellulose ether, ethylhydroxy ethylcellulose ether, ethylcellulose ether and hydroxy ethylcellulose ether.
  • said polysaccharide is a methylcellulose ether.
  • Such agents are commercially available such as METHOCEL (Dow Chemicals).
  • said polysaccharide ether has a molecular weight from 10000 to 200000, most preferably from 30000 to 150000.
  • the weight average molecular weight is obtained by standard analytical methods as described in Polymer handbooks.
  • a preferred method is light scattering from polymer solutions as originally defined by Debye.
  • compositions of the present invention comprise from 0.01 % to 10%, preferably from 0.01 % to 3%, most preferably from 0.1 % to 2% of said nonionic polysaccharide ethers.
  • the detergent composition preferably comprises said lipase enzyme and said polysacchardie ether at a ratio of from 10000:1 to 1:10, preferably from 1000:1 to 1:1.
  • the lipase being expressed in LU and the nonionic polysaccharide ether being expressed in milligrams.
  • the detergent composition comprises at least 1 % of a surfactant system.
  • Surfactants useful herein include the conventional Cn-Cig alkyl benzene sulphonates ("LAS") and primary, branched-chain and random C10-C20 alkyl sulphates ("AS"), the Cl0 ⁇ Cl8 secondary (2,3) alkyl sulphates of the formula CH3(CH2) x (CHOS ⁇ 3 ' M + ) CH3 and CH3 (CH2) y (CHOS ⁇ 3 _ M + ) CH2CH3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulphates such as oleyl sulphate, the Cjo-Cig alkyl alkoxy sulphates ("AE X S”; especially EO 1-7 ethoxy sulphates), C ⁇ -C ⁇ alkyl alkoxy carboxylates (
  • the conventional nonionic and amphoteric surfactants such as the C12-C18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxy lates (especially ethoxylates and mixed ethoxy /propoxy), C12-C18 betaines and sulphobetaines ("sultaines"), C10-C18 amine oxides, and the like, can also be included in the overall compositions.
  • the C10-C1 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C18 N-methylglucamides. See WO 9,206,154.
  • sugar- derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N-(3-methoxypropyl) glucamide.
  • the N-propyl through N-hexyl C12-C18 glucamides can be used for low sudsing.
  • C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10-C16 soaps may be used.
  • Mixtures of anionic and nonionic surfactants are especially useful.
  • Other conventional useful surfactants such as cationics are listed in standard texts.
  • the compositions comprise from 1 % to 80%, preferably from 5% to 50%, most preferably from 10% to 40% of a surfactant.
  • Preferred surfactants for use herein are linear alkyl benzene sulphonate, alkyl sulphates and alkyl alkoxylated nonionics or mixtures thereof.
  • the detergent compositions may comprise a number of optional conventional detergent adjuncts such as builders, chelants, polymers, antiredeposition agents and the like.
  • Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of paniculate soils.
  • the level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least 1 % builder. Liquid formulations typically comprise from 5% to 50%, more typically about 5% to 30%, by weight, of detergent builder. Granular formulations typically comprise from 10% to 80%, more typically from 15% to 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
  • Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, orthophosphates and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137).
  • compositions herein function surprisingly well even i the presence of the so-called "weak” builders (as compared wit phosphates) such as citrate, or in the so-called "underbuilt” situation tha may occur with zeolite or layered silicate builders.
  • silicate builders are the alkali metal silicates, particularly those having a Si ⁇ 2:Na2 ⁇ ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described i U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • Hoechst commonly abbreviated herein as "SKS-6”
  • the Na SKS-6 silicate builder does not contain aluminum.
  • NaSKS-6 has the delta-Na2Si2 ⁇ 5 morphology form of layered silicate.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi ⁇ 2 +i-yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
  • Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
  • delta-Na2Si2 ⁇ 5 (NaSKS-6 form) is most preferred for use herein.
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
  • Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
  • x Na ⁇ 2 [(Al ⁇ 2)l2(Si ⁇ 2)i2]-xH 2 0 wherein x is from about 20 to about 30, especially about 27.
  • This material is known as Zeolite A.
  • the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
  • Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate builders encompasses the ether poly carboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,8 and 4,102,903.
  • detergency builders include the eth hydroxypolycarboxylates, copolymers of maleic anhydride with ethyle or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphon acid, and carboxymethyloxysuccinic acid, the various alkali met ammonium and substituted ammonium salts of polyacetic acids such ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic aci poly maleic acid, benzene 1,3,5-tricarboxylic aci carboxymethyloxysuccinic acid, and soluble salts thereof.
  • polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic aci poly maleic acid,
  • Citrate builders e.g., citric acid and soluble salts there (particularly sodium salt), are polycarboxylate builders of particul importance for heavy duty liquid detergent formulations due to the availability from renewable resources and their biodegradability. Citrat can also be used in granular compositions, especially in combination wit zeolite and/or layered silicate builders. Oxydisuccinates are als especially useful in such compositions and combinations.
  • succinic acid builders include the C5-C20 alkyl and alken succinic acids and salts thereof.
  • a particularly preferred compound of thi type is dodecenylsuccinic acid.
  • succinate builder examples include: laurylsuccinate, my ristyl succinate, palmitylsuccinate, dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the lik Laurylsuccinates are the preferred builders of this group, and ar described in European Patent Application 86200690.5/0,200,263 published November 5, 1986.
  • the detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents.
  • chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents include ethy lenediaminetetracetates , N-hydroxyethy lethylenediaminetriacetates , nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetra- aminehexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as l,2-dihydroxy-3,5 disulfobenzene.
  • a preferred biodegradable chelator for use herein i ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer a described in U.S. Patent 4,704,233, November 3, 1987, to Hartman an Perkins.
  • EDDS ethylenediamine disuccinate
  • these chelating agents will generally comprise fro 0.1 % to 10% more preferably, from 0.1 % to 3.0% by weight of suc compositions.
  • Polymeric soil release agents are characterized by having bot hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion o washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • the polymeric soil release agents useful herein especially include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophile component has hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably comprising at least about 25% oxyethylene units and more preferably, especially for such components having about 20 to 30 oxypropylene units, at least about 50% oxyethylene units; or
  • the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100.
  • Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as M ⁇ 3S(CH2) n OCH2CH2 ⁇ -, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.
  • Polymeric soil release agents useful in the present invention also include copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like.
  • Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly (vinyl ester), e.g., Ci-C ⁇ vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
  • polyalkylene oxide backbones such as polyethylene oxide backbones.
  • Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
  • One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
  • the molecular weight of this polymeric soil release agent i in the range of from about 25,000 to about 55,000. See U.S. Paten 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 t Basadur issued July 8, 1975.
  • Another preferred polymeric soil release agent is a polyester wit repeat units of ethylene terephthalate units contains 10-15% by weight o ethylene terephthalate units together with 90-80% by weight o polyoxyethylene terephthalate units, derived from a polyoxyethylen glycol of average molecular weight 300-5,000.
  • this polyme include the commercially available material ZELCON 5126 (fro Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857 issued October 27, 1987 to Gosselink.
  • Another preferred polymeric soil release agent is a sulfonate product of a substantially linear ester oligomer comprised of a oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repea units and terminal moieties covalently attached to the backbone.
  • These soil release agents are described fully in U.S. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
  • Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds o U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
  • Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.
  • soil release agents will generally comprise from about 0.01 % to about 10.0%, by weight, of the detergent compositions herein, typically from about 0.1 % to about 5%, preferably from about 0.2% to about 3.0%.
  • Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-l,2-propylene units. The repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end- caps.
  • a particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1 ,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate.
  • Said soil release agent also comprises from about 0.5% to about 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • the detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators.
  • bleaching agents will typically be at levels of from 1 % to 40%, more typically from 5% to 30%, of the detergent composition, especially for fabric laundering.
  • the amount of bleach activators will typically be from 0.1 % to 60%, more typically from 0.5% to 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
  • the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents.
  • Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used. A preferred percarbonate bleach comprises dry particles having a average particle size in the range from about 500 micrometers to abou 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers.
  • the percarbonate can be coated with silicate, borate or water- soluble surfactants. Preferred coatings are based on carbonate/sulphate mixtures. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
  • bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983.
  • Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.
  • bleaching agents can also be used.
  • Peroxygen bleaching agents, the perborates, e.g., sodium perborate (e.g., mono- or tetra-hydrate) , the percarbonates, etc. are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator.
  • bleach activators e.g., sodium perborate (e.g., mono- or tetra-hydrate)
  • bleach activators e.g., sodium perborate (e.g., mono- or tetra-hydrate)
  • bleach activators e.g., sodium perborate (e.g., mono- or tetra-hydrate)
  • bleach activators e.g., mono- or tetra-hydrate
  • nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. 4,634,551 for other typical bleaches and activators useful herein.
  • Highly preferred amido-derived bleach activators are those of the formulae:
  • RlN(R5)C(0)R2C(0)L or R1C(0)N(R5)R2C(0)L wherein Rl is an alkyl group containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, R ⁇ is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group.
  • a leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydroxyl anion.
  • a preferred leaving group is phenol sulfonate.
  • bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6- nonanamidocaproyl)- oxybenzenesulfonate, (6-decanamido- caproy oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551, incorporated herein by reference.
  • Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by reference.
  • a highly preferred activator of the benzoxazin-type is:
  • Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams, acyl pyrolidone and acyl valerolac arns of the formulae:
  • R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms.
  • Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5- trimethylhexanoyl caprolactam, nonanoyl caprolactam, decano caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octano valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonano valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereo See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985 incorporated herein by reference, which discloses acyl cap rolac tarns adsorbed into sodium perborate.
  • Other preferred activators are cationi
  • Bleaching agents other than oxygen bleaching agents are als known in the art and can be utilized herein.
  • One type of non-oxyge bleaching agent of particular interest includes photoactivated bleachin agents such as the sulfonated zinc and/or aluminum phthalocyanines. Se U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used detergent compositions will typically contain from 0.025% to 1.25%, b weight, of such bleaches, especially sulfonate zinc phthalocyanine.
  • the bleaching compounds can be catalyzed by means of manganese compound.
  • manganese compound Such compounds are well known in the art an include, for example, the manganese-based catalysts disclosed in U.S Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat 5,114,606; and European Pat. App. Pub. Nos. 549,271 Al, 549,272A1 544,440A2, and 544,490A1; Preferred examples of these catalysts included Mn IV 2( u_ 0)3(l ,4,7-trimethyl-l ,4,7-triazacyclononane)2(PF6)2.
  • metal-based bleach catalysts include thos disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611.
  • the use o manganese with various complex ligands to enhance bleaching is als reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; 5,227,084;
  • Polymeric dispersing agents can advantageously be utilized at levels from 0.1 % to 7%, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders.
  • Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, paniculate soil release peptization, and anti-redeposition.
  • Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
  • Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • the presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.
  • Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued march 7, 1967.
  • Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent.
  • Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers in the acid for preferably ranges from about 2,000 to 100,000, more preferably fro about 5,000 to 90,000, most preferably from about 7,000 to 80,000.
  • Th ratio of acrylate to maleate segments in such copolymers will generall range from about 30:1 to about 1:1, more preferably from about 70:30 t 30:70.
  • Water-soluble salts of such acrylic acid/maleic acid copolymer can include, for example, the alkali metal, ammonium and substitute ammonium salts.
  • Soluble acrylate/maleate copolymers of this type ar known materials which are described in European Patent Application No 66915, published December 15, 1982, as well as in EP 193,360 published September 3, 1986, which also describes such polymer comprising hydroxypropylacrylate.
  • Still other useful dispersing agent include the maleic/acrylic/vinyl alcohol or acetate terpolymers.
  • Suc materials are also disclosed in EP 193,360, including, for example, th 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
  • PEG polyethylen glycol
  • PEG can exhibit dispersing agent performance as well a act as a clay soil removal-antiredeposition agent.
  • Typical molecula weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1 ,000 to about 50,000, more preferably from abou 1,500 to about 10,000.
  • Polyamino acid dispersing agents such as polyaspartate and polyglutamate may also be used, especially in conjunction with zeolite builders. Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of about 10,000.
  • compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antire- deposition properties.
  • Granular detergent compositions which contain these compounds typically contain from about 0.01 % to about 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent compositions typically contain about 0.01 % to about 5%.
  • the most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxy lated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986.
  • Another group of preferred clay soil removal-antiredeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984.
  • Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985.
  • Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein.
  • Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.
  • compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process.
  • dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N- oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from 0.01 % to 10% by weight of the composition, preferably from 0.01 % to 5%, and more preferably from 0.05% to 2%.
  • Preferred polyamin N-oxides are those wherein R is a heterocyclic group such as pyridine pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
  • the N-0 group can be represented by the following genera structures:
  • Rj, R2, R3 are aliphatic, aromatic, heterocyclic or alicycli groups or combinations thereof; x, y and z are 0 or 1 ; and the nitrogen o the N-0 group can be attached or form part of any of the aforementione groups.
  • the amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred pKa ⁇ 6.
  • Any polymer backbone can be used as long as the amine oxid polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are poly vinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof.
  • These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
  • the amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
  • the polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO".
  • poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1 :4.
  • Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers are also preferred for use herein.
  • the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis. Vol 113.
  • the PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N- vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1 , most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched.
  • compositions also may employ a polyvinylpyrrolidone (“PVP”) having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000.
  • PVP's are known to persons skilled in the detergent field; see, for example, EP- A-262,897 and EP-A-256,696, incorporated herein by reference.
  • Compositions containing PVP can also contain polyethylene glycol (“PEG”) having an average molecular weight from about 500 to about 100,000, preferably from about 1,000 to about 10,000.
  • PEG polyethylene glycol
  • the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1, and more preferably from about 3:1 to about 10:1.
  • the detergent compositions herein may also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from 0.01 % to 1 % by weight of such optical brighteners.
  • hydrophilic optical brighteners useful in the present invention are those having the structural formula: wherein Rl is selected from anilino, N-2-bis-hydroxyethyl and NH-2 hydroxyethyl; R2 is selected from N-2-bis-hydroxy ethyl, N-2 hydroxyethyl-N-methylamino, mo ⁇ hilino, chloro and amino; and M is salt-forming cation such as sodium or potassium.
  • Rl is anilino
  • R2 is N-2-bis hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4', bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2 ,2 ' - stilbenedisulfonic acid and disodium salt.
  • This particular brightene species is commercially marketed under the tradename Tinopal-UNPA GX by Ciba-Geigy Co ⁇ oration. Tinopal-UNPA-GX is the preferre hydrophilic optical brightener useful in the detergent compositions herein.
  • Rj is anilino
  • R2 is N-2-hydroxyethyl N-2-methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'- bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2- yl)amino]2, 2' -stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Co ⁇ oration.
  • Rl is anilino
  • R2 is mo ⁇ hilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6- mo ⁇ hilino-s-triazine-2-yl)amino]2, 2 '-stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Co ⁇ oration.
  • the specific optical brightener species selected for use in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described.
  • the combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone. Without being bound by theory, it is believed that such brighteners work this way because they have high affinity for fabrics in the wash solution and therefore deposit relatively quick on these fabrics.
  • the extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient".
  • the exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.
  • the detergent composition may comprise any other ingredients commonly employed in conventional detergent compositions such as soaps, suds suppressors, softeners, brighteners, additional enzymes and enzyme stabilisers.
  • compositions of the present invention may be used in laundry detergent compositions, fabric treatment compositions and fabric softening compositions in addition to hard surface cleaners.
  • the compositions may be formulated as conventional granules, bars, pastes, powders or liquids.
  • the detergent compositions are manufactured in conventional manner, for example in the case of powdered detergent compositions, spray drying or spray mixing processes may be utilised.
  • the polysaccharide ether and lipase enzyme combination of th present invention are present at aqueous concentrations of from lppm t 500ppm, preferably from 5ppm to 300ppm in the wash solution preferably at a pH of from 7 to 11, preferably from 9 to 10.5.
  • the present invention also relates to a method of laundering fabric which comprises contacting said fabric with an aqueous laundry liquo containing conventional detersive ingredients described herein in additio to the lipase enzyme and nonionic polysaccharide ether of the presen invention.
  • aqueous laundry liquo containing conventional detersive ingredients described herein in additio to the lipase enzyme and nonionic polysaccharide ether of the presen invention.
  • polyester and polyester-cotton blend fabrics are used.
  • XYEZ A Ci - Ciy predominantly linear primary alcohol condensed with an average of Z moles of ethylene oxide
  • TFAA C i -C 18 alkyl N-methy 1 glucamide .
  • NaSKS-6 Crystalline layered silicate of formula ⁇ - Na2Si2 ⁇ 5
  • MA/AA Copolymer of 30:70 maleic/acrylic acid, average molecular weight about 70,000.
  • Lipase 2 Lipase enzyme sold under the tradename of lipolase by Novo Nordisk A/S, having an activity of lOOKLU/g
  • Lipase 1 Lipase enzyme derived from Humicola lanuginosa strain DSM 4106
  • Zeolite A 10.2 10.2 10.2 10.2 10.2 10.2 10.2 10.2 10.
  • Soil removal testing using a Miele washing machine, short cycle, 40 °C, Newcastle city water with hardness of 12dH, single dosage was used. The staining mixtures were evenly spread over the fabric with a brush and left to dry over the bench overnight.
  • s denotes that the obseerved difference is statistically significant at a 95% confidence level.
  • Panel score Detergent Detergent Detergent units composition A composition B composition C
  • Chicken** Chicken Provencal, SchwartzTM j Mc Cormick Foods.
  • Tuna*** Tuna Provencal, Colman's sauce for tunaTM ⁇ Colmans.
  • Granular fabric cleaning compositions in accord with the invention are prepared as follows:
  • Granular fabric cleaning compositions in accord with the invention are prepared as follows:
  • Zeolite A 26.0 26.0 26.0 26.0 26.0
  • Granular fabric cleaning compositions in accord with the invention which are especially useful in the laundering of coloured fabrics are prepared as follows:
  • Granular fabric cleaning compositions in accord with the invention are prepared as follows:
  • a granular fabric cleaning compositions in accord with the invention which provide "softening through the wash” capability are prepared as follows:
  • Zeolite A 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0
  • Granular suds suppressor 1.0 1.0 4.0 4.0 1.0 4.0
  • a liquid fabric cleaning composition in accordance with the invention was prepared as follows:-

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  • Detergent Compositions (AREA)

Abstract

La présente invention se rapporte à une composition détersive comprenant une lipase combinée à un éther de polysaccharide non ionique, qui confèrent à la composition des caractéristiques d'élimination des taches améliorées.
PCT/US1996/001644 1995-02-15 1996-02-06 Compositions detersives comprenant des ethers de polysaccharide non ioniques et des lipases WO1996025477A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP8525003A JPH11501958A (ja) 1995-02-15 1996-02-06 ノニオン系多糖エーテル及びリパーゼ酵素を含有した洗剤組成物
EP96904584A EP0820502A4 (fr) 1995-02-15 1996-02-06 Compositions detersives comprenant des ethers de polysaccharide non ioniques et des lipases
BR9607507A BR9607507A (pt) 1995-02-15 1996-02-06 Composições detergentes contendo éteres de polissacarideros n o-ionicos e enzimas lipase
MXPA/A/1997/006228A MXPA97006228A (en) 1995-02-15 1997-08-14 Detergent compositions that comprise non-ionic polyacaride eteres and lip enzymes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9502917A GB2297979A (en) 1995-02-15 1995-02-15 Detergent compositions containing a lipase enzyme
GB9502917.9 1995-02-15

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GB2315767A (en) * 1996-08-01 1998-02-11 Procter & Gamble Detergent compositions for laundering clothes with metal sulphate and a chelant
US5658870A (en) * 1996-09-26 1997-08-19 Leu; Shiow Jiuan Freida Composition of super molecule active solid cleaning agent
DE19850012A1 (de) * 1998-10-30 2000-05-04 Aladin Ges Fuer Innovative Mik Rohrreiniger
US7319112B2 (en) 2000-07-14 2008-01-15 The Procter & Gamble Co. Non-halogenated antibacterial agents and processes for making same
CN101501173B (zh) * 2006-01-23 2011-12-14 宝洁公司 包含酶和光漂白剂的组合物
AR059155A1 (es) * 2006-01-23 2008-03-12 Procter & Gamble Composiciones que comprenden enzimas y fotoblanqueadores
JP5378140B2 (ja) * 2009-10-07 2013-12-25 花王株式会社 液体洗浄剤組成物の製造方法
EP2581438A1 (fr) * 2011-10-12 2013-04-17 The Procter and Gamble Company Composition de détergent
WO2019111936A1 (fr) * 2017-12-06 2019-06-13 花王株式会社 Composition d'agent de lavage liquide pour produits textiles

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4174305A (en) * 1975-04-02 1979-11-13 The Procter & Gamble Company Alkyl benzene sulfonate detergent compositions containing cellulose ether soil release agents
US4532067A (en) * 1984-01-11 1985-07-30 Lever Brothers Company Liquid detergent compositions containing hydroxypropyl methylcellulose
WO1992005249A1 (fr) * 1990-09-13 1992-04-02 Novo Nordisk A/S Variantes lipasiques
WO1994025577A1 (fr) * 1993-04-23 1994-11-10 Novo Nordisk A/S Variantes de lipases

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4136038A (en) * 1976-02-02 1979-01-23 The Procter & Gamble Company Fabric conditioning compositions containing methyl cellulose ether
US4740326A (en) * 1987-02-19 1988-04-26 The Procter & Gamble Company Soil release polymer coated substrate containing a laundry detergent for improved cleaning performance

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
US4174305A (en) * 1975-04-02 1979-11-13 The Procter & Gamble Company Alkyl benzene sulfonate detergent compositions containing cellulose ether soil release agents
US4532067A (en) * 1984-01-11 1985-07-30 Lever Brothers Company Liquid detergent compositions containing hydroxypropyl methylcellulose
WO1992005249A1 (fr) * 1990-09-13 1992-04-02 Novo Nordisk A/S Variantes lipasiques
WO1994025577A1 (fr) * 1993-04-23 1994-11-10 Novo Nordisk A/S Variantes de lipases

Non-Patent Citations (1)

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Title
See also references of EP0820502A4 *

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CN1181104A (zh) 1998-05-06
GB9502917D0 (en) 1995-04-05
EP0820502A4 (fr) 1998-12-23
MX9706228A (es) 1997-10-31
BR9607507A (pt) 1997-12-23
EP0820502A1 (fr) 1998-01-28
GB2297979A (en) 1996-08-21
JPH11501958A (ja) 1999-02-16

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