EP3433346B1 - Composition de détergent pour lessive - Google Patents

Composition de détergent pour lessive Download PDF

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Publication number
EP3433346B1
EP3433346B1 EP17704507.7A EP17704507A EP3433346B1 EP 3433346 B1 EP3433346 B1 EP 3433346B1 EP 17704507 A EP17704507 A EP 17704507A EP 3433346 B1 EP3433346 B1 EP 3433346B1
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Prior art keywords
laundry detergent
detergent composition
aqueous liquid
liquid laundry
composition according
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German (de)
English (en)
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EP3433346A1 (fr
Inventor
Stephen Norman Batchelor
Jayne Michelle Bird
Andrew David Green
Clare Anne JONES
Alyn James Parry
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Unilever Global IP Ltd
Unilever IP Holdings BV
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Unilever NV
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/94Mixtures with anionic, cationic or non-ionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/046Salts
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723Polyamines or polyalkyleneimines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/04Carboxylic acids or salts thereof
    • C11D1/06Ether- or thioether carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/75Amino oxides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/90Betaines

Definitions

  • the present invention provides an alkoxylated polyethylene imine polymer and surfactant formulation for use in domestic laundry.
  • WO2013/087286 discloses liquids formulations containing alkyl ether carboxylic acids, betaines, anionic surfactant, non-ionic surfactant for providing softening benefits.
  • WO2014/060235 discloses a laundry detergent composition comprising (a) nonionic surfactant, (b) anionic surfactant, (c) alkyl ether carboxylic acid or carboxylate salt thereof, and, (d) a polyglucosamine or a copolymer of glucosamine and N-acetylglucosamine; and to its use to soften fabrics.
  • an aqueous liquid laundry detergent composition comprising:
  • the present invention provides a domestic method of treating a textile, the method comprising the steps of:
  • the surfactant used is preferably as preferred for the composition aspects of the present invention.
  • Domestic methods are preferably conducted in a domestic washing machine or by hand washing.
  • the temperature of the wash is preferably from 285 to 313K.
  • the main wash time is preferably 5 to 30 minutes.
  • the textile is preferably an item of clothing, bedding or table cloth.
  • Preferred items of clothing are cotton containing shirts, trousers, underwear and jumpers.
  • Linear alkyl benzene sulfonate Weights of Linear alkyl benzene sulfonate are calculated as the protonated form.
  • the linear alkyl benzene sulfonate has an alkyl chain length of C8 to C15, preferably C12 to C14.
  • Linear alkyl benzene sulphonate may be obtained, by sulphonating commercially available linear alkyl benzene (LAB); suitable LAB includes low 2-phenyl LAB, such as those supplied by Sasol under the tradename Isochem® or those supplied by Petresa under the tradename Petrelab®, other suitable LAB include high 2-phenyl LAB, such as those supplied by Sasol under the tradename Hyblene®.
  • Another suitable route is alkyl benzene sulphonate that is obtained by DETAL catalyzed process, preferably having 8 to 15 carbon atoms. Other synthesis routes, such as HF, may also be suitable.
  • Weights of alkyl ether sulfate are calculated as the protonated form, R 1 -(OCH 2 CH 2 ) m -OSO 3 H.
  • R 1 is C10 to C22 saturate or unsaturated linear alkyl chain, more preferably a saturated C12 to C16 linear alkyl chain, most preferably C12 linear alkyl chain (lauryl).
  • the average number of moles of ethoxylation per mole of surfactant is m, m is preferably 0.5 to 1.5.
  • Weights of alkyl ether carboxylic acid are calculated as the protonated form, R 2 -(OCH 2 CH 2 ) n -OCH 2 COOH. They may be used as salt version for example sodium salt, or amine salt.
  • the alkyl chain may be linear or branched, preferably it is linear.
  • the alkyl chain may be aliphatic or contain one cis or trans double bond.
  • Alkyl ether carboxylic acid are available from Kao (Akypo®), Huntsman (Empicol®) and Clariant (Emulsogen®).
  • the zwitterionic surfactant contains a linear C8 to C16 aliphatic alkyl chain and a positive and negative charged atom within the surfactant molecule.
  • the zwitterionic surfactants are betaines and amine oxides.
  • the amine oxide is preferably of the structure:
  • R 3 is C12-C14, most preferably C12 (lauryl).
  • Amine Oxides are available from Huntsman, for example, Empigen® OB.
  • the betaine is preferably a carbobetaine.
  • the carbobetaine is preferably selected from the structures:
  • R 4 is C12-C14, most preferably C12 (lauryl).
  • Betaines are available from Huntsman, for example Empigen® BB. Cocoamidopropyl betaine (Cas-No 61789-40-0) is most preferred.
  • the zwitterionic is most preferably a carbobetaine.
  • the aqueous liquid laundry detergent may comprise Non-ionic surfactant, preferably an alkyl ethoxylated non-ionic surfactant.
  • Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having an aliphatic hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids or amides, especially ethylene oxide either alone or with propylene oxide.
  • the preferred nonionic detergent compounds are the condensation products of aliphatic C 8 to C 18 primary or secondary linear or branched alcohols with ethylene oxide.
  • the alkyl ethoxylated non-ionic surfactant is a C 8 to C 18 primary alcohol with a mole average ethoxylation of 7EO to 9EO units.
  • the fraction (weight% of non-ionic)/(weight% of anionic surfactant) is from 0 to 0.2, more preferably 0 to 0.05. Most preferably the formulation does not contain non-ionic.
  • the aqueous liquid laundry detergent may comprises from 0 to 4wt% of further surfactants, for example thos described in " Surface Active Agents” Vol. 1, by Schwartz & Perry, Interscience 1949 , Vol. 2 by Schwartz, Perry & Berch, Interscience 1958 , in the current edition of " McCutcheon's Emulsifiers and Detergents” published by Manufacturing Confectioners Company or in " Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981 or in Anionic Surfactants: Organic Chemistry edited by Helmut W. Stache (Marcel Dekker 1996 ) .
  • further surfactants for example thos described in " Surface Active Agents” Vol. 1, by Schwartz & Perry, Interscience 1949 , Vol. 2 by Schwartz, Perry & Berch, Interscience 1958 , in the current edition of " McCutcheon's Emulsifiers and Detergents” published by Manufacturing Confectioners Company or in " Tenside-Taschenbuch
  • Suitable further anionic detergent compounds are; alkyl sulphates, especially those obtained by sulphating linear or branched C 8 to C 18 alcohols; soaps; alkyl (preferably methyl) ester sulphonates, and mixtures thereof.
  • the alkoxylated polyethyelene imine comprises a polyethyleneimine backbone wherein the modification of the polyethyleneimine backbone is intended to leave the polymer without quaternisation.
  • Such materials may be represented as PEI(X)YAO where X represents the molecular weight of the unmodified PEI and Y represents the average moles of alkoxylation (AO) per available NH in the unsubstituted polyethyleneimine backbone.
  • Y is preferably from 7 to 40 more preferably it is in the range of 16 to 26, most preferably 18 to 22.
  • X is selected to be from about 300 to about 10000 weight average molecular weight and is preferably about 600.
  • the alkoxylation is preferably selected from ethoxylation or propoxylation, or a combination of the two, Ethoxylation is most preferred.
  • the alkoxy chains may be capped with groups selected from: H; CH 3 ; SO 3 - ; CH 2 COO - ; PO 3 2- ; C 2 H 5 ; n-propyl, i-propyl; n-butyl; t-butyl; and, sulfosuccinate, most preferably H.
  • alkoxylated PEI is PEI(600)20EO.
  • Terephthalate Polyester Soil Release Polymer comprise polymers of aromatic dicarboxylic acids and alkylene glycols (including polymers containing polyalkylene glycols), as described in WO2009/153184 , EP2692842 and WO2014/019903 .
  • Terephthalate Polyester Soil Release Polymer examples include the REPEL-O-TEX® line of polymers supplied by Rhodia, including REPEL-O-TEX® SRP6 and REPEL-O-TEX® SF-2.
  • Suitable soil release polymers include TexCare® polymers, including TexCare® SRA-100, TexCare® SRA-300, TexCare® SRN-100, TexCare® SRN-170, TexCare® SRN-240, TexCare® SRN-300, and TexCare® SRN-325, all supplied by Clariant.
  • Preferred structure are -[(Z) a -O-OC-Ar-CO-] b and (Z) a -O-OC-[Ar-CO-O-C 3 H 6 -O-OC] b -Ar-COO-(Z) a , where Ar is selected from 1,4 substituted phenylene and 1,3 substituted phenylene substituted in the 5 position with a sulphonates (SO 3 - ) group; Z is selected from ethoxy;propoxy; and mixtures of ethoxy and propoxy; a is from 5 to 100 and b from 2 to 40.
  • C 3 H 6 is i-propyl.
  • the alkoxy chains are capped with groups selected from H; CH 3 ; SO 3 - ; CH 2 COO - ; PO 3 2- ; C 2 H 5 ; n-propyl, i-propyl; n-butyl; t-butyl; and, sulfosuccinate.
  • the Terephthalate Polyester Soil Release Polymer is: wherein c is from 4 to 9; d is from 1 to 3; e is from 40 to 50.
  • the composition may comprise one or more further polymers.
  • suitable polymers are carboxymethylcellulose, poly (ethylene glycol), poly(vinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
  • Polymers present to prevent dye deposition may be present, for example poly(vinylpyrrolidone), poly(vinylpyridine-N-oxide), and poly(vinylimidazole).
  • Such polymers are preferably present at levels of less then 0.5wt%.
  • composition is preferably devoid of silicone polymers and polymers bearing quaternised N groups.
  • the detergent compositions may also optionally contain relatively low levels of organic detergent builder or sequestrant material.
  • organic detergent builder or sequestrant material examples include the alkali metal, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates.
  • Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, ethylene diamine tetra-acetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid, and citric acid.
  • DEQUESTTM organic phosphonate type sequestering agents sold by Monsanto and alkanehydroxy phosphonates.
  • suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties.
  • such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and their salts, such as those sold by BASF under the name SOKALANTM.
  • the aqueous liquid laundry detergent formunation comprise from 0.1% to 2.0 wt% builder and sequesterant material. Citrate is most preferred.
  • Dyes are described in Color Chemistry Synthesis, Properties and Applications of Organic Dyes and Pigments, (H Zollinger, Wiley VCH, Zurich, 2003 ) and, Industrial Dyes Chemistry, Properties Applications. (K Hunger (ed), Wiley-VCH Weinheim 2003 ).
  • Shading Dyes for use in laundry detergents preferably have an extinction coefficient at the maximum absorption in the visible range (400 to 700nm) of greater than 5000 L mol -1 cm -1 , preferably greater than 10000 L mol -1 cm -1 .
  • the dyes are blue or violet in colour.
  • Preferred shading dye chromophores are azo, azine, anthraquinone, and triphenylmethane.
  • Preferred mono-azo dyes contain a heterocyclic ring and are most preferably thiophene dyes.
  • Alkoxylated thiophene dyes are discussed in WO/2013/142495 and WO/2008/087497 .
  • Preferred examples of thiophene dyes are shown below: and,
  • Azine dye are preferably selected from sulphonated phenazine dyes and cationic phenazine dyes. Preferred examples are acid blue 98, acid violet 50, dye with CAS-No 72749-80-5 , acid blue 59.
  • the shading dye may be present in the composition in range from 0.0001 to 0.5 wt %, preferably 0.001 to 0.1 wt%. Depending upon the nature of the shading dye there are preferred ranges depending upon the efficacy of the shading dye which is dependent on class and particular efficacy within any particular class. As stated above the shading dye is a blue or violet shading dye.
  • a mixture of shading dyes may be used.
  • the shading dye is most preferably a reactive blue anthraquinone dye covalently linked to an alkoxylated polyethyleneimine.
  • the alkoxylation is preferably selected from ethoxylation and propoxylation, most preferably propoxylation.
  • 80 to 95 mol% of the N-H groups in the polyethylene imine are replaced with iso-propyl alcohol groups by propoxylation.
  • the polyethylene imine before reaction with the dye and the propoxylation has a molecular weight of 600 to 1800.
  • An example structure of a preferred reactive anthraquinone covalently attached to a propoxylated polyethylene imine is:
  • Preferred reactive anthraquinone dyes are: Reactive blue 1; Reactive blue 2; Reactive blue 4; Reactive blue 5; Reactive blue 6; Reactive blue 12; Reactive blue 16; reactive blue 19; Reactive blue 24 ; Reactive blue 27; Reactive blue 29; Reactive blue 36; Reactive blue 44; Reactive blue 46 ; Reactive blue 47; reactive blue 49; Reactive blue 50; Reactive blue 53; Reactive blue 55; Reactive blue 61; Reactive blue 66; Reactive blue 68; Reactive blue 69; Reactive blue 74; Reactive blue 86; Reactive blue 93; Reactive blue 94; Reactive blue101; Reactive blue103; Reactive blue114; Reactive blue117; Reactive blue125; Reactive blue141; Reactive blue142; Reactive blue 145; Reactive blue 149; Reactive blue 155; Reactive blue 164; Reactive blue 166; Reactive blue 177; Reactive blue 181; Reactive blue 185; Reactive blue 188; Reactive blue 189; Reactive
  • the dyes are listed according to Colour Index (Society of Dyers and Colourists/American Association of Textile Chemists and Colorists) classification.
  • proteases hydrolyse bonds within peptides and proteins, in the laundry context this leads to enhanced removal of protein or peptide containing stains.
  • suitable proteases families include aspartic proteases; cysteine proteases; glutamic proteases; aspargine peptide lyase; serine proteases and threonine proteases. Such protease families are described in the MEROPS peptidase database (http://merops.sanger.ac.uk/). Serine proteases are preferred. Subtilase type serine proteases are more preferred.
  • the term "subtilases" refers to a sub-group of serine protease according to Siezen et al., Protein Engng.
  • Serine proteases are a subgroup of proteases characterized by having a serine in the active site, which forms a covalent adduct with the substrate.
  • the subtilases may be divided into 6 subdivisions, i.e. the Subtilisin family, the Thermitase family, the Proteinase K family, the Lantibiotic peptidase family, the Kexin family and the Pyrolysin family.
  • subtilases are those derived from Bacillus such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in; US7262042 and WO09/021867 , and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89/06279 and protease PD138 described in ( WO93/18140 ).
  • proteases may be those described in WO92/175177 , WO01/016285 , WO02/026024 and WO02/016547 .
  • trypsin-like proteases are trypsin (e.g. of porcine or bovine origin) and the Fusarium protease described in WO89/06270 , WO94/25583 and WO05/040372 , and the chymotrypsin proteases derived from Cellumonas described in WO05/052161 and WO05/052146 .
  • proteases are the variants described in: WO92/19729 , WO96/034946 , WO98/201 15 , WO98/201 16 , WO99/01 1768 , WO01/44452 , WO03/006602 , WO04/03186 , WO04/041979 , WO07/006305 , WO1 1/036263 , WO1 1/036264 , especially the variants with substitutions in one or more of the following positions: 3, 4, 9, 15, 27, 36, 57, 68, 76, 87, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 106, 1 18, 120, 123, 128, 129, 130, 160, 167, 170, 194, 195, 199, 205, 206, 217, 218, 222, 224, 232, 235, 236, 245, 248, 252 and 274 using the BPN' numbering.
  • subtilase variants may comprise the mutations: S3T, V4I, S9R, A15T, K27R, *36D, V68A, N76D, N87S,R, *97E, A98S, S99G,D,A, S99AD, S101 G,M,R S103A, V104I,Y,N, S106A, G1 18V,R, H120D,N, N123S, S128L, P129Q, S130A, G160D, Y167A, R170S, A194P, G195E, V199M, V205I, L217D, N218D, M222S, A232V, K235L, Q236H, Q245R, N252K, T274A (using BPN' numbering).
  • protease is a subtilisins (EC 3.4.21.62).
  • subtilases are those derived from Bacillus such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in; US7262042 and WO09/021867 , and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89/06279 and protease PD138 described in ( WO93/18140 ).
  • the subsilisin is derived from Bacillus, preferably Bacillus lentus, B.
  • subtilisin is derived from Bacillus gibsonii or Bacillus Lentus.
  • Suitable commercially available protease enzymes include those sold under the trade names names Alcalase®, Blaze®; DuralaseTm, DurazymTm, Relase®, Relase® Ultra, Savinase®, Savinase® Ultra, Primase®, Polarzyme®, Kannase®, Liquanase®, Liquanase® Ultra, Ovozyme®, Coronase®, Coronase® Ultra, Neutrase®, Everlase® and Esperase® all could be sold as Ultra® or Evity® (Novozymes A/S).
  • Maxatase® Maxacal®, Maxapem®, Purafect®, Purafect Prime®, PreferenzTm, Purafect MA®, Purafect Ox®, Purafect OxP®, Puramax®, Properase®, EffectenzTm, FN2®, FN3®, FN4®, Excellase®, Opticlean® and Optimase® (Danisco/DuPont), AxapemTM (Gist-Brocases N.V.),
  • BLAP BLAP (sequence shown in Figure 29 of US 5,352,604 with the following mutations S99D + SIOI R + S103A + V104I + G159S, hereinafter referred to as BLAP), BLAP R (BLAP with S3T + V4I + V199M + V205I + L217D), BLAP X (BLAP with S3T + V4I + V205I) and BLAP F49 (BLAP with S3T + V4I + A194P + V199M + V205I + L217D) - all from Henkel/Kemira; and KAP (Bacillus alkalophilus subtilisin with mutations A230V + S256G + S259N) from Kao.
  • One or more further enzymes are preferred present in a laundry composition of the invention and when practicing a method of the invention.
  • the level of each enzyme in the laundry composition of the invention is from 0.0001 wt% to 0.1 wt% protein.
  • the further enzyme is selected from: alpha-amylases; lipases; and, cellulases.
  • Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola (synonym Thermomyces ), e.g. from H. lanuginosa ( T. lanuginosus ) as described in EP 258 068 and EP 305 216 or from H. insolens as described in WO 96/13580 , a Pseudomonas lipase, e.g. from P. alcaligenes or P. pseudoalcaligenes ( EP 218 272 ), P. cepacia ( EP 331 376 ), P. stutzeri ( GB 1,372,034 ), P.
  • lipase variants such as those described in WO 92/05249 , WO 94/01541 , EP 407 225 , EP 260 105 , WO 95/35381 , WO 96/00292 , WO 95/30744 , WO 94/25578 , WO 95/14783 , WO 95/22615 , WO 97/04079 and WO 97/07202 , and WO 00/60063 .
  • LipolaseTM and Lipolase UltraTM LipexTM and LipocleanTM (Novozymes A/S).
  • the method of the invention may be carried out in the presence of phospholipase classified as EC 3.1.1.4 and/or EC 3.1.1.32.
  • phospholipase is an enzyme which has activity towards phospholipids.
  • Phospholipids such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an outer (sn-1) and the middle (sn-2) positions and esterified with phosphoric acid in the third position; the phosphoric acid, in turn, may be esterified to an amino-alcohol.
  • Phospholipases are enzymes which participate in the hydrolysis of phospholipids.
  • phospholipases A 1 and A 2 which hydrolyze one fatty acyl group (in the sn-1 and sn-2 position, respectively) to form lysophospholipid
  • lysophospholipase or phospholipase B
  • Phospholipase C and phospholipase D release diacyl glycerol or phosphatidic acid respectively.
  • the method of the invention may be carried out in the presence of cutinase classified in EC 3.1.1.74.
  • the cutinase used according to the invention may be of any origin.
  • Preferably cutinases are of microbial origin, in particular of bacterial, of fungal or of yeast origin.
  • amylases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, e.g. a special strain of B. licheniformis, described in more detail in GB 1,296,839 , or the Bacillus sp. strains disclosed in WO 95/026397 or
  • WO 00/060060 Commercially available amylases are DuramylTM, TermamylTM, Termamyl UltraTM, NatalaseTM, StainzymeTM, FungamylTM and BANTM (Novozymes A/S), RapidaseTM and PurastarTM (from Genencor International Inc.).
  • Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g. the fungal cellulases produced from Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxysporum disclosed in US 4,435,307 , US 5,648,263 , US 5,691,178 , US 5,776,757 , WO 89/09259 , WO 96/029397 , and WO 98/012307 .
  • CelluzymeTM Commercially available cellulases include CelluzymeTM, CarezymeTM, CellucleanTM, EndolaseTM, RenozymeTM (Novozymes A/S), ClazinaseTM and Puradax HATM (Genencor International Inc.), and KAC-500(B)TM (Kao Corporation). CellucleanTM is preferred.
  • Suitable peroxidases/oxidases include those of plant, bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include peroxidases from Coprinus, e.g. from C. cinereus, and variants thereof as those described in WO 93/24618 , WO 95/10602 , and WO 98/15257 . Commercially available peroxidases include GuardzymeTM and NovozymTM 51004 (Novozymes A/S).
  • Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g., WO 92/19709 and WO 92/19708 .
  • a polyol such as propylene glycol or glycerol
  • a sugar or sugar alcohol lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid
  • alkyl groups are sufficiently long to form branched or cyclic chains, the alkyl groups encompass branched, cyclic and linear alkyl chains.
  • the alkyl groups are preferably linear or branched, most preferably linear.
  • the composition preferably comprises a fluorescent agent (optical brightener).
  • fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
  • Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN.
  • Di-styryl biphenyl compounds e.g. Tinopal (Trade Mark) CBS-X
  • Di-amine stilbene di-sulphonic acid compounds e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH
  • Pyrazoline compounds e.g. Blankophor SN.
  • Preferred fluorescers are: sodium 2 (4-styryl-3-sulphophenyl)-2H-napthol[1,2-d]triazole, disodium 4,4'-bis ⁇ [(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulophonate, disodium 4,4'-bis ⁇ [(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulphonate, and disodium 4,4'-bis(2-sulphostyryl)biphenyl.
  • the total amount of the fluorescent agent or agents used in the composition is preferably from 0.0001 to 0.5 wt %, more preferably 0.005 to 2 wt %, most preferably 0.05 to 0.25 wt %.
  • the aqueous solution used in the method has a fluorescer present.
  • the fluorescer is present in the aqueous solution used in the method preferably in the range from 0.0001 g/l to 0.1 g/l, more preferably 0.001 to 0.02 g/l.
  • the composition may comprise a perfume.
  • the perfume is preferably in the range from 0.001 to 3 wt %, more preferably 0.05 to 0.5 wt%, most preferably from 0.1 to 1 wt %.
  • CTFA Cosmetic, Toiletry and Fragrance Association
  • the perfume comprises at least one note (compound) from: alpha-isomethyl ionone, benzyl salicylate; citronellol; coumarin; hexyl cinnamal; linalool; Pentanoic acid, 2-methyl-, ethyl ester; octanal; benzyl acetate; 1,6-octadien-3-ol, 3,7-dimethyl-, 3-acetate; cyclohexanol, 2-(1,1-dimethylethyl)-, 1-acetate; delta-damascone; beta-ionone; verdyl acetate; dodecanal; hexyl cinnamic aldehyde; cyclopentadecanolide; benzeneacetic acid, 2-phenylethyl ester;amyl salicylate; beta-caryophyllene; ethyl undecylenate; geranyl an
  • Useful components of the perfume include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press ; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostr and; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA ).
  • compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components.
  • top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955 ]).
  • Preferred top-notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.
  • the Research Institute for Fragrance Materials provides a database of perfumes (fragrances) with safety information.
  • Perfume top note may be used to cue the whiteness and brightness benefit of the invention.
  • perfume components which it is advantageous to encapsulate include those with a relatively low boiling point, preferably those with a boiling point of less than 300, preferably 100-250 Celsius. It is also advantageous to encapsulate perfume components which have a low CLog P (ie. those which will have a greater tendency to be partitioned into water), preferably with a CLog P of less than 3.0.
  • these materials have been called the "delayed blooming" perfume ingredients and include one or more of the following materials: allyl caproate, amyl acetate, amyl propionate, anisic aldehyde, anisole, benzaldehyde, benzyl acetate, benzyl acetone, benzyl alcohol, benzyl formate, benzyl iso valerate, benzyl propionate, beta gamma hexenol, camphor gum, laevo-carvone, d-carvone, cinnamic alcohol, cinamyl formate, cis-jasmone, cis-3-hexenyl acetate, cuminic alcohol, cyclal c, dimethyl benzyl carbinol, dimethyl benzyl carbinol acetate, ethyl acetate, ethyl aceto acetate, ethy
  • compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components from the list given of delayed blooming perfumes given above present in the perfume.
  • perfumes with which the present invention can be applied are the so-called 'aromatherapy' materials. These include many components also used in perfumery, including components of essential oils such as Clary Sage, Eucalyptus, Geranium, Lavender, Mace Extract, Neroli, Nutmeg, Spearmint, Sweet Violet Leaf and Valerian.
  • the laundry treatment composition does not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid.
  • a peroxygen bleach e.g., sodium percarbonate, sodium perborate, and peracid.
  • indefinite article “a” or “an” and its corresponding definite article “the” as used herein means at least one, or one or more, unless specified otherwise.
  • the EPEI Ethoxylated PolyEthylene Imine
  • the EPEI was a PEI of 600 molecular weight with 20 moles of ethoxylate per NH on the base PEI; it is available as Sokalan HP20 ex BASF.
  • the SRP Soil Removal Polymer
  • the SRP is as described in WO2014/019903 (Unilever).
  • the viscosity of the formulation were measured using a Paar Physica MCR300 is a commercial stress rheometer.
  • the inventive formulation F1 and F2 containing the alkyl ether carboxylic acid have higher viscosity then the control with sodium lauryl ether sulfate alone.
  • the inventive formulation F1 and F2 containing the alkyl ether carboxylic acid have higher viscosity then the control with sodium lauryl ether sulfate alone.

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Claims (11)

  1. Composition de détergent de lessive liquide aqueuse comprenant :
    (i) de 2 à 10 % en masse d'un tensioactif anionique de benzènesulfonate d'alkyle linéaire ;
    (ii) de 0,5 à 4 % en masse de tensioactif zwitterionique choisi parmi : oxyde d'amine et carbobétaïnes ;
    (iii) de 0,1 à 4 % en masse d'un sel de métal alcalin ;
    (iv) de 1 à 5 % en masse d'une polyéthylène imine alcoxylée ;
    (v) de 1 à 10 % en masse d'un tensioactif anionique d'acide alkyléther carboxylique de la structure suivante :

            R2-(OCH2CH2)n-OCH2-COOH,

    dans laquelle :
    R2 est choisi parmi des chaînes alkyle linéaires ou ramifiées en C10 à C26 saturées et mono-insaturées, de préférence des chaînes alkyle linéaires en C12 à C20, encore mieux une chaîne alkyle linéaire en C16 à C18, et dans laquelle n est choisi de 6 à 20 ;
    (vi) de 0 à 10 % en masse d'un tensioactif anionique d'alkyléther sulfate avec de 0,5 à 1,5 mol d'équivalent d'éthoxylation ;
    (vii) de 0 à 2 % en masse d'un polymère détachant les salissures de polyester de téréphtalate ;
    (viii) de 0 à 4 % en masse d'un tensioactif non-ionique ; et,
    (ix) de 0,0 à 0,2 % en masse d'une enzyme protéase, dans laquelle la composition de détergent de lessive comprend au total de 10 à 20 % en masse de tensioactif anionique.
  2. Composition de détergent de lessive liquide aqueuse selon la revendication 1, dans laquelle la composition comprend de 1,5 à 2,5 % en masse d'un tensioactif zwitterionique et de 0,5 à 2 % en masse d'un sel de métal alcalin.
  3. Composition de détergent de lessive liquide aqueuse selon la revendication 1 ou 2, dans laquelle la composition comprend de 2,5 à 5 % en masse d'un tensioactif anionique d'alkyléther sulfate.
  4. Composition de détergent de lessive liquide aqueuse selon l'une quelconque des revendications précédentes, dans laquelle la composition comprend de 3 à 5 % en masse d'un tensioactif anionique d'acide alkyléther carboxylique.
  5. Composition de détergent de lessive liquide aqueuse selon l'une quelconque des revendications précédentes, dans laquelle la composition comprend de 2,5 à 5 % en masse d'un tensioactif anionique de benzènesulfonate d'alkyle linéaire.
  6. Composition de détergent de lessive liquide aqueuse selon l'une quelconque des revendications précédentes, dans laquelle la polyéthylène imine alcoxylée est une polyéthylène imine éthoxylée.
  7. Composition de détergent de lessive liquide aqueuse selon l'une quelconque des revendications précédentes, dans laquelle la composition comprend de 0,2 à 1 % en masse d'un polymère détachant les salissures de polyester de téréphtalate.
  8. Composition de détergent de lessive liquide aqueuse selon la revendication 7, dans laquelle le polymère détachant les salissures de polyester de téréphtalate est :
    Figure imgb0011
    dans laquelle c est de 4 à 9 ; b est de 1 à 3 ; e est de 40 à 50.
  9. Composition de détergent de lessive liquide aqueuse selon l'une quelconque des revendications précédentes, dans laquelle n est de 8 à 12, et R2 est choisi parmi une chaîne alkyle linéaire en C16 à C18 saturée et mono-insaturée.
  10. Composition de détergent de lessive liquide aqueuse selon l'une quelconque des revendications précédentes, dans laquelle le sel de métal alcalin est le chlorure de sodium.
  11. Procédé domestique de traitement d'un textile, le procédé comprenant les étapes consistant à :
    (i) traiter un textile avec 1 g/l d'une solution aqueuse de la composition de détergent de lessive comme définie dans l'une quelconque des revendications précédentes ; et,
    (ii) laisser ladite solution de détergent de lessive aqueuse rester en contact avec le textile pendant de 10 minutes à 2 jours puis rincer et sécher le textile.
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Publication number Priority date Publication date Assignee Title
EP3440170B1 (fr) * 2016-04-08 2020-04-08 Unilever PLC Composition de détergent pour lessive
EP3555255B1 (fr) * 2016-12-15 2020-06-24 Unilever PLC Composition de détergent pour lessive
WO2020259947A1 (fr) * 2019-06-28 2020-12-30 Unilever Plc Composition détergente
WO2020259948A1 (fr) * 2019-06-28 2020-12-30 Unilever Plc Composition détergente
CN115698246A (zh) 2020-06-08 2023-02-03 联合利华知识产权控股有限公司 提高蛋白酶活性的方法
WO2025168447A1 (fr) 2024-02-07 2025-08-14 Evonik Operations Gmbh Polyesters utilisés en tant que dispersants pour actifs agricoles

Family Cites Families (79)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1296839A (fr) 1969-05-29 1972-11-22
GB1372034A (en) 1970-12-31 1974-10-30 Unilever Ltd Detergent compositions
DK187280A (da) 1980-04-30 1981-10-31 Novo Industri As Ruhedsreducerende middel til et fuldvaskemiddel fuldvaskemiddel og fuldvaskemetode
US4760025A (en) 1984-05-29 1988-07-26 Genencor, Inc. Modified enzymes and methods for making same
WO1987000859A1 (fr) 1985-08-09 1987-02-12 Gist-Brocades N.V. Nouveaux enzymes lipolytiques et leur utilisation dans des compositions de detergents
EP0258068B1 (fr) 1986-08-29 1994-08-31 Novo Nordisk A/S Additif enzymatique pour détergent
NZ221627A (en) 1986-09-09 1993-04-28 Genencor Inc Preparation of enzymes, modifications, catalytic triads to alter ratios or transesterification/hydrolysis ratios
DE3854249T2 (de) 1987-08-28 1996-02-29 Novonordisk As Rekombinante Humicola-Lipase und Verfahren zur Herstellung von rekombinanten Humicola-Lipasen.
JPS6474992A (en) 1987-09-16 1989-03-20 Fuji Oil Co Ltd Dna sequence, plasmid and production of lipase
EP0394352B1 (fr) 1988-01-07 1992-03-11 Novo Nordisk A/S Detergent enzymatique
DK6488D0 (da) 1988-01-07 1988-01-07 Novo Industri As Enzymer
JP3079276B2 (ja) 1988-02-28 2000-08-21 天野製薬株式会社 組換え体dna、それを含むシュードモナス属菌及びそれを用いたリパーゼの製造法
JP2728531B2 (ja) 1988-03-24 1998-03-18 ノボ ノルディスク アクティーゼルスカブ セルラーゼ調製品
US5648263A (en) 1988-03-24 1997-07-15 Novo Nordisk A/S Methods for reducing the harshness of a cotton-containing fabric
GB8915658D0 (en) 1989-07-07 1989-08-23 Unilever Plc Enzymes,their production and use
ES2144990T3 (es) 1989-08-25 2000-07-01 Henkel Of America Inc Enzima proteolitica alcalina y metodo de produccion.
DK0528828T4 (da) 1990-04-14 1998-08-31 Genencor Internat Gmbh Alkaliske bacillus-lipaser, DNA-sekvenser, der koder herfor, og bacilli der producerer sådanne lipaser
DK0548228T3 (da) 1990-09-13 1999-05-10 Novo Nordisk As Lipasevarianter
DK58491D0 (da) 1991-04-03 1991-04-03 Novo Nordisk As Hidtil ukendte proteaser
AU666660B2 (en) 1991-04-30 1996-02-22 Procter & Gamble Company, The Built liquid detergents with boric-polyol complex to inhibit proteolytic enzyme
EP0511456A1 (fr) 1991-04-30 1992-11-04 The Procter & Gamble Company Détergents liquides contenant un ester aromatique de l'acide borique pour inhibition d'enzyme protéolitique
ES2121014T3 (es) 1991-05-01 1998-11-16 Novo Nordisk As Enzimas estabilizadas y composiciones detergentes.
DK28792D0 (da) 1992-03-04 1992-03-04 Novo Nordisk As Nyt enzym
DK72992D0 (da) 1992-06-01 1992-06-01 Novo Nordisk As Enzym
DK88892D0 (da) 1992-07-06 1992-07-06 Novo Nordisk As Forbindelse
DE69434242T2 (de) 1993-04-27 2006-01-12 Genencor International, Inc., Palo Alto Neuartige Lipasevarianten zur Verwendung in Reinigungsmitteln
DK52393D0 (fr) 1993-05-05 1993-05-05 Novo Nordisk As
JP2859520B2 (ja) 1993-08-30 1999-02-17 ノボ ノルディスク アクティーゼルスカブ リパーゼ及びそれを生産する微生物及びリパーゼ製造方法及びリパーゼ含有洗剤組成物
EP0724631A1 (fr) 1993-10-13 1996-08-07 Novo Nordisk A/S Variants de peroxydase stables par rapport a h 2?o 2?
DE69434962T2 (de) 1993-10-14 2008-01-17 The Procter & Gamble Company, Cincinnati Proteasehaltige reinigungsmittel
JPH07143883A (ja) 1993-11-24 1995-06-06 Showa Denko Kk リパーゼ遺伝子及び変異体リパーゼ
MX9603542A (es) 1994-02-22 1997-03-29 Novo Nordisk As Metodo para preparar una variante de una enzima lipolitica.
CA2186592C (fr) 1994-03-29 2008-02-19 Helle Outtrup Amylase alcaline issue d'un bacille
WO1995030744A2 (fr) 1994-05-04 1995-11-16 Genencor International Inc. Lipases a resistance aux tensioactifs amelioree
AU2884595A (en) 1994-06-20 1996-01-15 Unilever Plc Modified pseudomonas lipases and their use
AU2884695A (en) 1994-06-23 1996-01-19 Unilever Plc Modified pseudomonas lipases and their use
BE1008998A3 (fr) 1994-10-14 1996-10-01 Solvay Lipase, microorganisme la produisant, procede de preparation de cette lipase et utilisations de celle-ci.
CN1167503A (zh) 1994-10-26 1997-12-10 诺沃挪第克公司 一种具有脂解活性的酶
JPH08228778A (ja) 1995-02-27 1996-09-10 Showa Denko Kk 新規なリパーゼ遺伝子及びそれを用いたリパーゼの製造方法
CN1182451A (zh) 1995-03-17 1998-05-20 诺沃挪第克公司 新的内切葡聚糖酶
DE69637907D1 (de) 1995-05-05 2009-06-04 Novozymes As Protease-varianten und verbindungen
EP0839186B1 (fr) 1995-07-14 2004-11-10 Novozymes A/S Enzyme modifiee a activite lipolytique
JP4068142B2 (ja) 1995-08-11 2008-03-26 ノボザイムス アクティーゼルスカブ 新規の脂肪分解酵素
BR9711479B1 (pt) 1996-09-17 2009-08-11 variante de celulase tendo uma resistência aumentada a tensìdeo de ánion.
AU730286B2 (en) 1996-10-08 2001-03-01 Novo Nordisk A/S Diaminobenzoic acid derivatives as dye precursors
CN1530443A (zh) 1996-11-04 2004-09-22 ŵ����÷�����޹�˾ 枯草杆菌酶变异体和组合物
AU4772697A (en) 1996-11-04 1998-05-29 Novo Nordisk A/S Subtilase variants and compositions
WO1999011768A1 (fr) 1997-08-29 1999-03-11 Novo Nordisk A/S Variants de la protease et compositions
AR016969A1 (es) 1997-10-23 2001-08-01 Procter & Gamble VARIANTE DE PROTEASA, ADN, VECTOR DE EXPRESIoN, MICROORGANISMO HUESPED, COMPOSICIoN DE LIMPIEZA, ALIMENTO PARA ANIMALES Y COMPOSICIoN PARA TRATAR UN TEXTIL
KR20010108379A (ko) 1999-03-31 2001-12-07 피아 스타르 리파제 변이체
ES2532606T3 (es) 1999-03-31 2015-03-30 Novozymes A/S Polipéptidos con actividad de alfa-amilasa alcalina y ácidos nucleicos que los codifican
NZ517409A (en) 1999-08-31 2004-05-28 Novozymes As RP-II properties with amino acid substitutions used in detergent compositions and additives
CA2394971C (fr) 1999-12-15 2016-01-19 Novozymes A/S Variants de subtilase a performance de nettoyage amelioree sur des taches d'oeuf
CN1337553A (zh) 2000-08-05 2002-02-27 李海泉 地下观光游乐园
WO2002016547A2 (fr) 2000-08-21 2002-02-28 Novozymes A/S Enzymes subtilases
DK200101090A (da) 2001-07-12 2001-08-16 Novozymes As Subtilase variants
DE10162728A1 (de) 2001-12-20 2003-07-10 Henkel Kgaa Neue Alkalische Protease aus Bacillus gibsonii (DSM 14393) und Wasch-und Reinigungsmittel enthaltend diese neue Alkalische Protease
JP2005531307A (ja) 2002-06-26 2005-10-20 ノボザイムス アクティーゼルスカブ 変化した免疫原性を有するスブチラーゼ及びスブチラーゼ変異体
TWI319007B (en) 2002-11-06 2010-01-01 Novozymes As Subtilase variants
WO2005040372A1 (fr) 2003-10-23 2005-05-06 Novozymes A/S Protease a stabilite amelioree dans les detergents
BRPI0416797A (pt) 2003-11-19 2007-04-17 Genencor Int serina proteases, ácidos nucléicos codificando enzimas de serina e vetores e células hospedeiras incorporando as mesmas
EP1739161B1 (fr) * 2005-06-20 2009-04-01 KAO CHEMICALS GmbH composition promouvant l'équme
ATE529505T1 (de) 2005-07-08 2011-11-15 Novozymes As Subtilase varianten
ATE486927T1 (de) 2007-01-19 2010-11-15 Procter & Gamble Wäschepflegemittel mit weisstöner für cellulosehaltige substrate
DE102007038031A1 (de) 2007-08-10 2009-06-04 Henkel Ag & Co. Kgaa Mittel enthaltend Proteasen
RU2470070C2 (ru) 2008-01-04 2012-12-20 Дзе Проктер Энд Гэмбл Компани Композиции, содержащие фермент и подкрашивающий агент для тканей
EP2085070A1 (fr) 2008-01-11 2009-08-05 Procter & Gamble International Operations SA. Compositions de nettoyage et/ou de traitement
BRPI0909707A2 (pt) 2008-02-29 2015-08-25 Procter & Gamble Composição detergente que compreende lipase.
EP2247720A2 (fr) 2008-02-29 2010-11-10 The Procter & Gamble Company Composition de détergent contenant une lipase
MY159940A (en) 2008-06-06 2017-02-15 Procter & Gamble Detergent composition comprising a variant of a family 44 xyloglucanase
PL2300586T3 (pl) 2008-06-16 2015-08-31 Unilever Nv Ulepszenia dotyczące czyszczenia tkanin
MX339581B (es) 2009-09-25 2016-06-01 Novozymes As Variantes de subtilasa.
CN102648277B (zh) 2009-09-25 2015-05-20 诺维信公司 蛋白酶变体的用途
CN103975050B (zh) * 2011-12-12 2017-02-22 荷兰联合利华有限公司 洗衣组合物
BR112014013668B1 (pt) * 2011-12-12 2022-05-10 Unilever Ip Holdings B.V Composição detergente líquida para lavar roupa
TR201900214T4 (tr) 2012-03-19 2019-02-21 Milliken & Co Karboksilat Boyalar
EP2692842B1 (fr) 2012-07-31 2014-07-30 Unilever PLC Compositions concentrées de détergent liquide
ES2593825T3 (es) * 2012-07-31 2016-12-13 Unilever N.V. Composiciones detergentes líquidas alcalinas para lavado de ropa que comprenden poliésteres
BR112015008051B1 (pt) 2012-10-17 2021-06-15 Unilever Ip Holdings B.V. Composição detergente para lavar roupa, método para amaciar tecidos e uso de uma emulsão aquosa

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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EP3433346A1 (fr) 2019-01-30

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