WO2016206838A1 - Laundry detergent composition - Google Patents

Laundry detergent composition Download PDF

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Publication number
WO2016206838A1
WO2016206838A1 PCT/EP2016/059425 EP2016059425W WO2016206838A1 WO 2016206838 A1 WO2016206838 A1 WO 2016206838A1 EP 2016059425 W EP2016059425 W EP 2016059425W WO 2016206838 A1 WO2016206838 A1 WO 2016206838A1
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WO
WIPO (PCT)
Prior art keywords
laundry detergent
detergent composition
composition according
esterase
alkyi
Prior art date
Application number
PCT/EP2016/059425
Other languages
French (fr)
Inventor
Stephen Norman Batchelor
Jayne Michelle Bird
Original Assignee
Unilever Plc
Unilever N.V.
Conopco, Inc., D/B/A Unilever
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever Plc, Unilever N.V., Conopco, Inc., D/B/A Unilever filed Critical Unilever Plc
Priority to CN201680034960.7A priority Critical patent/CN107771210B/en
Priority to EP16718712.9A priority patent/EP3313968B1/en
Priority to BR112017027405-1A priority patent/BR112017027405B1/en
Publication of WO2016206838A1 publication Critical patent/WO2016206838A1/en
Priority to ZA2017/07505A priority patent/ZA201707505B/en

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Classifications

    • 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
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/08Silicates
    • 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
    • C11D3/10Carbonates ; Bicarbonates
    • 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
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/128Aluminium silicates, e.g. zeolites
    • 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
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • 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
    • C11D3/3707Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627Preparations containing enzymes, e.g. protease or amylase containing lipase
    • 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
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38636Preparations containing enzymes, e.g. protease or amylase containing enzymes other than protease, amylase, lipase, cellulase, oxidase or reductase
    • 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
    • C11D3/40Dyes ; Pigments
    • 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
    • C11D3/50Perfumes
    • 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
    • C11D1/008Polymeric surface-active agents
    • 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
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • C11D2111/12

Definitions

  • the present invention concerns the use of alkoxylated polyarylphenols with a lipid esterase in a detergent formulation.
  • Lipid esterase are enzymes that hydrolyse the ester bonds in a lipid. They can be produced by a large number of living cells for example bacteria, yeasts and fungi. In the laundry context cleaning lipid esterase are well-known which enhance the cleaning of fabrics.
  • cleaning lipid esterases examples include first wash lipases.
  • GB 2 007 692 discloses anti-soiling and anti-redeposition adjuvants for detergent compositions include at least one polymer A, said polymer itself having anti-soiling and anti- redeposition properties, at least one solubilizing and dispersing agent B for said polymer A, and at least one water repellent C for said agent B.
  • EP 2 767 581 discloses a method of laundering a fabric comprising the steps of; (i) contacting the fabric with a lipid esterase selected from class E.C. 3.1.1 .3, class E.C.
  • the present invention provides a laundry detergent composition comprising:
  • lipid esterase at a level of from 0.0005 to 0.5 wt % of pure enzyme, preferably from 0.05 to 0.3 wt %, wherein the lipid esterase is selected from Triacylglycerol lipase (E.C. 3.1 .1.3); Carboxylic ester hydrolase (E.C. 3.1 .1.1 ); Cutinase (E.C.
  • the level of enzyme as referred to as "pure” is simply the level as measured calculated as in the pure form of enzyme rather than in admixture with adjuncts as the enzyme is
  • the present invention provides a domestic method of treating a textile, the method comprising the step of: treating a textile with an aqueous solution of 0.5 to 20 g/L of the laundry detergent composition as defined herein.
  • the domestic method is preferably conducted at a temperature from 283 to 313K under atmospheric pressure in domestic tap water.
  • the alkoxylated polyarylphenol dispersant is a phenol to which aryl groups are covalently attached and the molecule is alkoxylated preferably with ethoxy groups.
  • the alkoxylated polyarylphenol may be charged or uncharged, preferably negatively charged or uncharged, most preferably uncharged (neutral).
  • the alkoxylated polyarylphenol is an alkoxylated tristyrylphenol.
  • the alkoxylated polyarylphenol contains an average of 5 to 70 alkoxy groups, preferably 10 to 30 alkoxy groups.
  • the alkoxylation is ethoxylation.
  • the alkoxylated polyarylphenol has 2 or 3 aryl groups attached to the phenol. Preferably they are in the 2,4 or 2,4,6 position on the phenol.
  • the alkoxylate is attached to the 1 position.
  • the alkoxylate may be capped by charged groups such as phosphate or sulphate.
  • the alkoxylate is capped by a hydrogen atom.
  • the aryl group in the alkoxylated polyarylphenol is preferably selected from, phenyl, tolyl, naphthyl, tetrahydronaphthyl, indanyl, indenyl, styryl, pyridyl, quinolinyl, and mixtures thereof, most preferably styryl.
  • the alkoxylated polyarylphenol is polyethylene glycol mono(2,4,6-tris(1 - phenylethyl)phenyl) ether (CAS-No: 70559-25-0) with the following structure:
  • n is selected from 5 to 70, preferably n is selected from: 10; 1 1 ; 12; 13; 14; 15; 16; 17; 18; 19; 20; 21 ; 22; 23; 24; 25; 26; 27; 28; 29; 30; 31 ; 32; 33; 34; 35; 36; 37; 38; 39; 40; 41 ; 42; 43; 44; 45; 46; 47; 48; 49; 50; 51 ; 52; 53; and, 54, most preferably n is selected from: 10; 1 1 ; 12; 13; 14; 15; 16; 17; 18; 19; 20; 21 ; 22; 23; 24; 25; 26; 27; 28; 29; 30.
  • n is the average numbers of moles of alkoxy units in the polyalkoxy chain.
  • Rhodia under the Soprophor trade name
  • Clariant under the Emulsogen trade name
  • Aoki Oil Industrial Co under the Blaunon trade name
  • Stepan under the Makon trade name
  • TOHO Chemical Industry Co under the Sorpol trade name.
  • alkoxylated polyarylphenol dispersant is not considered a surfactant and does not contribute numerically to the surfactant as defined herein.
  • Cleaning lipid esterases are preferable active at alkaline pH in the range 7 to 1 1 , most preferably they have maximum activity in the pH range 8 to 10.5.
  • the lipid esterase is selected from lipase enzymes in E.C. class 3.1 or 3.2 or a combination thereof.
  • the cleaning lipid esterases are selected from: (1 ) Triacylglycerol lipases (E.C. 3.1.1 .3)
  • Suitable triacylglycerol lipases can be selected from variants of the Humicola lanuginosa (Thermomyces lanuginosus) lipase.
  • Other suitable triacylglycerol lipases can be selected from variants of Pseudomonas lipases, e.g., from P. alcaligenes or P. pseudoalcaligenes (EP 218 272), P. cepacia (EP 331 376), P. stutzeri (GB 1 ,372,034), P. fluorescens,
  • Suitable carboxylic ester hydrolases can be selected from wild-types or variants of carboxylic ester hydrolases endogenous to B. gladioli, P. fluorescens, P. putida, B.
  • Suitable cutinases can be selected from wild-types or variants of cutinases endogenous to strains of Aspergillus, in particular Aspergillus oryzae, a strain of Alternaria, in particular Alternaria brassiciola, a strain of Fusarium, in particular Fusarium solani, Fusarium solani pisi, Fusarium oxysporum, Fusarium oxysporum cepa, Fusarium roseum culmorum, or Fusarium roseum sambucium, a strain of Helminthosporum, in particular Helminthosporum sativum, a strain of Humicola, in particular Humicola insolens, a strain of Pseudomonas, in particular Pseu
  • the cutinase is selected from variants of the Pseudomonas mendocina cutinase described in WO 2003/076580 (Genencor), such as the variant with three substitutions at I 178M, F180V, and S205G.
  • the cutinase is a wild-type or variant of the six cutinases endogenous to Coprinopsis cinerea described in H. Kontkanen et al, App. Environ.
  • the cutinase is a wild-type or variant of the two cutinases endogenous to Trichoderma reesei described in WO2009007510 (VTT).
  • the cutinase is derived from a strain of Humicola insolens, in particular the strain Humicola insolens DSM 1800.
  • Humicola insolens cutinase is described in WO 96/13580 which is hereby incorporated by reference.
  • the cutinase may be a variant, such as one of the variants disclosed in WO 00/34450 and WO 01/92502.
  • Preferred cutinase variants include variants listed in Example 2 of WO 01/92502.
  • Preferred commercial cutinases include Novozym 51032 (available from Novozymes, Bagsvaerd, Denmark).
  • Suitable sterol esterases may be derived from a strain of Ophiostoma, for example
  • Ophiostoma piceae a strain of Pseudomonas, for example Pseudomonas aeruginosa, or a strain of Melanocarpus, for example Melanocarpus albomyces.
  • the sterol esterase is the Melanocarpus albomyces sterol esterase described in H. Kontkanen et al, Enzyme Microb Technol., 39, (2006), 265-273. Suitable wax-ester hydrolases may be derived from Simmondsia chinensis.
  • the lipid esterase is most preferably selected from a Triacylglycerol lipases (E.C. 3.1.1 .3).
  • Examples of EC 3.1.1.3 lipases include those described in WlPO publications WO 00/60063, WO 99/42566, WO 02/062973, WO 97/04078, WO 97/04079 and US 5,869,438.
  • Preferred lipases are produced by Absidia reflexa, Absidia corymbefera, Rhizmucor miehei, Rhizopus deleman Aspergillus niger, Aspergillus tubigensis, Fusarium oxysporum, Fusarium heterosporum, Aspergillus oryzea, Penicilium camembertii, Aspergillus foetidus, Aspergillus niger, Thermomyces lanoginosus (synonym: Humicola lanuginosa) and Landerina penisapora, particularly Thermomyces lanoginosus. Certain preferred lipases are supplied by Novozymes under the tradenames.
  • Lipolase®, Lipolase Ultra®, Lipoprime®, Lipoclean® and Lipex® registered tradenames of Novozymes
  • LIPASE P "AMANO®” available from Areario Pharmaceutical Co. Ltd., Nagoya, Japan
  • AMANO-CES® commercially available from Toyo Jozo Co., Tagata, Japan
  • Chromobacter viscosum lipases from Amersham Pharmacia Biotech., Piscataway, New Jersey, U.S.A. and Diosynth Co., Netherlands, and other lipases such as Pseudomonas gladioli.
  • suitable lipases include the "first cycle lipases" described in WO 00/60063 and U.S. Patent 6,939,702 Bl, preferably a variant of SEQ ID No. 2, more preferably a variant of SEQ ID No. 2 having at least 90% homology to SEQ ID No. 2 comprising a substitution of an electrically neutral or negatively charged amino acid with R or K at any of positions 3, 224, 229, 231 and 233, with a most preferred variant comprising T23 IR and N233R mutations, such most preferred variant being sold under the tradename Lipex® (Novozymes).
  • lipases can be used in combination (any mixture of lipases can be used). Suitable lipases can be purchased from Novozymes, Bagsvaerd, Denmark; Areario Pharmaceutical Co. Ltd., Nagoya, Japan; Toyo Jozo Co., Tagata, Japan; Amersham
  • Lipid esterase with with reduced potential for odor generation and a good relative
  • the laundry composition comprises an anionic charged surfactant (which includes a mixture of the same).
  • the weight fraction of non-ionic surfactant/anionic surfactant is from 0 to 0.3, preferably 0 to 0.1.
  • Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher alkyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher Cs to Cis alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl Cg to C20 benzene sulphonates, particularly sodium linear secondary alkyl C10 to C15 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.
  • the anionic surfactant is preferably selected from: linear alkyl benzene sulphonate; alkyl sulphates; alkyl ether sulphates; soaps; alkyl (preferably methyl) ester sulphonates, and mixtures thereof.
  • the most preferred anionic surfactants are selected from: linear alkyl benzene sulphonate; alkyl sulphates; alkyl ether sulphates and mixtures thereof.
  • the alkyl ether sulphate is a C12-C14 n-alkyl ether sulphate with an average of 1 to 3EO (ethoxylate) units.
  • Sodium lauryl ether sulphate is particularly preferred (SLES).
  • the linear alkyl benzene sulphonate is a sodium Cn to C15 alkyl benzene sulphonates.
  • the alkyl sulphates is a linear or branched sodium C12 to C18 alkyl sulphates.
  • Sodium dodecyl sulphate is particularly preferred, (SDS, also known as primary alkyl sulphate).
  • liquid formulations preferably two or more anionic surfactant are present, for example linear alkyl benzene sulphonate together with an alkyl ether sulphate.
  • 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.
  • Specific nonionic detergent compounds are the condensation products of aliphatic Cs to Cis primary or secondary linear or branched alcohols with ethylene oxide.
  • the alkyl ethoxylated non-ionic surfactant is a Cs to C18 primary alcohol with an average ethoxylation of 7EO to 9EO units.
  • nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "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.
  • the surfactants used are saturated.
  • surfactants such as those described in EP-A-328 177 (Unilever), which show resistance to salting-out, the alkyl polyglycoside surfactants described in
  • EP-A-070 074, and alkyl monoglycosides are examples of the detergent compositions based on anionic or anionic/non-ionic surfactants.
  • the detergent compositions based on anionic or anionic/non-ionic surfactants is however the more preferred embodiment.
  • Builders or Complexinq Agents Builder materials may be selected from 1 ) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
  • calcium sequestrant builder materials examples include alkali metal polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetra-acetic acid.
  • Examples of precipitating builder materials include sodium orthophosphate and sodium carbonate.
  • Examples of calcium ion-exchange builder materials include the various types of water- insoluble crystalline or amorphous aluminosilicates, of which zeolites are the well known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070.
  • the composition may also contain 0-65 % of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or
  • alkenylsuccinic acid nitrilotriacetic acid or the other builders mentioned below.
  • Many builders are also bleach-stabilising agents by virtue of their ability to complex metal ions.
  • Zeolite and carbonate carbonate (including bicarbonate and sesquicarbonate) are preferred builders, with carbonates being particularly preferred.
  • the composition may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is typically present at a level of less than 15%w.
  • Aluminosilicates are materials having the general formula: 0.8-1.5 M 2 0. AI2O3. 0.8-6 Si0 2 , where M is a monovalent cation, preferably sodium. These materials contain some bound water and are required to have a calcium ion exchange capacity of at least
  • the preferred sodium aluminosilicates contain 1.5-3.5 S1O2 units in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature. The ratio of surfactants to
  • alumuminosilicate (where present) is preferably greater than 5:2, more preferably greater than 3:1 .
  • phosphate builders may be used.
  • 'phosphate' embraces diphosphate, triphosphate, and phosphonate species.
  • Other forms of builder include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst).
  • the laundry detergent formulation is a non-phosphate built powder laundry detergent formulation, i.e., contains less than 1 wt% of phosphate.
  • the powder laundry detergent formulations are predominantly carbonate built. Powders, should preferably give an in use pH of from 9.5 to 1 1.
  • the powder laundry detergent has linear alkyl benzene sulfonate surfactant at a level of greater than 80 wt% of the total anionic surfactant present.
  • mono propylene glycol is present at a level from 1 to 30 wt%, most preferably 2 to 18 wt%, to provide the formulation with appropriate, pourable viscosity.
  • the composition preferably comprises a fluorescent agent (optical brightener).
  • fluorescent agents are well known and many such fluorescent agents are available commercially.
  • these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
  • the total amount of the fluorescent agent or agents used in the composition is generally from 0.0001 to 0.5 wt %, preferably 0.005 to 2 wt %, more preferably 0.01 to 0.1 wt %.
  • 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.
  • Preferred fluorescers are fluorescers with CAS-No 3426-43-5; CAS-No 35632-99-6; CAS-No 24565-13-7; CAS-No 12224-16-7; CAS-No 13863-31 -5; CAS-No 4193-55-9; CAS-No 16090- 02-1 ; CAS-No 133-66-4; CAS-No 68444-86-0; CAS-No 27344-41 -8.
  • fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-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' disulphonate, 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 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 preferably comprises a perfume.
  • perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.
  • 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
  • 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 Nostrand; 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.
  • Perfume top note may be used to cue the whiteness and brightness benefit of the invention.
  • perfume may be encapsulated, typical 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
  • perfume ingredients 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, of relatively low boiling point and relatively low CLog P 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,
  • 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,
  • 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.
  • composition may comprise one or more further polymers. Examples are:
  • carboxymethylcellulose poly (ethylene glycol), polyvinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic 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 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.
  • Dye weights refer to the sodium or chloride salts unless otherwise stated.
  • a powder laundry detergent was prepared of the following formulation:
  • the formulation was used to wash eight 5x5cm EMPA 1 17 stain monitor (blood/milk/ink stain on polycotton) in a tergotometer set at 200rpm. A 60 minute wash was conducted in 800ml of 26° French Hard water at 35°C, with 1.5g/L of the formulation. To simulate oily soil (7.4 g) of an SBL2004 soil strip (ex Warwick Equest) was added to the wash liquor.
  • ⁇ _ * L * (treatment)-L * (control without enzyme or alkoxylated polyarylphenol) Higher ⁇ _ * value equate to better cleaning.
  • Triacylglycerol lipase EC no. 3.1.1.3
  • Lipex® ex Novozymes The enzyme was added to give 0.3wt% pure active protein to the formulation.
  • the combination of lipase and alkoxylated polyarylphenol with 10, 15 and 54EO to the formulation increases the stain removal as seen by higher AL * values compared to the reference control values.
  • the combination of lipase and alkoxylated polyarylphenol with 10EO, and 16EO gives a greater increase in stain removal than expected from combination of the effects of the single components.
  • For 16EO/lipase a value of 0.29+3.45 3.74 is expected and 8.25 obtained.
  • the formulation was remade with the addition of mix of amylase, mannase and pectinase enzymes (Stainzyme ® Novozyme , Mannaway ® Novozymes, Pectawash ® Novozymes)

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Abstract

A laundry detergent composition comprising: (i) from 0.5 to 20 wt% of a alkoxylated polyarylphenol having an average of 5 to 70 alkoxy groups; (ii) from 4 to 50 wt% of an anionic surfactant, other than the alkoxylated polyarylphenol; and, (iii) a lipid esterase at a level of from 0.0005 to 0.5 wt % of pure enzyme, wherein the lipid esterase is selected from Triacylglycerol lipase (E.C. 3.1.1.3); Carboxylic ester hydrolase (E.C. 3.1.1.1); Cutinase (E.C. 3.1.1.74); Sterol esterase (E.C. 3.1.1.13); and, Wax-ester hydrolase (E.C. 3.1.1.50). A domestic method of treating a textile, the method comprising the step of: treating a textile with an aqueous solution of 0.5 to 20 g/L of the laundry detergent composition.

Description

LAUNDRY DETERGENT COMPOSITION
FIELD OF INVENTION
The present invention concerns the use of alkoxylated polyarylphenols with a lipid esterase in a detergent formulation.
BACKGROUND OF THE INVENTION
Lipid esterase are enzymes that hydrolyse the ester bonds in a lipid. They can be produced by a large number of living cells for example bacteria, yeasts and fungi. In the laundry context cleaning lipid esterase are well-known which enhance the cleaning of fabrics.
Examples of cleaning lipid esterases include first wash lipases.
Lipid esterases are discussed in Enzymes in Detergency edited by Jan H. Van Ee„ Onno Misset and Erik J. Baas (1997 Marcel Dekker, New York). GB 2 007 692 discloses anti-soiling and anti-redeposition adjuvants for detergent compositions include at least one polymer A, said polymer itself having anti-soiling and anti- redeposition properties, at least one solubilizing and dispersing agent B for said polymer A, and at least one water repellent C for said agent B. EP 2 767 581 discloses a method of laundering a fabric comprising the steps of; (i) contacting the fabric with a lipid esterase selected from class E.C. 3.1.1 .3, class E.C. 3.1.1 .1 or a combination thereof; (ii) contacting the fabric from step (i) with a soil; (iii) contacting the fabric from step (ii) with a laundry detergent composition, wherein the laundry detergent composition optionally comprises a detersive surfactant, and optionally comprises a lipid esterase.
There is a need to improve the performance of cleaning lipid esterase enzymes in detergent formulations. SUMMARY OF THE INVENTION
We have found that the combination of a lipid esterase and alkoxylated polyarylphenols gives enhanced cleaning.
In one aspect the present invention provides a laundry detergent composition comprising:
(i) from 0.5 to 20 wt%, preferably from 2 to 14 wt%, most preferably from 3 to 9 wt%, of an alkoxylated polyarylphenols having an average of 5 to 70 alkoxy groups
(ii) from 4 to 50 wt% of an anionic surfactant, other than the alkoxylated polyarylphenol, preferably the level of anionic surfactant is from 6 to 30 wt%, more preferably from 8 to 20 wt%; and, (iii) a lipid esterase at a level of from 0.0005 to 0.5 wt % of pure enzyme, preferably from 0.05 to 0.3 wt %, wherein the lipid esterase is selected from Triacylglycerol lipase (E.C. 3.1 .1.3); Carboxylic ester hydrolase (E.C. 3.1 .1.1 ); Cutinase (E.C. 3.1 .1 .74); Sterol esterase (E.C. 3.1.1.13); and, Wax-ester hydrolase (E.C. 3.1 .1.50). The level of enzyme as referred to as "pure" is simply the level as measured calculated as in the pure form of enzyme rather than in admixture with adjuncts as the enzyme is
commercially provided.
In another aspect the present invention provides a domestic method of treating a textile, the method comprising the step of: treating a textile with an aqueous solution of 0.5 to 20 g/L of the laundry detergent composition as defined herein.
The domestic method is preferably conducted at a temperature from 283 to 313K under atmospheric pressure in domestic tap water. DETAILED DESCRIPTION OF THE INVENTION Alkoxylated polyarylphenol dispersant
The alkoxylated polyarylphenol dispersant is a phenol to which aryl groups are covalently attached and the molecule is alkoxylated preferably with ethoxy groups. The alkoxylated polyarylphenol may be charged or uncharged, preferably negatively charged or uncharged, most preferably uncharged (neutral).
Preferably the alkoxylated polyarylphenol is an alkoxylated tristyrylphenol.
The alkoxylated polyarylphenol contains an average of 5 to 70 alkoxy groups, preferably 10 to 30 alkoxy groups. Preferably the alkoxylation is ethoxylation.
Preferably the alkoxylated polyarylphenol has 2 or 3 aryl groups attached to the phenol. Preferably they are in the 2,4 or 2,4,6 position on the phenol. The alkoxylate is attached to the 1 position. The alkoxylate may be capped by charged groups such as phosphate or sulphate. Preferably the alkoxylate is capped by a hydrogen atom.
The aryl group in the alkoxylated polyarylphenol is preferably selected from, phenyl, tolyl, naphthyl, tetrahydronaphthyl, indanyl, indenyl, styryl, pyridyl, quinolinyl, and mixtures thereof, most preferably styryl.
Most preferably, the alkoxylated polyarylphenol is polyethylene glycol mono(2,4,6-tris(1 - phenylethyl)phenyl) ether (CAS-No: 70559-25-0) with the following structure:
Figure imgf000004_0001
Where n is selected from 5 to 70, preferably n is selected from: 10; 1 1 ; 12; 13; 14; 15; 16; 17; 18; 19; 20; 21 ; 22; 23; 24; 25; 26; 27; 28; 29; 30; 31 ; 32; 33; 34; 35; 36; 37; 38; 39; 40; 41 ; 42; 43; 44; 45; 46; 47; 48; 49; 50; 51 ; 52; 53; and, 54, most preferably n is selected from: 10; 1 1 ; 12; 13; 14; 15; 16; 17; 18; 19; 20; 21 ; 22; 23; 24; 25; 26; 27; 28; 29; 30.
The designation n is the average numbers of moles of alkoxy units in the polyalkoxy chain.
Compounds are available from industrial suppliers, for example Rhodia under the Soprophor trade name; from Clariant under the Emulsogen trade name; Aoki Oil Industrial Co under the Blaunon trade name; from Stepan under the Makon trade name; from TOHO Chemical Industry Co under the Sorpol trade name.
In the context of the current invention the alkoxylated polyarylphenol dispersant is not considered a surfactant and does not contribute numerically to the surfactant as defined herein.
Lipid Esterases
Cleaning lipid esterases are discussed in Enzymes in Detergency edited by Jan H. Van Ee, Onno Misset and Erik J. Baas (1997 Marcel Dekker, New York).
Cleaning lipid esterases are preferable active at alkaline pH in the range 7 to 1 1 , most preferably they have maximum activity in the pH range 8 to 10.5. The lipid esterase is selected from lipase enzymes in E.C. class 3.1 or 3.2 or a combination thereof.
The cleaning lipid esterases are selected from: (1 ) Triacylglycerol lipases (E.C. 3.1.1 .3)
(2) Carboxylic ester hydrolase (E.C. 3.1.1.1 )
(3) Cutinase (E.C. 3.1.1.74)
(4) Sterol esterase (E.C. 3.1.1.13)
(5) Wax-ester hydrolase (E.C. 3.1.1.50) Suitable triacylglycerol lipases can be selected from variants of the Humicola lanuginosa (Thermomyces lanuginosus) lipase. Other suitable triacylglycerol lipases can be selected from variants of Pseudomonas lipases, e.g., from P. alcaligenes or P. pseudoalcaligenes (EP 218 272), P. cepacia (EP 331 376), P. stutzeri (GB 1 ,372,034), P. fluorescens,
Pseudomonas sp. strain SD 705 (WO 95/06720 and WO 96/27002), P. wisconsinensis (WO 96/12012), Bacillus lipases, e.g., from B. subtilis (Dartois et al. (1993), Biochemica et Biophysica Acta, 1 131 , 253-360), B. stearothermophilus (JP 64/744992) or B. pumilus (WO 91/16422). Suitable carboxylic ester hydrolases can be selected from wild-types or variants of carboxylic ester hydrolases endogenous to B. gladioli, P. fluorescens, P. putida, B. acidocaldarius, B. subtilis, B. stearothermophilus, Streptomyces chrysomallus, S. diastatochromogenes and Saccaromyces cerevisiae. Suitable cutinases can be selected from wild-types or variants of cutinases endogenous to strains of Aspergillus, in particular Aspergillus oryzae, a strain of Alternaria, in particular Alternaria brassiciola, a strain of Fusarium, in particular Fusarium solani, Fusarium solani pisi, Fusarium oxysporum, Fusarium oxysporum cepa, Fusarium roseum culmorum, or Fusarium roseum sambucium, a strain of Helminthosporum, in particular Helminthosporum sativum, a strain of Humicola, in particular Humicola insolens, a strain of Pseudomonas, in particular Pseudomonas mendocina, or Pseudomonas putida, a strain of Rhizoctonia, in particular Rhizoctonia solani, a strain of Streptomyces, in particular Streptomyces scabies, a strain of Coprinopsis, in particular Coprinopsis cinerea, a strain of Thermobifida, in particular Thermobifida fusca, a strain of Magnaporthe, in particular Magnaporthe grisea, or a strain of Ulocladium, in particular Ulocladium consortiale.
In a preferred embodiment, the cutinase is selected from variants of the Pseudomonas mendocina cutinase described in WO 2003/076580 (Genencor), such as the variant with three substitutions at I 178M, F180V, and S205G.
In another preferred embodiment, the cutinase is a wild-type or variant of the six cutinases endogenous to Coprinopsis cinerea described in H. Kontkanen et al, App. Environ.
Microbiology, 2009, p2148-2157. In another preferred embodiment, the cutinase is a wild-type or variant of the two cutinases endogenous to Trichoderma reesei described in WO2009007510 (VTT).
In a most preferred embodiment the cutinase is derived from a strain of Humicola insolens, in particular the strain Humicola insolens DSM 1800. Humicola insolens cutinase is described in WO 96/13580 which is hereby incorporated by reference. The cutinase may be a variant, such as one of the variants disclosed in WO 00/34450 and WO 01/92502.
Preferred cutinase variants include variants listed in Example 2 of WO 01/92502. Preferred commercial cutinases include Novozym 51032 (available from Novozymes, Bagsvaerd, Denmark).
Suitable sterol esterases may be derived from a strain of Ophiostoma, for example
Ophiostoma piceae, a strain of Pseudomonas, for example Pseudomonas aeruginosa, or a strain of Melanocarpus, for example Melanocarpus albomyces.
In a most preferred embodiment the sterol esterase is the Melanocarpus albomyces sterol esterase described in H. Kontkanen et al, Enzyme Microb Technol., 39, (2006), 265-273. Suitable wax-ester hydrolases may be derived from Simmondsia chinensis. The lipid esterase is most preferably selected from a Triacylglycerol lipases (E.C. 3.1.1 .3).
Examples of EC 3.1.1.3 lipases include those described in WlPO publications WO 00/60063, WO 99/42566, WO 02/062973, WO 97/04078, WO 97/04079 and US 5,869,438. Preferred lipases are produced by Absidia reflexa, Absidia corymbefera, Rhizmucor miehei, Rhizopus deleman Aspergillus niger, Aspergillus tubigensis, Fusarium oxysporum, Fusarium heterosporum, Aspergillus oryzea, Penicilium camembertii, Aspergillus foetidus, Aspergillus niger, Thermomyces lanoginosus (synonym: Humicola lanuginosa) and Landerina penisapora, particularly Thermomyces lanoginosus. Certain preferred lipases are supplied by Novozymes under the tradenames. Lipolase®, Lipolase Ultra®, Lipoprime®, Lipoclean® and Lipex® (registered tradenames of Novozymes) and LIPASE P "AMANO®" available from Areario Pharmaceutical Co. Ltd., Nagoya, Japan, AMANO-CES®, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from Amersham Pharmacia Biotech., Piscataway, New Jersey, U.S.A. and Diosynth Co., Netherlands, and other lipases such as Pseudomonas gladioli. Additional useful lipases are described in WlPO publications WO 02062973, WO 2004/101759, WO 2004/101760 and WO 2004/101763. In one embodiment, suitable lipases include the "first cycle lipases" described in WO 00/60063 and U.S. Patent 6,939,702 Bl, preferably a variant of SEQ ID No. 2, more preferably a variant of SEQ ID No. 2 having at least 90% homology to SEQ ID No. 2 comprising a substitution of an electrically neutral or negatively charged amino acid with R or K at any of positions 3, 224, 229, 231 and 233, with a most preferred variant comprising T23 IR and N233R mutations, such most preferred variant being sold under the tradename Lipex® (Novozymes).
The aforementioned lipases can be used in combination (any mixture of lipases can be used). Suitable lipases can be purchased from Novozymes, Bagsvaerd, Denmark; Areario Pharmaceutical Co. Ltd., Nagoya, Japan; Toyo Jozo Co., Tagata, Japan; Amersham
Pharmacia Biotech., Piscataway, New Jersey, U.S.A; Diosynth Co., Oss, Netherlands and/or made in accordance with the examples contained herein. Lipid esterase with with reduced potential for odor generation and a good relative
performance, are particularly preferred, as described in WO2007/087243. These include lipoclean ® (Novozyme)
Surfactant
The laundry composition comprises an anionic charged surfactant (which includes a mixture of the same).
Preferably the weight fraction of non-ionic surfactant/anionic surfactant is from 0 to 0.3, preferably 0 to 0.1.
Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher alkyl radicals.
Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher Cs to Cis alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl Cg to C20 benzene sulphonates, particularly sodium linear secondary alkyl C10 to C15 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.
The anionic surfactant is preferably selected from: linear alkyl benzene sulphonate; alkyl sulphates; alkyl ether sulphates; soaps; alkyl (preferably methyl) ester sulphonates, and mixtures thereof.
The most preferred anionic surfactants are selected from: linear alkyl benzene sulphonate; alkyl sulphates; alkyl ether sulphates and mixtures thereof. Preferably the alkyl ether sulphate is a C12-C14 n-alkyl ether sulphate with an average of 1 to 3EO (ethoxylate) units. Sodium lauryl ether sulphate is particularly preferred (SLES). Preferably the linear alkyl benzene sulphonate is a sodium Cn to C15 alkyl benzene sulphonates. Preferably the alkyl sulphates is a linear or branched sodium C12 to C18 alkyl sulphates. Sodium dodecyl sulphate is particularly preferred, (SDS, also known as primary alkyl sulphate).
In liquid formulations preferably two or more anionic surfactant are present, for example linear alkyl benzene sulphonate together with an alkyl ether sulphate.
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. Specific nonionic detergent compounds are the condensation products of aliphatic Cs to Cis primary or secondary linear or branched alcohols with ethylene oxide.
Preferably the alkyl ethoxylated non-ionic surfactant is a Cs to C18 primary alcohol with an average ethoxylation of 7EO to 9EO units.
The nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "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. Preferably the surfactants used are saturated. Also applicable are surfactants such as those described in EP-A-328 177 (Unilever), which show resistance to salting-out, the alkyl polyglycoside surfactants described in
EP-A-070 074, and alkyl monoglycosides. The detergent compositions based on anionic or anionic/non-ionic surfactants is however the more preferred embodiment.
Builders or Complexinq Agents Builder materials may be selected from 1 ) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetra-acetic acid.
Examples of precipitating builder materials include sodium orthophosphate and sodium carbonate. Examples of calcium ion-exchange builder materials include the various types of water- insoluble crystalline or amorphous aluminosilicates, of which zeolites are the well known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070. The composition may also contain 0-65 % of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or
alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below. Many builders are also bleach-stabilising agents by virtue of their ability to complex metal ions. Zeolite and carbonate (carbonate (including bicarbonate and sesquicarbonate) are preferred builders, with carbonates being particularly preferred.
The composition may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is typically present at a level of less than 15%w. Aluminosilicates are materials having the general formula: 0.8-1.5 M20. AI2O3. 0.8-6 Si02, where M is a monovalent cation, preferably sodium. These materials contain some bound water and are required to have a calcium ion exchange capacity of at least
50 mg CaO/g. The preferred sodium aluminosilicates contain 1.5-3.5 S1O2 units in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature. The ratio of surfactants to
alumuminosilicate (where present) is preferably greater than 5:2, more preferably greater than 3:1 .
Alternatively, or additionally to the aluminosilicate builders, phosphate builders may be used. In this art the term 'phosphate' embraces diphosphate, triphosphate, and phosphonate species. Other forms of builder include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst).
Most preferably the laundry detergent formulation is a non-phosphate built powder laundry detergent formulation, i.e., contains less than 1 wt% of phosphate. Preferably the powder laundry detergent formulations are predominantly carbonate built. Powders, should preferably give an in use pH of from 9.5 to 1 1. Preferably the powder laundry detergent has linear alkyl benzene sulfonate surfactant at a level of greater than 80 wt% of the total anionic surfactant present.
In the aqueous liquid laundry detergent it is preferred that mono propylene glycol is present at a level from 1 to 30 wt%, most preferably 2 to 18 wt%, to provide the formulation with appropriate, pourable viscosity.
Fluorescent Agent
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.
The total amount of the fluorescent agent or agents used in the composition is generally from 0.0001 to 0.5 wt %, preferably 0.005 to 2 wt %, more preferably 0.01 to 0.1 wt %. 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. Preferred fluorescers are fluorescers with CAS-No 3426-43-5; CAS-No 35632-99-6; CAS-No 24565-13-7; CAS-No 12224-16-7; CAS-No 13863-31 -5; CAS-No 4193-55-9; CAS-No 16090- 02-1 ; CAS-No 133-66-4; CAS-No 68444-86-0; CAS-No 27344-41 -8.
Most preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-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' disulphonate, 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 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 formulation cleans, whitens and brightens the fabric. Perfume
The composition preferably comprises a perfume. Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.
Preferably 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 anthranilate; alpha-irone; beta-phenyl ethyl benzoate; alpa-santalol; cedrol; cedryl acetate; cedry formate; cyclohexyl salicyate; gamma-dodecalactone; and, beta phenylethyl phenyl acetate. 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 Nostrand; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA).
It is commonplace for a plurality of perfume components to be present in a formulation. In the 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.
In perfume mixtures preferably 15 to 25 wt% are top notes. 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 International Fragrance Association has published a list of fragrance ingredients (perfumes) in 201 1 . (http://www.ifraorq.Org/en-us/inqredients#.U7Z4hPldWzk) 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. Some or all of the perfume may be encapsulated, typical 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, of relatively low boiling point and relatively low CLog P 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, ethyl amyl ketone, ethyl benzoate, ethyl butyrate, ethyl hexyl ketone, ethyl phenyl acetate, eucalyptol, eugenol, fenchyl acetate, flor acetate (tricyclo decenyl acetate) , frutene (tricycico decenyl propionate) , geraniol, hexenol, hexenyl acetate, hexyl acetate, hexyl formate, hydratropic alcohol, hydroxycitronellal, indone, isoamyl alcohol, iso menthone, isopulegyl acetate, isoquinolone, ligustral, linalool, linalool oxide, linalyl formate, menthone, menthyl acetphenone, methyl amyl ketone, methyl anthranilate, methyl benzoate, methyl benyl acetate, methyl eugenol, methyl heptenone, methyl heptine carbonate, methyl heptyl ketone, methyl hexyl ketone, methyl phenyl carbinyl acetate, methyl salicylate, methyl-n-methyl anthranilate, nerol, octalactone, octyl alcohol, p-cresol, p- cresol methyl ether, p-methoxy acetophenone, p-methyl acetophenone, phenoxy ethanol, phenyl acetaldehyde, phenyl ethyl acetate, phenyl ethyl alcohol, phenyl ethyl dimethyl carbinol, prenyl acetate, propyl bornate, pulegone, rose oxide, safrole, 4-terpinenol, alpha- terpinenol, and /or viridine. It is commonplace for a plurality of perfume components to be present in a formulation. In the 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.
Another group of 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.
It is preferred that the laundry treatment composition does not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid.
Polymers
The composition may comprise one or more further polymers. Examples are
carboxymethylcellulose, poly (ethylene glycol), polyvinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid
copolymers. Where 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 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.
Dye weights refer to the sodium or chloride salts unless otherwise stated.
Experimental Examples
A powder laundry detergent was prepared of the following formulation:
Figure imgf000015_0001
The formulation was used to wash eight 5x5cm EMPA 1 17 stain monitor (blood/milk/ink stain on polycotton) in a tergotometer set at 200rpm. A 60 minute wash was conducted in 800ml of 26° French Hard water at 35°C, with 1.5g/L of the formulation. To simulate oily soil (7.4 g) of an SBL2004 soil strip (ex Warwick Equest) was added to the wash liquor.
Once the wash had been completed the cotton monitors were rinsed once in 400ml clean water, removed dried and the colour measured on a reflectometer and expressed as the CIE L*a*b* values. Stain removal was calculates as the ΔΙ_* value:
ΔΙ_* = L*(treatment)-L*(control without enzyme or alkoxylated polyarylphenol) Higher ΔΙ_* value equate to better cleaning.
Equivalent Formulations but with the addition of 13.3 wt% alkoxylated polyarylphenol which were polyethylene glycol mono(2,4,6-tris(1 -phenylethyl)phenyl) ether (CAS-No: 70559-25-0) with an average of 10, 16 and 54 ethylene oxide groups.
Experiments were repeated with and without the addition of a lipid esterase enzyme
(Triacylglycerol lipase: EC no. 3.1.1.3) to the wash liquor. (Lipex® ex Novozymes). The enzyme was added to give 0.3wt% pure active protein to the formulation.
95% confidence limits are also given calculated from the standard deviation on the measurements from the 8 monitors.
Figure imgf000016_0001
The combination of lipase and alkoxylated polyarylphenol with 10, 15 and 54EO to the formulation increases the stain removal as seen by higher AL* values compared to the reference control values. The combination of lipase and alkoxylated polyarylphenol with 10EO, and 16EO gives a greater increase in stain removal than expected from combination of the effects of the single components. For 10EO/lipase an AL* value of 0.73+3.45=4.18 is expected and 7.15 obtained. For 16EO/lipase a value of 0.29+3.45=3.74 is expected and 8.25 obtained.
The formulation was remade with the addition of mix of amylase, mannase and pectinase enzymes (Stainzyme ® Novozyme , Mannaway ® Novozymes, Pectawash ® Novozymes)

Claims

1. A laundry detergent composition comprising:
(i) from 0.5 to 20 wt% of a alkoxylated polyarylphenol having an average of 5 to 70 alkoxy groups;
(ii) from 4 to 50 wt% of an anionic surfactant, other than the alkoxylated
polyarylphenol; and,
(iii) a lipid esterase at a level of from 0.0005 to 0.5 wt % of pure enzyme, wherein the lipid esterase is selected from Triacylglycerol lipase (E.C. 3.1.1 .3); Carboxylic ester hydrolase (E.C. 3.1.1.1 ); Cutinase (E.C. 3.1 .1 .74); Sterol esterase (E.C. 3.1 .1.13); and, Wax-ester hydrolase (E.C. 3.1 .1.50).
A laundry detergent composition according to claim 1 , wherein the lipid esterase is a Triacylglycerol lipases (E.C. 3.1.1.3).
A laundry detergent composition according to claim 1 or 2, wherein the alkoxylated polyarylphenol has 2 or 3 aryl groups attached to the phenol and they are in the 2,4 or 2,4,6 position on the phenol.
A laundry detergent composition according to any one of claims 1 to 3, wherein the alkoxylated polyarylphenol has 10 to 30 alkoxy groups and the alkoxylation is ethoxylation and the aryl group is styryl.
A laundry detergent composition according any one of the preceding claims, wherein the alkoxylated polyarylphenol dispersant is:
Figure imgf000017_0001
6. A laundry detergent composition according to any one of the preceding claims, where in the composition is is a non-phosphate built powder laundry detergent formulation.
7. A laundry detergent composition according to any one of the preceding claims,
wherein the lipid esterase is present at a level of from 0.05 to 0.3 wt % of pure enzyme.
8. A laundry detergent composition according to any one of the preceding claims,
wherein the anionic charged surfactant is selected from: linear alkyi benzene sulphonate; alkyi sulphates; alkyi ether sulphates; soaps; methyl ester sulphonates; and mixtures thereof.
9. A laundry detergent composition according to any one of the preceding claims,
wherein the anionic surfactant is selected from: linear alkyi benzene sulphonate; alkyi sulphates; alkyi ether sulphates; and mixtures thereof.
10. A laundry detergent composition according to any one of the preceding claims,
wherein the level of anionic surfactant is from 8 to 20 wt%. 1 1 . A laundry detergent composition according to any one of the preceding claims,
wherein the weight fraction of non-ionic surfactant/anionic surfactant is from 0 to 0.1.
12. A domestic method of treating a textile, the method comprising the step of: treating a textile with an aqueous solution of 0.5 to 20 g/L of the laundry detergent composition according to any one of the preceding claims.
PCT/EP2016/059425 2015-06-26 2016-04-27 Laundry detergent composition WO2016206838A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020104158A1 (en) * 2018-11-20 2020-05-28 Unilever Plc Detergent composition

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3853338B1 (en) * 2018-09-18 2022-08-17 Unilever Global Ip Limited Detergent composition
WO2021043764A1 (en) * 2019-09-02 2021-03-11 Unilever Global Ip Limited Detergent composition

Citations (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1372034A (en) 1970-12-31 1974-10-30 Unilever Ltd Detergent compositions
GB2007692A (en) 1977-11-02 1979-05-23 Rhone Poulenc Ind Anti-soiling and anti-redesposition compositions which can be used in detergency
EP0070074A2 (en) 1981-07-13 1983-01-19 THE PROCTER & GAMBLE COMPANY Foaming surfactant compositions
EP0218272A1 (en) 1985-08-09 1987-04-15 Gist-Brocades N.V. Novel lipolytic enzymes and their use in detergent compositions
JPS6474992A (en) 1987-09-16 1989-03-20 Fuji Oil Co Ltd Dna sequence, plasmid and production of lipase
EP0328177A2 (en) 1988-02-10 1989-08-16 Unilever N.V. Liquid detergents
EP0331376A2 (en) 1988-02-28 1989-09-06 Amano Pharmaceutical Co., Ltd. Recombinant DNA, bacterium of the genus pseudomonas containing it, and process for preparing lipase by using it
EP0384070A2 (en) 1988-11-03 1990-08-29 Unilever Plc Zeolite P, process for its preparation and its use in detergent compositions
WO1991016422A1 (en) 1990-04-14 1991-10-31 Kali-Chemie Aktiengesellschaft Alkaline bacillus lipases, coding dna sequences therefor and bacilli which produce these lipases
WO1995006720A1 (en) 1993-08-30 1995-03-09 Showa Denko K.K. Novel lipase, microorganism producing the lipase, process for producing the lipase, and use of the lipase
WO1996012012A1 (en) 1994-10-14 1996-04-25 Solvay S.A. Lipase, microorganism producing same, method for preparing said lipase and uses thereof
WO1996013580A1 (en) 1994-10-26 1996-05-09 Novo Nordisk A/S An enzyme with lipolytic activity
WO1996027002A1 (en) 1995-02-27 1996-09-06 Novo Nordisk A/S Novel lipase gene and process for the production of lipase with the use of the same
WO1997004079A1 (en) 1995-07-14 1997-02-06 Novo Nordisk A/S A modified enzyme with lipolytic activity
US5869438A (en) 1990-09-13 1999-02-09 Novo Nordisk A/S Lipase variants
WO1999042566A1 (en) 1998-02-17 1999-08-26 Novo Nordisk A/S Lipase variant
WO2000034450A1 (en) 1998-12-04 2000-06-15 Novozymes A/S Cutinase variants
WO2000060063A1 (en) 1999-03-31 2000-10-12 Novozymes A/S Lipase variant
WO2001092502A1 (en) 2000-06-02 2001-12-06 Novozymes A/S Cutinase variants
WO2002062973A2 (en) 2001-02-07 2002-08-15 Novozymes A/S Lipase variants
WO2003076580A2 (en) 2002-03-05 2003-09-18 Genencor International, Inc. High throughput mutagenesis screening method
US20040087458A1 (en) * 2002-11-01 2004-05-06 Nicca U.S.A., Inc. Surfactant blends for removing oligomer deposits from polyester fibers and polyester processing equipment
WO2004101760A2 (en) 2003-05-12 2004-11-25 Genencor International, Inc. Novel lipolytic enzyme elip
WO2004101763A2 (en) 2003-05-12 2004-11-25 Genencor International, Inc. Novel lipolytic enzyme lip1
WO2004101759A2 (en) 2003-05-12 2004-11-25 Genencor International, Inc. Novel lipolytic enzyme lip2
US20050107281A1 (en) * 2003-11-17 2005-05-19 Clariant Gmbh Ether carboxylic acids based on alkoxylated styrylphenols
WO2007087243A2 (en) 2006-01-23 2007-08-02 The Procter & Gamble Company Detergent compositions
WO2009007510A1 (en) 2007-07-10 2009-01-15 Valtion Teknillinen Tutkimuskeskus Novel esterases and their use
EP2767581A1 (en) 2013-02-19 2014-08-20 The Procter & Gamble Company Method of laundering a fabric

Patent Citations (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1372034A (en) 1970-12-31 1974-10-30 Unilever Ltd Detergent compositions
GB2007692A (en) 1977-11-02 1979-05-23 Rhone Poulenc Ind Anti-soiling and anti-redesposition compositions which can be used in detergency
EP0070074A2 (en) 1981-07-13 1983-01-19 THE PROCTER & GAMBLE COMPANY Foaming surfactant compositions
EP0218272A1 (en) 1985-08-09 1987-04-15 Gist-Brocades N.V. Novel lipolytic enzymes and their use in detergent compositions
JPS6474992A (en) 1987-09-16 1989-03-20 Fuji Oil Co Ltd Dna sequence, plasmid and production of lipase
EP0328177A2 (en) 1988-02-10 1989-08-16 Unilever N.V. Liquid detergents
EP0331376A2 (en) 1988-02-28 1989-09-06 Amano Pharmaceutical Co., Ltd. Recombinant DNA, bacterium of the genus pseudomonas containing it, and process for preparing lipase by using it
EP0384070A2 (en) 1988-11-03 1990-08-29 Unilever Plc Zeolite P, process for its preparation and its use in detergent compositions
WO1991016422A1 (en) 1990-04-14 1991-10-31 Kali-Chemie Aktiengesellschaft Alkaline bacillus lipases, coding dna sequences therefor and bacilli which produce these lipases
US5869438A (en) 1990-09-13 1999-02-09 Novo Nordisk A/S Lipase variants
WO1995006720A1 (en) 1993-08-30 1995-03-09 Showa Denko K.K. Novel lipase, microorganism producing the lipase, process for producing the lipase, and use of the lipase
WO1996012012A1 (en) 1994-10-14 1996-04-25 Solvay S.A. Lipase, microorganism producing same, method for preparing said lipase and uses thereof
WO1996013580A1 (en) 1994-10-26 1996-05-09 Novo Nordisk A/S An enzyme with lipolytic activity
WO1996027002A1 (en) 1995-02-27 1996-09-06 Novo Nordisk A/S Novel lipase gene and process for the production of lipase with the use of the same
WO1997004078A1 (en) 1995-07-14 1997-02-06 Novo Nordisk A/S A modified enzyme with lipolytic activity
WO1997004079A1 (en) 1995-07-14 1997-02-06 Novo Nordisk A/S A modified enzyme with lipolytic activity
WO1999042566A1 (en) 1998-02-17 1999-08-26 Novo Nordisk A/S Lipase variant
WO2000034450A1 (en) 1998-12-04 2000-06-15 Novozymes A/S Cutinase variants
US6939702B1 (en) 1999-03-31 2005-09-06 Novozymes A/S Lipase variant
WO2000060063A1 (en) 1999-03-31 2000-10-12 Novozymes A/S Lipase variant
WO2001092502A1 (en) 2000-06-02 2001-12-06 Novozymes A/S Cutinase variants
WO2002062973A2 (en) 2001-02-07 2002-08-15 Novozymes A/S Lipase variants
WO2003076580A2 (en) 2002-03-05 2003-09-18 Genencor International, Inc. High throughput mutagenesis screening method
US20040087458A1 (en) * 2002-11-01 2004-05-06 Nicca U.S.A., Inc. Surfactant blends for removing oligomer deposits from polyester fibers and polyester processing equipment
WO2004101760A2 (en) 2003-05-12 2004-11-25 Genencor International, Inc. Novel lipolytic enzyme elip
WO2004101763A2 (en) 2003-05-12 2004-11-25 Genencor International, Inc. Novel lipolytic enzyme lip1
WO2004101759A2 (en) 2003-05-12 2004-11-25 Genencor International, Inc. Novel lipolytic enzyme lip2
US20050107281A1 (en) * 2003-11-17 2005-05-19 Clariant Gmbh Ether carboxylic acids based on alkoxylated styrylphenols
WO2007087243A2 (en) 2006-01-23 2007-08-02 The Procter & Gamble Company Detergent compositions
WO2009007510A1 (en) 2007-07-10 2009-01-15 Valtion Teknillinen Tutkimuskeskus Novel esterases and their use
EP2767581A1 (en) 2013-02-19 2014-08-20 The Procter & Gamble Company Method of laundering a fabric

Non-Patent Citations (15)

* Cited by examiner, † Cited by third party
Title
"Chemicals Buyers Directory 80th Annual Edition", 1993, SCHNELL PUBLISHING CO
"Enzymes in Detergency", 1997, MARCEL DEKKER
"Fenaroli's Handbook of Flavor Ingredients", 1975, CRC PRESS
"International Buyers Guide", 1992, CFTA PUBLICATIONS
"list of fragrance ingredients (perfumes", 2011, THE INTERNATIONAL FRAGRANCE ASSOCIATION
DARTOIS ET AL., BIOCHEMICA ET BIOPHYSICA ACTA, vol. 1131, 1993, pages 253 - 360
H. KONTKANEN ET AL., APP. ENVIRON. MICROBIOLOGY, 2009, pages 2148 - 2157
H. KONTKANEN ET AL., ENZYME MICROB TECHNOL., vol. 39, 2006, pages 265 - 273
H. STACHE: "Tenside-Taschenbuch", 1981, CARL HAUSER VERLAG
M. B. JACOBS: "Synthetic Food Adjuncts", 1947
MCCUTCHEON: "McCutcheon's Emulsifiers and Detergents", BY MANUFACTURING CONFECTIONERS COMPANY
POUCHER, JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS, vol. 6, no. 2, 1955, pages 80
S. ARCTANDER: "Perfume and Flavor Chemicals", 1969
SCHWARTZ; PERRY: "Surface Active Agents", vol. 1, 1949, INTERSCIENCE
SCHWARTZ; PERRY; BERCH: "SURFACE ACTIVE AGENTS", vol. 2, 1958, INTERSCIENCE

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020104158A1 (en) * 2018-11-20 2020-05-28 Unilever Plc Detergent composition

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