BR112017004978B1 - Detergent composition for washing clothes and domestic method of treating a fabric - Google Patents

Abstract

The present invention provides a household laundry bleach and bleach composition comprising a charged surfactant, negatively charged alkoxylated polyarylphenol and fragrance.

Description

Field of Invention

[0001] The present invention relates to the use of bleaching and bleaching compositions for washing clothes.

Background of the Invention

[0002] Maintaining and improving the whiteness and whiteness of fabrics during household laundry is desirable. One problem is the redeposition of dirt removed from one garment to another. The problem is exacerbated by the presence of human oils (tallow) in garments and in the wash which serves to enhance the deposition of dirt in the wash. This process leads to an overall loss of whiteness and cleanliness across the wash load. To ameliorate this problem, dispersing polymer, such as an alkoxylated polyethylene imines, has been widely added to laundry detergents. Ethoxylated PEI (PEI = polyethylene imine) is known as an anti-redeposition polymer from CA 121 0009. Certain cellulase enzymes have also been used to prevent redeposition by altering the surface properties of cotton fabrics. Novozymes describes in WO02/099091 and WO04/053039 cellulases for use in washing household laundry.

[0003] EP1321510 (Shipley) describes an industrial cleaning composition that contains an alkoxylated polyarylphenol to remove photoresist organic chemical residues that are used in the manufacture of semiconductors and other electronic devices and circuits. Organic chemical residues are materials left over from the production process and include photoinitiators, thermoinitiators, acrylic and methacrylic monomers.

Summary of the Invention

[0004] There is a need for additional technologies to reduce redeposition and enhance cleaning in household laundry products.

[0005] Negatively charged alkoxylated polyarylphenols have been found to potentiate the whiteness and bleaching of garments during household washing.

[0006] In one aspect, the present invention provides a laundry detergent composition comprising: (i) loaded surfactant, preferably the level of loaded surfactant is from 4 to 50% by weight, more preferably from 6 to 30% by weight, more preferably from 8 to 20% by weight; (ii) negatively charged alkoxylated polyarylphenol, preferably at a level of from 0.1 to 20% by weight, more preferably from 0.5 to 10% by weight, more preferably from 2 to 9% by weight; and (iii) fragrance, preferably 0.05 to 0.5% by weight of fragrance.

em que R é selecionado entre: SO3; COO- e PO32-, preferivelmente selecionado entre: SO3- e COO-, em que n é selecionado entre: 10; 11; 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 e 54; e a fragrância, preferivelmente de 0,05 a 0,5% em peso de fragrância.[0007] In another aspect, the present invention provides a laundry detergent composition comprising: (i) from 4 to 50% by weight, more preferably from 6 to 30% by weight, most preferably from 8 to 20% by weight of anionic surfactant selected from: linear alkylbenzene sulfonates; alkyl sulfates and alkyl ether sulfates; and mixtures thereof; (ii) from 0.5 to 10% by weight, more preferably from 2 to 9% by weight of negatively charged alkoxylated polyarylphenol having the following structure:

wherein R is selected from: SO3; COO- and PO32-, preferably selected from: SO3- and COO-, where n is selected from: 10; 11; 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; and fragrance, preferably from 0.05 to 0.5% by weight of fragrance.

[0008] In a further aspect, the present invention provides a domestic method of treating a fabric, the method comprising the steps of: (i) treating a fabric with an aqueous solution of the negatively charged alkoxylated polyarylphenol, the aqueous solution comprising of 10 ppm to 5000 ppm of the negatively charged alkoxylated polyarylphenol; and up to 6 g/L, preferably 0.2 to 4 g/L, of a surfactant; and, (ii) optional rinsing and drying of the fabric.

[0009] In the method, the level of fragrance in the aqueous solution is preferably from 0.1 to 100 ppm, more preferably from 1 to 10 ppm.

[0010] In the method aspects of the present invention, the surfactant used is preferably as preferred for the compositional aspects of the present invention.

[0011] The fabric is preferably an item of clothing, bedding or tablecloth. Favorite clothing items are shirts, pants, underwear and sweaters that contain cotton.

Detailed Description of the Invention alkoxylated polyarylphenol

[0012] Preferably, the negatively charged alkoxylated polyarylphenol is an alkoxylated tristyrylphenol.

[0013] Preferably, the negatively charged alkoxylated tristyrylphenol is a polyethylene glycol monoether (2,4,6-tris(1-phenylethyl)phenyl) derivative. Preferably, the alkoxylated polyarylphenol contains an average of from 2 to 70 alkoxy groups, more preferably from 10 to 54 alkoxy groups.

[0014] Preferably, the alkoxylation is ethoxylation.

[0015] Preferably, the negatively charged alkoxylated polyarylphenol has 2 or 3 aryl groups attached to the phenol. Preferably, they are at position 2,4 or 2,4,6 on the phenol. The alkoxylate is attached to the 1-position. Preferably, the alkoxylate is covered by a negatively charged group.

[0016] Preferably, the charged groups have sodium or potassium as a counterion.

[0017] The aryl group in the negatively charged alkoxylated polyarylphenol is preferably selected from phenyl, tolyl, naphthyl, tetrahydronaphthyl, indanyl, indenyl, styryl, pyridyl, quinolinyl, and mixtures thereof.

em que R é selecionado entre SO3; COO- e PO32-, selecionado preferivelmente entre SO3- e COO-.[0018] More preferably, the negatively charged alkoxylated polyarylphenol is one with the following structure:

wherein R is selected from SO3; COO- and PO32-, preferably selected from SO3- and COO-.

[0019] Preferably n=2 to 70, more preferably n=4 to 54, most preferably n=10 to n=54.

[0020] The designation n is the average number of moles of alkoxy units in the polyalkoxy chain.

[0021] Compounds are available from industrial suppliers, e.g. Rhodia, Clariant, Aoki Oil Industrial Co, Stepan and TOHO Chemical Industry Co.

[0022] In the context of the present invention, negatively charged alkoxylated polyarylphenol is not considered a surfactant and does not numerically contribute to the surfactant as defined herein.

[0023] “Negatively” charged refers to the charge at pH = 8 in water.

Surfactant

[0024] The laundry composition comprises loaded surfactant and the most preferred loaded surfactant is anionic surfactant (which includes a mixture thereof).

[0025] Suitable anionic detergent compounds that can be used are generally water-soluble alkali metal salts of organic sulfates and sulfonates that have alkyl radicals containing from approximately 8 to approximately 22 carbon atoms, the term alkyl being used to include the moiety alkyl of higher alkyl radicals.

[0026] Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulfates, especially those obtained by sulfation of C8 to C18 higher alcohols, produced, for example, from tallow or coconut oil, C9 to C20 alkylbenzene sulfonate sodium and potassium, particularly linear secondary sodium C10 to C15 alkylbenzene sulfonate; and sodium alkylglyceryl ether sulfate, especially those ethers of higher alcohols derived from tallow and coconut oil and synthetic alcohols derived from petroleum.

[0027] The anionic surfactant is preferably selected from: linear alkylbenzene sulfonate; alkyl sulfates; alkyl ether sulfates; soaps; alkyl (preferably methyl) ester sulfonate, and mixtures thereof.

[0028] The most preferred anionic surfactants are selected from: linear alkylbenzene sulfonate; alkyl sulfates; alkyl ether sulfates and mixtures thereof. Preferably, the alkyl ether sulfate is a C 12 -C 14 alkyl ether n-sulfate with an average of 1 to 3 EO (ethoxylate) units. Sodium lauryl ether sulfate (SLES) is particularly preferred. Preferably, the linear alkylbenzene sulfonate is a sodium C11 to C15 alkylbenzene sulfonate. Preferably, the alkyl sulfates is a linear or branched C12 to C18 sodium alkyl sulfate. Sodium dodecyl sulfate is particularly preferred (SDS, also known as primary alkyl sulfate).

[0029] The level of anionic surfactant in the laundry composition is preferably from 4 to 50% by weight, more preferably from 6 to 30% by weight and most preferably from 8 to 20% by weight.

[0030] Preferably, two or more anionic surfactants are present, for example linear alkylbenzene sulfonate together with an alkyl ether sulfate.

[0031] Preferably, the laundry composition in addition to the anionic surfactant comprises non-ionic alkyl ethoxylated surfactant, preferably from 2 to 8% by weight of alkyl alkoxylated, preferably non-ionic ethoxylated surfactant.

[0032] Suitable nonionic detergent compounds that 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 sodium oxide. ethylene either alone or with propylene oxide. Specific nonionic detergent compounds are the condensation products of linear or branched primary or secondary C8 to C18 aliphatic alcohols with ethylene oxide.

[0033] Preferably, the alkyl ethoxylated nonionic surfactant is a C8 to C18 primary alcohol with an average ethoxylation of 7EO to 9EO units.

[0034] The non-ionic and anionic surfactants of the surfactant system can be chosen from the surfactants 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 the Manufacturing Confectioners Company or in “Tenside-Taschenbuch”, H. Stache, 2nd Ed., Carl Hauser Verlag, 1981.

[0035] Preferably, the surfactants used are saturated.

[0036] Also applicable are surfactants such as those described in EP-A-328 177 (Unilever), which demonstrate resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides.

[0037] In another aspect, the charged surfactant may be a cationic so that the formulation is a fabric softener. Detergent compositions based on anionic or anionic/nonionic surfactants are, however, the most preferred embodiment.

Cationic Compound

[0038] When the present invention is used as a fabric softener, it must contain a cationic compound.

[0039] The most preferred are quaternary ammonium compounds.

[0040] It is advantageous if the quaternary ammonium compound is a quaternary ammonium compound that has at least one C12 to C22 alkyl chain.

em que R1 é uma cadeia alquila ou alquenila C12 a C22; R2, R3 e R4 são selecionados de forma independente a partir de cadeias alquilas C1 a C4 e X- é um ânion compatível. Um composto preferido deste tipo é o composto de amônio quaternário brometo de cetiltrimetilamônio quaternário.[0041] It is preferred if the quaternary ammonium compound has the following formula:

wherein R1 is a C12 to C22 alkyl or alkenyl chain; R2, R3 and R4 are independently selected from C1 to C4 alkyl chains and X- is a compatible anion. A preferred compound of this type is the quaternary ammonium compound cetyltrimethylammonium quaternary ammonium bromide.

[0042] A second class of materials for use with the present invention is the quaternary ammonium of the above structure, wherein R1 and R2 are independently selected from the C12 to C22 alkyl or alkenyl chain; R3 and R4 are independently selected from the C1 to C4 alkyl chains and X- is a compatible anion.

[0043] The composition optionally comprises a silicone.

Anti-limescale agents or Complexing Agents

[0044] Anti-limestone agent materials can be selected from 1) calcium sequestering materials, 2) precipitating materials, 3) calcium ion exchange materials, and 4) mixtures thereof.

[0045] Examples of calcium sequestering descaling agent materials include alkali metal phosphonates such as sodium tripolyphosphate and organic sequestering agents such as ethylenediamine tetraacetic acid.

[0046] Examples of precipitating descaling agent materials include sodium orthophosphate and sodium carbonate.

[0047] Examples of calcium ion exchange anti-limestone materials include the various types of water-insoluble crystalline or amorphous aluminosilicates whose zeolites are well-known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), C zeolite, X zeolite, Y zeolite and also P-type zeolite as described in EP-A-0,384,070.

[0048] The composition may also contain 0 to 65% of an anti-limescale agent or complexing agent, such as ethylenediamine tetraacetic acid, diethylonetriaminepentaacetic acid, alkyl or alkenylsuccinic acid, nitrilotriacetic acid or other anti-limestone agents mentioned below. Many descaling agents are also bleach stabilizing agents by virtue of their ability to complex metal ions.

[0049] Zeolite and carbonate (carbonate (including bicarbonate and sesquicarbonate)) are preferred descaling agents, with carbonates being particularly preferred.

[0050] The composition may contain as an anti-limestone agent a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is normally present at a level of less than 15% by weight. Aluminosilicates are materials that have the general formula: 0.8-1.5 M2O. Al2O3. 0.8-6 SiO2 where M is a monovalent cation, preferably sodium. These materials contain some water binding and must have a calcium ion exchange capacity of at least 50 mg CaO/g. Preferred sodium aluminosilicates contain 1.5-3.5 SiO2 units in the above formula. They can be easily prepared by the reaction between sodium silicate and sodium aluminate, as widely described in the literature. The ratio of surfactants to aluminosilicates (where present) is preferably greater than 5:2, more preferably greater than 3:1.

[0051] As an alternative or in addition to aluminosilicate descaling agents, phosphate descaling agents can be used. In the art, the term 'phosphate' encompasses diphosphate, triphosphate and phosphonate species. Other forms of descaling agents include silicates such as soluble silicates, metasilicates, layered silicates (eg SKS-6 from Hoechst).

[0052] Preferably, the laundry detergent formulation is a laundry detergent formulation with a non-phosphate construction, i.e., it contains less than 1% by weight of phosphate. Preferably, the laundry detergent powder formulations are predominantly carbonate descaling agents. Powders should preferably provide an in-use pH of 9.5 to 11.

[0053] More preferably, the laundry detergent is an aqueous liquid laundry detergent, preferably having a pH of 7 to 9.

[0054] In the aqueous liquid laundry detergent, it is preferred that the monopropylene glycol be present at a level of from 1 to 30% by weight, more preferably from 2 to 18% by weight, to provide the appropriate pour-on viscosity.

Fluorescent Agent

[0055] The composition preferably comprises a fluorescent agent (optical brightener). Fluorescent agents are well known and many such fluorescent agents are commercially available. Typically, these fluorescing agents are supplied and used in the form of their alkali metal salts, for example sodium salts.

[0056] Preferred classes of fluorescing agents are: Diestyryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, diamine stilbene disulfonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and pyrazoline compounds, for example, Blankophor SN.

[0057] Preferred fluorescent agents are: Sodium 2-(4-styryl-3-sulfophenyl)-2H-naptol[1,2-d]triazole, 4,4'-bis{[(4-anilino-6- (N-methyl-N-2 hydroxyethyl)amino 1,3,5-triazine-2-yl)]amino}stilbene-2-2' disodium disulfonate, 4,4'-bis{[(4-anilino-6-morpholino -1,3,5-triazine-2-yl)]amino}stilbene-2-2' disodium disulfonate and disodium 4,4'-bis(2-sulfostyryl)biphenyl.

Fragrance

[0058] The composition comprises a fragrance. The fragrance is preferably in the range from 0.001 to 3% by weight, more preferably from 0.05 to 0.5% by weight, most preferably from 0.1 to 1% by weight. Many suitable examples of fragrances are provided in CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemical Buyers Yearbook, 80th Annual Edition, published by Schnell Publishing Co.

[0059] Preferably, the fragrance comprises at least one note (compound) among: alpha-isomethylionone, benzyl salicylate; citronellol; coumarin; cinnamal hexyl; linalool; pentanoic acid, 2-methyl-, ethyl ester; octanal; benzyl acetate; 1,6-octadiene-3-ol, 3,7-dimethyl-, 3-acetate; cyclohexanol, 2-(1,1-dimethylethyl)-, 1-acetate; delta-damascone; beta-ionone; verdel acetate; dodecanal; cinnamic hexyl aldehyde; cyclopentadecanolide; benzeneacetic acid, 2-phenylethyl ester; amyl salicylate; beta-caryophyllene; ethyl undecylenate; geranyl anthranilate; alpha-pyrone; beta-phenylethyl benzoate; alpha-santalol; cedrol; cedryl acetate; cedar shape; cyclohexyl salicylate; gamma-dodecalactone and beta phenylethyl phenyl acetate.

[0060] Useful fragrance compounds include materials of natural and synthetic origin. They include unique compounds and mixtures. Specific examples of these components can be found in the current literature, for example, in Fenaroli's Flavoring Ingredients Manual, 1975, CRC Press; Synthetic Food Supplements, 1947 by M. B. Jacobs, edited by Van Nostrand; or Fragrance and Chemical Flavorings by S. Arctander 1969, Montclair, N.J. (USA). It is commonplace for a plurality of fragrance components to be present in a formulation. In the compositions of the present invention, it is contemplated that there will be four or more, preferably five or more, more preferably six or more or even seven or more different fragrance components.

[0061] In fragrance blends, preferably 15 to 25% by weight are top notes. The starting 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.

[0062] The International Fragrance Association published a list of fragrance ingredients (perfumes) in 2011. (http://www.ifraorg.org/en-us/ingredients#.U7Z4hPldWzk)

[0063] The Research Institute for Fragrance Materials provides a perfume (fragrance) database with safety information.

[0064] The fragrance's top note can be used to suggest the whiteness and shine benefit of the invention.

[0065] Some or all fragrances can be encapsulated, typical fragrance components that are advantageous to encapsulate include those with a relatively low boiling point, preferably those with a boiling point of less than 300, preferably 100 to 250 degrees Celsius. It is also advantageous to encapsulate fragrance components that have a low CLog P (ie those that will have a greater tendency to break down in water), preferably with a CLog P of less than 3.0. These relatively low boiling, relatively low CLog P materials have been termed “late bloom” fragrance ingredients and include one or more of the following materials: allyl caproate, amyl acetate, amyl propionate, anis aldehyde, anisole, benzaldehyde , benzyl acetate, benzyl acetone, benzyl alcohol, benzyl formate, benzyl isovalerate, benzyl propionate, beta gamma hexenol, camphor gum, levo-carvone, d-carvone, cinnamic alcohol, cinnamyl formate, cis-jasmone , cis-3-hexenyl acetate, cuminic alcohol, c-cyclal, dimethyl benzyl carbinol, dimethyl benzyl carbinol acetate, ethyl acetate, ethyl acetate acetate, ethyl amyl ketone, ethyl benzoate, ethyl butyrate, ethyl hexyl ketone, ethyl acetate ethyl phenyl, eucalyptol, eugenol, fenquil acetate, fluoracetate (tricycle decenyl acetate), fructene (tricycle decenyl propionate), geraniol, hexenol, hexenyl acetate, hexyl acetate, hexyl formate, hydroxy alcohol co, hydroxycitronellal, indone, isoamyl alcohol, isomenthone, isopulegyl acetate, isoquinolone, lygustral, linalool, linalool oxide, linalyl formate, menthone, menthylacetophenone, methyl amyl ketone, methyl anthranilate, methyl benzoate, methyl benyl acetate, methyl eugenol, methyl heptenone, methyl heptin 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, phenylethyl alcohol, phenyl ethyl dimethyl carbinol, prenyl acetate, propyl bonate, pulegone, rose oxide, safrole, 4- terpinenol, alpha-terpinenol and/or viridine. It is routine for a plurality of fragrance 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 fragrance components from the given list of late blooming fragrances provided above present in the fragrance.

[0066] Another group of fragrances to which the present invention can be applied are the so-called 'aromatherapy' materials. These include many components also used in perfumery, including essential oil components such as Sage Sage, Eucalyptus, Geranium, Lavender, Nutmeg Flower Extract, Neroli, Nutmeg, Mint, Sweet Violet Leaf and Valerian.

[0067] It is preferred that the laundry treatment composition does not contain a peroxygen bleach, for example, sodium percarbonate, sodium perborate and peracid.

polymers

[0068] The composition may comprise one or more of the following polymers. Examples are carboxymethylcellulose, poly(ethylene glycol), poly(vinyl alcohol), polycarboxylates such as polyacrylates, maleic acid/acrylic acid copolymer and lauryl methacrylate/acrylic acid copolymers.

[0069] Polymers present to prevent dye deposition that may be present, for example, poly(vinylpyrrolidone), poly(vinylpyridine-N-oxide) and poly(vinylimidazole).

enzymes

[0070] One or more preferred enzymes are present in a laundry composition of the invention and in practicing a method of the invention.

[0071] Preferably, the level of each enzyme in the laundry composition of the invention is from 0.0001% by weight to 0.1% by weight of protein.

[0072] Preferably, the enzyme is selected from: proteases; lipases and cellulases, preferably the protease.

[0073] Enzymes especially contemplated include proteases, alpha-amylases, cellulases, lipases, peroxidases/oxidases, pectate lyases and mannanases, or mixtures thereof.

[0074] Suitable lipases include those of bacterial or fungal origin. Chemically modified or genetically engineered protein mutants are included. Examples of useful lipases include lipases from Humicola (synonymous with Thermomyces), for example 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 lipase from Pseudomonas, 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 species strain SD 705 ( WO 95/06720 and WO 96/27002 ), P. wisconsinensis ( WO 96/12012 ), a lipase from Bacillus, e.g. from B. subtilis (Dartois et al. (1993), Biochemica et Biophysica Acta, 1131, 253-360), B. stearothermophilus (JP 64/744992) or B. pumilus (WO 91/16422).

[0075] Other examples are 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, WO 97/07202 and WO 00/60063.

[0076] Preferred commercially available lipase enzymes include Lipolase™ and Lipolase Ultra™, Lipex™ and Lipoclean™ (Novozymes A/S).

[0077] The method of the invention can be carried out in the presence of phospholipase classified as EC 3.1.1.4 and/or EC 3.1.1.32. As used herein, the term phospholipase is an enzyme that has activity towards phospholipids.

[0078] Phospholipids, such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids at an outer (sn-1) and intermediate (sn-2) position and esterified with phosphoric acid at the third position; phosphoric acid, in turn, can be esterified to an amino alcohol. Phospholipases are enzymes that participate in the hydrolysis of phospholipids. Several types of phospholipase activity can be distinguished, including phospholipases A1 and A2, which hydrolyze a fatty acyl group (at the sn-1 and sn-2 position, respectively) to form lysophospholipids; and lysophospholipase (or phospholipase B), which can hydrolyze the remaining fatty acyl group into lysophospholipid. Phospholipase C and phospholipase D (phosphodiesterases) release diacyl glycerol or phosphatidic acid, respectively.

[0079] Suitable proteases include those of animal, plant or microbial origin. Microbial origin is preferred. Chemically modified or genetically engineered protein mutants are included. The protease may be a serine protease or metalloprotease, preferably an alkaline microbial protease or a trypsin-like protease. Commercially preferred protease enzymes include Alcalase™, Savinase™, Primase™, Duralase™, Dyrazym™, Esperase™, Everlase™, Polarzyme™, and Kannase™ (Novozymes A/S), Maxatase™, Maxacal™, Maxapem™ , Properase™, Purafect™, Purafect OxP™, FN2™ and FN3™ (Genencor International Inc.).

[0080] The method of the invention can be carried out in the presence of cutinase classified in EC 3.1.1.74. The cutinase used according to the invention can be of any origin. Preferably, the cutinases are of microbial origin, in particular of bacterial, fungal or yeast origin.

[0081] Suitable amylases (alpha and/or beta) include those of bacterial or fungal origin. Chemically modified or genetically engineered protein mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, for example, a special strain of B. licheniformis, described in more detail in GB 1,296,839, or strains of the Bacillus species disclosed in WO 95/026397 or WO 00/ 060060 Commercially available amylases are Duramyl™, Termamyl™, Termamyl Ultra™, Natalase™, Stainzyme™, Fungamyl™ and BAN™ (Novozymes A/S), Rapidase™ and Purastar™ (from Genencor International Inc.).

[0082] Suitable cellulases include those of bacterial or fungal origin. Chemically modified or genetically engineered protein mutants are included. Suitable cellulases include cellulases of the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, for example 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 . Commercially available cellulases include Celluzyme™, Carezyme™, Celluclean™, Endolase™, Renozyme™ (Novozymes A/S), Clazinase™ and Puradax HA™ (Genencor International Inc.), and KAC-500(B)™ (Kao Corporation ). Celluclean™ is preferred.

[0083] Preferred peroxidases/oxidases include those of plant, bacterial or fungal origin. Chemically modified or genetically engineered protein mutants are included. Examples of useful peroxidases include peroxidases from Coprinus, for example from C. cinereus, and variants thereof as described in WO 93/24618, WO 95/10602 and WO 98/15257. Commercially available peroxidases include Guardzyme™ and Novozym™ 51004 (Novozymes A/S).

[0084] Additional enzymes suitable for use are discussed in WO2009/087524 , WO2009/090576 , WO2009/107091 , WO2009/111258 and WO2009/148983 .

Enzyme Stabilizers

[0085] Any enzyme present in the composition can be stabilized using conventional stabilizing agents, for example a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid or a boric acid derivative, for example , an aromatic ester borate, or a phenylboronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described, for example, in WO 92/19709 and WO 92/19708.

[0086] Where alkyl groups are long enough to form branched or cyclic chains, alkyl groups encompass branched, cyclic and straight alkyl chains. Alkyl groups are preferably linear or branched, more preferably linear.

[0087] The indefinite article “a” or “an” and its corresponding definite article “the”, as used herein, mean at least one, or one or more, unless otherwise specified.

Experiment Example 1

[0088] An aqueous liquid detergent for washing clothes of the following formulation was prepared: Table 1

[0089] The formulation was used to wash both pieces of 5 x 5 cm cotton mesh cloth in a tergotometer set at 200 rpm. One hour wash was conducted in 800 ml of 6° French hard water at 20°C, with 2.3 g/l of the formulation. To simulate particulate soiling, 0.04 g/L of 100% compressed carbon black (eg, Sigma-Aldrich) was added to the wash liquid.

[0090] Once the wash was completed, the cotton monitors were rinsed twice in 500 mL of clean water, removed dry and the color measured in a reflectometer and expressed as the CIE L*a*b* values.

[0091] Formulations were tested containing Sokalan HP20 (BASF), a PEI(600) 20EO ethoxylated polyethylene imine polymer, a comparator polymer for anti-redeposition benefits. Formulations were tested containing a negatively charged alkoxylated polyarylphenol, Dispersogen LFH ex Clariant, (tristyrylphenol polyoxyethylene phosphoric acid (anionic) ester).

[0092] The results are summarized in the table below. The 95% confidence limits are also provided calculated from the standard deviation in the measurements from the 8 monitors. The L* value is the average of the measurements from the 8 monitors. Table 2

[0093] Negatively charged alkoxylated polyarylphenol increases the L* of the monitors. High L* values equate to whiter, cleaner fabrics. Negatively charged alkoxylated polyarylphenol provides significantly better benefits than ethoxylated polyethyleneimine.

Example 2

[0094] An aqueous liquid detergent for washing clothes of the following formulation was prepared: Table 3

[0095] The formulation was used to wash 5 x 5 cm cotton knitted garments in a tergotometer set at 200 rpm. One hour wash in 800 mL of 26° French hard water at 20° C was conducted with 2.3 g/L of the formulation. To simulate particulate matter 0.04 g/L of 100% compressed carbon black (ex Sigma-Aldrich) was added to the wash liquid. To simulate oily dirt (6.3 g), dirt blade SBL2004 (ex Warwick Equest) was added to the washing liquid.

[0096] Once the wash was completed, the cotton monitors were rinsed twice in 500 mL of clean water, removed dry and the color measured in a reflectometer and expressed as CIE L*a*b* values

[0097] Formulations were tested containing TAMOL® NN7718 (BASF), the polycondensate product of naphthalene sulfonic acid and formaldehyde, and lignin sulfonate as comparison sulfonated aromatic polymers for anti-redeposition benefits.

[0098] The formulation was tested containing a negatively charged alkoxylated polyarylphenol, Dispersogen LFH ex Clariant, (tristyrylphenol polyoxyethylene phosphoric acid (anionic) ester).

[0099] The results are summarized in the table below. The 95% confidence limits are also given from the standard deviation across the 8 monitor measurements. The L* value is the average of the measurements from the 8 monitors. Table 4

[0100] Negatively charged alkoxylated polyarylphenol increased the L* value of the monitors. High L* values equate to cleaner whiter fabrics. Negatively charged alkoxylated polyarylphenol provides significantly better benefits than naphthalene sulfonic acid and formaldehyde condensate or lignin sulfonate.

Claims (18)

1. A laundry detergent composition, characterized in that it comprises: (i) from 4 to 50% by weight of a loaded surfactant preferably selected from: linear alkylbenzene sulfonate; alkyl sulfate; alkyl ether sulfate and mixtures thereof; (ii) from 0.1 to 20% by weight of a negatively charged alkoxylated polyarylphenol, the preferred structure having:

wherein R is selected from: SO3; COO-; and PO32-, preferably selected from: SO3- and COO-; wherein n is selected from: 10; 11; 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; and (iii) from 0.001 to 3% by weight of a fragrance, wherein the numerical percentage of negatively charged alkoxylated polyarylphenol and charged surfactant are counted independently. A laundry detergent composition according to claim 1, characterized in that the negatively charged alkoxylated polyarylphenol is negatively charged alkoxylated tristyrylphenol. A laundry detergent composition according to claim 1, characterized in that the negatively charged alkoxylated polyarylphenol is negatively charged ethoxylated polyarylphenol. Laundry detergent composition according to claim 2, characterized in that the negatively charged alkoxylated tristyrylphenol is negatively charged polyethylene glycol monoether (2,4,6-tris(1-phenylethyl)phenyl). A laundry detergent composition according to any one of claims 1 to 4, characterized in that the negatively charged alkoxylated polyarylphenol contains an average of 2 to 70 alkoxy groups. A laundry detergent composition according to claim 5, characterized in that the negatively charged alkoxylated polyarylphenol contains an average of 10 to 54 alkoxy groups. A laundry detergent composition according to any one of claims 1 to 6, characterized in that the negatively charged alkoxylated polyarylphenol is present at a level of from 0.5 to 10% by weight, more preferably from 2 to 9% by weight. Weight. A laundry detergent composition according to any one of claims 1 to 7, characterized in that the loaded surfactant is an anionic surfactant. 9. Laundry detergent composition, according to claim 8, characterized in that the anionic surfactant is selected from: linear alkylbenzene sulfonate; alkyl sulfates; alkyl ether sulfates; soaps; methyl ester sulfonates and mixtures thereof. 10. Laundry detergent composition, according to claim 9, characterized in that the anionic surfactant is selected from: linear alkylbenzene sulfonate; alkyl sulfates; alkyl ether sulfates and mixtures thereof. A laundry detergent composition according to any one of claims 8 to 10, characterized in that the level of anionic surfactant is from 4 to 50% by weight. A laundry detergent composition according to any one of claims 1 to 11, characterized in that it comprises from 2 to 8% by weight of ethoxylated alkyl nonionic surfactant. A laundry detergent composition according to any one of claims 1 to 12, characterized in that the fragrance comprises one or more of note compounds of: alpha-isomethylionone, benzyl salicylate; citronellol; coumarin; cinnamal hexyl; linalool; pentanoic acid, 2-methyl-, ethyl ester; octanal; benzyl acetate; 1,6-octadiene-3-ol, 3,7-dimethyl-, 3-acetate; cyclohexanol, 2-(1,1-dimethylethyl)-, 1-acetate; delta-damascone; beta-ionone; verdel acetate; dodecanal; cinnamic hexyl aldehyde; cyclopentadecanolide; benzeneacetic acid, 2-phenylethyl ester; amyl salicylate; beta-caryophyllene; ethyl undecylenate; geranyl anthranilate; alpha-pyrone; beta-phenylethyl benzoate; alpha-santalol; cedrol; cedryl acetate; cedar shape; cyclohexyl salicylate; gamma-dodecalactone and beta-phenylethyl phenyl acetate. A laundry detergent composition, according to claim 1, characterized in that it comprises: (i) from 4 to 50% by weight of anionic surfactant selected from: linear alkylbenzene sulfonate; alkyl sulfate; alkyl ether sulfate and mixtures thereof (ii) from 0.5 to 10% by weight of negatively charged alkoxylated polyarylphenol having the following structure:

wherein R is selected from: SO3; COO-; and PO32-, preferably selected from: SO3- and COO-; wherein n is selected from: 10; 11; 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; and, (iii) from 0.001 to 3% by weight of a fragrance. A laundry detergent composition according to any one of claims 1 to 14, characterized in that it comprises from 0.0001% by weight to 0.1% by weight of protein from an enzyme selected from: proteases; lipases; cellulases and mixtures thereof, preferably comprising a protease. A laundry detergent composition according to any one of claims 1 to 15, wherein the laundry detergent composition is an aqueous liquid laundry detergent composition. A domestic method of treating a fabric, comprising the steps of: (i) treating said fabric with an aqueous solution of a laundry detergent composition as defined in any one of claims 1 to 16, to aqueous solution comprising from 10 ppm to 5000 ppm of said negatively charged alkoxylated polyarylphenol; and up to 6 g/L of surfactant; and, (ii) optionally rinsing and drying said fabric. Home method of treating a fabric, according to claim 17, characterized in that the aqueous solution comprises from 0.2 to 4 g/L of a surfactant.