BR112018016674B1 - Detergent composition for washing clothes and domestic method of treating a fabric - Google Patents

Abstract

The present invention provides a home laundry composition.

Description

Field of Invention

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

History of the Invention

[0002] Maintaining and improving the cleanliness of fabrics during domestic laundry is desirable.

[0003] Protease enzymes are used in laundry detergent formulations to remove protein-containing stains from fabrics. The protease enzyme does not work well at low temperatures and short wash times.

[0004] There is a need to increase stain removal in laundry formulations containing protease enzymes for low temperature quick washes.

Summary of the Invention

[0005] There is a need for technologies to increase stain removal in laundry formulations containing protease enzymes.

[0006] We found that alkoxylated substituted phenol (ASP) dispersants, when incorporated into laundry detergents with a protease enzyme, enhance stain removal.

em que X é selecionado do grupo consistindo de etoxi, e misturas de grupos etoxi e propoxi, em que o número de grupos etoxi é superior ao número de grupo propoxi, e em que n varia de 6 a 70, preferivelmente de 8 a 34; mais preferivelmente n é selecionado entre 14; 15; 16; 17; 18; 19; 20; 21; 22; 23; 24; 25; 26; 27; 28; 29; 30; 31 e 32; preferivelmente X é etoxi; Y é selecionado do grupo consistindo de R1; OR1, COOR5; F; Cl; Br; I; CN; e NO2, em que R1 é um grupo alquil linear ou ramificado C1 a C4 e em que R5 é um grupo alquil linear ou ramificado C1 a C18, preferivelmente R5 é um grupo alquil linear ou ramificado C1 a C4, mais preferivelmente R5 é metil; preferivelmente Y é selecionado entre metil, etil, metoxi, etoxi, mais preferivelmente metoxi ou metil; R2 e R3 são selecionados do grupo consistindo de grupos alquil linear ou ramificado C1 a C3; e grupo aril; preferivelmente R2 e R3 são selecionados dentre estiril e cumil, mais preferivelmente estiril, preferivelmente tanto R2 quanto R3 estão na posição orto em relação ao o grupo -O-[X]n-T; T é selecionado do grupo consistindo de H; CH3; SO3-; CH2COO-; PO32-; C2H5; n-propil, i-propil; n-butil; t-butil e sulfosuccinato; T é preferivelmente H; (ii) de 0 a 50% em peso de tensoativo, diferente do dispersante de fenol alcoxilado substituído; preferivelmente o tensoativo é selecionado do grupo consistindo de tensoativos aniônicos e não iônicos, preferivelmente o nível de tensoativo varia de 4 a 40% em peso, mais preferivelmente de 6 a 30% em peso, mais preferivelmente de 8 a 20% em peso; preferivelmente a fração do peso de tensoativo não iônico/tensoativo aniônico varia de 0 a 0,3, preferivelmente de 0 a 0,15, mais preferivelmente de 0,05 a 0,12; e, (iii) de 0,0005 a 0,2% em peso de uma enzima protease, preferivelmente de 0,002 a 0,05% em peso.[0007] In one aspect, the present invention provides a laundry detergent composition comprising: (i) from 0.5 to 20% by weight, preferably 1 to 10% by weight, more preferably 2 to 6% by weight weight of a substituted alkoxylated phenol dispersant having the following structure:

wherein X is selected from the group consisting of ethoxy, and mixtures of ethoxy and propoxy groups, wherein the number of ethoxy groups is greater than the number of propoxy group, and wherein n ranges from 6 to 70, preferably from 8 to 34; more preferably n is selected from 14; 15; 16; 17; 18; 19; 20; 21; 22; 23; 24; 25; 26; 27; 28; 29; 30; 31 and 32; preferably X is ethoxy; Y is selected from the group consisting of R1; OR1, COOR5; F; Cl; BR; I; CN; and NO2 , wherein R1 is a linear or branched C1 to C4 alkyl group and wherein R5 is a linear or branched C1 to C18 alkyl group, preferably R5 is a linear or branched C1 to C4 alkyl group, more preferably R5 is methyl; preferably Y is selected from methyl, ethyl, methoxy, ethoxy, more preferably methoxy or methyl; R2 and R3 are selected from the group consisting of linear or branched C1 to C3 alkyl groups; and aryl group; preferably R2 and R3 are selected from styryl and cumyl, more preferably styryl, preferably both R2 and R3 are in the ortho position to the -O-[X]nT group; T is selected from the group consisting of H; CH3; SO3-; CH2COO-; PO32-; C2H5; n-propyl, i-propyl; n-butyl; t-butyl and sulfosuccinate; T is preferably H; (ii) from 0 to 50% by weight of surfactant, other than the substituted alkoxylated phenol dispersant; preferably the surfactant is selected from the group consisting of anionic and nonionic surfactants, preferably the level of surfactant ranges from 4 to 40% by weight, more preferably from 6 to 30% by weight, more preferably from 8 to 20% by weight; preferably the nonionic surfactant/anionic surfactant weight fraction ranges from 0 to 0.3, preferably from 0 to 0.15, more preferably from 0.05 to 0.12; and, (iii) from 0.0005 to 0.2% by weight of a protease enzyme, preferably from 0.002 to 0.05% by weight.

[0008] The level of protease enzyme in the laundry composition of the invention is the level of pure protein.

[0009] Preferably, the composition further comprises from 0.0001 to 0.5% by weight of a fluorescent agent and/or from 0.0001% by weight to 0.1% by weight of toning dye.

[0010] The laundry detergent composition is preferably selected from a granular detergent powder; an aqueous liquid laundry detergent; more preferably the laundry detergent composition is an aqueous liquid laundry detergent composition.

[0011] In another 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 substituted alkoxylated phenol dispersant, the aqueous solution comprising of 10 ppm to 5000 ppm, more preferably from 100 ppm to 1000 ppm, of the substituted alkoxylated phenol dispersant as defined herein; from 0.01 to 1 ppm of a protease enzyme and from 0 to 6 g/L, preferably 0.2 to 1 g/L, of a surfactant other than the substituted alkoxylated phenol dispersant; and, (ii) optional rinsing and drying of the fabric.

[0012] In the method, the level of the protease in the aqueous solution is more preferably from 0.02 to 0.2 ppm.

[0013] In the method, the surfactant is of the type as preferred herein.

[0014] 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.

[0015] In the method aspects of the present invention, the surfactant used is preferably as preferred for the composition aspects of the present invention.

[0016] Domestic methods are preferably carried out in a domestic washing machine or by hand washing.

[0017] The wash temperature is preferably from 285 to 313 K. The main wash time is preferably from 5 to 30 minutes.

[0018] 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 substituted alkoxylated phenol

[0019] In the context of the present invention, substituted alkoxylated phenol (ASP) is not considered a surfactant and does not contribute numerically to the surfactant as defined herein.

[0020] The most preferred aryl groups are phenyl and substituted phenyl.

[0021] C1 to C3 linear or branched alkylaryl groups are C1 to C3 linear or branched alkyl groups substituted by an aromatic group, for example: styryl, cumyl, benzyl.

[0022] A styryl group is -CH(CH3 )Ph; a cumyl group is -C(CH3 )2 Ph; a benzyl group is CH2Ph, where Ph is phenyl.

[0023] The value n is the average number of moles of alkoxyl groups. The value of n can be measured using NMR.

[0024] Sulfoccinate has the structure, represented as Na salt:

[0025] An example of ASP structures of the invention is:

[0026] The most preferred ASP framework is

[0027] ASP in combination with the protease enzyme enhances the removal of stains and reduces the redeposition of dirt, in which both enhance the whiteness of the fabrics.

Surfactant

[0028] The laundry composition may comprise anionic and non-ionic surfactant (which includes a mixture thereof).

[0029] The non-ionic and anionic surfactants of the surfactant system can be chosen from the group of 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. or in Anionic Surfactants: Organic Chemistry edited by Helmut W. Stache (Marcel Dekker 1996).

[0030] 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.

[0031] Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulfates, especially those obtained by sulfating C8 to C18 higher alcohols, produced, for example, from tallow or coconut oil, sodium alkylbenzene sulfonates and C9 to C20 potassium, particularly C10 to C15 linear secondary sodium alkylbenzene sulfonates; and sodium alkyl glyceryl ether sulfates, especially those ethers of higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.

[0032] The anionic surfactant is preferably selected from the group consisting of linear alkylbenzene sulfonate; alkyl sulfates; alkyl ether sulfates; alkyl ether carboxylates; soaps; alkyl (preferably methyl) ester sulfonates and mixtures thereof.

[0033] The most preferred anionic surfactants are selected from the group consisting of linear alkylbenzene sulfonate; alkyl sulfates; alkyl ether sulfates and mixtures thereof. Preferably, the alkyl ether sulfate is a C12-C14 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 C11 to C15 sodium alkylbenzene sulfonate. Preferably, the alkyl sulfates are a linear or branched C12 to C18 sodium alkyl sulfate. Sodium dodecyl sulfate is particularly preferred (SDS, also known as primary alkyl sulfate).

[0034] The level of anionic surfactant in the laundry composition is preferably from 4 to 40% by weight, more preferably from 6 to 30% by weight and most preferably from 8 to 20% by weight.

[0035] Preferably, two or more anionic surfactants are present, for example linear alkylbenzene sulfonate together with an alkyl ether sulfate.

[0036] Preferably, the laundry composition, in addition to the anionic surfactant, comprises alkyl ethoxylated nonionic surfactant.

[0037] 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.

[0038] Preferably, the alkyl ethoxylated nonionic surfactant is a C8 to C18 primary alcohol with an average ethoxylation of 7 EO units to 9 EO units.

[0039] Preferably, the surfactants used are saturated.

[0040] Surfactants such as those described in EP-A-328 177 (Unilever), which demonstrate resistance to desalination, the alkyl polyglycosides surfactants described in EP-A-070 074, and alkyl monoglycosides are also applicable.

Builders or Complexing Agents

[0041] The complexing agent materials may be selected from the group consisting of 1) calcium sequestering materials, 2) precipitating materials, 3) calcium ion exchange materials and 4) mixtures thereof.

[0042] Examples of calcium sequestering complexing agent materials include alkali metal polyphosphates such as sodium tripolyphosphate and organic sequestering agents such as ethylenediamine tetraacetic acid.

[0043] Examples of precipitating complexing agent materials include sodium orthophosphate and sodium carbonate.

[0044] Examples of calcium ion exchange complexing agent 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) , zeolite C, zeolite X, zeolite Y and also type P zeolite as described in EP-A-0,384,070.

[0045] The composition may also contain from 0 to 65% of a builder or complexing agent, such as ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, alkyl or alkenylsuccinic acid, nitrilotriacetic acid or other complexing agents mentioned below. Many complexing agents are also bleach stabilizing agents by virtue of their ability to complex metal ions.

[0046] Zeolite and carbonate (carbonate (including bicarbonate and sesquicarbonate)) are preferred complexing agents, with carbonates being particularly preferred.

[0047] The composition may contain as a complexing 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 bound water 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.

[0048] As an alternative or in addition to aluminosilicate complexing agents, phosphate complexing agents can be used. In the art, the term "phosphate" encompasses diphosphate, triphosphate and phosphonate species. Other forms of complexing agents include silicates such as soluble silicates, metasilicates, layered silicates (eg SKS-6 from Hoechst).

[0049] Preferably, the laundry detergent formulation is a laundry detergent formulation formed without phosphate, i.e., it contains less than 1% by weight of phosphate. Preferably, the laundry detergent powder formulations are predominantly formed of carbonate. Powders should preferably provide an in-use pH of 9.5 to 11.

[0050] More preferably, the laundry detergent is an aqueous liquid laundry detergent, preferably having a pH of 7 to 9.

[0051] 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 formulation with appropriate pour-on viscosity.

Fluorescent Agent

[0052] 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.

[0053] 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.

[0054] 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.

[0055] The total amount of the fluorescing agent or agents used in the composition is preferably 0.0001 to 0.5% by weight, more preferably 0.005 to 2% by weight, more preferably 0.05 to 0.25% by weight.

[0056] The aqueous solution used in the method has a fluorescent agent present. The fluorescent agent is present in the aqueous solution used in the method, preferably in the range of 0.0001 g/L to 0.1 g/L, more preferably 0.001 to 0.02 g/L.

Fragrance

[0057] The composition preferably 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 examples of suitable perfumes are provided in 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.

[0058] 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 phenylethylphenyl acetate.

[0059] Useful fragrance compounds include materials of both natural and synthetic origins. They include unique compounds and mixtures. Specific examples of these components can be found in the current literature, for example, 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).

[0060] It is common for a plurality of perfume 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 perfume components.

[0061] In perfume blends, preferably 15 to 25% by weight are top notes. Headnotes 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 top note of the fragrance 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 point and 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- jasmon, 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, acetate Ethylphenyl, Eucalyptol, Eugenol, Fenchyl Acetate, Floracetate (Tricycle Decenyl Acetate), Fructene (Tricycle Decenyl Propionate), Geraniol, Hexenol, Hexenol Acetate, Hexyl Acetate, Hexyl Formate, Hydra Alcohol tropic, hydroxycitronellal, indone, isoamyl alcohol, isomenthone, isopulegyl acetate, isoquinolone, ligustral, 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, phenylethyl acetate, phenylethyl alcohol, phenylethyl dimethyl carbinol, prenyl acetate, propyl bonate, pulegone, rose oxide, safrole, 4- terpinenol, alpha-terpinenol and/or viridine. It is common 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 fragrance components from the provided 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 so-called "aromatherapy" materials. These include many components also used in perfumery, including essential oil components such as Salvia sclarea, 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/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.

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

toning dye

[0070] The dyes are described in Color Chemistry Synthesis, Properties and Applications of Organic Dyes and Pigments, (H Zollinger, Wiley VCH, Zürich, 2003) and, Industrial Dyes Chemistry, Properties Applications. (K Hunger (ed), Wiley-VCH Weinheim 2003).

[0071] The toning dyes for use in laundry detergents preferably have an extinction coefficient at maximum absorption in the visible range (400 to 700 nm) greater than 5000 L mol-1 cm-1, preferably greater than 10000 L mol- 1 cm-1. The dyes are blue or violet in color.

[0072] Preferred toning dye chromophores are azo, azine, anthraquinone and triphenylmethane.

[0073] The azo, anthraquinone, phthalocyanine and triphenylmethane dyes preferably have a net anionic charge or are uncharged. The azine preferably has a net anionic or cationic charge. Blue or violet toning dyes are deposited on the fabric during the wash or rinse step of the washing process providing a visible hue to the fabric. In that sense, the dye provides a blue or violet color to a white fabric with a hue angle of from 240 to 345, more preferably from 250 to 320, most preferably from 250 to 280. The white fabric used in this test is woven cotton sheeting. not mercerized targeted.

[0074] Toning dyes are discussed in WO2005/003274, WO2006/032327(Unilever), WO 2006/032397(Unilever), WO2006/045275(Unilever), WO 2006/027086(Unilever), WO 2008/017570(Unilever ), WO 2008/141880 (Unilever), WO2009/132870(Unilever), WO 2009/141173 (Unilever), WO 2010/099997(Unilever), WO 2010/102861(Unilever), WO 2010/148624(Unilever), WO2008 /087497 (P&G), WO2011/011799 (P&G), WO2012/054820 (P&G), WO2013/142495 (P&G) and WO2013/151970 (P&G).

[0075] The mono-azo dyes preferably contain a heterocyclic ring and are more preferably thiophene dyes. Mono-azo dyes are preferably alkoxylated and are preferably uncharged or anionically charged at pH=7. Alkoxylated thiophene dyes are discussed in WO/2013/142495 and WO/2008/087497. Preferred examples of thiophene dyes are shown below:

[0076] The bis-azo dyes are preferably sulfonated bis-azo dyes. Preferred examples of sulfonated bis-azo compounds are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, direct violet 66, violet direct 99 and alkoxylated versions of these. Bis-azo alkoxylated dyes are discussed in WO2012/054058 and WO2010/151906.

[0077] An example of a bis-azo alkoxylated dye is:

em que: X3 é selecionado do grupo consistindo de -H; -F; -CH3; -C2H5; -OCH3; e, -OC2H5; X4 é selecionado do grupo consistindo de -H; -CH3; -C2H5; -OCH3; e, — OC2H5; Y2 é selecionado do grupo consistindo de -OH; -OCH2CH2OH; - CH(OH)CH2OH; -OC(O)CH3; e, C(O)OCH3.[0078] The azine dyes are preferably selected from sulfonated phenazine dyes and cationic phenazine dyes. Preferred examples are acid blue 98, acid violet 50, CAS No. 72749-80-5, acid blue 59, and the phenazine dye selected from:

wherein: X3 is selected from the group consisting of -H; -F; -CH3; -C2H5; -OCH3; and, -OC2H5; X4 is selected from the group consisting of -H; -CH3; -C2H5; -OCH3; and, — OC2H5; Y2 is selected from the group consisting of -OH; -OCH2CH2OH; - CH(OH)CH2OH; -OC(O)CH3; and, C(O)OCH3 .

[0079] The toning dye is present in the composition in the range of 0.0001 to 0.5% by weight, preferably 0.001 to 0.1% by weight. Depending on the nature of the toning dye, there are preferred ranges depending on the effectiveness of the toning dye, which depends on the particular class and effectiveness within a particular class. As described above, the toning dye is a blue or violet toning dye.

[0080] A mixture of toning dyes can be used.

[0081] The toning dye is most preferably a reactive blue anthraquinone dye covalently linked to an alkoxylated polyethyleneimine. Alkoxylation is preferably selected from ethoxylation and propoxylation, more preferably propoxylation. Preferably, 80 to 95 mol% of the N-H groups on the polyethyleneimine are replaced with isopropyl alcohol groups by propoxylation. Preferably, the polyethyleneimine, prior to reaction with the dye and propoxylation, has a molecular weight of 600 to 1800.

[0082] An example structure of a preferred reactive anthraquinone covalently linked to a propoxylated polyethyleneimine is:

[0083] Preferred reactive anthraquinone dyes are: Reactive Blue 1; Reactive Blue 2; Reactive Blue 4; Reactive blue 5; Reactive blue 6; Reactive Blue 12; Reactive Blue 16; reactive blue 19; Reactive blue 24; Reactive blue 27; Reactive Blue 29; Reactive blue 36; Reactive Blue 44; Reactive Blue 46; Reactive Blue 47; Reactive Blue 49; Reactive Blue 50; Reactive Blue 53; Reactive Blue 55; Reactive blue 61; Reactive Blue 66; Reactive blue 68; Reactive Blue 69; Reactive blue 74; Reactive blue 86; Reactive Blue 93; Reactive Blue 94; Reactive Blue 101; Reactive Blue 103; Reactive Blue 114; Reactive Blue 117; Reactive Blue 125; Reactive Blue 141; Reactive Blue 142; Reactive Blue 145; Reactive Blue 149; Reactive Blue 155; Reactive Blue 164; Reactive Blue 166; Reactive Blue 177; Reactive Blue 181; Reactive Blue 185; Reactive Blue 188; Reactive Blue 189; Reactive Blue 206; Reactive Blue 208; Reactive Blue 246; Reactive Blue 247; Reactive Blue 258; Reactive Blue 261; Reactive Blue 262; Reactive Blue 263; and Reactive Blue 172.

[0084] Dyes are listed according to the Color Index classification (Society of Dyers and Colourists/American Association of Textile Chemists and Colorists).

Protease Enzyme

[0085] Protease enzymes hydrolyze bonds within peptides and proteins; in the context of laundry, this results in greater removal of stains containing protein or peptide. Examples of suitable protease families include aspartic proteases; cysteine proteases; glutamic proteases; asparagine peptide lyase; serine proteases and threonine proteases. These protease families are described in the MEROPS peptidase database (http://merops.sanger.ac.uk/). Serine proteases are preferred. Subtilase-type serine proteases are more preferred. The term "subtilases" refers to a serine protease subgroup according to Siezen et al., Protein Engng. 4 (1991) 719-737 and Siezen et al. Protein Science 6 (1997) 501-523. Serine proteases are a subgroup of proteases characterized by having a serine at the active site, which forms a covalent adduct with the substrate. Subtilases can be divided into 6 subdivisions, namely the Subtilisin family, the Thermitase family, the Proteinase K family, the Lantibiotic Peptidase family, the Kexin family, and the Pyrolysin family.

[0086] Examples of subtilases are those derived from bacilli, such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in US7262042 and WO09/021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89/06279 and protease PD138 described in WO93/18140. Other useful proteases may be those described in WO92/175177, WO01/016285, WO02/026024 and WO02/016547. Examples of trypsin-like proteases are trypsin (e.g. of porcine or bovine origin) and the Fusarium protease described in WO89/06270, WO94/25583 and WO05/040372, and the Cellumonas-derived chymotrypsin proteases described in WO05/052161 and WO05/052146.

[0087] Other examples of useful proteases are the variants described in: WO92/19729, WO96/034946, WO98/20115, WO98/20116, WO99/011768, WO01/44452, WO03/006602, WO04/03186, WO04/041979 , WO07/006305, WO11/036263, WO11/036264, especially variants with substitutions at one or more of the following positions: 3, 4, 9, 15, 27, 36, 57, 68, 76, 87, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 106, 118, 120, 123, 128, 129, 130, 160, 167, 170, 194, 195, 199, 205, 206, 217, 218, 222, 224, 232, 235, 236, 245, 248, 252 and 274 using BPN' numbering. The most preferred subtilase variants may comprise the mutations: S3T, V4I, S9R, A15T, K27R, *36D, V68A, N76D, N87S,R, *97E, A98S, S99G,D,A, S99AD, S101 G,M, R S103A, V104I,Y,N, S106A, G1 18V,R, H120D,N, N123S, S128L, P129Q, S130A, G160D, Y167A, R170S, A194P, G195E, V199M, V205I, L217D, N218D, M222S, A222S, A222V K235L, Q236H, Q245R, N252K, T274A (using BPN' numbering).

[0088] More preferably, the protease is a subtilisin (EC 3.4.21.62).

[0089] Examples of subtilases are those derived from bacilli, such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in US7262042 and WO09/021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89/06279 and protease PD138 described in WO93/18140. Preferably, the subsilysin is derived from bacilli, preferably Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii as described in US 6,312,936 BI, US 5,679,630, US 4,760,025 , US7,262,042 and WO09/021867. More preferably, the subtilisin is derived from Bacillus gibsonii or Bacillus lentus.

[0090] Suitable commercially available protease enzymes include those marketed under the tradenames Alcalase®, Blaze®; DuralaseTm, DurazymTm, Relase®, Relase® Ultra, Savinase®, Savinase® Ultra, Primase®, Polarzyme®, Kannase®, Liquanase®, Liquanase® Ultra, Ovozyme®, Coronase®, Coronase® Ultra, Neutrase®, Everlase® and Esperase®, all could be marketed as Ultra® or Evity® (Novozymes A/S).

[0091] Those marketed under the trade names Maxatase®, Maxacal®, Maxapem®, Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®, Excellase® and Purafect OXP® by Genencor International.

[0092] Those marketed under the trade names Maxatase®, Maxacal®, Maxapem®, Purafect®, Purafect Prime®, PreferenzTm, Purafect MA®, Purafect Ox®, Purafect OxP®, Puramax®, Properase®, EffectenzTm, FN2®, FN3® , FN4®, Excellase®, Opticlean® and Optimase® (Danisco/DuPont), Axapem™ (Gist-Brocases N.V.),

[0093] Those available from Henkel/Kemira, namely BLAP (sequence shown in Figure 29 of US 5,352,604 with the following mutations S99D + SlOl R + S103A + V104I + G159S, hereinafter called BLAP), BLAP R (BLAP with S3T + V4I + V199M + V205I + L217D), BLAP X (BLAP with S3T + V4I + V205I) and BLAP F49 (BLAP with S3T + V4I + A194P + V199M + V205I + L217D) - all from Henkel/Kemira; and KAP (Bacillus alkalophilus subtilisin with A230V + S256G + S259N mutations) from Kao.

Other Enzymes

[0094] One or more other enzymes are preferably present in a laundry composition of the invention and in practicing a method of the invention.

[0095] Preferably, the level of each enzyme in the laundry composition of the invention ranges from 0.0001% by weight to 0.1% by weight of protein.

[0096] Preferably, the additional enzyme is selected from: alpha-amylases; lipases and cellulases, preferably a protease.

[0097] 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, for example 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).

[0098] 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 and WO 97/07202, WO 00/60063.

[0099] Preferred commercially available lipase enzymes include Lipolase™ and Lipolase Ultra™, Lipex™ and Lipoclean™ (Novozymes A/S).

[0100] 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.

[0101] Phospholipids, such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an outer (sn-1) and intermediate (sn-2) position and esterified with phosphoric acid in 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 that hydrolyze a fatty acyl group (at the sn-1 and sn-2 positions, 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.

[0102] 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.

[0103] 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.).

[0104] Suitable cellulases include those of bacterial or fungal origin. Chemically modified or genetically engineered protein mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, for example, the fungal cellulases produced from Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxysporum disclosed in US 4,435,307, US 5,648,263 , US 5,691,178 , US 5,776,757 , WO 89/09259 , WO 96/029397 and WO 98/012307 . 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 ). CellucleanTM is preferred.

[0105] Suitable 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).

[0106] Additional suitable enzymes for use are discussed in WO2009/087524 , WO2009/090576 , WO2009/107091 , WO2009/111258 and WO2009/148983 .

Enzyme Stabilizers

[0107] 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-formylphenylboronic acid, and the composition can be formulated as described, for example, in WO 92/19709 and WO 92/19708.

[0108] When the alkyl groups are long enough to form branched or cyclic chains, they will encompass branched, cyclic and linear alkyl chains. Alkyl groups are preferably linear or branched, more preferably linear.

[0109] 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.

Experimental part Example 1

[0110] An aqueous liquid laundry detergent of the following formulation was prepared:

[0111] The formulation was used to wash 8 EMPA 117 stain monitors (polycotton blood/milk/ink stains) in a tergotometer set at 200 rpm. A 20 minute wash in 800 mL of 26° French hard water at 25°C was conducted with 2.3 g/L of the formulation. To simulate oily dirt, 7.2 g of an SBL2004 dirt blade (ex Warwick Equest) was added to the wash liquid.

[0112] Once the wash was completed, the cotton monitors were rinsed once in 400 mL of clean water, removed, dried and the color was measured in a reflectometer and expressed as CIE L*a*b* values.

[0113] Equivalent Formulations, but with the addition of 8.7% by weight of the ASP dispersant (n = 20):

[0114] The experiments were repeated with and without the addition of a subtilisin serine protease (EC No. 232-752-2) to the washing liquid (Evity® 16L ex Novozymes). The enzyme was added to provide 0.009% by weight of pure active protein for the formulation.

[0115] 95% confidence limits are also provided, calculated from the standard deviation in measurements from the 8 monitors.

[0116] Once the wash was completed, the cotton displays were rinsed once in 400 mL of clean water, removed, dried and the color was measured in a reflectometer and expressed as CIE L*a*b* values. The anti-redeposition cleaning benefit was expressed as the value ΔL:ΔL = L(dispersant) - L(control)

[0117] The higher the ΔL value, the greater the prevention of black carbon dirt deposit. 95% confidence limits based on the 8 separate cotton monitors were calculated. The formulations were carried out with and without the addition of 8.7% by weight of the dispersant:

[0118] The cleaning benefit was expressed as the value ΔL:ΔL = L(test) - L(control)

[0119] The higher the ΔL value, the greater the prevention of carbon black dirt deposit.

[0120] ASP dispersant alone and protease alone potentiate stain removal. A further increase is observed when the 2 are combined and ΔL= 4.05 is greater than expected from the sum of individual performance, 1.55 + 1.32 = 2.88.

Claims (15)

1. A laundry detergent composition, characterized in that it comprises: (i) from 0.5 to 20% by weight of a substituted alkoxylated phenol dispersant having the following structure:

wherein X is selected from the group consisting of ethoxy; and mixtures of ethoxy and propoxy groups, wherein the number of ethoxy groups is greater than the number of propoxy groups, and wherein n is from 6 to 70; Y is selected from the group consisting of R1; OR1, COOR5; F; Cl; BR; I; CN; and NO2, wherein R1 is a C1 to C4 linear or branched alkyl group and R5 is selected from C1 to C18 linear or branched alkyl groups; R2 and R3 are selected from the group consisting of linear or branched C1 to C3 alkylaryl groups; and aryl groups; T is selected from the group consisting of H; CH3; SO3-; CH2COO-; PO32-; C2H5; n-propyl, i-propyl; n-butyl; t-butyl and sulfosuccinate; (ii) from 0 to 50% by weight of surfactant other than substituted alkoxylated phenol; and, (iii) from 0.0005 to 0.2% by weight of a protease enzyme. Detergent composition for washing clothes, according to claim 1, characterized in that R2 and R3 are selected from styryl and cumyl. Detergent composition for laundry, according to claim 1, characterized in that R2 and R3 are styryl and both R2 and R3 are in the ortho position with respect to the -O-[X]n-T group. A laundry detergent composition according to any one of claims 1, 2 or 3, characterized in that X is ethoxy. Detergent composition for washing clothes, according to any one of claims 1 to 4, characterized in that n varies from 8 to 34. A laundry detergent composition according to any one of claims 1 to 5, characterized in that the surfactant is selected from the group consisting of anionic and non-ionic surfactants and the surfactant level varies from 4 to 40% by weight. 7. A laundry detergent composition, according to any one of claims 1 to 6, characterized in that the non-ionic surfactant/anionic surfactant weight fraction varies from 0 to 0.3. A laundry detergent composition according to claim 6 or 7, characterized in that the anionic surfactant is selected from the group consisting of linear alkylbenzene sulfates; alkyl sulfate and alkyl ether sulfates; and mixtures thereof. A laundry detergent composition according to any one of claims 1 to 8, characterized in that the level of substituted alkoxylated phenol dispersant varies from 1 to 10% by weight. A laundry detergent composition according to any one of claims 1 to 9, characterized in that T is H. 11. Detergent composition for washing clothes, according to any one of claims 1 to 10, characterized in that Y is selected from: methyl; ethyl; methoxy and ethoxy. Detergent composition for laundry, according to claim 1, characterized in that the substituted alkoxylated phenol dispersant is:

and the protease enzyme is a subtilisin (EC 3.4.21.62). 13. Detergent composition for washing clothes, according to any one of claims 1 to 12, characterized in that n is selected from: 14; 15; 16; 17; 18; 19; 20; 21; 22; 23; 24; 25; 26; 27; 28; 29; 30; 31; and, 32. 14. Domestic method of treating a fabric, characterized in that the method comprises the steps of: (i) treating a fabric with an aqueous solution of the substituted alkoxylated phenol dispersant, the aqueous solution comprising from 10 ppm to 5000 ppm of the phenol dispersant substituted alkoxylated as defined in any one of claims 1 to 13; from 0.01 to 1 ppm of a protease enzyme; and from 0 to 6 g/L of a surfactant other than the substituted alkoxylated phenol dispersant; and (ii) optional rinsing and drying of the fabric. Home method of treating a fabric, according to claim 14, characterized in that, in the method, the protease enzyme is a subtilisin (EC 3.4.21.62).