CN110869480B

CN110869480B - Whitening composition

Info

Publication number: CN110869480B
Application number: CN201880045612.9A
Authority: CN
Inventors: S·N·巴切洛尔; C·布雷法; J·迪德里希斯; K·J·姆奇; S·罗曼斯基; C·谢弗
Original assignee: Unilever IP Holdings BV
Current assignee: Unilever IP Holdings BV
Priority date: 2017-07-07
Filing date: 2018-07-04
Publication date: 2021-08-13
Anticipated expiration: 2038-07-04
Also published as: WO2019008036A1; ZA201908604B; EP3649222B1; CN110869480A; EP3649222A1; AR112380A1; BR112020000201A2

Abstract

The present invention provides a laundry cleaning composition comprising: i) from 0.2 to 20 weight percent of an alkoxylated dispersant having the following structure (F1):

wherein: x is selected from: an ethoxy group; and a mixture of ethoxy groups 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; m is selected from: 2 and 3; r₁Selected from: uncharged C12 to C20 alkyl; an uncharged aryl group; and an uncharged alkylaryl group, wherein the alkyl group of the alkylaryl group is saturated straight or branched C1 to C3; t is selected from: h; CH (CH)₃；SO₃ ^‑；CH₂COO^‑；PO₃ ^2‑；C₂H₅(ii) a N-propyl, isopropyl; n-butyl; a tertiary butyl group; and sulfosuccinates; (ii)0 to 50 weight percent of a surfactant other than the alkoxylated dispersant; (iii) an active ingredient selected from one or more of the following: 0.001 to 3% by weight of a perfume; 0.0001 to 0.5 wt% of a fluorescent agent;and 0.0001 wt% to 0.1 wt% of an enzyme. The invention further relates to a domestic method of treating a fabric comprising treating the fabric with an aqueous liquor comprising the alkoxylated dispersant.

Description

Whitening composition

Technical Field

The present invention relates to laundry cleaning compositions.

Background

It is desirable to use less water in home laundry washing. This can be achieved by reducing the number of water rinses performed after the initial wash. Reducing the number of rinses increases redeposition of soil removed in the wash, thereby reducing overall cleaning. The presence of human sebum on clothing and in the wash liquor exacerbates this problem, which serves to enhance the deposition of soil in the wash. There is a need for improved dispersants that prevent the deposition of soils present in wash liquor onto fabrics. Such ingredients are preferably biodegradable and enhance stain removal.

Disclosure of Invention

There is a need for techniques to reduce redeposition and enhance cleaning in household laundry products.

We have found that selected Alkoxylated Dispersants (AD) enhance whiteness and brightness of clothes when added to laundry detergents during home laundering.

In a first aspect, the present invention provides a laundry cleaning composition comprising:

(i) from 0.2 to 20 wt%, preferably from 0.5 to 12 wt%, most preferably from 1 to 10 wt% of an alkoxylated dispersant having the structure:

wherein:

x is selected from: an ethoxy group; and a mixture of ethoxy groups 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;

m is selected from: 2 and 3;

R₁selected from: uncharged C12 to C20 alkyl; an uncharged aryl group; and an uncharged alkylaryl group, wherein the alkyl group of the alkylaryl group is saturated straight or branched C1 to C3;

t is selected from: h; CH (CH)₃；SO₃ ^-；CH₂COO^-；PO₃ ^2-；C₂H₅(ii) a N-propyl, isopropyl; n-butyl; a tertiary butyl group; and sulfosuccinates;

(ii)0 to 50 weight percent of a surfactant other than the alkoxylated dispersant; and

(iii) an active agent selected from one or more of the following: 0.001 to 3% by weight of a perfume; 0.0001 to 0.5 wt% of a fluorescent agent; and 0.0001 wt% to 0.1 wt% of an enzyme.

Preferably, in the alkoxylated dispersant structure, R₁Is an alkylaryl group.

Preferably, in the alkoxylated dispersant structure, T is not H.

Preferably, in the alkoxylated dispersant structure, X is ethoxy.

Preferably, in the alkoxylated dispersant structure, the average number n of moles of alkoxy groups is from 6 to 40, more preferably from 9 to 30, most preferably from 10 to 20. Preferably, in the alkoxylated dispersant structure, T is CH₃。

Preferably, R₁Selected from phenylethyl and benzyl. More preferably, R₁Is benzyl.

Preferably, the alkoxylated dispersant is selected from:

preferred laundry cleaning compositions comprise a surfactant other than the alkoxylated dispersant in an amount of from 4 to 40 wt%, more preferably from 4 to 35 wt%, most preferably from 6 to 30 wt%.

Preferably, the surfactant other than the alkoxylated dispersant comprises an anionic and/or nonionic surfactant.

More preferably, the weight fraction of nonionic surfactant to anionic surfactant is from 0 to 0.3. This means that the nonionic surfactant may be present (or it may be absent if the weight fraction is 0), but if the nonionic surfactant is present, the weight fraction of the nonionic surfactant is preferably at most 30% of the total weight of anionic surfactant + nonionic surfactant, wherein the alkoxylated dispersant is not considered a surfactant as defined herein.

Preferably, the anionic surfactant is selected from: linear alkyl benzene sulfonate; an alkyl sulfate; alkyl ether sulfates; and mixtures thereof. If present, the nonionic surfactant is preferably an alcohol ethoxylate, more preferably C with an average of 3-10 moles of ethylene oxide₁₀-C₁₈Alcohol ethoxylates, most preferably C with an average of 5 to 9 moles of ethylene oxide₁₂-C₁₅An alcohol ethoxylate.

The laundry cleaning composition is preferably an aqueous laundry liquid detergent composition. Preferably, the pH of the aqueous liquid detergent composition is from 6 to 8.5, preferably from 6.5 to 7.5, even more preferably from 6.8 to 7.2, most preferably 7.0.

Preferably, the active ingredient is an enzyme and includes one or more of: proteases, alpha-amylases, cellulases, lipases, peroxidases/oxidases, pectate lyases and mannanases, or mixtures thereof. More preferably, the enzyme is a protease, most preferably a serine protease of the subtilase (subtilase) type.

In a second aspect, the present invention provides a domestic method of treating a fabric, the method comprising the steps of:

(i) treating the fabric with an aqueous solution of an alkoxylated dispersant as defined in the first aspect of the invention;

the aqueous solution comprises from 10ppm to 5000ppm, preferably from 100ppm to 1000ppm of an alkoxylated dispersant as defined herein; and 0 to 6g/L, preferably 0.5 to 6g/L, more preferably 1 to 5g/L of a surfactant other than the alkoxylated dispersant; and

(ii) optionally rinsing and drying the fabric;

wherein in said method one or more active ingredients selected from perfumes, fluorescers and enzymes are present in said aqueous solution of said alkoxylated dispersant,

wherein the perfume, if present, is present in the aqueous solution in an amount of from 0.1 to 100 ppm; preferably 1 to 10 ppm.

Wherein the fluorescer, if present, is present in the aqueous solution in an amount of from 0.0001 to 0.1g/L, preferably from 0.001 to 0.02 g/L; and

wherein the enzyme, if present, is present in the aqueous solution in an amount of 0.01 to 10ppm, preferably 0.05 to 1 ppm.

In the method aspect of the invention, the surfactant used is preferably as preferred in the composition aspect of the invention.

The domestic method is preferably carried out in a domestic washing machine or by hand washing. The washing temperature is preferably 285 to 335K.

The fabric is preferably an item of used clothing, bedding or tablecloth. Preferred articles of clothing are through-the-hole cotton-containing shirts, pants, undergarments and pullovers.

Detailed Description

Alkoxylated dispersants

The alkoxylated dispersant has the following structure:

wherein:

preferably, R₁Is an alkylaryl group, most preferably a benzyl group.

T is selected from: h; CH (CH)₃；SO₃ ^-；CH₂COO^-；PO₃ ^2-；C₂H₅(ii) a N-propyl and isopropyl; n-butyl; a tertiary butyl group; and sulfosuccinates; preferably, T is not H, most preferably, T is CH₃。

The value of m is selected from 2 and 3, preferably 2.

The alkoxylated dispersant is preferably trimellitic anhydride or pyromellitic dianhydride and T- (X)_nPolyethers in the form of-OH and R₁-reaction product formation of an alcohol in the OH form, wherein R₁Selected from uncharged C12 to C20 alkyl groups; an uncharged aryl group; and an uncharged alkylaryl group, wherein the alkyl group of the alkylaryl group is saturated straight or branched C1 to C3;

preferably, R₁-OH is selected from 2-phenylethanol and benzyl alcohol.

R₁May be substituted by further uncharged organic groups, e.g. when R is₁When containing a benzene ring, the benzene ring may be substituted by methyl, ethyl, methoxy, ethoxy, Cl, NO₂And (4) substitution. When R is₁when-OH is an aromatic alcohol, for example, phenol can be used in the reaction. Preferably, trimellitic anhydride or pyromellitic dianhydride is reacted with a polyetherShould then react with R₁-OH alcohol reaction. Preferably, trimellitic anhydride or pyromellitic dianhydride is reacted with 1 molar equivalent of polyether and then with R₁-OH alcohol reaction.

X is selected from OCH₂CH₂(ethoxy) and OCH (CH)₃)CH₂(propoxy) and mixtures thereof, wherein the number of ethoxy groups is greater than the number of propoxy groups if a mixture is used. If X comprises propoxy, preferably the ethoxy/propoxy molar ratio is greater than 2, more preferably greater than 5.

If X is a mixture of ethoxy and propoxy groups, they may be distributed blockwise, or periodically and/or statistically.

X is most preferably OCH₂CH₂(ethoxy).

The value of n is the average number of moles of alkoxy groups. The value of n can be measured using NMR. n has a value of 6 to 70, preferably 6 to 40, more preferably 9 to 30. In practice, the value of n may be 9, 10, 11, 12, 13, 14 individually; 15; 16; 17; 18; 19; 20; 21; 22; 23; 24; 25; 26; 27; 28; 29 or 30. Most preferably, n may have a value of 10 to 20.

The alkoxylated dispersant may alternatively be formed by: acid anhydrides and R₁-OH reaction followed by alkoxylation with an epoxide, however, this route is not preferred.

Chlorinated trimellitic anhydride can also be used.

In the context of the present invention, alkoxylated dispersants are not considered surfactants and do not contribute numerically to surfactants as defined herein.

Sulfosuccinate (Sulfoccinate) has the following structure:

a preferred example of the structure of the AD of the present invention is

And isomers thereof.

The most preferred AD structure is:

the alkoxylated dispersants prevent the deposition of soils present in the wash liquor onto fabrics. The alkoxylated dispersants may also enhance stain removal.

Active ingredient

The laundry cleaning composition comprises an active ingredient selected from one or more of the following: 0.001 to 3% by weight of a perfume; 0.0001 to 0.5 wt% of a fluorescent agent; and 0.0001 wt% to 0.1 wt% of an enzyme.

Contemplated enzymes include proteases, alpha-amylases, cellulases, lipases, peroxidases/oxidases, pectate lyases and mannanases or mixtures thereof. Preferably, the enzyme is selected from: protease, alpha-amylase; cellulase and lipase, or mixtures thereof. More preferably, the enzyme is a protease, more preferably a subtilisin-type serine protease.

Preferred perfumes and fluorescers are described herein.

Surface active agent

The laundry composition may comprise anionic and nonionic surfactants (which include mixtures of anionic and nonionic surfactants).

The surfactant is present at a level of from 0 to 50% by weight. This means that the surfactant need not be present, but preferably it is present.

Preferred laundry cleaning compositions comprise surfactant at a level of from 4 to 40 wt%, more preferably from 4 to 35 wt%, most preferably from 6 to 30 wt%.

Preferably, the surfactant comprises an anionic and/or nonionic surfactant.

Suitable nonionic and anionic surfactants may be selected from "Surface Active Agents", Vol.1, Schwartz & Perry, Interscience 1949; volume 2, Schwartz, Perry & Berch, Interscience 1958; surfactants described in the current version of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing conditioners Company, or "Tenside-Taschenbuch", H.Stache, 2 nd edition, Carl Hauser Verlag, 1981, or International Surfactants, edited by Helmut W.Stache, Organic Chemistry (Marcel Dekker 1996).

Suitable anionic detergent compounds which may be used are typically water-soluble alkali metal salts of organic sulphuric and sulphonic acids having an alkyl group containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher alkyl groups.

Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, in particular higher C by reaction, for example from tallow or coconut oil₈To C₁₈Those obtained by sulfation of alcohols; alkyl ether carboxylic acids; alkyl radical C₉To C₂₀Sodium and potassium benzene-sulphonates, especially linear secondary alkyl C₁₀To C₁₅Sodium benzenesulfonate; and sodium alkyl glyceryl ether sulfates, particularly those ethers of higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.

The anionic surfactant is preferably selected from: linear alkyl benzene sulfonate; an alkyl sulfate; alkyl ether sulfates; alkyl ether carboxylic acids; soap; alkyl (preferably methyl) ester sulfonates and mixtures thereof.

More preferred anionic surfactants are selected from: linear alkyl benzene sulfonate; an alkyl sulfate; alkyl ether sulfates and mixtures thereof. Preferably, the alkyl ether sulphate is C with an average of 1 to 3 EO (ethoxylate) units₁₂-C₁₄N-alkyl ethersA sulfate salt. Sodium Lauryl Ether Sulfate (SLES) is particularly preferred. Preferably, the linear alkylbenzene sulfonate is C₁₁To C₁₅Sodium alkyl benzene sulfonate. Preferably, the alkyl sulfates are linear or branched C₁₂To C₁₈Sodium alkyl sulfate. Sodium dodecyl sulfate (SDS, also known as primary alkyl sulfate) is particularly preferred.

Preferably, two or more anionic surfactants are present, for example linear alkyl benzene sulphonate together with alkyl ether sulphate.

Most preferably, the anionic surfactant is selected from: linear alkyl benzene sulfonate; an alkyl sulfate; alkyl ether sulfates; and mixtures thereof.

The composition may comprise anionic and/or nonionic surfactants.

Preferably, the weight fraction of nonionic surfactant to anionic surfactant is from 0 to 0.3. This means that the nonionic surfactant may be present (or it may be absent if the weight fraction is 0), but if the nonionic surfactant is present, the weight fraction of the nonionic surfactant is preferably at most 30% of the total weight of anionic surfactant + nonionic surfactant.

Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having an aliphatic hydrophobic group and a reactive hydrogen atom, such as aliphatic alcohols, acids or amides, with ethylene oxide, in particular (alone or together with propylene oxide). Specific nonionic detergent compounds are aliphatic C₈To C₁₈Condensation products of linear or branched primary or secondary alcohols with ethylene oxide.

Most preferably, if present, the nonionic surfactant is an alcohol ethoxylate, more preferably a C10-C18 alcohol ethoxylate having an average of 3-10 moles of ethylene oxide, most preferably a C12-C15 alcohol ethoxylate having an average of 5-9 moles of ethylene oxide.

Preferably, the surfactant used is saturated.

Also suitable are surfactants such as those which exhibit resistance to salting out as described in EP-A-328177 (Unilever), alkylpolyglycoside surfactants as described in EP-A-070074, and alkylmonoglycosides.

Cationic compounds

The surfactant may comprise a cationic surfactant.

Most preferred are quaternary ammonium compounds.

If the quaternary ammonium compound is a compound having at least one C₁₂To C₂₂Quaternary ammonium compounds of the alkyl chain are advantageous.

If the quaternary ammonium compound has the formula:

wherein R is¹Is C₁₂To C₂₂An alkyl or alkenyl chain; r²、R³And R⁴Independently selected from C₁To C₄Alkyl chain, and X^-Are compatible anions, are preferred. A preferred compound of this type is the quaternary ammonium compound cetyl trimethyl quaternary ammonium bromide.

A second class of materials for use with the present invention are quaternary amines having the structure described above, wherein R¹And R²Independently selected from C₁₂To C₂₂An alkyl or alkenyl chain; r³And R⁴Independently selected from C₁To C₄Alkyl chain, and X^-Are compatible anions.

The composition optionally comprises a silicone.

Perfume

One or more perfumes may be present as all or part of the active ingredient of the laundry cleaning composition.

The composition preferably comprises a perfume. The perfume is preferably present in the range of from 0.001 to 3 wt%, more preferably from 0.05 to 0.5 wt%, most preferably from 0.1 to 1 wt%. Many suitable examples of fragrances are provided in CTFA (Cosmetic, Toiletry and Fragrance Association)1992International layers Guide, published by CFTA Publications, and OPD 1993Chemicals layers Directory 80th annular Edition, published by Schnell Publishing Co.

Preferably, the fragrance comprises at least one of the following notes (compounds): alpha-isomethyl ionone, benzyl salicylate; citronellol; coumarin; hexyl cinnamic aldehyde; linalool; 2-methyl pentanoic acid ethyl ester; octanal; benzyl acetate; 3, 7-dimethyl-1, 6-octadien-3-ol 3-acetate; 2- (1, 1-dimethylethyl) -cyclohexanol 1-acetate; delta-damascone (damascone); beta-ionone; tricyclodecenyl acetate (verdyl acetate); dodecanal; hexyl cinnamaldehyde (hexyl cinnnamic aldehyde); cyclopentadecanolide; 2-phenylethyl phenylacetate; amyl salicylate; beta-caryophyllene; ethyl undecylenate; geranyl anthranilate; α -irone; beta-phenylethyl benzoate; α -santalol; cedrol; cedryl acetate; cedryl formate (cedry format); cyclohexyl salicylate; gamma-dodecalactone, and beta-phenylethylphenyl acetate.

Useful components of perfumes include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components can be found in the literature, for example, in the Feraroli's Handbook of flavour Ingredients, 1975, CRC Press; synthetic Food adjacents, 1947, m.b. jacobs, edited by Van nonstrand; or Perfun and flavour Chemicals, S.arctander, 1969, Montclair, N.J. (USA).

It is common for multiple perfume components to be present in a formulation. In the compositions of the present invention, it is envisaged that four or more, preferably five or more, more preferably six or more, or even seven or more different perfume components will be present.

In the perfume mixture, preferably 15 to 25% by weight is 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 oil, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.

The international daily-use perfumery association has issued a list of fragrance ingredients (fragrances) in 2011. (http:// www.ifraorg.org/en-us/ingredients #. U7Z4 hPldWzk).

The international daily fragrance institute provides a database of fragrances (fragrances) with safety information.

Perfume top notes may be used to indicate the benefits of the present invention.

Some or all of the perfume may be encapsulated, typical perfume components which facilitate encapsulation include those having a relatively low boiling point, preferably a boiling point of less than 300 ℃, preferably 100 ℃ and 250 ℃. It is also advantageous to encapsulate perfume components having a low Clog P (i.e. those that will have a higher tendency to be distributed into water), preferably having a Clog P of less than 3.0. These materials having relatively low boiling points and relatively low CLog P have been referred to as "delayed blooming" perfume ingredients and comprise one or more of the following materials:

allyl hexanoate, amyl acetate, amyl propionate, anisaldehyde, anisole, benzaldehyde, benzyl acetate, benzyl acetone, benzyl alcohol, benzyl formate, benzyl isovalerate, benzyl propionate, β - γ hexenol, camphor gum, l-carvone, d-carvone, cinnamyl alcohol, cinnamyl formate (cinamyl form), cis-jasmone, cis-3-hexenyl acetate, cuminol, cyclal c, dimethyl benzyl methanol acetate, ethyl acetoacetate, ethyl ethylacetoacetate, ethylamyl ketone, ethyl benzoate, ethyl butyrate, ethylhexyl ketone, ethylphenyl acetate, eucalyptol, eugenol, fenchyl acetate (fenchyl acetate), flor acetate (tricyclodecenyl acetate), tricyclodecene propionate, geraniol, hexenol, hexenyl acetate, hexyl acetate, Hexyl formate, solanol (hydroacetylalcohol), hydroxycitrocitronellal, indanone, isoamyl alcohol, isomenthone, isopulegyl acetate, isoquinolinone, ligustral, linalool oxide, linalyl formate, menthone, menthylacetone, methyl amyl ketone, methyl anthranilate, methyl benzoate, methyl benzyl acetate, methyl eugenol, methyl heptenone, methyl heptyne carbonate, methyl heptyne ketone, methyl hexyl ketone, methyl phenyl methyl acetate, methyl salicylate, methyl-n-methyl anthranilate, nerol, octolactone, octanol, p-cresol methyl ether, p-methoxyacetophenone, p-methylacetone, phenyl acetaldehyde, phenyl ethyl acetate, phenyl ethyl alcohol, Phenylethyldimethylcarbinol, prenyl acetate, propyl borate, pulegone, rose oxide, safrole, 4-terpinenol (4-terpinenol), alpha-terpinenol, and/or phenylacetaldehyde dimethanol acetal (viridine). It is common for multiple perfume components to be present in a formulation. 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 present in the perfume from the given list of delayed release perfumes given above.

Another group of fragrances that may be employed with the present invention are the so-called "aromatherapy" materials. These include many components that are also used in perfumes, including components of essential oils, such as sage, eucalyptus, geranium, lavender, dried nutmeg skin (Mace) extract, neroli, nutmeg, spearmint, sweet violet leaves, and valerian. It is preferred that the laundry treatment composition is devoid of peroxygen bleach, such as sodium percarbonate, sodium perborate and peracids.

Fluorescent agent

One or more fluorescers may be present as all or part of the active ingredient of the laundry cleaning composition.

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

Preferred classes of fluorescers are: distyrylbiphenyl compounds such as Tinopal (trademark) CBS-X; diamine stilbene disulfonic acid compounds such as Tinopal DMS pure Xtra and Blankophor (trade Mark) HRH; and pyrazoline compounds such as Blankophor SN.

Preferred fluorescent agents are: sodium 2 (4-styryl-3-sulfophenyl) -2H-naphthol [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' disulfonate, disodium 4,4' -bis { [ (4-anilino-6-morpholinyl-1, 3, 5-triazin-2-yl) ] amino } stilbene-2-2 ' disulfonate, and disodium 4,4' -bis (2-sulfostyryl) biphenyl.

The total amount of the fluorescent agent or agents used in the composition is preferably from 0.0001 to 0.5 wt%, more preferably from 0.005 to 2 wt%, most preferably from 0.05 to 0.25 wt%.

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

Enzyme

The enzyme may be present as all or part of the active ingredient of the laundry cleaning composition.

One or more enzymes are preferably present in the laundry compositions of the present invention and are present when carrying out the methods of the present invention.

If present, each enzyme is present in the laundry compositions of the present invention at a level of from 0.0001 wt% to 0.1 wt%.

The amount of enzyme present in the composition is preferably related to the amount of enzyme as pure protein.

Contemplated enzymes include proteases, alpha-amylases, cellulases, lipases, peroxidases/oxidases, pectate lyases and mannanases or mixtures thereof.

Preferably, the enzyme is selected from: protease, alpha-amylase; cellulases and lipases.

Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include those from: humicola (Humicola) (synonym thermophilic fungi (Thermomyces)), for example from h.lanuginosa (t.lanuginosus) as described in EP 258068 and EP 305216 or from h.insolens as described in WO 96/13580; pseudomonas lipases, for example from pseudomonas alcaligenes (p. alcaligenes) or pseudomonas pseudoalcaligenes (p. pseudoalcaligenes) (EP 218272), pseudomonas cepacia (p.cepacia) (EP 331376), pseudomonas stutzeri (GB 1,372,034), pseudomonas fluorescens (p. fluoroscens), pseudomonas strains SD 705(WO 95/06720 and WO 96/27002), p.wisconsinensis (WO 96/12012); bacillus lipases, for example from Bacillus subtilis (B.subtilis) (Dartois et al (1993), Biochemica et Biophysica Acta,1131,253-360), Bacillus stearothermophilus (B.stearothermophilus) (JP 64/744992) or Bacillus pumilus (B.pumilus) (WO 91/16422).

Further examples are lipase variants, such as those described in WO 92/05249, WO 94/01541, EP 407225, EP 260105, WO 95/35381, WO 96/00292, WO 95/30744, WO 94/25578, WO 95/14783, WO 95/22615, WO 97/04079 and WO97/07202, WO 00/60063.

Preferred commercially available lipases include Lipolase^TMAnd Lipolase Ultra^TM、Lipex^TMAnd Lipoclean^TM(Novozymes A/S)。

The process of the invention may be carried out in the presence of a phospholipase classified under EC 3.1.1.4 and/or EC 3.1.1.32. As used herein, the term phospholipase is an enzyme that is active on phospholipids.

Phospholipids, such as lecithin or phosphatidylcholine, consist of glycerol esterified at the outer (sn-1) and middle (sn-2) positions with two fatty acids and phosphorylated at the third position; phosphoric acid, in turn, can be esterified to an amino alcohol. Phospholipases are enzymes involved in phospholipid hydrolysis. Can distinguish between various types of phospholipase activity, including phospholipase A₁And A₂Which hydrolyses one 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 groups in lysophospholipid. Phospholipase C and phospholipase D (phosphodiesterases) release diacyl glycerol or phosphatidic acid, respectively.

Proteases hydrolyze the peptides and bonds within the protein, which results in increased removal of protein or peptide containing stains in a laundry environment. Examples of suitable protease families include aspartic proteases; a cysteine protease; a protease of glutamate; an asparagine peptide lyase; serine proteases and threonine proteases. Such protease families are described in the MEROPS peptidase database (http:// polymers. sanger. ac. uk /). Serine proteases are preferred. The subtilisin type serine proteases are more preferred. The term "subtilase" refers to a subgroup of serine proteases 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 subset of proteases characterized by a serine at the active site that forms a covalent adduct with a substrate. Subtilases can be divided into 6 sub-classes, namely the Subtilisin (Subtilisin) family, the thermolysin (thermolase) family, the proteinase K family, the lanthionine (Lantibiotic) peptidase family, the Kexin family and the Pyrrolysin family.

Examples of subtilases are those derived from Bacillus such as Bacillus lentus, Bacillus alkalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in US7262042 and WO09/021867, as well as subtilisin (subtilisin lentitus), subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89/06279, and the protease PD138 described in WO 93/18140. Other useful proteases may be those described in WO92/175177, WO01/016285, WO02/026024 and WO 02/016547. Examples of trypsin-like proteases are trypsin (e.g.of porcine or bovine origin) and fusarium protease as described in WO89/06270, WO94/25583 and WO05/040372, and chymotrypsin derived from Cellulomonas (Cellumonas) as described in WO05/052161 and WO 05/052146.

Most preferably, the protease is subtilisin (EC 3.4.21.62).

Examples of subtilases are those derived from Bacillus such as Bacillus lentus, Bacillus alkalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in US7262042 and WO09/021867, as well as subtilisin tarda, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89/06279, and protease PD138 described in WO 93/18140. Preferably, the subtilisin is derived from Bacillus, preferably Bacillus lentus, Bacillus alkalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii, as described in U.S. Pat. No. 6,312,936B1, U.S. Pat. No. 5,679,630, U.S. Pat. No. 4,760,025, U.S. Pat. No. 7,262,042 and WO 09/021867. Most preferably, the subtilisin is derived from Bacillus gibsonii or Bacillus lentus.

Suitable commercially available proteases include those under the trade name

Duralase^TM、Durazym^TM、

Ultra、

Ultra、

Ultra、

Ultra、

And

those sold, all as

Or

(NovozymeS A/S).

Cutinases classified under EC 3.1.1.74 may be used in the present invention. The cutinase to be used according to the invention may be of any origin. Preferably, the cutinase is of microbial origin, in particular of bacterial, fungal or yeast origin.

Suitable amylases (alpha and/or beta) include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, such as particular strains of Bacillus licheniformis described in more detail in GB 1,296,839, or strains of Bacillus disclosed in WO 95/026397 or WO 00/060060. A commercially available amylase is Duramyl^TM、Termamyl^TM、Termamyl Ultra^TM、Natalase^TM、Stainzyme^TM、Fungamyl^TMAnd BAN^TM(Novozymes A/S)、Rapidase^TMAnd Purastar^TM(from Genencor International Inc.).

Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from: fungal cellulases produced by bacillus, pseudomonas, humicola, fusarium, thielavia, acremonium, e.g. 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^TM、Carezyme^TM、Celluclean^TM、Endolase^TM、Renozyme^TM(Novozymes A/S)、Clazinase^TMAnd Puradax HA^TM(Genencor International Inc.) and KAC-500(B)^TM(Kao Corporation)。Celluclean^TMIs preferred.

Suitable peroxidases/oxidases include those of plant, bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include those from Coprinus, e.g.from Coprinus cinereusOxidases, and variants thereof, such as those described in WO 93/24618, WO 95/10602, and WO 98/15257. Commercially available peroxidases include Guardzyme^TMAnd Novozym^TM51004(Novozymes A/S)

Further suitable enzymes are discussed in WO2009/087524, WO2009/090576, WO2009/107091, WO2009/111258 and WO 2009/148983.

The aqueous solution used in the process preferably has an enzyme present. The enzyme is preferably present in the aqueous solution used in the process at a concentration in the range of from 0.01 to 10ppm, preferably from 0.05 to 1 ppm.

Enzyme stabilizer

Any enzyme present in the composition may be stabilized using conventional stabilizers, for example polyols such as propylene glycol or glycerol; a sugar or sugar alcohol; lactic acid; boric acid or boric acid derivatives, for example aromatic borates, or phenyl boronic acid derivatives, for example 4-formylphenyl boronic acid, and compositions which may be formulated as described, for example, in WO 92/19709 and WO 92/19708.

Builders or complexing agents

Builder materials may be present. If present, they are typically selected from the group consisting of 1) calcium chelator material, 2) precipitation material, 3) calcium ion exchange material, and 4) mixtures thereof.

Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate, and organic sequestrants, such as ethylenediaminetetraacetic acid.

Examples of precipitating builder materials include sodium orthophosphate and sodium carbonate.

Examples of calcium ion exchange builder materials include various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, for example zeolite ｃA, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and the zeolite P type described in EP- ｃA-0,384,070.

The composition may also contain 0 to 65% of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, alkyl or alkenyl succinic acid, nitrilotriacetic acid, or other builders as described below.

Preferably, the laundry cleaning formulation is a non-phosphate building laundry detergent formulation, i.e. comprising less than 1 wt% phosphate.

Most preferably, the laundry cleaning formulation is an aqueous liquid laundry detergent.

In aqueous liquid laundry detergents it is preferred that monopropylene glycol is present at a level of from 1 to 30 wt%, most preferably from 2 to 18 wt%.

Polymer and method of making same

The composition may preferably comprise one or more polymers. Example polymers are carboxymethyl cellulose, poly (ethylene glycol), poly (vinyl alcohol), polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.

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

Toning dye (shading dye)

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

Hueing dyes for laundry compositions preferably have a maximum absorption in the visible range (400-700nm) of greater than 5000L mol^-1cm^-1Preferably greater than 10000L mol^-1cm^-1The extinction coefficient of (a). The color of the dye is blue or violet.

Preferably, the composition comprises a hueing dye. Preferably, the hueing dye is present at 0.0001 to 0.1 wt% of the composition.

Preferred shading dye chromophores are azo, azine, anthraquinone and triphenylmethane.

Azo, anthraquinone, phthalocyanine and triphenylmethane dyes preferably carry a net anionic charge or no charge. Azines preferably carry a net anionic or cationic charge. During the washing or rinsing step of the washing process, a blue or violet shading dye is deposited onto the fabric, providing a visible shade to the fabric. In this regard, the dye imparts a blue or violet color to the white cloth with a hue angle of 240 to 345, more preferably 250 to 320, most preferably 250 to 280. The white cloth used in this test was a bleached, non-mercerized woven cotton sheet.

Hueing dyes are discussed in WO2005/003274, WO2006/032327(Unilever), WO2006/032397(Unilever), WO2006/045275(Unilever), WO2006/027086(Unilever), WO2008/017570(Unilever), WO2008/141880(Unilever), WO2009/132870(Unilever), WO2009/141173(Unilever), WO2010/099997(Unilever), WO2010/102861(Unilever), WO2010/148624(Unilever), WO2008/087497(P & G), WO2011/011799(P & G), WO2012/054820(P & G), WO2013/142495(P & G) and WO2013/151970(P & G).

The monoazo dyes preferably contain a heterocyclic ring, and are most preferably thiophene dyes. The monoazo 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:

the disazo dye is preferably a sulfonated disazo dye. Preferred examples of sulfonated bisazo 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, direct violet 99 and alkoxylated forms thereof. Alkoxylated disazo dyes are discussed in WO2012/054058 and WO 2010/151906.

Examples of alkoxylated disazo dyes are:

thiophene dyes are available from Milliken under the trade names Liquitin Violet DD and Liquitin Violet ION.

The azine dye is preferably selected from sulphonated phenazine dyes and cationic phenazine dyes. Preferred examples are acid blue 98, acid violet 50, dyes having CAS number 72749-80-5, acid blue 59, and phenazine dyes selected from the group consisting of:

wherein:

X₃selected from: -H, -F, -CH₃，-C₂H₅，-OCH₃and-OC₂H₅；

X₄Selected from: -H, -CH₃，-C₂H₅，-OCH₃and-OC₂H₅；

Y₂Selected from: -OH, -OCH₂CH₂OH，-CH(OH)CH₂OH，-OC(O)CH₃And C (O) OCH₃。

The hueing dye is present in the composition in the range of 0.0001 to 0.5 wt%, preferably 0.001 to 0.1 wt%. Depending on the nature of the hueing dye, there is a preferred range depending on the potency of the hueing dye, which depends on the class and the specific potency within any particular class. As mentioned above, the hueing dye is a blue or violet hueing dye.

Mixtures of hueing dyes may be used.

Most preferably, the hueing dye is a reactive blue anthraquinone dye covalently linked to an alkoxylated polyethyleneimine. The alkoxylation is preferably selected from ethoxylation and propoxylation, most preferably propoxylation. Preferably, 80 to 95 mole% of the N-H groups in the polyethyleneimine are replaced by isopropanol groups by propoxylation. Preferably, the molecular weight of the polyethyleneimine is 600 to 1800 prior to reaction with the dye and propoxylation.

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

others (Misc)

When the alkyl group is long enough to form a branched or cyclic chain, the alkyl group includes branched, cyclic, and linear alkyl chains. The alkyl group is preferably linear or branched, more preferably linear.

As used herein, the indefinite article "a" or "an" and its corresponding definite article "the" mean at least one, or one or more, unless otherwise specified.

Test of

The following examples are intended to illustrate the invention in detail, without however limiting it thereto.

Synthesis of

Trimellitic acid used was purchased from ACROS Organics. Trimellitic anhydride and pyromellitic acid used were purchased from Alfa Aesar. Phenoxyethanol, p-toluenesulfonic acid and titanium isopropoxide were used as obtained from Merck. Methanesulfonic acid, 4-dodecylbenzenesulfonic acid isomer mixture, and benzyl alcohol were used from Sigma Aldrich.

The lauryl/myristyl alcohol and cetearyl alcohol used are technical-grade masses, their molecular weights being determined before use as follows: the hydroxyl number (OH-number) was measured and the molecular weight was subsequently calculated ("Gebrauchsmol" per hydroxyl function). In this case, the OH value can be measured in accordance with DIN 53240.

The acid number (acid value) can be measured according to DIN EN ISO 2114.

Polyglykols M is a monohydroxy functional polyethylene glycol monomethyl ether (M-PEG, CAS-Nr.9004-74-4).

Polyglykol M500 is a linear monohydroxy functional polyethylene glycol monomethyl ether (M-PEG) having a molecular weight of 470-530 g/mol.

Polyglykol M750 is a linear monohydroxy-functional polyethylene glycol monomethyl ether (M-PEG) having a molecular weight of 720-780 g/mol.

Polyglykol M1000 is a linear monohydroxy-functional polyethylene glycol monomethyl ether (M-PEG) having a molecular weight of 970-1060 g/mol.

Polyglykol M1250 is a linear monohydroxy-functional polyethylene glycol monomethyl ether (M-PEG) having a molecular weight of 1125-1375 g/mol.

Polyglykol M2000 is a linear monohydroxy-functional polyethylene glycol monomethyl ether (M-PEG) having a molecular weight of 1800-2200 g/mol.

The degree of alkoxylation of the methylpolyethylene glycols used can be checked using NMR spectroscopy, for example using methods analogous to those described in R.Stevanova, D.Rankoff, S.Panayotova, S.L.Spassov, J.Am.oil chem.Soc.,65,1516-¹H-NMR spectrum. For this purpose, the samples were derivatized by reacting them with trichloroacetyl isocyanate and measured as a solution in tritiated chloroform containing 1 weight percent (1 weight percent) tetramethylsilane as an internal standard.

The esterification reaction is controlled by determining the residual amount of alcohol (e.g., benzyl alcohol, phenoxyethanol, lauryl myristyl alcohol, and cetearyl alcohol) by GC-FID calibration is performed with pure starting material Gas Chromatography (GC) is performed using a Hewlett Packard GC 6890 with an autosampler coupled to a Flame Ionization Detector (FID).

For the quantification of benzyl alcohol, the samples were separated on a 50m × 0.2mm, 0.33 μm membrane column. The column temperature was initially maintained at 50 ℃, then the temperature was increased to 175 ℃ at a rate of 5 ℃/min and from 175 ℃ to 300 ℃ at a rate of 25 ℃/min. The syringe temperature was maintained at 250 ℃ and the injection volume was 1.0 μ L in split mode. Helium was used as a carrier gas with a constant pressure of 1.8 bar. Samples were prepared by diluting 500mg samples (analyzed in duplicate) with 5ml of methanol.

For the quantification of phenoxyethanol, cetearyl alcohol and dodecanol, samples were separated on 25m × 0.32mm, 0.52 μm membrane columns. The column temperature was initially maintained at 50 ℃ and then the temperature was raised to 250 ℃ at a rate of 10 ℃/min and maintained for 6.5 minutes. The syringe temperature was maintained at 250 ℃ and the injection volume was 1.0 μ L in split mode. Helium was used as a carrier gas with a constant pressure of 0.9 bar. Samples were prepared by diluting 500mg samples (analyzed in duplicate) with 5ml of methanol.

Thin Layer Chromatography (TLC) was performed using TLC Silica Gel 60F 254 plates from Merck. The aromatics were detected by UV light (both 254 and 366 nm).

All examples were performed according to standard procedures, unless otherwise indicated. All reagents and amounts are listed in table I.

The selected alcohol alkoxylate was heated to 80 ℃ with stirring under nitrogen. The selected polycarboxylic acid or anhydride is then added in portions over 5 minutes. The reaction mixture was then stirred at 80 ℃ for 2.5 hours. The product (hereinafter referred to as precursor) was isolated and the acid number was determined, these are listed in Table I, column AN 1.

Some amount of precursor (listed in the "PC" column of table I) was mixed with the selected alcohol and catalyst and heated to the temperature listed in table I while stirring under nitrogen. The reaction mixture was stirred at the temperatures indicated for the times indicated in table I and the water was distilled off. For all examples except examples 1,2, 10 and 11, the product was then isolated after cooling and the acid number of the final product was determined and listed as AN 2in Table I.

In the case of examples 10 and 11, after completion of the stirring for the time indicated in Table I, a vacuum of 500 mbar was applied for 3 hours at 180 ℃ with stirring.

Abbreviations used in table I are as follows:

AA alcohol alkoxylates

PCA polycarboxylic acids

PC precursor

BA benzyl alcohol

PE Phenoxyethanol

C16/18 Centaleic acid stearyl alcohol

Acid value of AN1 precursor

Acid number of AN2 Final product

M750 Polyglykol M 750

M1250 Polyglykol M 1250

TMAA trimellitic anhydride

pTsOH p-toluenesulfonic acid

Table I: EXAMPLES dispersant compositions

As a comparative example, sample C1 of table I was isolated after the first synthesis step without reaction with alcohol.

An aqueous liquid laundry detergent was prepared having the following formulation:

table II: liquid laundry detergent formulations

Application example 1 anti-redeposition benefit

The formulation was used to wash eight pieces of 5 x 5cm knitted cotton pieces in a tergitometer set at 200 rpm. A one hour wash was carried out at 20 ℃ in 800ml of water with French hardness 26 ℃ using 2.3g/L of the formulation shown in Table II. To simulate redepositable particulate soils, 0.04g/L of 100% compressed carbon black (from Alfa Aesar) was added to the wash liquor. To simulate oily sebum soils, 7.2g of SBL2004 soil strip (from Warwick Equest) was added to the wash liquor.

Once the wash had been completed, the cotton samples were rinsed once in 400ml of clear water, removed, dried, and the color measured on a reflectometer and expressed as CIE L a b values. Anti-redeposition benefits are expressed as Δ L values:

Δ L ═ L (control)

The greater the Δ L value, the greater the degree of inhibition of soot scale deposition. The 95% confidence limits based on 8 independent cotton samples were calculated. Formulations were prepared with and without the addition of 8.7 wt% of the dispersant of table I. The results are given in table III.

Table III: anti-redeposition benefits

Exemplary dispersants	ΔL	95％
			Example 1	4.4	0.3
Example 2	2.5	0.3
			Example 3	2.5	0.3
Example 4	3.1	0.2
			Example C1 (reference)	0.5	0.3

The dispersants of the present invention enhance antiredeposition.

Claims

1. A laundry cleaning composition comprising:

(i)0.2 to 20 weight percent of an alkoxylated dispersant having the structure:

wherein:

x is ethoxy, wherein n is 6 to 70;

m is 2;

t is CH₃；

(iii) an active ingredient selected from one or more of the following: 0.001 to 3% by weight of a perfume; 0.0001 to 0.5 wt% of a fluorescent agent; and 0.0001 wt% to 0.1 wt% of an enzyme.

2. A laundry cleaning composition according to claim 1 comprising from 0.5 to 12 wt% of the alkoxylated dispersant.

3. A laundry cleaning composition according to claim 1 comprising from 1 to 10 wt% of the alkoxylated dispersant.

4. A laundry cleaning composition according to claim 1, wherein R₁Is an alkylaryl group.

5. A laundry cleaning composition according to any of claims 1-4, wherein n is from 6 to 40.

6. A laundry cleaning composition according to claim 5, wherein n is from 9 to 30.

7. A laundry cleaning composition according to claim 5, wherein n is from 10 to 20.

8. A laundry cleaning composition according to any of claims 1-4, wherein R₁Selected from phenylethyl and benzyl.

9. A laundry cleaning composition according to claim 8, wherein R₁Is benzyl.

10. The laundry cleaning composition according to any one of claims 1-4, wherein the alkoxylated dispersant is selected from the group consisting of:

11. the laundry cleaning composition according to any of claims 1-4, wherein the surfactant is present at a level of from 4 to 40 wt% and the surfactant comprises an anionic and/or nonionic surfactant, wherein the alkoxylated dispersant is not considered a surfactant as defined herein.

12. A laundry cleaning composition according to claim 11, wherein the surfactant is present at a level of from 4 to 35 wt%.

13. A laundry cleaning composition according to claim 11, wherein the surfactant is present at a level of from 6 to 30 wt%.

14. A laundry cleaning composition according to claim 11, wherein the weight fraction of nonionic surfactant to anionic surfactant is from 0 to 0.3.

15. A laundry cleaning composition according to claim 11, wherein the anionic surfactant is selected from: linear alkyl benzene sulfonate; an alkyl sulfate; alkyl ether sulfates; and mixtures thereof.

16. A laundry cleaning composition according to claim 11, comprising a nonionic surfactant, wherein the nonionic surfactant is an alcohol ethoxylate.

17. A laundry cleaning composition according to claim 16, wherein the nonionic surfactant is a C10-C18 alcohol ethoxylate having an average of 3-10 moles of ethylene oxide.

18. A laundry cleaning composition according to claim 16, wherein the nonionic surfactant is a C12-C15 alcohol ethoxylate having an average of 5-9 moles of ethylene oxide.

19. The laundry cleaning composition according to any one of claims 1-4, wherein the composition is an aqueous liquid detergent composition having a pH of from 6 to 8.5.

20. A laundry cleaning composition according to claim 19, wherein the composition is an aqueous liquid detergent composition having a pH of from 6.5 to 7.5.

21. A laundry cleaning composition according to claim 19, wherein the composition is an aqueous liquid detergent composition having a pH of from 6.8 to 7.2.

22. A laundry cleaning composition according to claim 19, wherein the composition is an aqueous liquid detergent composition having a pH of 7.0.

23. A laundry cleaning composition according to any of claims 1-4, wherein the active ingredient is an enzyme and comprises one or more of: protease, alpha-amylase, cellulase, lipase, peroxidase/oxidase, pectate lyase, and mannanase, or a mixture thereof.

24. A laundry cleaning composition according to claim 23, wherein the enzyme is a protease.

25. A laundry cleaning composition according to claim 23, wherein the enzyme is a subtilisin-type serine protease.

26. A domestic method of treating a fabric, the method comprising the steps of:

(i) treating the fabric with an aqueous solution of an alkoxylated dispersant as defined in any one of claims 1 to 10;

the aqueous solution comprises from 10ppm to 5000ppm of the alkoxylated dispersant; and 0 to 6g/L of a surfactant other than the alkoxylated dispersant; and

(ii) optionally rinsing and drying the fabric;

wherein the perfume, if present, is present in the aqueous solution in an amount of from 0.1 to 100 ppm;

wherein the fluorescer, if present, is present in the aqueous solution in an amount of from 0.0001g/L to 0.1 g/L; and wherein the enzyme, if present, is present in the aqueous solution in an amount of 0.01 to 10 ppm.

27. The method of claim 26, wherein the aqueous solution comprises from 100ppm to 1000ppm of the alkoxylated dispersant.

28. The method of claim 26 wherein the aqueous solution comprises 0.5 to 6g/L of a surfactant other than the alkoxylated dispersant.

29. The method of claim 26 wherein the aqueous solution comprises 1 to 5g/L of a surfactant other than the alkoxylated dispersant.

30. The method of claim 26, wherein the fluorescer, if present, is present in the aqueous solution in an amount of 0.001 to 0.02 g/L.

31. The method of claim 26, wherein the enzyme, if present, is present in the aqueous solution in an amount of 0.05 to 1 ppm.