EP3417039B1

EP3417039B1 - Whitening composition

Info

Publication number: EP3417039B1
Application number: EP16798543.1A
Authority: EP
Inventors: Stephen Norman Batchelor; Jayne Michelle Bird; Carsten Cohrs; Jan DIEDERICHS; Dirk Leinweber; Kevin James MUTCH; Steffen ROMANSKI
Original assignee: Unilever PLC
Current assignee: Unilever PLC
Priority date: 2016-02-17
Filing date: 2016-11-22
Publication date: 2019-07-10
Anticipated expiration: 2036-11-22
Also published as: CN108603139A; BR112018016129B1; BR112018016129A2; EP3417039A1; AR107625A1; CN108603139B; WO2017140391A1; ZA201804914B

Description

Field of Invention

The present invention concerns the use of whitening and brightening laundry compositions.

Background of the Invention

There is a desire to use less water in the domestic laundering of clothes. This may be achieved by reducing the number of water rinses done after the initial washing. Reducing the number of rinses increases the redeposition of soil removed in the wash, thereby reducing the overall cleaning. The problem is exacerbated by the presence of human sebum on garments and in the wash liquor, which serves to enhance the deposition of soil in the wash. WO2012/054820 A1 discloses a solid laundry detergent composition comprising detersive surfactant, bluing agent, C.I. fluorescent brightener 206 and anti-redeposition agent.
There is a need for improved dispersants to prevent deposition of soil in the wash liquor to the fabric. Such ingredients are preferably biodegradable and increase stain removal.

Summary of the Invention

There is a need for technologies to reduce redeposition and enhance cleaning in domestic laundry products.
We have found that selected alkoxylated dispersants (AD) when incorporated into laundry detergents enhance whiteness and brightness of garments during domestic laundry.
In one aspect the present invention provides a laundry detergent composition comprising:

(i) from 0.5 to 20 wt%, preferably 1 to 10 wt%, most preferably 2 to 6 wt% of an alkoxylated dispersant of the following structure:
wherein
- X is selected from: ethoxy; and mixtures of ethoxy and propoxy groups where the number of ethoxy groups is greater than the number of propoxy groups, and wherein n is from 6 to 70; preferably n is selected from 9, 10, 11, 12, 13, 14; 15; 16; 17; 18; 19; 20; 21; 22; 23; 24; 25; 26; 27; 28; 29, and, 30; most preferably n is from 10 to 20; preferably X is ethoxy;
- Y is selected from: NH; NCH₃ and, O, preferably O;
- R₁ is selected from: saturated C10 to C26 linear or branched alkyl chains; mono-unsaturated C10 to C26 linear or branched alkyl chains; aryl groups; and, alkyl-aryl groups wherein the alkyl group of the alkyl-aryl is a saturated linear or branched C1 to C10; Preferably R₁ is selected from: saturated C12 to C18 linear or branched alkyl chains; and mono-unsaturated C12 to C18 linear or branched alkyl chains; and, benzyl; most preferably R₁ is selected from: stearyl; cetyl; oleyl; lauryl; and, isotridecyl;
- T is selected from: H; CH₃; SO₃ ^-; CH₂COO^-; PO₃ ^2-; C₂H₅; n-propyl, i-propyl; n-butyl; t-butyl; and, sulfosuccinate; preferably T is H.
(ii) from 0 to 50 wt% surfactant, other than the alkoxylated dispersant; preferably the surfactant is selected from: anionic and non-ionic surfactants, preferably the level of surfactant is from 4 to 40 wt%, more preferably 6 to 30 wt%, most preferably 8 to 20 wt%; preferably the weight fraction of non-ionic surfactant/anionic surfactant is from 0 to 0.3, preferably 0 to 0.15, most preferably 0.05 to 0.12;
(iii) from 0.001 to 3 wt % perfume.

Interger (iii), the perfume, may be replaced or the composition additionally comprises from 0.0001 to 0.5 wt % of a fluorescent agent and/or from 0.0001 wt% to 0.1 wt% enzyme; the enzyme is preferably a protease, most preferably a subtilase type serine protease.
The laundry detergent composition is preferably an aqueous laundry liquid detergent composition.
In another aspect the present invention provides a domestic method of treating a textile, the method comprising the steps of:

(i) treating a textile with an aqueous solution of the alkoxylated dispersant the aqueous solution comprising from 10 ppm to 5000 ppm, preferably from 100 ppm to 1000 ppm, of the alkoxylated dispersant as defined herein; and, 0 to 6 g/L of a surfactant, preferably 0.2 to 1 g/L, other than the alkoxylated dispersant; and,
(ii) optionally rinsing and drying the textile.

In the method the surfactant is of the type as preferred herein.
In the method the level of the perfume in the aqueous solution is preferably from 0.1 to 100 ppm, more preferably from 1 to 10 ppm.
In the method the level of the protease in the aqueous solution is preferably from 0.01 to 1ppm, more preferably from 0.02 to 0.2 ppm.
In the method aspects of the present invention the surfactant used is preferably as preferred for the composition aspects of the present invention.
Domestic methods are preferably conducted in a domestic washing machine or by hand washing. The temperature of the wash is preferably from 285 to 335K.
The textile is preferably an item of used clothing, bedding or table cloth. Preferred items of clothing are worn cotton containing shirts, trousers, underwear and jumpers.

Detailed Description of the Invention

Alkoxylated Dispersant

In the context of the current invention the alkoxylated dispersant is not considered a surfactant and does not contribute numerically to the surfactant as defined herein.
The most preferred aryl groups are phenyl and substituted phenyl.
The COYR₁ group may be ortho, meta, or para to the -O-[X]_n-T group; preferably the COYR₁ group is ortho or para to the -O-[X]_n-T group; most preferably the the COYR₁ group is para to the -O-[X]_n-T group.
C1 to C3 linear or branched alkyl aryl groups are C1 to C3 linear or branched alkyl groups substituted by an aromatic group, for example: styryl, cumyl, benzyl. A styryl group is - CH(CH₃)Ph; a cumyl group is -C(CH₃)₂Ph; a benzyl group is CH₂Ph, where Ph is phenyl.
A stearyl group is CH₃(CH₂)₁₇-; a lauryl group is CH₃(CH₂)₁₁-; an oleyl group is CH₃(CH₂)₇CH=CH(CH₂)₈-, where the double bond is preferably cis; an isotridecyl group.
The isotridecyl group is a multibranched isotridecyl group produced by the hydroformulation of trimerised n-butene prior to provide an isotridecyl alcohol which is then esterified. The isotridecyl group consists of a variety of differently branched C13 isomers likely of the form:
Preferably the composition is an aqueous liquid having a pH from 6 to 8.5, more preferably from 6.5 to 7.5.
The value n is the mole average number of alkoxyl groups. The value of n may be measured using NMR.
Sulfoccinate has the structure:
Preferred examples of structures of the AD of the invention are:
The most preferred AD structures are:

Surfactant

The laundry composition may comprises anionic and non-ionic surfactant (which includes a mixture of the same).
The nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981 or in Anionic Surfactants: Organic Chemistry edited by Helmut W. Stache (Marcel Dekker 1996) .
Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher alkyl radicals.
Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher C₈ to C₁₈ alcohols, produced for example from tallow or coconut oil, Alkyl ether carboxylic acids; sodium and potassium alkyl C₉ to C₂₀ benzene sulphonates, particularly sodium linear secondary alkyl C₁₀ to C₁₅ benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.
The anionic surfactant is preferably selected from: linear alkyl benzene sulphonate; alkyl sulphates; alkyl ether sulphates; soaps; alkyl (preferably methyl) ester sulphonates, and mixtures thereof.
The most preferred anionic surfactants are selected from: linear alkyl benzene sulphonate; alkyl sulphates; alkyl ether sulphates and mixtures thereof. Preferably the alkyl ether sulphate is a C₁₂-C₁₄ n-alkyl ether sulphate with an average of 1 to 3EO (ethoxylate) units. Sodium lauryl ether sulphate is particularly preferred (SLES). Preferably the linear alkyl benzene sulphonate is a sodium C₁₁ to C₁₅ alkyl benzene sulphonates. Preferably the alkyl sulphates is a linear or branched sodium C₁₂ to C₁₈ alkyl sulphates. Sodium dodecyl sulphate is particularly preferred, (SDS, also known as primary alkyl sulphate).
The level of anionic surfactant in the laundry composition is preferably from 4 to 40 wt%, more preferably 6 to 30 wt%, and most preferably 8 to 20 wt%.
Preferably two or more anionic surfactant are present, for example linear alkyl benzene sulphonate together with an alkyl ether sulphate.
Preferably the laundry composition in addition to the anionic surfactant comprises alkyl exthoylated non-ionic surfactant.
Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having an aliphatic hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids or amides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are the condensation products of aliphatic C₈ to C₁₈ primary or secondary linear or branched alcohols with ethylene oxide.
Preferably the alkyl ethoxylated non-ionic surfactant is a C₈ to C₁₈ primary alcohol with an average ethoxylation of 7EO to 9EO units.
Preferably the surfactants used are saturated.
Also applicable are surfactants such as those described in EP-A-328 177 (Unilever), which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074 , and alkyl monoglycosides.
In another aspect the charged surfactant may be a cationic such that the formulation is a fabric conditioner. The detergent compositions based on anionic or anionic/non-ionic surfactants is however the more preferred embodiment.

Cationic Compound

When the present invention is used as a fabric conditioner it needs to contain a cationic compound.
Most preferred are quaternary ammonium compounds.
It is advantageous if the quaternary ammonium compound is a quaternary ammonium compound having at least one C₁₂ to C₂₂ alkyl chain.
It is preferred if the quaternary ammonium compound has the following formula:
in which R₁ is a C₁₂ to C₂₂ alkyl or alkenyl chain; R², R³ and R⁴ are independently selected from C₁ to C₄ alkyl chains and X^- is a compatible anion. A preferred compound of this type is the quaternary ammonium compound cetyl trimethyl quaternary ammonium bromide.
A second class of materials for use with the present invention are the quaternary ammonium of the above structure in which R¹ and R² are independently selected from C₁₂ to C₂₂ alkyl or alkenyl chain; R³ and R⁴ are independently selected from C₁ to C₄ alkyl chains and X^- is a compatible anion.
The composition optionally comprises a silicone.

Builders or Complexing Agents

Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate and organic sequestrants, such as ethylene diamine tetra-acetic acid.
Examples of precipitating builder materials include sodium orthophosphate and sodium carbonate.
Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are well known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070 .
The composition may also contain 0-65 % of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below. Many builders are also bleach-stabilising agents by virtue of their ability to complex metal ions.
For powder detergents, zeolite and carbonate (carbonate (including bicarbonate and sesquicarbonate)) are preferred builders with carbonates being particularly preferred.
The composition may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is typically present at a level of less than 15%w. Aluminosilicates are materials having the general formula:

0.8-1.5 M₂O. Al₂O₃. 0.8-6 SiO₂

where M is a monovalent cation, preferably sodium. These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g. The preferred sodium aluminosilicates contain 1.5-3.5 SiO₂ units in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature. The ratio of surfactants to alumuminosilicate (where present) is preferably greater than 5:2, more preferably greater than 3:1.
Alternatively, or additionally to the aluminosilicate builders, phosphate builders may be used. In this art the term 'phosphate' embraces diphosphate, triphosphate, and phosphonate species. Other forms of builder include silicates, such as soluble silicates, metasilicates, layered silicates (e.g. SKS-6 from Hoechst).
Preferably the laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e., contains less than 1 wt% of phosphate. Preferably powder laundry detergent formulations are predominantly carbonate built. Powders, should preferably give an in use pH of 9.5-11. In powder formulation the alkoxylated dispersant is preferably granulated separately to the alkaline salts, and most preferably with an acidic component, to reduce hydrolysis on storage.
The laundry detergent formulation is most preferably an aqueous liquid, preferably an aqueous liquid having a pH from 6 to 8.5, most preferably an aqueous liquid have a pH from 6.5 to 7.5.
In the aqueous liquid laundry detergent it is preferred that mono propylene glycol is present at a level from 1 to 30 wt%, most preferably 2 to 18 wt%, to provide the formulation with appropriate, pourable viscosity.

Fluorescent Agent

The composition preferably comprises a fluorescent agent (optical brightener). Fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN.
Preferred fluorescers are: sodium 2 (4-styryl-3-sulphophenyl)-2H-napthol[1,2-d]triazole, disodium 4,4'-bis{[(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1,3,5-triazin-2-yl)]amino}stilbene-2-2' disulophonate, disodium 4,4'-bis{[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino} stilbene-2-2' disulphonate, and disodium 4,4'-bis(2-sulphostyryl)biphenyl.
The total amount of the fluorescent agent or agents used in the composition is preferably from 0.0001 to 0.5 wt %, more preferably 0.005 to 2 wt %, most preferably 0.05 to 0.25 wt %.
The aqueous solution used in the method has a fluorescer present. The fluorescer is present in the aqueous solution used in the method preferably in the range from 0.0001 g/l to 0.1 g/l, more preferably 0.001 to 0.02 g/l.

Perfume

The composition comprises a perfume. The perfume is preferably in the range from 0.001 to 3 wt %, more preferably 0.05 to 0.5 wt%, most preferably 0.1 to 1 wt %. Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.
Preferably the perfume comprises at least one note (compound) from: alpha-isomethyl ionone, benzyl salicylate; citronellol; coumarin; hexyl cinnamal; linalool; Pentanoic acid, 2-methyl-, ethyl ester; octanal; benzyl acetate; 1,6-octadien-3-ol, 3,7-dimethyl-, 3-acetate; cyclohexanol, 2-(1,1-dimethylethyl)-, 1-acetate; delta-damascone; beta-ionone; verdyl acetate; dodecanal; hexyl cinnamic aldehyde; cyclopentadecanolide; benzeneacetic acid, 2-phenylethyl ester;amyl salicylate; beta-caryophyllene; ethyl undecylenate; geranyl anthranilate; alpha-irone; beta-phenyl ethyl benzoate; alpa-santalol; cedrol; cedryl acetate; cedry formate; cyclohexyl salicyate; gamma-dodecalactone; and, beta phenylethyl phenyl acetate.
Useful components of the perfume include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA).
It is commonplace for a plurality of perfume components to be present in a formulation. In the compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components.
In perfume mixtures preferably 15 to 25 wt% are top notes. Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]). Preferred top-notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.
The International Fragrance Association has published a list of fragrance ingredients (perfums) in 2011. (http://www.ifraorg.org/en-us/ingredients#.U7Z4hPldWzk)
The Research Institute for Fragrance Materials provides a database of perfumes (fragrances) with safety information.
Perfume top note may be used to cue the benefit of the invention.
Some or all of the perfume may be encapsulated, typical perfume components which it is advantageous to encapsulate, include those with a relatively low boiling point, preferably those with a boiling point of less than 300, preferably 100-250 Celsius. It is also advantageous to encapsulate perfume components which have a low CLog P (i.e., those which will have a greater tendency to be partitioned into water), preferably with a CLog P of less than 3.0. These materials, of relatively low boiling point and relatively low CLog P have been called the "delayed blooming" perfume ingredients and include one or more of the following materials:
allyl caproate, amyl acetate, amyl propionate, anisic aldehyde, anisole, benzaldehyde, benzyl acetate, benzyl acetone, benzyl alcohol, benzyl formate, benzyl iso valerate, benzyl propionate, beta gamma hexenol, camphor gum, laevo-carvone, d-carvone, cinnamic alcohol, cinamyl formate, cis-jasmone, cis-3-hexenyl acetate, cuminic alcohol, cyclal c, dimethyl benzyl carbinol, dimethyl benzyl carbinol acetate, ethyl acetate, ethyl aceto acetate, ethyl amyl ketone, ethyl benzoate, ethyl butyrate, ethyl hexyl ketone, ethyl phenyl acetate, eucalyptol, eugenol, fenchyl acetate, flor acetate (tricyclo decenyl acetate), frutene (tricyclco decenyl propionate), geraniol, hexenol, hexenyl acetate, hexyl acetate, hexyl formate, hydratropic alcohol, hydroxycitronellal, indone, isoamyl alcohol, iso menthone, isopulegyl acetate, isoquinolone, ligustral, linalool, linalool oxide, linalyl formate, menthone, menthyl acetphenone, methyl amyl ketone, methyl anthranilate, methyl benzoate, methyl benyl acetate, methyl eugenol, methyl heptenone, methyl heptine carbonate, methyl heptyl ketone, methyl hexyl ketone, methyl phenyl carbinyl acetate, methyl salicylate, methyl-n-methyl anthranilate, nerol, octalactone, octyl alcohol, p-cresol, p-cresol methyl ether, p-methoxy acetophenone, p-methyl acetophenone, phenoxy ethanol, phenyl acetaldehyde, phenyl ethyl acetate, phenyl ethyl alcohol, phenyl ethyl dimethyl carbinol, prenyl acetate, propyl bornate, pulegone, rose oxide, safrole, 4-terpinenol, alpha-terpinenol, and /or viridine. It is commonplace for a plurality of perfume components to be present in a formulation. In the compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components from the list given of delayed blooming perfumes given above present in the perfume.
Another group of perfumes with which the present invention can be applied are the so-called aromatherapy' materials. These include many components also used in perfumery, including components of essential oils such as Clary Sage, Eucalyptus, Geranium, Lavender, Mace Extract, Neroli, Nutmeg, Spearmint, Sweet Violet Leaf and Valerian. It is preferred that the laundry treatment composition does not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid.

Polymers

The composition may comprise one or more further polymers. Examples are carboxymethylcellulose, poly (ethylene glycol), 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).

Shading Dye

Dyes are described in Color Chemistry Synthesis, Properties and Applications of Organic Dyes and Pigments, (H Zollinger, Wiley VCH, Zurich, 2003) and, Industrial Dyes Chemistry, Properties Applications. (K Hunger (ed), Wiley-VCH Weinheim 2003).
Shading Dyes for use in laundry detergents preferably have an extinction coefficient at the maximum absorption in the visible range (400 to 700nm) of greater than 5000 L mol^-1 cm^-1, preferably greater than 10000 L mol^-1 cm^-1. The dyes are blue or violet in colour.
Preferably the shading dye is present at from 0.0001 to 0.1wt% of the composition.
Preferred shading dye chromophores are azo, azine, anthraquinone, and triphenylmethane.
Azo, anthraquinone, phthalocyanine and triphenylmethane dyes preferably carry a net anionic charged or are uncharged. Azine preferably carry a net anionic or cationic charge. Blue or violet shading dyes deposit to fabric during the wash or rinse step of the washing process providing a visible hue to the fabric. In this regard the dye gives a blue or violet colour to a 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 is bleached non-mercerised woven cotton sheeting.
Shading 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).
Mono-azo dyes preferably contain a heterocyclic ring and are most preferably thiophene dyes. The 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:

and,
Bis-azo dyes are preferably sulphonated bis-azo dyes. Preferred examples of sulphonated 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, direct violet 99 and alkoxylated versions thereof. Alkoxylated bis-azo dyes are discussed in WO2012/054058 and WO2010/151906 .
An example of an alkoxylated bis-azo dye is:
Azine dye are preferably selected from sulphonated phenazine dyes and cationic phenazine dyes. Preferred examples are acid blue 98, acid violet 50, dye with CAS-No 72749-80-5, acid blue 59, and the phenazine dye selected from:
wherein:

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

The shading dye is present is present in the composition in range from 0.0001 to 0.5 wt %, preferably 0.001 to 0.1 wt%. Depending upon the nature of the shading dye there are preferred ranges depending upon the efficacy of the shading dye which is dependent on class and particular efficacy within any particular class. As stated above the shading dye is a blue or violet shading dye.
A mixture of shading dyes may be used.
The shading dye is most preferably a reactive blue anthraquinone dye covalently linked to an alkoxylated polyethyleneimine. The alkoxylation is preferably selected from ethoxylation and propoxylation, most preferably propoxylation. Preferably 80 to 95 mol% of the N-H groups in the polyethylene imine are replaced with iso-propyl alcohol groups by propoxylation. Preferably the polyethylene imine before reaction with the dye and the propoxylation has a molecular weight of 600 to 1800.
An example structure of a preferred reactive anthraquinone covalently attached to a propoxylated polyethylene imine is:
Preferred reactive anthraquinone dyes are: Reactive blue 1; Reactive blue 2; Reactive blue 4; Reactive blue 5; Reactive blue 6; Reactive blue 12; Reactive blue 16; reactive blue 19; Reactive blue 24 ; Reactive blue 27; Reactive blue 29; Reactive blue 36; Reactive blue 44; Reactive blue 46 ; Reactive blue 47; reactive blue 49; Reactive blue 50; Reactive blue 53; Reactive blue 55; Reactive blue 61; Reactive blue 66; Reactive blue 68; Reactive blue 69; Reactive blue 74; Reactive blue 86; Reactive blue 93; Reactive blue 94; Reactive blue101; Reactive blue103; Reactive blue114; Reactive blue117; Reactive blue125; Reactive blue141; Reactive blue142; Reactive blue 145; Reactive blue 149; Reactive blue 155; Reactive blue 164; Reactive blue 166; Reactive blue 177; Reactive blue 181; Reactive blue 185; Reactive blue 188; Reactive blue 189; Reactive 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.
The dyes are listed according to Colour Index (Society of Dyers and Colourists/American Association of Textile Chemists and Colorists) classification.

Enzymes

One or more enzymes are preferred present in a laundry composition of the invention and when practicing a method of the invention.
Preferably the level of each enzyme in the laundry composition of the invention is from 0.0001 wt% to 0.1 wt% protein.
Ccontemplated enzymes include proteases, alpha-amylases, cellulases, lipases, peroxidases/oxidases, pectate lyases, and mannanases, or mixtures thereof.
Preferably the enzyme is selected from: alpha-amylases; proteases; lipases; and, cellulases, preferably a protease.
Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola (synonym Thermomyces), e.g. from H. lanuginosa (T. lanuginosus) as described in EP 258 068 and EP 305 216 or from H. insolens as described in WO 96/13580 , a Pseudomonas lipase, e.g. from P. alcaligenes or P. pseudoalcaligenes ( EP 218 272 ), P. cepacia ( EP 331 376 ), P. stutzeri ( GB 1,372,034 ), P. fluorescens, Pseudomonas sp. strain SD 705 ( WO 95/06720 and WO 96/27002 ), P. wisconsinensis ( WO 96/12012 ), a Bacillus lipase, 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 ).
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 .
Preferred commercially available lipase enzymes include Lipolase™ and Lipolase Ultra™, Lipex™ and Lipoclean™ (Novozymes A/S).
The method of the invention may be carried out in the presence of phospholipase classified as EC 3.1.1.4 and/or EC 3.1.1.32. As used herein, the term phospholipase is an enzyme which has activity towards phospholipids.
Phospholipids, such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an outer (sn-1) and the middle (sn-2) positions and esterified with phosphoric acid in the third position; the phosphoric acid, in turn, may be esterified to an amino-alcohol. Phospholipases are enzymes which participate in the hydrolysis of phospholipids. Several types of phospholipase activity can be distinguished, including phospholipases A₁ and A₂ which hydrolyze one fatty acyl group (in the sn-1 and sn-2 position, respectively) to form lysophospholipid; and lysophospholipase (or phospholipase B) which can hydrolyze the remaining fatty acyl group in lysophospholipid. Phospholipase C and phospholipase D (phosphodiesterases) release diacyl glycerol or phosphatidic acid respectively.
Protease enzymes hydrolyse bonds within peptides and proteins, in the laundry context this leads to enhanced removal of protein or peptide containing stains. Examples of suitable proteases families include aspartic proteases; cysteine proteases; glutamic proteases; aspargine peptide lyase; serine proteases and threonine proteases. Such protease families are described in the MEROPS peptidase database (http://merops.sanger.ac.uk/). Serine proteases are preferred. Subtilase type serine proteases are more preferred. The term "subtilases" refers to a sub-group of serine protease according to Siezen et al., Protein Engng. 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 in the active site, which forms a covalent adduct with the substrate. The subtilases may be divided into 6 sub-divisions, i.e. the Subtilisin family, the Thermitase family, the Proteinase K family, the Lantibiotic peptidase family, the Kexin family and the Pyrolysin family.
Examples of subtilases are those derived from Bacillus such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in; US7262042 and WO09/021867 , and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89/06279 and protease PD138 described in ( WO93/18140 ). 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 chymotrypsin proteases derived from Cellumonas described in WO05/052161 and WO05/052146 .
Most preferably the protease is a subtilisins (EC 3.4.21.62).
Examples of subtilases are those derived from Bacillus such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in; US7262042 and WO09/021867 , and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89/06279 and protease PD138 described in ( WO93/18140 ). Preferably the subsilisin is derived from Bacillus, 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 . Most preferably the subtilisin is derived from Bacillus gibsonii or Bacillus Lentus.
Suitable commercially available protease enzymes include those sold under the trade names names Alcalase®, Blaze®; DuralaseTm, DurazymTm, Relase®, Relase® Ultra, Savinase®, Savinase® Ultra, Primase®, Polarzyme®, Kannase®, Liquanase®, Liquanase® Ultra, Ovozyme®, Coronase®, Coronase® Ultra, Neutrase®, Everlase® and Esperase® all could be sold as Ultra® or Evity® (Novozymes A/S).
The method of the invention may be carried out in the presence of cutinase. classified in EC 3.1.1.74. The cutinase used according to the invention may be of any origin.
Preferably cutinases are of microbial origin, in particular of bacterial, of fungal or of yeast origin.
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, e.g. a special strain of B. licheniformis, described in more detail in GB 1,296,839 , or the Bacillus sp. strains disclosed in WO 95/026397 or WO 00/060060 . Commercially available amylases are Duramyl™, Termamyl™, Termamyl Ultra™, Natalase™, Stainzyme™, Fungamyl™ and BAN™ (Novozymes A/S), Rapidase™ and Purastar™ (from Genencor International Inc.).
Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g. the fungal cellulases produced from Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxysporum disclosed in US 4,435,307 , US 5,648,263 , US 5,691,178 , US 5,776,757 , WO 89/09259 , WO 96/029397 , and WO 98/012307 . Commercially available cellulases include Celluzyme™, Carezyme™, Celluclean™, Endolase™, Renozyme™ (Novozymes A/S), Clazinase™ and Puradax HA™ (Genencor International Inc.), and KAC-500(B)™ (Kao Corporation). Celluclean™ is preferred.
Suitable peroxidases/oxidases include those of plant, bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include peroxidases from Coprinus, e.g. from C. cinereus, and variants thereof as those described in WO 93/24618 , WO 95/10602 , and WO 98/15257 . Commercially available peroxidases include Guardzyme™ and Novozym™ 51004 (Novozymes A/S).
Further enzymes suitable for use are discussed in WO2009/087524 , WO2009/090576 , WO2009/107091 , WO2009/111258 and WO2009/148983 .

Enzyme Stabilizers

Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708 .
Where alkyl groups are sufficiently long to form branched or cyclic chains, the alkyl groups encompass branched, cyclic and linear alkyl chains. The alkyl groups are preferably linear or branched, most preferably linear.
The indefinite article "a" or "an" and its corresponding definite article "the" as used herein means at least one, or one or more, unless specified otherwise.

Experimental

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

Ingredient	Weight%
Mono propylene glycol	2.2
triethylamine	1.5
C12-C15 alcohol ethoxylate with 7 moles of ethylene oxide	1.2
Linear alkyl benzene sulfonate	4.6
Sodium laureth ether sulphate with 1 moles of ethylene oxide	5.8
Citric acid	2.0
CaCl₂ dihydrate	0.2
NaCl	0.2
Tinopal CBS-X (fluorescer BASF)	0.3
Sodium Hydroxide	To pH=8.4
Alkoxylate dispersant	See text
Water	balance

The formulation was used to wash eight 5x5cm knitted cotton cloth pieces in a tergotometer set at 200rpm. A one hour wash was conducted in 800ml of 26° French Hard water at 20°C, with 2.3g/L of the formulation. To simulate particulate soil 0.04g/L of 100% compressed carbon black (ex Alfa Aesur) was added to the wash liquor. To simulate oily soil (7.2 g) of an SBL2004 soil strip (ex Warwick Equest) was added to the wash liquor.
Once the wash had been completed the cotton monitors were rinsed once in 400ml clean water, removed dried and the colour measured on a reflectometer and expressed as the CIE L*a*b* values. The cleaning benefit was expressed as the ΔL value: $Δ L = L (dispersant) - L (control)$

The larger the ΔL value the greater the prevention of deposition of the carbon black soil. 95% confidence limits based on the 8 separate cotton monitors were calculated.
The results are given in the table below.

dispersant	n	ΔL	95%
	10	9.5	0.4
	20	10.7	0.3
Oleyl alkyl chain	20	10.7	0.3
	10	11.7	0.3
	20	4.2	0.2
Isotridecyl alkyl chain	20	4.2	0.2
	10	4.1	0.2
Oleyl alkyl chain	10	4.1	0.2
	10	1.7	0.5
Benzyl group (an alkyl aryl group)	10	1.7	0.5

The double bond in the oleyl chain may also be trans as well as cis.

Claims

A laundry detergent composition comprising:
(i) from 0.5 to 20 wt%, preferably from 1 to 10 wt.%, of an alkoxylated dispersant of the following structure:
wherein
X is selected from: ethoxy; and mixtures of ethoxy and propoxy groups where 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: NH; NCH₃; and, O;

R₁ is selected from: saturated C10 to C26 linear or branched alkyl chains; mono-unsaturated C10 to C26 linear or branched alkyl chains; aryl groups; and, alkyl-aryl groups wherein the alkyl group of the alkyl-aryl is a saturated linear or branched C1 to C10;

T is selected from: H; CH₃; SO₃ ^-; CH₂COO^-; PO₃ ^2-; C₂H₅; n-propyl, i-propyl; n-butyl; t-butyl; and, sulfosuccinate;

(ii) from 0 to 50 wt% surfactant, other than the alkoxylated dispersant;

(iii) an active selected from one or more of the following: from 0.001 to 3 wt % perfume; from 0.0001 to 0.5 wt % of fluorescent agent; and, from 0.0001 wt% to 0.1 wt% of an enzyme.
A laundry detergent composition according to claim 1, wherein Y is O.
A laundry detergent composition according to claim 1 or 2, wherein the COYR₁ group is ortho or para to the -O-[X]_n-T group.
A laundry detergent composition according to claim 1, 2 or 3, wherein X is ethoxy.
A laundry detergent composition according to any one of the preceding claims, wherein n is selected from: 9; 10; 11; 12; 13; 14; 15; 16; 17; 18; 19; 20; 21; 22; 23; 24; 25; 26; 27; 28; 29; and 30.
A laundry detergent composition according to any one of the preceding claims, wherein the surfactant is selected from: anionic and non-ionic surfactants and the level of surfactant is from 4 to 40 wt%.
A laundry detergent composition according to any one of the preceding claims, wherein the weight fraction of non-ionic surfactant/anionic surfactant is from 0 to 0.3.
A laundry detergent composition according claim 6 or 7, wherein the anionic surfactant is selected from: linear alkyl benzene sulphonates; alkyl sulphates; and, alkyl ether sulphates; and mixtures thereof.
A laundry detergent composition according to any one of the preceding claims, wherein T is H.
A laundry detergent composition according to any one of the preceding claims, wherein R₁ is selected from: saturated C12 to C18 linear or branched alkyl chains; and mono-unsaturated C12 to C18 linear or branched alkyl chains; and, benzyl.
A laundry detergent composition according to claim 10, wherein R₁ is selected from: stearyl; cetyl; oleyl; lauryl; and, isotridecyl;
A laundry detergent composition according to claim 1, wherein the the alkoxylated dispersant is selected from:
A laundry detergent composition according to any one of the preceding claims, wherein composition is an aqueous liquid having a pH from 6 to 8.5, preferably from 6.5 to 7.5.
A domestic method of treating a textile, the method comprising the steps of:
(i) treating a textile with an aqueous solution of the alkoxylated dispersant, the aqueous solution comprising from 10 ppm to 5000 ppm of the alkoxylated dispersant as defined in any one of the preceding claims; and, 0 to 6 g/L of a surfactant, other than the alkoxylated dispersant; and,

(ii) optionally rinsing and drying the textile.
A domestic method of treating a textile according to claim 14 wherein the level of the perfume in the aqueous solution is from 0.1 to 100 ppm.