EP3194545B1

EP3194545B1 - Whitening composition

Info

Publication number: EP3194545B1
Application number: EP15744901.8A
Authority: EP
Inventors: Stephen Norman Batchelor; Jayne Michelle Bird
Original assignee: Unilever PLC; Unilever NV
Current assignee: Unilever PLC; Unilever NV
Priority date: 2014-09-18
Filing date: 2015-07-29
Publication date: 2018-10-10
Anticipated expiration: 2035-07-29
Also published as: CN106661503A; EP3194545A1; BR112017004339A2; BR112017004339B1; CL2017000604A1; AR101881A1; WO2016041680A1; CN106661503B; CO2017001201A2; AU2015317182A1

Description

Field of Invention

The present invention concerns the use of laundry liquid detergent compositions.

Background of the Invention

Dyes are widely used to colour liquid laundry detergents.
Shading dyes are blue or violet dyes which are substantive to fabrics during the wash process, and enhance whiteness by eliminating yellowness on white fabrics.
White fabrics yellow due to ageing on repeat wash/wear cycles.
Liquid detergents may be used to directly treat stains on fabrics. For liquid detergents that contain dyes, in the neat contact stain treatment process of the undiluted detergent on the fabric, the dye may stain the fabric. Methods to ameliorate this problem are required.
WO 2012/159778 A1 discloses a liquid laundry detergent composition comprising a shading dye, surfactant and a modified lignin polymer for reduced staining properties in neat contact with a textile.
US 2005/107281 A1 discloses ether carboxylic acids based on alkoxylated styrylphenols and to their use as surface-active additives.
Alkoxylated polyaryl or alkoxylated polyalkyl phenol are disclosed in FR 1 313 944 A , GB 1 337 190 A and GB 2 007 692 A .

Summary of the Invention

There is a need for further technologies to reduce neat contact dye staining in coloured domestic liquid laundry products.
We have found that alkoxylated polyaryl and polyalkyl phenols reduce neat contact dye staining of coloured domestic liquid laundry products.
In one aspect the present invention provides a laundry aqueous liquid detergent composition comprising:

(i) from 4 to 50 wt% of a charged surfactant, preferably the level of charged surfactant is 6 to 30 wt%, most preferably 8 to 20 wt%;
(ii) from 0.1 to 20 wt% of an alkoxylated polyaryl or alkoxylated polyalkyl phenol of the following structure:
wherein R₁, is selected from linear or branched C3-C15 alkyl groups and aryl groups, X is selected from ethoxy or propoxy groups; n is from 2 to 70, T is selected from H, SO₃ ^-; COO^-; and, PO₃ ^2-, preferably H and SO₃ ^-; preferably the alkoxylated polyaryl or alkoxylated polyalkyl phenol is at a level of 0.5 to 10 wt%, most preferably 2 to 9 wt%; and,
(iii) dye, preferably 0.0001 to 0.1 wt% of blue or violet shading dye,

Preferably the laundry detergent composition comprises:

(i) from 4 to 50 wt%, more preferably 6 to 30 wt%, most preferably 8 to 20 wt% of anionic surfactant selected from: linear alkyl benzene sulphonates; alkyl sulphates; alkyl ether sulphates; and mixtures thereof;
(ii) from 0.5 to 10wt% of uncharged alkoxylated polyarylphenol of the following structure:
wherein n is selected from: 10; 11; 12; 13; 14; 15; 16; 17; 18; 19; 20; 21; 22; 23; 24; 25; 26; 27; 28; 29; 30; 31; 32; 33; 34; 35; 36; 37; 38; 39; 40; 41; 42; 43; 44; 45; 46; 47; 48; 49; 50; 51; 52; 53; and, 54; and
(iii) dye, preferably 0.0001 to 0.01 wt% dye.

In a further aspect the present invention provides a domestic method of treating a textile, the method comprising the steps of:

(i) treating a textile directly with the laundry liquid detergent as defined, and,
(ii) allowing said liquid detergent to remain in contact with the textile for 30 minutes to 2 days then washing the textile in water, optionally rinsing and drying the textile.

Typically the liquid detergent will be applied to stains on the textile rather than to the entire textile, prior to washing.
In the method embodiments of the invention the surfactant used is preferably as preferred for the embodiments of the invention which are described herein with reference to compositions.
The textile is preferably an item of clothing, bedding or table cloth. Preferred items of clothing are cotton containing shirts, trousers, underwear and jumpers.

Detailed Description of the Invention

Alkoxylated polyarylphenol and polyalkylphenol

Preferably the alkoxylated polyarylphenol and alkoxylated polyalkylphenol is an uncharged (neutral) alkoxylated tristyrylphenol.
Preferably the alkoxylated tristyrylphenol is a polyethylene glycol mono(2,4,6-tris(1-phenylethyl)phenyl) ether.
Preferably the alkoxylated polyarylphenol contains an average of 2 to 70 alkoxy groups, most preferably 10 to 54 alkoxy groups.
Preferably the alkoxylationed is ethoxylation.
The aryl group in the alkoxylated polyarylphenol is preferably selected from, phenyl, tolyl, naphthyl, tetrahydronaphthyl, indanyl, indenyl, styryl, pyridyl, quinolinyl, and mixtures thereof.
Most preferably the alkoxylated polyarylphenol is a polyethylene glycol mono(2,4,6-tris(1-phenylethyl)phenyl) ether (CAS-No: 70559-25-0) with the following structure:
Preferably n = 2 to 70, more preferably n = 10 to 54, most preferably n = 16 and n = 20.
The designation n is the average numbers of moles of alkoxy units in the polyalkoxy chain.
Compounds are available from industrial suppliers, for example Rhodia under the Soprophor trade name; from Clariant under the Emulsogen trade name; Aoki Oil Industrial Co under the Blaunon trade name; from Stepan under the Makon trade name; from TOHO Chemical Industry Co under the Sorpol trade name.
In the context of the current invention the alkoxylated polyarylphenol or the alkoxylated polyalkylphenol is not considered a surfactant and does not contribute numerically to the surfactant content as defined herein.

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).
Dyes are soluble in the medium of application, in this case a laundry detergent liquid.
Dyes for use in liquid 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. Preferably the dyes are blue or violet in colour.
Preferred dye chromophores are azo, azine, anthraquinone, phthalocyanine and triphenylmethane.
Azo, anthraquinone, phthalocyanine and triphenylmethane dyes preferably carry a net anionic charged or are uncharged. Azine dyes preferably carry a net anionic or cationic charge.
Preferred non-shading dyes are selected are selected from blue dyes, most preferably anthraquinone dyes bearing sulphonate groups and triphenylmethane dye bearing sulphonate groups. Preferred compounds are acid blue 80, acid blue 1, acid blue 3; acid blue 5, acid blue 7, acid blue 9, acid blue 11, acid blue 13, acid blue 15, acid blue 17, acid blue 24, acid blue 34, acid blue 38, acid blue 75, acid blue 83, acid blue 91, acid blue 97, acid blue 93, acid blue 93:1, acid blue 97, acid blue 100, acid blue 103, acid blue 104, acid blue 108, acid blue 109, acid blue 110, and acid blue 213.
Blue or violet Shading dyes are most preferred. 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 260 to 320, most preferably 270 to 300. The white cloth used in this test is bleached non-mercerised woven cotton sheeting.
The shading dye's fabric substantivity makes the neat contact staining worse.
Shading dyes are discussed in WO2005/003274 , WO2006/032327 (Unilever), WO2006/032397 (Unilever), WO2006/045275 (Unilever), WO 2006/027086 (Unilever), WO2008/017570 (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).
A mixture of shading dyes may be used.
The shading dye chromophore is most preferably selected from mono-azo, bis-azo and azine.
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 WO2013/142495 and WO2008/087497 . 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 WO/2010/151906 .
An example of an alkoxylated bis-azo dye is :
Azine dyes 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 liquid composition in range from 0.0001 to 0.1wt %. 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.

Surfactant

The laundry composition comprises charged surfactant and it is most preferred that the charged surfactant is anionic surfactant (which includes a mixture of the same).
Suitable anionic detergent compounds which may be used are usually watersoluble 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, 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 50 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, preferably from 2 to 8 wt% of alkyl alkoxylated, preferably ethoxylated, 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.
The nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981.
Preferably the surfactants used are saturated.
Also applicable are surfactants such as those described in EP-A-328 177 (Unilever), which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074 , and alkyl monoglycosides.
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 the well known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070 .
The composition may also contain 0-65 % of a builder or complexing agent such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid or the other builders mentioned below. Many builders are also bleach-stabilising agents by virtue of their ability to complex metal ions.
Zeolite and carbonate (carbonate (including bicarbonate and sesquicarbonate)) are preferred builders with carbonates being particularly preferred.
The composition may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is typically present at a level of less than 15%w. Aluminosilicates are materials having the general formula:

0.8-1.5 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.
Most preferably the laundry detergent is an aqueous liquid laundry detergent, preferably with a pH of from 7 to 9.
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-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' disulphonate, disodium 4,4'-bis{[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino} stilbene-2-2' disulphonate, and disodium 4,4'-bis(2-sulphostyryl)biphenyl.
Preferred fluorescers are fluorescers with CAS-No 3426-43-5; CAS-No 35632-99-6; CAS-No 24565-13-7; CAS-No 12224-16-7; CAS-No 13863-31-5; CAS-No 4193-55-9; CAS-No 16090-02-1; CAS-No 133-66-4; CAS-No 68444-86-0; CAS-No 27344-41-8.

Perfume

The composition preferably comprises a perfume. Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.
Preferably the perfume comprises at least one note (compound) from: alpha-isomethyl ionone, benzyl salicylate; citronellol; coumarin; hexyl cinnamal; linalool; pentanoic acid, 2-methyl-, ethyl ester; octanal; benzyl acetate; 1,6-octadien-3-ol, 3,7-dimethyl-, 3-acetate; cyclohexanol, 2-(1,1-dimethylethyl)-, 1-acetate; delta-damascone; beta-ionone; verdyl acetate; dodecanal; hexyl cinnamic aldehyde; cyclopentadecanolide; benzeneacetic acid, 2-phenylethyl ester;amyl salicylate; beta-caryophyllene; ethyl undecylenate; geranyl anthranilate; alpha-irone; beta-phenyl ethyl benzoate; alpa-santalol; cedrol; cedryl acetate; cedryl formate; cyclohexyl salicylate; 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#.U7Z4hPIdWzk )
The Research Institute for Fragrance Materials provides a database of perfumes (fragrances) with safety information.
Perfume top note may be used to cue the whiteness and brightness benefit of the invention.
Some or all of the perfume may be encapsulated, typical perfume components which it is advantageous to encapsulate, include those with a relatively low boiling point, preferably those with a boiling point of less than 300, preferably 100-250 Celsius. It is also advantageous to encapsulate perfume components which have a low Log P (ie. those which will be partitioned into water), preferably with a Log P of less than 3.0. These materials, of relatively low boiling point and relatively low Log 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).

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.
Especially contemplated enzymes include proteases, alpha-amylases, cellulases, lipases, peroxidases/oxidases, pectate lyases, and mannanases, or mixtures thereof.
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.
Suitable proteases include those of animal, vegetable or microbial origin. Microbial origin is preferred. Chemically modified or protein engineered mutants are included. The protease may be a serine protease or a metallo protease, preferably an alkaline microbial protease or a trypsin-like protease. Preferred commercially available protease enzymes include Alcalase™, Savinase™, Primase™, Duralase™, Dyrazym™, Esperase™, Everlase™, Polarzyme™, and Kannase™, (Novozymes A/S), Maxatase™, Maxacal™, Maxapem™, Properase™, Purafect™, Purafect OxP™, FN2™, and FN3™ (Genencor International Inc.).
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

Example 1

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

Ingredient	Weight%
Mono propylene glycol	2
triethylamine	1.5
C12-C15 alcohol ethoxylate with 7 moles of ethylene oxide	2.1
Linear alkyl benzene sulfonate	8.4
Sodium laureth ether sulphate with 3 moles of ethylene oxide	10.5
Citric acid	0.5
perfume	0.3
dye	0.006
Sodium Hydroxide	To pH=8.4
uncharged alkoxylated polyarylphenol	See text
Water	balance

The formulation was used to pretreat 10x10cm woven cotton cloth pieces; 1 ml of the formulation was placed in the centre of the cotton and rubbed in a circular motion. The cotton was then left lying on a flat non-porous surface for 24 hours and washing at a liquor to cloth ratio of 100:1 in 26° French Hard water at 20°C, in a plastic bottle placed on an orbital shaker (150rpm) for 1 hour. The cotton was removed and the colour of the cotton measured using a reflectometer. The colour was measured at the centre of the cloth, where the detergent was applied and also at the edge of the cloth, where the neat applied detergent did not reach. The colour was expressed as the CIE L*a*b* values and the difference in colour between the edge and the centre measured as Δb_stain: $Δ b_{stain} = b (edge) - b (stain)$
The larger Δb_stain value the greater the difference in colour between the centre and edge and the more visible the stain.
The experiment was repeated with different levels of dye and level of uncharged alkoxylated polyarylphenol. The polyarylphenol used was polyethylene glycol mono(2,4, 6-tris(1-phenylethyl)phenyl) ether with different levels of ethoxylation (16 and 54EO).
The dye used was a phenazine dye of structure:

The results are summarised in the table below.

Formulation	Δb_stain:
Control (no dye or polyarylphenol)	-0.09
Dye and no polyarylphenol	3.1
Dye and 2wt% 16EO polyarylphenol	2.32
Dye and 8wt% 16EO polyarylphenol	1.38
Dye and 2wt% 54EO polyarylphenol	2.69
Dye and 8wt% 54EO polyarylphenol	2.44

The polyarylphenol reduced the neat contact staining of the dye, as seen by the reduction in Δb_stain value. The 16EO compound was the more effective.

Example 2

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
Lionear 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
dye	0.045
Tinopal CBS-X (fluorescer BASF)	0.3
Sodium Hydroxide	To pH=8.4
alkoxylated polyaryl or polyalkyl phenol	See text
Water	balance

The formulation was used to pretreat 10x10cm woven cotton cloth pieces; 1 ml of the formulation was placed in the centre of the cotton and rubbed in a circular motion. The cotton was then left lying on a flat non-porous surface for 24 hours and washing at a liquor to cloth ratio of 100:1 in 26° French Hard water at 20°C, in a plastic bottle placed on an orbital shaker (150rpm) for 1 hour. The cotton was removed and the colour of the cotton measured using a reflectometer. The colour was measured at the centre of the cloth, where the detergent was applied and also at the edge of the cloth, where the neat applied detergent did not reach. The blue colour due to the dye was measured as the Reflectance at 590nm, as this is the maximum absorbance of the dye in the visible spectrum and is unaffected by fluorescence. The difference in colour between the edge and the centre measured as ΔR(590)_stain: $ΔR {(590)}_{stain} = R {(590)}_{edge} - R {(590)}_{stain}$
The larger ΔR(590)_stain value the greater the difference in colour between the centre and edge and the more visible the stain.
Three different polyalkyl/polyaryl phenol ethers were used:

(a) 2,4,6 Tributyl phenol ether sulphate with 7 EO
(b) 2,4,6 Tributyl phenol ether with 13 EO
(c) 2,4,6 Tristyryl phenol ether phosphate

The dye used:

The results are summarised in the table below.

Formulations	ΔR(590)_stain
Control (no dye or polyaryl/alkylphenol)	-1.0
Dye and no polyaryl/alkylphenol	30.7
Dye and 8wt% 2,4,6 Tributyl phenol ether sulphate with 7 EO	19.4
Dye and 8wt% 2,4,6 Tributyl phenol ether with 13 EO	21.2
Dye and 8wt% 2,4,6 Tristryl phenol ether phosphate	4.3

The polyaryl/alkyl phenol reduced the neat contact staining of the dye, as seen by the reduction in ΔR(590)_stain value. This occurs for all 3 compounds: the alkoxylated polyalkyl phenol with and without a sulphonates group and for the alkoxylated polyaryl phenol with the sullphonate group. The polyaryl phenol has best performance.

Claims

A laundry aqueous liquid detergent composition comprising:
(i) from 4 to 50 wt% of a charged surfactant,

(ii) from 0.1 to 20 wt% of an alkoxylated polyaryl or alkoxylated polyalkyl phenol of the following structure:
wherein R₁, is selected from linear or branched C3-C15 alkyl groups and aryl groups, X is selected from ethoxy or propoxy groups; n is from 2 to 70, T is selected from H, SO₃ ^-; COO^- and PO₃ ^2-, preferably H and SO₃ ^-; and,

(iii) dye,
wherein the alkoxylated polyarylphenol or the alkoxylated polyalkylphenol is not considered a surfactant and does not contribute numerically to the surfactant content.
A laundry aqueous liquid detergent composition according to claim 1, wherein the R¹ is selected from n-butyl and styryl.
A laundry aqueous liquid detergent composition according to claim 1, wherein T is selected from H and SO₃ ^-.
A laundry aqueous liquid detergent composition according to claim 1, wherein the alkoxylated polyaryl or alkoxylated polyalkyl phenol is a polyethylene glycol mono(2, 4,6-tris(1-phenylethyl)phenyl) ether.
A laundry aqueous liquid detergent composition according to any one of claim 1 to 4, wherein the alkoxylated polyarylphenol or alkoxylated polyalkyl phenol contains an average of 2 to 70 alkoxy groups.
A laundry aqueous liquid detergent composition according to claim 5, wherein the alkoxylated polyarylphenol or alkoxylated polyalkyl phenol contains an average of 10 to 54 alkoxy groups.
A laundry aqueous liquid detergent composition according to any one of the preceding claims, wherein alkoxylated polyarylphenol or alkoxylated polyalkyl phenol is present at a level of from 0.5 to 10 wt%, most preferably 2 to 9 wt%.
A laundry aqueous liquid detergent composition according to any one of the preceding claims, wherein the charged surfactant is an anionic surfactant.
A laundry aqueous liquid detergent composition according to claim 8, wherein the anionic surfactant is selected from: linear alkyl benzene sulphonate; alkyl sulphates; alkyl ether sulphates; soaps; methyl ester sulphonates; and mixtures thereof.
A laundry aqueous liquid detergent composition according to claim 9, wherein the anionic surfactant is selected from: linear alkyl benzene sulphonate; alkyl sulphates; alkyl ether sulphates; and mixtures thereof.
A laundry aqueous liquid detergent composition according to any one of the preceding claims, wherein the dye is a blue or violet shading dye present at a level from 0.0001 to 0.1 wt%.
A laundry aqueous liquid detergent composition according to any one of the preceding claims, wherein the composition comprises from 2 to 8 wt% of alkyl ethoxylated non-ionic surfactant.
A laundry aqueous liquid detergent composition according to any one of the preceding claims, wherein the dye is selected from: azo, anthraquinone, phthalocyanine, triphenylmethane dyes carrying a net anionic charge or that are uncharged and azine dyes carrying a net anionic or cationic charge.
A laundry detergent composition according to claim 1 comprising:
(i) from 4 to 50 wt% of anionic surfactant selected from: linear alkyl benzene sulphonate; alkyl sulphate; alkyl ether sulphate; and mixtures thereof.

(ii) from 0.5 to 10 wt% of uncharged alkoxylated polyarylphenol of the following structure:
wherein n is selected from: 10; 11; 12; 13; 14; 15; 16; 17; 18; 19; 20; 21; 22; 23; 24; 25; 26; 27; 28; 29; 30; 31; 32; 33; 34; 35; 36; 37; 38; 39; 40; 41; 42; 43; 44; 45; 46; 47; 48; 49; 50; 51; 52; 53; and, 54; and,

(iii) from 0.0001 to 0.5 wt % of blue or violet shading dye.
A laundry aqueous liquid detergent composition according to any one of the preceding claims, wherein the dye is selected from blue or violet shading dyes
A laundry aqueous liquid detergent composition according to claim 15, wherein the dye is selected from: sulphonated bis-azo dyes; alkoxylated mono-azo dyes; sulphonated phenazine dyes; acid blue 98, acid violet 50, dye with CAS-No 72749-80-5; acid blue 59; and, phenazine dye of structure:
wherein:
X₃ is selected from: -H; -F; -CH₃; -C₂H₅; -OCH₃; and, -OC₂H₅;

X₄ is selected from: -H; -CH₃; -C₂H₅; -OCH₃; and, -OC₂H₅; and,

Y₂ is selected from: -OH; -OCH₂CH₂OH; -CH(OH)CH₂OH; -OC(O)CH₃; and, C(O)OCH₃.
A domestic method of treating a textile, the method comprising the steps of:
(i) treating a textile directly with the laundry liquid detergent as defined in any one of claims 1 to 16, and,

(ii) allowing said liquid detergent to remain in contact with said textile for 30 minutes to 2 days then washing said textile in water, optionally rinsing and drying said textile.