WO2016041679A1

WO2016041679A1 - Whitening composition

Info

Publication number: WO2016041679A1
Application number: PCT/EP2015/067348
Authority: WO
Inventors: Stephen Norman Batchelor; Jayne Michelle Bird
Original assignee: Unilever Plc; Unilever N.V.; Conopco, Inc., D/B/A Unilever
Priority date: 2014-09-18
Filing date: 2015-07-29
Publication date: 2016-03-24
Also published as: CL2017000561A1; CN106661504A; BR112017004791A2; AR101879A1; EP3194546A1; AU2015317181A1; CN106661504B; CO2017001206A2; BR112017004791B1; EP3194546B1

Abstract

The present invention provides a laundry 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, (iii) from 0.0001 to 0.5 wt% of a blue or violet shading dye, and (iv) from 0.0001 to 0.5 wt % of a fluorescer. Domestic method of treating a textile, the method comprising the step of treating a textile with an aqueous solution of uncharged alkoxylated polyarylphenol or alkoxylated polyalkyl phenol, the aqueous solution comprising from 10 ppm to 5000 ppm of the alkoxylated polyarylphenol or alkoxylated polyalkyl phenol, 1 ppb to 5ppm of blue or violet shading dye, 0.0001 g/l to 0.1 g/l of fluorescer and up to 6 g/L of surfactant. Domestic method of treating a textile, the method comprising the step of treating a textile with an aqueous solution of the laundry detergent composition, said aqueous solution comprising from 10 ppm to 5000 ppm of uncharged alkoxylated polyarylphenol or alkoxylated polyalkyl phenol, 1 ppb to 5ppm of blue or violet shading dye, 0.0001 g/l to 0.1 g/l of fluorescer and up to 6 g/L of surfactant.

Description

WHITENING COMPOSITION

Field of Invention

The present invention concerns the use of whitening and brightening laundry

compositions.

Background of the Invention

Maintaining and improving the whiteness and brightness of textiles during domestic laundry are desirable. A problem is the redeposition of soil removed from one garment onto another. The problem is exacerbated by the presence of human oils (sebum) on garments and in the wash which serves to enhance the deposition of soil in the wash. This process leads to an overall loss of whiteness and cleaning across the washing load. To ameliorate this problem, dispersing polymer such as an alkoxylated polyethylene imines have been widely added to washing detergents. Ethoxylated PEI (PEI = polyethylene imine) is known as an anti redeposition polymer from CA 1210009. Certain Cellulase enzymes have also been used to prevent redeposition by altering the surface properties of cotton fabrics. Novozymes describes in WO02/099091 and WO04/053039 cellulases for use in domestic laundry.

Shading dyes and fluorescers are use in detergent formulations to enhance whiteness and brightness.

EP1321510 (Shipley) describes an industrial cleaning composition that contain an alkoxylated polyarylphenol for stripping organic chemical residues from photoresists that are used in the manufacture of semi-conductors and other electronic devices and circuits. The organic chemical residues are materials left over from the production process and include photointiators, thermoinitiators, acrylic and methacrylic monomers. Summarv of the Invention

There is a need for further technologies to reduce redeposition and enhance cleaning in domestic laundry products containing shading dyes and fluorescers.

We have found that alkoxylated polyaryl and alkoxylated polyalkyl phenols enhance whiteness and brightness of garments during domestic laundry.

In one aspect the present invention provides a laundry detergent composition comprising:

(i) charged surfactant, preferably the level of charged surfactant is from 4 to 50 wt%, more preferably 6 to 30 wt%, most preferably 8 to 20 wt%;

(ii) alkoxylated polyaryl or alkoxylated polyalkyl phenol, of the following structure:

wherein Ri , 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 at a level from 0.1 to 20 wt%, more preferably 0.5 to 10 wt%, most preferably 2 to 9 wt%; and. a blue or violet shading dye, preferably 0.0001 to 0.5 wt% of a blue or violet shading dye; and, a fluorescer, preferably from 0.0001 to 0.5 wt % of a fluorescer. In another aspect the present invention provides a laundry detergent composition comprising:

(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 sulphonate; alkyl sulphate; alkyl ether sulphate; and mixtures thereof.

(ii) from 0.5 to 10 wt% of an uncharged alkoxylated polyarylphenol, preferably at a level from 0.1 to 20 wt%, more preferably 0.5 to 10 wt%, most preferably 2 to

9 wt%, of the following structure:

wherein n is selected from: 10; 1 1 ; 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;

(iii) from 0.0001 to 0.5 wt% of a blue or violet shading dye; and, (iv) from 0.0001 to 0.5 wt% of fluorescer.

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 with an aqueous solution of uncharged alkoxylated

polyarylphenol or alkoxylated polyalkyi phenol, the aqueous solution comprising from 10 ppm to 5000 ppm of the uncharged alkoxylated polyarylphenol or alkoxylated polyalkyi phenol; 1 ppb to 5ppm of a blue or violet shading dye; 1 ppb to 5ppm of a fluorescer and up to 6 g/L, preferably 0.2 to 4 g/L, of surfactant; and, (ii) optionally rinsing and drying the textile.

In the method the surfactant used is preferably as preferred for the composition. 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 polyalkylphenol are 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 or alkoxylated polyalkyl phenol contains an average of 2 to 70 alkoxy groups, most preferably 10 to 54 alkoxy groups.

Preferably the alkoxylation 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 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, 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 alkoxylated polyalkyi phenol is not considered a surfactant and does not contribute numerically to the surfactant as defined herein.

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.

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 2009/141 173 (Unilever), WO 2010/099997(Unilever), WO 2010/102861 (Unilever), WO 2010/148624(Unilever), WO2008/087497 (P&G), WO201 1/01 1799 (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:

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 1 1 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(0)CH₃; and, C(0)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:

(Structure I).

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 bluel 01 ; Reactive blue103; Reactive blue1 14; Reactive blue1 17; Reactive bluel 25; Reactive bluel 41 ; Reactive bluel 42; 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.

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 water- soluble alkali metal salts of organic sulphates and sulphonates having alkyi radicals containing from about 8 to about 22 carbon atoms, the term alkyi being used to include the alkyi portion of higher alkyi radicals.

Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyi sulphates, especially those obtained by sulphating higher Cs to Ci8 alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyi C9 to C20 benzene sulphonates, particularly sodium linear secondary alkyi C10 to C15 benzene sulphonates; and sodium alkyi 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 alkyi benzene

sulphonate; alkyi sulphates; alkyi ether sulphates; soaps; alkyi (preferably methyl) ester sulphonates, and mixtures thereof. The most preferred anionic surfactants are selected from: linear alkyi benzene sulphonate; alkyi sulphates; alkyi ether sulphates and mixtures thereof.

Preferably the alkyi 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 alkyi benzene sulphonate is a sodium C11 to C15 alkyi benzene sulphonates. Preferably the alkyi sulphates is a linear or branched sodium C12 to C18 alkyi sulphates. Sodium dodecyl sulphate is particularly preferred, (SDS, also known as primary alkyi 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 alkyi benzene sulphonate together with an alkyi ether sulphate. Preferably the laundry composition in addition to the anionic surfactant comprises alkyi exthoylated non-ionic surfactant, preferably from 2 to 8 wt% of alkyi 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 Cs to C18 primary or secondary linear or branched alcohols with ethylene oxide.

Preferably the alkyi ethoxylated non-ionic surfactant is a Cs 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:

R2

U

R1— N-R3 X in which R¹ is a C12 to C22 alkyl or alkenyl chain; R², R³ and R⁴ are independently selected from Ci 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 Ci to C₄ alkyl chains and X^" is a compatible anion.

The composition optionally comprises a silicone.

Builders or Complexinq 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 M₂0. AI2O3. 0.8-6 Si0₂ 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 S1O2 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 9.5-1 1 .

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 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.

The total amount of the fluorescent agent or agents used in the composition is generally from 0.0001 to 0.5 wt %, preferably 0.005 to 2 wt %, more preferably 0.01 to 0.1 wt %.

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 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. Most preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-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' 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.

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 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; 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 201 1. (http://www.ifraorq.Org/en-us/inqredients#.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 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 CLog P (ie. 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 (thcyclco 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 vi dine. 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), polyvinyl 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, 1 131 , 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 Ai 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 , WO2009/1 1 1258 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.

Dye weights refer to the sodium or chloride salts unless otherwise stated.

Experimental

Example 1

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

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 staining of the detergent liquid measured using a reflectometer (UV included Ganz whiteness measurement). The colour was measured in 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 Ganz whiteness values, and the difference in colour between the edge and the centre measured as AGanzstain:

AGanzstain = b(edge)-b(stain)

The larger AGanz_stain value the greater the difference in colour between the centre and edge and the more visible the stain. A AGanz_stain closest to zero indicates most even whiteness which is preferred. The shading dye used was the shading dye of Structure (I) in text (anthaquinone dye linked to a propoxylated polyethyl imine). The experiment was repeated with different levels of dye and level and ethoxylated 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 results are summarised in the table below.

The polyarylphenol reduced the neat contact staining of the detergent, as seen reduction in AGanz_stain value.

Example 2

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

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 (UV included). 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

Abstain:

Abstain - b(edge)-b(stain)

The larger Abstain value the greater the difference in colour between the centre and edge and the more visible the stain. The Abstain included the staining of the shading dye and fluorescer.

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 Tristryl phenol ether phosphate.

The dye used:

The results are summarised in the table below.

The polyaryl.alkyi phenol reduced the neat contact staining of the formulation containing shading dye and fluorescer, as seen by the reduction in Abstain value.

Claims

1. A laundry 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 polyalkyi phenol, of the following structure:

wherein Ri, 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, S0₃; COO^" and P0₃ ^2", preferably H and S0₃ ^" ; from 0.0001 to 0.5 wt% of a blue or violet shading dye; and, from 0.0001 to 0.5 wt % of a fluorescer.

A laundry detergent composition according to claim 1 , wherein the Ri is selected from n-butyl and styryl.

A laundry detergent composition according to claim 1 , wherein T is selected from H and S0₃ ^".

A laundry detergent composition according to claim 1 , wherein the alkoxylated polyaryl or alkoxylated polyalkyi phenol is a polyethylene glycol mono(2,4,6-tris(1 - phenylethyl)phenyl) ether.

5. A laundry detergent composition according to any one of claim 1 to 4, wherein the alkoxylated polyarylphenol or alkoxylated polyalkyi phenol contains an average of 2 to 70 alkoxy groups. 6. A laundry detergent composition according to claim 5, wherein the alkoxylated

polyarylphenol or alkoxylated polyalkyi phenol contains an average of 10 to 54 alkoxy groups.

7. A laundry detergent composition according to any one of the preceding claims, wherein alkoxylated polyarylphenol or alkoxylated polyalkyi phenol is present at a level of from 0.5 to 10 wt%, most preferably 2 to 9 wt%.

8. A laundry detergent composition according to any one of the preceding claims, wherein the charged surfactant is anionic surfactant.

9. A laundry detergent composition according to claim 8, wherein the laundry

detergent composition is a laundry aqueous liquid detergent composition and the anionic surfactant is selected from: linear alkyi benzene sulphonate; alkyi sulphates; alkyi ether sulphates; soaps; methyl ester sulphonates; and mixtures thereof.

10. A laundry aqueous liquid detergent composition according to claim 9, wherein the anionic surfactant is selected from: linear alkyi benzene sulphonate; alkyi sulphates; alkyi ether sulphates; and mixtures thereof. 1 1 . A laundry aqueous liquid detergent composition according to any one of the

preceding claims, wherein the level of anionic surfactant is from 6 to 30 wt%.

12. A laundry aqueous liquid detergent composition according to any one of the

preceding claims, wherein the composition comprises from 2 to 8 wt% of alkyi ethoxylated non-ionic surfactant.

13. A laundry aqueous liquid detergent composition according to any one of the

preceding claims, wherein the shading dye is a reactive blue anthraquinone dye covalently linked to an alkoxylated polyethyeneimine.

14. A laundry detergent composition according to claim 1 comprising: from 4 to 50 wt% of anionic surfactant is selected from: linear alkyl benzene sulphonate; alkyl sulphate; and, alkyl ether sulphate; and, mixtures thereof; from 0.5 to 10 wt% of an uncharged alkoxylated polyarylphenol of the following structure:

wherein n is selected from: 10; 1 1 ; 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;

(iii) from 0.0001 to 0.5 wt% of blue or violet shading dye; and,

(iv) from 0.0001 to 0.5 wt% of fluorescer.

15. A laundry detergent composition according to any one of the preceding claims, wherein the fluorescer is selected from a fluorescer 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.

16. A laundry detergent composition according to any one of the preceding claims, wherein the laundry detergent composition is a laundry aqueous liquid detergent composition. A domestic method of treating a textile, the method comprising the step of: treating a textile with an aqueous solution of uncharged alkoxylated polyarylphenol or alkoxylated polyalkyi phenol, the aqueous solution comprising from 10 ppm to 5000 ppm of the alkoxylated polyarylphenol or alkoxylated polyalkyi phenol; 1 ppb to 5ppm of blue or violet shading dye; 0.0001 g/l to 0.1 g/l of fluorescer and, up to 6 g/L of surfactant.

A domestic method of treating a textile, the method comprising the step of: treating a textile with an aqueous solution of a laundry detergent composition according to any of claims 1 -16, said aqueous solution comprising from 10 ppm to 5000 ppm of uncharged alkoxylated polyarylphenol or alkoxylated polyalkyi phenol ; 1 ppb to 5ppm of blue or violet shading dye; 0.0001 g/l to 0.1 g/l of fluorescer and, up to 6 g/L of surfactant.