WO2013011071A1 - Liquid laundry composition - Google Patents

Liquid laundry composition Download PDF

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Publication number
WO2013011071A1
WO2013011071A1 PCT/EP2012/064120 EP2012064120W WO2013011071A1 WO 2013011071 A1 WO2013011071 A1 WO 2013011071A1 EP 2012064120 W EP2012064120 W EP 2012064120W WO 2013011071 A1 WO2013011071 A1 WO 2013011071A1
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Prior art keywords
liquid laundry
composition according
laundry composition
dyes
sulphonated aromatic
Prior art date
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PCT/EP2012/064120
Other languages
French (fr)
Inventor
Stephen Norman Batchelor
Jayne Michelle Bird
Original Assignee
Unilever Plc
Unilever N.V.
Hindustan Unilever Limited
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Priority to EP11174801 priority Critical
Priority to EP11174801.8 priority
Application filed by Unilever Plc, Unilever N.V., Hindustan Unilever Limited filed Critical Unilever Plc
Publication of WO2013011071A1 publication Critical patent/WO2013011071A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40Dyes ; Pigments
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40Dyes ; Pigments
    • C11D3/42Brightening agents ; Blueing agents

Abstract

The present invention concerns liquid laundry compositions incorporating a sulphonated aromatic formaldehyde polycondensate.

Description

LIQUID LAUNDRY COMPOSITION

TECHNICAL FIELD

The present invention concerns liquid laundry compositions incorporating a sulphonated aromatic formaldehyde polycondensate.

BACKGROUND OF THE INVENTION

WO2010/084039 (Unilever) disclosed shading dyes in spray dried granules containing alkali metal salts of the condensation products of naphthalenesulphonic acids and formaldehyde for use in powder detergents; the condensation product serves to reduce dye migration in the powder thus retaining the aesthetic appeal of the powder.

Elastane is a widely used material in underwear and support wear and upon washing with surfactant becomes grey. SUMMARY OF THE INVENTION

There is a need to ameliorate the greying of nylon-elastane when liquid detergents are used to treat textiles. We have found that a liquid composition containing a surfactant and a

sulphonated aromatic formaldehyde polycondensate has improved properties when textiles containing elastane are treated with the composition; there is reduced greying of the elastane. We have also found that the performance of a shading dye is improved by addition to such a composition. In one aspect the present invention provides a laundry liquid laundry detergent composition comprising:

(a) from 0.0001 to 0.01 wt %, preferably from 0.001 to 0.005 w%, of a blue or violet shading dye;

(b) from 1 to 70 wt% of a surfactant;

(c) from 0.1 to 30 wt% of a sulphonated aromatic formaldehyde polycondensate; and,

(d) the remainder of the composition being diluents and adjuncts to100 wt %.

In another aspect the present invention provides a method of treating a textile, the textile comprising elastane, the method comprising the steps of:

(i) applying the liquid laundry composition to a textile;

(ii) rinsing the textile with water; and,

(iii) optionally drying the textile.

DETAILED DESCRIPTION OF THE INVENTION

SULPHONATED AROMATIC FORMALDEHYDE POLYCONDENSATE

The presence of sulphonated aromatic formaldehyde polycondensate reduces the greying of elastane.

A sulphonated aromatic formaldehyde polycondensate is the condensation product of sulphonated aromatic compounds with formaldehyde.

The sulphonated aromatic formaldehyde polycondensate may be produced by the condensation reaction of: 1 . aromatic sulfonic acids and benzoyl chloride or benzoin.

2. alkylarylsulfonic acids with a halogen arylsulfonic acid

3. sulphonated phenols or napthols with formaldehyde. The products may be ethoxylated. The sulfonic acid groups may be sulfomethyl groups.

The steps of polycondensation, ethoxylation, sulfonation or sulfomethylation may occur in any sequential order, but the ethoxylation, sulfonation or sulfomethylation are preferred to take place before the polycondensation.

Preferred alkali metal salts of the present invention are alkali metal salts of the condensation products of naphthalenesulphonic acids and formaldehyde;

naphthalenesulphonic acids, cresol and formaldehyde; diphenylethersulphonic acids and formaldehyde; toluenesulphonic acids and formaldehyde;

isopropylbenzenesulphonic acids and formaldehyde; cresolsulphonic acids and formaldehyde. Most preferably alkali metal salts of the condensation products of naphthalenesulphonic acids and formaldehyde. A commercial example available is TAMOL™, a trade name from BASF. Other suitable commercial examples are produced by Lanxess, Rohm and Haas Co, BASF and Dow Chemical Company.

Examples of the synthesis of sulphonated aromatic formaldehyde polycondensate are given in GB1 101671 (Ciba-Geigy), US3957680 (Mitsui), DE1 163284

(Hoechst), US3781 169 (Hoechst) and US3874891 (Hoechst). Preferred structures are:

Figure imgf000005_0001

Where k is from 1 to 4, preferably 1 to 2, most preferably 1 .

Figure imgf000005_0002

Where Ri is C1 -C4 alkyl, preferably methyl or iso-propyl.

Where j is from 4 to 40, preferably 5 to 20.

Y Y Y

0 0 Q Where Y is selected from [X-0]m-S03H; [X-0]m-S03CH3; [X-0]m-H and [X-0]m- CH3., where X is an ethyl or propyl group; m is 1 to 20, preferably 2 to 8; and n is 2 to 25. The aromatic groups are preferably substituted by groups selected from C1 -C14 alkyl groups and S03H.

Preferably, the minimum level of residual formaldehyde from the polycondensation is 200 PPM, more preferably 50 PPM and even more preferably 10 PPM.

SHADING DYE

Shading dyes deposit to fabric during the wash or rinse step of the washing process providing a visible hue to the fabric.

Shading dyes are discussed in WO2005/003274, WO2006/032327(Unilever), WO2006/032397(Unilever), WO2006/045275(Unilever), WO

2006/027086(Unilever), WoO2008/017570(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) and WO201 1/01 1799 (P&G).

Shading of white garments may be done with any colour depending on consumer preference. Blue and Violet are particularly preferred shades and consequently preferred dyes or mixtures of dyes are ones that give a blue or violet shade on white fabrics. The shading dyes used in the present invention are preferably blue or violet. A mixture of shading dyes may be used and indeed are preferred for treating mixed fibre textiles. 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 chromophore is preferably selected from the group comprising: mono-azo, bis-azo, triphenylmethane, triphenodioxazine, phthalocyanin, naptholactam, azine and anthraquinone. Most preferably mono-azo, bis-azo, azine and anthraquinone.

Most preferably the dye bears at least one sulfonate group.

Many examples of shading dyes are found in the classes of basic, solvent, acid, direct and disperse dyes.

Preferred shading dyes are selected from direct dyes, acid dyes, hydrophobic dyes, cationic dyes and reactive dyes.

The shading dye is present is present in the liquid composition in range from 0.0001 to 0.01 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 most preferably a blue or violet shading dye. Direct Dyes

Direct violet and direct blue dyes are preferred.

Preferably the dye is a bis-azo dye.

Most preferably, the direct dye is a direct violet of the following structures:

Figure imgf000008_0001
or

Figure imgf000008_0002
wherein:

the ring bearing R3 and R may be independently naphthyl or phenyl as shown; Ri is selected from: hydrogen and C1 -C4-alkyl, preferably hydrogen;

R2 is selected from: hydrogen, C1 -C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably phenyl;

R3 and R are independently selected from: hydrogen and C1 -C4-alkyl, preferably hydrogen or methyl;

X and Y are independently selected from: hydrogen, C1 -C4-alkyl and C1 -C4- alkoxy; preferably the dye has X= methyl; and, Y = methoxy and n is 0, 1 or 2, preferably 1 or 2.

Preferred dyes 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 , and direct violet 99. Bis-azo copper containing dyes such as direct violet 66 may be used. Benzidene based dyes are not preferred.

Preferably the direct dye is present at 0.00001 wt% to 0.0010 wt% of the composition.

In another embodiment the direct dye may be covalently linked to the photo- bleach, for example as described in WO2006/024612 and WO2010/099997.

Acid dyes

Cotton substantive acid dyes give benefits to cotton containing garments.

Preferred dyes and mixes of dyes are blue or violet. Preferred acid dyes are: (i) azine dyes, wherein the dye is of the following core structure:

Figure imgf000009_0001
wherein Ra, Rb, Rc and Rd are selected from: H, an branched or linear C1 to C7- alkyl chain, benzyl a phenyl, and a naphthyl;

the dye is substituted with at least one SO3" or -COO" group;

the B ring does not carry a negatively charged group or salt thereof;

and the A ring may further substituted to form a naphthyl;

the dye is optionally substituted by groups selected from: amine, methyl, ethyl, hydroxyl, methoxy, ethoxy, phenoxy, CI, Br, I, F, and NO2. Preferred azine dyes are: acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50. Other preferred non-azine acid dyes are acid violet 17, acid black 1 and acid blue 29.

Preferably the acid dye is present at 0.0005 wt% to 0.01 wt% of the composition.

Hydrophobic dyes

The composition may comprise one or more hydrophobic dyes selected from benzodifuranes, methine, triphenylmethanes, napthalimides, pyrazole,

napthoquinone, anthraquinone and mono-azo or di-azo dye chromophores.

Hydrophobic dyes are dyes which do not contain any charged water solubilising group. Hydrophobic dyes may be selected from the groups of disperse and solvent dyes. Blue and violet anthraquinone and mono-azo dye are preferred. Preferred dyes include solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.

The hydrophobic dye may be an alkoxylated dye, preferably an alkoxylated mono- azo thiophene dye.

Preferably the hydrophobic dye is present at 0.0001 wt% to 0.01 wt% of the composition.

Cationic dyes

Cationic dyes bear a cationic charge. Cationic mono-azo, phenazines, triphenyl methane and anthraquinone dyes are preferred. Cationic Mono-azo dye and phenazine dyes are most preferred. To avoid hydrolysis for mono-azo and anthraquinone dyes preferably the cationic charge is present as a quaternary amine on a pendant chain. The dyes may be alkoxylated and mono-azo dyes may additionally bear anionic charged groups, preferably also on pendant chains.

Mono-azo dyes containing a hetrocyclic ring are particularly preferred, such as thiophenes. Preferred cationic phenazine dyes are of the form:

Figure imgf000011_0001
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.

Reactive dyes

Reactive dyes are dyes which contain an organic group capable of reacting with an aliphatic C-OH, C-NH2 or C-NH-C group to form a covalent bond. They deposit onto cotton. Preferably the reactive group is hydrolysed or reactive group of the dyes has been reacted with an organic species such as a polymer, so as to the link the dye to this species. Dyes may be selected from the reactive violet and reactive blue dyes listed in the Colour Index International. Preferably the reactive dye is reacted with a polymer containing NH2 or NH groups.

Surfactant

The composition comprises between 1 to 70 wt % of a surfactant, most preferably 10 to 30 wt %. The surfactant acts as a detergent. In general, 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.

Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are C6 to C22 alkyl phenol- ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic Cs to Cie primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.

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 acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher Cs to Cie alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl Cg 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 preferred anionic detergent compounds are sodium C11 to C15 alkyl benzene sulphonates and sodium C12 to Cie alkyl sulphates. Also applicable are surfactants such as those described in EP-A-328 177 (Unilever), which shows resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides.

Preferred surfactant systems are mixtures of anionic with nonionic detergent active materials, in particular the groups and examples of anionic and nonionic surfactants pointed out in EP-A-346 995 (Unilever). Especially preferred is surfactant system that is a mixture of an alkali metal salt of a C16 to Cie primary alcohol sulphate together with a C12 to C15 primary alcohol 3 to 7 EO ethoxylate. The nonionic detergent is preferably present in amounts greater than 10%, e.g. 25 to 90 wt % of the surfactant system. Anionic surfactants can be present for example in amounts in the range from about 5% to about 40 wt % of the surfactant system. In another aspect which is also preferred the surfactant may be a cationic such that the composition is a fabric conditioner.

To facilitate ease of use the composition is preferably packed in pack sizes of 0.5 to 5kg. To reduce moisture ingress, the composition is preferably packs in laminated cardboard packs or sealed plastic bags. DILUENTS AND ADJUNCTS

The diluents and adjuncts facilitate the composition are generally other than the shading dye, surfactant; and the modified lignin polymer. The diluents and adjuncts may facilitate fluidization of the composition and/or provide bulking or functionality to the composition. These include water, alcohol etc. Below are found suitable diluents and adjuncts but the composition is not limited to such.

Detergencv Builder

One or more detergency builders may be suitably present in the liquid detergent composition of the invention.

Examples of suitable organic detergency builders, when present, include the alkaline metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates, carboxymethyloxysuccinates, carboxymethyloxymalonates, ethylene diamine-N,N-disuccinic acid salts, polyepoxysuccinates, oxydiacetates, triethylene tetramine hexa-acetic acid salts, N-alkyl imino diacetates or dipropionates, alpha sulpho-fatty acid salts, dipicolinic acid salts, oxidised polysaccharides, polyhydroxysulphonates and mixtures thereof.

Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamino-tetraacetic acid, nitrilo-triacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids and citric acid, tartrate mono succinate and tartrate di succinate. 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. The total amount of the fluorescent agent or agents used in the composition is generally from 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: 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' disulfonate, disodium 4,4'-bis{[(4-anilino-6- morpholino-1 ,3,5-triazin-2-yl)]amino} stilbene-2-2' disulfonate, and disodium 4,4'- bis(2-sulfostyryl)biphenyl.

It is preferred that the aqueous solution used in the method has a fluorescer present. When a fluorescer is present in the aqueous solution used in the method it is preferably in the range from 0.0001 g/l to 0.1 g/l, preferably 0.001 to 0.02 g/l.

Perfume

Preferably the composition comprises a perfume. The perfume is preferably in the range from 0.001 to 3 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. It is commonplace for a plurality of perfume components to be present in a composition. 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.

Perfume and top note may be used to cue the whiteness benefit of the invention.

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 other polymers. Examples are carboxymethylcellulose, poly (ethylene glycol), polyvinyl alcohol),

polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacry late/acrylic acid copolymers.

Polymers present to prevent dye deposition, for example poly(vinylpyrrolidone), poly(vinylpyridine-N-oxide), and poly(vinylimidazole), are preferably absent from the composition.

Enzymes

One or more enzymes are preferred present in a composition of the invention and when practicing a method of the invention. Preferably the level of each enzyme 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 (7.

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. alcaiigenes 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™, 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.

The enzyme and the shading dye may show some interaction and should be chosen such that this interaction is not negative. Some negative interactions may be avoided by encapsulation of one or other of enzyme or shading dye and/or other segregation within the product.

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™, Celluclean™, Carezyme™, Endolase™,

Renozyme™ (Novozymes A/S), Clazinase™ and Puradax HA™ (Genencor International Inc.), and KAC-500(B)™ (Kao Corporation).

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). Enzvme 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. 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.

Average molecular weights refer to weight average molecular weights.

Example 1

The following liquid compositions were made:

Reference Example 1

example A

LAS 4.9 4.9

NI(7EO) 7.3 7.3

SLES(3EO) 2.4 2.4

Carbobetaine 0.9 0.9

Alkyl Betaine 0.9 0.9

1 ,2-propanediol 15 15

Triethanolamine 2 2

Perfume 1 .4 1 .4

sulphonated aromatic 0 8.7

formaldehyde polycondensate

Water remainder remainder

LAS is sodium Cn to C15 alkyl benzene sulphonate.

NI(7EO) is R-(OCH2CH2)nOH, where R is an alkyl chain of C12 to C15, and n is 7. SLES(3EO) is sodium lauryl ether sulfate with 3 ethoxy groups.

The Alkyl Betaine used was Empigen BB (ex Huntsman).

The sulphonated aromatic formaldehyde polycondensate used was TAMOL™ NN7718 (ex BASF) and is a napthalenesulfonic acid polycondensate sodium salt All values are wt%.

The compositions were used to wash a mixture of white fabrics: woven cotton, knitted cotton, micro-fibre polyester, woven polycotton and knitted nylon-elastane at a Liquor to cloth ratio of 10: 1 in a linitester. The fabrics were of equal area. 26° French hard water was used and each wash lasted 30 minutes and was followed by a running rinse. The compositions were used at 2.3g/L. To simulate soiling, soil strips were added to each wash cycle, the weight ratio of soil strips to the white fabrics was 7: 1. The soil strips used were SBL 2004 Soil Ballast Fabrics (ex wfk Testgewebe GmbH ) and multimix soil ballast fabric (ex CFT Holland) in the weight ratio of 1 :2.

After 5 washes the white clothes were removed, dried and the colour measured using a reflectometer and expressed as the CIE L*a*b* values. The L* values represent the greying of the fabric.

The results are given for nylon-elastane below:

Figure imgf000022_0001

The liquid containing the napthalenesulfonic acid polycondensate sodium salt maintains the whiteness as shown by the large L* value.

Claims

We claim:
1 . A laundry liquid laundry detergent composition comprising:
(a) from 0.0001 to 0.01 wt % of a blue or violet shading dye;
(b) from 1 to 70 wt% of a surfactant;
(c) from 0.1 to 30 wt% of a sulphonated aromatic formaldehyde
polycondensate; and,
(d) the remainder of the composition being diluents and adjuncts to100 wt %.
2. A liquid laundry composition according to claim 1 , wherein the sulphonated aromatic formaldehyde polycondensate is a naphthalenesulphonic acid formaldehyde polycondensate.
3. A liquid laundry composition according to claim 1 or 2, wherein the sulphonated aromatic formaldehyde polycondensate is an ethoxylated
sulphonated aromatic formaldehyde polycondensate.
4. A liquid laundry composition according to claim any preceding claim, wherein the sulphonated aromatic formaldehyde polycondensate is substituted by one or more sulfonic acid groups.
5. A liquid laundry composition according to claim any preceding claim, wherein the sulphonated aromatic formaldehyde polycondensate is substituted by one or more sulfomethyl groups.
6. A liquid laundry composition according to any preceding claim 1 , 3, 4 and 5, wherein the sulphonated aromatic formaldehyde polycondensate is obtainable by condensation of a diphenylethersulphonic acid and formaldehyde.
7. A liquid laundry composition according to any one of claims 1 to 5, wherein the sulphonated aromatic formaldehyde polycondensate is obtainable by the condensation of toluenesulphonic acids and formaldehyde.
8. A liquid laundry composition according to claim 4, wherein the sulphonated aromatic formaldehyde polycondensate is obtainable by condensation product of isopropylbenzenesulphonic acids and formaldehyde.
9. A liquid laundry composition according to claim 4, wherein the sulphonated aromatic formaldehyde polycondensate is the condensation product of
cresolsulphonic acids and formaldehyde.
10. A liquid laundry composition according to any one of claims 6 to 9, wherein the minimum level of residual formaldehyde from the polycondensation is 200 PPM.
1 1 . A liquid laundry composition according to any one of the preceding claims, wherein the shading dyes are selected from direct dyes, acid dyes, hydrophobic dyes, cationic dyes and reactive dyes.
12. A liquid laundry composition according to claim 1 1 , wherein the shading dye chromophore is selected from the group comprising: mono-azo, bis-azo, triphenylmethane, triphenodioxazine, phthalocyanin, naptholactam, azine and anthraquinone.
13. A liquid laundry composition according to any one of the preceding claims, wherein the liquid laundry composition is a laundry fabric conditioner.
14. A method of treating a textile for ameliorating the greying of nylon- elastane, the textile comprising elastane, the method comprising the steps of:
(i) applying the liquid laundry composition to a textile, the liquid laundry composition as defined in any one of claims 1 to 13;
(ii) rinsing the textile with water; and,
(iii) optionally drying the textile.
PCT/EP2012/064120 2011-07-21 2012-07-18 Liquid laundry composition WO2013011071A1 (en)

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WO2015091176A1 (en) * 2013-12-17 2015-06-25 Henkel Ag & Co. Kgaa Color-safe detergents
WO2015091174A1 (en) * 2013-12-17 2015-06-25 Henkel Ag & Co. Kgaa Anti-redeposition detergents
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WO2016041649A1 (en) * 2014-09-18 2016-03-24 Unilever Plc Liquid whitening composition
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WO2016041676A1 (en) * 2014-09-18 2016-03-24 Unilever Plc Whitening composition
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CN106661504B (en) * 2014-09-18 2019-07-12 荷兰联合利华有限公司 Lightening compositions

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BR112014001378A2 (en) 2017-03-01
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EP2734610A1 (en) 2014-05-28
AR087267A1 (en) 2014-03-12

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