WO2012130492A1

WO2012130492A1 - Dye polymer

Info

Publication number: WO2012130492A1
Application number: PCT/EP2012/050896
Authority: WO
Inventors: Stephen Norman Batchelor; Jayne Michelle Bird
Original assignee: Unilever Plc; Unilever N.V.; Hindustan Unilever Limited
Priority date: 2011-03-25
Filing date: 2012-01-20
Publication date: 2012-10-04
Also published as: AR085482A1

Abstract

The present invention relates to reactive dyes bound to polyviny alcohol and their use.

Description

DYE POLYMER

FIELD OF INVENTION

The present invention relates to polyvinyl alcohol polymers tethered to reactive dyes and their use.

BACKGROUND OF THE INVENTION

WO2006/055787 (Procter & Gamble) discloses laundry formulations containing a cellulose ether polymer covalently bound to a reactive dye for whitening the fabric. Cellulose ethers show poor water solubility and form thick pastes in water.

Effective reaction with the reactive dyes requires the cellulose ether to be present in aqueous solution at high concentration to reduce the side reaction of dye hydrolysis that produces unwanted hydrolysed dye that is untethered to the polymer.

SUMMARY OF THE INVENTION

We have found in contrast to using cellulose ether polymer as a dye support that employing polyvinyl alcohols enables a more facile synthesis and provides deposition to a wide range of fabrics. Surprisingly reactive dyes may be easily tethered to PVA and deposit to fabrics in the wash in contrast to the prior art.

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

(i) from 2 to 70 wt% of a surfactant; and,

(ii) from 0.01 to 20.0 wt%, preferably 0.2 to 6wt%, of a dye polymer. In another aspect the present invention provides a domestic method of treating a textile, the method comprising the steps of:

(i) treating a textile with an aqueous solution of the dye polymer as, the aqueous solution comprising from 100 ppb to 5000 ppm, of the dye polymer; and, from 0.0 g/L to 3 g/L,, preferably 0.2 g/L to 3 g/L, of a surfactant; and,

(ii) optionally rinsing and drying the textile.

DETAILED DESCRIPTION

The dye-polymers show very little staining to fabric when neat detergent product is applied to fabric.

The Dye Polymer

The dye polymer may be any colour, allowing a variety of hues to be given to fabric.

The dye polymer is preferably blue or violet in colour. In this regard, a blue or violet colour is provided to the cloth to give a hue angle of 230 to 345, more preferably 265 to 330, most preferably 270 to 300. The cloth used is white bleached non-mercerised woven cotton sheeting.

The dye polymer may be formed by reacting a reactive dye with a polyvinyl alcohol. The reaction is preferably conducted in an aqueous solution. The reactive dye is tethered to the polyvinyl alcohol by a covalent bond. The dye polymer is a polyvinylalcohol polymer where at least one of the OH groups of the polyvinylalcohol polymer has been reacted with the reactive group of a reactive dye so that the chromophore of the reactive dye is covalently bound (tethered) to the polyvinylalcohol polymer.

Preferably the weight average molecular weight of the dye polymer is from 1000 to 2000000, more preferably 20000 to 200000.

Where exact formula cannot be determined, the molecular weights are

determined by dynamic light scattering using a Zetasizer Nano (Malvern). The reactive dye is preferably selected from: reactive blue; reactive black; reactive red; and, reactive violet dyes. Preferably, the reactive dyes are selected from mixtures of: reactive black and reactive red; reactive blue and reactive red;

reactive black and reactive violet; and, reactive blue and reactive violet, wherein the number of blue or black dye moieties is in excess of the red or violet dye moieties. Preferably, the reactive dye is negatively charged and is selected from a chromophore selected from the group comprising of: azo; anthraquinone;

phthalocyanine; and, triphendioxazine.

When polyvinylalcohol is referred to as being covalently bound to a reactive dye one skilled in the art will understand that the reactive group is no longer present in the dye polymer. This is exemplified below for three reactive groups:

O HO— polymer 0 Opolymer

II H₂ H₂ II II H₂ I

dye— S— C -C -OS0₃Na dye— S— C=CH₂ * dye— S— C -CH₂

alkali II H alkali

O

F Opolymer

N- ,_x HO— polymer N

dye— N *~ dye- N

alkali

NHP NHPh

A hydrolysed reactive dyes is one in which the reactive groups has reacted with the hydroxide anion, HO^", rather than the polymer. The composition of the invention comprise less than 100ppm of hydrolysed reactive dye per l OOOOppm of dye polymer., more preferably less than 50ppm, most preferably less than 5ppm. Most preferably hydrolysed reactive dyes are not present in the composition. Such dyes may be removed by dialysis or careful control of the reactions conditions. Polvvinylalcohol

A polvvinylalcohol is a polymer of formula:

Polyvinyl alcohols may be made by hydrolysis of polyvinyl acetate. In partially hydrolysed polyvinylalcohols the polymer contains vinyl alcohol and vinyl acetate units. Preferably partially hydrolysed grades are used where the molar vinyl alcohol content is greater than the molar vinyl acetate contents. More preferably the polymer is 75 to 95 mole % hydrolyzed, most preferably 85 to 90 mole % hydrolyzed.

Reactive Dyes

Reactive dyes are described in Industrial Dyes (K. Hunger ed, Wiley VCH 2003). Many Reactive dyes are listed in the colour index (Society of Dyers and Colourists and American Association of Textile Chemists and Colorists). Reactive dyes consist of a dye chromophore covalently bound to a reactive group. Reactive groups react with hydroxyl groups to form a covalent bound, preferably by a substitution or addition reaction.

Reactive yellow and reactive Orange dyes are preferably chosen from mono-azo and bis-azo compounds, most preferably mono-azo.

Blue and violet dye chromophores are preferably selected from anthraquinone, bis-azo, triphenodioxazine, and phthalocyanine, more preferably anthraquinone, bis-azo, and triphenodioxazine, most preferably bis-azo and triphenodioxazine.

Red and violet reactive dyes may be mixed with the blue and violet reactive dyes to provide the correct hue. Reactive red dye chromophores are preferably selected from mono and bis-azo dyes. To avoid differential build up on multiple treatments, if more than one colour is present, for example a reactive red and a reactive blue, they are preferably bound to the same polymer backbone. A preferred blue bis-azo dye is of the form:

Where one or both of the A and B rings are substituted by a reactive group.

The A and B rings may be further substituted by sulphonate groups (SOsNa).

The A and B rings may be further substituted with suitable uncharged organic groups, preferably with a molecular weight lower than 200. Preferred groups are -

A preferred blue anthraquinone dye is of the form:

where the C ring is substituted by a reactive group. The dye may be further substituted with sulphonate groups (SOsNa) and suitable uncharged organic groups, preferably with a molecular weight lower than 200. Preferred uncharged organic groups are-CH₃, -C2H5, and -OCH3.

A preferred triphenodioxazine dye is of the form:

Where the D and E rings are substituted by a reactive groups. Preferably the D and E rings are further substituted by sulphonate groups (SOsNa).

A preferred red azo dye is of the form

Where the F ring is optionally extended to form a naphthyl group are optionally substituted groups selected from sulphonate groups (SOsNa) and a reactive group.

G is selected from a reactive group, H, or alky group. A reactive group must be present on the dye.

With the exception of copper phthalocyanine dyes, metal complex dyes are not preferred. Reactive groups are preferably selected from heterocyclic reactive groups and, a sulfooxyethylsulfonyl reactive group (-S0₂CH₂CH₂OS0₃Na).

The heterocyclic reactive groups are preferably nitrogen contains aromatic rings bound to a halogen or an ammonium group, which react with NH₂ or NH groups of the polymers to form a covalent bond. The halogen is preferred. More preferred heterocylic reactive groups are dichlorotriazinyl, difluorochloropyrimidine, monofluorotrazinyl, monofluorochlorotrazinyl, dichloroquinoxahne, difluorotriazine, monochlorotriazinyl, and trichloropyrimidine.

The reactive group may be linked to the dye chromophore via an alkyl spacer for example: dye-NH-CH₂CH₂-reactive group.

Especially preferred heterocylic reactive groups are:

wherein Ri is selected from H or alkyl, preferably H.

X is selected from F or CI.

When X = CI, Z₁ is selected from -CI, -NR₂R₃, -OR₂, -S0₃Na

When X = F, Z is selected from -NR₂R₃

R₂ and R₃ are independently selected from H, alkyl and aryl groups. Aryl groups are preferably phenyl and are preferably substituted by -S0₃Na or - S0₂CH₂CH₂OS0₃Na. Alkyl groups are preferably methyl or ethyl.

The phenyl groups may be further substituted with suitable uncharged organic groups, preferably with a molecular weight lower than 200. Preferred groups include -CH₃, -C₂H₅, and -OCH₃. The alkyl groups may be further substituted with suitable uncharged organic groups, preferably with a molecular weight lower than 200. Preferred groups include -CH₃, -C₂H₅, -OH, -OCH₃, -OC₂H₄OH. Most preferred heterocylic reactive groups are selected from

and H H Where n = 1 or 2, preferably 1 .

Preferably the reactive dye contains more than one reactive group, preferably two or three. An untethered hydrolysed reactive dyes is one in which the reactive groups have reacted with the hydroxide anion, HO^", rather than the polymer. Preferably the composition contains less than 100ppm of untethered hydrolysed reactive dye per l OOOOppm dye-polymer, more preferably less than 20ppm. Most preferably untethered hydrolysed reactive dyes are not present in the composition. Such dyes may be removed by dialysis or careful control of the reaction conditions.

Where a reactive dye has been tethered to the polymer to form one or more covalent bonds and has a hydrolysed reactive group this is not classed as an unteathered reactive dye.

Examples of reactive dyes are reactive blue 2, reactive blue 4, reactive blue 5, reactive blue 7, reactive blue 15, reactive blue 19, reactive blue 27, reactive blue29, reactive blue 49, reactive blue 50, reactive blue 74, reactive blue 94, reactive blue 246, reactive blue 247, reactive blue 247, reactive blue 166, reactive blue 109, reactive blue 187, reactive blue 213, reactive blue 225, reactive blue 238, reactive blue 256. Further structures are exemplified below:

SURFACTANT

The composition comprises between 2 to 70 wt % of a surfactant, most preferably 10 to 30 wt %. 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 C18 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 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 preferred anionic detergent compounds are sodium C11 to C15 alkyl benzene sulphonates and sodium C12 to C18 alkyl sulphates. 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. 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 Ci6 to Ci8 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 formulation is a fabric conditioner. To facilitate ease of use the formulation is preferably packed in pack sizes of 0.5 to 5kg. To reduce moisture ingress, the formulation is preferably packs in laminated cardboard packs or sealed plastic bags.

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

l ₊

R1 -N-R3 X

I

R4 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.

A detergent composition according to claim 1 in which the ratio of (ii) cationic material to (iv) anionic surfactant is at least 2: 1 .

Other suitable quaternary ammonium compounds are disclosed in EP 0 239 910 (Proctor and Gamble).

It is preferred if the ratio of cationic to nonionic surfactant is from 1 : 100 to 50:50, more preferably 1 :50 to 20:50.

The cationic compound may be present from 1 .5 wt % to 50 wt % of the total weight of the composition. Preferably the cationic compound may be present from 2 wt % to 25 wt %, a more preferred composition range is from 5 wt % to 20 wt %.

The softening material is preferably present in an amount of from 2 to 60% by weight of the total composition, more preferably from 2 to 40%, most preferably from 3 to 30% by weight. The composition optionally comprises a silicone.

Builders or Complexing agents: Builder materials may be selected from 1 ) calcium seguestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.

Examples of calcium seguestrant builder materials include alkali metal

polyphosphates, such as sodium tripolyphosphate and organic seguestrants, 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 best 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. 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. AI₂O₃. 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 S 1O2 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 the laundry detergent formulation is carbonate built.

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 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. 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 formulation.

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 (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™, 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™, 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).

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.

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.

Experimental Example 1

5g of Polyvinyl alcohol (Mowiol^® 4-98, Mw~27000, ex Aldrich) was dissolved in 50g of water with 10g of NaCI and 10g of soda ash. The solution was heated to 323K and 0.5g of anthraquinone dye reactive blue 19 added and stirred for 45 minutes then cooled. The water was removed by evaporation and the coloured dye-polymer particles separated. The small levels of residual hydrolysed dye were removed by decantation. The so-formed polymer was code PVA-RB19.

The synthesis was repeated with the azo dye Reactive Red 239. The so-formed polymer was code PVA-RR239.

Example 2

The following liquid detergent formulations were created:

% composition

Composition 1 Composition 2 Composition 3 reference

1 ,2-propanediol 8.6 8.6 8.6

Triethanolamine 3.1 3.1 3.1

Glycerol 4.8 4.8 4.8

C14-C15 alkyl 7- 19.2 19.2 19.2

ethoxylate

Linear alkyl benzene 12.8 12.8 12.8

sulfonate

C12-C18 fatty acid 4.6 4.6 4.6

Sodium C12-C14 6.4 6.4 6.4

alkyl ethoxy 3 sulfate

PVA-RB19 0 3.5 3.5

PVA-RR239 0 0 1.7

Sequesterant¹ 0.5 0.5 0.5

Perfume 1.4 1.4 1.4

Fluoerscer² 0.1 0.1 0.1

NaOH to pH 8.3

water balance balance balance ¹ Dequest 2066

² Tinopal 5BMGX

PVA-RB19 and PVA-RR239 are the polymers synthesised in example 1 .

The formulation were used to wash a mixture of white fabrics: woven cotton, knitted cotton, woven polycotton, micro-fibre polyester, knitted nylon-elastane at a Liquor to cloth ratio of 10: 1 in a linitester. Demineralised water was used and each wash lasted 30 minutes and was followed by a running rinse. The formulations were used at 2.0g/L.

After the wash the white clothes were removed, dried and the colour measured using a relflectometer and expressed as the CIE L^*a^*b^* values. A Ab value was calculated: Ab = b(control without polymer) - b(wash with polymer)

A +ve value indicates a blueing of the fabric compared to the control. Bluer fabrics appear whiter to the eye.

The results are shown in the table below:

The formulation containing the dye polymer increases the whiteness of the polyester and cotton fabrics.

Claims

We Claim:

1 . A laundry treatment composition comprising:

(i) from 2 to 70 wt% of a surfactant; and,

(ii) from 0.01 to 20.0 wt% of a dye polymer, the dye polymer obtainable by reacting a reactive dye with a polyvinyl alcohol.

2. A laundry treatment composition according to claim 1 , wherein the reactive dye is selected from: reactive blue; reactive black; reactive red; and, reactive violet dyes.

3. A laundry treatment composition according to claim 2, wherein the reactive dyes are selected from mixtures of: reactive black and reactive red; reactive blue and reactive red; reactive black and reactive violet; and, reactive blue and reactive violet, wherein the number of blue or black dye moieties is in excess of the red or violet dye moieties.

4. A laundry treatment composition according to any one of the preceding

claims, wherein: the reactive dye is negatively charged and is selected from a chromophore selected from the group comprising of: azo; anthraquinone; phthalocyanine; and, triphendioxazine.

5. A laundry treatment composition according to any one of the preceding

claims, wherein the reactive dye has reactive group selected from the group comprising: dichlorotriazinyl; difluorochloropyrimidine; monofluorotrazinyl; dichloroquinoxaline; vinylsulfone; difluorotriazine; monochlorotriazinyl;

bromoacrlyamide; and, trichloropyrimidine.

6. A laundry treatment composition according to any preceding claim, wherein the weight average molecular weight of the dye polymer is from 1000 to 2 000 000.

7. A laundry treatment composition according to claim 6, wherein the average molecular weight of the dye polymer is from 20 000 to 200 000.

8. A laundry treatment composition according to any preceding claim, wherein the molar vinyl alcohol content of the polyvinyl alcohol is greater than the molar vinyl acetate content.

9. A laundry treatment composition according to claim 8 wherein in the

polyvinyl alcohol contains from 75 to 95 mole % vinyl alcohol units and from 5 to 25 mol % acetate units.

10. A domestic method of treating a textile, the method comprising the steps of:

(i) treating a textile with an aqueous solution of the laundry treatment composition as defined in any one of claims 1 to 9, the aqueous solution comprising from 100 ppb to 5000 ppm, of the dye polymer; and, from 0.0 g/L to 3 g/L, preferably 0.2 g/L to 3 g/L, of a surfactant; and,

(ii) optionally rinsing and drying the textile.

1 1 . A domestic method of treating a textile according to claim 10, wherein the aqueous solution comprises a fluorescer in the range from 0.0001 g/l to 0.1 g/l.