WO2015074821A1

WO2015074821A1 - Hair colouring composition

Info

Publication number: WO2015074821A1
Application number: PCT/EP2014/072724
Authority: WO
Inventors: Karl John Hunter
Original assignee: Unilever Plc; Unilever N.V.; Conopco, Inc., D/B/A Unilever
Priority date: 2013-11-21
Filing date: 2014-10-23
Publication date: 2015-05-28

Abstract

The invention relates to a hair colour composition. The dyeing of hair using oxidative dyes (including polyphenols) oxidised by atmospheric oxygen (from the air or an air foam) and catalysed by the enzyme laccase is known. As laccase uses atmospheric oxygen to oxidise dyes, its efficiency is limited by both the availability of dissolved oxygen in the aqueous solution in which the enzyme and dyes are applied and also the diffusion of oxygen from air into the solution as the dissolved oxygen is depleted by the reaction. The inventors have observed that significant colour changes are observed over 30 minutes with selected polyphenols when treated with laccase in the presence of oxygen foams. Thus in a first aspect of the invention, a hair colour composition is provided, the hair colour composition comprising: (a) A polyphenol selected from the group consisting of catechin, epicatechin and a mixture thereof; (b) A laccase; (c) A surfactant; and (d) Pure oxygen or an oxygen generator; wherein the pure oxygen or oxygen generated by the oxygen generator is in the form of foam; and wherein the composition has a pH of 4.5 to 7.0, preferably less than or equal to 6.0.

Description

HAIR COLOURING COMPOSITION

The invention relates to a hair colour composition. Takada et al. (J. of Oleo Sci., 52, 10, 557-563 (2003)) describes a hair colour composition comprising laccase and catechin at pH 5.

WO 2012/084568 (Unilever et al) discloses that hair colourant formulations fall into three main categories designated permanent, semi-permanent and temporary. Permanent hair colourant formulations are oxidative dye systems and generally contain paraphenylene diamine (PPD) and resorcinol, both of which have been shown to cause sensitisation and mutagenicity. Furthermore, severe oxidising conditions are required which in themselves cause skin irritation and sensitization as well as hair fibre damage. The inventive method addresses the aforementioned disadvantages by providing a method of colouring hair fibres, the method comprising the step of applying a hair colour composition, the hair colour composition comprising: (a) (+)-catechin, (-)-catechin, (+)-epicatechin, (-)-epicatechin or mixtures thereof; (b) a hydrogen peroxide generator or hydrogen peroxide; and (c) a peroxidase and; wherein the composition has a pH of 4.5 to 7.0, preferably less than or equal to 6.0.

WO 99/15137 (Novo Nordisk A S) discloses an enzymatic foam composition adapted for dyeing keratinous fibres comprising: 1 ) at least one oxidation enzyme, typically an oxidoreductase selected from laccases and related enzymes, oxidases and peroxidases; 2) at least one foaming agent; 3) at least one dye precursor. Permanent hair dyes are very resistant to sunlight, shampooing and other hair treatments and need only be refreshed about once a month as new hair grows out. With these dyeing systems, the dyes are created directly in and on the hair. Small aromatic dye precursors (e.g. p-phenylene- diamine and o-aminophenol) penetrate deep into the hair, where they are oxidised by an oxidising agent to coloured polymeric compounds. These coloured compounds are larger than the dye precursors and cannot be washed out of the hair. Traditionally, hydrogen peroxide has been used as the oxidising agent and also as a bleaching agent. The use of hydrogen peroxide in dye compositions has some disadvantages, however, as it damages the hair. Further, oxidative dyeing often demands high pH (normally around pH 9-10), which also inflicts damage on the hair and irritation to the scalp. To overcome the disadvantages of using hydrogen peroxide it has been suggested to use oxidation enzymes to replace hydrogen peroxide. The problem arises, however, when using such oxidation enzymes to dye keratinous fibrous such as human hair, that oxygen is the limiting factor in the enzymatic reaction, since the reaction proceeds relatively quickly, especially for laccases. This is especially the case with compositions having a relatively high viscosity, such as gels and mousses. As a result, the reaction proceeds extensively at the parts of the hair lying at the hair/air interface, since the laccase at the interface has access to an adequate supply of oxygen from the air. In contrast, the major portion of the hair lying below this interface, i.e. between the air and the scalp, does not have access to adequate oxygen for the enzymatic oxidation to proceed after exhaustion of oxygen present in the reaction media, whereby the reaction proceeds slower (or comes to a complete stop) and this part of the hair is dyed relatively little compared to the surface hair fibres. Hair dyeing compositions comprising an oxidation enzyme and a foaming agent result in improved uniformity of the dyeing effect, in particular an improved dyeing of the parts of the hair removed from the air interface. Examples include laccase, sodium dodecyl sulphate and as the dye precursor p-phenylene-diamine or o-aminophenol. However catechin is included elsewhere in a long list of suitable dye precursors.

EP 0 958 806 A (Novo Nordisk A S) discloses that oxidation-type hair dye compositions generally comprises an oxidation dye and an oxidizing agent, which are reacted with each other just before use and applied to hair to be dyed therewith. Heretofore, hydrogen peroxide has been essentially used as the oxidizing agent. However, it is known that hydrogen peroxide causes damage to hair, and most consumers are dissatisfied at their hair damaged thereby. A technique of using oxidase in place of hydrogen peroxide has been proposed. The case of using laccase does not require using hydrogen peroxide in the hair dye system, and is expected to cause little damage to hair. However, in laccase- containing hair dye compositions, the laccase does not react well to the intended degree owing to the fluidity and the liquid properties of the compositions. A hair dye composition is provided which can effectively dye hair, the hair dye composition comprising laccase and a developer along with a surfactant and/or a water-soluble polymer substance. Example 1 describes a foam composition comprising p-phenylene-diamine, laccase and a cationated cellulose at pH 6. Example 2 describes a hair mousse composition comprising toluene-2, 5-diamine, p-aminophenol, m-aminophenol, laccase and N-cocoyl-L-glutamate triethanolamine. Example 3 describes a hair foam composition comprising p-phenylene- diamine, laccase and polyoxyethylene stearyl ether. Catechin is also mentioned elsewhere as a suitable developer. Summary of the invention

Thus dyeing of hair using oxidative dyes (including polyphenols) oxidised by atmospheric oxygen (from the air or an air foam) and catalysed by the enzyme laccase is known. As laccase uses atmospheric oxygen to oxidise dyes, its efficiency is limited by both the availability of dissolved oxygen in the aqueous solution in which the enzyme and dyes are applied and also the diffusion of oxygen from air into the solution as the dissolved oxygen is depleted by the reaction. The inventors have observed that significant colour changes are observed over 30 minutes with selected polyphenols when treated with laccase in the presence of oxygen foams.

Thus in a first aspect of the invention, a hair colour composition is provided, the hair colour composition comprising:

(a) A polyphenol selected from the group consisting of catechin, epicatechin and a mixture thereof;

(b) A laccase;

(c) A surfactant; and

(d) Pure oxygen or an oxygen generator;

wherein the pure oxygen or oxygen generated by the oxygen generator is in the form of foam; and

wherein the composition has a pH of 4.5 to 7.0, preferably less than or equal to 6.0.

In a second aspect of the invention, a method for colouring hair fibres is provided, the method comprising the steps of:

(a) Treating hair fibres with the hair colour composition of the first aspect of the invention; and then

(b) Washing the treated hair fibres;

wherein when the hair colour composition is in the form of a two part composition wherein a first part comprises hydrogen peroxide, and a second part comprises catalase or a metal catalyst, the first and second parts are combined either before or during the step of treating the hair fibres.

The term "oxygen generator" means, for the purposes of this specification, anything which generates or produces oxygen. Detailed description of the invention

A first aspect of the invention, a hair colour composition is provided, the hair colour composition comprising:

(b) A laccase;

(c) A surfactant; and

(d) Pure oxygen or an oxygen generator;

Preferably the polyphenols are selected from the group consisting of (+)-catechin, (-)- epicatchin and mixtures thereof. Typically the hair colour composition comprises 2-60, 5- 30, 10-20 mM polyphenol.

The laccase can be selected from the group consisting of cyanobacteria of the genuses Leptolyngbya, Oscillatoria and Phormidium; bacteria of the genuses Bacillus, Escherichia, Pseudomonas, Shigella, Sinorhizobium, Stenotrophomonas, Streptomyces, and Thermus; fungi of the genuses Agaricus, Agrocybe, Albatrellus, Athelia, Botryotinia, Cantharellus, Ceriporiopsis, Cerrena, Chaetomium, Cladosporium, Clitocybe, Coniothyrium, Coprinopsis, Coriolisimus, Coriolopsis, Cortinarius, Cryptococcus, Cyathus, Daedalea, Emericella, Fomes, Fomitella, Fusarium, Ganoderma, Hypocrea, Inocybe, Lactarius, Lentinula, Lepiota, Lepista, Leptonia, Loweporus, Lyophyllum, Magnaporthe, Marasmius, Melanocarpus, Myceliophthora, Myriogonium, Myrothecium, Neurospora, Panus, Paraconiothyrium, Parasola, Peltigera, Penicillium, Peniophora, Perenniporia, Phellinus, Phlebia, Phoma, Pleurotus, Podospora, Polyporus, Pycnoporus, Ramaria, Rhizoctonia, Rigidoporus, Russula, Scytalidium, Solorina, Steccherinum, Trametes, Tricholoma, Trichophyton, Volvariella; plants of the genuses Acer, Mangifera, Pistacia, Pleiogynium, Populus, Prunus, Rhus, Schinus and Toxicodendron; and mixtures thereof. Typically the hair colour composition comprises 2-20, preferably 4-16, most preferably 8-12 U.ml^"1 laccase.

The surfactant can be selected from the group consisting of non-ionic, anionic, cationic, amphoteric, zwitterionic and mixtures thereof. When the surfactant is a non-ionic surfactant, the non-ionic surfactant can be selected from the group consisting of polyethylene glycol ethers, fatty alcohols, fatty acid amides, fatty acid glucosides, fatty acid sorbitans, alkyl ethers, monoglycerides, polysorbates and mixtures thereof. In particular, the non-ionic surfactants can be selected from the group consisting of polyethylene glycol ethers such as Cetomacrogol 1000, narrow range ethoxylates, octaethylene glycol monododecyl ether and pentaethylene glycol monododecyl ether; fatty alcohols such as cetostearyl alcohol, cetyl alcohol, oleyl alcohol and stearyl alcohol; fatty acid amides such as cocamide DEA and cocamide MEA; fatty acid glucosides such as lauryl glucoside and octyl glucoside; fatty acid sorbitans such as sorbitan monostearate and sorbitan tristearate; alkyl ethers such as decyl glucoside, octylphenoxypolyethoxyethanol, isoceteth-20, nonylphenol ethoxylates, nonyl phenoxypolyethoxylethanol, Poloxamer and polyglycerol polyricinoleate; monoglycerides such as monolaurin; and polysorbates such as Polysorbate 20 and Polysorbate 80.

Anionic surfactants can be selected from the group consisting of alkyl suphate salts such as ammonium lauryl sulphate, dioctyl sodium sulphosuccinate, potassium lauryl sulphate, sodium dodecyl sulphate and sodium laureth sulphate; alkylsulphonate salts such as sodium dodecylbenzenesulphonate, perfluorobutanesulphonic acid and perfluorooctanesulphonic acid; perfluoro-fatty acids such as perfluorononanoic acid and perfluorooctanoic acid; alkylamino acid salts such as sodium lauroyl sarcosinate; and organic acid salts such as sodium stearate.

Cationic surfactants can be quaternary ammonium alkyl salts such as benzalkonium chloride, benzethonium chloride, cetrimonium bromide, cetrimonium chloride, dimethyldioctadecylammonium chloride, and lauryl methyl gluceth-10 hydroxypropyl dimonium chloride, tetramethylammonium hydroxide.

Amphoteric or zwitterionic surfactants can be selected from the group consisting of 3-[(3- cholamidopropyl)dimethylammonio]-1 -propanesulfonate (CHAPS), cocamidopropyl betaine, cocamidopropyl hydroxysultaine, hydroxysultaine, lecithin and proteins.

A preferred surfactant is Triton X-100 (an octyl phenol ethoxylate). Typically the hair colour composition comprises 0.1 -10, 0.1 -5, 0.1 -2 % w/w surfactant. In one embodiment, the oxygen generator is a combination of hydrogen peroxide and catalase. Catalase decomposes hydrogen peroxide to oxygen and water. The oxygen generator may also be a combination of hydrogen peroxide and a metal catalyst. Preferably the metal catalyst is selected from the group consisting of ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, gold, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, tantalum, tungsten, and mixtures thereof. More preferably, the metal catalyst is selected from the group consisting of ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, gold, and mixtures thereof. Typically the hair colour composition comprises 0.03- 0.5, 0.1 -0.5, 0.2-0.4 % w/w hydrogen peroxide. Typically the hair colour composition comprises 0.2-2, preferably 0.8-2, most preferably 1 .2-2 mg.ml^"1 catalase. Typically the hair colour composition comprises 0.1 -10, preferably 0.5-5, most preferably 1 -2 % w/w metal catalyst. The hair colour composition can be in the form of a two part composition, wherein a first part comprises hydrogen peroxide, and a second part comprises catalase or a metal catalyst.

The hair colour composition may take the form of a shampoo or hair conditioning composition, or a 2-in-1 conditioning shampoo composition.

Shampoo Compositions

Shampoo compositions will nearly always comprise a cleansing surfactant component in an aqueous base.

The cleansing surfactant may consist of a single surfactant, usually an anionic surfactant (to provide foam) such as sodium lauryl ether sulphate, or more commonly a mixture of sodium lauryl ether sulphate with a co-surfactant to provide mildness. The most preferred co-surfactant is cocoamidopropyl betaine.

The total amount of cleansing surfactant and co-surfactant in a shampoo composition may be from 1 to 50, preferably from 2 to 40, more preferably from 10 to 25 % w/w. Compositions comprising more than 25 % w/w cleansing surfactant a and co-surfactant re commonly considered concentrated shampoos. Examples of suitable anionic cleansing surfactants are the alkyi sulphates, alkyi ether sulphates, alkaryl sulphonates, alkanoyl isethionates, alkyi succinates, alkyi sulphosuccinates, alkyi ether sulphosuccinates, N-alkyl sarcosinates, alkyi phosphates, alkyi ether phosphates, and alkyi ether carboxylic acids and salts thereof, especially their sodium, magnesium, ammonium and mono-, di- and triethanolamine salts. The alkyi and acyl groups generally contain from 8 to 18, preferably from 10 to 16 carbon atoms and may be unsaturated. The alkyi ether sulphates, alkyi ether sulphosuccinates, alkyi ether phosphates and alkyi ether carboxylic acids and salts thereof may contain from 1 to 20 ethylene oxide or propylene oxide units per molecule.

Specific anionic cleansing surfactants for use in shampoo compositions of the invention include sodium oleyl succinate, ammonium lauryl sulphosuccinate, sodium lauryl sulphate, sodium lauryl ether sulphate, sodium lauryl ether sulphosuccinate, ammonium lauryl sulphate, ammonium lauryl ether sulphate, sodium dodecylbenzene sulphonate, triethanolamine dodecylbenzene sulphonate, sodium cocoyl isethionate, sodium lauryl isethionate, lauryl ether carboxylic acid and sodium N-lauryl sarcosinate.

Preferred anionic cleansing surfactants are selected from sodium lauryl sulphate and sodium lauryl ether sulphate(n)EO, (where n = 1 to 3); more preferably sodium lauryl ether sulphate(n)EO, (where n = 1 to 3); most preferably sodium lauryl ether sulphate(n)EO where n = 1.

The total amount of anionic cleansing surfactant in shampoo compositions of the invention generally ranges from 0.5 to 45, more preferably from 1.5 to 20 % w/w of the composition.

Preferably a shampoo composition of the invention further comprises a suspending agent. Suitable suspending agents are selected from polyacrylic acids, cross-linked polymers of acrylic acid, copolymers of acrylic acid with a hydrophobic monomer, copolymers of carboxylic acid-containing monomers and acrylic esters, cross-linked copolymers of acrylic acid and acrylate esters, heteropolysaccharide gums and crystalline long chain acyl derivatives. The long chain acyl derivative is desirably selected from ethylene glycol stearate, alkanolamides of fatty acids having from 16 to 22 carbon atoms and mixtures thereof. Ethylene glycol distearate and polyethylene glycol 3 distearate are preferred long chain acyl derivatives, since these impart pearlescence to the composition. Polyacrylic acid is available commercially as Carbopol 420, Carbopol 488 or Carbopol 493. Polymers of acrylic acid cross-linked with a polyfunctional agent may also be used; they are available commercially as Carbopol 910, Carbopol 934, Carbopol 941 and Carbopol 980. An example of a suitable copolymer of a carboxylic acid containing monomer and acrylic acid esters is Carbopol 1342. Carbopol 980 is the commonly used suspending agent though there is a growing desire to find an alternative. All Carbopol (trademark) materials are available from Goodrich.

Suitable cross-linked polymers of acrylic acid and acrylate esters are Pemulen TR1 or Pemulen TR2. A suitable heteropolysaccharide gum is xanthan gum.

Mixtures of any of the above suspending agents may be used. Preferred is a mixture of cross-linked polymer of acrylic acid and crystalline long chain acyl derivative.

Suspending agent will generally be present in a shampoo composition of the invention at levels of from 0.1 to 10, preferably from 0.5 to 6, more preferably from 0.9 to 4 % w/w of the composition. Generally such suspending agents are present at around 2 % w/w of the composition.

Shampoo compositions of the invention are generally aqueous, i.e. they have water or an aqueous solution or a lyotropic liquid crystalline phase as their major component. Suitably, the composition will comprise from 50 to 98, preferably from 60 to 90 % w/w of the composition.

Typically, shampoo compositions have a pH of around 5.5.

The shampoo compositions of the invention might also contain conditioning agents. Conditioning agents fall into three classes:

silicones (and cationic deposition polymers to assist in silicone deposition) cationic surfactants

· non-silicone oils

Where silicones are included, the composition is likely to also contain a cationic deposition polymer for enhancing deposition of the silicone. Further, a silicone-containing composition is likely to be lamellar as opposed to isotropic. Isotropic compositions do not deposit silicone effectively. Suitable silicones include polydiorganosiloxanes, in particular polydimethylsiloxanes which have the CTFA designation dimethicone. Also suitable for use in the compositions of the invention are polydimethyl siloxanes having hydroxyl end groups, which have the CTFA designation dimethiconol. A further preferred class of silicones for inclusion in shampoos and conditioners of the invention are amino functional silicones. By "amino functional silicone" is meant a silicone containing at least one primary, secondary or tertiary amine group, or a quaternary ammonium group. Examples of suitable amino functional silicones include polysiloxanes having the CTFA designation "amodimethicone". The total amount of silicone is preferably from 0.01 to 10, more preferably from 0.1 to 5, most preferably 0.5 to 3 % w/w of the composition of the invention.

Cationic deposition polymers are used to deposit the silicone to the hair surface and hence enhance performance.

Suitable cationic polymers may be homopolymers which are cationically substituted or may be formed from two or more types of monomers. The weight average (Mw) molecular weight of the polymers will generally be between 100 000 and 2 million Daltons. The polymers will have cationic nitrogen containing groups such as quaternary ammonium or protonated amino groups, or a mixture thereof. If the molecular weight of the polymer is too low, then the conditioning effect is poor. If too high, then there may be problems of high extensional viscosity leading to stringiness of the composition when it is poured.

The cationic nitrogen-containing group will generally be present as a substituent on a fraction of the total monomer units of the cationic polymer. Thus when the polymer is not a homopolymer it can contain spacer non-cationic monomer units. The ratio of the cationic to non-cationic monomer units is selected to give polymers having a cationic charge density in the required range, which is generally from 0.2 to 3.0 meq/gm. The cationic charge density of the polymer is suitably determined via the Kjeldahl method as described in the US Pharmacopoeia under chemical tests for nitrogen determination.

Suitable cationic polymers include, for example, copolymers of vinyl monomers having cationic amine or quaternary ammonium functionalities with water soluble spacer monomers such as (meth)acrylamide, alkyl and dialkyl (meth)acrylamides, alkyl (meth)acrylate, vinyl caprolactone and vinyl pyrrolidine. The alkyl and dialkyl substituted monomers preferably have C1 -C7 alkyl groups, more preferably C1 -3 alkyl groups. Other suitable spacers include vinyl esters, vinyl alcohol, maleic anhydride, propylene glycol and ethylene glycol. The cationic amines can be primary, secondary or tertiary amines, depending upon the particular species and the pH of the composition. In general secondary and tertiary amines, especially tertiary, are preferred.

The cationic polymers can comprise mixtures of monomer units derived from amine- and/or quaternary ammonium-substituted monomer and/or compatible spacer monomers.

Suitable cationic polymers include, for example cationic diallyl quaternary ammonium- containing polymers including, for example, dimethyldiallylammonium chloride homopolymer and copolymers of acrylamide and dimethyldiallylammonium chloride, referred to in the industry (CTFA) as Polyquaternium 6 and Polyquaternium 7, respectively; mineral acid salts of amino-alkyl esters of homo-and co-polymers of unsaturated carboxylic acids having from 3 to 5 carbon atoms; and cationic polyacrylamides. Other cationic polymers that can be used include cationic polysaccharide polymers, such as cationic cellulose derivatives, cationic starch derivatives, and cationic guar gum derivatives.

Cationic cellulose derivatives include the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium-substituted epoxide, referred to in the industry (CTFA) as Polyquaternium 24. These materials are available from the Amerchol Corporation, for instance under the tradename Polymer LM-200. Other suitable cationic polysaccharide polymers include quaternary nitrogen-containing cellulose ethers, and copolymers of etherified cellulose and starch. A particularly suitable type of cationic polysaccharide polymer that can be used is a cationic guar gum derivative, such as guar hydroxypropyltrimethylammonium chloride (commercially available from Rhodia in their JAGUAR trademark series). Examples of such materials are JAGUAR C13S, JAGUAR C14, JAGUAR C15, JAGUAR C17 and JAGUAR C16 Jaguar CHT and JAGUAR C162.

Mixtures of any of the above cationic polymers may be used. Cationic polymer will generally be present in a shampoo composition of the invention at levels of from 0.01 to 5, preferably from 0.05 to 1 , more preferably from 0.08 to 0.5 % w/w of the weight of the compositions of the invention. Cationic surfactants may be used in 2-in-1 shampoos to provide a conditioning benefit. However, since a shampoo composition is likely to also comprise anionic cleansing surfactants, the use of cationic surfactants is limited to compositions where the cationic surfactant is separated from the anionic phase by way of a stable conditioning gel phase made separately from the rest of the formulation and then incorporated afterwards.

A fatty alcohol is nearly always included in a conditioning composition and often included in 2-in-1 shampoos. Cetearyl alcohol is one of the preferred examples. Fibre actives are provided to repair or coat the hair fibres. Examples are trehalose (a disaccharide), adipic acid (dicarboxylic acid) and gluconolactone.

There are two classes of anti-dandruff active, namely the azoles and the pyrithiones. Both are active against the target fungi malassezia spp. The azoles include ketoconazole and climbazole which are fat soluble actives. The pyrithiones include zinc pyrithione (ZPT) which is insoluble and delivered as a particle to the scalp. Preferably, the anti-dandruff active is present at from 0.01 to 5, more preferably from 0.1 to 2.5 % w/w of the composition of the invention. Hair Conditioning Compositions

The compositions of the invention may also be hair conditioning compositions (also known as conditioners). Hair conditioning compositions may also be left on the head, i.e. not rinsed off after application. The main ingredients in a hair conditioner are the conditioning actives described above, the main actives being a cationic surfactant (e.g. behenyltrimmonium chloride), a silicone conditioning agent (e.g. aminosilicone (DC 7134)) and a non-silicone oil, and usually a fatty alcohol (e.g. cetearyl alcohol). Anti-dandruff actives may also be included in hair conditioning compositions of the invention.

Preferably, the cationic surfactants have the formula N+R1 R2R3R4 wherein R1 , R2, R3 and R4 are independently (C1 to C30) alkyl or benzyl. Preferably, one, two or three of R1 , R2, R3 and R4 are independently (C4 to C30) alkyl and the other R1 , R2, R3 and R4 group or groups are (C1 -C6) alkyl or benzyl. More preferably, one or two of R1 , R2, R3 and R4 are independently (C6 to C30) alkyl and the other R1 , R2, R3 and R4 groups are (C1 -C6) alkyl or benzyl groups. Optionally, the alkyl groups may comprise one or more ester (- OCO- or -COO-) and/or ether (-0-) linkages within the alkyl chain. Alkyl groups may optionally be substituted with one or more hydroxyl groups. Alkyl groups may be straight chain or branched and, for alkyl groups having 3 or more carbon atoms, cyclic. The alkyl groups may be saturated or may contain one or more carbon-carbon double bonds (e.g. oleyl). Alkyl groups are optionally ethoxylated on the alkyl chain with one or more ethyleneoxy groups.

Suitable cationic surfactants for use in conditioner compositions according to the invention include cetyltrimethylammonium chloride, behenyltrimethylammonium chloride, cetylpyridinium chloride, tetramethylammonium chloride, tetraethylammonium chloride, octyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octyldimethylbenzylammonium chloride, decyldimethylbenzylammonium chloride, stearyldimethylbenzylammonium chloride, didodecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, tallowtrimethylammonium chloride, dihydrogenated tallow dimethyl ammonium chloride (eg, Arquad 2HT/75 from Akzo Nobel), cocotrimethylammonium chloride, PEG-2-oleammonium chloride and the corresponding hydroxides thereof. Further suitable cationic surfactants include those materials having the CTFA designations Quaternium-5, Quaternium-31 and Quaternium-18. Mixtures of any of the foregoing materials may also be suitable. A particularly useful cationic surfactant for use in conditioners according to the invention is cetyltrimethylammonium chloride, available commercially, for example as GENAMIN CTAC, ex Hoechst Celanese. Another particularly useful cationic surfactant for use in conditioners according to the invention is behenyltrimethylammonium chloride, available commercially, for example as GENAMIN KDMP, ex Clariant. In conditioners of the invention, the level of cationic surfactant will generally range from 0.01 to 10, more preferably 0.05 to 7.5, most preferably 0.1 to 5 % by weight of the composition.

The compositions of the invention can contain emulsified droplets of a silicone condition agent, for enhancing conditioning performance as previously described.

Compositions according to the present invention may also comprise a dispersed, nonvolatile, water-insoluble, non-silicone oily conditioning agent. Preferably such non-silicone oily conditioning agents are present in the hair conditioning compositions of the invention. By "insoluble" is meant that the material is not soluble in water (distilled or equivalent) at a concentration of 0.1 % w/w at 25°C. Suitable non-silicone oils are selected from hydrocarbon oils, fatty esters and mixtures thereof.

Straight chain hydrocarbon oils will preferably contain from about 12 to about 30 carbon atoms. Also suitable are polymeric hydrocarbons of alkenyl monomers, such as C2-C6 alkenyl monomers. Specific examples of suitable hydrocarbon oils include paraffin oil, mineral oil, saturated and unsaturated dodecane, saturated and unsaturated tridecane, saturated and unsaturated tetradecane, saturated and unsaturated pentadecane, saturated and unsaturated hexadecane, and mixtures thereof. Branched-chain isomers of these compounds, as well as of higher chain length hydrocarbons, can also be used.

Suitable fatty esters are characterised by having at least 10 carbon atoms, and include esters with hydrocarbyl chains derived from fatty acids or alcohols, Monocarboxylic acid esters include esters of alcohols and/or acids of the formula R'COOR in which R' and R independently denote alkyl or alkenyl radicals and the sum of carbon atoms in R' and R is at least 10, preferably at least 20. Di- and trialkyl and alkenyl esters of carboxylic acids can also be used. Particularly preferred fatty esters are mono-, di- and triglycerides, more specifically the mono-, di-, and tri-esters of glycerol and long chain carboxylic acids such as C1 -C22 carboxylic acids. Preferred materials include cocoa butter, palm stearin, sunflower oil, soya bean oil and coconut oil.

The oily conditioning agent is suitably present at a level of from 0.05 to 10, preferably from 0.2 to 5, more preferably from about 0.5 to 3 % w/w of the composition of the invention. Hair conditioning compositions of the invention will typically also incorporate a fatty alcohol. The combined use of fatty alcohols and cationic surfactants in conditioning compositions is believed to be especially advantageous, because this leads to the formation of a lamellar phase, in which the cationic surfactant is dispersed. Representative fatty alcohols comprise from 8 to 22 carbon atoms, more preferably 16 to 22. Fatty alcohols are typically compounds containing straight chain alkyl groups. Examples of suitable fatty alcohols include cetyl alcohol, stearyl alcohol and mixtures thereof. The use of these materials is also advantageous in that they contribute to the overall conditioning properties of compositions of the invention. The level of fatty alcohol in the hair conditioning compositions of the invention will generally range from 0.01 to 10, preferably from 0.1 to 8, more preferably from 0.2 to 7, most preferably from 0.3 to 6 % w/w by weight of the composition. The weight ratio of cationic surfactant to fatty alcohol is suitably from 1 :1 to 1 :10, preferably from 1 :1 .5 to 1 :8, optimally from 1 :2 to 1 :5. If the weight ratio of cationic surfactant to fatty alcohol is too high, this can lead to eye irritancy from the composition. If it is too low, it can make the hair feel squeaky for some consumers.

More generally, the hair colour composition may be in the form of a gel, cream, mask, ointment, mousse or lotion.

(b) Washing the treated hair fibres;

Example

In this example, oxygen is provided by the decomposition of hydrogen peroxide in the presence of catalase. Triton X-100 non-ionic surfactant allows the generated oxygen to be retained in the test solutions in the form of foam.

Materials

Natural White hair swatches (International Hair Importers, NY, US)

Laccase from Myceliphthora thermophila, 33 000 U.mg protein^"1 (Novozymes A/S)

Catalase from bovine liver, 20 U.mg protein^"1 (Sigma-Aldrich)

Triton™ X-100 non-ionic surfactant (octyl phenol ethoxylate) (Sigma-Aldrich)

(+)-Catechin hydrate (a flavan-3-ol) (Sigma-Aldrich)

(-)-Epicatechin (a flavan-3-ol) (Sigma-Aldrich)

(-)-Epigallocatechin gallate (ester of epigallocatechin (a flavan-3-ol) and gallic acid (a phenolic acid)) (Sigma-Aldrich)

Gallic acid (phenolic acid) (Sigma-Aldrich)

Propyl gallate (ester of propanol and gallic acid) (Sigma-Aldrich)

Octyl gallate (ester of octanol and gallic acid) (Sigma-Aldrich) Caffeic acid (a hydroxycinnamic acid) (Sigma-Aldrich)

Luteolin (flavone) (Sigma-Aldrich)

Quercetin dihydrate (flavonol) (Sigma-Aldrich)

(±)-Taxifolin (flavanonol) (Sigma-Aldrich)

Method

Test solutions were prepared consisting of the relevant amounts of the test compound (for a final concentration of 0.05 to 17.5 mM) in 5 ml of 20 % w/w aqueous dimethyl sulphoxide (DMSO) in 50 mM Britton-Robinson (pH 6). The colour (CIE L^*a^*b^*) of the hair swatches were measured using a Minolta spectrophotometer (CM508d Minolta, UK). The hair swatches were then soaked in the test solutions for 30 minutes. Then a suspension of 4.0 ml of 25 U.mr¹ laccase and 5 mg.ml^"1 catalase in 1 % w/w Triton X-100 in Britton-Robinson (pH 6) was added, followed by 1 ml of water (no oxygen control) or 1 ml of 3 % w/w hydrogen peroxide (generates oxygen in the form of a foam due to presence of non-ionic surfactant). The resulting solution was massaged into the hair swatches for 30 seconds every 8 minutes over a period of 30 minutes. The hair swatches were then washed in warm water, dried using a hair dryer and the hair colour (L^*a^*b^*) measured using the spectrophotometer. The swatch was then shampooed for 30 seconds, washed again in warm water, dried using a hair dryer and the hair colour re-measured with the spectrophotometer. Results were generated in triplicate.

For generating an air foam, all of the components of the 'no oxygen control' were added and the solution foamed using an Ultra-Turrax T-25 homogeniser (Janke & Kunkel, Germany) for approximately 10 seconds at 8000 rpm. All other methodologies were the same.

Results

The changes in L^*a^*b^* for the polyphenols are summarised in table 1 and the corresponding P-values in table 2. From the results, it is clear that after dyeing and treatment with shampoo, only treatment with the oxygen generating test solutions comprising (+)-catechin or (-)-epicatechin resulted in significant colour changes, in particular it led to a significant increase in "a^*" and "b^*" values.

Table 1 : Changes in L^*a^*b^* and E^* values (with standard errors at 95 % confidence limits for n = 3) for white hair swatches following treatment with test solutions comprising the indicated polyphenolic compounds with (indicated "foam") and without (indicated "solution") a source of generating oxygen (hydrogen peroxide), before (A) and after (B) post-treatment shampoo. The indicated concentrations for the polyphenols are those in the final solution. (A)

Post-dyeing (mean ± SD)

Solution / foam

ΔΙ_* Aa* Ab* ΔΕ*

17.5 mM (+)-Catechin

Solution -2.01 ± 0.61 1.55 ±0.22 3.01 ±0.41 3.99 ±0.21

Foam -3.55 ± 1.33 3.79 ±1.52 8.08 ±1.43 9.64 ±2.29

17.5 m VI (-)-Epicatechin

Solution -0.27 ± 0.06 -0.09 ± 0.08 1.30 ± 0.17 1.34 ± 0.17

Foam -0.78 ±0.31 0.14 ±0.06 3.33 ± 0.65 3.45 ± 0.59

17.5 mM (-)-Epigallocatechin gallate

Solution -2.82 ± 0.43 0.18 ± 0.10 -0.05 ± 0.49 2.85 ± 0.42

Foam -3.11 ±0.08 -0.17 ± 0.04 3.14 ± 1.51 4.52 ± 1.02

17.5 mM Gallic acid

Solution -3.31 ± 1.10 -0.12 ± 0.11 -1.49 ±0.38 3.65 ± 1.08

Foam -4.99 ± 1.85 -0.35 ± 0.09 -2.35 ± 0.57 5.55 ±1.83

17.5 mM Propyl gallate

Solution -1.65 ±0.28 0.53 ± 0.34 -0.58 ± 0.77 1.95 ±0.30

Foam -2.17 ± 0.29 0.91 ±0.44 -0.02 ± 0.19 2.38 ± 0.44

5.0 mM Octyl gallate

Solution -0.52 ± 0.29 -0.01 ± 0.11 -0.08 ± 0.42 0.63 ±0.29

Foam 0.50 ±0.79 0.10 ±0.10 -0.44 ± 0.40 0.91 ±0.49

17.5 mM Caffeic acid

Solution -0.65 ± 0.85 -0.29 ± 0.23 -0.44 ± 0.70 0.95 ±0.99

Foam -1.65 ±0.49 -0.42 ± 0.37 -1.37 ±0.80 2.23 ±0.86

2.5 mM Luteolin

Solution -1.05 ±0.27 -0.37 ± 0.14 0.10 ± 0.21 1.14 ± 0.25

Foam -0.88 ± 0.82 -0.27 ± 0.05 0.43 ± 0.36 1.13 ±0.66

2.5 mM Quercetin

Solution -0.26 ± 0.43 -0.51 ± 0.14 2.17 ± 0.52 2.28 ±0.53

Foam -0.23 ± 0.44 -0.58 ±0.11 2.14 ± 0.26 2.26 ± 0.26 0.5 mM Taxifolin

Solution -0.80 ± 0.56 0.39 ±0.13 -0.31 ± 0.26 1.04 ±0.33

Foam -0.31 ± 0.17 0.19 ±0.07 -0.38 ± 0.24 0.54 ± 0.25

(B)

Post-shampoo (mean ± SD)

Solution / foam

ΔΙ_* Aa* Ab* ΔΕ*

17.5 mM (+)-Catechin

Solution -1.26 ±0.69 1.44 ±0.25 2.22 ± 0.45 2.97 ±0.66

Foam -3.08 ± 1.37 3.88 ±1.25 5.91 ±2.16 7.72 ±2.82

17.5 m VI (-)-Epicatechin

Solution -0.03 ± 0.42 -0.05 ± 0.09 0.79 ± 0.05 0.86 ±0.10

Foam -0.15 ±0.76 0.17 ±0.08 1.96 ±0.29 2.06 ± 0.38

17.5 mM (-)-Epigallocatechin gallate

Solution -0.72 ± 0.44 0.04 ± 0.04 -0.61 ± 0.57 0.96 ± 0.70

Foam -0.70 ± 0.22 -0.10 ± 0.11 0.20 ±0.13 0.75 ± 0.22

17.5 mM Gallic acid

Solution -2.05 ± 0.93 -0.06 ± 0.09 -1.07 ± 0.45 2.32 ±1.02

Foam -3.75 ± 1.29 0.00 ±0.05 -1.48 ± 0.47 4.04 ±1.35

17.5 mM Propyl gallate

Solution -0.92 ± 0.06 0.44 ±0.12 -1.13 ± 0.46 1.55 ±0.28

Foam -0.93 ± 0.87 0.76 ±0.40 -0.66 ± 0.05 1.43 ±0.81

5.0 mM Octyl gallate

Solution -0.29 ± 0.09 0.01 ±0.13 -0.43 ± 0.17 0.53 ±0.17

Foam 0.20 ± 0.25 0.06 ±0.07 -0.68 ±0.19 0.74 ±0.21

17.5 mM Caffeic acid

Solution -0.26 ±0.19 -0.56 ±0.14 -1.03 ±0.08 1.22 ±0.07

Foam -1.02 ± 0.46 -0.47 ± 0.44 -0.98 ± 0.94 1.63 ±0.79

2.5 mM Luteolin

Solution -0.37 ± 0.32 -0.42 ± 0.02 0.60 ± 0.49 0.88 ± 0.41

Foam -0.40 ± 0.54 -0.46 ± 0.02 1.14 ± 0.52 1.38 ±0.46

2.5 mM Quercetin

Solution 0.02 ±0.04 -0.58 ±0.10 1.96 ±0.49 2.05 ±0.47 Foam 0.05 ± 0.58 -0.54 ± 0.05 1 .97 ± 0.09 2.10 ± 0.13

0.5 mM Taxifolin

Solution -0.66 ± 0.57 0.18 ± 0.1 1 0.00 ± 0.04 0.72 ± 0.51

Foam -0.31 ± 0.18 0.08 ± 0.12 -0.44 ± 0.40 0.64 ± 0.19

Table 2: P-values for the data presented in table 1 . n.s. = not significant. The shaded cells indicate those values where was a significant difference between the colour change (AL^*, Aa^*, Ab^* or ΔΕ^*) of the white hair swatches following treatment with test solutions comprising the indicated polyphenolic compounds with and without a source of generating oxygen (hydrogen peroxide), before and after post-treatment shampoo.

(A)

(B)

Post-shampoo

Polyphenol

AL* Aa* Ab* ΔΕ*

17.5 mM (+)-Catechin n.s. £ 0.05 £ 0.05 £0.05

17.5 mM (-)-Epicatechin n.s. £ 0.05 £0.01 £0.01

17.5 mM (-)-Epigallocatechin

n.s. n.s. n.s. n.s.

gallate

17.5 mM Gallic acid n.s. n.s. n.s. n.s.

17.5 mM Propyl gallate n.s. n.s. n.s. n.s. 5.0 mM Octyl gallate n.s. n.s. n.s. n.s.

17.5 mM Caffeic acid n.s. n.s. n.s. n.s.

2.5 mM Luteolin n.s. n.s. n.s. n.s.

2.5 mM Quercetin n.s. n.s. n.s. n.s.

0.5 mM Taxifolin n.s. n.s. n.s. n.s.

The changes in L^*a^*b^* for the different foaming conditions are summarised in table 3 and the corresponding P-values in table 4 for test solutions comprising 17.5 mM (+)-catechin. From the results, it is clear that after dyeing and treatment with shampoo, treatment with the oxygen generating test solutions containing catechin produce more hair colour than in an air foam or a no-foam solution over the same 30 minute period, and that it produced a significant increase over both air foam and solution in terms of "a" values.

Table 3: Changes in L^*a^*b^* and ΔΕ^* values (with standard errors at 95 % confidence limits for n = 3) for white hair swatches following treatment with test solutions comprising a final concentration of catechin of 17.5 mM in an air foam generated by a blender (indicated "air foam"), an oxygen foam generated from hydrogen peroxide (indicated "oxygen foam") and without foam (indicated "solution"), before and after post-treatment shampoo.

Table 4: P-values for the data presented in table 3. n.s. = not significant. The shaded cells indicate those values where was a significant difference between the colour change {AL^*, Aa^*, Ab^* or ΔΕ^*) of the white hair swatches following treatment with test solutions comprising a final concentration of catechin of 17.5 mM under the conditions indicated before and after post-treatment shampoo.

After Dyeing

Air foam vs. Solution Oxygen foam vs. Solution Oxygen foam vs. Air foam

ΔΙ_^* n.s. n.s. n.s.

Aa^* n.s. ≤ 0.050 n.s.

However, it is not obvious that an increase in oxygen concentration (100 % vs 21 % in air) and/or pressure (as a result of the small size of the oxygen bubbles) would increase the rate of reaction, as the laccase used may already be working at its maximal velocity at the concentration of oxygen in the air. Also, the higher concentration and/or pressure of oxygen may not raise the rate of diffusion of the gas into solution sufficiently to increase the rate of reaction in practical terms.

Conclusion

The "a^*" value in L^*a^*b^* measurements indicates the colour spectrum from green to red wherein negative values indicate green and positive values indicate red. The "b^*" value in L^*a^*b^* measurements indicates the colour spectrum from blue to yellow wherein negative values indicate blue and positive values indicate yellow. Thus from the results, it is clear that treatment of white hair swatches with an oxygen generating test solutions comprising (+)-catechin or (-)-epicatechin resulted in significant increases in red and yellow colours in the same time period of 30 minutes, and produced a significantly stronger red colour with a catechin solution in the presence of an oxygen foam compared to a comparative solution in the presence of an air foam.

Claims

A hair colour composition comprising:

(b) A laccase;

(c) A surfactant; and

(d) Pure oxygen or an oxygen generator;

A hair colour composition according to claim 1 , wherein the laccase is selected from the group consisting of cyanobacteria of the genuses Leptolyngbya, Oscillatoria and Phormidium; bacteria of the genuses Bacillus, Escherichia, Pseudomonas, Shigella, Sinorhizobium, Stenotrophomonas, Streptomyces, and Thermus; fungi of the genuses Agaricus, Agrocybe, Albatrellus, Athelia, Botryotinia, Cantharellus, Ceriporiopsis, Cerrena, Chaetomium, Cladosporium, Clitocybe, Coniothyrium, Coprinopsis, Coriolisimus, Coriolopsis, Cortinarius, Cryptococcus, Cyathus, Daedalea, Emericella, Fomes, Fomitella, Fusarium, Ganoderma, Hypocrea, Inocybe, Lactarius, Lentinula, Lepiota, Lepista, Leptonia, Loweporus, Lyophyllum, Magnaporthe, Marasmius, Melanocarpus, Myceliophthora, Myriogonium, Myrothecium, Neurospora, Panus, Paraconiothyrium, Parasola, Peltigera, Penicillium, Peniophora, Perenniporia, Phellinus, Phlebia, Phoma, Pleurotus, Podospora, Polyporus, Pycnoporus, Ramaria, Rhizoctonia, Rigidoporus, Russula, Scytalidium, Solorina, Steccherinum, Trametes, Tricholoma, Trichophyton, Volvariella; plants of the genuses Acer, Mangifera, Pistacia, Pleiogynium, Populus, Prunus, Rhus, Schinus and Toxicodendron; and mixtures thereof.

A hair colour composition according to claim 1 or claim 2, wherein the surfactant is selected from the group consisting of non-ionic, anionic, cationic, amphoteric, zwitterionic and mixtures thereof.

A hair colour composition according to claim 3, wherein the non-ionic surfactant is selected from the group consisting of polyethylene glycol ethers, fatty alcohols, fatty acid amides, fatty acid glucosides, fatty acid sorbitans, alkyl ethers, monoglycerides, polysorbates and mixtures thereof. A hair colour composition according to any one of the preceding claims, wherein the surfactant is an octyl phenol ethoxylate.

A hair colour composition according to any one of the preceding claims, wherein the oxygen generator is a combination of hydrogen peroxide and catalase.

A hair colour composition according to any one of claims 1 to 5, wherein the oxygen generator is a combination of hydrogen peroxide and a metal catalyst.

A hair colour composition according to claim 7, wherein the metal catalyst is selected from the group consisting of ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, gold, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, tantalum, tungsten, and mixtures thereof.

A hair colour composition according to claim 8, wherein the metal catalyst is selected from the group consisting of ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, gold, and mixtures thereof.

A hair colour composition according to any one of the preceding claims comprising 2-60, 5-30, 10-20 mM polyphenol.

A hair colour composition according to any one of the preceding claims comprising 2-20, preferably 4-16, most preferably 8-12 U.ml^"1 laccase.

A hair colour composition according to any one of the preceding claims comprising 0.1 -10, 0.1 -5, 0.1 -2 % w/w surfactant.

A hair colour composition according to any one of claims 6 to 12 comprising 0.03- 0.5, 0.1 -0.5, 0.2-0.4 % w/w hydrogen peroxide.

A hair colour composition according to any one of claims 6, and 10 to 13 comprising 0.2-2, preferably 0.8-2, most preferably 1.2-2 mg.ml^"1 catalase.

A hair colour composition according to any one of claims 7 to 14 comprising 0.1 -10, preferably 0.5-5, most preferably 1 -2 % w/w metal catalyst. A hair colour composition according to any one of claims 6 to 15 in the form of a two part composition, wherein a first part comprises hydrogen peroxide, and a second part comprises catalase or a metal catalyst.

A method for colouring hair fibres comprising the steps of:

(a) Treating hair fibres with the hair colour composition of any one of the preceding claims; and then

(b) Washing the treated hair fibres;

wherein when the hair colour composition is in the form of a two part composition according to claim 16, the first and second parts are combined either before or during the step of treating the hair fibres.