EP1450754A1

EP1450754A1 - Hair treatment compositions

Info

Publication number: EP1450754A1
Application number: EP20020779514
Authority: EP
Inventors: Paul Alfred Cornwell; Frances Ann Ellis; Christophe Michel Finel
Original assignee: Unilever PLC; Unilever NV
Current assignee: Unilever PLC; Unilever NV
Priority date: 2001-11-27
Filing date: 2002-10-28
Publication date: 2004-09-01
Also published as: WO2003045340A1; AU2002342865A1; JP2005513029A; AR037420A1; BR0214259A

Abstract

An aqueous hair treatment composition comprising: i) from 0.01 to 5.0 wt% of a cationic amino acid; ii) from 0.01 to 5.0 wt% of an antioxidant iii) from 0.005 to 5.0 wt% of a hydrolysed protein; and iv) from 0.005 to 5.0 wt% of an amino acid having an aliphatic side chain.

Description

HAIR TREATMENT COMPOSITIONS

FIELD OF THE INVENTION

This invention relates to hair treatment compositions containing agents to thicken and prevent damage of hair.

BACKGROUND AND PRIOR ART

Human hair is comprised of keratin a tough fibrous protein. Hair is routinely exposed to a variety of activities that compromise its structure. For example, simple grooming and styling results in loss of cuticle scale. Loss of cuticle exposes the hair ' s inner cortex to further damage and eventually leads to hair breakage. Thus the quality of hair is affected by the age of the hair.

Hair is also affected by the age of the person. Ageing affects the hair in several different ways; it looses its colour, it gets finer, less dense and drier.

Unsurprisingly the consumer wishes to have undamaged, youthful looking hair. The present invention addresses this problem in that it prevents damage of hair and so keeps the hair looking youthful .

Amino acids are known to be important for the nourishment of the human hair root and the growth of human hair. GB 1 401 089 describes hair treatment compositions containing natural amino acids or protein hydrolysates . EP 0 186 025 discloses cosmetic preparations for care of skin and hair with a hydrolysate of almond protein. A composition containing L-leucine, L-isoleucine and L-valine to stimulate growth and regeneration of hair and nails is described in WO 92/00720.

The use of leucine and lysine is described in WO 00/71086 to prevent the formation of split ends. W0 98/51265 describes compositions with hydrolysed proteins having an abundance of anionic acids and a divalent cationic compound. The compositions are said to provide an excellent finishing effect and superior protection against the environment .

SUMMARY OF THE INVENTION

This invention provides an aqueous hair treatment composition comprising: i) from 0.01 to 5.0 wt% of a cationic amino acid; ii) from 0.01 to 5.0 wt% of an antioxidant; iii) from 0.005 to 5.0 wt% of a hydrolyzed protein; and iv) from 0.005 to 5.0 wt% of an amino acid having an aliphatic side chain.

Also claimed is the use of the above composition to re- thicken hair and to prevent damage of the hair.

This invention also relates to a method of treating hair by applying to the hair a composition as described above. DETAILED DESCRIPTION AND PREFERRED EMBODIMENTS

Cationic Amino Acid (i)

Amino acids (i) having an basic side chain may be selected from lysine, arginine and histidine and mixtures thereof.. Lysine and arginine are positively charged at neutral pH, whereas histidine can be uncharged or positively charged depending on its local environment.

Preferably the amino acid (i) is selected from lysine and arginine, and mixtures thereof. Lysine is the most preferred amino acid (i) for the use according to the invention.

Simple derivatives of the amino acid (i) may be employed, such as salts and hydrosalts.

The total amount of amino acid (i) ranges from 0.01% to 5% by weight based on total weight of the hair treatment composition in which it is employed. Preferably, the amount of amino acid (i) is at least 0.1%, and will ideally range from 0.1% to 2% by weight based on total weight. These amino acids are present in addition to the amino acids present in the hydrolyzed protein.

Antioxidant (ii)

The composition comprises an antioxidant. Suitable antioxidants include compounds such as diazolidinyl urea, iodopropynyl butylcarbamate, vitamin E, vitamin E acetate, vitamin C, butylated hydroxytoluene, methylparaben, and mixtures thereof. Especially preferred is tocopheryl acetate.

The total amount of antioxidant (ii) ranges from 0.01% to 5% by weight based on total weight of the hair treatment composition in which it is employed. Preferably, the amount of antioxidant (ii) is at least 0.05%, and will ideally range from 0.05% to 2% by weight based on total weight.

It is preferable if the weight ratio of antioxidant (ii)to cationic amino acid (I) is from 0.1:1 to 1:1.

Hydrolysed Protein (iii)

The term "hydrolysed protein, " as used herein, refers to the product of the hydrolysis of homogeneous or heterogeneous proteins, or their respective components, derivatives or combinations thereof, from sources including, but not limited to, plants and their respective components, seeds, animal bones, connective tissue, animal keratin, bovine and porcine collagen, human hair, wool, silk, elastin, reticulin, milk, egg, wheat, corn, soya, oats, casein, albumin, or any collagenous or keratinic substance, or derivatives thereof. With respect to the compositions of the present invention, there is no restriction on the source of protein, protein components or derivatives, provided that the hydrolyzate has the desired physical properties described herein. However, preferred protein sources include keratin, soya, milk, collagen, wheat and their respective components, derivatives or combinations thereof. Additional preferred protein sources may be identified as proteins having desirable amino acid compositions, as set forth below. Suitable derivatives include proteins chemically modified to alter their ionic charge, for example, by sulfonation or succinylation. The compositions of the present invention are not limited to hydrolyzed proteins produced from naturally occurring proteins. Synthetic proteins, peptides, or amino acids as well as naturally occurring proteins, peptides or amino acids or mixtures of naturally occurring and synthetic proteins and/or peptides and/or amino acids may also be used according to the invention. Hydrolyzed protein prepared from various proteins, their respective components, and derivatives may be combined and used in the composition of the present invention. Moreover, a hydrolyzed protein may be supplemented by the addition of one or more natural or synthetic peptides or amino acids to achieve the ionic characteristics or sulphur content discussed below. Methods for producing hydrolyzed proteins from the above-mentioned protein sources include, but are not limited to: 1) acid hydrolysis; 2) alkali hydrolysis; and 3) enzyme hydrolysis using a suitable protease. These methods, along with several others, for preparing hydrolyzed proteins are well known in the art. Further, hydrolyzed proteins suitable for the compositions of the present invention are commercially available.

Preferably the ratio of anionic amino acids to cationic amino acids within the hydrolysed protein is less than 2 to 1. More preferably the ratio of anionic amino acids to cationic amino acids within the hydrolysed protein is from 1.2:1 to 1.6: 1. The hydrolysed protein is suitably broken down to it's constituent amino acids. Preferably at least 50% of the hydrolysate is free amino acids, more preferably 90% is free amino acids .

In a preferred embodiment the source of the hydrolysed protein is wheat or soya, in the most preferred form the source of hydrolysed protein is collagen.

The total amount of hydrolysed protein ranges from 0.005 to 5.0 % by weight based on total weight of the hair treatment composition in which it is employed. Preferably, the amount of hydrolyzed protein (iii) is at least 0.01%, and will ideally range from 0.01% to 2% by weight based on total weight.

Amino acid having aliphatic side chain (iv)

Amino acids (iv) having an aliphatic side chain may be selected from glycine, alanine, valine, leucine and isoleucine, and mixtures thereof. Glycine has a hydrogen atom as its side chain, alanine has a methyl group, and larger hydrocarbon chains (three and four carbons long) are found in valine, leucine and isoleucine. These larger aliphatic side chains are hydrophobic.

Preferably the amino acid (iv) is selected from valine, leucine and isoleucine, and mixtures thereof. Isoleucine is the most preferred amino acid (iv) for the use according to the invention. Simple derivatives of the amino acid (iv) may be employed, such as salts and hydrosalts .

The total amount of amino acid (iv) may suitably range from 0.005% to 5% by weight based on total weight of the hair treatment composition in which it is employed. Preferably, the amount of amino acid (iv) will ideally range from 0.01% to 2% by weight based on total weight. These amino acids are present in addition to the amino acids present in the hydrolysed protein, and the cationic amino acid.

Sulphur containing amino acids

It is preferable if in addition to the amino acids listed above if a sulphur containing amino acid is present. Such sulphur amino acids include cysteine and methionine .

Product Form

Advantageously, compositions comprising the hydrolysed protein complex according to the invention can be formulated as a shampoo, conditioner or styling product.

Shampoo

If a shampoo the composition will accordingly comprise one or more cleansing surfactants, which are cosmetically acceptable and suitable for topical application to the hair. O 03/045340

Suitable cleansing surfactants, which may be used singularly or in combination, are selected from anionic, amphoteric and zwitterionic surfactants, and mixtures thereof.

Examples of anionic surfactants are the alkyl sulphates, alkyl ether sulphates, alkaryl sulphonates, alkanoyl isethionates, alkyl succinates, alkyl sulphosuccinates, N- alkyl sarcosinates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, and alpha-olefin sulphonates, especially their sodium, magnesium, ammonium and mono-, di- and triethanolamine salts. The alkyl and acyl groups generally contain from 8 to 18 carbon atoms and may be unsaturated. The alkyl ether sulphates, alkyl ether phosphates and alkyl ether carboxylates may contain from 1 to 10 ethylene oxide or propylene oxide units per molecule.

Preferred anionic surfactants include sodium oleyl succinate, ammonium lauryl sulphosuccinate, ammonium lauryl sulphate, sodium dodecylbenzene sulphonate, triethanolamine dodecylbenzene sulphonate, sodium cocoyl isethionate, sodium lauryl isethionate and sodium N-lauryl sarcosinate. The most preferred anionic surfactants are sodium lauryl sulphate, triethanolamine monolauryl phosphate, sodium lauryl ether sulphate 1 EO, 2EO and 3EO, ammonium lauryl sulphate and ammonium lauryl ether sulphate 1E0, 2EO and 3EO.

Examples of amphoteric and zwitterionic surfactants include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulphobetaines (sultaines) , alkyl glycinates, alkyl carboxyglycinates, alkyl amphopropionates, alkylamphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, wherein the alkyl and acyl groups have from 8 to 19 carbon atoms. Preferred amphoteric and zwitterionic surfactants include lauryl amine oxide, cocodimethyl sulphopropyl betaine and preferably lauryl betaine, cocamidopropyl betaine and sodium cocamphopropionate .

The cleansing surfactant (s) may be present in shampoo compositions for use according to the invention in a total amount of from about 1 to about 40% by weight based on the total weight of the shampoo composition, preferably from about 2 to about 30% by weight, optimally from about 10% to 30% by weight .

Shampoos for use according to the invention can also include nonionic surfactants to help impart aesthetic, physical or cleansing properties to the composition. The nonionic surfactant can be included in an amount ranging from 0% to about 5% by weight based on total weight.

For example, representative nonionic surfactants include condensation products of aliphatic (C₈ - Cι₈) primary or secondary linear or branched chain alcohols or phenols with alkylene oxides, usually ethylene oxide and generally having from 6 to 30 ethylene oxide groups.

Other representative nonionics include mono- or di-alkyl alkanolamides . Examples include coco mono- or di- ethanolamide and coco mono-isopropanolamide. Further nonionic surfactants which can be included are the alkylpolyglycosides (APGs) . Typically, the APG is one which comprises an alkyl group connected (optionally via a bridging group) to a block of one or more glycosyl groups. Preferred APGs are defined by the following formula:

RO - (G)_n

wherein R is a branched or straight chain alkyl group which may be saturated or unsaturated and G is a saccharide group.

R may suitably represent a mean alkyl chain length of from about C₅ to about C₂₀. Preferably R represents a mean alkyl chain length of from about C₈ to about C₁₂. Most preferably the value of R lies between about 9.5 and about 10.5. G may be selected from C₅ or C₆ monosaccharide residues, and is preferably a glucoside . G may be selected from the group comprising glucose, xylose, lactose, fructose, mannose and derivatives thereof. Preferably G is glucose.

The degree of polymerisation, n, may have a value of from about 1 to about 10 or more. Preferably, the value of n lies in the range of from about 1.1 to about 2. Most preferably the value of n lies in the range of from about 1.3 to about 1.5.

Suitable alkyl polyglycosides are commercially available and include for example those materials identified as: Oramix NS10 ex Seppic; Plantaren 1200 and Plantaren 2000 ex Henkel . Likewise shampoos for use according to the invention can include other emulsifiers, conditioning agents, inorganic salts, humectants and similar materials to provide the composition with desirable aesthetic or physical properties.

Representative conditioning agents include silicones. Silicones are particularly preferred conditioning agents for hair. Representative silicones include volatile and nonvolatile silicones, such as for example polyalkylsiloxanes (optionally end-capped with one or more hydroxyl groups) , polyalkylaryl siloxanes, siloxane gums and resins, cyclomethicones, aminofunctional silicones, quaternary silicones and mixtures thereof.

Preferred silicones include polydimethylsiloxanes (of CTFA designation dimethicone) , siloxane gums, aminofunctional silicones (of CTFA designation amodimethicone) and hydroxylated polydimethylsiloxanes (of CTFA designation dimethiconol) .

Various methods of making emulsions of particles of silicones are available and are well known and documented in the art .

Suitable silicone emulsions are commercially available in a pre-emulsified form. This is particularly preferred since the pre-formed emulsion can be incorporated into the shampoo composition by simple mixing.

Examples of suitable pre-formed emulsions include emulsions DC2-1310, DC2-1865, DC2-1870, DC2-1766 and DC2-1784, available from Dow Corning. These are emulsions or of dimethiconol. Siloxane gums are also available in a pre- emulsified form, which is advantageous for ease of formulation. A preferred example is the material available from Dow Corning as DC X2-1787, which is an emulsion of cross-linked dimethiconol gum.

The amount of silicone incorporated into compositions for use according to the invention depends on the level of conditioning desired and the material used. A preferred amount is from 0.01 to about 10% by weight of the total composition although these limits are not absolute. The lower limit is determined by the minimum level to achieve conditioning and the upper limit by the maximum level to avoid making the hair and/or skin unacceptably greasy. We have found that an amount of silicone of from 0.5 to 1.5% by weight of the total composition, is a particularly suitable level .

A further preferred class of conditioning agents are per- alk(en)yl hydrocarbon materials, used to enhance the body, volume and stylability of hair.

EP 567 326 and EP 498 119 describe suitable peralk(en)yl hydrocarbon materials for imparting stylability and enhanced body to hair. Preferred materials are polyisobutylene materials available from Presperse, Inc. under the PERMETHYL trade name .

The amount of per-alk (en) yl hydrocarbon material incorporated into compositions for use according to the invention depends on the level of body and volume enhancement desired and the specific material used. A preferred amount is from 0.01 to about 10% by weight of the total composition although these limits are not absolute. The lower limit is determined by the minimum level to achieve the body and volume enhancing effect and the upper limit by the maximum level to avoid making the hair unacceptably stiff. We have found that an amount of per- alk(en)yl hydrocarbon material of from 0.5 to 2% by weight of the total composition is a particularly suitable level.

Shampoo compositions for use according to the invention may also include a polymeric cationic conditioning compound that is substantive to the hair and imparts conditioning properties to the hair.

The polymeric cationic conditioning compound will generally be present at levels of from 0.01 to 5%, preferably from about 0.05 to 1%, more preferably from about 0.08% to about 0.5% by weight. Synthetic or naturally derived polymers having a quaternised nitrogen atom are useful . The molecular weight of the polymer will generally be between 5 000 and 10 000 000, typically at least 10 000 and preferably in the range 100 000 to about 2 000 000.

Representative synthetic quaternised polymers include, for example: cationic copolymers of 1-vinyl-2-pyrrolidine and 1- vinyl-3-methyl-imidazolium salt (e.g., Chloride salt) (referred to in the industry by the Cosmetic, Toiletry, and Fragrance Association, "CTFA". as Polyquaternium-16) ; copolymers of 1-vinyl-2-pyrrolidine and dimethylaminoethyl methacrylate (referred to in the industry by CTFA as Polyquaternium-11) ; cationic diallyl quaternary ammonium- containing polymers including, for example, dimethyldiallylammonium chloride homopolymer (referred to in the industry (CTFA) as Polyquaternium 6) ; mineral acid salts of amino-alkyl esters of homo-and co-polymers of unsaturated carboxylic acids having from 3 to 5 carbon atoms, as described in U.S. Patent 4,009,256; and cationic polyacrylamides as described in W095/22311.

Representative naturally-derived quaternised polymers include quaternised cellulosic compounds and cationic guar gum derivatives, such as guar hydroxypropyltrimonium chloride. Examples are JAGUAR C-13S, JAGUAR C-15, and JAGUAR-C17, commercially available from Meyhall in their JAGUAR trademark series .

Conditioner

Compositions for use in accordance with the invention may also be formulated as a hair conditioner for the treatment of hair (typically after shampooing) and subsequent rinsing. Such formulations will then accordingly comprise one or more conditioning surfactants which are cosmetically acceptable and suitable for topical application to the hair.

Suitable conditioning surfactants are selected from cationic surfactants, used singly or in admixture. Examples include quaternary ammonium hydroxides or salts thereof, e.g chlorides. Suitable cationic surfactants 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, cocotrimethylammonium 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 hair conditioners of the invention is cetyltrimethylammonium chloride, available commercially, for example as GENAMIN CTAC, ex Hoechst Celanese.

In hair conditioners for use according to the invention, the level of cationic surfactant is preferably from 0.01 to 10%, more preferably 0.05 to 5%, most preferably 0.1 to 2% by weight of the composition.

Conditioners for use according to the invention advantageously incorporate a fatty alcohol material . The combined use of fatty alcohol materials 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 20. Examples of suitable fatty alcohols include cetyl alcohol, stearyl alcohol and mixtures thereof .

The level of fatty alcohol materials is conveniently from 0.01 to 10%, preferably from 0.1 to 5% by weight of the composition. The weight ratio of cationic surfactant to fatty alcohol is suitably from 10:1 to 1:10, preferably from 4:1 to 1:8, optimally from 1:1 to 1:4.

Conditioners for use according to the invention can include other emulsifiers, conditioning agents, inorganic salts, humectants and similar materials to provide the composition with desirable aesthetic or physical properties. Silicones, as described above for shampoo compositions, are particularly preferred conditioning agents for hair.

As further optional components for inclusion in shampoo or conditioner compositions for use according to the invention, in addition to water, may be mentioned the following conventional adjunct materials known for use in cosmetic compositions: suspending agents, thickeners, pearlescing agents, opacifiers, salts, perfumes, buffering agents, colouring agents, emollients, moisturisers, foam stabilisers, sunscreen materials, antimicrobial agents, preservatives, antioxidants, natural oils and extracts, propellants. Hair styling Composition

Hair styling compositions preferably comprise a nonionic surfactant in an amount ranging from 0.01% to 5%, preferably from 0.01% to 1%, most preferably from 0.02% to 0.8% by weight based on total weight .

Examples of suitable nonionic surfactants are condensation products of aliphatic (Cβ-Ciβ) primary or secondary linear or branched chain alcohols or phenols with alkylene oxides, usually ethylene oxide and generally having at least 15, preferably at least 20, most preferably from 30 to 50 ethylene oxide groups . Other suitable nonionics include esters of sorbitol, esters of sorbitan anhydrides, esters of propylene glycol, fatty acid esters of polyethylene glycol, fatty acid esters of polypropylene glycol, ethoxylated esters and polyoxyethylene fatty ether phosphates.

Of particular use are those nonionic surfactants of general formula R(EO)x H, where R represents a straight or branched chain alkyl group having an average carbon chain length of 12-18 carbon atoms and x ranges from 30 to 50. Specific examples include steareth-40, steareth-50, ceteareth-30, ceteareth-40, ceteareth-50 and mixtures thereof. Suitable commercially available examples of these materials include Unicol SA-40 (Universal Preserv-A-Chem) , Empilan KM50 (Albright and Wilson) , NONION PS-250 (Nippon Oils & Fats) , Volpo CS50 (Croda Inc) , and Incropol CS-50 (Croda Inc) .

As some of the above-described nonionic surfactants form particularly stable foams, it may be preferable, depending on product form, to include anti-foam ingredients to reduce foaming to provide a foam stability preferred by the consumer. For example, in the case of hair styling mousse product forms, consumers generally prefer that the foam generated collapses after less than five minutes after discharge, for ease of spreading on the hair.

The invention accordingly provides, in a further aspect, a hair styling mousse incorporating an anti-foam ingredient.

By "anti-foam ingredient" is meant an agent which inhibits the build up of foam, or which reduces foam or entrapped air by causing the bubbles to burst, thus releasing the air. Most commercial anti-foam ingredients are mixtures of, inter alia, surface-active agents, hydrocarbons, alcohols, and polymers, to increase their effectiveness in multiple applications. Examples of anti-foaming agents suitable for personal care applications include bisphenylhexamethicone, dimethicone fluid, dimethiconol fluid, hexamethyldisiloxane, hexyl alcohol, isopropyl alcohol, petroleum distillates, phenethyl disiloxane, phenyl trimethicone, Polysilicone-7, propyl alcohol, silica dimethyl silylate, silica silylate, tetramethyl decynediol, trimethylsiloxysilicate, and mixtures thereof .

Typical levels of antifoams would be 0.01% to 0.4%, ideally 0.04% to 0.2% although other levels may be suitable depending on type. Examples are the materials SL, SR, S575 and S369 from Wacker and MSA Compound from Dow Corning. Compositions of the present invention will also include water, preferably distilled or deionised, as a solvent or carrier for the polymers and other components. Water will typically be present in amounts ranging from 30% to 98%, preferably from 60% to 95% by weight based on total weight.

Alcohol may optionally be employed as a co-solvent in compositions of the invention as this can enhance the performance of the styling composition. A suitable alcohol is an aliphatic straight or branched chain monohydric alcohol having 2 to about 4 carbon atoms. Isopropanol and especially ethanol are preferred. A suitable level for the alcohol is up to 20%, preferably from 5% to 15%, by weight based on total weight .

The styling compositions of the invention may suitably be in aerosol form. A particularly preferred product form is an aerosol hair mousse. Aerosol hair mousse compositions are emitted from the aerosol container as a foam which is then typically worked through the hair with fingers or a hair styling tool and either left on the hair or rinsed out.

Aerosol-form compositions of the invention will include an aerosol propellant (v) which serves to expel the other materials from the container, and forms the mousse character in mousse compositions. The aerosol propellant included in styling compositions of the present invention can be any liquefiable gas conventionally used for aerosol containers. Examples of suitable propellants include dimethyl ether and hydrocarbon propellants such as propane, n-butane and isobutane. The propellants may be used singly or admixed. Water insoluble propellants, especially hydrocarbons, are preferred because they form emulsion droplets on agitation and create suitable mousse foam densities .

The amount of the propellant used is governed by normal factors well known in the aerosol art. For mousses the level of propellant is generally up to 30%, preferably from 2% to 30%, most preferably from 3% to 15% by weight based on total weight of the composition. If a propellant such as dimethyl ether includes a vapour pressure suppressant (e.g. trichloroethane or dichloromethane) , for weight percentage calculations, the amount of suppressant is included as part of the propellant.

The method of preparing aerosol hair styling mousse compositions according to the invention follows conventional aerosol filling procedures. The composition ingredients (not including the propellant) are charged into a suitable pressurisable container which is sealed and then charged with the propellant according to conventional techniques.

Compositions of the invention may also take a non-foaming product form, such as a hair styling cream or gel. Such a cream or gel will include a structurant or thickener, typically at a level of from 0.1% to 10%, preferably 0.5% to 3% by weight based on total weight.

Examples of suitable structurants or thickeners are polymeric thickeners such as carboxyvinyl polymers . A carboxyvinyl polymer is an interpolymer of a monomeric mixture comprising a monomeric olefinically unsaturated carboxylic acid, and from about 0.01% to about 10% by weight of the total monomers of a polyether of a polyhydric alcohol. Carboxyvinyl polymers are substantially insoluble in liquid, volatile organic hydrocarbons and are dimensionally stable on exposure to air. Suitably the molecular weight of the carboxyvinyl polymer is at least 750,000, preferably at least 1,250,000, most preferably at least 3,000,000. Preferred carboxyvinyl polymers are copolymers of acrylic acid cross-linked with polyallylsucrose as described in US Patent 2,798,053. These polymers are provided by B.F. Goodrich Company as, for example, CARBOPOL 934, 940, 941 and 980. Other materials that can also be used as structurants or thickeners include those that can impart a gel-like viscosity to the composition, such as water soluble or colloidally water soluble polymers like cellulose ethers (e.g. methylcellulose , hydroxyethylcellulose , hydroxypropylmethylcellulose and carboxymethylcellulose) , guar gum, sodium alginate, gum arabic, xanthan gum, polyvinyl alcohol, polyvinyl pyrrolidone , hydroxypropyl guar gum, starch and starch derivatives, and other thickeners, viscosity modifiers, gelling agents, etc. It is also possible to use inorganic thickeners such as bentonite or laponite clays .

The hair styling compositions of the invention can contain a variety of nonessential , optional components suitable for rendering the compositions more aesthetically acceptable or to aid use, including discharge from the container, of the product. Such conventional optional ingredients are well known to those skilled in the art, e.g. preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidazolidinyl urea, fatty alcohols such as cetearyl alcohol, cetyl alcohol and stearyl alcohol, pH adjusting agents such as citric acid, succinic acid, sodium hydroxide and triethanolamine, colouring agents such as any of the FD&C or D&C dyes, perfume oils, chelating agents such as ethylenediamine tetraacetic acid, and polymer plasticising agents such as glycerin, silicones and propylene glycol.

The invention will now be further illustrated by the following, non-limiting Examples. Examples according to the invention are illustrated by a number, comparative Examples are illustrated by a letter.

Examples

Combing during the grooming process damages hair. In this experiment the hair's resistance to cuticle damage is tested in vitro.

In the cuticle abrasion test clipped hairs are placed inside a high shear mixer which chips of cuticle scales. Stronger, damage resistance hair looses less cuticle scales than weaker hair.

Two clean, 7g switches of Spanish dark brown hair were used for each treatment .

Switches were treated with the following Examples:

Example A SLES 14 wt%, 2 wt % CAP (Sodium laurylethersulphate and cetylamidopropyl betaine) Example B SLES 14 wt%, 2 wt % CAPB 1% Collagen amino acid

(Crotein MCAA ex Croda) Example 1 SLES 14 wt%, 2 wt % CAPB lwt% Collagen amino acid

(Crotein MCAA ex Croda) , lwt% Lysine (as hydrochloride salt), 0.1 wt% isoleucine , 0.6 wt% tocopheryl acetate.

Wetted switches were washed in 0.7g/litre of product for two intervals of 30 seconds, rinsing in warm water for 30 seconds after each wash. Switches were dried and left to equilibriate .

Each pair of switches was cut into 1cm lengths and combined to create a total sample of 14g that was mixed. For each treatment 3 times 4g samples from this mix were each added to 200g of deionised water and mixed vigorously in a Waring blender (Full power) for 1 minute. The liquor was decanted off and centrifuged at 4,300 RPM. The resulting clear liquor was decanted off leaving cuticle sediment at the bottom of each tube .

The cuticles were washed, passed through a series of sieves of 425 and 53 microns. The sieves were washed. The resulting samples were freeze dried and weighed.

It can be seen that the Example according to the invention has significantly better recovery than the comparative Examples .

An example according to the invention were prepared having the following formula: Example 2

Sodium laureth sulfate 8.00%

Cocoamidopropyl betaine 4.00% Guar hydroxypropyltrimonium chloride 0.01%

Dimethiconol 0.50%

Mica 0.20% Carbomer 0.40%

Sodium benzoate 0.50%

Salt 1.00%

Citric acid 0.20%

Perfume 0.50% L-Isoleucine 0.10%

L-Lysine 0.10%

Vitamin E acetate 0.05%

Collagen amino acids 0.10%

Water to 100%

Claims

1. An aqueous hair treatment composition comprising: i) from 0.01 to 5.0 wt% of a cationic amino acid; ii) from 0.01 to 5.0 wt% of an antioxidant; iii) from 0.005 to 5.0 wt% of a hydrolysed protein; and iv) from 0.005 to 5.0 wt% of an amino acid having an aliphatic side chain.

2. A composition as claimed in claim 1, in which the source of the hydrolysed protein is collagen.

3. A composition according to claim 1 or claim 2 in which the cationic amino acid is lysine.

4. A composition according to any preceding claim in which the antioxidant is tocopheryl acetate.

5. A composition according to any preceding claim in which the weight ratio of antioxidant to cationic amino acid is from 0.1:1 to 1:1.

6. A composition according to any preceding claim in which the aliphatic amino acid is isoleucine.

7. A composition according to any preceding claim further comprising a sulphur containing amino acid.

8. Use of a composition according to any preceding claim to re-thicken hair.

9. Use of a composition according to any preceding claim to prevent damage of hair.

10. A method of treating hair comprising the step of applying to the hair a composition according to any one of claims 1 to 7.