WO2001062215A2

WO2001062215A2 - Hair treatment compositions and their use

Info

Publication number: WO2001062215A2
Application number: PCT/US2001/005585
Authority: WO
Inventors: Stevan David Jones; Dieter Hans Josef Langsch
Original assignee: The Procter & Gamble Company
Priority date: 2000-02-25
Filing date: 2001-02-22
Publication date: 2001-08-30
Also published as: WO2001062215A3; AU2001247214A1; GB0004534D0

Abstract

The present invention relates to methods of reducing sun-induced fade of the colour applied to fibres such as hair, especially human hair, by means of artificial colouring agents, especially oxidative colouring agents, and to compositions for use in such methods; wherein said method utilises a treatment composition comprising a salt or complex of a transition metal or rare earth metal, or mixtures thereof.

Description

The Procter & Gamble Company

Hair Treatment Compositions and Their Use The present invention relates to methods of reducing sun-induced fade of the colour applied to fibres such as hair/ especially human hair, by means of artificial colouring agents, especially oxidative colouring agents, and to compositions for use in such methods.

It is well known to provide colour to hair by dyeing (artificial colouring) , to change a natural hair colour and/or to cover grey hair. Various means are known for doing this. These include direct dye compositions such as vegetable dyes, but when a more permanent colour is required, oxidative colouring systems are generally used.

In these systems various aromatic compounds, commonly known as developers (also known as precursors or primary intermediates) , together with various other aromatic compounds, . commonly known as couplers, are applied to the hair. It is necessary that an oxidising agent is also present for formation of colour. These systems provide a permanent colour to the hair, generally by means d-f a stepwise reaction sequence in which developer molecules are activated by oxidation and react with couplers to form reactive di ers. These then continue reacting to form, coloured trimers. They are usually aromatic and/or highly conjugated molecules. It is believed that the monomeric developers and couplers, and to a lesser extent the dimers, diffuse into the hair shaft during the course of the reaction. When inside the hair shaft, the dimers react further to form coloured trimers which are too large to diffuse out easily and are thus trapped, giving the hair an artificial colour.

It is important for consumers that artificially applied colour remains in the hair for a significant period of time and remains substantially the same as when applied. However, over time artificially applied colours do tend to fade and fading is accelerated in particular by exposure to sunlight. This effect is commonly known as sαn-fade. Various systems have been marketed commercially which aim to alleviate the sun-fade problem. Some such products are intended for application by the consumer prior to or during washing the hair, and others are "leave-on" products, which are applied to the hair subsequent to washing and conditioning, usually before drying.

These products tend to include uv absorbers and/or anti-oxidants of the types commonly used in products for sun protection of skin. These include benzophenone-3 and benzophenone-4, octyl methoxycinnamate, glyoxylic acid, sunflower extract, tocopherol acetate (vitamin E acetate) and other vitamin E based compounds, retinyl palmitate (vitamin A palmitate) and other vitamin A based compounds, and ascorbic acid (vitamin C) and other vitamin C based compounds, etc. By these means the commercial products aim to reduce sun-fade.

However, some fading of artificially applied colour nevertheless does occur over time even when these products are used and it would be desirable to reduce this further. The known compositions for protecting skin from UV radiation have included a wide variety of different materials. . For instance, EP-A-321,929 discloses a composition containing copper 3 ' 5 ^■ diisopropyl salicylate, which is said to be known as a free radical scavenger. Various compositions are disclosed in _. JP-A-09/040528 in which salts, including cerium salts, are impregnated into materials such as silica and titania and the resulting impregnated pigments are included as components of UV protective skin compositions. WO93/04666, EP-A-518,772 and EP-A-513,773 disclose the use of nanopig ents as components of compositions which protect skin and hair from UV light. These nanopigments include salts of cerium.

Various metal salts have been disclosed for use in compositions which are to be applied to the hair. For instance, copper and iron salts amongst . others are often included as components of hair colouring compositions. JP01/066109, JP63/014712 and JP62/132313 each disclose compositions which are apparently intended to permanently wave and colour the hair at the same time. These compositions include metal salts such as copper acetates and iron sulphates. Other compositions for application to hair which contain salts of metals such as cerium and iron have been disclosed in US 4,614,200 (in which the composition is intended to improve body and hydrophobicity) , US 4,551,330 (a conditioner composition) and FR 2,291,740 (a composition intended to stabilise hair structure, remove odour after treatments such as permanent waving or to be a pretreatment before a dyeing or bleaching process) .

Various other compositions have been disclosed which include cerium compounds as UV blockers. These are usually skin sun-screens.

However, none of these address the problem with which this invention is concerned, which is to reduce the sun- induced fade of artificially applied colour.

The invention is particularly concerned with the problem of providing methods and treatments for reducing the sun-induced fade of artificially applied hair colours, in particular in comparison with those which have hitherto been commercially successful and considered effective in alleviating this problem. A further problem with which the invention is concerned is the sun-induced fade of colours applied to types of fibrous substrate other than hair. For instance, the colours applied to textile fibres can fade from clothes which are left to dry whilst exposed to sunlight; textile fibres such as those used in fabrics which form furniture coverings and curtains can fade over time if exposed to sunlight. The present invention aims to alleviate these problems also.

According to a first aspect of the invention we provide a method of reducing sun-induced fade of the colour applied to artificially coloured fibres comprising applying to the artificially coloured fibres a treatment composition comprising a salt or complex of a transition metal or rare' earth metal, or mixtures thereof.

We find, most surprisingly, that the inclusion of these salts and complexes of transition metals and rare earth metals, especially in amounts of at least 50 ppm, can greatly improve the retention of artificially applied colour when the coloured fibres are subjected to sunlight. This is particularly surprising given that transition metal salts in particular are generally accepted as accelerants of the damage which can be caused to hair and skin by sunlight. For instance, US 5,709,848 uses chelating agents in order the protect skin and hair, on the basis that salts of transition metals such as copper and iron accelerate oxidative damage to skin. We find that the application of treatment compositions as defined is particularly beneficial in prevention of sun- induced fade of artificial colour, especially that provided by oxidative colouring agents (of the types discussed above) . In particular, we find that methods according to the invention give significant benefits in comparison with the commercially available products which comprise UV absorbers and anti-oxidants, and also show benefits in comparison with other well known UV-absorbers and anti- oxidants . The fibres may be any fibres to which colour has been artificially applied. For instance, they may be textile fibres, for instance natural fibres such as cotton, wool and linen or synthetic fibres such as polyester, polyamide (eg nylon) , acrylic and polyethylene terephthalate. Such fibres may for instance be in the form of textiles for garments, fabrics for household furnishings such as furniture and curtains, or carpets. In some cases the fibres may even be in the form of cellulosic fibres, for instance as wallpaper. However, the invention is particularly beneficial when the fibres are textile, especially wool or cotton, fibres or, in particular, hair .fibres, especially human hair fibres, and these are the most preferred fibrous substrate in the invention.

Treatment compositions used in the first aspect of the invention may have any pH, in particular from 3 to 10.5, but give particular benefits when the pH is at least 5.5. Thus in a second aspect of the invention we provide a treatment composition suitable for reducing sun-induced fade of the colour applied to artificially coloured fibres, the composition comprising at least one salt or complex of a transition metal or a rare earth metal and in which the composition has a pH of at least 5.5.

The composition of the second aspect of the invention may of course be used in the process of the first aspect of the ^• invention. The pH is preferably at least 6.0, more preferably at least 6.1, in particular at least 6.5. In general the pH of treatment compositions according to the second aspect of the invention and treatment compositions used in the first aspect of the invention is not more than 9.5, preferably not more than 8. The treatment composition of both the first and second aspects of the invention comprises a salt or complex which may be a transition metal salt or complex. Preferably the transition metal is a first row transition metal, more preferably cobalt, nickel or copper, especially copper. Alternatively, the salt or complex may be of a rare earth metal (also known as lanthanides or inner transition metals) , preferably cerium.

Suitable anions in the case of salts include chloride, nitrate and acetate. Suitable ligands in the case of complexes include ammonium, NO.,, CN and Cl. Copper acetate is ^'pre erred.

The salt or complex is generally present in an amount of at least 0.1 ppm, based on total weight of the treatment composition. Particularly good results are achieved when the amount is at least 50 ppm, especially at least 100. ppm, and in particular at least 200 ppm. Generally the amount is not more than 10,000 ppm, preferably not more than 5,000 ppm, and often not more than 600 ppm.

In both aspects of the invention the treatment composition may be in any suitable application form. The application form is chosen according to the fibrous substrate to which the treatment composition is to be applied. As discussed above, the fibres are preferably hair fibres and in this case the composition is preferably in the form of a milk or other liquid product, a mousse (aerosol or non-aerosol) , a hair spray (aerosol or non- aerosol) , a conditioner (aerosol or non-aerosol) a gel, a spray gel, a wax or any other cosmetic "leave-on" delivery form known within the industry. hen the fibres are textile fibres, the composition may be in the form of a spray (aerosol or non-aerosol) or a foam (aerosol or non-aerosol) or in the form of a fabric conditioner to be applied to garments after washing, for instance as a liquid composition to be contacted with garments at the end of an automatic clothes washing cycle. When the fibres are in the form of fabrics used for household items such as curtains and furniture coverings the treatment composition is advantageously in the form of a spray (aerosol or non-aerosol) or mousse (aerosol or non- aerosol) .

We find surprisingly that for certain compositions of the invention, better results are achieved when the composition is in the form of a spray or mousse, in comparison with a milk formulation, especially when the fibres are hair fibres.

It is preferred to include in the composition^' a benzotriazole derivative. We find that particular benzotriazole derivatives can give additional benefits over compositions comprising the compound of Formula I alone. Suitable derivatives are disclosed in W098/22447 and W098/23252. Their disclosure is incorporated herein and benzotriazole derivatives disclosed in these publications may be used in the invention. Particularly preferred derivatives are disclosed in EP-A-824,909 and the disclosure of this publication is incorporated herein. In particular, benzotriazole derivatives of the Formula (II) below may be used:

wherein R is hydrogen or chlorine, R is C -C alkyl and M is hydrogen, sodium or potassium.

In a particularly preferred aspect of the invention the composition additionally comprises sodium 3-(2H- benzotriazol-2-yl) -5-sec-butyl-4-hydroxybenzene sulfonate, also known as sodium tinuvin sulfonate, which is available from Ciba Specialty Chemicals under the name TinoGard HS (formerly known as TinoGard UV-i) . we find that this particular active gives benefits in reducing sun-induced fade of artificial colour in fibres, especially hair. Preferred levels are from 0.01 to 10%.

Preferably the composition also comprises a polymer which is a homopolymer of dimethylaminoethylmethacrylate quaternised with methyl chloride (also known as polyquaternium 37) or a copolymer of acrylamide and dimethylaminoethylmethacrylate quaternised with methyl chloride. Normally the polymer is cross-linked, generally with an ethylenically unsaturated compound such as methylene bis acrylamide (MBA) . Particularly preferred polymers of this type include Salcare SC-96, a product available from Ciba Specialty Chemicals which comprises polyquaternium 37.

We find surprisingly that this particular compound provides wash fade benefits, that is it retards fade of artificially applied colour due to repeated washing, especially on hair. This wash fade benefit may be achieved when the fibres are hair and the treatment composition is applied to artificially coloured hair prior to wetting the hair, eg by washing. It may also be achieved when the treatment composition is applied to artificially coloured hair subsequent to washing the hair by application of a shampoo composition and subsequent rinsing of the shampoo composition from the hair. These wash fade benefits arise in particular when the treatment composition is a "leave- on" composition, ie the treatment composition is applied to the hair, it is not rinsed from the hair and the hair is subsequently dried.

The composition may also comprise actives of the Formula I, RC(0)OR , wherein R^' can be substituted or unsubstituted and is a linear or branched C-_.._;- alkyl or alkenyl group or a cyclic aromatic or aliphatic group comprising a single cyclic ring and having total carbon chain length C.)._lS, and R^' is an aryl group having at least 3 hydroxyl substituents. Compositions containing such actives as essential ingredients are discussed in our copending application number ... , reference AS01020GB. Preferably the additional active is a C .• alkyl ester of gallic acid, especially propyl gallate.

The compositions may also comprise known UV absorbers and anti-oxidants such as octyl methoxy cinnamate, benzophenones , eg benzophenone-3 and benzophenone-4 , vitamin E derived compounds such as tocopherol acetate, p- amino benzoic acid, butylmethoxy dibenzoyl methane (Avobenzone) and homosalate.

Suitable anti-oxidants include vitamin A (retinol) , vitamin A acid, esters and acid esters eg retinyl palmitate; vitamin C and its derivatives eg ascorbic acid, ascorbyl esters of fatty acids, eg ascorbyl palmitate, magnesium ascorbyl phosphate; vitamin E and its derivatives eg alpha-tocopherol, tocopherol linoleate, tocopherol nicotinate, tocopherol acetate, sorbate, retinoate and other esters; Trolox (6-hydroxy-2 , 5 , 7 , 8-tetramethylchrσman- 2-carboxylic acid) ; vitamin B and derivatives eg cresol and its derivatives; butylated hydroxy benzoic acids and their salts; butylated hydroxy toluene; butylated hydroxy anisole; t-butyl hydroquinone; uric acid and its salts; sorbic acids and its salts; i≤oascorbic acid; hindered and non-hindered amines; a ino acids eg, glycine, histidine, tyrosine, tryptophan, and derivatives thereof; imidazoles eg urocanic acid; sulfhydryl compounds (eg glutathione) / dihydroxyfu aric acid and its salts; chlorogenic acid; lipoiσ acid; caffeic acid; rosmarinic acid; tetrahydrocurcumin; green tea extract; catechin; sodium sulfite; sodium metabisulfite; sodium thiosulfite; thiols eg thioglycerol, thiosorbitol , thiourea, thioglycolic acid; cysteine hydrochloride; N-acetyl cysteine, cyεteine, cystine, cystamine, and derivatives thereof; 1,4- diazobicyclo- (2, 2, 2) -octane; copper II Bis (3,5-di- isopropyϊsalicylate) ; SuperOxide Dismutase; carotenes eg beta carotene; carotenoids; gamma oryzanol; grape seed extract; pine bark extract; carnosol extract; rosmanol extract; peptides^" eg D,L carnosine, D-carnosine, - carnosine and derivatives. ultra violet filtering agents suitable for topical application are useful in the treatment compositions herein. A wide variety of ultra violet filtering agents are described in US Patent No. 5,087,445, to Haffey et al., . issued February 11, 1992; US Patent No. 5,073,372, to Turner et al, issued December 17, 1991; US Patent No. 5,073,371, to Turner et al issued December 17, 1991; and Segarin, et al, at Chapter VIII, pages 189 et seq., of Cosmetics Science and Technology. Preferred among those ultra violet filtering agents which are useful in the compositions of the instant invention are those selected^' from 2-ethylhexyl p-methoxycinnamate, 2-ethylhexyl N,N- dimethyl-p-aminobenzoate, p-aminobenzoic acid, 2- phenylbenzimidazσle-5-sulfonic acid, octocrylene, oxybenzone, ho omenthyl salicylate, octyl salicylate, 4,4'- methoxy-t-buty Id i benz oy l e th a ne , 4-isopropyl dibenzoyl ethane, 3-benzylidene camphor, 3- (4- ethylbenzylidene) camphor, titanium dioxide, zinc oxide, silica, iron oxide, Parsol MCX, Eusolex 6300, Octocrylene, Parsol 1789, and mixtures thereof.

Still other useful ultra violet filtering agents are those disclosed in US Patent No. 4,937,370, to Sabatelli, issued June 26, 1990; and US Patent No. 4,999,186, to Sabatelli et al, issued March 12, 1991. The ultra violet filtering agents disclosed therein have, in a single molecule, two distinct chromophore moieties which exhibit different ultra-violet radiation absorption spectra. One of the chromophore moieties absorbs predominantly in the UVB radiation range and the other absorbs strongly in the UVA radiation range. These ultra violet filtering agents provide higher efficacy, broader UV absorption, lower skin penetration and longer lasting efficacy relative to conventional ultra violet filtering agents. Especially preferred examples of these ultra violet filtering agents include those selected from 4-N,N-(2- ethylhexyl)methylaminobenzoic acid ester of 2,4- dihydroxybenzophenone, 4-N,N-(2-ethylhexyl) methylaminobenzoic acid ester with 4 - hydroxydibenzoylmethane, 4-N, - (2-ethylhexyl) methylamino- benzoic acid ester of -hydroxy- 4 -( - hydroxyethoxy)benzophenone, 4-N,N-(2-ethylhexyl)- hyla inobenzoic acid ester of 4-(2- hydroxyethoxy) dibenzoylmethane, and mixtures thereof.

When the fibres to be treated are hair fibres, as is preferred, the treatment composition may also include any other known components of hair treatment compositions, for instance conditioning agents such as fatty alcohols, eg cetyl alcohol, cationic polymeric materials and silicones, surfactants, which can be non-ionic, anionic, cationic or amphoteric and are preferably non-ionic or cationic, fixative polymers (specifically in hair sprays, mousses, gels and waxes) especially non-ionic, anionic or cationic, as used in industry hairsprays, mousses, gels and waxes, solubilisers, perfume, buffer, preservative, chelating agents, hydrotrope, other hair treating agents, such as amino acids and vitamins, and water.

Cationic surfactants which can be used in the invention preferably contain amino or quaternary ammonium moieties. The cationic surfactant will preferably, though not necessarily, be insoluble in the treatment composition. Cationic surfactants among those useful herein are disclosed in the following documents, all incorporated by reference herein: M.C. Publishing Co., MσCutcheon's Detergents & Emulsifiers (North American edition 1979) ; Schwartz et al, Surface Active Agents, Their Chemistry and Technology, New York: Interscience Publishers, 1949; US Patent 3,155,591, Hilfer, issued November 3, 1964; US Patent 3,929,678, Laughlin et al, issued December 30, 1975; US Patent 3,959,461, Bailey et al, issued May 25, 1976; and US Patent 4,387,090, Bolich, Jr., issued June 7, 1983.

Among the quaternary ammonium-containing cationic surfactant materials useful herein are those of the general formula:

wherein R₁-R are independently an aliphatic group of from about l to about 22 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkyla ido, hydroxyalkyl , aryl or alkylaryl group having from about 1 to about 22^' carbon atoms; and X is a salt-forming anion such as those selected from halogen (eg chloride, bromide) , acetate, citrate, lactate, glycolate, phosphate, nitrate, sulfate, and alkylsulfate radicals. The aliphatic groups may contain, in addition to carbon and hydrogen atoms, ether linkages, and other groups such as amino groups. The longer chain aliphatic groups, eg, those of about 12 carbons, or higher, 1.2 can be saturated or unsaturated. Especially preferred are di-long chain (e.g., di C₁₂ -C₂₂ , preferably C₁₆-C₁₈ , aliphatic, preferably alkyl) and di-short chain (e.g., C_x- c₃ alkyl, preferably C₁-c₂ alkyl) quaternary ammonium salts.

Salts of primary, secondary and tertiary fatty amines are also suitable cationic surfactant materials. The alkyl groups of such amines preferably have from about 12 to about 22 carbon atoms, and may be substituted or unsubstituted. Such amines useful herein, include stearamido propyl dimethyl a ine, diethyl amino ethyl steara ide, dimethyl stearamine, dimethyl soyamine, soyamine, myristyl amine, tridecyl amine, ethyl stearylamine, N-tallowpropane diamine, ethoxylated (with 5 moles of ethylene oxide) stearylamine, dihydroxy ethyl stearylamine, and arachidylbehenylamine . Suitable amine salts include the halogen, acetate, phosphate, nitrate, citrate, lactate, and alkyl sulfate salts. Such salts include stearylamine hydrochloride, soyamine chloride, stearylamine formate, N-tallowpropane diamine dichloride and stearamidopropyl dimethyla ine citrate. Cationic amine surfactants included among those useful in the present invention are disclosed in US Patent 4,275,055, Nachtigal, et al, issued June 23, 1981. Cationic surfactants are preferably used at levels of from about 0.1% to about 10%, more preferably from about 0.25% to about 5%, most preferably from about 0.5% to about 2%, by weight of the composition.

The treatment compositions useful in the present invention can also comprise one or more cationic polymer conditioning agents (instead of or in addition to the cationic polymer conditioning agent of the type discussed above and of which polyquaternium 37 is an example) . Cationic polymers are typically used in the same ranges as disclosed above for cationic surfactants.

As used herein, the term "polymer" shall include materials whether made by polymerization of one type of monomer or made by two (i.e., copolymers) or more types of monomers .

The cationic polymers generally have a weight average molecular weight which is at least about 5,000, typically at least about 10,000, and is less than about 10 million. Preferably, the molecular weight is from about 100,000 to about 2 million. The cationic polymers will generally have cationic nitrogen-containing moieties such as quaternary ammonium or cationic amino moieties, and mixtures thereof. Any anionic counterions can be utilized for the cationic polymers so long as the water solubility criteria is met. Suitable counterions include halides (eg, C , Br, I, or F, preferably Cl, Br, or I), sulfate, and ethylsulfate. Others can also be used, as this list is not exclusive.

The cationic nitrogen-containing moiety will be present generally as a substituent, on a fraction of the total monomer units of the cationic hair conditioning polymers. Thus, the cationic polymer can comprise copolymers, terpoly ers, etc. of quaternary ammonium or cationic a ine-substituted monomer units and other non-cationic units referred to herein as spacer monomer units. Such polymers are known in the art, and a variety can be found in the CTFA Cosmetic Ingredient Dictionary, 3rd edition, edited by Estrin, Crosley, and Haynes, (The Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, D.C., 1982).

Suitable cationic polymers include, for example, copolymers of vinyl monomers having cationic amine or quaternary ammonium functionalities with water soluble spacer monomers such as acrylamide, methacrylamide, alkyl and dialkyl acryla ides, alkyl and dialkyl methacrylamides, alkyl acrylate, alkyl methacrylate, vinyl caprolactone, and vinyl pyrrolidone. The alkyl and dialkyl substituted monomers preferably have C -C- alkyl groups, more preferably C -C^ alkyl groups. Other suitable spacer monomers include vinyl esters, vinyl alcohol (made by hydrolysis of polyvinyl acetate) , 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.

Amine-substituted vinyl monomers can be polymerised in the amine form, and then optionally can be converted to ammonium by a quaternization reaction. Amines can also be similarly quaternised subsequent to formation of the polymer. For example, tertiary amine functionalities can be quaternised by reaction with a salt of the formula R'X wherein R" is a short chain alkyl, preferably a C₁-C₇ alkyl, more preferably a C-₁-C2 alkyl, and X is an anion which forms a water soluble salt with the quaternized 'ammonium.

Suitable cationic amino and quaternary ammonium monomers include, for example, vinyl compounds substituted with dialkylaminoalkyl acrylate, dialkylaminoalkyl ethac y late , onoa Iky lami noa Iky 1 acrylate, monoa Iky 1 a inoa Iky 1 methacr y la te , trialkyl methacryloxyalkyl ammonium salt, trialkyl acryloxyalkyl ammonium salt, diallyl quaternary ammonium salts, and vinyl quaternary ammonium monomers having cyclic cationic nitrogen-containing rings such as pyridinium, imidazolium, and quaternised pyrrolidone, e.g., alkyl vinyl imidazolium, alkyl vinyl pyridinium, alkyl vinyl pyrrolidone salts. The alkyl portions of these monomers are preferably lower alkyls such as the C1-C3 alkyls, more preferably and C alkyls. Suitable amine-substituted vinyl monomers for use herein include dialkylaminoalkyl acrylate, dialkylaminoalkyl methacry late, dialkylaminoalkyl acrylamide, and dialkylaminoalkyl methacrylamide, wherein the alkyl groups are preferably ι~ - hydrocarbyls, more preferably C1-C3, alkyls. The cationic polymers hereof can comprise mixtures of monomer units derived from amine- and/or quaternary ammonium-substituted monomer and/or compatible spacer monomers .

Suitable cationic hair conditioning polymers include, for example: copolymers of l-vinyl-2-pyrrolidone and l-vinyl-3-methylimidazolium salt (eg, chloride salt) (referred to in the industry by the Cosmetic, Toiletry, and Fragrance Association, "CTFA", as Polyquaternium-16) , such as those commercially available from BASF Wyandotte Corp. (Parsippany, NJ, USA) under the LUVIQUAT tradename (eg, LUVIQUAT FC 370) ; copolymers of l-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate (referred to in the industry by CTFA as Polyquaternium-ii) such as those commercially available from Gaf Corporation (Wayne, NJ, USA) under the GAFQUAT tradename (eg, GAFQUAT 755N) ; cationic diallyl quaternary ammonium-containing polymers, including, for example, di ethyldiallylammonium chloride homopolymer and copolymers of acrylamide and dimethyldiallylammonium chloride, referred to in the industry (CTFA) as Polyquaternium 6 and Polyquaternium 7, respectively; and 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 US Patent 4,009,256, incorporated herein by reference.

Other cationic polymers that can be used include polysaccharide polymers, such as cationic cellulose derivatives and cationic starch derivatives.

Cationic polysaccharide polymer materials suitable for use herein include those of the formula:

wherein: A is an anhydroglucose residual group, such as a starch or cellulose anhydroglucose residual, R is an alkylene oxyalkylene-, polyoxyalkylene, or hydroxyalkylene group, or combination thereof, R , R₂ > ^{and R}3 independently are alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18 carbon atoms, and the total number of carbon atoms for each cationic moiety (ie, the sum of carbon atoms in _x, R₂ and R₃) preferably being about 20 or less, and X is an anionic counterion, as previously described. .

Cationic cellulose is available from Amerchol Corp. (Edison, NJ, USA) in their Polymer JR(RTM) and LR(RTM) series of polymers, as salts of hydroxyethyl cellulose reacted with tri ethyl ammonium substituted epoxide, referred to in the industry (CTFA) as Polyquaternium 10. Another type of cationic cellulose includes the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium-substituted opoxide, referred to in the industry (CTFA) as Polyquaternium 24. These materials are available from Amerchol Corp. (Edison, NJ, USA) under the tradename Polymer LM-200(RTM). Other cationic polymers that can be used include cationic guar gum derivatives, such as guar hydroxypropyltrimonium chloride (commercially available from Celanese Corp. in their Jaguar R series) . other materials include quaternary nitrogen-containing cellulose ethers (eg, as described in US Patent 3,962,418, incorporated by reference herein), and copolymers of etherified cellulose and starch (eg, as described in US Patent 3,958,581, incorporated herein by reference) .

The treatment composition of the present invention can also include soluble or insoluble silicone conditioning agents. By soluble what is meant is that the silicone conditioning agent is miscible with the aqueous carrier of the composition so as to form part of the same phase. By insoluble what is meant is that the silicone forms a separate, discontinuous phase from the aqueous carrier, such as in the form of an emulsion or a suspension of droplets of the silicone. The silicone hair conditioning agent can be used in the treatment composition at levels of from about 0.05% to about 10% by weight of the composition, preferably from about 0.1% to about 6%, more preferably from about 0.5% to about 5%, most preferably from about 0.5% to about 3%.

Soluble silicones include silicone copolyols, such as diroethicone copolyols, e.g. polyether siloxane- odified polymers, such as polypropylene oxide and/or polyethylene oxide modified polydimethylsiloxane, wherein the level of ethylene and/or propylene oxide sufficient to allow solubility in the composition.

Preferred, however, are insoluble silicones. The insoluble silicone hair conditioning agent for use herein preferably has viscosity of from about 1,000 to about 2,000,000 centistokes at 25^CC, more preferably from about 10,000 to about 1,800,000, even more preferably from about 100,000 to about 1,500,000. The viscosity can be measured by means of a glass capillary viscometer as set forth in Dow Corning Corporate Test Method CTM0004, July 20, 1970.

Suitable volatile silicones include cyclomethicone. Suitable insoluble, nonvolatile silicone fluids include polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers, and mixtures thereof. Other insoluble, nonvolatile silicone fluids having hair conditioning properties can also be used. The term "nonvolatile" as used herein shall mean that the silicone has a boiling point of at least about 260°C, preferably at least about 275°C, more preferably at least about 300°C. Such materials exhibit very low or no significant vapor pressure at ambient conditions. The term "silicone fluid" shall mean flowable silicone materials having a viscosity of less than 1,000,000 centistokes at 25^βC. Generally, the viscosity of the fluid will be between about 5 and 1,000,000 centistokes at 25°C, preferably between about 10 and about 300,000 centistokes .

Silicone fluids also include polyalkyl or polyaryl siloxanes with the following structure:

wherein R is alkyl or aryl, and x-is an integer from about 7 to about 8,000. "A" represents groups which block the ends of the silicone chains.

The alkyl or aryl groups substituted on the siloxane chain (R) or at the ends of the siloxane chains (A) may have any structure as long as the resulting silicones remain fluid at room temperature, are hydrophobic, are not irritating, toxic or otherwise harmful when applied to hair, are compatible with the other components of the composition, are chemically stable under normal use and storage conditions, and are capable of being deposited on and of conditioning hair.

Suitable A groups include methyl, methoxy, ethoxy, propoxy, and aryloxy. The two R groups on the silicone atom may represent the same group or different groups. Preferably, the two R groups represent the same group. Suitable R groups include methyl, ethyl, propyl, phenyl, methylphenyl and phenyl ethyl. The preferred silicones are polydimethyl siloxane, polydiethylsiloxane, and polymethylphenylsiloxane. Polydimethylsiloxane is especially preferred.

The nonvolatile polyalkylsilox^'ane fluids that may be used include, for example, polydimethylsiloxanes. These siloxanes are available, for example, from the General Electric Company in their Viscasil/R and SF 96 series, and from Dow Corning in their Dow Corning 200 series.

The polyalkylaryl siloxane fluids that may be used ^' also include, for example, polymethylphenylsiloxanes. These siloxanes are available, for example, from the General Electric Company as SF 1075 methyl phenyl fluid or from Dow Corning as 556 Cosmetic Grade Fluid.

Especially preferred, for enhancing the shine characteristics of hair, are highly arylated silicones, such as highly phenylated polyethyl silicone having refractive indices of about 1.46 or higher, especially about 1.52 or higher. When these high refractive index silicones are used, they should be mixed with a spreading agent, such as a surfactant or a silicone resin, to decrease the surface tension and enhance the film forming ability of the material.

The polyether siloxane copolymers that may be used include, for example, a polypropylene oxide modified polydimethylsiloxane (e.g., Dow Corning DC-1248) although ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used. The ethylene oxide and polypropylene oxide level should be sufficiently low to prevent solubility in the composition hereof.

References disclosing suitable silicone fluids include U.S. Patent 2,826,551, Geen; US Patent 3,964,500, Drakoff, issued June 22, 1976; US Patent 4,364,837, Pader; and British Patent 849,433, Woolston. All of these patents are incorporated herein by reference. Also incorporated herein by reference is Silicon Compounds distributed by Petrarch Systems, Inc., 1984. This reference provides an extensive (though not exclusive) listing of suitable silicone fluids.

Another silicone hair conditioning material that can be especially useful as a silicone conditioning agent is insoluble silicone gum. The term "silicone gum", as used herein, means polyorganosiloxane materials having a viscosity at 25°C of greater than or equal to 1,000,000 centistokes. silicone gums are described by Petrarch and others including US Patent 4,152,416, Spitzer et al., issued May 1, 1979 and Noll, Walter, Chemistry and Technology of Silicones, New York: Academic Press 1968. Also describing silicone gums are General Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76. All of these described references are incorporated herein by reference. The "silicone gums" will typically have a mass molecular weight in excess of about 200,000, generally between about 200,000 and about 1,000,000. Specific examples include polydimethylsiloxane, (polydimethylsiloxane) ( ethylvinylsiloxane ) copolymer , poly (di ethylsiloxane) (diphenyl siloxane) (methyl vinylsiloxane) copolymer and mixtures thereof. Preferably the silicone hair conditioning agent comprises a mixture of a polydimethylsiloxane gum, having a viscosity greater than about 1,000,000 centistokes and polydimethylsiloxane fluid having a viscosity of fro about 10 centistokes to about 100,000 centistokes, wherein the ratio of gum to fluid is from about 30:70 to about 70:30, preferably from about 40:60 to about 60:40.

An optional ingredient that can be included in the silicone conditioning agent is silicone resin. Silicone resins are highly crosslinked polymeric siloxane systems. The cross-linking is introduced through the incorporation of trifunctiσnal and tetrafunctional silanes with onofunctional or difunctional, or both, silanes during manufacture of the silicone resin. As is well understood in the' art, the degree of cross-linking that is required in order to result in a silicone resin will vary according to the specific silane units incorporated into the silicone resin. In general, silicone materials which have a sufficient level of trifunctional and tetrafunctional siloxane monomer units (and hence, a sufficient level of crosslinking) such that they dry down to a rigid, or hard, film are considered to be silicone resins. The ratio of oxygen atoms to silicon atoms is indicative of the level of crosslinking in a particular silicone material. Silicone materials which have at least about 1.1 oxygen atoms per silicon atom will generally be silicone resins herein. Preferably, the ratio of oxyge silicon atoms is at least about 1.2:1.0. Silanes used in the manufacture of silicone resins include monomethyl-, dimethyl-, trimethyl-, onophenyl-, diphenyl-, ethylphenyl- , monovinyl-, and methylvinyl-chlorosilanes, and tetra- chlorosilane, with the methyl-substituted silanes being most commonly utilized. Preferred resins are offered by General Electric as GE SS4230 and SS4267. Commercially available silicone resins will generally be supplied in a dissolved form in a low viscosity volatile or nonvolatile silicone fluid. The silicone resins for use herein should be supplied and incorporated into the present compositions in such dissolved form, as will be readily apparent to those skilled in the art.

Silicone resins can enhance deposition of silicone on the hair and can enhance the glossiness of hair with high refractive index volumes. Background material on silicones including sections discussing silicone fluids, gums, and resins, as well as manufacture of silicones, can be found in Encyclopedia of Polymer Science and Engineering, Volume 15, Second Edition, pp 204-308, John Wiley & Sons, Inc., 1989, incorporated herein by reference.

Silicone materials and silicone resins in particular can conveniently be identified according to a shorthand nomenclature system well known to those skilled in the art as "MDTQ" nomenclature. Under this system, the silicone is described according to presence of various siloxane monomer units which make up the silicone. Briefly, the symbol M denotes the monofunctional unit (CH3) 3SiO) ., ; D denotes the difunctional unit (CH₃)₂siθ; T denotes the trifunctional unit (CH3) Si0_lι5; and Q denotes the quadri- or tetra-functional unit Si0₂. Primes of the unit symbols, e.g., M', D¹, T', and Q' denote substituents other than methyl, and must be specifically defined for each occurrence. Typical alternate substituents include groups such as vinyl, phenyls, -amines, hydroxyls, etc. The molar ratios of the various units, either in terms of subscripts to the symbols indicating the total number of each type of unit in the silicone (or an average thereof) or as specifically indicated ratios in combination with molecular weight complete the description of the silicone material under the MDTQ system. Higher relative molar amounts of T, Q, T' and/or Q' to D, D', M and/or or M* in a silicone resin is indicative of higher levels of cross-linking. As discussed before, however, the overall level of cross-linking can also be indicated by the oxygen to silicon ratio.

The silicone resins for use herein which are preferred are MQ, MT, MTQ, MQ and MDTQ resins. Thus, the preferred silicone substituent is methyl. Especially preferred are MQ resins wherein the M:Q ratio is from about 0.5:1.0 to about 1.5: l.O and the average molecular weight of the resin is from about 1000 to about 10,000.^'

The treatment compositions useful .in the present invention can also comprise water-soluble nonionic surfactant (s) . Surfactants of this class include C₁₂- C1 fatty acid mono-and diethanolamides, sucrose 01 05585

polyester surfactants and polyhydroxy fatty acid amide surfactants having the general formula below.

R₀-C-N— 2-

The preferred N-alkyl, N-alkoxy or N-aryloxy, polyhydroxy fatty acid amide surfactants according to the above formula are those in which R₃ is C₅-C₃₁ hydrσcarbyl, preferably C5-C1₉ hydrocarbyl, including straight-chain and branched chain alkyl and alkenyl, or mixtures thereof and R₉ is typically hydrogen, C _ - C₃ alkyl or hydroxyalkyl, preferably methyl, or a group of formula -R¹-θ-R² wherein R¹ is C₂-C₃ hydrocarbyl including straight-chain, branched-chain and cyclic (including aryl), and is preferably C -C₄ alkylene, R² is C^-Cs straight-chain, branched-chain and cyclic hydrocarbyl including aryl and oxyhydrocarbyl, and is preferably C₁-C₄ alkyl, especially methyl, or phenyl. Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 2 (in the case of glyceraldehyde) or at least 3 hydroxyIs (in the case of other reducing sugars) directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z₂ preferably will be derived from a reducing sugar in a reductive a ination reaction, most preferably Z₂ is a glycityl moiety. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilised as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z₂. It should be understood that it is by no means intended to exclude other suitable raw materials. 2₂ preferably will be selected from the group consisting of -CH - (CHOH)_n-CH₂OH, -CH(CH₂OH)-(CHOH)_n_₁-CH₂H, CH₂ (CHOH) ₂(CH0R') CHOH) -CH₂0H, where n is an integer from 1 to 5, inclusive, and R¹ is H or a cyclic mono- or polysaccharide, and alkoxylated derivatives thereof. As noted, most preferred are glycit ls wherein n is , particularly -CH₂- (CHOH) ₄-CH₂OH.

The most preferred polyhydroxy fatty acid amide has the formula R₈ (CO)N (CH₃) CH₂ (CHOH) ₄CH₂0H wherein R_s is a C6-C19 straight chain alkyl or alkenyl group. In compounds of the above formula, Rg-CO-N< can be, for example, cocoamide, steara ide, olea ide, lauraroide, myristamide, capricamide, palmiamide, tallowamide, etc.

Suitable oil derived nonioniσ surfactants for use herein include water soluble vegetable and animal- derived emollients such as triglycerides with a polyethyleneglycol chain inserted, ethoxylated mono and di-glycerides, polyethoxylated lanolins and ethoxylated butter derivatives. One preferred class of oil-derived nonionic surfactants for use herein have the general formula below:

o i:

RC0CH₂CH(0H) CH₂ (OCH₂CH₂ ) _n0H

wherein n is from about 5 to about 200, preferably from about 20 to about 100, more preferably from about 30 to about 85, and wherein R comprises an aliphatic radical having on average from about 5 to 20 carbon atoms, preferably from about 7 to 18 carbon atoms.

Suitable ethoxylated oils and fats of this class include polyethyleneglycol derivatives of glyceryl cocoate, glyceryl caproate, glyceryl caprylate, glyceryl tallowate, glyceryl palmate, glyceryl stearate, glyceryl laurate, glyceryl oleate, glyceryl ricinoleate, and glyceryl fatty esters derived from triglycerides, such as palm oil, almond oil, and corn oil, preferably glyceryl tallowate and glyceryl cocoate .

Preferred for use herein are polyethyleneglycol based polyethoxylated C9-C15 fatty alcohol nonionic surfactants containing an average of from about 5 to about 50 ethyleneoxy moieties per mole of surfactant.

Suitable polyethylene glycol based polyethoxylated C9-C3.5 fatty alcohols suitable for use herein include C₉-Cn Pareth-3, Cg-Cn .Pareth-4 , C₉-

C3.1 Pareth-5, Cg-C^j. Pareth-6, g -Cn Pareth-7 , Cg-C^ Pareth-8, C₁₁-C₁₅ Pareth-3 , C₁₁-C₁5 Pareth-4 , C₁₁-C₁₅ Pareth-5,

Pareth-8, C^-C_]^ Pareth-9, C^-c^ Pareth-10, C^-C^ Pareth-ll, C^-Cis Pareth-12, Cn-C ^ Pareth-13 and ^C ₁₁~^C15 Pareth-14. PEG 40 hydrogenated castor oil is commercially available under the tradename Cremophor (RTM) from BASF. PEG 7 glyceryl cocoate and PEG 20 glyceryl laurate are commercially available from Henkel under the tradenames Cetiol (RTM) HE and La acit (RTM) GML 20 respectively. Cg-Cn Pareth-8 is commercially available from Shell Ltd under the tradename Dobanol (RTM) 91-8. Particularly preferred for use herein are - polyethylene glycol ethers of ceteryl alcohol such as Ceteareth 25 which is available from BASF under the trade name Cremaphor A25.

Also suitable for use herein are nonionic surfactants derived from composite vegetable fats extracted from the - fruit of the Shea Tree (Butyrospermu Karkii Kotschy) and derivatives thereof. Similarly, ethoxylated derivatives of -Mango, Cocoa and Illipe butter may be used in compositions according to the invention. Although these are classified as ethoxylated nonionic surfactants it is understood that a certain proportion may remain as non-ethoxylated vegetable oil or fat.

Other suitable oil-derived nonionic surfactants include ethoxylated derivatives of almond oil, peanut oil, rice bran oil, wheat germ oil, linseed oil, jojoba oil, oil of apricot pits, walnuts, palm nuts, pistachio nuts, sesame seeds, rapeseed, cade oil, corn oil, peach pit oil, poppyseed oil, pine oil, castor oil, soybean oil, avocado oil, safflower oil, coconut oil, hazelnut oil, olive oil, grapeseed oil, and sunflower seed oil.

Amphoteric surfactants suitable for use in the treatment compositions useful in the present method include:

(a) imidazolinium surfactants of formula (VII)

c2^H4^OR2

CH₂Z

N

wherein R^ is C₇-C22 alkyl or alkenyl, R₂ is hydrogen or CH2Z, each Z is independently C0₂M or CH C0₂M, and M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium; and/or ammonium derivatives of formula (VIII)

C₂H₄0H R₁C0NH(CH₂) ₂N⁺CH₂Z

^R2 TU Ol/05585

27 wherein ]_, R₂ and z are as defined above;

(b) aminoalkanoates of formula (IX)

R₁NH(CH₂)_nC0₂M

iminodialkanoates of formula (X)

RlN[(CH₂)_mC0₂M]₂

and i inopolyalkanoates of formula (XI)

R₁_(N(CH₂)p]_qN[CH₂C0₂M]₂

I CH₂C0₂M

wherein n, m, p, and q are numbers from 1 to 4, and R₁ and M are independently selected from the groups specified above; and

(c) mixtures thereof.

Suitable amphoteric surfactants of type (a) are marketed under the trade name Miranol and Empigen and are understood to comprise a complex mixture of species. Traditionally, the Miranols have been described as having the general formula (VII) , although the CTFA Cosmetic Ingredient Dictionary, 3rd Edition indicates the non-cyclic structure (VIII) while the 4th Edition indicates yet another structural isσmer in which R₂ ^^s O-linked -rather than N-linked. In practice, a complex mixture of cyclic and non-cyclic species is likely to exist and both definitions are given here for sake of completeness. Preferred for use herein, however, are the non-cyclic species.

Examples of suitable amphoteric surfactants of type (a) include compounds of formula XII and/or XIII in which Ri is CgHi₇ (especially iso-capryl) , C9H ₉ and ^C1₁ ^H ₂3 alkyl. Especially preferred are the compounds in which R_ is C₉H19, Z is C0₂M and R₂ is H; the compounds in which Ri is C₁₁H _3/ Z is C0₂M and R₂ is CH₂C0₂M; and the compounds in which Rj. is C₁]_H₂3 1 is C0₂M and R₂ is H.

In CTFA nomenclature, materials suitable for use in the present invention inc lude cocoamphocarboxypropioπate , cσcoamphocarboxy propionic acid, and especially cocoamphoacetate and cocoa phodiacεtate (otherwise referred to as cocoamphocarboxyglycinate) . Speci ic commercial products include those sold under the trade names of Ampholak 7TX (sodium carboxy methyl tallow polypropyl amine) , Empigen CDL60 and CDR 60 (Albright & Wilson) ; Miranol H2M Cone; Miranol C2M Cone. N.P., Miranol C2M Cone. O.P.; Miranol C2M SF, Miranol CM Special (Rhδne- Poulenc) ; Alkateric 2CIB (Alkaril Chemicals) ; Amphoterge W-2 (Lonza, Inc.); Monateric CDX-33, onateric CSH-32 (Mona Industries) ; Rewoteric AM-2C (Rewo Chemical Group) ; and Schercotic MS-2 (Scher Chemicals) . Further examples of amphoteric surfactants suitable for use herein include Octoxynol-l (RTM), polyoxethylene (1) octylphenyl ether; Nonoxynol-4 (RTM) , polyoxyethylene (4) nonylphenyl ether; and Nonσxynol-9, polyoxyethylene (9) nonylphenyl ether.

It will be understood that a number of commercially-available amphoteric surfactants of this type are manufactured and sold in the form of electroneutral complexes with, for example, hydroxide counterions or with anionic sulfate or sulfonate surfactants, especially those of the sulfated 03-0_3.3 alcohol, Cg-C₁₈ ethoxylated alcohol or C_S-C_1S acyl glyceride types. Note also that the concentrations and weight ratios of the amphoteric surfactants are based herein on the uncomplexed forms of the surfactants, any anionic surfactant counterions being considered as part of the overall anionic surfactant component content.

Examples of preferred amphoteric surfactants of type (b) include N-alkyl polytrimethylene poly-, carboxy ethyla ines sold under the trade names Ampholak X07 and Ampholak 7CX by Berol Nobel and also salts, especially the triethanola monium salts and salts of N- lauryl-beta-amino propionic acid and N-lauryl-imino- dipropionic acid. Such materials are sold under the trade name Deriphat by Henkel and Mirataine by Rhδne- Poulenc.

Water-soluble auxiliary zwitterionic surfactants suitable for inclusion in the treatment compositions useful in the present method include alkyl betaines of the formula R₅R₅R₇N" (CH )_rιC0₂M ^and amido betaines of the formula (XII) below:

^R6

R₅CON,(CH₂) _roN (CH₂) _nC0₂M i

wherein R5 is C^-C^ alkyl or alkenyl, Rg and R₇ are independently C3.-C₃ alkyl, M is H, alkali metal, alkaline earth metal, ammonium or alkanolam onium, and n, m are each numbers from 1 to 4. Preferred betaines include cocoamidopropyldimethylcarboxy ethyl betaine, laurylamidopropyldimethylcarboxy ethyl betaine and Tego betaine (RTM) .

Water-soluble auxiliary sultaine surfactants suitable for inclusion in the compositions of the present invention include alkyl sultaines of the formula (XIII) below: R,

I R₁CON(CH₂)_mN'(CH₂)nCH(OH)CH₂S0₃-M⁺

R3 w h e r e i n

R_l is C7 to c₂₂ alkyl or alkenyl, R₂ a R₃ are independently C_j. to C alkyl, M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium and and n are numbers from 1 to 4. Preferred for use herein is coco amido propylhydroxy sultaine.

Water-soluble auxiliary amine oxide surfactants suitable for inclusion in the compositions of the present invention include alkyl amine oxide R₅R_{6 7} O and amido amine oxides of the formula (XIV) below:

*6

R₅CON(CH₂)_mN 0

R?

wherein R5 is C^j. to C₂₂ alkyl or alkenyl, Rg and R₇ are independently Ci to C₃ alkyl, M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium and m is a number from 1 to 4. Preferred amine oxides include cocoa idopropyla ine oxide, lauryl dimethyl amine oxide and myristyl dimethyl amine oxide.

The treatment compositions useful in the present method can contain a variety of other optional components suitable for rendering, such compositions more cosmetically or aesthetically acceptable or to provide them with additional usage benefits. Such conventional optional ingredients are well-known to those skilled in the art. A wide variety of additional ingredients can be formulated into the present compositions. These include: other conditioning agents; hair-hold polymers; additional thickening agents and suspending agents such as xanthan gum, guar gum, hydroxyethyl cellulose, methyl cellulose, hydroxyethylcellulose, starch and starch derivatives; viscosity modifiers such as methanola ides of long chain fatty acids such as cocomonoethanol amide; crystalline suspending agents; pearlescent aids such as ethylene glycol distearate; preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidazolidinyl urea; polyvinyl alcohol; ethyl alcohol; pH adjusting agents such as citric acid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxide and sodium carbonate; salts, in general, such as potassium acetate and sodium chloride; hair reducing agents, such as the thioglycolates ; perfumes; and polymer plasticizing agents, such as glycerin, disobutyl adipate, butyl stearate, and propylene glycol.

Also suitable for use herein as conditioning agents when the fibres are hair fibres are liquid polyol carboxylic acid esters. These polyol esters are derived from a polyol with one or more carboxylic acids. In other words, these esters contain a moiety derived from a polyol and one or more moieties derived from a carboxylic acid. These carboxylic acid esters can also be described as liquid polyol fatty acid esters, because the terms carboxylic acid and fatty acid are often used interchangeably by those skilled in the art. As used herein, the term liquid means a fluid which is visibly flowable (to the naked eye) under ambient conditions (about 1 atmosphere of pressure at about 25°C) . The liquid polyol polyesters suitable for use herein comprise certain polyols, especially sugars, sugar alcohols or sugar ethers, esterified with at least two fatty acid groups. The polyol starting material, however, preferably has at least about four esterifiable hydroxyl groups. Examples of preferred polyols are sugars, including onosaccharides and disaccharides, sugar alcohols or sugar ethers. Examples of monosaccharides containing four hydroxyl groups are xylose and arabinose and the sugar alcohol derived from xylose, which has five hydroxyl groups, ie, xylitol. The onσsaccharide, erythrose, is also suitable in the practice of this invention since it contains three hydroxyl groups, as is the sugar alcohol derived from erythrose, ie, erythritol, which contains four hydroxyl groups. Suitable five hydroxyl group-containing monosaccharides are galactose, fructose, and sorbose. Sugar alcohols containing six hydroxyl groups derived from the hydrolysis products of sucrose, as well as glucose and sorbose, eg, sorbitol, are also suitable. Examples of disaccharide polyols which can be used include maltose, lactose, and sucrose, all of which contain eight hydroxyl groups. In addition, sugar ethers are also suitable for the practise of this invention, such as, sorbitan.

The polyols used in such liquid polyol esters preferably have from about 4 to about 12, more preferably from about 4 to about 11, and most preferably from about 4 to about S hydroxyl groups. Preferred polyols for preparing the polyesters suitable for use herein are selected from the group consisting of erythritol, xylitol, sorbitol, glucose, and sucrose. Sucrose is especially preferred.

The preferred polyol starting material having at least four hydroxyl groups must be esterified on at least two of the hydroxyl groups with a fatty acid containing from about 8 to about 22 carbon atoms, preferably from about 8 to about 14 carbon atoms. Examples of such fatty acids include caprylic, capric, lauric, myristic, myristoleic, palmitic, palmitoleic, stearic, oleic, ricinoleic, linoleic, linolenic, eleostearic, arachidic, arachidonic, behenic, and erucic acids. The fatty acids can be derived from naturally occurring or synthetic fatty acids; they can be saturated or unsaturated, including positional and geometrical iso ers. However, in order to provide liquid polyesters of the type suitable for use herein, at least about half of the fatty acid incorporated into the polyester molecule must be unsaturated fatty acids, saturated short chain fatty acids, or mixtures thereof. The liquid polyol fatty acid polyesters suitable for use as conditioning agents herein must contain at least two fatty acid ester groups. It is not necessary that all of the hydroxyl groups of the polyol be esterified with fatty acids, but it is preferable that the polyester contain no more than two unesterified hydroxyl groups. Most preferably, substantially all of the hydroxyl groups of the polyol are esterified with fatty acid,s, ie, the polyol moiety is substantially completely esterified. The fatty acids esterified to the polyol molecule can be the same or mixed, but as noted above, a substantial amount of the unsaturated acid ester groups and/or saturated short chain acid ester groups must be present to provide liquidity. To illustrate the above points, a sucrose di-fatty acid- ester would be suitable, but is not preferred because it has more than two unesterified hydroxyl groups. A sucrose hexa-fatty acid ester would be preferred because it has no more than two unesterified hydroxyl groups. Highly preferred compounds in which all the hydroxyl groups are esterified with fatty acids include the liquid sucrose octa-substituted fatty acid esters.

The following are non-limiting examples of specific liquid polyol fatty acid polyesters containing at least two fatty acid ester groups suitable for use in the present invention: glucose dioleate, the glucose diesters of soybean oil or cotton seed oil fatty acids (unsaturated) , the annose diesters of mixed soybean oil or cotton seed oil fatty acids, the galactose diesters of oleic acid, the arabinose diesters of linoleic acid, xylose dilinoleate, sorbitol dioleate, sucrose dioleate, glucose trioleate, the glucose triesters of soybean oil or cotton seed oil fatty acids (unsaturated) , the mannose triesters of mixed soybean oil or cotton seed oil fatty acids, the galactose triesters of oleic acid, the arabinose triesters of linoleic acid, xylose trilinoleate, sorbitol^~ trioleate, sucrose trioleate, glucose tetraoleate, the glucose tetraesters of soybean oil or cotton seed oil fatty acids (unsaturated) , the mannose tetraesters of mixed soybean oil or cotton seed oil fatty acids, the galactose tetraesters of oleic acid, the arabinose tetraesters of linoleic acid, xylose tetralinoleate, galactose pentaoleate, sorbitol tetraoleate, the sorbitol hexaesters of unsaturated soybean oil or cotton seed oil fatty acids, xylitol pentaoleate, sucrose tetraoleate, sucrose pentaoletate, sucrose hexaoleate, sucrose hepatoleate, sucrose octaoleate, and mixtures thereof.

The preferred liquid polyol polyesters of the present invention have complete melting points below about 30^CC, preferably below about 27.5^βc, and more preferably below about 25^UC. Complete melting points reported herein are measured by Differential Scanning Calorimetry (DSC). The term "complete melting point", as used herein means a melting point as measured by the well-known technique of Differential Scanning Calorimetry (DSC) . The complete melting point is the temperature at the intersection of the baseline, ie the specific heat line, with the line tangent to the trailing edge of the endothermic peak. Typically a scanning temperature of 5"C/minute is used in the present invention in measuring the complete melting points. A technique for measuring complete melting points is more fully described in US-A-5 , 3.06 , 51 , to Letton et al, issued April 26, 1994. Exemplary liquid polyol carboxylic acid esters suitable for use herein are sucrose polyεoyate or sucrose polycottonseedoate available from Procter and Gamble.

The polyol fatty acid polyesters suitable for use herein can be prepared by a variety of methods well known to those skilled in the art. These methods include: transesterification of the polyol with methyl, ethyl or glycerol fatty acid esters using a variety of catalysts; acylation of the polyol with a fatty acid chloride; acylation of the polyol with a fatty acid anhydride; and acylation of the polyol with a fatty acid, per se. See US-A-3 , 463 , 699 , to Rizzi, issued June 15, 1976; and US-A-4 , 51^'7 , 360 and 4,518,772 to Volpenhein issued 1985.

In the method according to the invention a treatment composition comprising a salt or complex of a transition metal or a rare earth metal is applied to artificially coloured fibres, preferably hair. Of course, the treatment composition may be a composition according to the second aspect of the invention. In the method of the invention the treatment composition may have. ny of the additional features discussed above.

When the fibres are textile fibres, the composition is generally applied to the fibres and not removed until the next occasion on which the fibres are washed or otherwise cleaned.

When the fibres are hair, various treatment methods may be used. The examples include the following.

The colour applied may be of any hue and shade. The invention is concerned with prevention of sun-induced fade of artificially applied colour. It is not directed to the prevention of fade of any natural colour, such as melanin in the case of hair fibres. Generally the molecules which provide the artificial colour are no greater than tetrameric in size, where a monomer is defined as a single 4, 5 or 6 membered ring, preerably a 6 membered aromatic ring. The method may involve application of the treatment composition and subsequent rinsing of the treatment composition from the hair. By "subsequent rinsing" we mean rinsing from the hair not more than one hour after application, preferably not more than 30 minutes, and more preferably not more than 10 minutes after application of the treatment composition. However, preferably the treatment composition is a "leave-on" composition which is applied to the hair and not rinsed off subsequently. That is, it is not rinsed off within a period of one hour, preferably not within 3 hours. Generally it is not rinsed off until the next occasion on which the hair is washed.

Preferably the method is a method in which the hair is washed by application of a shampoo composition which after lathering is rinsed from the hair in a first rinsing step. Optionally the process may comprise application of a conditioning composition to the hair subsequent to the first rinsing step. The conditioning composition is generally rinsed from the hair in a second rinsing step.

The treatment composition is applied to the hair subsequent to washing and optional conditioning and preferably before the hair is dried. The composition is then allowed to remain on the hair whilst it is dried, by application of heat (eg hair dryer) or otherwise.

Alternatively, the composition may be applied in a method which is not a washing method. That is, the hair is not washed immediately prior to application of the treatment compositions. By "immediately prior to" we mean less than one hour before application. Thus in an alternative aspect the composition is applied more than one hour after washing, generally more than two or three hours after washing and in particular after the hair is substantially dry.

According to a third aspect of the invention we provide a kit for the reduction of sun-induced fade of the colour applied to artificially coloured fibres comprising (i) a treatment composition which comprises a salt or complex of a transition metal or a rar earth metal and (ii) instructions to apply the treatment composition to artificially coloured fibres.

The composition may have any of the features discussed above and the instructions may instruct any of the method steps discussed above.

We have surprisingly found that the defined salts and complexes are capable of reducing sun-induced fade of artificial colour and consequently in a fourth aspect of the invention we provide use for the reduction of sun-induced fade of the colour applied to artificially coloured fibres, preferably hair, of a salt or complex of a transition metal or a rare earth metal.

The invention will now be illustrated with reference to the following examples: Examples

In these examples, various standard tests are used, as follows.

A. Hair Switches

The hair switches used are European medium brown or light brown hair, six inches in length, 1.5 grams in weight. They have been bleached and coloured according to the Bleaching Protocol (B) and Colouring Protocol (C) below. The hair has not previously been subjected to any cosmetic treatments involving chemically reactive products such as permanent waves, bleaches and dyes.

B. Bleaching Protocol Chemical bleaching of hair is performed using Clairol Born Blonde. Contents are mixed as instructed on the packet, and 4g of product is applied to each l .5g switch. The product is massaged into the hair by means of a milking action with the thumb and forefinger, until each switch is uniformly covered with product. Four switches are treated at the same time. Switches are then left in a tray for 30 minutes wrapped loosely in clingfilm, and subsequently rinsed with water for 2 minutes. To wash the switches 0.2 ml of commercially available Prell shampoo is applied by syringe. Shampoo is massaged through the hair, lathered in for 30 seconds, again using a milking action, after which the hair switches are rinsed for one minute. This washing process is then repeated one more time. All water used is deionised water at a temperature of 37°c and flow rate of 6 1/min. Switches are dried for one hour in an oven at 40 ±2°C

C. Colouring Protocol

Chemical dyeing of hair switches is achieved using oxidative dyes from the L'Oreal Recital, Preference range. Two colours are used: Santa Cruz Deep Copper Red; Palma Natural Brown.

Contents of pack are mixed as instructed and applied to the hair. 3g of product is applied to each 1.5g switch. Subsequent procedures are as noted above for Bleaching Protocol (B) . Two hair treatment protocols are used to assess effectiveness of treatment compositions in preventing sun-fade. These are as follows.

Protocol 1 (shampoo plus leave-on treatment only) 1- Hair switches (A) are subjected to the Bleaching Protocol (B) and Colouring Protocol above. Colour measurements are taken according to the Colour Measurement Protocol (D) below.

2. Shampoo: Switches are washed using commercially available Pantene shampoo. A maximum of four switches are washed at any one time. Shampooing is carried out as follows. The switches are wetted for 10 seconds. 0.2 ml shampoo is applied to each hair switch using a syringe (preferably a 1 ml syringe) . The switches are lathered for 30 seconds using a "milking" action and rinsed for 30 seconds. ^' This process is repeated one more time. 3. Treatment Composition: The treatment composition is applied as follows. Each switch is placed in a bulldog clip, post washing. Each switch is rub-dried down five times with a cotton towel, then combed until all hair "knots" are removed. The switch is smoothed and spread to approximately 1 inch width. 0.2 ml of the treatment composition is applied to the top of each side of each hair switch using a syringe, and then milked through the hair for 10 seconds. The hair switch is then combed through a total of 5 times from top to bottom.

4. Blow Dry: The hair is then dried for 1.5 minutes on each side using a hairdryer set at 6 inches from the hair, and aimed at the top-to-middle of the switch, in the middle, on high heat and high power. During drying, and before the hair switch is turned around to dry the second side, the hair is combed through three times, once after 30 seconds, once after 60 seconds and once after 90 seconds (this is before turning the switch around) . 5. Colour Readings: Colour readings are then taken using the Colour Measurement Protocol (D) below. Colour readings are taken from 3 switches per treatment leg. 6,. Irradiation: The switch is then irradiated using the Irradiation Protocol (E) below. This mimics exposure to mid-European, mid June/July/August , one full day (dawn to dusk) of sunshine.

7. Steps 1 to 6 are repeated as shown in Table 1 below. It is to be noted that each cycle (1 to 7) does not include each step, because it ^■ is intended to mimic actual consumer activities of hair washing and/or hair conditioning and/or hair treatment. Each cycle is intended to represent one consumer day and a series of seven cycles is thus defined as a "weekly cycle". usually this set of cycles is repeated three times, to simulate three weeks' exposure. Table 1

Protocol 2 (Pre-wash treatment, shampoo, rinse-off conditioner, intensive conditioner, leave-on treatment) Step 1 is as in Protocol 1.

A series of cycles is followed as shown in Table 2 below. In these cycles, which again are intended to mimic consumer activity, the shampoo step (2) , application of treatment composition (3) , blow drying (4), colour readings (5) and irradiation step (5) are each carried out in the same way as in Protocol 1. Additional- steps are carried out as follows: a. Pre-wash treatment: commercially available Pantene pre-wash colour protector is applied to each hair switch, 2 pumps to each side of each hair switch and spread evenly through the hair for 30 seconds. b. Rinse-off Conditioner: commercially available Pantene conditioner is applied to each switch, 0.2 ml to each hair switch using a syringe. The conditioner is milked into the hair for 30 seconds, left for 30 seconds and rinsed for 30 seconds. c. Intensive conditioner: commercially available Pantene intensive conditioner is applied to the hair, 0.2 ml to each hair switch using a 1 ml syringe. The conditioner is milked for 30 seconds, left for 5 minutes and rinsed for 30 seconds.

In this Protocol also, a series of seven cycles simulates one consumer week and is defined as a "weekly cycle". Table 2

Protocols 1 and 2 mimic typical European consumer usage which involves washing of hair three to four times per week and application of the treatment composition each day is also included. D. Colour Measurement Protocol Colour values were obtained using the abScan 2 0/45 SN-14173 spectrocolorimeter (Hunter Associates Laboratory, Inc., Restpm, VA) . The colorimeter quantifies colour by applying the CIE Lab measurement system, so as to remove the subjectivity of visual assessment. Results are expressed in terms of the Hunter L, a, b.colour scale which is calculated relative to CIE illu inant D_r.v, to the 10° standard observer. A particular colour is expressed as a point in a three coordinate system and the , a, b colour scale can be defined as follows:

L*,a*,b* colour space

L is a measure of lightness and varies from 100 for perfect white to zero for black. The chromaticity dimensions, a and b, give perspective of colour, where a is a measure of redness when positive and greenness when negative. b is a measure of yellowness when the value is plus and blueness when the value is minus.

The most important units for these experiments are ΔE units. These represent the difference (in colour) between two points in the 3-coordinate system. Using the L*, a*, b* values as a base, ΔE is calculated using the following equation:

In the results given, ΔE represents the colour difference between original colour (the colour of the bleached, coloured hair switch before any treatment cycles under Protocols 1 and 2) and the colour after the various cycles of treatment. One benefit of this colour scale is that -the distance between two points in the system is proportional to the visual difference between two samples. For an average observer a colour difference greater than 2 units of ΔE is noticeable.

To measure colour, hair switches are fitted onto specially designed spring-loaded (top and bottom) sample holders, which keep the hair taut and in place for reproducible readings. The diameter of the Hunter Labscan port-hole over which the hair to be colour- measured is laid is 0.5 inches and eight measurements are taken per switch, four on each side, taken from various points from top to bottom of the switch. A total of at least 3 hair switches per treatment are read for accuracy of results analysis. E. Irradiation Protocol

Irradiation is performed in a Xenotest Alpha sunlight simulator available from Alplas Technology (Oxford, UK) .

Each switch is combed and laid on an Alplas supplied frame. Each frame is approximately 14cm x 5cm and the hair is laid top to bottom on top of the frame, with the top of the switch resting on the top of the frame, and the bottom of the switch resting on the bottom of the frame, with the hair spread within the gap so that it is approximately 1 inch in width from top to bottom. The bottom of the switch is taped to the bottom of the frame, then the top end to the top of the frame. The second frame is placed on top of the switch to "sandwich" the hair and then the clamped hair is placed inside an Alplas supplied frame holder, where a bottom screw, included in the holder, is screwed tight, to firmly fix the frames and hair within the frame holder, at the bottom of the frame holder. The top of the switch is pulled to align the hair so that the switch is semi-taut and simultaneously the top screw, also included in the frame holder, is screwed tight, to firmly fix the frames and hair within the frame holder, at the top of the frame holder. The top overhang of the switch is taped down to the top of the frame holder.

The frame holder is then fitted into a holding cell (minimum of 10 such holding cells per unit) inside the Xenotest unit, ready for irradiation. The filter used is the Xenochrome 300. The apparatus is set in turning mode. Irradiance is 44 w/m" and the chamber temperature 39 °C. The relative humidity is 65%. The fan speed is set at 1,500 rpm. Irradiation time is as shown in Tables 1 and 2 above, where 3 hours in the Xenotest unit under these conditions mimics an average full midsummer (June, July, August) mid-European day of sunshine (dawn to dusk) . Example 1

In this test treatment compositions comprising copper acetate (CuAc) , propyl gallate and TinoGard uv-i are compared with a control. The test control is water plus 0.2% methyl paraben, 0.1% propyl paraben and 0.7% benzyl alcohol as preservative. To compare the fade protection of the system comprising copper acetate with the test control, the actives were added to the control chassis in the amounts shown in Table 3 below. Testing was carried out using protocol 1. The hair switches tested were natural medium brown,, dyed using L'Oreal Santa Cruz Red. Table 3

These results demonstrate that the compositions according to the invention each give better fade results (ie more fade protection) than the control, both at pH 4.5 and pH 6.5. The compositions of the invention gave better results when formulated at pH 6.5 than at pH 4.5.

Example 2

In this test compositions comprising cerium salts and copper acetate were tested. The control was a serum containing none of the actives of the invention and having the composition shown in Table 4 below. The amounts of active (added to the serum) and results are shown in Table 5 below. Testing was done using protocol 5585

45

2 above. In each case, the hair switches tested were bleached medium brown hair, dyed using L'Oreal Palma brown.

Table 4

* Commercial product from Nipa . Laboratories comprising methyl paraben, propyl paraben, benzyl alcohol (all preservatives) .

Table 5

Example 3

In the following test, carried out using protocol l, hair switches used were natural medium brown, dyed using L'Oreal Santa Cruz Red, with no prior bleaching process. The control was the water-based control used in Example 1 above. Results are shown in Table 6 below. Table 6

This demonstrates the improved sun-fade prevention which can be obtained using copper acetate.

Claims

1. A method of reducing sun-induced fade of the colour applied to artificially coloured fibres comprising applying to artificially coloured fibres a treatment composition comprising a salt or complex of a transition metal or rare earth metal, or mixtures thereof.

2. A method according to claim 1 in which the treatment composition has pH from 3 to 10.5, preferably at least 5.5, more preferably at least 6, most preferably at least 6.5.

3. A method according to claim 1 or claim 2 in which the fibres are textile fibres, preferably naturally derived fibres, more preferably cotton or wool.

4. A method according to claim 1 or claim 2 in which the fibres are hair, preferably human hair.

5. A method according to claim 4 comprising washing the hair by application of a shampoo composition and subsequent rinsing of the shampoo composition from the hair in a first rinsing step prior to application of the treatment composition.

6. A method according to claim 5 comprising applying a conditioning composition to the hair subsequent to the first rinsing step and subsequently rinsing the conditioning composition from the hair in a second rinsing step prior to application of the treatment composition.

7. A method according to claim 4 in which the hair is not washed immediately prior to application of the treatment composition.

8. A method according to claim 4 in which the treatment composition is not rinsed from the hair subsequent to application.

9. A method according to claim 8 in which the hair is dried, preferably by heating, without removal of the treatment composition from the hair.

10. A method according to claim 4 in which the hair has been artificially coloured by means of oxidative colouring agents.

11. A treatment composition suitable for reducing sun- induced fade of the colour applied to artificially coloured fibres, the composition comprising at least one salt or complex of, a transition metal or a rare earth metal and in which the composition has a pH of at least 5.5.

12. A composition according to claim 11 having a pH of at least 6, preferably at least 6.5.

13. A composition according to claim 11 or claim 12 having a pH not more than 10.5, preferably not more than 8.

14. A composition according to claim 11 in which the salt or complex is of copper, cobalt, nickel or cerium.

15. A composition according to claim 11 which comprises a the salt of a transition metal or rare earth metal, preferably a copper salt, more preferably copper acetate.

16. A composition according to any of claims 11 to 15 in which the salt or complex is present in an amount of from 0.1 ppm to 10,000 ppm, preferably 50 ppm to 5,000 ppm, more preferably 100 ppm to 600 ppm, based on total weight of the composition.

17. A composition according to any of claims 11 to 16 which is in the form of an aerosol mousse, a non-aerosol oussse, an aerosol hairspray, a non-aerosol hairspray, an aerosol conditioner, a non-aerosol conditioner, a gel, a spray-gel or a wax, and is preferably in the form of a mousse.

18. A composition according to any of claims 11 to. 17 additionally comprising a compound of the Formula III:

wherein R is hydrogen or chlorine, R, is C-.. alkyl or phenyl-C alkyl, R_: is c,. alkyl or SO_;iM, and M is hydrogen, sodium or potassium, and the compound is 5 preferably sodium 3-(2H-benzotriazol-2-yl) -5-sec-butyl- 4-hydroxybenzenesulfonate.

19. A composition according to claim 18 in which the composition of Formula I is sodium 3- (2H-benzo^'triazol-2- yl) -5-sec-butyl-4-hydroxybenzenesul onate.

10 20. A kit for the reduction of sun-induced fade of the colour applied to artificially coloured fibres comprising (i) a treatment composition which comprises a salt or complex of a transition metal or a rare earth metal or mixtures thereof and (ii) instructions to apply

15 the treatment composition to artificially coloured fibres.

21. A kit according to claim 20 in which the treatment composition has a pH of at least 5.5, preferably at least 6.

20 22. Use for the reduction of sun-induced fade of the colour applied to artificially coloured hair of a compound which is a salt or complex of a transition metal or a rare earth metal.

23. A method according to any of claims 1 to 10 or a kit

25 according to claim 20 or claim 21 in which the treatment composition has any of the additional features recited in claims 14 to 19.