Polysiloxane block copolymers in topical cosmetic and personal care compositions

A process for making a polysiloxane block copolymer which is built up from units of the formula &lsqb;A&rsqb; &lsqb;B&rsqb;, in which A is a polymeric block built up from radically polymerisable monomer, and B is a polysiloxane block, the process comprising the steps of forming a polysiloxane macroinitiator by grafting a radical initiator onto a polysiloxane via a nucleophilic displacement reaction between groups on the polysiloxane and radical initiator respectively, and reacting the polysiloxane macroinitiator so obtained with radically polymerisable monomers in an atom transfer radical polymerisation reaction to form a polysiloxane block copolymer. Also provided are cosmetic and personal care compositions, such as hair styling compositions, containing the polysiloxane block copolymers.

DETAILED DESCRIPTION AND PREFERRED EMBODIMENTS 
 Process The process of the present invention comprises two key reaction steps: 
 First Reaction Step The first reaction step involves forming a polysiloxane macroinitiator by grafting a radical initiator onto a polysiloxane via a nucleophilic displacement reaction between groups on the polysiloxane and radical initiator respectively. Typically the polysiloxane macroinitiator is formed by a nucleophilic displacement reaction between: (i) a polysiloxane which is end-capped with at least one group capable of nucleophilic attack via its O, N or S atom, and (ii) a radical initiator comprising at least one —C(O)X group, in which X is a leaving group capable substitution by the nucleophilic O, N or S atom of polysiloxane (i), and at least one organic halide group capable of generating a radical in the presence of a transition metal catalyst. The polysiloxane (i) may be linear, branched or hyperbranched, provided it is end-capped with at least one group as described above. By “end-capped” is meant that the group is at or near a terminal position of the polysiloxane. Examples of preferred polysiloxanes have the formula: &lsqb;Y(R 3 ) p -—Si(R 1 )(R 2 )—O—&lsqb;Si(R 1 )(R 2 )—O&rsqb; n Si (R 1 )(R 2 )—(R 4 ) q Z&rsqb; in which n is an integer of 5 to 1,000,000; R 1 and R 2 are independently selected from monovalent, optionally substituted, linear or branched C 1-18 hydrocarbon radicals, R 3 and R 4 are independently selected from divalent, optionally substituted, linear or branched C 1 -C 18 hydrocarbon radicals; p and q are integers having a value of 0 or 1, and Y and Z are independently selected from hydroxyl, —NH 2 and —NHR 5 where R 5 is a monovalent, optionally substituted, linear or branched C 1-18 hydrocarbon radical. Either, but not both, of Y and Z may also be hydrogen, or a monovalent, optionally substituted, linear or branched C 1-18 hydrocarbon radical thereby giving a mono-end-capped polysiloxane. Examples of monovalent, unsubstituted radicals are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl and tert-pentyl radical; alkoxy radicals, such as the methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, neo-pentoxy and tert-pentoxy radical; hexyl radicals, such as the n-hexyl radical; alkenyl radicals, such as the vinyl, allyl, 5-hexenyl, 4-vinylcyclohexyl and the 3-norbornenyl radical; cycloalkyl radicals, such as cyclopentyl, cyclohexyl, 4-ethylcyclohexyl and cycloheptyl radical; norbornyl radicals and methylcyclohexyl radicals; aryl radicals, such as the phenyl, biphenylyl, napthyl, anthryl and phenanthryl radical; alkaryl radicals, such as o-, m- and p-tolyl radical, xylyl radicals and ethylphenyl radical; and aralkyl radicals, such as the benzyl, styryl, and phenylethyl radicals. Examples of monovalent, substituted radicals are halogenated hydrocarbon radicals, such as the chloromethyl, 3-chloropropyl, 3-bromopropyl, 3,3,3-trifluoropropyl and 5,5,5,4,4,3,3-heptafluoropentyl radical and the chlorophenyl, dichlorophenyl and trifluorotolyl radical; mercaptoalkyl radicals, such as the 2-mercaptoethyl and 3-mercaptopropyl radical; cyanoalkyl radicals, such as the 2-cyanoethyl and 3-cyanopropyl radical; aminoalkyl radicals, such as the 3-aminopropyl, N-(2-aminoethyl)-3-aminopropyl and N-(2-aminoethyl)-3-amino-(2-methyl)propyl radical; aminoaryl radicals, such as the aminophenyl radical; acyloxyalkyl radicals, such as the 3-acryloxypropyl and 3-methacryloxypropyl radical; and hydroxyalkyl radicals, such as the hydroxypropyl radical. Preferred monovalent radicals are independently selected from unsubstituted or substituted C 1 to C 6 alkyl radicals or the phenyl radical, in particular the methyl, ethyl, propyl or phenyl radical. Examples of divalent hydrocarbon radicals are linear or branched saturated alkylene radicals, such as the methylene and ethylene radical, as well as propylene, butylene, pentylene, hexylene, cyclohexylene and octadecylene radicals; alkoxyalkylene radicals such as the methoxyethylene and ethoxyethylene radical; unsaturated alkylene or arylene radicals, such as the hexenylene radical and phenylene radicals; alkarylene radicals such as the methylphenylene and ethylphenylene radical, and alkoxyarylene radicals such as the methoxyphenylene and ethoxyphenylene radical. The divalent hydrocarbon radical R 3 and R 4 can be interrupted by divalent radicals, bonded to carbon atoms on both sides, such as —O—, —C(O)O—, —O(O)C—, —CONR—, —NR 6 C(O)— and —C(O)—, where R 6 is hydrogen or a monovalent, optionally substituted, linear or branched C 1-18 hydrocarbon radical as described above. Particularly preferred polysiloxanes corresponding to the above general formula have: n&equals;5 to 1,000,000, preferably 5 to 500; R 1 and R 2 &equals;methyl, p and q&equals;0 and Y and Z&equals;hydroxyl; or p and q&equals;1, R 3 and R 4 &equals;(CH 2 ) 3 and Y and Z&equals;NH 2 . The radical initiator (ii) comprises at least one —C(O)X group, in which X is a leaving group capable substitution by the nucleophilic O, N or S atom of polysiloxane (i), and at least one organic halide group capable of generating a radical in the presence of a transition metal catalyst. Examples of preferred radical initiators have the formula: R 7 —C(O)X where R 7 is the organic halide group and X is the leaving group. Preferably X is a halogen atom (F, Cl, Br or I). By “organic halide group” is meant any linear, branched or cyclic (aromatic or otherwise) carbon structure, whether substituted or unsubstituted, which also contains a halogen atom (F, Cl, Br or I). Preferred radical initiators have the general formula: C(R 8 )(R 9 )Hal′—(R 10 ) r —C(O)Hal where Hal′ and Hal independently denote halogen atoms, R 8 and R 9 are independently selected from hydrogen or a monovalent, optionally substituted, linear or branched C 1-18 hydrocarbon radical as described above, r is an integer having a value of 0 or 1, and R 10 is selected from divalent, optionally substituted, linear or branched C 1 - C 18 hydrocarbon radicals as described above. A particularly preferred radical initiator corresponding to the above general formula has: Hal and Hal′&equals;Br, R 8 and R 9 &equals;methyl and r&equals;0. The first reaction step involves a nucleophilic displacement reaction between (i) and (ii) under conventional reaction conditions. The nucleophilic O, N or S atom of polysiloxane (i) replaces leaving group X of radical initiator (ii), thereby linking (i) and (ii) to generate a polysiloxane macroinitiator. 
 SECOND REACTION STEP The second reaction step involves reacting the organic halide groups of the polysiloxane macroinitiator obtained in step (i) with radically polymerisable monomers in the presence of a catalytic or stoichiometric amount of a Cu (I) salt or other transitional metal species to form a polysiloxane block copolymer. In this reaction step, the organic halide groups act as initiators in the presence of the radically polymerisable monomers and the catalyst, resulting in the linking of a block of radically polymerisable monomers onto the polysiloxane macroinitiator by atom transfer radical polymerisation. This block of radically polymerisable monomers constitutes the polymeric block (denoted A) of the polysiloxane block copolymer as described above. The catalyst for the second reaction step is a transition metal salt, preferably a Cu(I) salt such as Cu(I) halide salts (Cl, F, Br, I) and which is preferably complexed to a ligand which is suitable for solubilising the Cu(I) salt in the reaction mixture. WO98/51261 describes preferred ligands for use in solubilising the Cu(I) salt in the reaction mixture (aprotic bidentates such as diphosphates, 2,2′ bipyridyl, C 1 -C 20 alkyl substituted bipyridyl and combinations thereof, most preferably 2,2′ bipyridyl complexed to a Cu(I) halide salt, in particular CuCl). WO98/51262 also refers to several journal articles which describe examples of the polymerisation process (atom transfer radical polymerisation) used in the second reaction step of the process of the present invention. Further examples of such descriptions can be found in Polymer Vol 39, No.21, pp 5163-5170 (Nakagawa et al) and Macromolecules 1997, 30, 2190-2193 (Haddleton et al). Those skilled in the art would understand that a variety of other ligands can also be employed. The polymerisation process of the second reaction step can be furnished in bulk, solution, emulsion and suspension, as would be understood by those skilled in the art. Radically polymerisable monomers suitable for use in the second reaction step of the process of the present invention are preferably ethylenically unsaturated monomers. By “polymerisable” is meant monomers that can be polymerised in accordance with the second reaction step of the process of the present invention using atom transfer radical polymerisation, more preferably “living” atom transfer radical polymerisation, in which polymer chain length and architecture can be controlled via stability of the radical, thus leading to improved monodispersity. By “ethylenically unsaturated” is meant monomers that contain at least one polymerisable carbon-carbon double bond (which can be mono-, di-, tri- or tetra -substituted). Either a single monomer or a combination of two or more monomers can be utilised. In either case, the monomers are selected to meet the physical and chemical requirements of the final polysiloxane block copolymer. Suitable ethylenically unsaturated monomers have the following general formula: H(R 11 )C&boxH;C(R 12 )(C(O)G) in which R 11 and R 12 are independently selected from hydrogen, C 1 -C 10 straight or branched chain alkyl, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethyl and 2-ethoxyethyl groups; G is selected from hydroxyl, —O(M) 2/v , —OR 13 , —NH 2 , —NHR 13 and —N(R 13 )(R 14 ); where M is a counter-ion of valency v selected from metal ions such as alkali metal ions and alkaline earth metal ions, ammonium ions and substituted ammonium ions such as mono-, di-, tri- and tetraalkylammonium ions, and each R 13 and R 14 is independently selected from hydrogen, C l -C 8 straight or branched chain alkyl, N,N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, and 2-ethoxyethyl. Representative non-limiting examples of monomers useful herein include protected or non-protected acrylic acid and methacrylic acid and salts, esters and amides thereof. The salts can be derived from any of the common nontoxic metal, ammonium, or substituted ammonium counter ions. The esters can be derived from C 1-40 straight chain, C 3-40 branched chain, or C 3-40 carbocyclic alcohols, from polyhydric alcohols having from about 2 to about 8 carbon atoms and from about 2 to about 8 hydroxyl groups (non-limiting examples of which include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerol, and 1,2,6-hexanetriol); from amino alcohols (non-limiting examples of which include aminoethanol, dimethylaminoethanol and diethylaminoethanol and their quaternised derivatives); or from alcohol ethers (non-limiting examples of which include methoxyethanol and ethoxyethanol). The amides can be unsubstituted, N-alkyl or N-alkylamino mono-substituted, or N,N-dialkyl, or N,N-dialkylamino disubstituted, wherein the alkyl or alkylamino groups can be derived from C 1-40 straight chain, C 3-40 branched chain, or C 3-40 carbocyclic moieties. In addition, the alkylamino groups can be quaternised. Also useful as monomers are protected and unprotected acrylic or/and methacrylic acids, salts, esters and amides thereof, wherein the substituents are on the two and three carbon position of the acrylic and/or methacrylic acids, and are independently selected from C 1-4 alkyl, hydroxyl, halide (—Cl, —Br,—F, —I), —CN, and —CO 2 H, for example methacrylic acid, ethacrylic acid, alpha-chloroacrylic acid and 3-cyano acrylic acid. The salts, esters, and amides of these substituted acrylic and methacrylic acids can be defined as described above for the acrylic/methacrylic acid salts, esters and amides. Other useful monomers include vinyl and allyl esters of C 1-40 straight chain, C 3-40 branched chain, or C3-40 carbocyclic carboxylic acids, vinyl and allyl halides (e.g. vinyl chloride, allyl chloride), (e.g. vinyl pyridine, allyl pyridine); vinylidene chloride; and hydrocarbons having at least one unsaturated carbon-carbon double bond (e.g. styrene, alpha-methylstyrene, t-butylstyrene, butadiene, isoprene, cyclohexadiene, ethylene, propylene, 1-butene, 2-butene, isobutylene, p-methylstyrene); and mixtures thereof. Preferred monomers useful herein include those selected from protected and unprotected acrylic acid, methacrylic acid, ethacrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, methyl ethacrylate, ethyl ethacrylate, n-butyl ethacrylate, iso-butyl ethacrylate, t-butyl ethacrylate, 2-ethylhexyl ethacrylate, decyl ethacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxypropyl methacrylate, glyceryl monoacrylate, glyceryl monoethacrylate, glycidyl methacrylate, glycidyl acrylaze, acrylamide, methacrylamide, ethacrylamide, N-methyl acrylamide, N,N-dimethyl acrylamide, N,N-dimethyl methacrylamide, N-ethyl acrylamide, N-isopropyl acrylamide, N-butyl acrylamide, N-t-butyl acrylamide, N,N-di-n-butyl acrylamide, N,N-diethylacrylamide, N-octyl acrylamide, N-octadecyl acrylamide, N,N-diethylacrylamide, N-phenyl acrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N-dodecyl methacrylamide, N,N-dimethylaminoethyl acrylamide, quaternised N,N-dimethylaminoethyl acrylamide, N,N-dimethylaminoethyl methacrylamide, quaternised N,N-dimethylaminoethyl methacrylamide N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, quaternised N,N-dimethyl-aminoethyl acrylate, quaternised N,N-dimethylaminoethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl ethacrylate, glyceryl acrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-methoxyethyl ethacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate, 2-ethoxyethyl ethacrylate, maleic acid, maleic anhydride and its half esters, fumaric acid, itaconic acid, itaconic anhydride and its half esters, crotonic acid, angelic acid, diallyldimethyl ammonium chloride, vinyl pyrrolidone vinyl imidazole, methyl vinyl ether, methyl vinyl ketone, maleimide, vinyl pyridine, vinyl furan, styrene sulphonate, allyl alcohol, allyl citrate, allyl tartrate, vinyl acetate, vinyl alcohol, vinyl caprolactam and mixtures thereof. More preferred monomers are those selected from methyl acrylate, methyl methacrylate, methyl ethacrylate, ethyl acrylate, ethyl methacrylate, ethyl ethacrylate, n-butyl acrylate, n-butyl methacrylate, n-butyl ethacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl ethacrylate, N-octyl acrylamide, 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and mixtures thereof. Most preferred monomers are those selected from N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, 2-ethylhexyl acrylate, hydroxyethyl methacrylate, N-octyl acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and mixtures thereof. 
 Polysiloxane Block Copolymers A typical polysiloxane block copolymer obtainable by the process described above is built up from units of the general formula &lsqb;A&rsqb;L&lsqb;B&rsqb;, in which A is a polymeric block built up from radically polymerisable monomer, B is a polysiloxane block and L is a divalent linker group which links the A and B blocks via O—Si, N—Si or S—Si bonds to the B block. Preferably L is selected from: —R 15 —C(O)—O—; —R 15 —O—C(O)—O—; —R 15 —C(O)—N(R 16 )—; —R 15 —O—C(O)—N(R 16 )—, or —R 15 —N(R 16 )—C(O)—N(R 17 )—; in which R 15 is a divalent, optionally substituted, linear or branched C 1 -C 18 hydrocarbon radical as described above, and R 16 and R 17 are independently selected from monovalent, optionally substituted, linear or branched C 1-18 hydrocarbon radicals as described above. The overall molecular architecture of the silicone block copolymers of the invention can be described by the formulas A-L-B, A-L-B-L-A, -(A-L-B) n -, wherein n is an integer of 2 or greater, or &lsqb;A-L-&rsqb; &lsqb;A-L-&rsqb;B&lsqb;-L-A&rsqb; &lsqb;-L-A&rsqb;, wherein A-L-B represents a diblock structure, A-L-B-L-A represents a triblock structure, -(A-L-B) n - represents a multiblock structure, and &lsqb;A-L-&rsqb; &lsqb;A-L-&rsqb;B&lsqb;-L-A&rsqb; &lsqb;-L-A&rsqb; represents a dendritic structure. 
 Cosmetic and Personal Care Compositions The polysiloxane block copolymers of the present invention are preferably formulated into hair care compositions, especially hairspray compositions, but can also be formulated into a wide variety of product types, including mousses, gels, lotions, tonics, sprays, shampoos, conditioners, rinses, hand and body lotions, facial moisturisers, sunscreens, anti-acne preparations, topical analgesics, mascaras, and the like. The carriers and additional components required to formulate such products vary with product type and can be routinely chosen by one skilled in the art. The following is a description of some of these carriers and additional components. 
 Carriers Hair care compositions of the present invention can comprise a carrier, or a mixture of such carriers, which are suitable for application to the hair. The carriers are present at from about 0.5% to about 99.5%, preferably from about 5.0% to about 99.5%, more preferably from about 10.0% to about 98.0%, of the composition. As used herein, the phrase “suitable for application to hair” means that the carrier does not damage or negatively affect the aesthetics of hair or cause irritation to the underlying skin. Carriers suitable for use with hair care compositions of the present invention include, for example, those used in the formulation of hair sprays, mousses, tonics, gels, shampoos, conditioners, and rinses. The choice of appropriate carrier will also depend on the particular copolymer to be used, and whether the product formulated is meant to be left on the surface to which it is applied (e.g., hair spray, mousse, tonic, or gel) or rinsed off after use (e.g., shampoo, conditioner, rinse). The carriers used herein can include a wide range of components conventionally used in hair care compositions. The carriers can contain a solvent to dissolve or disperse the particular copolymer being used, with water, the C1-C6 alcohols, lower alkyl acetate and mixtures thereof being preferred. The carriers can also contain a wide variety of additional materials such as acetone, hydrocarbons (such as isobutane, hexane, decene), halogenated hydrocarbons (such as Freons) and volatile silicon derivatives such as cyclomethicone. When the hair care composition is a hair spray, tonic, gel, or mousse the preferred solvents include water, ethanol, volatile silicone derivatives, and mixtures thereof. The solvents used in such mixtures may be miscible or immiscible with each other. Mousses and aerosol hair sprays can also utilise any of the conventional propellants to deliver the material as a foam (in the case of a mousse) or as a fine, uniform spray (in the case of an aerosol hair spray). Examples of suitable propellants include materials such as trichlorofluoromethane, dichlorodifluoromethane, difluoroethane, dimethylether, propane, n-butane or isobutane. A tonic or hair spray product having a low viscosity may also utilise an emulsifying agent. Examples of suitable emulsifying agents include nonionic, cationic, anionic surfactants, or mixtures thereof. If such an emulsifying agent is used, it is preferably present at a level of from about 0.01% to about 7.5% of the composition. The level of propellant can be adjusted as desired but is generally from about 3% to about 30% of mousse compositions and from about 15% to about 50% of the aerosol hair spray compositions. Suitable spray containers are well known in the art and include conventional, non-aerosol pump sprays i.e., “atomisers”, aerosol containers or cans having propellant, as described above, and also pump aerosol containers utilising compressed air as the propellant. Where the hair care compositions are conditioners and rinses the carrier can include a wide variety of conditioning materials. Where the hair care compositions are shampoos, the carrier can include, for example, surfactants, suspending agents, and thickeners. The carrier can be in a wide variety of forms. For example, emulsion carriers, including oil-in-water, water-in-oil, water-in-oil-in-water, and oil-in-water-in-silicone emulsions, are useful herein. These emulsions can cover a broad range of viscosities, e.g., from about 100 cps to about 200,000 cps. These emulsions can also be delivered in the form of sprays using either mechanical pump containers or pressurised aerosol containers using conventional propellants. These carriers can also be delivered in the form of a mousse. Other suitable topical carriers include anhydrous liquid solvents such as oils, alcohols, and silicones (e.g., mineral oil, ethanol, isopropanol, dimethicone, cyclomethicone, and the like); aqueous-based single phase liquid solvents (e.g., hydro-alcoholic solvent systems); and thickened versions of these anhydrous and aqueous-based single phase solvents (e.g., where the viscosity of the solvent has been increased to form a solid or semi-solid by the addition of appropriate gums, resins, waxes, polymers, salts, and the like). 
 Additional Components A wide variety of additional components can be employed in cosmetic and personal care compositions according to the present invention. Examples include the following: sunscreening agents such as 2-ethylhexyl p-methoxycinnamate, 2-ethylhexyl N,N-dimethyl-p-aminobenzoate, p-aminobenzoic acid, 2-phenylbenzimidazole-5-sulfonic acid, octocrylene, oxybenzone, homomenthyl salicylate, octyl salicylate, 4,4′-methoxy-t-butyldibenzoylmethane, 4-isopropyl dibenzoylmethane, 3-benzylidene camphor, 3-(4-methylbenzylidene) camphor, titanium dioxide, zinc oxide, silica, iron oxide, and mixtures thereof. anti-dandruff actives such as zinc pyrithione, piroctone olamine, selenium disulphide, sulphur, coal tar, and the like. conditioning agents for hair care compositions such as hydrocarbons, silicone fluids, and cationic materials. The hydrocarbons can be either straight or branched chain and can contain from about 10 to about 16, preferably from about 12 to about 16 carbon atoms. Examples of suitable hydrocarbons are decane, dodecane, tetradecane, tridecane, and mixtures thereof. Examples of suitable silicone conditioning agents useful herein can include either cyclic or linear polydimethylsiloxanes, phenyl and alkyl phenyl silicones, and silicone copolyols. Cationic conditioning agents useful herein can include quaternary ammonium salts or the salts of fatty amines. surfactants for hair shampoo and conditioner compositions. For a shampoo, the level is preferably from about 10% to about 30%, preferably from 12% to about 25%, of the composition. For conditioners, the preferred level of surfacant is from about 0.2% to about 3%. Surfactants useful in compositions of the present invention include anionic, nonionic, cationic, zwitterionic and amphoteric surfactants. carboxylic acid polymer thickeners. These crosslinked polymers contain one or more monomers derived from acrylic acid, substituted acrylic acids, and salts and esters of these acrylic acids and the substituted acrylic acids, wherein the crosslinking agent contains two or more carbon-carbon double bonds and derived from a polyhydric alcohol. Examples of carboxylic acid polymer thickeners useful herein are those selected from the group consisting of carbomers, acrylates/C10-C30 alkyl acrylate crosspolymers, and mixtures thereof. Compositions of the present invention can comprise from about 0.025% to about 1%, more preferably from about 0.05% to about 0.75% and most preferably from about 0.10% to about 0.50% of the carboxylic acid polymer thickeners. emulsifiers for emulsifying the various carrier components of the compositions of the invention. Suitable emulsifier types include polyethylene glycol 20 sorbitan monolaurate (Polysorbate 20), polyethylene glycol 5 soya sterol, Steareth-20, Ceteareth-20, PPG-2 methyl glucose ether distearate, Ceteth-10, Polysorbate 80, cetyl phosphate, potassium cetyl phosphate, diethanolamine cetyl phosphate, Polysorbate 60, glyceryl stearate, PEG-100 stearate, and mixtures thereof. The emulsifiers can be used individually or as a mixture of two or more and can comprise from about 0.1% to about 10%, more preferably from about 1% to about 7%, and most preferably from about 1% to about 5% of the compositions of the present invention. vitamins and derivatives thereof (e.g., ascorbic acid, vitamin E, tocopheryl acetate, retinoic acid, retinol, retinoids, and the like. cationic polymers (e.g., cationic guar gum derivatives such as guar hydroxypropyltrimonium chloride and hydroxypropyl guar hydroxypropyltrimonium chloride, available as the Jaguar C series from Rhone-Poulenc). preservatives, antioxidants, chelators and sequestrants; and aesthetic components such as fragrances, colourings, hair nutrients and essential oils. The invention will now be illustrated by the following non-limiting Examples: 
 EXAMPLES 
 Examples 1-8 ABA Triblock copolymers of the following general formula: 1 were prepared by atom transfer radical polymerisation (ATRP). Commercially available polydimethyl siloxanes (PDMS)-amine propyl terminated were halide functionalised to give an effective ATRP initiator. Controlled molecular weights were achieved with narrow polydispersities. 1 Mwt of Value Mwt of Value Total Mwt EXAMPLE Initiator of x DMAEMA of y of Polymer 1 3300 45 10000 64 13300 2 3300 45 4000 25 7300 3 3300 45 6000 40 9300 (NMR) 4 2000 27 15000 95 17000 (NMR) *5 800 7 10000 64 10800 6 3300 45 4700 30 8000 (NMR) *7 800 7 10000 64 10800 8 3300 45 10000 64 13300 *Examples 5 and 7 were prepared using an ester PDMS initiator rather than the pictured amide PDMS initiator, giving an -O- linkage in place of the pictured -(CH 3 ) 2 -NH- linkage in the final polymer. 
 Preparation Method Cu I Br (0.2732 g, 1.905 mmol) along with a magnetic stirrer bar was placed in a dry Schlenk flask which was then evacuated and flushed with nitrogen three times. 2-dimethylaminoethyl methacrylate (3.9 mL, 0.023 moles), toluene (7.2 mL) and the PDMS initiator (1) (2 g, 0.952 mmol) were added to the Schlenk using degassed syringes.* The solution was then deoxygenated by three freeze-pump-thaw cycles. Finally, once the flask had reached the desired reaction temperature of 90° C. the n-propyl-2-pyridinalmethanimine ligand (2) (0.54 mL, 3.809 mmol) was added with stirring. The reaction mixture immediately turned dark brown in colour on addition of the ligand. *Target molecular weight of DMAEMA blocks&equals;4000, molecular weight of initiator&equals;2000 (total&equals;6000). The ratio of &lsqb;monomer&rsqb;:&lsqb;initiator&rsqb; determines molecular weight of end polymer. In the described ATRP the required ratio of 2 &lsqb;monomer&rsqb;:&lsqb;initiator&rsqb; 25:1. The ratios for the other listed reagents are as follows; &lsqb;Cu I Br&rsqb;:&lsqb;Initiator&rsqb;&equals;1:2, &lsqb;Ligand&rsqb;:&lsqb;Cu I Br&rsqb;&equals;2:1 and solvent volume:monomer volume&equals;2:1. The monomer was purified by passing down a basic alumina column prior to use and purged with nitrogen for at least one hour. Toluene, which was used as a solvent for all polymerisations, was also degassed in this manner. Cu I Br was purified before use according to a published procedure. 1 1) Keller, R. N.; Wycoff, H. D. Inorganic Synthesis, 1947, 
 Purification of Polymer The resultant dark brown solution was passed down an alumina column several times using a conventional solvent such as dichloromethane or tetrahydrofuran. When the solution appeared colourless the solvent was removed under vacuum to yield a pale yellow solid. 
 RESULTS 
 Film Forming A solution of ethanol/water (55%:45%) was made up. A small sample of polymer (0.5 g) was added to the solution (10 mL). Some samples needed agitation but others dissolved straight away. A small quantity of solution (1 mL) was placed in a plastic dish and left to dry for 3 hours. 2 SOLUBILITY FILM 55% 100% FORMING 100% 100% ethanol/ Methyl EXAMPLE PROPERTIES water ethanol water Acetate 1 non tacky soluble soluble soluble soluble clear flexible 2 slightly soluble soluble soluble soluble yellow non tacky flexible 3 non tacky soluble soluble soluble soluble clear flexible 4 non tacky soluble soluble soluble soluble clear flexible 5 non tacky soluble soluble soluble soluble clear flexible 6 slightly soluble soluble soluble soluble yellow non tacky flexible 7 slightly soluble soluble soluble insoluble yellow non tacky brittle 8 slightly soluble soluble soluble insoluble yellow non tacky brittle 
 Bond Strength Analysis Diastron MTT600 parameters: % extension&equals;100 Rate (mm/min)&equals;10 Max force(g)&equals;200 Gauge force(gmf)&equals;2 5% aqueous alcohol solution (55% ethanol/water): 1 microliter pipetted onto junction Temperature&equals;20° C. Humidity 32 50% 3 EXAMPLE BOND STRENGTH (g) EXTENSION (%) 1 36.88 2.79 50.88 6.89 20.88 4.19 AVE &equals; 42.53 g AVE &equals; 6.76% 50.63 10.27 ST.DEV &equals; 13.7 ST.DEV &equals; 2.9 53.38 7.68 2 29.25 2.23 * * AVE &equals; 26.29 g AVE &equals; 2.45% 23.75 2.58 ST.DEV &equals; 2.77 ST.DEV &equals; 0.19 25.88 2.55 3 31.38 4.14 * * AVE &equals; 31.42 g AVE &equals; 4.17% 30.38 4.60 ST.DEV &equals; 1.06 ST.DEV &equals; 0.42 32.50 3.76 4 * 20.50 2.83 27.50 4.77 AVE &equals; 25.78 AVE &equals; 3.79% 29.88 4.75 ST.DEV &equals; 4.00 ST.DEV &equals; 1.12 25.25 2.82 5 56.00 6.23 26.00 3.21 45.25 5.55 AVE &equals; 42.42 g AVE &equals; 5.00% 43.88 ST.DEV &equals; 15.20 ST.DEV &equals; 1.58 40.38 6 * * 7.5 1.89 AVE &equals; 11.96 g AVE &equals; 1.57% 16.63 1.59 ST.DEV &equals; 4.56 ST.DEV &equals; 0.33 11.75 1.24 7 * * 24.13 4.73 AVE &equals; 19.50 g AVE &equals; 3.41% 22.00 3.24 ST.DEV &equals; 6.26 ST.DEV &equals; 1.25 12.38 2.25 8 * * 10.63 1.26 AVE &equals; 14.79 g AVE &equals; 1.61% 23.50 2.60 ST.DEV &equals; 7.54 ST.DEV &equals; 0.87 12.38 0.96 
 Sensory The polymer of Example 1 was formulated into a 55% VOC pumpspray( 4.2% resin , 55% ethanol, 40.8% water) This was sprayed on to a switch and compared against the commercial product Suave® Extra Hold(4.2% AMPHOMER®) pumpspray. The formulation with Example 1 had major wins on softness and least deposits( both before and after brushout).