AU8900998A - Cosmetic method for treating coloured hair to reduce colour fade - Google Patents

Description

WO 99/55295 PCT/US98/16496 COSMETIC METHOD FOR TREATING COLOURED HAIR TO REDUCE COLOUR FADE Technical Field 5 The present invention relates to a cosmetic method of treating mammalian coloured hair to reduce or prevent colour fade and/or colour shift. Background of the Invention 10 The desire to alter the colour of human hair is not only a facet of modern times. Since the days of the Roman Empire the colour of human hair has been routinely altered to accommodate the changes of fashion and style. However the attainment of precise initial colours which are retained by the hair for a desirable period has proved a more elusive goal. 15 Once the hair has been coloured there is a desire that the colour be retained in a consistent manner for a predictable period of time. Further, there is a desire for the colour to be resistant to fading, as occasioned by the actions of washing (also known as wash fastness) and other exterior factors such as the 20 action of the sun. It is, therefore, something of a balancing act between the desire to retain a consistent colour and the necessity of exposing the coloured hair to factors which would lead to colour fade and/or colour shift. Thus, it would be desirable to develop a method of treating coloured hair 25 that provides improved resistance to colour fade and/or colour shift, as occasioned, for example, by washing during a regular cleansing regimen, exposure to rain, exposure to water from other sources (e.g. from swimming) or by the action of the sun, thereby maintaining a more consistent colouration inbetween dye applications. 30 WO 99/55295 PCTIUS98/16496 2 Pre-treatment of hair prior to washing is known in the art. For example, US-4402936 (Kao) discloses a pre-treatment composition comprising a cyclic cationic group as having various beneficial conditioning effects. US-5700456 (L'Oreal) discloses a pre-treatment composition comprising a ceramide and a 5 cationic polymer for providing a de-tangling effect. GB-1570220 (L'Oreal) discloses a pre-treatment composition comprising cationic materials for the elimination of the bad effect of discolouration or dyeing treatments. JP 60087208 (Shiseido) discloses a pre-treatment comprising metal salts for preventing flux of protein components during shampooing and thereby protect 10 the hair in addition to improving chemically damaged hair. However, none of these references disclose the use of pre-treatment compositions on coloured hair for the prevention or reduction of colour fade/shift. It has surprisingly been found that treating the wet or dry coloured hair 15 with a composition comprising a hydrophobic and/or cationic conditioning agent prior to washing with shampoo or exposure to water will reduce or prevent colour fade and/or colour shift caused by said washing or exposure. Summary of the Invention 20 The present invention provides a cosmetic method for treating mammalian coloured hair to reduce or prevent colour fade and/or colour shift comprising; (a) treating the hair with a composition comprising a hydrophobic 25 and/or cationic conditioning agent; followed by (b) wetting the hair. Optionally the method can include treating the hair, after step (b), with a 30 composition comprising a conditioning agent and/or an ultra violet filtering agent.

WO 99/55295 PCTIUS98/16496 3 The method of the present invention provides a reduction or prevention of colour fade and/or colour shift of coloured hair. The method can help to maintain a more consistent colour and, therefore, can increase the time between dye 5 applications. Description The method of the present invention comprises at least two essential 10 steps, firstly a pre-treatment step and secondly a wetting step. Without intending necessarily to limit the scope of the invention, it is believed that pre-treatment with a composition comprising a conditioning agent 'seals' the hair thereby preventing or reducing the leaching out of dye molecules that can be caused by water. 15 As used herein "coloured hair" means hair which has been treated to alter its colour. In particular, this can be through a dyeing treatment which, permanently or temporarily, alters the hair's natural colour. 20 As used herein "colour fade and/or colour shift" means changes to the colour of coloured hair caused by the action of external conditions. In particular, this can be through exposure of the coloured hair to the sun or water. As used herein "reduction or prevention of colour fade and/or colour shift" 25 means impeding, retarding and/or arresting changes to the colour of hair. By reducing or preventing colour fade and/or colour shift a more consistent colour is achieved and the time between dye applications can be increased. As used herein "wetting of the hair" means exposure of the hair to water. 30 In particular, this exposure can be during a cleansing regimen with, for example, WO 99/55295 PCT/US98/16496 4 shampoo or through other activities such as swimming. When the method is a cleansing regimen, it is preferable that such a regimen is carried out frequently, preferably from once a day to once a week, more preferably from once a day to once every three days, most preferably once a day. 5 Pre-treatment step An essential step of the present method is a pre-treatment of the coloured hair with a composition comprising a conditioning agent. Any conditioning agent 10 suitable for use on hair may be used herein. Preferably the composition comprises at least one hydrophobic and/or cationic conditioning agent. Suitable conditioning agents include cationic surfactants, cationic polymers, volatile and non-volatile silicones (including soluble and insoluble silicones), nonvolatile hydrocarbons, saturated C 14 to C 2 2 straight chain fatty alcohols, nonvolatile 15 hydrocarbon esters, liquid polyol carboxylic acid esters, and mixtures thereof. Preferred conditioning agents are cationic surfactants, cationic polymers and silicones (especially insoluble silicones). Cationic Surfactants 20 Cationic surfactants useful in the present method, contain amino or quaternary ammonium moieties. The cationic surfactant will preferably, though not necessarily, be insoluble in the compositions hereof. Cationic surfactants among those useful herein are disclosed in the following documents, all incorporated by reference herein: M.C. Publishing Co., McCutcheon's, 25 Detergents & Emulsifiers, (North American edition 1979); Schwartz, et al., Surface Active Agents, Their Chemistry and Technology, New York: Interscience Publishers, 1949; U.S. Patent 3,155,591, Hilfer, issued November 3, 1964; U. S. Patent 3,929,678, Laughlin et al., issued December 30, 1975; U. S. Patent 3,959,461, Bailey et al., issued May 25, 1976; and U. S. Patent 4,387,090, 30 Bolich, Jr., issued June 7, 1983.

WO 99/55295 PCT/US98/16496 5 Among the quaternary ammonium-containing cationic surfactant materials useful herein are those of the general formula: RF' N R3 + 5 ~R, R4 wherein R 1

-R

4 are independently an aliphatic group of from about 1 to about 22 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having from about 1 to about 22 carbon atoms; and X is a 10 salt-forming anion such as those selected from halogen, (e.g. 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, e.g., those of about 12 carbons, or higher, can be saturated or 15 unsaturated. Especially preferred are di-long chain (e.g., di C 12

-C

2 2 , preferably

C

16

-C

18 , aliphatic, preferably alkyl). di-short chain (e.g., C 1

-C

3 alkyl, preferably

C

1

-C

2 alkyl) quaternary ammonium salts. Salts of primary, secondary and tertiary fatty amines are also suitable 20 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 amine, diethyl amino ethyl stearamide, dimethyl stearamine, dimethyl soyamine, soyamine, myristyl amine, tridecyl amine, ethyl stearylamine, N-tallowpropane 25 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 WO 99/55295 PCTIUS98/16496 6 salts include stearylamine hydrochloride, soyamine chloride, stearylamine formate, N-tallowpropane diamine dichloride and stearamidopropyl dimethylamine citrate. Cationic amine surfactants included among those useful in the present invention are disclosed in U.S. Patent 4,275,055, Nachtigal, et al., 5 issued June23, 1981. Cationic surfactants are preferably utilized 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. 10 Cationic Polymer Conditioninq Aqent The conditioning compositions useful in the present invention can also comprise one or more cationic polymer conditioning agents. The cationic polymer conditioning agents will preferably be water soluble. Cationic polymers 15 are typically used in the same ranges as disclosed above for cationic surfactants. By "water soluble" cationic polymer, what is meant is a polymer which is sufficiently soluble in water to form a substantially clear solution to the naked eye at a concentration of 0.1% in water (distilled or equivalent) at 250C. Preferably, 20 the polymer will be sufficiently soluble to form a substantially clear solution at 0.5% concentration, more preferably at 1.0% concentration. 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 25 more types of monomers. The cationic polymers hereof will 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 30 100,000 to about 2 million. The cationic polymers will generally have cationic WO 99/55295 PCTIUS98/16496 7 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 5 as the water solubility criteria is met. Suitable counterions include halides (e.g., Cl, Br, 1, or F, preferably Cl, Br, or I), sulfate, and methylsulfate. Others can also be used, as this list is not exclusive. The cationic nitrogen-containing moiety will be present generally as a 10 substituent, on a fraction of the total monomer units of the cationic hair conditioning polymers. Thus, the cationic polymer can comprise copolymers, terpolymers, etc. of quaternary ammonium or cationic amine-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 15 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 20 monomers having cationic amine or quaternary ammonium functionalities with water soluble spacer monomers such as acrylamide, methacrylamide, alkyl and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylate, alkyl methacrylate, vinyl caprolactone, and vinyl pyrrolidone. The alkyl and dialkyl substituted monomers preferably have C 1

-C

7 alkyl groups, more preferably 25 C 1

-C

3 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, 30 depending upon the particular species and the pH of the composition.

WO 99/55295 PCTIUS98/16496 8 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 quaternized subsequent to formation of the 5 polymer. For example, tertiary amine functionalities can be quaternized by reaction with a salt of the formula R'X wherein R' is a short chain alkyl, preferably a C 1

-C

7 alkyl, more preferably a C1-C3 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 methacrylate, monoalkylaminoalkyl acrylate, monoalkylaminoalkyl methacrylate, 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 quaternized 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 C1 and C2 alkyls. Suitable amine-substituted vinyl monomers for use herein include dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, dialkylaminoalkyl acrylamide, and dialkylaminoalkyl methacrylamide, wherein the alkyl groups are preferably C1-C7 hydrocarbyls, more preferably C1-C3, alkyls. 10 The cationic polymers hereof can comprise mixtures of monomer units derived from amine- and/or quaternary ammonium-substituted monomer and/or compatible spacer monomers. 15 Suitable cationic hair conditioning polymers include, for example: copolymers of 1-vinyl-2-pyrrolidone and 1-vinyl-3-methylimidazolium salt (e.g., chloride salt) (referred to in the industry by the Cosmetic, Toiletry, and Fragrance WO 99/55295 PCT/US98/16496 9 Association, "CTFA", as Polyquaternium-16), such as those commercially available from BASF Wyandotte Corp. (Parsippany, NJ, USA) under the LUVIQUAT tradename (e.g., LUVIQUAT FC 370); copolymers of 1-vinyl-2 -pyrrolidone and dimethylaminoethyl methacrylate (referred to in the industry by 5 CTFA as Polyquaternium-11) such as those commercially available from Gaf Corporation (Wayne, NJ, USA) under the GAFQUAT tradename (e.g., GAFQUAT 755N); cationic diallyl quaternary ammonium-containing polymers, including, for example, dimethyldiallylammonium chloride homopolymer and copolymers of acrylamide and dimethyldiallylammonium chloride, referred to in the industry 10 (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 U.S. Patent 4,009,256, incorporated herein by reference. 15 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: 20 R,

A-O(-R-N-R

3 X~) R2 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 1 , R 2 , and R 3 independently 25 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 (i.e., the sum of carbon atoms in R 1 , R 2 and R 3

)

WO 99/55295 PCT/US98/16496 10 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 5 their Polymer JR(RTM) and LR(RTM) series of polymers, as salts of hydroxyethyl cellulose reacted with trimethyl 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 10 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 15 nitrogen-containing cellulose ethers (e.g., as described in U.S. Patent 3,962,418, incorporated by reference herein), and copolymers of etherified cellulose and starch (e.g., as described in U.S. Patent 3,958,581, incorporated herein by reference). 20 As discussed above, the cationic polymer hereof is water soluble. This does not mean, however, that it must be soluble in the composition. Preferably however, the cationic polymer is either soluble in the composition, or in a complex coacervate phase in the composition formed by the cationic polymer and anionic material. Complex coacervates of the cationic polymer can be formed 25 with anionic surfactants or with anionic polymers that can optionally be added to the compositions hereof (e.g., sodium polystyrene sulfonate). Silicone Conditioning Agents The conditioning compositions of the present method can also include 30 soluble or insoluble silicone conditioning agents. By soluble what is meant is that WO 99/55295 PCT/US98/16496 11 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 5 silicone. The silicone hair conditioning agent will be used in the compositions hereof 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 10 about 5%, most preferably from about 0.5% to about 3%. Soluble silicones include silicone copolyols, such as dimethicone copolyols, e.g. polyether siloxane-modified polymers, such as polypropylene oxide, polyethylene oxide modified polydimethylsiloxane, wherein the level of 15 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 will preferably have viscosity of from about 1,000 to about 2,000,000 centistokes at 25 0 C, more preferably from about 20 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 CTMOO04, July 20, 1970. 25 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 30 has a boiling point of at least about 260 0 C, preferably at least about 275 0 C, more WO 99/55295 PCTIUS98/16496 12 preferably at least about 3000C 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 0 C. Generally, the viscosity of the fluid will be between about 5 and 5 1,000,000 centistokes at 250C, preferably between about 10 and about 300,000 centistokes. Silicone fluids hereof also include polyalkyl or polyaryl siloxanes with the following structure: 10 R R R I I I A-Si-O- Si-O -Si-A R _R _ R wherein R is alkyl or aryl, and x is an integer from about 7 to about 8,000 may be used. "A" represents groups which block the ends of the silicone chains. 15 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 neither irritating, toxic nor otherwise harmful when applied to the hair, are compatible with the other components of the composition, are chemically 20 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 25 group or different groups. Preferably, the two R groups represent the same group. Suitable R groups include methyl, ethyl, propyl, phenyl, methylphenyl and phenylmethyl. The preferred silicones are polydimethyl siloxane, WO 99/55295 PCT/US98/16496 13 polydiethylsiloxane, and polymethylphenylsiloxane. Polydimethylsiloxane is especially preferred. The nonvolatile polyalkylsiloxane fluids that may be used include, for 5 example, polydimethylsiloxanes. These siloxanes are available, for example, from the General Electric Company in their ViscasilR 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 10 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, 15 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, as described below to decrease the surface tension and enhance the film 20 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 25 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 30 2,826,551, Geen; U.S. Patent 3,964,500, Drakoff, issued June 22, 1976; U.S.

WO 99/55295 PCT/US98/16496 14 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 5 silicone fluids. Another silicone hair conditioning material that can be especially useful in the silicone conditioning agents is insoluble silicone gum. The term "silicone gum", as used herein, means polyorganosiloxane materials having a 10 viscosity at 250C of greater than or equal to 1,000,000 centistokes. Silicone gums are described by Petrarch and others including U.S. 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 15 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) (methylvinylsiloxane) copolymer, 20 poly(dimethylsiloxane) (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 25 centistokes and polydimethylsiloxane fluid having a viscosity of from 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 30 agent is silicone resin. Silicone resins are highly crosslinked polymeric WO 99/55295 PCT/US98/16496 15 siloxane systems. The cross-linking is introduced through the incorporation of trifunctional and tetrafunctional silanes with monofunctional 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 5 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 10 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 oxygen:silicon atoms is at least about 1.2:1.0. Silanes used in the manufacture of silicone resins include monomethyl-, dimethyl-, trimethyl-, 15 monophenyl-, diphenyl-, methylphenyl-, monovinyl-, and methylvinyl-chlorosilanes, and tetrachlorosilane, 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 20 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 25 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 WO 99/55295 PCT/US98/16496 16 Edition, pp 204-308, John Wiley & Sons, Inc., 1989, incorporated herein by reference. Silicone materials and silicone resins in particular, can conveniently be 5 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

(CH

3

)

3 SiO).

5 ; D denotes the difunctional unit (CH 3

)

2 SiO; T denotes the 10 trifunctional unit (CH 3 )SiO1.

5 ; and Q denotes the quadri- or tetra-functional unit Si0 2 . Primes of the unit symbols, e.g., M', D', 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 15 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 20 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 25 methyl. Especially preferred are MQ resins wherein the M:Q ratio is from about 0.5:1.0 to about 1.5:1.0 and the average molecular weight of the resin is from about 1000 to about 10,000. Wettinq Step 30 WO 99/55295 PCT/US98/16496 17 A second essential step of the present method is a wetting step to be carried out after the pre-treatment step. This can comprise exposing the pre treated hair, which may be wet or dry, to water, for example, rinsing or wetting during swimming or washing the pre-treated hair with a shampoo composition 5 comprising a surfactant. Any shampoo suitable for cleansing the hair may be used herein. Suitable surfactants for inclusion in the compositions of the invention generally have a lipophilic chain length of from about 8 to about 22 carbon atoms and can be selected from anionic, cationic, nonionic, amphoteric, zwitterionic surfactants and mixtures thereof. 10 Anionic Surfactants Anionic surfactants suitable for inclusion in the compositions useful in the present method include alkyl sulphates, ethoxylated alkyl sulphates, alkyl glyceryl ether sulfonates, methyl acyl taurates, fatty acyl glycinates, N-acyl glutamates, acyl 15 isethionates, alkyl sulfosuccinates, alkyl ethoxysulphosuccinates, alpha sulfonated fatty acids, their salts and/or their esters, alkyl ethoxy carboxylates, alkyl phosphate esters, ethoxylated alkyl phosphate esters, alkyl sulphates, acyl sarcosinates and fatty acid/protein condensates, and mixtures thereof. Alkyl and/or acyl chain lengths for these surfactants are C 12

-C

2 2 , preferably C 12

-C

1 8 20 more preferably

C

12

-C

14 . Nonionic Surfactants The compositions useful in the present method can also comprise water-soluble nonionic surfactant(s). Surfactants of this class include C12-C14 fatty acid 25 mono-and diethanolamides, sucrose polyester surfactants and polyhydroxy fatty acid amide surfactants having the general formula below. 0 R 9

R

8 C-N-Z 2 WO 99/55295 PCT/US98/16496 18 The preferred N-alkyl, N-alkoxy or N-aryloxy, polyhydroxy fatty acid amide surfactants according to the above formula are those in which R 8 is C5-C31 hydrocarbyl, preferably C6-C19 hydrocarbyl, including straight-chain and branched chain alkyl and alkenyl, or mixtures thereof and R 9 is typically 5 hydrogen, C1-C8 alkyl or hydroxyalkyl, preferably methyl, or a group of formula R 1

-O-R

2 wherein R 1 is C2-C8 hydrocarbyl including straight-chain, branched chain and cyclic (including aryl), and is preferably C2-C4 alkylene, R 2 is C1-C8 straight-chain, branched-chain and cyclic hydrocarbyl including aryl and oxyhydrocarbyl, and is preferably C1-C4 alkyl, especially methyl, or phenyl. Z 2 is 10 a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 2 (in the case of glyceraldehyde) or at least 3 hydroxyls (in the case of other reducing sugars) directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z 2 preferably will be derived from a reducing sugar in a reductive amination reaction, most preferably Z 2 is a 15 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 Z 2 . It should be 20 understood that it is by no means intended to exclude other suitable raw materials. Z 2 preferably will be selected from the group consisting of -CH 2 (CHOH)n-CH2OH, -CH(CH2OH)-(CHOH)n-1 -CH 2 H,

CH

2

(CHOH)

2

(CHOR')CHOH)-CH

2 OH, where n is an integer from 1 to 5, inclusive, and R' is H or a cyclic mono- or polysaccharide, and alkoxylated 25 derivatives thereof. As noted, most preferred are glycityls wherein n is 4, particularly -CH 2

-(CHOH)

4

-CH

2

OH.

WO 99/55295 PCT/US98/16496 19 The most preferred polyhydroxy fatty acid amide has the formula

R

8

(CO)N(CH

3

)CH

2

(CHOH)

4

CH

2 0H wherein R 8 is a C6-C19 straight chain alkyl or alkenyl group. In compounds of the above formula, R 8 -CO-N< can be, for example, cocoamide, stearamide, oleamide, lauramide, myristamide, 5 capricamide, palmiamide, tallowamide, etc. Suitable oil derived nonionic 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, 10 polyethoxylated lanolins and ethoxylated butter derivatives. One preferred class of oil-derived nonionic surfactants for use herein have the general formula below: 0

RCOCH

2

CH(OH)CH

2

(OCH

2

CH

2 )nOH 15 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. 20 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 25 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.

WO 99/55295 PCT/US98/16496 20 Suitable polyethylene glycol based polyethoxylated Cg-C15 fatty alcohols suitable for use herein include Cg-Cl1 Pareth-3, Cg-Cl1 Pareth-4, C9-Cl1 Pareth-5, Cg-Cl1 Pareth-6, Cg-Cl1 Pareth-7, Cg-Cl1 Pareth-8, C11-C15 5 Pareth-3, C11-C15 Pareth-4, C11-C15 Pareth-5, C11-C15 Pareth-6, C11-C15 Pareth-7, C11-C15 Pareth-8, C11-C15 Pareth-9, C11-C15 Pareth-10, C11-C15 Pareth-11, C11-C15 Pareth-12, C11-C15 Pareth-13 and C11-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 10 laurate are commercially available from Henkel under the tradenames Cetiol (RTM) HE and Lamacit (RTM) GML 20 respectively. C 9 -Cli Pareth-8 is commercially available from Shell Ltd under the tradename Dobanol (RTM) 91-8. Particulary 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 15 A25. Also suitable for use herein are nonionic surfactants derived from composite vegetable fats extracted from the fruit of the Shea Tree (Butyrospermum Karkii Kotschy) and derivatives thereof. Similarly, ethoxylated derivatives of Mango, 20 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 25 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.

WO 99/55295 PCT/US98/16496 21 Amphoteric Surfactants Amphoteric surfactants suitable for use in the compositions useful in the present method include: 5 (a) imidazolinium surfactants of formula (VII)

C

2

H

4 0R 2 'CH2 Z R N, N 10 wherein R 1 is C7-C22 alkyl or alkenyl, R 2 is hydrogen or CH 2 Z, each Z is independently CO 2 M or CH 2

CO

2 M, and M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium; and/or ammonium derivatives of formula (VIII) 15

C

2

H

4 OH

R

1

CONH(CH

2 ) 2

N+CH

2 Z R 2 wherein R 1 , R 2 and Z are as defined above; 20 (b) aminoalkanoates of formula (IX)

R

1 NH(CH2)nCO 2 M iminodialkanoates of formula (X) 25 WO 99/55295 PCTIUS98/16496 22

R

1 N[(CH2)mCO2M]2 and iminopolyalkanoates of formula (XI) 5 R1-[N(CH2)p]qN[CH 2

CO

2

M]

2

CH

2

CO

2 M wherein n, m, p, and q are numbers from 1 to 4, and R 1 and M are 10 independently selected from the groups specified above; and (c) mixtures thereof. Suitable amphoteric surfactants of type (a) are marketed under the trade name 15 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 isomer in which R 2 is O-linked rather than N-linked. In practice, a 20 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 25 formula XII and/or XIII in which R 1 is C 8

H

17 (especially iso-capryl), CgH1-g and

C

11

H

2 3 alkyl. Especially preferred are the compounds in which R 1 is CgH19, Z is CO 2 M and R 2 is H; the compounds in which R 1 is C 11

H

2 3 , Z is CO 2 M and

R

2 is CH 2

CO

2 M; and the compounds in which R 1 is C1 H 2 3 , Z is CO 2 M and R 2 is H.

WO 99/55295 PCT/US98/16496 23 In CTFA nomenclature, materials suitable for use in the present invention include cocoamphocarboxypropionate, cocoamphocarboxy propionic acid, and especially cocoamphoacetate and cocoamphodiacetate (otherwise referred to as 5 cocoamphocarboxyglycinate). Specific 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 Conc. Miranol C2M Conc. N.P., Miranol C2M Conc. O.P., Miranol C2M SF, Miranol CM Special (Rh6ne-Poulenc); Alkateric 2CIB (Alkaril Chemicals); 10 Amphoterge W-2 (Lonza, Inc.); Monateric CDX-38, Monateric 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-1 (RTM), polyoxethylene (1) octylphenyl ether; Nonoxynol-4 (RTM), polyoxyethylene (4) nonylphenyl ether and Nonoxynol-9, 15 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 20 sulfonate surfactants, especially those of the sulfated C 8

-C

18 alcohol, C 8

-C

18 ethoxylated alcohol or C 8

-C

18 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. 25 Examples of preferred amphoteric surfactants of type (b) include N-alkyl polytrimethylene poly-, carboxymethylamines sold under the trade names Ampholak X07 and Ampholak 7CX by Berol Nobel and also salts, especially the triethanolammonium salts and salts of N-lauryl-beta-amino propionic acid and N- WO 99/55295 PCT/US98/16496 24 lauryl-imino-dipropionic acid. Such materials are sold under the trade name Deriphat by Henkel and Mirataine by Rh6ne-Poulenc. Zwitterionic Surfactants 5 Water-soluble auxiliary zwitterionic surfactants suitable for inclusion in the compositions useful in the present method include alkyl betaines of the formula

R

5

R

6

R

7 N+ (CH2)nCO2M and amido betaines of the formula (XII) below: R6

R

5

CON(CH

2 )mN(CH 2 )nCO 2 M R7 10 wherein R 5 is C 11

-C

2 2 alkyl or alkenyl, R 6 and R 7 are independently C 1

-C

3 alkyl, M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium, and n, m are each numbers from 1 to 4. Preferred betaines include cocoamidopropyld imethylcarboxymethyl betaine, 15 laurylamidopropyldimethylcarboxymethyl 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: 20 R2 R1 CON(CH2)mN4+(CH2)nCH(OH)CH2SO3-M+ R3 WO 99/55295 PCT/US98/16496 25 wherein R 1 is C7 to C22 alkyl or alkenyl, R 2 and R 3 are independently C1 to C3 alkyl, M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium and m and n are numbers from 1 to 4. Preferred for use herein is coco amido 5 propylhydroxy sultaine. Water-soluble auxiliary amine oxide surfactants suitable for inclusion in the compositions of the present invention include alkyl amine oxide R 5

R

6

R

7 NO and amido amine oxides of the formula (XIV) below: 10 R6

R

5

CON(CH

2 )mN -- O R<7 wherein R 5 is C11 to C22 alkyl or alkenyl, R 6 and R 7 are independently C1 to 15 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 cocoamidopropylamine oxide, lauryl dimethyl amine oxide and myristyl dimethyl amine oxide. 20 Optional Steps The present method can additionally comprise one or more optional steps to be carried out after the wetting step. These additional steps can include treating the hair with a conditioning composition, treating the hair with a 25 conditioning composition additionally comprising an ultra violet filtering agent WO 99/55295 PCTIUS98/16496 26 and/or treating the hair with a composition comprising an ultra violet filtering agent. Any ultra violet filtering agents suitable for topical application are useful in 5 the conditioning, shampooing or ultra violet filtering compositions herein. A wide variety of ultra violet filtering agents are described in U.S. Patent No. 5,087,445, to Haffey et al., issued February 11, 1992; U.S. Patent No. 5,073,372, to Turner et al., issued December 17, 1991; U.S. Patent No. 5,073,371, to Turner et al. issued December 17, 1991; and Segarin, et al., at Chapter Vill, pages 189 et 10 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-phenylbenzimidazole-5 sulfonic acid, octocrylene, oxybenzone, homomenthyl salicylate, octyl salicylate, 15 4,4'-methoxy-t-butyld ibenzoylmethane, 4-isopropyl dibenzoylmethane, 3 benzylidene camphor, 3-(4-methylbenzylidene) camphor, titanium dioxide, zinc oxide, silica, iron oxide, Parsol MCX, Eusolex 6300, Octocrylene, Parsol 1789, and mixtures thereof. 20 Still other useful ultra violet filtering agents are those disclosed in U.S. Patent No. 4,937,370, to Sabatelli, issued June 26, 1990; and U.S. 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 25 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 30 selected from 4-N,N-(2-ethylhexyl)methylaminobenzoic acid ester of 2,4- WO 99/55295 PCT/US98/16496 27 dihydroxybenzophenone, 4-N,N-(2-ethylhexyl) methylaminobenzoic acid ester with 4-hydroxydibenzoylmethane, 4-N,N-(2-ethylhexyl)methylaminobenzoic acid ester of 2-hydroxy-4-(2-hydroxyethoxy)benzophenone, 4-N,N-(2-ethylhexyl) methylaminobenzoic acid ester of 4-(2-hydroxyethoxy)dibenzoylmethane, and 5 mixtures thereof. Other Ingredients The compositions useful in the present method can contain a variety of 10 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. 15 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 methanolamides of long chain fatty 20 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, sodium carbonate; salts, in 25 general, such as potassium acetate and sodium chloride; colouring agents, such as any of the FD&C or D&C dyes; hair oxidizing (bleaching) agents, such as hydrogen peroxide, perborate and persulfate salts; hair reducing agents, such as the thioglycolates; perfumes; sequestering agents, such as disodium ethylenediamine tetra-acetate; and polymer plasticizing agents, such as glycerin, WO 99/55295 PCTIUS98/16496 28 disobutyl adipate, butyl stearate, and propylene glycol; antioxidants, such as tocopheryl acetate and butyl hydroxy toluene. Also suitable for use herein as conditioning agents are liquid polyol 5 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 10 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 0 C). The liquid polyol polyesters suitable for use herein comprise certain polyols, 15 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 monosaccharides and disaccharides, sugar alcohols or sugar ethers. Examples of monosaccharides containing four hydroxyl groups are xylose and 20 arabinose and the sugar alcohol derived from xylose, which has five hydroxyl groups, i.e., xylitol. The monosaccharide, erythrose, is also suitable in the practice of this invention since it contains three hydroxyl groups, as is the sugar alcohol derived from erythrose, i.e., erythritol, which contains four hydroxyl groups. Suitable five hydroxyl group-containing monosaccharides are galactose, 25 fructose, and sorbose. Sugar alcohols containing six hydroxyl groups derived from the hydrolysis products of sucrose, as well as glucose and sorbose, e.g., 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 30 as, sorbitan.

WO 99/55295 PCT/US98/16496 29 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 8 hydroxyl groups. Preferred polyols for preparing the 5 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 10 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 15 saturated or unsaturated, including positional and geometrical isomers. 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. 20 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 25 polyol are esterified with fatty acids, i.e., 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. 30 WO 99/55295 PCT/US98/16496 30 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 5 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 10 present invention: glucose dioleate, the glucose diesters of soybean oil or cotton seed oil fatty acids (unsaturated), the mannose 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 15 (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 20 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. 25 The preferred liquid polyol polyesters of the present invention have complete melting points below about 300C, preferably below about 27.50C, and more preferably below about 250C. Complete melting points reported herein are measured by Differential Scanning Calorimetry (DSC). The term "complete 30 melting point", as used herein means a melting point as measured by the well- WO 99/55295 PCT/US98/16496 31 known technique of Differential Scanning Calorimetry (DSC). The complete melting point is the temperature at the intersection of the baseline, i.e. the specific heat line, with the line tangent to the trailing edge of the endothermic peak. Typically a scanning temperature of 5oC/minute is used in the present 5 invention in measuring the complete melting points. A technique for measuring complete melting points is more fully described in US-A-5,306,514, to Letton et al., issued April 26, 1994. Exemplary liquid polyol carboxylic acid esters suitable for use herein are 10 sucrose polysoyate 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 15 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-4,517,360 and 4,518,772 to Volpenhein issued 1985. 20 The shampoo, conditioning and ultra violet filtering compositions herein can be in the form of an emulsion, a cream, a gel or a foam.

WO 99/55295 PCT/US98/16496 32 Examples Example 1 1. As part of a daily cleansing regimen coloured hair is pre-treated using 5 currently marketed Pantene(RTM) conditioner. 2. The pre-treated hair is then washed with currently marketed Pantene(RTM) shampoo and rinsed with water. Example 2 10 1. As part of a daily cleansing regimen coloured hair is pre-treated using a conditioning composition of the following formula (A); Component (Wt.%) Oleyl Alcohol 1.00 15 PEG-7M 1 2.00 Polydimethylsiloxane 2 4.20 Silicone Resin 3 0.25 Pentaphenyl Trimethyl Trisiloxane 4 0.38 20 DL Panthenol 0.04 Panthenyl Ethyl Ether 0.34 Fragrance 0.30 Kathon(RTM) CG 5 0.03 Cetyl Alcohol 1.20 25 Stearyl Alcohol 0.80 Ditallow Dimethyl Ammonium Chloride 0.75 Stearamidopropyl Dimethylamine 1.00 WO 99/55295 PCT/US98/16496 33 Glycerol Monostearate 0.25 Citric Acid 0.19 Water to 100 5 1 PEG-7M is Polyethylene Glycol where n has an average value of about 7,000 and is commercially available under the tradename of Polyox WSR(RTM) N-750 from Union Carbide. 2 An 85%/15% (wt. basis) mixture of D5 Cyclomethicone and dimethicone gum (weight average molecular weight of about 400,000 to about 600,000). 3 Polytrimethyl hydrosilylsilicate, added as a 50 wt. % solution in decamethylcyclopentasiloxane, General Electric 10 Silicone Products, SS 4320. 4 Dow Corning 705, Dow Corning Corp. (Midland, MI, USA). 5 Methylchloroisothiazoline (and) methylisothiazoline, a preservative from Rohm & Haas Co., (Philadelphia, PA, USA). 15 2. The pre-treated hair is then washed with currently marketed Pantene(RTM) Ultra Mild shampoo and rinsed with water. Example 3 After colouring the coloured hair is pre-treated using currently marketed 20 Pantene(RTM) conditioner followed by rinsing the hair with water. Example 4 1. The coloured hair is pre-treated using currently marketed Pantene(RTM) conditioner. 25 2. The pre-treated hair is exposed to water through swimming. Example 5 1. As part of a daily cleansing regimen coloured hair is pre-treated using currently marketed Oil of Ulay(RTM) Active Hydrogel. 30 2. The pre-treated hair is then washed with currently marketed Pantene(RTM) shampoo and rinsed with water.

WO 99/55295 PCT/US98/16496 34 Example 6 1. As part of a daily cleansing regimen coloured hair is then pre-treated using currently marketed Pantene(RTM) conditioner. 2. The pre-treated hair is then washed with currently marketed 5 Pantene(RTM) shampoo and rinsed with water. 3. The washed hair is then conditioned using currently marketed Pantene(RTM) Conditioner. Example 7 10 1. As part of a daily cleansing regimen coloured hair is pre-treated using a conditioning composition of formula (A). 2. The pre-treated hair is then washed with currently marketed Pantene(RTM) Ultra Mild shampoo and rinsed with water. 3. The washed hair is then conditioned with a conditioning composition of 15 formula (A). Example 8 1. As part of a daily cleansing regimen the coloured hair is pre-treated using currently marketed Oil of Ulay(RTM) Active Hydrogel. 20 2. The pre-treated hair is then washed with currently marketed Pantene(RTM) shampoo and rinsed with water. 3. The washed hair is then conditioned using a conditioning composition of the following formula; 25 Component (Wt.%) Oleyl Alcohol 0.25 PEG-7M 1 1.00 Polydimethylsiloxane 2 4.20 Silicone Resin 3 0.25 30 Pentaphenyl Trimethyl WO 99/55295 PCT/US98/16496 35 Trisiloxane 4 0.38 DL Panthenol 0.04 Panthenyl Ethyl Ether 0.34 Fragrance 0.35 5 Kathon(RTM) CG 5 0.03 Cetyl Alcohol 1.80 Stearyl Alcohol 1.20 Ditallow Dimethyl Ammonium Chloride 0.75 10 Stearamidopropyl Dimethylamine 1.00 Glycerol Monostearate 0.25 Citric Acid 0.22 Hydroxyethyl Cellulose 0.25 15 Water to 100 1 PEG-7M is Polyethylene Glycol where n has an average value of about 7,000 and is commercially available under the tradename of Polyox WSR(RTM) N-750 from Union Carbide. 2. An 85%/15% (wt. basis) mixture of D5 Cyclomethicone and dimethicone gum (weight average molecular 20 weight of about 400,000 to about 600,000). 3. Polytrimethyl hydrosilylsilicate, added as a 50 wt. % solution in decamethylcyclopentasiloxane, General Electric Silicone Products, SS 4320. 4 Dow Corning 705, Dow Corning Corp. (Midland, MI, USA). 5 Methylchloroisothiazoline (and) methylisothiazoline, a preservative from Rohm & Haas Co., (Philadelphia, 25 PA, USA). Example 9 1. As part of a daily cleansing regimen the coloured hair is pre-treated using currently marketed Pantene(RTM) conditioner. 30 2. The pre-treated hair is then washed with currently marketed Pantene(RTM) shampoo and rinsed with water.

WO 99/55295 PCT/US98/16496 36 3. The washed hair is then conditioned currently marketed Pantene(RTM) conditioner and rinsed with water. 4. The hair is then treated with an an ultra violet filtering composition of the following formula; 5 Component (Wt %) Octyl Methoxycinnamate 6.00 % Glycerine 6.00 % Zinc oxide 3.00 % 10 Isohexadecane 2.00% Isopropyl Palmitate 2.00 % Polyacrylamide & C13-14 Isoparaffin & Laureth-4 (Sepigel 305) 1.55 % 15 Steareth-21 0.90% Cetyl alcohol 0.79 % Stearyl alcohol 0.79 % Behenyl alcohol 0.83 % Dimethicone & 20 Dimethiconol (DC - 2 1068 blend) 0.75 % SEFA Cottonate 0.50 % Tocopheryl Acetate 0.20 % DMDM Hydantoin & lodopropynyl Butylcarbamate (Glydant Plus) 0.20 % 25 Perfume MOD S/PCV 1745/7 0.20 % Disodium EDTA 0.10 % Steareth-2 0.10 % DEA-Oleth-3 Phosphate 0.06 % Water to 100 % 30 WO 99/55295 PCT/US98/16496 37 Example 10 1. As part of a daily cleansing regimen the coloured hair is pre-treated using a conditioning composition of the following formula; 5 Component (Wt.%) Oleyl Alcohol 1.00 PEG-14M 1 0.25 Polydimethylsiloxane 2 4.20 10 Silicone Resin 3 0.25 Pentaphenyl Trimethyl Trisiloxane 4 0.38 DL Panthenol 0.04 Panthenyl Ethyl Ether 0.34 15 Fragrance 0.35 Kathon(RTM)

CG

5 0.03 Cetyl Alcohol 1.80 Stearyl Alcohol 1.20 Ditallow Dimethyl 20 Ammonium Chloride 0.75 Stearamidopropyl Dimethylamine 1.00 Glycerol Monostearate 0.25 Citric Acid 0.22 25 Hydroxyethyl Cellulose 0.25 Water to 100 PEG-14M is Polyethylene Glycol where n has an average value of about 14,000 and is commercially available under the trade name of Polyox WSR(RTM) N-3000 from Union Carbide. 30 2 An 85%/15% (wt. basis) mixture of D5 Cyclomethicone and dimethicone gum (weight average molecular weight of about 400,000 to about 600,000).

WO 99/55295 PCT/US98/16496 38 3 Polytrimethyl hydrosilylsilicate, added as a 50 wt. % solution in decamethylcyclopentasiloxane, General Electric Silicone Products, SS 4320, 4 Dow Corning 705, Dow Corning Corp. (Midland, MI, USA). 5 Methylchloroisothiazoline (and) methylisothiazoline, a preservative from Rohm & Haas Co., (Philadelphia, PA, USA). 5 2. The pre-treated hair is then washed with currently marketed Pantene(RTM) shampoo and rinsed with water. 3. The washed hair is then conditioned currently marketed Pantene(RTM) conditioner and rinsed with water. 10 4. The hair is then treated with currently marketed Pantene(RTM) Serum Spray. Examples of other compositions useful herein comprising ultra violet filtering agents include: 15 Conditioning Spray Water QS 100 Polyquatermium 37, propylene glycol 1.000 dicaprylate/dicaprate, PPG-1 trideceth-6 PVPNA copolymer 0.500 DL-Panthenol (10%), Panthenyl ethyl ether (90%) 0.300 Dimethicone & Dimethiconal 0.500 PEG-4 0.450 DMDM Hydantoin 0.204 Fragrance 0.110 Polysorbate 80 0.063 Disodium EDTA 0.140 Octyl methoxycinnamate 0.010 Silk amino acids 0.003 PEG-5M 0.010 WO 99/55295 PCT/US98/16496 39 Benzophenone-4 0.010 Tocopheryl Acetate 0.030 Shampoo Water Purified QS 100 Ammonium Laureth-3 Sulfate 28% 28.402 Disodium Cocoamphodiacetate 38.5% 18.182 Glycol Distearate Molten Premix 2.000 Dimethicone 40/60 0.900 Tricedeceth-7 Carboxylic Acid 90% 0.560 Polyquaternium-10 0.150 Perfume 0.800 DL Panthenol 0.054 DL Pantyl B 0.066 PEG-78 Glyceryl Cocoate 60% 4.667 PEG-30 Glyceral Cocoate 3.500 Sodium Benzoate 0.250 DMDM Hydantoin 55% 0.200 Tetrasodium EDTA 87% 0.100 Sodium Chloride PVD 1.041 Citric Acid Anhydrous 0.650 Tocopheryl Acetate 0.03 Benzophenone-4 0.1 Octyl Methoxycinnamate 0.1 5 Rinse Conditioner Demineralised Water QS 100 15/85 Dimethicone/Cyclometh icone 4.2000 WO 99/55295 PCT/US98/16496 40 blend Stearamidopropyl Dimethylamine 1.0000 Cetyl alcohol 0.9600 Quaternium 18 0.7500 Stearyl alcohol 0.6400 PEG-2M 0.5000 Emulsifying Wax (Polawax/Lipowax) 0.5000 Benzyl Alcohol 0.4000 Pantyl B 0.2500 Hydroxyethylcellulose 0.2500 Glyceryl Monostearate 0.2500 Oleyl alcohol 0.2500 DMDM Hydantoin 0.2000 EDTA 0.1000 Citric acid anhydrous 0.1300 Perfume 0.3000 Octyl Methoxycinnamate 0.1000 Benzophenone 0.1000 Tocopheryl Acetate 0.0300 Intensive Conditioner Demineralised Water QS 100 15/85 Dimethicone/Cyclomethicone 4.3700 blend Stearamidopropyl Dimethylamine 2.0000 L-Glutamic Acid 0.6400 Cetyl alcohol 2.5000 Stearyl alcohol 4.5000 Benzyl Alcohol 0.4000 WO 99/55295 PCT/US98/16496 41 Pantyl B 0.2500 DMDM Hydantoin 0.2000 EDTA 0.1000 Perfume 0.3000 Octyl Methoxycinnamate 0.1000 Benzophenone 0.1000 Tocopheryl Acetate 0.0300 Conditioning Spray Demineralised Water qs100 Hexylene Glycol 4.0000 Keratin Amino Acids 1.0000 PVP 0.5000 PEG 60 Hydrogenated Castor Oil 0.5000 Dicetyldimonium Chloride 0.3800 DMDM Hydantoin (0.55%) 0.1375 Tetrasodium EDTA (87%) 0.1131 Pantethine 0.1000 Panthenol 0.0100 Silk Amino Acids 0.1000 Lactic Acid (85%) 0.451 Fragrance 0.1000 Tocopherol Acetate 0.03 Octyl Methoxycinnamate 1.00 Benzophenone-4 0.05 5 In all of the above examples the incidence of colour fade and/or colour shift was reduced or eliminated increasing the time between dyeing as a consequence.

Claims (9)

1. A cosmetic method of treating mammalian hair to reduce or prevent colour 5 fade and/or colour shift comprising; (a) treating the hair with a composition comprising a hydrophobic and/or cationic conditioning agent; followed by 10 (b) wetting the hair.

2. A cosmetic method according to Claim 1 wherein the hair of step (a) is wet.

3. A cosmetic method according to Claim 1 or 2 comprising an additional step 15 (c), to be carried out after step (b), of treating the hair with a composition comprising a conditioning agent.

4. A cosmetic method according to any of Claims 1 to 3 comprising an additional step (d), to be carried out after step (b) or (c), of treating the hair 20 with a composition comprising a ultra violet filter.

5. A cosmetic method according to any of Claims 1 to 4, wherein the composition comprising a conditioning agent of step (a) or step (c) is delivered as a foam. 25

6. A cosmetic method according to any of Claims 1 to 5, wherein the composition comprising a conditioning agent of step (a) or step (c) additionally comprises an ultra violet filter. WO 99/55295 PCT/US98/16496 43

7. A cosmetic method according to any of Claims 1 to 6, wherein the conditioning agent is selected from cationic surfactants, cationic polymers, nonvolatile silicones, volatile silicones, nonvolatile hydrocarbons, saturated C 14 to C22 straight chain fatty alcohols, nonvolatile hydrocarbon 5 esters, and mixtures thereof.

8. A cosmetic method according to any of Claims 1 to 7, wherein step (b) comprising washing the hair with a surfactant composition. 10

9. A cosmetic method according to Claim 8, wherein the surfactant composition comprises a surfactant selected from anionic, cationic, nonionic, amphoteric, zwitterionic surfactants.