GB2385056A

GB2385056A - Hair dyeing compositions comprising silicone elastomer

Info

Publication number: GB2385056A
Application number: GB0301656A
Authority: GB
Inventors: Stephanie Postiaux; Joanna Newton
Original assignee: Dow Corning Corp
Current assignee: Dow Silicones Corp
Priority date: 2002-01-30
Filing date: 2003-01-24
Publication date: 2003-08-13
Also published as: GB0301656D0; GB0202132D0

Abstract

A hair dyeing composition comprises a silicone elastomer, which preferably has at least one alkoxy or hydroxy containing group, more preferably in conjunction with higher alkyl groups substituted onto silicon atoms. The hair dyeing agent composition may be a non-oxidative composition or an oxidative composition. Particularly preferred are hair dyeing compositions comprising a silicone elastomer which is a Dimethicone crosspolymer or a resin modified silicone elastomer.

Description

HAIR DYEING AGENT COMPOSITION [0001] This invention is directed to a hair dyeing agent composition containing silicones, and more specifically relates to hair dyeing agent compositions containing a silicone elastomer, of superior washing resistance of superior colour fastness under light exposure. In particular the invention is directed to a non-oxidation (semi-permanent) hair dyeing agent composition containing a silicone elastomer, although some oxidation hair dyeing agent compositions are also included.

Oxidation hair dyeing agents are most widely used as permanent hair dyeing agents. Oxidation dye precursors in such hair dyeing agents penetrate into hair, and chemically impart a colour to the hair by means of colour formation resulting from oxidative polymerisation under the action of an oxidation agent. The process is generally one characterised by permanency in the dyeing effect. Non-oxidation dyeing agents are used for semi-permanent or non-permanent hair dyeing. In the present invention we are particularly concerned with the semi-permanent non-oxidation dyeing agents. These are sometimes also referred to as direct dyes. Semi-permanent dyeing will usually colour human hair for up to six subsequent shampoo washes, although a high proportion of colour is often lost after 2 or 3 washes.

[0003] Semi-permanent hair dyeing compositions are usually provided as singlecomponent products, and may contain a variety of additives in addition to a direct dye. As far as the forms of such oxidation hair dyeing agents are concerned, numerous twocomponent type products are known. They are used by mixing, at the time of hair dyeing, a first agent containing an oxidation dye precursor, and a second agent containing an oxidation agent. There are also single-component products which are powder-like. These products are used by mixing the one component with water at the time of hair dyeing. Multi-component products containing three or more agents are also known.

[0004] Hair dyeing agents containing silicones are known, and reference may be had, for example, to British Patent 2138845, which describes a process for dyeing hair using a hair dyeing agent composition containing a silicone derivative obtained by introducing tertiary

amino groups or quaternary ammonium groups into the side chain of polydiorganosiloxanes to produce deep colour tones. Japanese Kokai Patent Application Publication No. Hei 08 [1996]-040851 also discloses an oxidation hair dyeing agent composition, but it contains a saccharide derivative and a silicone. The silicone is exemplified by dimethylpolysiloxane, amino-modified polysiloxane, epoxy-modified polysiloxane, and a polyether-modified polysiloxane. In patent specification GB 217351, a dye composition is disclosed which comprises a direct dye, a cationic silicone surfactant which comprises a cationic silicone derivative, a hydroxy functional silicone derivative and a liquid vehicle. Japanese patent application, laid open, JP 395570/00 discloses an oxidation hair dyeing agent composition comprising a mixture of an oxidation dye precursor, a cyclic silicone, and a silicone elastomer. The cyclic silicone is described as including for example a cyclomethicone (CTFA nomenclature) or certain other cyclic siloxanes, and the silicone elastomer is described as a material known in the cosmetic industry generally referred to for example as Dimethicone Cross polymer. Some representative examples are elastomeric polymethylsiloxanes obtained by cross-linking, and which contain alkyl groups with 3-20 carbon atoms. Some other suitable silicone elastomers which can be used include materials obtained by cross-linking polymethylvinylsiloxane and polymethylhydrogensiloxane in the presence of a platinum catalyst; materials obtained by cross-linking a, (j) - dihydroxypolydimethylsiloxane with an hydrolysable group-containing organosilane; and materials obtained by cross-linking polymethylvinylsiloxane in the presence of an organic peroxide. Representative silicone elastomers are also described in US Patents 5654362, 5811487,5880210, and 5969035.

[0005] However, the problem with such compositions is that even if hair is dyed with such hair dyeing agent compositions, whether semi-permanent or permanent, the colour tone of the dyed hair tends to fade when hair is repeatedly washed with cold and hot water containing shampoo or soap or when it is exposed to light, in particular sunlight or other UV radiation sources.

[0006] There is a need to limit or eliminate the disadvantages of previously known non-oxidation or oxidation hair dyeing agent compositions, and to provide a hair dyeing agent composition in which colour tones of dyed hair are more resistant to fading when

exposed to sunlight or other UV radiation and which are not as easily affected by repeated washing with cold and hot water containing shampoo and soap than prior art compositions using silicones. Suggestions have been made in US patent 5843193, W09841186 application, WOOO/07550 application, EP 0890355 Al, W097/12594, JP patent specification 10265354 and JP patent specification 09095428.

[0007] It was unexpectedly discovered that non-oxidation hair dyeing agent compositions containing certain silicone elastomers had superior hair dyeing stability, both with respect to resistance to sunlight or UV radiation or with regard to washing resistance.

This was also surprisingly true for some silicone elastomers in some cases of oxidation hair dyeing agent compositions.

[0008) The present invention accordingly relates to a non-oxidation hair dyeing agent composition, characterised by the fact that it contains a silicone elastomer, preferably having at least one alkoxy or hydroxyl containing group. Surprisingly silicone elastomers which are particularly suitable for oxidation hair dyeing agent compositions contain alkoxy containing groups or hydroxyl containing groups in conjunction with higher alkyl groups substituted onto silicon atoms.

[0009] With regard to oxidation hair dyeing agent compositions, a two-component type composition is particularly provided, and it contains as a first agent or component a mixture of an oxidation dye precursor, a cyclic silicone, a silicone elastomer, an emulsifying agent, and water. This mixture is emulsified in water using the emulsifying agent. The second agent or component of the composition is an aqueous hydrogen peroxide solution.

[0010) The silicone elastomer used in the non-oxidation hair dyeing agent composition of this invention may be a material known in the cosmetic industry generally referred to for example as Dimethicone Crosspolymer. Some representative examples are elastomeric polymethylsiloxanes obtained by crosslinking, and which contain alkyl groups with 3-20 carbon atoms. Again, reference may be had to the CTFA's International Cosmetic Ingredient Dictionary. Some other suitable silicone elastomers which can be used include materials obtained by crosslinking polymethylvinylsiloxane and polymethylhydrogensiloxane

in the presence of a platinum catalyst; materials obtained by crosslinking a, - dihydroxypolydimethylsiloxane with an hydrolyzable group-containing organosilane; and materials obtained by crosslinking polymethylvinylsiloxane in the presence of an organic peroxide. Representative silicone elastomers are also described in US Patents 5654362, 5811487,5880210, and 5969035 and in US application 227516 filed 21 August 2002. It is particularly preferred that the silicone elastomers have an alkoxy containing substituent or a hydroxyl containing substituents which is linked to a silicon atom of the elastomer, preferably

an alkoxy or hydroxyl substituted polyoxyalkylene or alkoxy silane substituent.

Suitable silicone elastomers include those obtained by reacting (A) an =Si-H containing polysiloxane of formula R3SiO (R'2SiO) a (R"HSiO) bSiR3 and optionally an =Si-H containing polysiloxane of formula HR2SiO (R'2SiO) cSiR2H or formula HR2SiO (R'2SiO) a (R"HSiO) bSiR2H where R, R', and R" are alkyl groups with 1-6 carbon atoms; a is 0-250; b is 1-250; and c is 0-250; with (B) an alpha, omega-diene of formula CH2=CH (CH2) xCH=CH2 where x is 1-20. The reaction is conducted in the presence of a Group VIII transition metal, preferably platinum, catalyst, as described e. g. in US patents 3,715, 334 and 3,814, 730 and in the presence of (C) a low molecular weight silicone oil, for example low molecular weight linear or cyclic volatile or non-volatile alkyl and aryl

siloxanes, represented e. g. by compounds of the formulae RSiCRSiCySiRg, and (RSiO) z, where R is an alkyl group of 1-6 carbon atoms, or an aryl group such as phenyl, the value of y is 0-80, preferably 0-20, the value ofz is 0-9, preferably 4-6, and having a viscosity generally in the range of about 1-100 mm2/s-1, or other solvent, which may be (i) organic compounds, (ii) compounds containing a silicon atom, (iii) mixtures of organic compounds, (iv) mixtures of compounds containing a silicon atom, or (v) mixtures of organic compounds and compounds containing a silicon atom. Other alternatives are described in the prior art referred to above, which is hereby incorporated by reference. It is possible, but not preferred to crumble the silicone gel into a silicone powder using mechanical force and incorporate it as such in the dyeing agent. Alternatively additional low molecular weight silicone oil can be added to the gel, and the oil and the gel subjected to shear force, until a silicone paste is formed. The silicone elastomers here described are intended in the scope of the present invention for non-oxidation hair dyeing compositions only.

A more preferred silicone elastomer is made by a process comprising a first step of reacting (A') an =Si-H containing polysiloxane; and (B') a mono-alkenyl polyether; in the presence of a platinum catalyst, until (C') an =Si-H containing siloxane with polyether groups is formed, which in a second step is reacted with (D') an unsaturated hydrocarbon such as an alpha, omega-diene; in the presence of (E') a solvent and a Group VIII, preferably, platinum catalyst, until a silicone elastomer is formed by cross-linking and addition of=SiH across double bonds in the alpha, omega-diene. Additional solvent may be added to the silicone elastomer, followed by shearing the mixture until a silicone paste is formed.

Additionally, water may be added to the silicone paste, and the water and silicone paste subsequently sheared until a silicone emulsion is formed, which may this be formed free of the presence of a surfactant. Preferred options for components used in the above process are described in detail in the above referenced prior art. Preferences for (A') and (D') are as indicated above for (A) and (B). The mono-alkenyl polyether (B') is a compound of the formula CH2=CH (CH2) xO (CH2CH20) y (CH2CH3CHO) zT, or a compound of the formula

CH2=CH-Q-O (CH2CH20) y (CH2CH3CHO) zT, wherein T represents hydrogen or a CI-I0 alkyl, C 1-20 acyl group, Q is a divalent linking group containing unsaturation such as phenylene-CH-, : e is 1-6, y and z can be zero or have a value of 1-100, with the proviso that y and z cannot both be zero. The silicone elastomers here described are intended in the scope of the present invention for non-oxidation hair dyeing compositions only.

[0013] Particularly preferred are silicone elastomers which are made as described in the section immediately preceding, but where remaining =SiH groups are further reacted with higher alkene materials, preferably alkenes with terminal unsaturation, most preferably alkenes which are linear and have from 12 to 40 carbon atoms, most preferably from 12 to 20. This reaction is also an addition reaction, and may be carried out under similar circumstances as indicated above and in the relevant prior art, and may be carried out simultaneously with the hydrosilation addition reactions described above, or may be done subsequently. The benefit of doing it afterwards, is that there is no danger of competition between the two addition reactions, and that the number of alkyl substitutions which result from the addition reaction of the alkenes is easier to control. It is particularly preferred that the number of alkyl substitutions is small, and preferably the molar ratio of oxyalkylene to

higher alkyl substitutions is from 1: 10 to 100: 1, more preferably 1: 5 to 20 : 1, most preferably 1: 2 to 10: 1. The silicone elastomers here described are intended in the scope of the present invention for both oxidation and non-oxidation hair dyeing compositions.

Another preferred silicone elastomer is formed by providing a thermodynamically stable material comprising (A) a cross-linked siloxane comprising alkoxysilyl functionality,-X- SiR4n (OR5) 3-n, and cross-links,-E-Y-E-, with each end of such cross-links bonded to a silicon, wherein, X is a divalent group that is a hydrocarbon, a siloxane or some combination ofthese, R4 and R5 are independently monovalent hydrocarbon groups, El and E2 are independently-CHCH-or- CH=CH-, Y is a divalent group that is a hydrocarbon, a siloxane or some combination of these, and n is 0 to 2, which cross-linked siloxane comprising alkoxysilyl functionality is made by cross-linking, in the presence of a hydrosilylation catalyst, (1) an =SiH functional siloxane with (2) an alpha,

omega diene, diyne or ene-yne, with the provisos that at least one of (1) and (2) has alkoxysilyl functionality, -X-SiR4n (OR5h-n, where, X is a divalent group that is a hydrocarbon, a siloxane or some combination of these, R4 and R5 are independently monovalent hydrocarbon groups and n is 0 to 2, that (1), (2) and the catalyst are dispersed in a diluent, and that the weight ratio of (1) + (2) + the product of the cross-linking of (1) and (2) : diluent is 1: 100 to 10: 1 and (B) a diluent, which may be a single compound or a mixture of compounds, including silicones such as siloxanes, both linear and cyclic, organic oils, organic solvents and mixtures of these.

A specific embodiment of the type of elastomers is given below as a suggestion of the type of materials discussed, and is in no way limiting. A material wherein (A) is a cross-linked alkoxysilyl functional siloxane of average formula:

where, R is a monovalent hydrocarbon group (preferably one having 1 to 30 carbons or more preferably 1 to 12 carbons and especially alkyl, aryl, alkaryl, aralkyl, or combinations thereof with a very preferred choice being methyl); R2 is - (CHVdSiR4n (OR5h-n ; R3 is-E1-Y-E2-R9 or a siloxane containing (somewhere in its structure as pendant, internal, terminal or otherwise)-E1-Y-E2-R9 with EI in this last mentioned siloxane bonded to silicon as well as to Y, R4 and R5 are independently monovalent hydrocarbon groups (preferably one having 1 to 30 carbons or more preferably 1 to 12 carbons and especially alkyl, aryl, alkaryl, aralkyl, or combinations thereof, with very preferred choices for R 5 including methyl, ethyl or phenyl) ; El and E2 are independently-CH2CH2-or-CH=CH-; Y is a divalent group that is a hydrocarbon (especially one having 1 to 30 carbons), a siloxane or some combination of these with one preferred combinational Y being,

where RO is a monovalent hydrocarbon group (especially methyl) and p is 0 to 20,000 ; R9 is R 1

I (SiO) (which can be thought of as the"other side"of the cross link) ; I

a is 0-100, 000,000 ; b is 1-50, 000,000 ; c is 1-10, 000,000 ; d is 2-12 ; n is 0-2.

The silicone elastomers here described are intended in the scope of the present invention for both oxidation and non-oxidation hair dyeing compositions.

Yet another alternative silicone elastomer is a resin modified elastomer comprising : (A) a cross-linked siloxane comprising: (i) a siloxane polymer, (ii) resin functionality having the formula (R3Si01l2) x (Si04/z) y (RSi03/2) z and (iii) cross- links,-E-Y-E-, with each end of the cross-link is bonded to a silicon atom, wherein, each R is independently a divalent hydrocarbon group having 2 to 30 carbon atoms or a monovalent hydrocarbon group having 1 to 30 carbon atoms; wherein when R is a divalent hydrocarbon group it is bonded to the resin and to the siloxane polymer or a cross-link; each E is a divalent group

independently selected from-CHCH-or-CH=CH- ; Y is a divalent group that is a hydrocarbon, a siloxane or some combination of these ; and x is 1, y 0, z 0 and y + z 1 ; and (B) a diluent.

The hair dyeing agent compositions of the invention may also contain cyclic silicone materials, preferably in small proportions. These, generally volatile, materials are known in the cosmetic industry under The Cosmetic, Toiletry, and Fragrance Association (CTFA) name CYCLOMETHICONE. Reference may be had to the CTFA's International Cosmetic Ingredient Dictionary. Some representative examples are octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. These cyclic polydimethylsiloxanes generally have a degree of polymerisation of 3 to 7. In addition, it is also possible to use cyclic polymethylhydrogensiloxanes, cyclic polymethylvinylsiloxanes, and cyclic polymethylphenylsiloxanes, with low degree of polymerisation. Such other cyclic silicones are also known in the cosmetic and silicone industry.

[0017] If desired, the cyclic silicone can be included as a separate component, or in a mixture with the silicone elastomer. Its content in a mixture with the silicone elastomer is

preferably at least about 87 percent by weight, but its content may vary above or below this amount depending on the type and properties of the particular cyclic silicone used, as well as on the type and properties of the silicone elastomer. The cyclic silicone should, however, be readily miscible with other oily like ingredients included in the oxidation hair dyeing agent, and it should be easily emulsifiable in water under influence of an emulsifying agent. Thus, the mixture should exhibit a paste-like or soft gel-like consistency.

[0018] Although cyclic siloxanes are an optional ingredient, they are preferably used in a small amount where a paste-like or soft-gel like consistency is required. Where such consistency is required, too small an amount of the cyclic silicone in the mixture will not exhibit a paste-like or soft gel-like consistency. This may affect the amount of silicone elastomer available to adhere to the hair, with the result that it will have an effect on the ability to impart gloss and smoothness. For such applications the amount of cyclic silicone present preferably varies from 15-95 percent by weight, the remainder being the silicone elastomer.

[0019] The content of cyclic silicone and silicone elastomer in hair dyeing agent compositions of the invention is most preferably about 1.25 percent by weight, based on the total weight of the hair dyeing agent composition. If the amount is too large, then emulsification in water is difficult. If the content is too small, it is difficult to obtain any meaningful hair treatment effect. However, for most purposes, it has been found that the content can vary between 0.1-10 percent by weight. In addition, because the combination of cyclic silicone and silicone elastomer is oil-soluble, the combination is preferably emulsified in water using an emulsifying agent.

The non-oxidation hair dyeing agent composition comprises a direct dye, which has been described for example in GB patent specification 2,173, 515 and comprises anthraquinone, azo, nitro, basic, triariylmethane or disperse dyes or combinations thereof.

Further disclosures of suitable dyes includes the article in Journal of the Society of Cosmetic Chemistry, 35, 297 to 310, of September/October 1984, entitled chemistry of hair colorant processes by John F. Corbett. It lists as suitable direct dyes nitrophenylene-diamine and nitroaminophenol derivatives, supplemented by some aminoanthraquinones. Examples

include N- (2-hydroxyethyl)-2-nitroanline, N-tris (hydroxymethyl) methyl-4-nitro-ophenylenediamine, N - (2-hydroxyethyl) - 2-nitro-p-phenylenediamine, N, N, N-tris (2hydroxyethyl)-2-nitro-p-phenylenediamine, 0, N-bis (2-hydroxyethyl) - 2-amino-5-nitrophenol, 4- hydorxy- 2'-nitrodiphenylamine, 4-amino-4'-bis (2-hydroxyethyl) -aminoazobenzene, 1,4, 5,8-tetraaminoanthraquinone and 1,4-diaminoanthraquinone.

[0021] The amount of direct dye used in compositions according to the invention may range from 0,01 to 10% by weight of the composition. Suitably the dye, or when a mixture of dyes is used, each dye, may be present in an amount from 0.01 to 5% by weight, preferably 0.01 to 3% by weight, most preferably 0.1 to 1 % by weight.

The oxidation hair dyeing agent component of the composition of this invention is an oxidation dye precursor, and it can be an indole or indoline such as are described in Japanese Kokai Patent Application Publication No. 08 [1996]-040857/US 5690697 (November 1997). In addition, some examples of other types of oxidation dye precursors useful in the present invention include compounds such as p-phenylenediamine, p- nitro-o-phenylenediamine, p-chlor-o-phenylenediamine, p-nitro-m-phenylenediamine sulfate, and other phenylenediamines ; toluene-2,5-diamine, toluene-3, 4-diamine, toluene-2, 5-diamine sulfate, 2,4-diaminophenoxyethanol chloride, and other diamines; p-aminophenol, pmethylaminophenol, m-aminophenol-o-aminophenol, 5- (2-hydroxyethylamino) -2- methylphenol and other aminophenols; aminonitrophenol, 4, 4'-diaminophenylamine, and other diphenylamines; diaminophenylamines, N-phenyl-p-phenylenediamine, and other Nphenylphenylenediamines ; 2, 6-diaminopyridine, 2,5-diaminopyridine, and other diaminopyridines ; p-amino-o-cresol and other aminocresols; resorcinol; pyrogallol; phloroglucinol; catechol; and salts thereof.

While there are no particular limitations on the amount of oxidation dye precursor used, it should be present in amounts typically used in such applications, i. e., generally 0. 05-10 percent by weight based on the weight of the hair dyeing agent composition.

] The oxidation hair dyeing agent composition of the invention can be in a single-component form or a multi-component form made up of two or more agents. As a two-component form, for example, a suitable composition would include a two-part composition used by mixing at the time of hair dyeing, a first agent containing the oxidation dye, cyclic silicone, and silicone elastomer, with a second agent containing an oxidation agent. Alternatively, it could be in the form of a two-part composition used by mixing at the time hair dyeing, a first agent containing an oxidation dye, with a second agent containing the silicones and an oxidation agent. The ratio used for mixing together the first agent with the second agent should be 1: 1, but other ratios can be employed, provided they do not result in any adverse effects such as sagging, usability, or evenness of dyeing.

[0025] Any conventional oxidation agent can be used for the oxidation hair dyeing agent composition according to this invention. Some examples of suitable oxidation agents are set forth in Japanese Kokai Patent Application Publication No. Hei 08 [1996]-040851, referred to above. Thus, some representative and useful compositions include hydrogen peroxide, persulfuric acid salts, perboric acid salts, bromic acid salts, periodic acid salts, urea peroxide, percarbonic acid salts, peroxytripolyphosphoric acid salts, peroxybiphosphoric acid salts, and peroxyorthophosphoric acid salts. The most preferred oxidation agent based on its ease of use and general availability is a hydrogen peroxide solution.

Other ingredients can be included in the hair dyeing agent compositions of the invention provided the effects of the invention are not compromised. Some examples may be found in Japanese Kokai Patent Application Publication No. Hei 08 [1996]-040851, referred to above. Representative ingredient include materials, which in an oxidation hair dyeing agent composition are compatible with the first agent, but which are also useful in nonoxidation hair dyeing agent compositions, such as glycerin, propylene glycol, dipropylene glycol, polyethylene glycol, hyaluronic acid salts, diglycerin, 1,2-butylene glycol, pyrrolidone carboxylic acid salts, sorbitol, lactose, oligosaccharides, lanolin, squalane, liquid paraffin, Vaseline, higher fatty acids, triglycerides, and ester oils.

[0027] Additional examples of other ingredients are thioglycolic acid salts, L-ascorbic acid salts, hydrogen sulfites, hydrosulfites, hydrogen sulfates, and other anti-oxidants and

stabilizers; collagen hydrolyzate, gelatin hydrolyzate, silk protein hydrolyzate, elastin hydrolyzate, soybean protein hydrolyzate, and other protein hydrolyzates and their quaternary derivatives; ammonia water, alkanolamine, ammonium carbonate, sodium hydrogen carbonate, potassium hydroxide, and other alkali agents.

Because combinations including cyclic silicones, silicone elastomers, and other oil-soluble ingredients, are not easily dissolved in water, it is preferred to emulsify these materials in water using an emulsifying agent. Some examples of suitable nonionic surface active agents are polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene polyhydric alcohol fatty acid partial esters, polyoxyethylene hardened castor oil derivatives; octylpolyglycoside; polyglycerin fatty acid esters, polyglycerin alkyl ether; maltitol hydroxyalkyl ether, other sugar-alcohol hydroxyalkyl ethers; and fatty acid diethanolamide. Some anionic surface active agents which can be used include higher fatty acid salts, alkylbenzenesulfonic acid salts, phosphoric acid esters, alkylsulfuric acid salts, alkylsulfuric acid esters, and polyoxyethylene alkylsulfuric acid esters. Representative cationic surface active agents are amino acids, alkyltrimethylammonium salts, dialkyldimethylammonium salts, and alkyldimethylamine oxides. Mixtures of these surface active agents may also be employed.

[0029] Still further examples of other ingredients which can be included with the compositions are ethanol, butanol, propanol, isopropanol, benzyl alcohol, and other lower alcohols; 2-ethylhexyl alcohol, 2-hexyldecyl alcohol, 2-decyltetradecyl alcohol, isostearyl alcohol, cetostearyl alcohol, lauryl alcohol, stearyl alcohol, cetyl alcohol, and other higher alcohols; hydroxyethan diphosphonic acid, phenacetin, EDTA, and salts thereof ; parabens, stannates, and other sequestering agents and anti-septic agents; poly (dimethylallyl ammonium halide)-type cationic polymers, cationic polymers formed by condensation of tallowyl amine obtained from beef tallow fatty acids, propyleneamine, epichlorhydrin, and polyethylene glycol; cationic polymers formed by condensation of cocoyl amine obtained from coconut oil fatty acids, propyleneamine, epichlorhydrin, and polyethylene glycol; cationic polymers of dimethylamino methacrylate copolymer; cationic polymers of cellulose ether containing quaternary nitrogen; lauric acid diethanolamide, carboxymethyl cellulose, carboxyvinyl polymer, hydroxyethyl cellulose,

hydroxypropyl cellulose, methyl cellulose, xanthan gum, carrageenan, alginic acid salts, pectin, furcellaran, gum arabic, tragacanth gum, agar, bentonite, cross-linkable polyacrylic acid salts, and other such thickeners ; pH adjusting agents, fragrances, plant extracts, and drugs.

Some examples of ingredients suitable for combining with the second agent of oxidation hair dyeing agent compositions, or for use in non-oxidation hair dyeing agent compositions, include phenacetin, EDTA, and their salts ; parabens, stannates, and other sequestering agents and anti-septic agents ; liquid paraffin, Vaseline, and other oily ingredients ; 2-ethylhexyl alcohol, 2-hexyldecyl alcohol, 2-decyltetradecyl alcohol, isostearyl alcohol, cetostearyl alcohol, lauryl alcohol, stearyl alcohol, cetyl alcohol, and other higher alcohols ; polyoxyethylene alkyl ethers, alkylsulfuric acid ester salts, acyhnethyl taurine, and other surface active agents ; acids such as citric acid, malic acid, acetic acid, lactic acid, oxalic acid, tartaric acid, formic acid, levulinic acid, and other organic acids ; phosphoric acid, hydrochloric acid, and other inorganic acids ; pH-adjusting agents, fragrances, plant extracts, drugs, dyes, and water. If it is desired to include the cyclic silicone and silicone elastomer in the second agent instead of, or in addition to the first agent, the silicones should be emulsified in water using an emulsifying agent.

For semi-permanent dyeing, the composition is applied to the hair, left for a time, according to the extent of dyeing required, and rinsed off with water.

For oxidation compositions, the dyeing process is carried out by applying the oxidation hair dyeing agent composition of the invention to hair, and after allowing the oxidation hair dyeing agent composition to penetrate into the hair, it should remain on the hair for 5 to 30 minutes, preferably about 10 to 20 minutes, at normal temperature in the range of 15-40 C. The hair should then be washed with shampoo or soap containing water, and rinsed with water to wash away any remaining oxidation hair dyeing agent composition.

The following application examples are set forth in order to illustrate this invention in more detail. A number of examples follow, in which parts and percentages are expressed by weight unless otherwise indicated, and viscosity if measured at 250C and

normal atmospheric pressure. Examples for the preparation of silicone elastomers are given first, followed by examples and comparative examples of application on hair.

Example 1 [0034] 125 g of an organopolysiloxane with the average structure Me3SiO (Me2SiO) 34 (MeHSiO) 4SiMe3,4. 7 g of 1,5-hexadiene, and 365 g of decamethylcyclopentasiloxane were charged into a reaction vessel. 100 IÛ of a platinum catalyst solution in vinylsiloxane containing one weight percent of Pt in toluene was added while the solution was stirred. Gelation took place within one hour. The gel was left in the reactor for 8 hours, and then the gel was swollen with 500g of decamethylcyclopentasiloxane under a shear force. A uniform and transparent paste was obtained with a viscosity of 1.8 x 105 centipoise (mPa-s).

Example 2 [0035] 90 g of an organopolysiloxane with the average structure Me3SiO (Me2SiO) 93 (MeHSiO) 6SiMe3 and 7 g CH2=CHCH20 (CH2CH20) 7H were mixed with 700 g decamethylpentacyclosiloxane in a three-neck round bottom flask. To this solution, 200 pli of a Pt catalyst (i. e. , one weight percent platinum in two centistoke (mm2/s) polydimethylsiloxane fluid) was added. The solution was stirred and heated to maintain it at approximately 70 0 C. A polyether branched =SiH siloxane polymer was obtained in almost quantitative yield, to which was added 3 grams of 1,5-hexadiene were mixed with a further 200g of decamethylcyclopentasiloxane. 20 Al Platinum catalyst was added while the solution

was stirred. A uniform paste was obtained having a viscosity at a shear rate of 0. 02 s-l, of 1. 82 x 06cP/mPa-s.

Example 3 [0036] Example 2 was repeated, except that an additional 7 g of Gulftene 18, supplied by Chevron, was added to the composition and reacted into the formulation.

Example 4-6 [0037] Into an Escot EL 1 processor (mixer) is loaded 400.00 g (less the amount used to dilute the hexadiene added below-see note in Table 1) of decamethylcyclopentasiloxane (hereinafter"D$") and a measured amount (see Table 1) of a silicon hydride containing siloxane having an average structure, (Me3SiO) (Me2SiO) 93 (MeHSiO) 6 (SiMe3), (hereinafter, =SiH). The temperature controller is set to 70 C, and the wiper blades are adjusted to a setting of 15 and the homogenizer to a setting of 10. When the temperature reaches 70 C, 0.2 ml of a platinum catalyst with a Pt content of 0.52 weight percent is added, immediately followed by the required (see Table 1) vinyl (trimethoxy) silane (hereinafter,"VTMS"). The temperature is then increased to 7SoC and held for 30 minutes with continuing agitation. Next, an additional 0.8 ml of the same catalyst is added, immediately followed by the subsurface addition of a measured amount (see Table 1) of 1, 5-hexadiene (hereinafter,"HD") solution. The resulting exotherm (5- 10 C) indicates that the reaction is proceeding as desired. The system is then held at 75 C for 3 hours with the wiper blade at a setting of 15 and the homogenizer at a setting of 20. At the end of the three hour period, 3.50 g of a vinylsiloxane oligomer with the average structure [ (CH2=CH) SiMe20] (Me2SiO) g [SiMe2 (CH=CH2)] (hereinafter,"DVS") is added and mixed in at temperature for an additional 10 minutes. The mixture is then cooled by setting the temperature controller on the mixer to 200C while continuing the shear. After a cooling period of 30 minutes, the scraper is set to 20 and the homogenizer to 25 and 269.00 g of additional D is added in order to achieve 13% solids by weight in the mixture.

Table 1. Amounts Used in Examples 4-6 and Resulting Functionality

Example sSiH (g) HDa (g) VTMS (g) % Alkoxvsilvlb 4 96. 21 3. 27 0. 51 0. 5 5 95. 86 3. 12 1. 02 1. 0 6 93.77 2.22 4.01 4.0

Example 7-Preparation of semi-permanent hair dyeing agent compositions [0038] The composition comprised the following ingredients: 28 parts of a Base Oilin-water 097&num;, from Les Colorants Wackherr 4 parts of propylene glycol, 0.3 parts of Phenonip, 9 parts of Solvariane, 0.6 parts of Covariane Red W3123&num;, 0.6 parts of Covariane Purple W5121&num;, 0.85 parts of Covariane Blue W6122&num;, 0.2 parts of Covastyle TBQ&num;, 0.25 parts of disodium EDT A, sufficient 2-amino-2-methyl-1-propanol to bring the composition to a pH of 6 and sufficient water to reach a total weight of 100 parts. The formulation was used as the standard (comparative) composition, but an additional silicone elastomer material, as prepared in Examples 1 to 4 above was added to reach a total composition of 1.4% of silicone in the composition for the example compositions. The process used included melting the Base O/W at 70 C in a reaction vessel, weighing out in a separate vessel, the Solvariane, Phenoxetol, Propylene Glycol, Covariane and Covastyle, which were dissolved completely with stirring and gentle heating at 40-50 C. This solution was added to the base O/W 097, the container rinsed with a part of hot water, prior to adding the rest of hot water, followed by stirring until the mixture is homogenous. The di-sodium EDTA was then added at room temperature, and the pH adjusted to 6 with 2-amino-2-methyl-1-propanol. Additional water was then added to compensate for any water loss where appropriate. A colouring cream was obtained as a result.

Example 8-Preparation of permanent hair dyeing agent compositions [0039] A Colouring cream was prepared in a fume hood. The ingredients included for Phase A, 4.8 parts of Oxopearl, 34.2 parts of water, 1.8 parts of Carbopol 980 and 23 parts of Empicol ESB 3M. Phase B consisted of 0.22 parts of Covastyle PPD, 0.24 parts of Covastyle PAP, 0.7 parts of Covastyle AHT, 0.3 parts ofCovastyle AEB, 0.71 parts of Covastyle MBS, 0.96 parts of Covastyle ED and sufficient water to take the total weight of the composition to 100 parts. Phase C contained 10.2 parts of a 20% ammonia solution. The formulation was used as the standard (comparative) composition, but an additional silicone elastomer material, as prepared in Examples 1 to 4 above was added to reach a total composition of 1.4% of silicone in the composition for the example compositions. The process used for making the composition was to hydrate and dissolve the Carbopol 980 under

strong agitation (1500rpm) in a part of the water at 70-80 C, melt Oxopearl under agitation at 70-80 C in a separate beaker, in a water bath. When completely melted, the Carbopol was added, followed by the Empicol ESB 3M, under continuing agitation at a temperature of 70- 80 C, taking care to control the formation of foam. This provided phase A. In a stainless steel beaker, the different Covastyle dyes were mixed in accordance to the desired colour, they were solubilised in the rest of the water at 70 C, under slight agitation (300rpm), in a water bath, after covering the beaker with aluminium foil. This provided phase B. When solubilised, phase A was slowly added to phase B slowly, without agitation, and the mixture was allowed to cool to room temperature. After this, phase C (ammonia) was added at room temperature, and mixed until homogeneous, before rapidly adding phase D for the example agent compositions. The compositions were then kept in dark bottles, hermetically sealed, and kept in a dark place.

[0040] A developer was then prepared by melting Oxocera (7 parts) under agitation at 70-80 C, in a water bath, adding hot water (75 C) to a total weigh of the composition of 100 parts, under constant agitation and temperature for 30 minutes, followed by allowing the mixture to cool to room temperature under agitation. At that stage hydrogen peroxide (20 parts) was added at 30 C and mixed till uniform, the pH was adjusted with ortophosphoric acid (to reach pH of 2. 0) and add the silicone to reach a total composition of 1.4% of silicone in the composition for the example compositions.

Example 9-Application of semi-permanent hair dyeing agent compositions to hair.

[0041] Using the compositions prepared under Example 7,5 tresses of hair were wetted under running water at 37 C for 30 sec, followed by lathering each of them with 5 ml cream prepared under Example 7, applying the composition uniformly for 1 minute. The tresses were then packed in aluminium foil and left to rest for 30 minutes, after which the 5 tresses were wetted with 1 ml water and lather for 30 sec. The 5 tresses were then rinsed under running water at room temperature for 4 min (until the water is clear), and hung to dry.

Example 10-Application of permanent hair dyeing agent compositions to hair.

[0042] Using the compositions prepared under Example 8, equal parts of colouring cream and developer were mixed until they were completely homogeneous. This mixture was then used immediately after preparation. 5 tresses of hair were wetted under running water at 37 C for 30 sec, followed by lathering each of them with 5 ml cream prepared under Example 7, applying the composition uniformly for 1 minute. The tresses were then packed in aluminium foil and left to rest for 30 minutes, after which the 5 tresses were wetted with 1 ml water and lather for 30 sec. The 5 tresses were then rinsed under running water at 370C for 90 sec (until the water is clear), and hung to dry.

Example 11-Testing of treated hair tresses [0043] A Colour Sphere TCS Plus Spectrophotometer from BYK-Gardner USA was used to carry out all colour measurements. A tungsten light source was used. The CIELAB (Commission Internationale de l'Ec1airage) scale was used to measure the L*, a* and b* values. For all measurements it was necessary to calibrate the spectrophotometer with a white reference sample and a black reference sample.

[0044] The dried tresses were exposed to UV light for a period of 4 weeks, and measurements were made every week. Results are indicated in the attached Tables I to IV.

A separate set of tresses, as prepared according to Example 9 were washed repeatedly with a standard shampoo formulation for a total of 10 washes, and they were measured before the testing, as well as after 5 and 10 washes. Results are given in Tables V and VI.

Table I : L* values after UV exposure of semi-permanent dyed tresses

Silicone elastomer L* value before L* value after L* value after L* value after used exposure exposure for 2 exposure for 4 exposure for 6 weeks weeks weeks Example 1 35. 00 35. 50 35. 50 36. 50 Example 2 36. 00 36. 60 36. 90 37. 30 Example 3 35. 40 35. 50 35. 50 36. 80 Example 4 37. 00 37. 00 37. 60 38. 30 None (control) 37. 60 37. 90 38. 10 38. 00 Table II: a* values after UV exposure of semi-permanent dyed tresses

Silicone elastomer A* value before a* value after a* value after a* value after used exposure exposure for 2 exposure for 4 exposure for 6 weeks weeks weeks Example 1 18. 40 18. 20 18. 25 17. 80 Example 2 18. 50 18. 40 18. 50 18. 35 Example 3 18. 40 17. 80 17. 50 17. 25 Example 4 17. 90 17. 80 17. 75 17. 25 None (control) 17. 10 17. 50 17. 05 16. 90

Table III: L* values after UV exposure of permanent dyed tresses

Silicone elastomer L* value before L* value after L* value after L* value after used exposure exposure for 2 exposure for 4 exposure for 6 weeks weeks weeks Example 1 36. 10 35. 50 35. 50 35. 80 Example 2 36. 30 34. 80 35. 30 36. 00 Example 3 35. 20 36. 20 36. 80 37. 10 Example 4 37. 00 38. 20 38. 05 38. 00 None (control) 34. 90 35. 70 36. 00 35. 65 Table IV: a* values after UV exposure of permanent dyed tresses

Silicone elastomer a* value before a* value after a* value after A* value after used exposure exposure for 2 exposure for 4 exposure for 6 weeks weeks weeks Example 1 12. 00 12. 10 10. 70 11. 95 Example 2 12. 55 12. 20 12. 20 12. 50 Example 3 11. 45 11. 20 11. 40 11. 35 Example 4 11. 40 11. 30 11. 00 10. 75 None (control) 12. 15 12. 50 12. 60 12. 50 Table V: L* values after washing semi-permanent dyed tresses

Silicone elastomer used L* value before L* value after 5 L* value after 10 exposure washes washes Example 1 36. 80 40. 10 42. 80 Example 2 36. 80 40. 10 42. 00 Example 3 37. 00 41. 20 44. 00 None (control) 36. 20 41. 00 43. 00

Table VI: a* values after washing semi-permanent dyed tresses

Silicone elastomer used a* value before a* value after 5 a* value after 10 exposure washes washes Example 1 18. 20 16. 40 15. 40 Example 2 18. 50 16. 80 16. 20 Example 3 18. 50 16. 80 16. 20 None (control) 17. 20 16. 20 14. 80

Example 12-Use of resin-modified silicone elastomers [0045J (a) Into a vessel was added 33. 2 g of a MQ resin [a resin having the general formula (MezViSiOSy] (Mn = 4, 180, 2. 09 weight percent vinyl) and 430 g of decamethylcyclopentasiloxane. The mixture was heated to 700C and upon complete dissolution of the resin, 36. 5 g of the dimethyl methylhydrogen siloxane copolymer (DP = 93, 6. 6 mole percent methyl hydrogen groups) was added followed by 10 ppm of platinum catalyst. The mixture was held at 70 C with mixing for 1 hour. Next, 0. 65 g of 1, 5hexadiene was added and the mixture was stirred for an additional 3 hours.

Next, additional decamethylcyclopentasiloxane is added to achieve the desired level of solids.

(b) Into a vessel was added 45. 4 g of a MQ resin [a resin having the general formula (MezViSiOiSKy] (Mn = 4, 180, 2. 09 weight percent vinyl) and 400 g of decamethylcyclopentasiloxane. The mixture was heated to 70 C and upon complete dissolution of the resin, 53. 7 g of a dimethyl methylhydrogen siloxane copolymer (DP = 265, 6. 0 mole percent methyl hydrogen groups) was added followed by 10 ppm of platinum catalyst. The mixture was held at 70 C with mixing for 1 hour. Next, 0. 9 g of 1, 5hexadiene was added and the mixture was stirred for an additional 3 hours.

The above resin modified silicone elastomers were then formulated into semipermanent hair dyeing compositions of the type described in Example 7 above, and were tested in a manner similar to that described in Example 11 above. It was found that the results in wash and light resistance were better in both cases than those for compositions formulated with the silicone from Example 1 above.

Claims

CLAIMS I A hair dyeing agent composition, characterised by the fact that it contains a silicone elastomer.
2. A hair dyeing agent composition according to Claim 1, characterised by the fact that the silicone elastomer has at least one alkoxy or hydroxyl containing group.
3. A hair dyeing agent composition, characterised by the fact that it contains a silicone elastomer containing alkoxy containing groups or hydroxyl containing groups in conjunction with higher alkyl groups substituted onto silicon atoms.
4. A hair dyeing agent composition according to anyone of the previous claims, characterised in that it is a non-oxidation composition.
5. A hair dyeing agent composition according to Claim 3, characterised in that it is an oxidation composition.
6. A hair dyeing agent composition according to anyone of the preceding claims, characterised in that it comprises a silicone elastomer which is a Dimethicone Crosspolymer.
7. A hair dyeing agent composition according to anyone of the preceding claims, characterised in that it comprises a silicone elastomer which is obtained by crosslinking polymethylvinylsiloxane and polymethylhydrogensiloxane in the presence of a platinum catalyst; materials obtained by crosslinking a < - dihydroxypolydimethylsiloxane with an hydrolyzable group-containing organosilane; and materials obtained by crosslinking polymethylvinylsiloxane in the presence of an organic peroxide.

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8. A hair dyeing agent composition according to anyone of the preceding claims, characterised in that it comprises a silicone elastomer which is obtained by reacting (A) an =Si-H containing polysiloxane of formula R3SiO (R'2SiO) a (R"HSiO) bSiR3 and optionally an =Si-H containing polysiloxane of formula HR2SiO (R'2SiO) cSiR2H or formula HR2SiO (R'2SiO) a (R"HSiO) bSiR2H where R, R', and R"are alkyl groups with 1-6 carbon atoms; a is 0-250; b is 1-250; and c is 0-250; with (B) an alpha, omega-diene of formula CH2=CH (CH2) xCH=CH2 where x is 1-20, conducted in the presence of a Group VIII transition metal catalyst and in the presence of (C) a low molecular weight silicone oil, for example low molecular weight linear or cyclic volatile or non-volatile alkyl and aryl siloxanes.
9. A hair dyeing agent composition according to anyone of the preceding claims, characterised in that it comprises a silicone elastomer which is obtained by a

process comprising a first step of reacting (A') an =Si-H containing polysiloxane ; and (B') a mono-alkenyl polyether ; in the presence of a platinum catalyst, until (C') an =Si-H containing siloxane with polyether groups is formed, which in a second step is reacted with (D') an unsaturated hydrocarbon such as an alpha, omega-diene; in the presence of (E') a solvent

and a Group VIII catalyst, until a silicone elastomer is formed by cross-linking and addition of=SiH across double bonds in the alpha, omega-diene.
10. A hair dyeing agent composition according to Claim 9, characterised in that the silicone elastomer is obtained where remaining =SiH groups are further reacted with higher alkene materials, preferably alkenes with terminal unsaturation, most preferably alkenes which are linear and have from 12 to 40 carbon atoms, most preferably from 12 to 20.
11. A hair dyeing agent composition according to anyone of the preceding claims, characterised in that it comprises a silicone elastomer which is obtained is formed by providing a thermodynamically stable material comprising (A) a

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cross-linked siloxane comprising alkoxysilyl functionality,-X-SiROR. ) . n, and cross-links,-E1-Y-E2, with each end of such cross-links bonded to a silicon, wherein, X is a divalent group that is a hydrocarbon, a siloxane or some combination ofthese, R4 and R5 are independently monovalent hydrocarbon groups, E1 and E2 are independently-CH2CH2-or-CH=CH-, Y is a divalent group that is a hydrocarbon, a siloxane or some combination of these, and n is 0 to 2, which cross-linked siloxane comprising alkoxysilyl functionality is made by cross-linking, in the presence of a hydrosilylation

catalyst, (1) an =SiH functional siloxane with (2) an alpha, omega diene, diyne or ene-yne, with the provisos that at least one of (1) and (2) has alkoxysilyl functionality, -X-SiR4n (OR5h-n, where, X is a divalent group that is a hydrocarbon, a siloxane or some combination ofthese, R4 and R5 are independently monovalent hydrocarbon groups and n is 0 to 2, that (1), (2) and the catalyst are dispersed in a diluent, and that the weight ratio of (1) + (2) + the product of the cross-linking of (1) and (2): diluent is 1: 100 to 10: 1 and (B) a diluent, which may be a single compound or a mixture of compounds, including silicones such as siloxanes, both linear and cyclic, organic oils, organic solvents and mixtures of these.
12. A hair dyeing composition according to anyone of the preceding claims, characterised in that it comprises a resin modified silicone elastomer comprising: (A) a cross-linked siloxane comprising: (i) a siloxane polymer, (ii) resin functionality having the formula (R3Si01l2) x (SiO4/2) y (RSi03/2) z and (iii) cross-links,-E-Y-E-, with each end of the cross-link is bonded to a silicon atom, wherein, each R is independently a divalent hydrocarbon group having 2 to 30 carbon atoms or a monovalent hydrocarbon group having 1 to 30 carbon atoms; wherein when R is a divalent hydrocarbon group it is bonded to the resin and to the siloxane polymer or a cross-link; each E is a divalent group

independently selected from-CHCH-or-CH=CH- ; Y is a divalent group that is a hydrocarbon, a siloxane or some combination of these ; and x is y 0, z 0 and y + z 1 ; and (B) a diluent.