DESCRIPTION

TITLE OF INVENTION

COMPOSITION FOR KERATIN FIBERS

TECHNICAL FIELD

The present invention relates to a composition for keratin fibers, in particular, a composition for bleaching or dyeing keratin fibers such as hair.

BACKGROUND ART

It is known to dye keratin fibers, in particular hair, using dyeing compositions containing oxidative coloring precursors, generally called oxidative bases, such as ortho- or paraphenylenediamines, ortho- or para-aminophenols and heterocyclic compounds. These oxidative bases are generally combined with couplers. These oxidative bases and couplers are colorless or weakly colored compounds. However, when combined with oxidizing agents, they can provide colored dye molecules through an oxidative condensation process.

This type of coloring by oxidation, i.e., oxidative dyeing, makes it possible to get colors with very high visibility, coverage of white hair, and a wide variety of shades. Oxidative dyeing is widely used because of the high color uptake as compared with direct dyeing using so-called direct dyes.

In order to perform oxidative dyeing, typically, a composition comprising oxidative base(s), as well as coupler(s), with alkaline agent(s), is mixed with a developer composition comprising oxidizing agent(s) to prepare a ready-to-use composition, and then, the ready-to- use composition is applied onto keratin fibers.

The developer composition is capable of bleaching keratin fibers due to the function of the oxidizing agent(s) in the composition. Therefore, the developer composition as well as the ready-to-use composition (this may not include any oxidation base with or without any coupler) may be used to bleach keratin fibers.

DISCLOSURE OF INVENTION

The compositions used for oxidative dyeing keratin fibers may be in the form of a gel. These gel compositions have good usability because they are easy to apply onto keratin fibers. However, conventional gel-type compositions for oxidative dyeing often provide keratin fibers with poor texture such as a rough or hard feeling to the touch.

In order to improve the texture, a cationic polymer may be added to a composition for oxidative dyeing. However, the use of a cationic polymer may cause aggregations if the cationic polymer is combined with some types of anionic ingredients. The aggregations are not preferable in view of not only visual aspects but also usability of the composition.

In addition, of course, it is preferable for the composition for oxidative dyeing to be stable such that it does not change over time in terms of the aspect thereof and the like. Thus, an objective of the present invention is to provide a stable composition for keratin fibers, in particular for oxidative dyeing or bleaching of keratin fibers, which can be in the form of a homogeneous gel and can provide the keratin fibers with good texture such as a smooth and/or soft feeling to the touch, without causing aggregation.

The above objective can be achieved by a composition for keratin fibers, comprising:

(a) at least one compound selected from water-soluble silicones and derivatives thereof;

(b) at least one thickening agent;

(c) at least one polyol; and

(d) at least one oxidizing agent.

The (a) compound may be selected from polyether-modified silicones.

The (a) compound may be selected from the group consisting of PEG- 10 methyl ether dimethicone, PEG-11 methyl ether dimethicone, PEG-32 methyl ether dimethicone, PEG/PPG-18/18 dimethicone, PEG/PPG-19/19 dimethicone, PEG/PPG-20/20 dimethicone, PEG/PPG-20/22 butyl ether dimethicone, PEG/PPG-30/10 dimethicone, PEG-9 dimethicone, PEG- 10 dimethicone, PEG- 12 dimethicone, and a mixture thereof.

The amount of the (a) compound(s) in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight or less, and more preferably from 0.1% to 5% by weight or less, relative to the total weight of the composition.

The (b) thickening agent may be selected from polysaccharides.

The (b) thickening agent may be selected from xanthan gum, sclerotium gum and a mixture thereof.

The amount of the (b) thickening agent(s) in the composition according to the present invention may be from 0.05% to 10% by weight, preferably from 0.1% to 5% by weight, and more preferably from 0.5% to 2% by weight, relative to the total weight of the composition.

The (c) polyol may be selected from the group consisting of glycerin, ethyleneglycol, polyethyleneglycol, propyleneglycol, dipropyleneglycol, butyleneglycol, pentyleneglycol, and hexyleneglycol.

The amount of the (c) polyol(s) in the composition according to the present invention may be from 0.1% to 20% by weight, preferably from 0.5% to 15% by weight, and more preferably from 1% to 10% by weight, relative to the total weight of the composition.

The (d) oxidizing agent may be hydrogen peroxide.

The amount of the (d) oxidizing agent(s) in the composition according to the present invention may be from 0.1% to 20% by weight, preferably from 0.5% to 15% by weight, and more preferably from 1% to 10% by weight, relative to the total weight of the composition.

The composition according to the present invention may be a cosmetic composition for keratin fibers, preferably a cosmetic composition for bleaching or coloring keratin fibers, and more preferably a cosmetic composition for bleaching or coloring hair. The present invention also relates to a process for keratin fibers comprising the steps of:

(1) mixing a first composition and a second composition to prepare a mixture, wherein the first composition comprises

(a) at least one compound selected from water-soluble silicones and derivatives thereof,

(b) at least one thickening agent,

(c) at least one polyol, and

(d) at least one oxidizing agent, and the second composition comprises (e) at least one alkaline agent; and

(2) applying the mixture to the keratin fibers.

BRIEF DESCRIPTION OF DRAWINGS

Fig. 1 shows a front view of an example of a network formed by an associative polyurethane thickener in water in which the hydrophobic parts of the associative polyurethane thickener connect to form quasi-micelles which are indicated as flower micelles.

BEST MODE FOR CARRYING OUT THE INVENTION

After diligent research, the inventors have discovered that it is possible to provide a stable composition for keratin fibers, in particular for oxidative dyeing or bleaching of keratin fibers, which can be in the form of a homogeneous gel and can provide the keratin fibers with good texture such as a smooth and/or soft feeling to the touch, without causing aggregation.

Thus, the composition according to the present invention comprises:

(a) at least one compound selected from water-soluble silicones and derivatives thereof;

(b) at least one thickening agent;

(c) at least one polyol; and

(d) at least one oxidizing agent.

The composition according to the present invention can be used as a cosmetic composition for keratin fibers such as hair, preferably a cosmetic composition for oxidative dyeing or bleaching of keratin fibers.

Further, the composition according to the present invention can have good usability because it can be in the form of a gel, and no aggregation is caused, in particular when mixed with another composition comprising at least one alkaline agent.

Furthermore, the composition according to the present invention can provide keratin fibers with good texture such as a smooth and/or soft feeling to the touch.

The present invention also relates to a process for keratin fibers comprising the steps of:

(1) mixing a first composition and a second composition to prepare a mixture, wherein the first composition comprises

(a)' at least one compound selected from water-soluble silicones and derivatives thereof, (b) at least one thickening agent,

(c) at least one polyol, and

(d) at least one oxidizing agent, and the second composition comprises (e) at least one alkaline agent; and

(2) applying the mixture to the keratin fibers.

Hereafter, the composition and process according to the present invention will be described in a detailed manner.

[Composition]

(Water-Soluble Silicone and Derivative Thereof)

The composition according to the present invention includes (a) at least one compound selected from water-soluble silicones and derivatives thereof (hereafter, may be referred to as (a) compound). If two or more (a) compounds are used, they may be the same or different.

In one embodiment, the (a) compound is selected from water-soluble silicones.

The water-soluble silicones have a solubility in water, measured at 25°C, of at least 0.5% by weight. If the final appearance of water in which a silicone in question is mixed to have a certain concentration is transparent or clear, the silicone is determined to have a solubility of that concentration. Thus, the water-soluble silicone as the (a) compound can be solubilized in water such that the concentration of the water-soluble silicone in water is 0.5% by weight or more.

The water-soluble silicones may be chosen from polysiloxanes comprising at least one terminal or pendant monovalent polyoxyalkylene group, which may be categorized as polyoxyalkylene-modified silicones or polyether-modified silicones. The polysiloxanes may be poly dimethylsiloxane.

The polyoxyalkylene-modified silicones or polyether-modified silicones may be represented by formula (1):

R ² ₃ SiO(R ² ₂ SiO) _p (R ² PESiO) _q SiR ² ₃ (1) in which: the R ² radicals, which are identical or different, denote a monovalent hydrocarbon radical chosen from alkyl, aryl and aralkyl radicals having at most 10 carbon atoms; p varies from 0 to 150, preferably from 0 to 100 and more preferably from 0 to 30; q varies from 1 to 12, preferably from 1 to 10 and more preferably from 1 to 8; the poly ether group PE has the following formula (2):

-C _x H _2x (OC ₂ H ₄ ) _y (OC ₃ H ₆ ) _z OR ³ (2) in which: x varies from 1 to 8 and preferably varies from 2 to 4 and is more preferably equal to 3; y is greater than 0; z is greater than or equal to 0; the values of y and z being such that the total molecular weight of the polyoxyalkylene portion of the polyether group PE varies from 200 to 10000 and more preferably from 350 to 4000;

R ³ denotes hydrogen, a C ₁ -C ₈ alkyl group or a C ₂ -C ₈ acyl group.

It should be noted that, when z is other than 0, the polyoxyethylene and polyoxypropylene units can be distributed randomly along the polyether chain PE or distributed in blocks or else distributed both in blocks and randomly.

Preferably, the R ² radicals are chosen from C ₁ -C ₄ alkyl groups and hexyl, phenyl and benzyl groups. More particularly, the R ² radicals are chosen from alkyl groups, such as methyl, ethyl or butyl groups. More particularly still, they denote the methyl radical.

Preferably, the R ³ radicals are chosen from C ₁ -C ₄ alkyl groups and more particularly still denote the methyl radical.

The water-soluble silicones of formula (1) can be obtained according to the process described in the document U.S. Pat. No. 4,847,398.

Use is preferably made, among the water-soluble silicones of formula (1), of those of the following formula (1'):

Me ₃ SiO(MeSiO)p(MePESiO)qSiMe ₃ (1') in which p and q have the same values as indicated above for formula (1),

Me denotes the methyl radical, and

PE denotes:

-(CH ₂ ) ₃ (OC ₂ H ₄ ) _y (OC ₃ H ₆ ) OR ³ (2') where y and z have the same values as indicated above for formula (2), and

R ³ denotes hydrogen or a C ₁ -C ₄ alkyl group and more particularly the methyl radical.

Mention may be made, as other families of water-soluble silicones which can be used according to the present invention, of the branched silicones of the following formula (3):

(MeSiO) _q-2 [SiOMe ₂ ) _p/q OPE] _q (3) where p and q have the same values as indicated above in formula (1), Me signifies methyl and PE denotes the group of the following formula (4):

-(OC ₂ H ₄ )y(OC ₃ H ₆ ) _z R ³ (4) where y and z have the same values as indicated above in formula (2), and

R ³ denotes a C ₁ -C ₄ alkyl group and more particularly the methyl radical.

It is possible, of course, to use a mixture of the silicones of formula (1) and of formula (3). Such polyether-modified silicones are sold, for example, by OSI under the trade names Silwet L-7210® (INCI name: Dimethicone Copolyol), Silwet L-7220® (INCI name: Dimethicone Copolyol); Silwet L-7002®, Silwet L-7600® (INCI name: Dimethicone Copolyol), Silwet L- 7604® (INCI name: PEG-8 Dimethicone), Silwet L-7605®, Silwet L-7607®, Silwet 1614, Silwet L-7657®, Silwet L-7200® (INCI name: Dimethicone Copolyol), Silwet L-7230®, Silsoft 305® (INCI name: Dimethicone Copolyol), Silsoft 820® (INCI name: Dimethicone Copolyol), Silsoft 880® (INCI name: PEG-12 Dimethicone), Tego Wet 260®, Tego Wet 500®, Tego Wet 505® and Tego Wet 510®.

As examples of the polyether-modified silicones, mention may be made of PEG- 10 methyl ether dimethicone, PEG-11 methyl ether dimethicone, PEG-32 methyl ether dimethicone, PEG/PPG-18/18 dimethicone, PEG/PPG-19/19 dimethicone, PEG/PPG-20/20 dimethicone, PEG/PPG-20/22 butyl ether dimethicone, PEG/PPG-30/10 dimethicone, PEG-9 dimethicone, PEG- 10 dimethicone, PEG- 12 dimethicone, and a mixture thereof.

In one embodiment, the (a) compound is selected from the derivatives of water-soluble silicones.

The derivative of water-soluble silicone may be a water-soluble silicone in which at least one substituent is bonded at the polysiloxane backbone of the water-soluble silicone, preferably instead of a methyl group on the polydimethylsiloxane backbone.

As the substituent, mention may be made of, for example, an alkyl group, an alkenyl group, an alkoxyl group, an amino group, and a hydroxyl group.

The alkyl group may be a linear, branched or cyclic alkyl group. The alkyl group may be a linear or branched C ₁ -C ₆ alkyl group, preferably C ₁ -C ₄ alkyl group, such as a methyl group, an ethyl group, a propyl group, an i-propyl group and a butyl group. On the other hand, the alkyl group may be a cyclic C ₃ -C ₆ alkyl group, such as a cyclopentyl group and a cyclohexyl group.

The alkenyl group may be a C ₂ -C ₆ alkenyl group such as a vinyl group, an allyl group, a butylene group, a pentenyl group and a hexenyl group.

The alkoxy group may be a C ₁ -C ₆ alkoxy group such as a methoxy group, an ethoxy group and a propoxy group.

The above substituent may be further substituted with at least one group such as a halogen atom, an amino group, a nitro group, a cyano group, a hydroxyl group and an aromatic group such as a phenyl group.

As examples of the derivatives of water-soluble silicones, mention may be made of cetyl PEG/PPG-10/1 dimethicone, lauryl PEG/PPG-18/18 methicone, and a mixture thereof.

The amount of the (a) compound(s) in the composition according to the present invention is 0.01% by weight or more, preferably 0.05% by weight or more, and more preferably 0.1% by weight or more, relative to the total weight of the composition. It is even more preferable that the amount of the (a) compound(s) in the composition according to the present invention be 0.25% by weight or more, and particularly preferably 0.5% by weight or more, relative to the total weight of the composition.

On the other hand, the amount of the (a) compound(s) in the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, relative to the total weight of the composition. It is even more preferable that the amount of the (a) compound(s) in the composition according to the present invention be less than 2% by weight or less, and particularly preferably 1.5% by weight or less, relative to the total weight of the composition.

The amount of the (a) compound(s) in the composition according to the present invention may be from 0.01% to 15% by weight, preferably from 0.05% to 10% by weight, and more preferably from 0.1% to 5% by weight, relative to the total weight of the composition. It is even more preferable that the amount of the (a) compound(s) in the composition according to the present invention be from 0.25% to less than 2% by weight, and particularly preferably from 0.5% to 1.5% by weight, relative to the total weight of the composition.

(Thickening Agent)

The composition according to the present invention comprises (b) at least one thickening agent. A single type of thickening agent may be used, but two or more different types of thickening agent may be used in combination.

It is preferable that the (b) thickening agent be selected from the group consisting of:

(i) associative thickeners;

(ii) crosslinked acrylic acid homopolymers;

(iii) crosslinked copolymers of (meth)acrylic acid and of (C ₁ -C ₆ )alkyl acrylate;

(iv) nonionic homopolymers and copolymers comprising ethylenically unsaturated monomers of ester and/or amide type;

(v) ammonium acrylate homopolymers and copolymers of ammonium acrylate and of acrylamide;

(vi) polysaccharides ; and

(vii) C ₁₂ -C ₃₀ fatty alcohols.

(i) As used herein, the expression "associative thickener" means an amphiphilic thickener comprising both hydrophilic units and hydrophobic units, for example, at least one C ₈ -C ₃₀ fatty chain and at least one hydrophilic unit.

Representative associative thickeners that may be used are associative polymers chosen from: (aa) nonionic amphiphilic polymers comprising at least one fatty chain and at least one hydrophilic unit;

(bb) anionic amphiphilic polymers comprising at least one hydrophilic unit and at least one fatty-chain unit;

(cc) cationic amphiphilic polymers comprising at least one hydrophilic unit and at least one fatty-chain unit; and

(dd) amphoteric amphiphilic polymers comprising at least one hydrophilic unit and at least one fatty-chain unit, wherein the fatty chain contains from 10 to 30 carbon atoms.

The (aa) nonionic amphiphilic polymers comprising at least one fatty chain and at least one hydrophilic unit may, for example, be chosen from: (1) celluloses modified with groups comprising at least one fatty chain; examples that may be mentioned include: hydroxyethylcelluloses modified with groups comprising at least one fatty chain chosen from alkyl, arylalkyl, and alkylaryl groups, and in which the alkyl groups are, for example, C8-C22, such as the product Natrosol Plus Grade 330 CS(Ci-C6 alkyls) sold by the company Aquaion, and the product Bermocoll EHM 100 sold by the company Berol Nobel, and celluloses modified with polyalkylene glycol alkylphenyl ether groups, such as the product Amercell Polymer HM-1500 (polyethylene glycol (15) nonylphenyl ether) sold by the company Amerchol.

(2) hydroxypropyl guars modified with groups comprising at least one fatty chain, such as the product Esaflor HM 22 (C22 alkyl chain) sold by the company Lamberti, and the products Miracare XC95-3 (C14 alkyl chain) and RE205-1 (C20 alkyl chain) sold by the company Rhodia Chimie.

(3) polyether urethanes comprising at least one fatty chain, such as C10-C30 alkyl or alkenyl groups, for instance the products Elfacos T 210 and Elfacos T 212 sold by the company Akzo or the products Aculyn 44 and Aculyn 46 sold by the company Rohm & Haas.

(4) copolymers of vinylpyrrolidone and of hydrophobic fatty-chain monomers; examples that may be mentioned include: the products Antaron V216 and Ganex V216 (vinylpyrrolidone/hexadecene copolymer) sold by the company I.S.P., and the products Antaron V220 and Ganex V220 (vinylpyrrolidone/eicosene copolymer) sold by the company I.S.P.

(5) copolymers of C ₁ -C ₆ alkyl acrylates or methacrylates and of amphiphilic monomers comprising at least one fatty chain, such as the oxyethylenated methyl methacrylate/stearyl acrylate copolymer sold by the company Goldschmidt under the name Antil 208.

(6) copolymers of hydrophilic acrylates or methacrylates and of hydrophobic monomers comprising at least one fatty chain, such as a polyethylene glycol methacrylate/lauryl methacrylate copolymer.

The (bb) anionic amphiphilic polymers comprising at least one hydrophilic unit and at least one fatty-chain unit, may, for example, be chosen from those comprising at least one fattychain allyl ether unit and at least one hydrophilic unit comprising an ethylenic unsaturated anionic monomeric unit, for example, a vinylcarboxylic acid unit and further, for example, be chosen from units derived from acrylic acids, methacrylic acids, and mixtures thereof, wherein the fatty-chain allyl ether unit corresponds to the monomer of formula (I) below:

CH ₂ =C(Ri)CH ₂ OBnR (I) in which Ri is chosen from H and CH3, B is an ethyleneoxy radical, n is chosen from zero and integers ranging from 1 to 100, R is chosen from hydrocarbon-based radicals chosen from alkyl, arylalkyl, aryl, alkylaryl, and cycloalkyl radicals, containing from 10 to 30 carbon atoms, and further, for example, from 10 to 24 carbon atoms and even further, for example, from 12 to 18 carbon atoms.

In one embodiment, a unit of formula (I) is, for example, a unit in which Ri can be H, n can be equal to 10, and R can be a stearyl (Cis) radical. Anionic amphiphilic polymers of this type are described and prepared, according to an emulsion polymerization process, in patent EP-0 216 479 B2.

In one embodiment, anionic amphiphilic polymers are, for example, polymers formed from 20% to 60% by weight of acrylic acid and/or of methacrylic acid, from 5% to 60% by weight of lower alkyl (meth)acrylates, from 2% to 50% by weight of fatty-chain allyl ether of formula (I), and from 0% to 1% by weight of a crosslinking agent which is a well-known copolymerizable unsaturated polyethylenic monomer, for example, diallyl phthalate, allyl(meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate, and methylenebisacrylamide.

Examples of such polymers are crosslinked terpolymers of methacrylic acid, of ethyl acrylate, and of polyethylene glycol (10 EO) stearyl ether (Steareth-10), such as those sold by the company Ciba under the names Salcare SC 80 and Salcare SC 90, which are aqueous 30% emulsions of a crosslinked terpolymer of methacrylic acid, of ethyl acrylate, and of steareth- 10 allyl ether (40/50/10).

The anionic amphiphilic polymers may further be chosen, for example, from those comprising at least one hydrophilic unit of unsaturated olefinic carboxylic acid type, and at least one hydrophobic unit of a type such as a (C10-C30) alkyl ester of an unsaturated carboxylic acid. The hydrophilic unit of unsaturated olefinic carboxylic acid type corresponds to, for example, the monomer of formula (II) below: in which R ¹ is chosen from H, CH3, and C2H5, i.e., acrylic acid, methacrylic acid, and methacrylic acid units. The hydrophobic unit of a type such as a (C10-C30) alkyl ester of an unsaturated carboxylic acid corresponds to, for example, the monomer of formula (III) below: in which R ¹ is chosen from H, CH3, and C2H5 (i.e., acrylate, methacrylate, and methacrylate units) and is, for example, chosen from, for example, H (acrylate units) and CH3 (methacrylate units), and R ² is chosen from C10-C30 alkyl radicals, for example, C12-C22 alkyl radicals.

Examples of (Cio-C3o)alkyl esters of unsaturated carboxylic acids include lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, and dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate.

Anionic amphiphilic polymers of this type are disclosed and prepared, for example, according to U.S. Pat. Nos. 3,915,921 and 4,509,949.

Representative anionic amphiphilic polymers that can be used may further be chosen from polymers formed from a mixture of monomers comprising:

(7) acrylic acid, an ester of formula (IV) below: in which R ¹ is chosen from H and CH3, R ² is chosen from C10-C30 alkyl radicals, such as alkyl radicals containing from 12 to 22 carbon atoms, and a crosslinking agent; such as polymers derived from 95% to 60% by weight of the acrylic acid (hydrophilic unit), 4% to 40% by weight of C10-C30 alkyl acrylate (hydrophobic unit), and 0% to 6% by weight of crosslinking polymerizable monomer, or polymers derived from 98% to 96% by weight of the acrylic acid (hydrophilic unit), 1% to 4% by weight of C10-C30 alkyl acrylate (hydrophobic unit), and 0.1% to 0.6% by weight of crosslinking polymerizable monomer; or

(8) acrylic acid and lauryl methacrylate, such as the polymers formed from 66% by weight of acrylic acid and 34% by weight of lauryl methacrylate.

The crosslinking agent can be a monomer comprising the group

CH, = C^ with at least one other polymerizable group whose unsaturated bonds are not conjugated.

Mention may be made, for example, of polyallyl ethers such as polyallylsucrose and polyallylpentaerythritol.

Among said polymers above, mention may be made, for example, of the products sold by the company Goodrich under the trade names Pemulen TRI, Pemulen TR2, and Carbopol 1382, and further, for example, Pemulen TRI, and the product sold by the company S.E.P.C. under the name Coatex SX.

Among anionic amphiphilic fatty-chain polymers, mention may also be made, for example, of the ethoxylated copolymer of methacrylic acid/methyl acrylate/alkyl dimethyl-meta- isopropenylbenzylisocyanate sold under the name Viscophobe DB 1000 by the company Amerchol.

The (cc) cationic amphiphilic polymers used are, for example^ chosen from quatemized cellulose derivatives and polyacrylates comprising amino side groups.

The quatemized cellulose derivatives are, for example, chosen from quatemized celluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl, and alkylaryl groups comprising at least 8 carbon atoms, and mixtures thereof, and quatemized hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl, and alkylaryl groups comprising at least 8 carbon atoms, and mixtures thereof.

Quatemized and non-quatemized polyacrylates comprising amino side groups have, for example, hydrophobic groups, such as Steareth 20 (polyoxy-ethylenated(20) stearyl alcohol) and (Cio-C3o)alkyl PEG-20 itaconate. The alkyl radicals borne by the above quatemized celluloses and hydroxyethylcelluloses, for example, contain from 8 to 30 carbon atoms.

The aryl radicals, for example, are chosen from phenyl, benzyl, naphthyl, and anthryl groups.

Examples of quatemized alkylhydroxyethyl-celluloses comprising C8-C30 fatty chains are the products Quatrisoft LM 200, Quatrisoft LM-X 529-18-A, Quatrisoft LM-X 529-18B (C12 alkyl), and Quatrisoft LM-X 529-8 (Ci8 alkyl) sold by the company Amerchol, and the products Crodacel QM, Crodacel QL (C12 alkyl), and Crodacel QS (Cis alkyl) sold by the company Croda.

Examples of polyacrylates comprising amino side chains are the polymers 8781-124B or 9492-103 and Structure Plus from the company National Starch.

Among the (dd) amphoteric amphiphilic polymers comprising at least one hydrophilic unit and at least one fatty-chain unit, mention may be made, for example, of copolymers of methacrylamidopropyltrimethylammonium chloride/acrylic acid/Cio-Cso alkyl methacrylate, wherein the alkyl radical is, for example, a stearyl radical.

The associative thickeners in the compositions can have, for example, in solution or in dispersion at a concentration of 1 % active material in water, a viscosity, measured using a Rheomat RM 180 rheometer at 25°C, of greater than 0.1 ps and further, for example, of greater than 0.2 cp, at a shear rate of 200 s' ¹ .

The associative thickener may be an associative polymeric thickener, preferably an associative polyurethane thickener.

The associative polyurethane thickener may be cationic or nonionic.

Among the associative polyurethane thickeners, there may be mention of the associative polyurethane derivatives such as those obtained by polymerization: about 20% to 70% by weight of a carboxylic acid containing an a,β-monoethylenic unsaturation, about 20 to 80% by weight of a nonsurfactant monomer containing an a,β-monoethylenic unsaturation, about 0.5 to 60% by weight of a nonionic mono-urethane which is the product of the reaction of a monohydroxylated surfactant with a monoethylenically unsaturated monoisocyanate.

The like are described in particular in EP 173109 and more particularly in Example 3 thereof. More precisely, this polymer is a methacrylic acid/methyl acrylate/dimethyl metaisopropenyl benzyl isocyanate of ethoxylated behenyl alcohol (40 EO) terpolymer as an aqueous dispersion at 25%. This product is provided under the reference VISCOPHOBE DB1000 by the company AMERCHOL.

Also suitable are the cationic associative polyurethane thickeners the family of which has been described by the applicant in French Patent Application No. 0009609. They can be represented more particularly by the following general formula (A): R-X-(P) _n -[L-(Y) _m ] _r -L'- (P')p-X'-R' (A) in which: R and R', which are identical or different, represent a hydrophobic group or a hydrogen atom; X and X', which are identical or different, represent a group containing an amine functional group carrying or otherwise a hydrophobic group, or alternatively the group L"; L, L' and L", which are identical or different, represent a group derived from a diisocyanate; P and P', which are identical or different, represent a group containing an amine functional group carrying or otherwise a hydrophobic group; Y represents a hydrophilic group; r is an integer between 1 and 100, preferably between 1 and 50 and in particular between 1 and 25; n, m and p are each independently of the others between 0 and 1000; the molecule containing at least one protonated or quatemized amine functional group and at least one hydrophobic group.

In a very advantageous embodiment, the only hydrophobic groups of these polyurethanes are the groups R and R' at the chain ends.

According to a first preferred embodiment, the associative polyurethane thickener corresponds to formula (A) in which R and R' both represent independently a hydrophobic group, X, X' each represent a group L", n and p are between 1 and 1000, and L, L', L", P, P', Y and m have the meaning indicated in formula (A).

According to another preferred embodiment of the present invention, the associative polyurethane thickener corresponds to formula (A) in which R and R' both represent independently a hydrophobic group, X, X' each represent a group L", n and p are equal to 0, and L, L', L", Y and m have the meaning in formula (A) indicated above.

The fact that n and p are equal to 0 means that these polymers do not contain units derived from a monomer containing an amine functional group, incorporated into the polymer during polycondensation. The protonated amine functional groups of these polyurethanes result from the hydrolysis of isocyanate functional groups, in excess, at the chain end, followed by alkylation of the primary amine functional groups formed by alkylating agents containing a hydrophobic group, that is to say compounds of the RQ or R'Q type, in which R and R' are as defined above and Q denotes a leaving group such as a halide, a sulfate and the like.

In accordance with another preferred embodiment of the present invention, the associative polyurethane thickener corresponds to formula (A) in which R and R' both represent independently a hydrophobic group, X and X' both represent independently a group containing a quaternary amine, n and p are equal to zero, and L, L', Y and m have the meaning indicated in formula (A).

The number-average molecular mass of the cationic associative polyurethane thickeners is usually between 400 and 500000, in particular between 1000 and 400000, and ideally between 1000 and 300000 g/mol.

When X and/or X' denote a group containing a tertiary or quaternary amine, X and/or X' may represent one of the following formulae: in which:

R2 represents a linear or branched alkylene radical having from 1 to 20 carbon atoms, containing or otherwise a saturated or unsaturated ring, or an arylene radical, it being possible for one or more of the carbon atoms to be replaced by a heteroatom chosen from N, S, O, P; Ri and R3, which are identical or different, denote a linear or branched, C1-C30 alkyl or alkenyl radical, an aryl radical, it being possible for at least one of the carbon atoms to be replaced by a heteroatom chosen from N, S, O, and P;

A' is a physiologically acceptable counterion.

The groups L, L' and L" represent a group of formula: in which:

Z represents -O-, -S- or -NH-; and

R4 represents a linear or branched alkylene radical having from 1 to 20 carbon atoms, containing or otherwise a saturated or unsaturated ring, an arylene radical, it being possible for one or more of the carbon atoms to be replaced by a heteroatom chosen from N, S, O and P.

The groups P and P', comprising an amine functional group, may represent at least one of the following formulae: in which:

R ₅ and R ₇ have the same meanings as R ₂ defined above; R ₆ , R ₈ and R ₉ have the same meanings as R ₁ and R ₃ defined above; Rio represents a linear or branched alkylene group, which is optionally unsaturated and which may contain one or more heteroatoms chosen from N, O, S and P;

A" is a physiologically acceptable counterion.

As regards the meaning of Y, the expression hydrophilic group is understood to mean a polymeric or nonpolymeric water-soluble group. By way of example, there may be mentioned, when polymers are not involved, ethylene glycol, diethylene glycol and propylene glycol. In accordance with a preferred embodiment, in the case of a hydrophilic polymer, there may be mentioned, by way of example, polyethers, sulfonated polyesters, sulfonated polyamides, or a mixture of these polymers. Preferably, the hydrophilic compound is a polyether and in particular a polyethylene oxide or a polypropylene oxide.

The cationic associative polyurethane thickeners of formula (A) are formed from diisocyanates and from various compounds possessing functional groups containing a labile hydrogen. The functional groups containing a labile hydrogen may be alcohol functional groups, primary or secondary amine functional groups or thiol functional groups which give, after reaction with the diisocyanate functional groups, polyurethanes, polyureas and polythioureas, respectively. The term "polyurethanes" of the present invention covers these three types of polymers, namely polyurethanes proper, polyureas and polythioureas and copolymers thereof.

A first type of compounds entering into the preparation of the polyurethane of formula (A) is a compound containing at least one unit containing an amine functional group. This compound may be multifunctional, but preferably the compound is difunctional, that is to say, according to a preferred embodiment, this compound contains two labile hydrogen atoms carried for example by a hydroxyl, primary amine, secondary amine or thiol functional group. It is also possible to use a mixture of multifunctional and difunctional compounds in which the percentage of multifunctional compounds is low.

As indicated above, this compound may contain more than one unit containing an amine functional group. It is then a polymer carrying a repeat of the unit containing an amine functional group.

This type of compound may be represented by one of the following formulae: HZ-(P) _n -ZH, or HZ-(P') _p -ZH, in which Z, P, P', n and p are as defined above.

By way of example of a compound containing an amine functional group, there may be mentioned N-methyldi ethanolamine, N-tert-butyldiethanolamine, and N- sulfoethyldiethanolamine.

The second compound entering into the preparation of the polyurethane of formula (A) is a diisocyanate corresponding to the formula O=C=N-R4-N=C=O in which R4 is defined above.

By way of example, there may be mentioned methylenediphenyl diisocyanate, methylenecyclohexane diisocyanate, isophorone diisocyanate, toluene diisocyanate, naphthalene diisocyanate, butane diisocyanate, and hexane diisocyanate.

A third compound entering into the preparation of the polyurethane of formula (A) is a hydrophobic compound intended to form the terminal hydrophobic groups of the polymer of formula (A).

This compound consists of a hydrophobic group and a functional group containing a labile hydrogen, for example a hydroxyl, primary or secondary amine, or thiol functional group.

By way of example, this compound may be a fatty alcohol, such as, in particular, stearyl alcohol, dodecyl alcohol, and decyl alcohol. When this compound contains a polymeric chain, it may be for example a hydroxyl hydrogenated polybutadiene.

The hydrophobic group of the polyurethane of formula (A) may also result from the quatemization reaction of the tertiary amine of the compound containing at least one tertiary amine unit. Thus, the hydrophobic group is introduced by the quatemizing agent. This quatemizing agent is a compound of the RQ or R'Q type, in which R and R' are as defined above and Q denotes a leaving group such as a halide, a sulfate, and the like.

The cationic associative polyurethane thickener may additionally comprise a hydrophilic sequence. This sequence is provided by a fourth type of compound entering into the preparation of the polymer. This compound may be multifunctional. It is preferably difunctional. It is also possible to have a mixture where the percentage of multifunctional compound is low.

The functional groups containing a labile hydrogen are alcohol, primary or secondary amine, or thiol functional groups. This compound may be a polymer terminated at the chain ends by one of these functional groups containing a labile hydrogen.

By way of example, there may be mentioned, when polymers are not involved, ethylene glycol, diethylene glycol and propylene glycol.

In the case of a hydrophilic polymer, there may be mentioned, by way of example, polyethers, sulfonated polyesters, sulfonated polyamides, or a mixture of these polymers. Preferably, the hydrophilic compound is a polyether and in particular a polyethylene oxide or a polypropylene oxide.

The hydrophilic group noted Y in formula (A) is optional. Indeed, the units containing a quaternary or protonated amine functional group may suffice to provide the solubility or water-dispersibility necessary for this type of polymer in an aqueous solution. Although the presence of a hydrophilic group Y is optional, cationic associative polyurethane thickeners which contain such a group are nevertheless preferred.

The associative polyurethane thickener used in the present invention may also be nonionic, in particular nonionic polyurethane-polyethers. The nonionic polyurethane-polyethers may have both at least one hydrophilic moiety and at least one hydrophobic moiety. More particularly, said polymers may contain in their chain both hydrophilic sequences most often of a polyoxyethylenated nature and hydrophobic sequences which may be aliphatic linkages alone and/or cycloaliphatic and/or aromatic linkages.

Preferably, these polyether-polyurethanes comprise at least two lipophilic hydrocarbon chains, having from 6 to 30 carbon atoms, preferably from 6 to 20, separated by a hydrophilic sequence, it being possible for the hydrocarbon chains to be pendent chains or chains at the end of a hydrophilic sequence. In particular, it is possible for one or more pendent chains to be envisaged. In addition, the polymer may comprise a hydrocarbon chain at one end or at both ends of a hydrophilic sequence.

The polyether-polyurethanes may be polyblocks, in particular in triblock form. The hydrophobic sequences may be at each end of the chain (for example: triblock copolymer with hydrophilic central sequence) or distributed both at the ends and in the chain (polyblock copolymers for example). These same polymers may also be in the form of graft units or may be star-shaped.

The associative polyurethane thickener can form a network in water in which the hydrophobic part connects quasi-micelles as shown in Fig. 1.

Therefore, the associative polyurethane thickeners can increase the viscosity or consistency of the composition according to the present invention. Thus, after application of the composition according to the present invention, it can recover the original elasticity of the composition quickly.

The nonionic polyether-polyurethanes containing a fatty chain may be triblock copolymers whose hydrophilic sequence is a polyoxyethylenated chain comprising from 50 to 1000 oxyethylenated groups.

The nonionic polyether-polyurethanes comprise a urethane bond between the hydrophilic sequences, hence the origin of the name.

By extension, those whose hydrophilic sequences are linked by other chemical bonds to the hydrophobic sequences are also included among the nonionic polyether-polyurethanes containing a hydrophobic chain.

By way of examples of nonionic polyether-polyurethanes containing a hydrophobic chain which can be used in the present invention, it is also possible to use Rheolate® 205 containing a urea functional group sold by the company RHEOX or else the Rheolates® 208, 204 or 212, as well as Acrysol RM 184®.

There may also be mentioned the product ELFACOS T210® containing a C ₁₂ -C ₁₄ alkyl chain and the product ELFACOS T212® containing a C ₁₈ alkyl chain from AKZO.

The product DW 1206B® from ROHM & HAAS containing a C20 alkyl chain and with a urethane bond, sold at 20% dry matter content in water, may also be used.

It is also possible to use solutions or dispersions of these polymers in particular in water or in an aqueous-alcoholic medium. By way of examples of such polymers, there may be mentioned Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold by the company RHEOX. It is also possible to use the product DW 1206F and DW 1206 J provided by the company ROHM & HAAS.

The above-described polyether-polyurethanes which can be used can also be chosen from those described in the article by G. Fonnum, J. Bakke and Fk. Hansen-Colloid Polym. Sci 271, 380-389 (1993).

As the above-described polyether-polyurethanes, mention may be made of polyurethane- polyethers comprising in their chain at least one polyoxyethylenated hydrophilic block and at least one of hydrophobic blocks containing at least one sequence chosen from aliphatic sequences, cycloaliphatic sequences, and aromatic sequences.

It may be preferable that the polyurethane-polyethers comprise at least two hydrocarbonbased lipophilic chains having from 8 to 30 carbon atoms, separated by a hydrophilic block, and wherein the hydrocarbon-based chains are chosen from pendent chains and chains at the end of the hydrophilic block.

According to a specific form of the present invention, use will be made of a polyurethane/polyether that may be obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 mol of ethylene oxide, (ii) a polyoxyethylenated stearyl alcohol comprising 100 mol of ethylene oxide, and (iii) a diisocyanate.

Such polyurethane/polyethers are sold especially by the company Elementis under the name Rheolate FX 1100® and Rheoluxe 811®, which is a polycondensate of polyethylene glycol containing 136 mol of ethylene oxide, of stearyl alcohol polyoxyethylenated with 100 mol of ethylene oxide and of hexamethylene diisocyanate (HDI) with a weight-average molecular weight of 40000 (INCI name: PEG-136/Steareth-100/HDI Copolymer).

According to another specific form of the present invention, use will be made of a polyurethane/polyether that may be obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 mol of ethylene oxide, (ii) stearyl alcohol or decyl alcohol, and (iii) at least one diisocyanate.

Such polyurethane/polyethers are sold in particular by the company Rohm & Haas under the names Aculyn 46® and Aculyn 44®.

Aculyn 46® having the INCI name: PEG-150/Stearyl Alcohol/SMDI Copolymer, is a polycondensate of polyethylene glycol comprising 150 or 180 mol of ethylene oxide, of stearyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI) at 15% by weight in a matrix of maltodextrin (4%) and water (81%) (INCI name: PEG-150/Stearyl Alcohol/SMDI Copolymer).

Aculyn 44® (PEG-150/Decyl Alcohol/SMDI Copolymer) is a polycondensate of polyethylene glycol comprising 150 or 180 mol of ethylene oxide, of decyl alcohol and of methylenebis(4- cyclohexyl isocyanate) (SMDI) at 35% by weight in a mixture of propylene glycol (39%) and water (26%) (INCI name: PEG-150/Decyl Alcohol/SMDI Copolymer).

As the associative polyurethanes, it is preferable to use a compound represented by the following formula (1):

R ¹ -{(O-R ² ) _k -OCONH-R ³ [-NHCOO-(R ⁴ -O) _n -R ⁵ ] _h } _m (l) wherein R ¹ represents a hydrocarbon group, R ² and R ⁴ independently represent alkylene groups having 2 to 4 carbon atoms, which alkylene groups may be identical or different from each other, or a phenylethylene group, R ³ represents a hydrocarbon group, which may optionally have a urethane bond, R ⁵ represents a branched chain or secondary hydrocarbon group, m represents a number of at least 2, h represents a number of at least 1, k represents a number within the range of 1 to 500, and n represents a number within the range of 1 to 200.

The hydrophobically modified polyurethane that is represented by the general formula (1) shown above is obtained by, for example, reacting at least one polyether polyol that is represented by the formula R ¹ -[(O-R ² ) _k -OH] _m , at least one polyisocyanate that is represented by the formula R ³ -(NCO) _h+l , and at least one monoalcohol that is represented by the formula HO-(R ⁴ -O) _n -R ⁵ .

In such cases, R ¹ to R ⁵ in the general formula (1) are determined by the compounds R ¹ - (O- R ² ) _k -OH] _m , R ³ -(NCO) _h+l and HO-(R ⁴ -O) _n -R ⁵ . The loading ratios among the three compounds are not particularly limited and should preferably be such that the ratio of the isocyanate group derived from the polyisocyanate to the hydroxyl group derived from the polyether polyol and the polyether monoalcohol is selected within the range of NCO/OH of between 0.8:1 and 1.4:1.

The polyether polyol compound that is represented by the formula R ¹ -[(O-R ² ) _k -OH] _m and that may be used preferably for obtaining the associative thickener represented by the general formula (1) may be obtained from addition polymerization of an m-hydric polyol with an alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, or epichlorohydrin, or with styrene oxide, and the like.

The polyols should preferably be di- to octa-hydric polyols. Examples of the di- to octa- hydric polyols include dihydric alcohols, such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, and neopentyl glycol; trihydric alcohols, such as glycerol, trioxy isobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl- 1,2, 3 -propanetriol, 2-methyl-

2.3.4-butanetriol, 2-ethyl- 1,2, 3 -butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-

3.4.5-heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol, pentamethylglycerol, pentaglycerol, 1,2,4- butanetriol, 1,2,4-pentanetriol, trimethylolethane, and trimethylolpropane; tetrahydric alcohols, such as pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1, 2,4,5- pentanetetrol, and 1,3,4,5-hexanetetrol; pentahydric alcohols, such as adonitol, arabitol, and xylitol; hexahydric alcohols, such as dipentaerythritol, sorbitol, mannitol, and iditol; and octahydric alcohols, such as sucrose.

Also, R ² is determined by the alkylene oxide, styrene oxide, or the like, which is subjected to the addition. Particularly, for availability and excellent effects, an alkylene oxide having 2 to 4 carbon atoms, or styrene oxide is preferable.

The alkylene oxide, styrene oxide, or the like, to be subjected to the addition may be subjected to single polymerization, or random polymerization or block polymerization of at least two members. The procedure for the addition may be a conventional procedure. Also, the polymerization degree k may be selected within the range of 0 to 1 ,000, preferably within the range of 1 to 500, and more preferably within the range of 10 to 200. Further, the ratio of the ethylene group occupying R ² should preferably be within the range of 50 to 100 mass % with respect to the total quantity of R ² . In such cases, the associative thickener appropriate for the purposes of the present invention is obtained.

Furthermore, the molecular weight of the polyether polyol compound that is represented by the formula R ¹ -[(O-R ² ) _k -OH] _m should preferably be selected within the range of 500 to 100,000, and should more preferably be selected within the range of 1,000 to 50,000. The polyisocyanate that is represented by the formula R ³ -(NCO) _h+l and that may be used preferably for obtaining the hydrophobically modified polyether urethane represented by the general formula (1) employed in accordance with the present invention is not limited particularly in so far as the polyisocyanate has at least two isocyanate groups in the molecule. Examples of the polyisocyanates include aliphatic diisocyanates, aromatic diisocyanates, alicyclic diisocyanates, biphenyl diisocyanate, phenylmethane diisocyanate, phenylmethane triisocyanate, and phenylmethane tetraisocyanate.

Also, it is possible to employ dimers and trimers (isocyanurate bonds) of the above- enumerated polyisocyanates. Further, it is possible to employ a biuret obtained by a reaction with an amine.

Furthermore, it is possible to employ a polyisocyanate having a urethane bond obtained by a reaction of the aforesaid polyisocyanate compound and a polyol. As the polyol, di- to octa- hydric polyols are preferable, and the above-enumerated polyols are preferable. In cases where a tri- or higher-hydric polyisocyanate is used as the polyisocyanate that is represented by the formula R ³ -(NCO) _n+l , it is preferable to employ the aforesaid polyisocyanate having the urethane bond.

The polyether monoalcohol that is represented by the formula HO-(R ⁴ -O) _n -R ⁵ and that may be used preferably for obtaining the hydrophobically modified polyether urethane represented by the general formula (1) employed in accordance with the present invention is not limited particularly in so far as the polyether monoalcohol is a polyether of a straight chain, branched chain, or secondary monohydric alcohol. The polyether monoalcohol may be obtained by addition polymerization of the straight chain, branched chain, or secondary monohydric alcohol with an alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, or epichlorohydrin, or with styrene oxide, and the like.

The compound represented by the general formula (1) may be produced by, for example, heating at a temperature of 80 to 90°C for 1 to 3 hours and thereby causing a reaction to occur in the same manner as that in the ordinary reaction of a polyether and an isocyanate.

As the compound represented by the general formula (1), polyethyleneglycol- 240/decyltetradeceth-20/hexamethylene diisocyanate copolymer is preferable. The polyethyleneglycol-240/decyltetradeceth-20/hexamethylene diisocyanate copolymer is also referred to as PEG-240/HDI copolymer bis-decyltetradeceth-20 ether.

According to the present invention, it is preferable that the associative polyurethane thickener be selected from Steareth-100/PEG-136/HDI Copolymer sold by the company Rheox under the name of Rheolate FX 1100, PEG-240/HDI Copolymer Bis-decyltetradeceth-20 ether sold by the company Asahi Denka under the name of Adekanol GT-700, and mixtures thereof.

(ii) Among the crosslinked acrylic acid homopolymers that may be mentioned are those crosslinked with an allylic alcohol ether of the sugar series. Mention may be made of carbomer, which is a homopolymer of acrylic acid crosslinked with an allyl ether of pentaerythritol, an allyl ether of sucrose, or an allyl ether of propylene, such as the products sold under the names Carbopol 980, 981, 954, 2984, and 5984 by the company Lubrizol or the products sold under the names Synthalen M and Synthalen K by the company 3 VS A.

(iii) The crosslinked copolymers of (meth)acrylic acid and of C ₁ -C ₆ alkyl acrylate can be chosen from crosslinked copolymers of methacrylic acid and of ethyl acrylate as an aqueous dispersion comprising 38% active material sold, for example, under the name Viscoatex 538C by the company Coatex, and crosslinked copolymers of acrylic acid and of ethyl acrylate as an aqueous dispersion comprising 28% active material sold under the name Aculyn 33 by the company Rohm & Haas. Crosslinked copolymers of methacrylic acid and of ethyl acrylate include an aqueous dispersion comprising 30% active material sold under the name CARBOPOL AQUA SF-1 by the company NOVEON.

(iv) Among the nonionic homopolymers or copolymers comprising ethylenically unsaturated monomers of ester and/or amide type, mention may be made of the products sold under the names: Cyanamer P250 by the company Cytec (polyacrylamide); PMMA MBX-8C by the company US Cosmetics (methyl methacrylate/ethylene glycol dimethacrylate copolymer); Acryloid B66 by the company Rohm & Haas (butyl methacrylate/methyl methacrylate copolymer); and BPA 500 by the company Kobo (polymethyl methacrylate).

(v) Ammonium acrylate homopolymers that may be mentioned include the product sold under the name Microsap PAS 5193 by the company Hoechst.

Copolymers of ammonium acrylate and of acrylamide include the product sold under the name Bozepol C Nouveau or the product PAS 5193 sold by the company Hoechst (which are described and prepared in documents FR-2 416 723, U.S. Pat. No. 2,798,053, and U.S. Pat. No. 2,923,692).

(vi) The polysaccharides are, for example, chosen from glucans, modified and unmodified starches (such as those derived, for example, from cereals, for instance wheat, com, or rice, from vegetables, for instance yellow peas, and tubers, for instance potatoes or cassava), amylose, amylopectin, glycogen, dextrans, celluloses, and derivatives thereof (e.g., methylcelluloses, hydroxyalkylcelluloses, hydroxyethylcelluloses, and carboxymethylcelluloses), mannans, xylans, lignins, arabans, galactans, galacturonans, chitins, chitosans, glucuronoxylans, arabinoxylans, xyloglucans, glucomannans, pectic acids, and pectins, alginic acid and alginates, arabinogalactans, carrageenans, agars, glycosaminoglucans, gum arabics, gum tragacanths, ghatti gums, karaya gums, carob gums, galactomannans, such as guar gums, and nonionic derivatives thereof (e.g., hydroxypropyl guar), sclerotium gum and xanthan gums, and mixtures thereof.

For example, the polysaccharides that may be used are chosen from those described, for example, in "Encyclopedia of Chemical Technology", Kirk-Othmer, Third Edition, 1982, Volume 3, pp. 896-900, and Volume 15, pp. 439-458, in "Polymers in Nature" by E. A. MacGregor and C. T. Greenwood, published by John Wiley & Sons, Chapter 6, pp. 240-328, 1980, and in "Industrial Gums-Polysaccharides and their Derivatives", edited by Roy L. Whistler, Second Edition, published by Academic Press Inc., the content of these three publications being entirely incorporated by reference.

For example, starches, guar gums, celluloses, and derivatives thereof can be used.

Among the starches that may be used, mention may be made, for example, of macromolecules in the form of polymers comprising base units which are anhydroglucose units. The number of these units and their assembly make it possible to distinguish between amylose (linear polymer) and amylopectin (branched polymer). The relative proportions of amylose and amylopectin, as well as their degree of polymerization, can vary according to the botanical origin of the starches.

The molecules of starches used may have cereals or tubers as their botanical origin. Thus, the starches can be, for example, chosen from maize, rice, cassava, tapioca, barley, potato, wheat, sorghum, and pea starches.

Starches generally exist in the form of a white powder, insoluble in cold water, whose elementary particle size ranges from 3 to 100 microns.

The starches may be optionally C ₁ -C ₆ hydroxyalkylated or C ₁ -C ₆ acylated (such as acetylated). The starches may have also undergone heat treatments.

Distarch phosphates or compounds rich in distarch phosphate, such as the product provided under the references PREJEL VA-70-T AGGL (gelatinized hydroxypropylated cassava distarch phosphate) or PREJEL TK1 (gelatinized cassava distarch phosphate) or PREJEL 200 (gelatinized acetylated cassava distarch phosphate) by the company AVEBE, may also be used.

The guar gums can be modified or unmodified.

The unmodified guar gums are, for example, the products sold under the name Vidogum GH 175 by the company Unipectine and under the names Meypro-Guar 50 and Jaguar C by the company Meyhall.

The modified nonionic guar gums are, for example, modified with C ₁ -C ₆ hydroxyalkyl groups.

Among the hydroxyalkyl groups that may be mentioned, for example, are hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxybutyl groups.

These guar gums are well known in the prior art and can be prepared, for example, by reacting the corresponding alkene oxides such as propylene oxides, with the guar gum so as to obtain a guar gum modified with hydroxypropyl groups.

The degree of hydroxyalkylation, which corresponds to the number of alkylene oxide molecules consumed by the number of free hydroxyl functions present on the guar gum, may, for example, range from 0.4 to 1.2.

Such nonionic guar gums optionally modified with hydroxyalkyl groups are sold, for example, under the trade names Jaguar HP8, Jaguar HP60, Jaguar HP120, Jaguar DC 293, and Jaguar HP 105 by the company Rhodia Chimie (Meyhall) or under the name Galactasol 4H4FD2 by the company Aquaion.

Among the celluloses and cellulose derivatives, such as cellulose modified with hydroxylalkyl groups, that are used are, for example, hydroxypropylmethylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose, as well as hydrophobicized hydroxypropylmethylcellulose.

Mention may be made of the products sold under the names Klucel E F, Klucel H, Klucel L H F, Klucel M F, and Klucel G by the company Aquaion.

(vii) The fatty alcohols are, for example, chosen from myristyl alcohol, cetyl alcohol, stearyl alcohol, and behenyl alcohol.

It is preferable that the (b) thickening agent be selected from hydrophilic thickeners. The hydrophilic thickeners can thicken an aqueous phase if the composition according to the present invention includes water.

It is preferable that the (b) thickening agent be selected from polysaccharides, and more preferably polysaccharides derived from microorganisms, and even more preferably xanthan gum, sclerotium gum and a mixture thereof.

The amount of the (b) thickening agent(s) in the composition according to the present invention may be 0.05% by weight or more, preferably 0.1% by weight or more, and more preferably 0.5% by weight or more, relative to the total weight of the composition.

The amount of the (b) thickening agent(s) in the composition according to the present invention may be 10% by weight or less, preferably 5% by weight or less, and more preferably 2% by weight or less, relative to the total weight of the composition.

The amount of the (b) thickening agent(s) in the composition according to the present invention may be from 0.05% to 10% by weight, preferably from 0.1% to 5% by weight, and more preferably from 0.5% to 2% by weight, relative to the total weight of the composition.

(Polyol)

The composition according to the present invention comprises (c) at least one polyol. Two or more different types of (c) polyols may be used in combination. Thus, a single type of (c) polyol or a combination of different types of (c) polyols may be used.

The term “polyol” here means an alcohol having two or more hydroxy groups, and does not encompass a saccharide or a derivative thereof. The derivative of a saccharide includes a sugar alcohol which is obtained by reducing one or more carbonyl groups of a saccharide, as well as a saccharide or a sugar alcohol in which the hydrogen atom or atoms in one or more hydroxy groups thereof has or have been replaced with at least one substituent such as an alkyl group, a hydroxyalkyl group, an alkoxy group, an acyl group or a carbonyl group.

The polyols used in the present invention are liquid at ambient temperature such as 25 °C under atmospheric pressure (760 mmHg or 105 Pa).

The polyol may be a C ₂ -C ₂₄ polyol, preferably a C ₂ -C ₉ polyol, comprising at least 2 hydroxy groups, and preferably 2 to 5 hydroxy groups.

The polyol may be a natural or synthetic polyol. The polyol may have a linear, branched or cyclic molecular structure.

The polyol may be selected from glycerins and derivatives thereof, and glycols and derivatives thereof. The polyol may be selected from the group consisting of glycerin, diglycerin, polyglycerin, ethyleneglycol, diethyleneglycol, propyleneglycol, dipropyleneglycol, butyleneglycol, pentyleneglycol, hexyleneglycol, C ₆ -C ₂₄ polyethyleneglycol, 1,3 -propanediol, 1 ,4-butanediol, 1,5-pentanediol, and a mixture thereof. It is preferable that the (c) polyol be selected from the group consisting of glycerin, ethyleneglycol, polyethyleneglycol, propyleneglycol, dipropyleneglycol, butyleneglycol, pentyleneglycol, hexyleneglycol, and a mixture thereof.

The amount of the (c) polyol(s) in the composition according to the present invention may be from 0.1% by weight or more, preferably 0.5% by weight or more, and more preferably from 1% by weight or more, relative to the total weight of the composition.

The amount of the (c) polyol(s) in the composition according to the present invention may be from 20% by weight or less, preferably from 15% by weight or less, and more preferably from 10% by weight or less, relative to the total weight of the composition.

The amount of the (c) polyol(s) in the composition according to the present invention may be from 0.1% to 20% by weight, preferably from 0.5% to 15% by weight, and more preferably from 1% to 10% by weight, relative to the total weight of the composition.

(Oxidizing Agent)

The composition according to the present invention comprises at least one (d) oxidizing agent. If two or more (d) oxidizing agents are used, they may be the same or different.

The (d) oxidizing agent may be chosen from hydrogen peroxide, peroxygenated salts, and compounds capable of producing hydrogen peroxide by hydrolysis. For example, the (d) oxidizing agent can be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates and ferricyanides and per salts such as perborates and persulphates. At least one oxidase enzyme chosen, for example, from laccases, peroxidases and 2-electron oxidoreductases such as uricase may also be used as the (d) oxidizing agent, where appropriate in the presence of the respective donor or co-factor thereof.

In one embodiment, the (d) oxidizing agent is hydrogen peroxide, and the composition according to the present invention is an aqueous hydrogen peroxide solution.

In one embodiment, when the composition according to the present invention is an aqueous hydrogen peroxide solution, it may comprise at least one hydrogen peroxide stabilizer, which may be chosen, for example, from alkali metal and alkaline-earth metal pyrophosphates, alkali metal and alkaline-earth metal stannates, phenacetin and salts of acids and of oxyquinoline, for example, oxyquinoline sulphate. In another embodiment, at least one stannate optionally in combination with at least one pyrophosphate is used.

It is also possible to use salicylic acid and its salts, pyridinedicarboxylic acid and its salts, and paracetamol.

In the composition according to the present invention in the form of an aqueous hydrogen peroxide solution, the concentration of the hydrogen peroxide stabilizer may range from 0.0001% to 5% by weight such as from 0.01% to 2% by weight, relative to the total weight of the composition.

In the composition according to the present invention in the form of an aqueous hydrogen peroxide solution, the concentration ratio of the hydrogen peroxide to the possible at least one stabilizer may range from 0.05:1 to 1,000:1, such as from 0.1 :1 to 500:1 and further such as from 1:1 to 200:1.

The amount of the (d) oxidizing agent(s) in the composition according to the present invention may be from 0.1% by weight or more, preferably 0.5% by weight or more, and more preferably from 1% by weight or more, relative to the total weight of the composition.

The amount of the (d) oxidizing agent(s) in the composition according to the present invention may be from 20% by weight or less, preferably from 15% by weight or less, and more preferably from 10% by weight or less, relative to the total weight of the composition.

The amount of the (d) oxidizing agent(s) in the composition according to the present invention may be from 0.1% to 20% by weight, preferably from 0.5% to 15% by weight, and more preferably from 1% to 10% by weight, relative to the total weight of the composition.

(Water)

The composition according to the present invention may comprise water.

The water can be in the aqueous phase of the composition according to the present invention if the composition is in the form of an emulsion.

If the composition according to the present invention is in the form of a W/O or O/W emulsion, the aqueous phase of the composition according to the present invention can be dispersed or inner phases in the W/O emulsion or a continuous or outer phase in the O/W emulsion.

The amount of the water in the composition according to the present invention may be 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more, relative to the total weight of the composition.

On the other hand, the amount of the water in the composition according to the present invention may be 95% by weight or less, preferably 93% by weight or less, and more preferably 90% by weight or less, relative to the total weight of the composition.

The amount of the water may be from 50% to 95% by weight, preferably from 60% to 93% by weight, and more preferably from 70% to 90% by weight, relative to the total weight of the composition.

If the composition according to the present invention includes water, the composition has a measurable pH. The pH of the composition according to the present invention may be less than 7, preferably 6 or less, and more preferably 5 or less. Thus, the composition according to the present invention is acidic. It is preferable that the pH of the composition according to the present invention be 3 or more, more preferably 3.5 or more, and even more preferably 4 or more.

The pH may be adjusted to the desired value using at least one acidifying agent and/or at least one basifying agent.

The acidifying agents can be, for example, mineral or organic acids, for instance hydrochloric acid, phosphoric acid, carboxylic acids, for instance tartaric acid, citric acid, and lactic acid, or sulphonic acids.

The acidifying agent may be present in an amount ranging from less than 5% by weight, preferably from 3% by weight or less, and more preferably from 1% by weight or less, relative to the total weight of the composition.

The basifying agent may be, for example, any inorganic or organic basic agents which are commonly used in cosmetic products such as ammonia; alkanolamines such as mono-, di- and tri-ethanolamine, isopropanolamine; sodium and potassium hydroxides; urea, guanidine and their derivatives; basic amino acids such as lysine or arginine; and diamines such as those described in the structure below: wherein

R denotes an alkylene such as propylene optionally substituted by a hydroxyl or a C ₁ -C ₄ alkyl radical, and R ₁ , R ₂ , R ₃ , and R ₄ independently denote a hydrogen atom, an alkyl radical, or a C ₁ -C ₄ hydroxyalkyl radical, which may be exemplified by 1,3 -propanediamine, and derivatives thereof. Arginine, urea, and monoethanolamine may be preferable.

It is preferable that the amount of the basifying agent in the composition according to the present invention be as small as possible.

Thus, it is preferable that the composition comprise at least one basifying agent in an amount of 0.5% by weight or less, preferably 0.3% by weight or less, and more preferably 0.1% by weight or less, relative to the total weight of the composition, or the composition may comprise no basifying agent.

(Other Ingredients)

The composition according to the present invention may also include at least one optional or additional ingredient.

The amount of the optional or additional ingredient(s) is not limited, but may be from 0.01% to 30% by weight, preferably from 0.1% to 20% by weight, and more preferably from 1% to 10% by weight, relative to the total weight of the composition according to the present invention.

The optional or additional ingredient(s) may be selected from the group consisting of oils; cationic, anionic, nonionic or amphoteric surfactants; UV filters; peptides and derivatives thereof; protein hydrolyzates; swelling agents and penetrating agents; agents for combating hair loss; anti-dandruff agents; suspending agents; sequestering agents; opacifying agents; vitamins or provitamins; fragrances; preserving agents, stabilizers; and mixtures thereof.

The aqueous phase of the composition according to the present invention may include, in addition to water, one or several cosmetically acceptable organic solvents, which may be alcohols: in particular monovalent alcohols such as ethyl alcohol, isopropyl alcohol, benzyl alcohol and phenylethyl alcohol; sugars; sugar alcohols; and ethers such as ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol monomethyl, monoethyl and monobutyl ether, and butylene glycol monomethyl, monoethyl and monobutyl ethers.

The organic solvent(s) may then be present in a concentration of from 0.01% to 30% by weight, preferably from 0.1% to 20% by weight, and more preferably from 1% to 15% by weight, relative to the total weight of the composition.

(Preparation)

The composition according to the present invention can be prepared by mixing the abovedescribed essential and optional ingredients in a conventional manner.

For example, the composition according to the present invention can be prepared by a process comprising the step of mixing

(a) at least one compound selected from water-soluble silicones and derivatives thereof;

(b) at least one thickening agent;

(c) at least one polyol; and

(d) at least one oxidizing agent.

For the above ingredients (a) to (d), those explained above can be used.

It is possible to further mix therein any of the optional ingredients.

[Use]

The composition according to the present invention is preferably used for cosmetic purposes of keratin fibers. Thus, the composition according to the present invention is preferably a cosmetic composition for keratin fibers, in particular for bleaching or coloring keratin fibers.

As the keratin fibers, mention may be made of hair, eyebrows and eyelashes.

If the composition according to the present invention explained above is used for bleaching keratin fibers such as hair, for example, the composition according to the present invention may be used as it is or as a mixture with another composition comprising (e) at least one alkaline agent explained below.

Alternatively, if the composition according to the present invention is used for dyeing keratin fibers such as hair, the composition according to the present invention can be used as a mixture with another composition comprising (e) at least one alkaline agent and (f) at least one dye. In this case, the composition according to the present invention can function as a developer.

The above mixture may be regarded as a ready-to-use composition. For the purposes of the present invention, the expression "ready-to-use composition" is defined herein as a composition to be applied immediately to keratin fibers such as hair. The ready-to-use composition can also be a cosmetic composition for keratin fibers, in particular for bleaching or coloring keratin fibers, such as hair.

The mixing ratio of the composition according to the present invention and another composition is not limited. The mixing ratio may be 1 :3 to 3:1, preferably 1 :2 to 2:1, and more preferably 1 : 1 , as the weight ratio thereof.

(Alkaline Agent)

The composition to be mixed with the composition according to the present invention comprises (e) at least one alkaline agent. If two or more (e) alkaline agents are used, they may be the same or different.

The (e) alkaline agent is different from the (a) compound.

The (e) alkaline agent may comprise at least one selected from alkanolamines, derivatives of alkanolamines (alkanolamine derivatives), and salts of alkanolamines or alkanolamine derivatives.

The alkanolamines have an alkane structure with at least one hydroxyl group and at least one amino group.

As the alkanolamines, mention may be made of, for example, mono-, di-, and triethanolamines. The alkanolamine may be selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N-dimethylethanolamine, 2-amino-2 -methyl- 1 -propanol, triisopropanolamine, 2-amino-2-methyl- 1,3 -propanediol, 3-amino-l,2-propanediol, 3- dimethylamino-l,2-propanediol, tris(hydroxymethylamino)methane, and a mixture thereof.

The alkanolamine derivative may be selected from alkanolamines in which the hydrogen atom on the nitrogen atom, if present, of the amino group in the alkanolamines is substituted with at least one substituent.

As the substituent, mention may be made of, for example, an alkyl group, an alkenyl group, and an alkynyl group.

The alkyl group may be a linear, branched or cyclic alkyl group. The alkyl group may be a linear or branched C ₁ -C ₆ alkyl group, preferably C ₁ -C ₄ alkyl group, such as a methyl group, an ethyl group, a propyl group, an i-propyl group and a butyl group. On the other hand, the alkyl group may be a cyclic C ₃ -C ₆ alkyl group, such as a cyclopentyl group and a cyclohexyl group.

The alkenyl group may be a C ₂ -C ₆ alkenyl group such as a vinyl group, an allyl group, a butylene group, a pentenyl group and a hexenyl group.

The alkynyl group may be a C ₂ -C ₆ alkynyl group such as an ethynyl group, and a propanyl group.

The above substituent may be further substituted with at least one group such as a halogen atom, a nitro group, a cyano group, a hydroxyl group and an aromatic group such as a phenyl group.

The (e) alkaline agent may also comprise an additional basifying agent. The additional basifying agent may be selected from inorganic and/or organic basifying agents.

As the inorganic basifying agent, mention may be made of, for example, sodium and potassium hydroxide.

As the inorganic basifying agent, ammonia may be used. However, it is preferable that the amount of ammonia in the composition according to the present invention be as small as possible. For example, the amount of ammonia in the composition according to the present invention may be 1% by weight or less, preferably 0.1% by weight or less, and more preferably 0.01% by weight or less. It is most preferable that the composition according to the present invention include no ammonia.

As the organic basifying agent, mention may be made of, for example, urea, guanidine and derivatives thereof; diamines such as those described in the structure below: wherein

R denotes an alkylene such as propylene optionally substituted by a hydroxyl or a C ₁ -C ₄ alkyl radical, and R ₁ , R ₂ , R ₃ , and R ₄ independently denote a hydrogen atom, an alkyl radical, or a C ₁ -C ₄ hydroxyalkyl radical, which may be exemplified by 1,3 -propanediamine, and derivatives thereof.

The type of the salts of alkanolamines and alkanolamine derivatives is not limited. The salts may be acid salts. As acid salts, mention may be made of, for example, inorganic acid salts such as hydrochloride, sulfates, nitrates, and phosphates, and organic acid salts such as citrates, oxalates, acetates, formats, maleates, and tartrates.

The amount of the (e) alkaline agent(s) in the composition to be mixed with the composition according to the present invention may be from 0.1% by weight or more, preferably 0.5% by weight or more, and more preferably from 1% by weight or more, relative to the total weight of the former composition.

The amount of the (e) alkaline agent(s) in the composition to be mixed with the composition according to the present invention may be from 15% by weight or less, preferably from 10% by weight or less, and more preferably from 5% by weight or less, relative to the total weight of the former composition.

The amount of the (e) alkaline agent(s) in the composition to be mixed with the composition according to the present invention may be from 0.1% to 15% by weight, preferably from 0.5% to 10% by weight, and more preferably from 1% to 5% by weight, relative to the total weight of the former composition.

(Dye) The composition to be mixed with the composition according to the present invention may comprise (f) at least one dye. If two or more (f) dyes are used, they may be the same or different.

It is preferable that the dye be selected from oxidative dyes.

The oxidative dyes may be selected from oxidation bases and couplers.

The oxidation base can be selected from those conventionally known in oxidation dyeing, preferably from the group consisting of ortho- and para-phenylenediamines, double bases, ortho- and para-aminophenols, heterocyclic bases, and the acid addition salts thereof.

There may be mentioned in particular:

- (I) the para-phenylenediamines of the following formula (I) and their addition salts with an acid: in which:

Ri represents a hydrogen atom, a C ₁ -C ₄ alkyl radical, a monohydroxy(C ₁ -C ₄ alkyl) radical, a polyhydroxy-(C ₂ -C ₄ alkyl) radical, a ( C ₁ -C ₄ )alkoxy(C ₁ -C ₄ )alkyl radical, a C ₁ -C ₄ alkylradical substituted with a nitrogen-containing group, a phenyl radical, or a 4' -aminophenyl radical; R2 represents a hydrogen atom, a C ₁ -C ₄ alkyl radical, a monohydroxy(C ₁ -C ₄ alkyl) radical, a polyhydroxy(C2-C4 alkyl) radical, a (C ₁ -C ₄ )alkoxy(C ₁ -C ₄ )alkyl radical, or a C ₁ -C ₄ alkyl radical substituted with a nitrogen-containing group;

Ri and R2 may also form with the nitrogen atom carrying them a 5- or 6-membered nitrogencontaining heterocycle optionally substituted with one or more alkyl, hydroxyl, or ureido groups;

R3 represents a hydrogen atom, a halogen atom such as a chlorine atom, a C ₁ -C ₄ alkyl radical, a sulpho radical, a carboxyl radical, a monohydroxy(C ₁ -C ₄ alkyl) radical, a hydroxy(C ₁ -C ₄ alkoxy) radical, an acetylamino(C ₁ -C ₄ alkoxy) radical, a mesylamino(C ₁ -C ₄ alkoxy) radical, or a carbamoylamino(C ₁ -C ₄ alkoxy) radical; and

R represents a hydrogen or halogen atom or a C ₁ -C ₄ alkyl radical.

Among the nitrogen-containing groups of formula (I) above, there may be mentioned in particular the amino, mono(C ₁ -C ₄ )alkylamino, (C ₁ -C ₄ )dialkylamino, (C ₁ -C ₄ )trialkylamino, monohydroxy(C ₁ -C ₄ )alkylamino, di(monohydroxy(C ₁ -C ₄ )alkyl)amino, imidazolinium, and ammonium radicals.

Among the para-phenylenediamines of formula (I) above, mention may be more particularly made of para-phenylenediamine, para-tolylenediamine, 2-chloro-paraphenylenediamine, 2,3- dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para- phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethylpara- phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl- paraphenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(β-hydroxyethyl)- paraphenylenediamine, 4-N,N-bis(β-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(β- hydroxyethyl)amino-2-chloroaniline, 2-p-hydroxyethyl-para-phenylenediamine, 2-fluoro- paraphenylenediamine, 2-isopropyl-para-phenylenediamine, N-(β-hydroxypropyl)- paraphenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3- methylpara-phenylenediamine, N,N-(ethyl-β-hydroxyethyl)-para-phenylenediamine, N-(β,γ- dihydroxypropyl)-para-phenylenediamine, N-(4’-aminophenyl)-para-phenylenediamine, N- phenyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2-β- acetylamino-ethyloxy-para-phenylenediamine, N-(β-methoxyethyl)-para-phenylenediamine, 2-methyl- 1 -N-β-hydroxyethyl-para-phenylenediamine, N-(4-aminophenyl)-3-hydroxy- pyrrolidine, 2-[{2-[(4-Aminophenyl)amino]ethyl}(2-hydroxyethyl)amino]-eth anol, and their addition salts with an acid.

Among the para-phenylenediamines of formula (I) above, most particularly preferred are para-phenylenediamine, para-tolylenediamine, 2-isopropyl-paraphenylenediamine, 2-β- hydroxyethyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2,6- dimethyl -para-phenylenediamine, 2, 6-diethyl -para-phenylenediamine, 2,3 -dimethyl-para- phenylenediamine, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 2-chloro-para- phenylenediamine, and their addition salts with an acid.

- (II) According to the present invention, “double bases” are understood to mean compounds containing at least two aromatic rings on which amino and/or hydroxyl groups are carried.

Among the double bases which can be used as oxidation bases in the dyeing compositions in accordance with the present invention, mention may be made in particular of compounds corresponding to the following formula (II), and their addition salts with an acid: in which:

- Z ₁ and Z ₂ , which are identical or different, represent a hydroxyl or -NH ₂ radical which may be substituted with a C ₁ -C ₄ alkyl radical or with a linking arm Y;

- the linking arm Y represents a linear or branched alkylene chain comprising from 1 to 14 carbon atoms, which may be interrupted by or which may end with one or more nitrogen- containing groups and/or one or more heteroatoms such as oxygen, sulphur, or nitrogen atoms, and optionally substituted with one or more hydroxyl or C ₁ -C ₆ alkoxy radicals;

- R5 and Re represent a hydrogen or halogen atom, a C ₁ -C ₄ alkyl radical, a monohydroxy(C ₁ - C ₄ alkyl) radical, a polyhydroxy(C ₂ -C ₄ alkyl) radical, an amino(C ₁ -C ₄ alkyl) radical, or a linking arm Y;

- R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , and R ₁₂ , which are identical or different, represent a hydrogen atom, a linking arm Y, or a C ₁ -C ₄ alkyl radical; it being understood that the compounds of formula (II) contain only one linking arm Y per molecule.

Among the nitrogen-containing groups of formula (II) above, mention may be made in particular of the amino, mono(C ₁ -C ₄ )alkylamino, (C ₁ -C ₄ )dialkylamino, (C ₁ -C ₄ )trialkylamino, monohydroxy(C ₁ -C ₄ )alkylamino, imidazolinium, and ammonium radicals. Among the double bases of formulae (II) above, mention may be more particularly made of N,N’-bis(β-hydroxyethyl)-N,N’-bis(4’-aminophenyl)-l,3 -diaminopropanol, N,N’-bis(β- hydroxyethyl)-N,N ’ -bis(4 ’ -aminophenyl)ethylenediamine, N,N’ -bis(4-aminophenyl)- tetramethylenediamine, N,N’ -bis(β-hydroxyethyl)-N,N’ -bis(4- aminophenyl)tetramethylenediamine, N,N’-bis(4-methylaminophenyl)tetramethylenediamine, N,N’-bis(ethyl)-N,N’-bis(4’-amino-3 ’-methylphenyl)ethylene-diamine, 1 ,8-bis(2,5- diaminophenoxy)-3,5-dioxaoctane, and their addition salts with an acid.

Among these double bases of formula (II), N,N’-bis(p-hydroxyethyl)-N,N’-bis(4’- aminophenyl)- 1,3 -diaminopropanol, l,8-bis(2,5-diaminopherioxy)-3,5-dioxaoctane, or one of their addition salts with an acid are particularly preferred.

- (Ill) The para-aminophenols corresponding to the following formula (III), and their addition salts with an acid: in which:

- R ₁₃ represents a hydrogen atom, or a halogen atom such as fluorine, a C ₁ -C ₄ alkyl, monohydroxy(C ₁ -C ₄ alkyl), (C ₁ -C ₄ )alkoxy(C ₁ -C ₄ )-alkyl, amino(C ₁ -C ₄ alkyl), or hydroxy(Ci- C4)alkylamino-(C ₁ -C ₄ alkyl) radical,

- R14 represents a hydrogen atom, or a halogen atom such as fluorine, a C ₁ -C ₄ alkyl, monohydroxy(C ₁ -C ₄ alkyl), polyhydroxy(C2-C4 alkyl), amino(C ₁ -C ₄ alkyl), cyano(C ₁ -C ₄ alkyl), or (C ₁ -C ₄ )alkoxy(C ₁ -C ₄ )alkyl radical.

Among the para-aminophenols of formula (III) above, mention may be more particularly made of para-aminophenol, 4-amino-3 -methylphenol, 4-amino-3-fluorophenol, 4-amino-3- hydroxymethylphenol, 4-amino-2 -methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino- 2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(β- hydroxyethylaminomethyl)phenol, and their addition salts with an acid.

- (IV) The ortho-aminophenols which can be used as oxidation bases in the context of the present invention are chosen in particular from 2-aminophenol, 2-amino-l-hydroxy-5- methylbenzene, 2-amino-l-hydroxy-6-methylbenzene, 5-acetamido-2-aminophenol, and their addition salts with an acid.

- (V) Among the heterocyclic bases which can be used as oxidation bases in the dyeing compositions in accordance with the present invention, mention may be more particularly made of pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, and their addition salts with an acid.

Among the pyridine derivatives, mention may be more particularly made of the compounds described for example in Patents GB 1,026,978 and GB 1,153,196, such as 2,5- diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6- methoxypyridine, 2-(β-methoxyethyl)amino-3-amino-6-methoxypyridine, 3,4- diaminopyridine, and their addition salts with an acid. Among the pyrimidine derivatives, mention may be more particularly made of the compounds described, for example, in Patents DE 2 359 399; JP 88-169571; and JP 91-10659, or patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6- triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6- diaminopyrimidine, 2,5,6-triamino-pyrimidine, and the pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which there may be mentioned pyrazolofl ,5-a]-pyrimidine-3,7-diamine; 2,5-dimethyl-pyrazolo[l,5-a]-pyrimidine- 3,7-diamine; pyrazolofl ,5-a]pyrimidine-3,5-diamine; 2,7-dimethylpyrazolo[l,5-a]pyrimidine- 3,5-diamine; 3-aminopyrazolo[l ,5-a]pyrimidin-7-ol; 3-amino-pyrazolo[l ,5-a]pyrimidin-5-ol; 2-(3-amino-pyrazolo-[l,5-a]pyrimidin-7-ylamino)ethanol, 2-(7-aminopyrazolo[l,5- a]pyrimidin-3-ylamino)ethanol, 2-[(3-amino-pyrazolo[l,5-a]pyrimidin-7-yl)-(2-hydroxy- ethyl)amino] -ethanol, 2-[(7-aminopyrazolo[l,5-a]-pyrimidin-3-yl)-(2- hydroxyethyl)amino] ethanol, 5,6-dimethylpyrazolo-[1,5-a]pyrimidine-3,7-diamine, 2,6- dimethylpyrazolo-[l,5-a]pyrimidine-3,7-diamine, 2,5,N7,N7-tetramethyl-pyrazolo[l,5- a]pyrimidine-3 ,7-diamine, 3 -amino-5 -methyl-7-imidazolylpropyl-aminopyrazolo [ 1,5 - a] - pyrimidine, their addition salts and their tautomeric forms, when a tautomeric equilibrium exists, and their addition salts with an acid.

Among the pyrazole derivatives, mention may more particularly be made of the compounds described in Patents DE 3 843 892 and DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749, and DE 195 43 988 such as 4,5-diamino-l-methylpyrazole, 3,4-diaminopyrazole, 4,5-diamino-l-(4’-chlorobenzyl)-pyrazole, 4,5-diamino- 1,3- dimethylpyrazole, 4,5 -diamino-3 -methyl- 1-phenylpyrazole, 4,5-diamino- l-methyl-3- phenylpyrazole, 4-amino-l,3-dimethyl-5-hydrazino-pyraZole, l-benzyl-4,5-diamino-3- methyl-pyrazole, 4,5-diamino-3-tert-butyl- 1 -methylpyrazole, 4,5-diamino- 1 -tertbutyl-3- methylpyrazole, 4,5-diamino-l-(β-hydroxyethyl)-3-methylpyrazole, 4,5 -diamino- 1-(β- hydroxyethyl)pyrazole, 4,5-diamino-l -ethyl-3 -methylpyrazole, 4,5-diamino-l -ethyl-3-(4’- methoxyphenyl)pyrazole, 4,5-diamino- 1 -ethyl-3-hydroxy-methylpyrazole, 4,5-diamino-3- hydroxymethyl-1 -methylpyrazole, 4,5-diamino-3-hydroxymethyl-l-isopropyl-pyrazole, 4,5- diamino-3 -methyl- 1 -isopropyl-pyrazole, 4-amino-5-(2’-aminoethyl)amino-l,3- dimethylpyrazole, 3,4,5-triaminopyrazole, l-methyl-3,4,5-triamino-pyrazole, 3, 5 -diamino- 1- methyl-4-methylaminopyrazole, 3,5-diamino-4-(β-hydroxy-ethyl)amino- 1 -methylpyrazole, and their addition salts with an acid.

Among the heterocyclic bases which can be used as oxidation bases, mention may more particularly be made of diaminopyrazolopyrazolones and especially 2,3-diamino-6,7-dihydro- 1H5H-[pyrazolol,2,a]pyrazol-l-one and the addition salts of these diaminopyrazolopyrazolones with an acid.

The coupler may be an oxidation coupler which can be selected from those conventionally known in oxidation dyeing, preferably from the group consisting of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthols, heterocyclic couplers, and the acid addition salts thereof.

The heterocyclic couplers may be selected from the group consisting of indole derivatives, indoline derivatives, sesamol and its derivatives, pyridine derivatives, pyrazolotriazole derivatives, pyrazolones, indazoles, benzimidazoles, benzothiazoles, benzoxazoles, 1,3- benzodioxoles, quinolines, and their addition salts with an acid.

These couplers are more particularly chosen from 2,4-diamino-l-(β- hydroxyethyloxy)benzene, 2-methyl-5-aminophenol, 5-N-(β-hydroxyethyl)amino-2- methylphenol, 3 -aminophenol, 2-chloro-3-amino-6-methylphenol, 1,3 -dihydroxybenzene, 1 ,3-dihydroxy-2-methylbenzene, 4-chloro- 1 ,3 -dihydroxybenzene, 2-amino-4-(β- hydroxyethylamino)- 1 -methoxybenzene, 1 ,3 -diaminobenzene, 2-methyl-5- hydroxyethylaminophenol, 4-amino-2-hydroxytoluene, 1 ,3-bis(2,4-diaminophenoxy)- propane, sesamol, 1-amino-2-methoxy-4,5-methylene-dioxybenzene, a-naphthol, 6- hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxy-indoline, 2,6- dihydroxy-4-methylpyridine, 1 -H-3 -methylpyrazol-5 -one, 1 -phenyl-3 -methylpyrazol-5 -one, 2-amino-3 -hydroxypyridine, 3,6-dimethyl-pyrazolo[3,2-c]-1,2,4-triazole, 2,6- dimethylpyrazolo[1,5-b]-1,2,4-triazole, and their addition salts with an acid.

In general, the addition acid salts of the oxidation bases and couplers are chosen in particular from hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates, and acetates.

The amount of the (f) dye(s) in the composition to be mixed with the composition according to the present invention may be 0.05% by weight or more, preferably 0.1% by weight or more, and more preferably 0.5% by weight or more, relative to the total weight of the composition. It is even more preferable that the amount of the (f) dye(s) in the composition to be mixed with the composition according to the present invention be 1% by weight or more, relative to the total weight of the composition.

On the other hand, the amount of the (f) dye(s) in the composition to be mixed with the composition according to the present invention may be 15% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, relative to the total weight of the composition. It is even more preferable that the amount of the (f) dye(s) in the composition to be mixed with the composition according to the present invention be 3% by weight or less, relative to the total weight of the composition.

The amount of the (f) dye(s) in the composition to be mixed with the composition according to the present invention may be from 0.05% to 15% by weight, preferably from 0.1% to 10% by weight, and more preferably from 0.5% to 5% by weight, relative to the total weight of the composition. It is even more preferable that the amount of the (f) dye(s) in the composition to be mixed with the composition according to the present invention be from 1 % to 3% by weight, relative to the total weight of the composition.

[Kit]

The present invention also relates to a kit for keratin fibers, preferably a cosmetic kit, and more preferably a cosmetic kit for bleaching or dyeing keratin fibers, in particular hair, comprising: a first compartment comprising a first composition comprising

(a) at least one compound selected from water-soluble silicones and derivatives thereof;

(b) at least one thickening agent;

(c) at least one polyol; and

(d) at least one oxidizing agent, and a second compartment comprising a second composition comprising

(e) at least one alkaline agent. The second composition may further comprise (f) at least one dye.

For the above ingredients (a) to (f), those explained above can be used.

It is possible to use the kit by, for example, dispensing or discharging the first composition from the first compartment, while dispensing or discharging the second composition from the second compartment, followed by treating keratin fibers such as hair with the mixture of the first and second compositions.

The mixture of the first and second compositions may be regarded as the ready-to-use composition as explained above.

The mixing ratio of the first and second compositions is not limited. The mixing ratio may be 1 :3 to 3 : 1 , preferably 1 :2 to 2: 1 , and more preferably 1 : 1 , as the weight ratio thereof.

[Process]

The present invention also relates to a process, preferably a cosmetic process, and more preferably a cosmetic process for bleaching or dyeing keratin fibers, in particular hair, comprising the steps of:

(1) mixing a first composition and a second composition to prepare a mixture, wherein the first composition comprises

(a) at least one compound selected from water-soluble silicones and derivatives thereof,

(b) at least one thickening agent,

(c) at least one polyol, and

(d) at least one oxidizing agent, and the second composition comprises (e) at least one alkaline agent; and

(2) applying the mixture to the keratin fibers.

The second composition may further comprise (f) at least one dye.

For the above ingredients (a) to (f), those explained above can be used.

The mixture of the first and second compositions may be regarded as the ready-to-use composition as explained above.

The mixing ratio of the first and second compositions is not limited. The mixing ratio may be 1 :3 to 3:1, preferably 1 :2 to 2:1, and more preferably 1 :1, as the weight ratio thereof.

It is preferable that the process according to the present invention further comprise a step of washing, with or without drying, keratin fibers before and/or after the step of applying the mixture of the first and second compositions, as a ready-to-use composition, onto the keratin fibers.

The step of applying the ready-to-use composition onto the keratin fibers can be performed by a conventional applicator such as a brush, or even by the hands. The keratin fibers to which the ready -to-use composition has been applied can be left for an appropriate time which is required to treat the keratin fibers. The time length for the treatment is not limited, but it may be from 1 minute to 1 hour, preferably 1 minute to 30 minutes. For example, the time for dyeing the keratin fibers may be from 1 to 30 minutes, preferably 20 to 30 minutes.

EXAMPLES

The present invention will be described in a more detailed manner by way of examples. However, these examples should not be construed as limiting the scope of the present invention. The examples below are presented as non-limiting illustrations in the field of the present invention.

[Examples 1 and 2 and Comparative Examples 1 -7]

The following compositions according to Examples 1 and 2 and Comparative Examples 1-7, shown in Table 1 , as a gel, were prepared by mixing the ingredients shown in Table 1. The numerical values for the amounts of the ingredients shown in Table 1 are all based on “% by weight” as raw materials.

[Evaluations]

(Production)

The aspect of each of the compositions according to Examples 1 and 2 and Comparative Examples 1-7 was visually observed just after the preparation of the composition, and evaluated in accordance with the following criteria.

Good: Homogeneous transparent or translucent gel

Poor: Not homogeneous transparent or translucent gel

The results are shown in Table 1.

(Stability)

Each of the compositions according to Examples 1 and 2 and Comparative Examples 5-7 which were evaluated as “good” with regard to “Production” was stored for 2 weeks. The change in the aspect of the composition was visually observed and evaluated in accordance with the following criteria.

Good: No change

Fair Slight change but acceptable

Poor: Unacceptable change

The results are shown in Table 1.

(Mixing)

Each of the compositions, among those according to Examples 1 and 2 and Comparative Examples 5-7 which were evaluated as “good” with regard to “Production” was mixed with a dye composition, in the form of a gel, with the formulation shown in Table 2 below. The mixing weight ratio of each of the compositions according to Examples 1 and 2 and Comparative Examples 5-7 and the dye composition was 1:1.

Table 2

The aspect of the mixture thus obtained was visually observed just after the preparation of the mixture, and evaluated in accordance with the following criteria.

Good: No aggregation in the mixture

Poor: Aggregation in the mixture

The results are shown in Table 1.

(Cosmetic Effects)

Each of the compositions, among those according to Examples 1 and 2 and Comparative Examples 5 and 6, which were evaluated as “good” with regard to “Production” and “Mixing” was mixed with a dye composition, in the form of a gel, with the formulation shown in Table 2 above. The mixing weight ratio of each of the compositions according to Examples 1 and 2 and Comparative Examples 5 and 6 and the dye composition was 1 :1.

16.2 g of the mixture thus obtained was applied onto 5.4 g (27 cm) of a bleached Japanese hair swatch. The hair swatch was left for 20 minutes at 27°C. The hair swatch was then washed with water, followed by shampooing, rinsing and drying.

The smoothness and softness of the hair swatch was evaluated by 5 panelists during rinsing and after rinsing off (wet condition) in accordance with the following criteria.

Good: Smooth and soft

Fair: Not Rough and not hard

Poor: Rough and hard

The results are shown in Table 1.

(Summary) The compositions according to Examples 1 and 2 were in the form of a homogeneous gel, while the compositions according to Comparative Examples 1-4 were not.

Dimethicone and aminopropyldimethicone used in Comparative Examples 1 and 2, respectively, are not water-soluble. Also, amodimethicone used in Comparative Example 3 is not water-soluble.

Thus, the compositions according to Comparative Examples 1-4 were withdrawn from further comparative tests.

The composition according to Example 1 was stable over time. The composition according to Example 2 was also stable such that only acceptable slight change was observed. On the other hand, the compositions according to Comparative Examples 6 and 7 were unstable.

The compositions according to Examples 1 and 2 were able to avoid causing aggregation when they were mixed with a dye composition. On the other hand, the composition according to Comparative Example 7 could not avoid causing aggregation when they were mixed with a dye composition.

Thus, the compositions according to Comparative Example 7 was withdrawn from further comparative tests.

The compositions according to Examples 1 and 2 were able to provide keratin fibers with good texture such as a smooth and soft feeling to the touch. On the other hand, the compositions according to Comparative Examples 5 and 6 could not.

The compositions according to Examples 1 and 2 were able to be used for bleaching or dyeing keratin fibers.

In summary, the compositions according to Examples 1 and 2 were stable and in the form of a homogeneous gel, and could provide keratin fibers with good texture such as a smooth and soft feeling to the touch, without causing aggregation.