The present invention relates to a composition comprising an aqueous dispersion of polyurethane particles, a cationic surfactant, a silicone compound and a clay.

The present invention also relates to a process for treating keratin materials, especially keratin fibres, in particular human keratin fibres such as the hair, using said composition.

The hair is generally damaged and embrittled by the action of external atmospheric agents such as light and bad weather, and by mechanical or chemical treatments, such as brushing, combing, bleaching, permanent-waving and/or dyeing. As a result of this, the hair is often difficult to manage, and in particular is difficult to disentangle or to style, and heads of hair, even thick hair, do not readily maintain a good-looking style, because of a lack of vigour, volume and responsiveness of the hair.

This degradation to the hair is increased, moreover, by the repetition of permanent hair colouring treatments, which involves applying to the hair one or more dye precursors and an oxidizing agent.

Thus, to overcome this, it is now common practice to use styling or care products that allow the hair to be conditioned by especially giving it body, mass or volume.

These styling or care products are generally cosmetic hair compositions comprising one or more polymers with high affinity for the hair, which most often have the function of forming a film on the hair surface in order to modify its surface properties and especially to condition it or to give it particular optical properties.

One drawback associated with the use of these hair compositions lies in the fact that the cosmetic effects imparted by such compositions have a tendency to disappear, especially as of the first shampoo wash.

In order to overcome this drawback, it may be envisaged to increase the persistence of the deposit of polymers by directly performing free-radical polymerization of certain monomers on the hair. However, the treatments thus obtained result in the degradation of the fibre and the hair thus treated is generally difficult to disentangle. Because of their good film- forming properties, latexes constitute a family of polymers that is commonly used in the cosmetics industry, and more particularly in the makeup field. They are for example found in mascara, lip pencil, eyeliner or else eyeshadow compositions.

In the hair field, latexes are found mainly in products for shaping the head of hair and/or for form retention of the hairstyle (styling), where their ability to form a coating film is used for shaping the hair and providing volume or density. Document WO 92/21316 describes compositions based on silicone and latex. The results obtained with the compositions of said document are however unsatisfactory in terms of the coating effect and the persistence of the properties, especially with respect to shampooing.

Moreover, the sensory properties of latexes on the hair do not meet the expectations of consumers who find a dry, laden, not very cosmetic feel to be unacceptable. The cosmetic benefits could be considerably improved if, conversely to the products for shaping the head of hair and/or for form retention of the hairstyle (styling), the method of application was a rinse-off method. However, latexes have the particularity of being removed with water.

Thus, there is a real need to develop a composition for the treatment of keratin materials, especially keratin fibres, and in particular human keratin fibres such as the hair, which makes it possible to obtain satisfactory styling properties, and also good properties in terms of coating, body, density and volume, while at the same time conferring good cosmetic properties (suppleness, softness) and good disentangling properties on the fibres. These properties must also be persistent with respect to shampooing operations.

The applicant has discovered, surprisingly, that a composition comprising an aqueous dispersion of polyurethane, a cationic surfactant, a silicone compound and a clay makes it possible to achieve the objectives set out above.

A subject of the present invention is in particular a composition comprising:

- one or more aqueous dispersions of polyurethane particles,

- one or more cationic surfactants,

- one or more silicone compounds, preferably chosen from linear silicone block copolymers, amino silicones other than the linear silicone block copolymers, and mixtures thereof, and

- one or more clays; the weight ratio of the total amount of polyurethane to the total amount of the cationic surfactant(s) preferably being less than or equal to 12.

Even after rinsing, the composition according to the present invention makes it possible to obtain a deposit at the surface of the keratin materials, which gives them good styling properties, and good properties in terms of volume, density and body. This deposit is, moreover, persistent with respect to several shampooing operations.

In addition, the keratin materials treated with the composition of the invention exhibit a better coating, which is more uniform and smoother, thus leading to better cosmetic properties, and in particular fibres that are more individualized.

By virtue of the invention, it is thus possible to improve the cosmetic properties of compositions based on polyurethane latex, while at the same time obtaining a styling benefit, whether this is by leave-on application, or else by rinse-off application (the application being followed by rinsing).

Another subject of the present invention is a process for treating keratin materials, especially keratin fibres, in particular human keratin fibres such as the hair, comprising a step of applying, to said keratin materials, a composition as defined above, optionally followed by a step of rinsing said keratin materials.

Other subjects, characteristics, aspects and advantages of the invention will emerge even more clearly on reading the description and the examples that follow.

In the text hereinbelow, unless otherwise indicated, the limits of a range of values are included in that range, in particular in the expressions "between" and "ranging from ... to ...".

Moreover, the expression "at least one" used in the present description is equivalent to the expression "one or more".

The composition

The composition according to the present invention comprises one or more aqueous dispersions of polyurethane particles. The dispersion(s) can be simple dispersions in the aqueous medium of the composition. Mention may be made, as a specific case of dispersions, of latexes.

More particularly, the polyurethane(s) present in the aqueous dispersions that can be used in the present invention result from the reaction of:

- a prepolymer of formula (A) below:

in which:

- Ri represents a divalent radical of a dihydroxylated compound,

- R ₂ represents a radical of an aliphatic or cycloaliphatic polyisocyanate,

- R ₃ represents a radical of a low-molecular- weight diol, optionally substituted with one or more ionic groups,

- n represents an integer ranging from 1 to 5, and

- m is greater than 1 ;

- at least one chain extender according to the formula H2N-R4-NH2 (B), in which R ₄ represents an alkylene or alkylene oxide radical which is not substituted with one or more ionic or potentially ionic groups; and

- at least one chain extender according to the formula H ₂ N-R ₅ -NH ₂ (C), in which R ₅ represents an alkylene radical substituted with one or more ionic or potentially ionic groups.

Among the dihydroxylated compounds that can be used according to the present invention, mention may in particular be made of the compounds having two hydroxyl groups and a number-average molecular weight from approximately 700 to approximately 16 000, and preferably from approximately 750 to approximately 5000. By way of example of dihydroxylated compounds having a high molecular weight, mention may be made of polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, polyhydroxylated polyacetates, polyhydroxylated polyacrylates, polyhydroxylated amide polyesters, polyhydroxylated polyalkadienes, polyhydroxylated polythioethers, and mixtures thereof. Preferably, the hydroxylated compounds are chosen from polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, and mixtures thereof.

The polyisocyanates that can be used according to the present invention are in particular chosen from organic diisocyanates with a molecular weight of approximately 112 to 1000, and preferably approximately 140 to 400.

Preferably, the polyisocyanates are chosen from diisocyanates and more particularly from those represented by the general formula R ₂ (NCO) ₂ , in which R2 represents a divalent aliphatic hydrocarbon-based group having from 4 to 18 carbon atoms, a divalent cycloaliphatic hydrocarbon-based group having from 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon-based group having from 7 to 15 carbon atoms or a divalent aromatic hydrocarbon-based group having from 6 to 15 carbon atoms.

Preferably, R ₂ represents an organic diisocyanate. By way of example of organic diisocyanates, the following may in particular be chosen: tetramethylene diisocyanate, l,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3- diisocyanatocyclohexane, 1 ,4-diisocyanatocyclohexane, 3-isocyanatomethyl-3,5,5- trimethy ley clo hexane isocyanate (isophorone diisocyanate or IPDI), bis(4- isocyanatocyclohexyl)methane, 1 ,3-bis(isocyanatomethyl)cyclo hexane, 1 ,4- bis(isocyanatomethyl)cyclo hexane, bis(4-isocyanato-3-methyl-cyclohexyl)methane, isomers of toluene diisocyanate (TDI) such as toluene 2,4-diisocyanate, toluene 2,6- diisocyanate and mixtures thereof, hydrogenated toluene diisocyanate, diphenylmethane 4,4’-diisocyanate and mixtures with its diphenylmethane 2,4- diisocyanate isomers and optionally diphenylmethane 2,2'-diisocyanate isomers, naphthalene 1 ,5-diisocyanate, and mixtures thereof.

Preferably, the diisocyanates are aliphatic and cycloaliphatic diisocyanates, and are more preferentially chosen from l,6-hexamethylene diisocyanate, 3- isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate, and mixtures thereof.

The expression "low-molecular- weight diol" is intended to mean, according to the present invention, a diol with a molecular weight of approximately 62 to 700, and preferably from 62 to 200. These diols may comprise aliphatic, alicyclic or aromatic groups. Preferably, they comprise only aliphatic groups.

Preferably, R ₃ represents a low-molecular- weight diol having more than 20 carbon atoms, more preferentially chosen from ethylene glycol, diethylene glycol, 1,2- propanediol, 1,3 -propanediol, l,4-butanediol, 1, 3-butylene glycol, neopentyl glycol, butyl ethyl propanediol, cyclohexanediol, 1, 4-cyclohexane dimethanol, 1,6- hexanediol, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl)propane), and mixtures thereof.

The low-molecular- weight diols may optionally comprise ionic or potentially ionic groups. Examples of low-molecular- weight diols containing ionic or potentially ionic groups are in particular described in patent US 3 412 054. Such compounds are preferably chosen from dimethylolbutanoic acid, dimethylolpropionic acid, polycapro lactone diols containing a carboxyl group, and mixtures thereof. If low-molecular- weight diols containing ionic or potentially ionic groups are used, they are preferably used in an amount such that less than 0.30 meq of COOH per gram of polyurethane is present in the polyurethane dispersion.

The prepolymer is extended by means of two chain extender families. The first chain extender family corresponds to the compounds of general formula H2N-R4- NH ₂ (B), in which R ₄ represents an alkylene or alkylene oxide radical which is not substituted with one or more ionic or potentially ionic groups.

The chain extenders of formula (B) are preferably chosen from alkylene diamines, such as hydrazine, ethylenediamine, propylenediamine, 1,4- butylenediamine, piperazine; alkylene oxide diamines, such as 3-{2-[2-(3- aminopropoxy)ethoxy] ethoxy} propylamine (also known as dipropylamine diethylene glycol or DPA-DEG available from Tomah Products, Milton, Wis.), 2-methyl- 1,5- pentanediamine (Dytec A from DuPont), hexanediamine, isophorone diamine, 4,4- methylenedi(cyclohexylamine), ether-amines of the DPA series, available from Tomah Products, Milton, Wis., such as dipropylamine propylene glycol, dipropylamine dipropylene glycol, dipropylamine tripropylene glycol, dipropylamine polypropylene glycol), dipropylamine ethylene glycol, dipropylamine poly(ethylene glycol), dipropylamine 1, 3-propanediol, dipropylamine 2-methyl- 1, 3-propanediol, dipropylamine l,4-butanediol, dipropylamine l,3-butanediol, dipropylamine 1,6- hexanediol and dipropylamine cyclo hexane- 1, 4-dimethanol; and mixtures thereof.

The second chain extender family corresponds to the compounds of general formula H ₂ N-R ₅ -NH ₂ (C), in which R ₅ represents an alkylene radical substituted with one or more ionic or potentially ionic groups. Such compounds preferably have an ionic or potentially ionic group and two groups that can react with isocyanate groups. Such compounds can optionally comprise two groups that react with isocyanate groups and one group which is ionic or capable of forming an ionic group.

The ionic or potentially ionic group may preferably be chosen from ternary or quaternary ammonium groups or groups that can be converted into such groups, a carboxyl group, a carboxylate group, a sulfonic acid group and a sulfonate group. The at least partial conversion of groups that can be converted into a ternary or quaternary ammonium group salt can be carried out before or during the mixing with water.

The chain extenders of formula (C) are preferably chosen from diaminosulfonates, for instance the sodium salt of N-(2-aminoethyl)-2- aminoethanesulfonic acid (ASA), the sodium salt of N-(2-aminoethyl)-2- aminopropionic acid, and mixtures thereof.

The polyurethane that can be used according to the present invention can optionally also comprise compounds which are respectively located at the chain ends and terminate said chains (chain terminators). Such compounds are described in particular in patents US 7 445 770 and/or US 7 452 770.

Preferably, the aqueous dispersion of polyurethane particles has a viscosity of less than 2000 mPa.s at 23°C, more preferentially less than 1500, and even better still less than 1000. Even more preferably, the aqueous polyurethane dispersion has a glass transition temperature of less than 0°C.

Likewise preferably, the aqueous polyurethane dispersion has a solids (or active material, or dry matter) content, on the basis of the weight of the dispersion, of from 20% to 60% by weight, more preferentially from 25% to 55% by weight and even better still from 30% to 50% by weight. This is intended to mean that the polyurethane content (dry matter) of the aqueous dispersion is preferably from 20% to 60% by weight, more preferentially from 25% to 55% by weight and even better still from 30% to 50% by weight, relative to the total weight of the dispersion.

Likewise preferably, the aqueous dispersion of polyurethane particles has a glass transition temperature (Tg) less than or equal to -25°C, preferably less than

-35°C, and more preferentially less than -40°C.

The polyurethane particles may have an average diameter ranging up to approximately 1000 nm, for example from approximately 50 nm to approximately 800 nm, better still from approximately 100 nm to approximately 500 nm. These particle sizes can be measured with a laser particle sizer (for example Brookhaven BI90).

As non-limiting examples of aqueous polyurethane dispersions, mention may be made of those sold under the name Baycusan® by Bayer such as, for example, Baycusan® Cl 000 (INCI name: polyurethane-34), Baycusan® Cl 001 (INCI name: polyurethane-34), Baycusan® Cl 003 (INCI name: polyurethane-32), Baycusan® Cl 004 (INCI name: polyurethane-35) and Baycusan® Cl 008 (INCI name: polyurethane-48).

Mention may also be made of the aqueous polyurethane dispersions of isophthalic acid/adipic acid copolymer/hexylene gly co 1/neopentyl gly co 1/ dimethylo 1 acid/isophoronediisocyanate (INCI name: Polyurethane- 1, such as Luviset® Pur, BASF), the polyurethane of polycarbonate, polyurethane and aliphatic polyurethane of aliphatic polyester (such as Neorez® series, DSM, such as Neorez® R989, Neorez® and R-2202).

According to a preferred embodiment, the aqueous dispersion of polyurethane particles may be chosen from aqueous dispersions of particles of compounds having the INCI name polyurethane-35.

The total amount of the aqueous dispersion(s) of polyurethane particles, present in the composition according to the invention, preferably ranges from 0.01% to 25% by weight, more preferentially from 0.1% to 20% by weight, and better still from 0.2% to 15% by weight, relative to the total weight of the composition.

The total amount of the polyurethane (dry matter), present in the composition according to the invention, preferably ranges from 0.01% to 10% by weight, more preferentially from 0.05% to 8% by weight, and better still from 0.1% to 5% by weight, relative to the total weight of the composition.

The composition according to the present invention also comprises one or more cationic surfactants.

The term "cationic surfactant" is intended to mean a surfactant that is positively charged when it is contained in the compositions according to the invention. This surfactant may bear one or more positive permanent charges or may contain one or more cationizable functions in the compositions according to the invention.

The cationic surfactant(s) are preferably chosen from primary, secondary and tertiary fatty amines, which are optionally polyoxyalkylenated, salts thereof, and quaternary ammonium salts, and mixtures thereof.

The fatty amines generally comprise at least one Cs to C30 hydrocarbon-based chain.

Mention may in particular be made, as quaternary ammonium salts, for example, of:

(a) those corresponding to general formula (I) below:

in which:

- the R-28 to R31 groups, which can be identical or different, represent a linear or branched aliphatic group including from 1 to 30 carbon atoms or an aromatic group, such as aryl or alkylaryl, at least one of the R28 to R31 groups denoting a group including from 8 to 30 carbon atoms, preferably from 12 to 24 carbon atoms; and

- X is an anion chosen from the group of halides, phosphates, acetates, lactates, (Ci- C ₄ )alkyl sulfates, (Ci-C ₄ )alkylsulfo nates and (Ci-C ₄ )alkylarylsulfo nates.

The aliphatic groups may comprise heteroatoms especially such as oxygen, nitrogen, sulfur and halogens. The aliphatic groups are chosen, for example, from Ci to C30 alkyl, Ci to C30 alkoxy, (CY-CY) polyoxyalkylene, Ci to C30 alkylamide, (C12- C22)alkylamido(C2-C6)alkyl, (Ci2-C22)alkyl acetate, and Ci to C30 hydroxyalkyl groups.

Among the quaternary ammonium salts of formula (I), those that are preferred are, on the one hand, tetraalkylammonium salts, for instance dialkyldimethylammonium or alkyltrimethylammonium salts in which the alkyl group contains approximately from 12 to 22 carbon atoms, in particular behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium or benzyldimethylstearylammonium salts, or, on the other hand, the palmitylamidopropyltrimethylammonium salt, the stearamidopropyltrimethylammonium salt, the stearamidopropyldimethylcetearylammonium salts, or the stearamidopropyldimethyl(myristyl acetate)ammonium salts sold under the name Ceraphyl® 70 by the company Van Dyk. It is preferred in particular to use the chloride salts of these compounds.

(b) quaternary ammonium salts of imidazoline, for instance those of formula

(II) below:

in which:

R32 represents an alkenyl or alkyl group comprising from 8 to 30 carbon atoms, for example derived from tallow fatty acids,

- R33 represents a hydrogen atom, a Ci to C ₄ alkyl group or an alkenyl or alkyl group comprising from 8 to 30 carbon atoms,

R34 represents a Ci to C ₄ alkyl group,

R ₃₅ represents a hydrogen atom or a Ci to C ₄ alkyl group,

X is an anion chosen from the group of halides, phosphates, acetates, lactates, alkyl sulfates, alkyl- or alkylarylsulfonates in which the alkyl and aryl groups preferably comprise, respectively, from 1 to 20 carbon atoms and from 6 to 30 carbon atoms.

Preferably, R32 and R33 denote a mixture of alkenyl or alkyl groups comprising from 12 to 21 carbon atoms, for example derived from tallow fatty acids, R ₃₄ denotes a methyl group and R35 denotes a hydrogen atom. Such a product is sold, for example, under the name Rewoquat ^® W 75 by the company Rewo;

(c) di- or triquatemary ammonium salts, in particular of formula (III):

in which:

R36 denotes an alkyl radical including approximately from 16 to 30 carbon atoms, which is optionally hydroxylated and/or interrupted with one or more oxygen atoms,

R37 is chosen from hydrogen or an alkyl radical comprising from 1 to 4 carbon atoms or a group (R36a)(R37a)(R38a)N-(CH ₂ )3,

R36a, R37a, R38a, R38, R39, R ₄ o and R41, which may be identical or different, are chosen from hydrogen and an alkyl radical comprising from 1 to 4 carbon atoms, and

X is an anion chosen from the group of halides, acetates, phosphates, nitrates and methyl sulfates. Such compounds are, for example, Finquat CT-P, sold by the company Finetex (Quatemium 89), and Finquat CT, sold by the company Finetex (Quatemium 75),

(d) quaternary ammonium salts containing at least one ester function, such as those of formula (IV) below:

in which:

- R ₄₂ is chosen from Ci to C ₆ alkyl groups and Ci to C ₆ hydroxyalkyl or dihydroxyalkyl groups;

- R ₄₃ is chosen from:

- the group

- the R ₄₇ groups, which are linear or branched, saturated or unsaturated Ci to C22 hydrocarbon-based groups,

- a hydrogen atom;

- R ₄₅ is chosen from:

- the group

- the R49 groups, which are linear or branched, saturated or unsaturated Ci to C ₆ hydrocarbon-based groups,

- a hydrogen atom;

- R44, R46 and R48, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C 7 to C21 hydrocarbon-based groups;

- r, s and t, which may be identical or different, are integers having values from 2 to

6;

- y is an integer ranging from 1 to 10;

- x and z, which may be identical or different, are integers having a value from 0 to

10; - X is a simple or complex, organic or mineral anion;

with the proviso that the sum x + y + z is from 1 to 15, that when x is 0 then R ₄₃ denotes R47, and that when z is 0 then R45 denotes R49.

The alkyl groups R42 may be linear or branched, and more particularly linear. Preferably, R42 denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl group, and more particularly a methyl or ethyl group.

Advantageously, the sum x + y + z is from 1 to 10.

When R43 is a hydrocarbon-based group R47, it may be long and contain from 12 to 22 carbon atoms, or may be short and contain from 1 to 3 carbon atoms.

When R45 is a hydrocarbon-based group R49, it preferably contains 1 to 3 carbon atoms.

Advantageously, R44, R46 and R48, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C1 1 to C21 hydrocarbon-based groups, and more particularly from linear or branched, saturated or unsaturated C11 to C21 alkyl and alkenyl groups.

Preferably, x and z, which may be identical or different, are equal to 0 or 1.

Advantageously, y is equal to 1.

Preferably, r, s and t, which may be identical or different, are equal to 2 or 3, and even more particularly are equal to 2.

The anion X is preferably a halide (chloride, bromide or iodide) or an alkyl sulfate, more particularly methyl sulfate. However, use may be made of methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate or lactate, or any other anion that is compatible with the ammonium bearing an ester function.

The anion X is even more particularly chloride or methyl sulfate.

Use is made more particularly in the dye composition according to the invention of the ammonium salts of formula (IV) in which:

R ₄₂ denotes a methyl or ethyl group;

x and y are equal to 1 ;

z is equal to 0 or 1 ;

r, s and t are equal to 2;

R ₄₃ is chosen from: - the group

- methyl, ethyl or Ci ₄ to C ₂₂ hydrocarbon-based groups,

- a hydrogen atom;

R ₄₅ is chosen from:

- the group

- a hydrogen atom;

R ₄₄ , R ₄₆ and R ₄₈ , which may be identical or different, are chosen from saturated or unsaturated, linear or branched C ₁₃ to C ₁₇ hydrocarbon-based groups and preferably from saturated or unsaturated, linear or branched C ₁₃ to C ₁₇ alkyl and alkenyl groups.

Advantageously, the hydrocarbon-based groups are linear.

Examples that may be mentioned include the compounds of formula (IV) such as the diacyloxyethyldimethylammonium, diacyloxyethylhydroxyethylmethylammonium,

monoacyloxyethyldihydroxyethylmethylammonium,

triacyloxyethylmethylammonium and monoacyloxyethylhydroxyethyldimethylammonium salts (chloride or methyl sulfate in particular), and mixtures thereof. The acyl groups preferably contain 14 to 18 carbon atoms and are derived more particularly from a plant oil such as palm oil or sunflower oil. When the compound contains several acyl groups, these groups may be identical or different.

These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, alkyldiethanolamine or alkyldiisopropanolamine, which are optionally oxyalkylenated, with C ₁₀ to C ₃₀ fatty acids or with mixtures of C ₁₀ to C ₃₀ fatty acids of plant or animal origin, or by transesterification of their methyl esters. This esterification is followed by a quatemization using an alkylating agent such as an alkyl halide (preferably a methyl or ethyl halide), a dialkyl sulfate (preferably a methyl or ethyl sulfate), methyl methanesulfonate, methyl para-toluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin. Such compounds are sold, for example, under the names Dehyquart ^® by the company Henkel, Stepanquat ^® by the company Stepan, Noxamium ^® by the company CECA or Rewoquat ^® WE 18 by the company Rewo-Witco.

Among these compounds, mention may be made especially of dipalmitoylethylhydroxyethylmethylammonium methosulfate.

The composition according to the present invention may contain, for example, a mixture of quaternary ammonium monoester, diester and triester salts with a weight majority of diester salts.

Use may also be made of the ammonium salts containing at least one ester function that are described in patents US-A-4 874 554 and US-A-4 137 180.

Use may be made of behenoylhydroxypropyltrimethylammonium chloride sold by KAO under the name Quatarmin BTC 131.

Preferably, the ammonium salts containing at least one ester function contain two ester functions.

Among the quaternary ammonium salts containing at least one ester function, which may be used, it is preferred to use dipalmitoylethylhydroxyethylmethyl- ammonium salts.

Preferably, the surfactant(s) present in the composition according to the invention are chosen from quaternary ammonium salts of general formula (I) below, more preferentially from cetyltrimethylammonium salts, behenyltrimethylammonium salts and mixtures thereof, and even better still from cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, cetyltrimethylammonium methosulfate, behenyltrimethylammonium chloride, behenyltrimethylammonium bromide, behenyltrimethylammonium methosulfate and mixtures thereof.

The total amount of the cationic surfactant(s), present in the composition according to the invention, preferably ranges from 0.01% to 15% by weight, more preferentially from 0.05% to 10% by weight, and better still from 0.1% to 5% by weight, relative to the total weight of the composition.

The weight ratio of the total amount of polyurethane (active material) to the total amount of the cationic surfactant(s), present in the composition according to the invention, is preferably less than or equal to 12, and more preferentially less than or equal to 10. More particularly preferably, this weight ratio ranges from 0.5 to 12.0, preferentially from 1.0 to 11.0 and even better still from 2.5 to 10.0, or even from 3.5 to 8.0.

The composition according to the present invention also comprises one or more silicone compounds, preferably chosen from linear silicone block copolymers, amino silicones other than the linear silicone block copolymers, and mixtures thereof.

The silicone copolymer(s) that can be used in the composition according to the invention are linear block copolymers, that is to say non-crosslinked copolymers, obtained by chain extension and not by crosslinking.

The term "block copolymer" (or "sequential copolymer") denotes a polymer comprising at least two distinct blocks (sequences). Each block of the polymer results from one type of monomer or from several different types of monomer. This means that each block can be constituted of a homopolymer or a copolymer; this copolymer constituting the block can in turn be random or alternating.

The silicone copolymer that can be used in the composition according to the present invention preferably comprises at least two distinct silicone blocks (or sequences), each block resulting from the polymerization of at least one type of silicone monomer or of several types of silicone monomer, as described below.

It should also be noted that the copolymer is "linear", in other words the structure of the polymer is neither branched, nor star-shaped, nor grafted.

The linear silicone block copolymer(s) are advantageously provided in the form of particles in dispersion in an aqueous medium.

The aqueous dispersion of block copolymer particles is a silicone-in-water (Sil/W) emulsion, the oil globules of which are constituted of a silicone of high viscosity, such that these globules appear to form as "flexible particles".

The size of the linear silicone block copolymer particles can vary widely. Preferably, in the present patent application, the linear silicone block copolymer particles generally exhibit a number-average size of less than or equal to 2 microns and preferably of less than or equal to 1 micron.

The aqueous dispersions of linear silicone block copolymer particles that can be used in the composition according to the invention can be chosen in particular from those described in the document EP-A-874 017, the teaching of which is incorporated herein by reference. According to this document, it is possible in particular to obtain the linear silicone block copolymers constituting these particles by a chain-extension reaction, in the presence of a catalyst, starting from at least:

- (a) a polysiloxane (i) having at least one reactive group and preferably one or two reactive groups per molecule; and

- (b) an organosilicone compound (ii) which reacts with the polysiloxane (i) via a chain-extension reaction.

In particular, the polysiloxane (i) is chosen from the compounds of formula

(V):

R2 R1 R2

R2 - [O- Si ] -O- Si R2

R2 R1 R2

(V) in which Ri and R ₂ represent, independently of one another, a hydrocarbon-based group having from 1 to 20 carbon atoms and preferably from 1 to 10 carbon atoms, such as methyl, ethyl, propyl or butyl, or an aryl group, such as phenyl, or a reactive group, and n is an integer greater than 1, provided that there are on average between one and two reactive groups per polymer.

The term "reactive group" is intended to mean any group that is capable of reacting with the organosilicone compound (ii) to form a block copolymer. Mention may be made, as reactive groups, of hydrogen; aliphatically unsaturated groups, in particular vinyl, allyl or hexenyl groups; the hydroxyl group; alkoxy groups, such as methoxy, ethoxy or propoxy groups; alkoxyalkoxy groups; the acetoxy group; amino groups, and mixtures thereof. Preferably, more than 90% and better still more than 98% of the reactive groups are at the chain end, that is to say that the R ₂ radicals generally constitute more than 90% and even 98% of the reactive groups.

n may especially denote an integer ranging from 5 to 30, preferably from 10 to 30 and better still from 15 to 25.

The polysiloxanes of formula (V) are linear polymers, that is to say comprising few branches and generally less than 2 mol% of siloxane units. Moreover, the Ri and R ₂ groups can optionally be substituted with amino groups, epoxy groups, groups comprising sulfur, silicon or oxygen. Preferably, at least 80% of the Ri groups are alkyl groups and better still methyl groups.

Preferably, the reactive R ₂ group at the chain end is an aliphatically unsaturated group and in particular a vinyl group.

Advantageously, Ri represents a methyl group and R ₂ at the chain end represents a vinyl group.

Mention may in particular be made, as polysiloxanes (i), of dimethylvinylsiloxypolydimethylsiloxane, compound of formula (V) in which the Ri radicals are methyl radicals and the R ₂ radicals at the chain end are vinyl radicals, whereas the two other R ₂ radicals are methyl radicals.

The organosilicone compound (ii) can be chosen from the polysiloxanes of formula (V) or the compounds which act as chain extenders. If it is a compound of formula (V), the polysiloxane (i) will comprise a first reactive group and the organosilicone compound (ii) will comprise a second reactive group which will react with the first group. If it is a chain extender, it can be a silane, a siloxane (disiloxane or trisilo xane) or a silazane.

Preferably, the organosilicone compound (ii) is a liquid organohydrogenpolysiloxane of formula (VI):

in which n is an integer greater than 1 and preferably greater than 10, for example ranging from 2 to 100, preferably from 10 to 30 and better still from 15 to 25. According to a specific embodiment of the invention, n is equal to 20.

The silicone block copolymers used according to the invention are advantageously free of oxyalkylene groups, especially free of oxyethylene and/or oxypropylene groups.

The catalyst for the reaction between the polysiloxane and the organosilicone compound may be chosen from metals and especially from platinum, rhodium, tin, titanium, copper and lead. It is preferably platinum or rhodium.

The silicone copolymer particle dispersion that can be used in the composition according to the invention may especially be obtained, for example, by mixing (a) water, (b) at least one emulsifier, (c) the polysiloxane (i), (d) the organosilicone compound (ii) and (e) a catalyst. Preferably, one of the constituents (c), (d) or (e) is added last to the mixture, in order for the chain-extension reaction to begin only in the dispersion.

Mention may be made, as emulsifiers capable of being used in the preparation process described above in order to obtain the aqueous dispersion of particles, of non ionic or ionic (anionic, cationic or amphoteric) emulsifiers. They are preferably non ionic emulsifiers which can be chosen from polyalkylene glycol ethers of a fatty alcohol comprising from 8 to 30 carbon atoms and preferably from 10 to 22 carbon atoms; polyoxyalkylenated and in particular polyoxyethylenated sorbitan alkyl esters, where the alkyl radical comprises from 8 to 30 carbon atoms and preferably from 10 to 22 carbon atoms; polyoxyalkylenated and in particular polyoxyethylenated alkyl esters, where the alkyl radical comprises from 8 to 30 carbon atoms and preferably from 10 to 22 carbon atoms; polyethylene glycols; polypropylene glycols; diethylene glycols; and mixtures thereof. The amount of emulsifier(s) is generally from 1% to 30% by weight, relative to the total weight of the reaction mixture.

The emulsifier that can be used in order to obtain the aqueous dispersion of particles is preferably chosen from polyethylene glycol ethers of fatty alcohols and their mixtures, and in particular polyethylene glycol ethers of alcohols comprising 12 or 13 carbon atoms and from 2 to 100 oxyethylene units and preferably from 3 to 50 oxyethylene units, and mixtures thereof. Mention may be made, for example, of C12- C13 Pareth-3, C12-C13 Pareth-23 and mixtures thereof.

According to a specific embodiment of the invention, the dispersion of silicone copolymer particles is obtained from dimethylvinylsiloxypolydimethylsiloxane (or divinyl dimethicone) as compound (i) and from the compound of formula (VI) with preferably n = 20 as compound (ii), preferably in the presence of a catalyst of platinum type, and the dispersion of particles is preferably obtained in the presence of C12-C13 Pareth-3 and C12-C13 Pareth-23 as emulsifiers.

Preferably, the silicone copolymer present in the composition according to the invention is a divinyl dimethicone / dimethicone copolymer, and more preferentially a divinyl dimethicone / dimethicone copolymer in the form of an aqueous dispersion.

Use may in particular be made, as dispersion of silicone copolymer particles, of the product sold under the name HMW 2220 by Dow Coming (CTFA name: divinyl dimethicone/dimethicone copolymer/C 12-C 13 Pareth-3/Ci2-Ci ₃ Pareth-23), which is a 60% aqueous dispersion of divinyl dimethicone/dimethicone copolymer comprising C12-C13 Pareth-3 and C12-C13 Pareth-23, said dispersion comprising approximately 60% by weight of copolymer, 2.8% by weight of C12-C13 Pareth-23, 2% by weight of C12-C13 Pareth-3 and 0.31% by weight of preservatives, the remainder to 100% being water.

According to the invention, the term“amino silicone” denotes any silicone comprising at least one primary, secondary or tertiary amine or one quaternary ammonium and more particularly at least one primary amine.

The amino silicones other than the linear silicone block copolymers, that can be used in the composition according to the present invention, can be chosen from the silicones of formula (VII) below:

(R ¹ ) _a (T) _3-a -Si[OSi(T) ₂ ]n-[OSi(T) _b (R ¹ ) _2-b ]m-OSi(T) _3-a -(Rl) _a (VII) in which:

- T is a hydrogen atom, a phenyl radical, a hydroxyl (-OH) radical, a Ci-C ₈ alkyl radical, preferably a methyl radical, or a Ci-Cs alkoxy radical, and more preferentially a methyl,

- a denotes the number 0 or an integer from 1 to 3, and preferably 0,

- b denotes 0 or 1 , and preferably 1 ,

- m and n are numbers such that the sum (n + m) can vary in particular from 1 to 2000 and especially from 50 to 150, n denotes a number from 0 to 1999 and in particular from 49 to 149 and m denotes a number from 1 to 2000 and in particular from 1 to 10; and

- Ri is a monovalent radical of formula -C _q Th _q L in which q is a number from 2 to 8, it being possible for one or more hydrogen atoms to be substituted with a hydroxyl group, and L is an optionally quatemized amino group chosen from the groups:

-N(R ² )-CH ₂ -CH ₂ -N(R ^,2 )2 ;

-N(R ² ) ₂ ;

-N ⁺ (R ² ) ₃ Q ;

-N ⁺ (R ² ) (H) ₂ Q ;

-N ⁺ (R ² ) ₂ HQ- ;

-N(R ² )-CH ₂ -CH ₂ -N ⁺ (R ^,2 )(H) ₂ Q , in which R ² and R ² denote a hydrogen atom, a phenyl, a benzyl or a saturated monovalent hydrocarbon-based radical, for example a C1-C20 alkyl radical, and Q represents an anion, such as, for example, fluoride, chloride, bromide or iodide.

In particular, the amino silicones corresponding to the definition of the formula (VII) are chosen from the compounds corresponding to the formula below:

in which

- R, R' and R", which may be identical or different, denote a C1-C4 alkyl, preferably CH3, radical, a C1-C4 alkoxy, preferably methoxy, radical or an OH radical;

- A represents a linear or branched C3-C8 and preferably C3-C6 alkylene radical; and

- m and n are integers that are dependent on the molecular weight and of which the sum is between 1 and 2000.

According to a first possibility, R, R’ and R”, which may be identical or different, represent a C1-C4 alkyl, preferably methyl, radical or a hydroxyl radical, A represents a Ci-C ₈ , preferably C3-C4, alkylene radical, and m and n are such that the weight-average molecular weight of the compound is between 5000 and 500 000 approximately. The compounds of this type are named“amodimethicone” in the CTFA dictionary.

According to a second possibility, R, R’ and R”, which may be identical or different, represent a C1-C4 alkoxy or hydroxyl radical, at least one of the R or R” radicals is an alkoxy radical and A represents a C3 alkylene radical. The hydroxyl/alkoxy mole ratio is preferably between 0.2/1 and 0.4/1 and is advantageously equal to 0.3/1. Moreover, m and n are such that the weight-average molecular weight of the compound is between 2000 and 10 ⁶ . More particularly, n is between 0 and 999 and m is between 1 and 1000, the sum of n and m being between 1 and 1000.

In this category of compounds, mention may be made, inter alia, of the product Belsil ^® ADM 652 sold by Wacker.

According to a third possibility, R and R”, which may be different, represent a Ci-C ₄ alkoxy or hydroxyl radical, at least one of the R and R” radicals is an alkoxy radical, R’ represents a methyl radical and A represents a C ₃ alkylene radical. The hydroxyl/alkoxy mole ratio is preferably between 1/0.8 and 1/1.1 and is advantageously equal to 1/0.95. Moreover, m and n are such that the weight-average molecular weight of the compound is between 2000 and 200 000. More particularly, n is between 0 and 999 and m is between 1 and 1000, the sum of n and m being between 1 and 1000.

More particularly, mention may be made of the product Fluid WR ^® 1300 sold by Wacker.

The amino silicones that can be used in the composition in accordance with the invention preferably have the general formula (IX) below:

in which:

- A denotes a linear or branched C ₂ -Cs and preferably C ₂ -Cs, better still C ₃ , alkylene radical,

- Ri and R ₂ denote, independently of one another, a C ₁ -C ₄ alkyl, preferably methyl, radical or a C ₁ -C ₄ alkoxy, preferably methoxy, radical or a hydroxyl radical, and

- m and n are numbers such that the weight-average molecular weight (MW) is greater than or equal to 75 000. Preferably, the radicals Ri are identical and denote a hydroxyl radical.

Preferably, the viscosity of the amino silicone is greater than 25 000 mm¾, measured at 25°C.

More preferably, the viscosity of the amino silicone is between 30 000 and 200 000 mm ² /s at 25°C and more preferably still between 50 000 and 150 000 mm ² /s, measured at 25°C, and better still from 70 000 to 120 000 mm ² /s. The viscosities of the silicones are, for example, measured according to Standard ASTM 445, Appendix C.

Preferably, the cationic charge of the amino silicone is less than or equal to 0.5 meq/g, preferably ranging from 0.01 to 0.1 meq/g and better still from 0.03 to 0.06 meq/g.

Preferably, the amino silicone has a weight-average molecular weight ranging from 75 000 to 1 000 000 and more preferentially still ranging from 100 000 to 200 000.

The weight-average molecular weights of these amino silicones are measured by gel permeation chromatography (GPC) at ambient temperature, as polystyrene equivalent. The columns used are m styragel columns. The eluent is THF and the flow rate is 1 ml/min. 200 mΐ of a 0.5% by weight solution of silicone in THF are injected. Detection is performed by refractometry and UV-metry.

A particularly preferred amino silicone corresponding to this formula (IX) is, for example, the Xiameter MEM-8299 ^® Emulsion from the company Dow Coming.

It is noted that the molecular weight of these silicones is determined by gel permeation chromatography (ambient temperature, polystyrene standard, m styragem columns, eluent THF, flow rate of 1 mm/minute, 200 mΐ of a solution containing 0.5% by weight of silicone in THF are injected, and detection is performed by refractometry and UV-metry).

A product corresponding to the definition of formula (VII) is in particular the polymer known in the CTFA dictionary as “trimethylsilyl amodimethicone”, corresponding to formula (X) below:

in which n and m have the meanings given above in accordance with formula (VIII).

Such compounds are described, for example, in EP 95238; a compound of formula (IX) is sold, for example, under the name Q2-8220 by the company OSI.

Other amino silicones according to the invention are quatemized amino silicones, in particular:

(a) the compounds corresponding to formula (XI) below:

in which:

- R ³ represents a Ci-Cis alkyl radical, for example a methyl radical;

- R ⁴ represents a divalent hydrocarbon-based radical, in particular a Ci-Cis alkylene radical;

- Q is an anion, in particular chloride;

- r represents a mean statistical value from 2 to 20 and in particular from 2 to 8; and

- s represents a mean statistical value from 20 to 200 and in particular from 20 to 50.

Such compounds are described more particularly in patent US 4 185 087. A compound falling within this class is the product sold by the company Union Carbide under the name Ucar Silicone ALE 56.

(b) the quaternary ammonium silicones of formula (XII):

in which:

- R ₇ , which may be identical or different, represent a monovalent hydrocarbon-based radical containing from 1 to 8 carbon atoms and in particular a Ci-C ₈ alkyl radical, for example methyl;

- Re represents a divalent hydrocarbon-based radical, in particular a Ci-Cis alkylene radical or a divalent Ci-Cis, for example Ci-Cs, alkyleneoxy radical linked to the Si via an SiC bond;

- Rs, which may be identical or different, represent a hydrogen atom, a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a

Ci-Cis alkyl radical, a C ₂ -C ₁₈ alkenyl substituent or a -FU-NHCOR? radical;

- X is an anion such as a halide ion, especially chloride, or an organic acid salt (acetate, etc.); and

- r represents a mean statistical value from 2 to 200 and in particular from 5 to 100.

These silicones are described, for example, in patent application EP-A 0 530

974.

(c) the amino silicones of formula (XIII):

in which:

- Ri, R ₂ , R ₃ and R ₄ , which may be identical or different, denote a C ₁ -C ₄ alkyl radical or a phenyl group,

- R ₅ denotes a C ₁ -C ₄ alkyl radical or a hydroxyl group,

- n is an integer ranging from 1 to 5,

- m is an integer ranging from 1 to 5,

and in which x is selected such that the amine number is between 0.01 and 1 meq/g.

Preferably, the amino silicones of the invention are non-quatemized, that is to say that they do not comprise a nitrogen atom having a permanent charge (quaternary ammonium group).

Preferably, the amino silicones of the invention are not block polymers.

The silicones which are particularly preferred in accordance with the invention are the polysiloxanes comprising amino groups, such as amodimethicones or trimethylsilylamodimethicones, and in particular the compounds of formulae (VIII), (IX) and (X).

When the amino silicones of the invention are used, a particularly advantageous embodiment is their joint use with cationic and/or non- ionic surfactants.

Use may be made, by way of example, of the product sold under the name Cationic Emulsion DC 929 by Dow Coming, which comprises, in addition to amodimethicone, a cationic surfactant comprising a mixture of products corresponding to the formula:

in which R ⁵ denotes C14-C22 alkenyl and/or alkyl radicals derived from tallow fatty acids and known under the CTFA name tallowtrimonium chloride, in combination with a non-ionic surfactant having formula:

C ₉ Hi ₉ -C ₆ H ₄ -(OC ₂ H ₄ )io-OH, known under the CTFA name Nonoxynol 10. Use may also be made, for example, of the products sold under the names Xiameter MEM-0939 Emulsion and Xiameter MEM-0949 Emulsion by Dow Coming, which comprise, in addition to amodimethicone, a cationic surfactant which is trimethylcetylammonium chloride and a non-ionic surfactant of formula: C ₁₃ H ₂₇ - (OC ₂ H ₄ )i ₂ -OH, known under the CTFA name Tridecethl2. Mention may also be made of the product sold under the reference Belsil ADM 6060 by Wacker, which comprises, in addition to amodimethicone, a non-ionic surfactant Trideceth-lO.

In particular, when these amino silicones are used, a particularly advantageous embodiment is their use in the form of an oil-in-water emulsion.

The oil- in- water emulsion preferably comprises one or more surfactants. The surfactants may be of any nature, but are preferably cationic and/or non-ionic.

The silicone particles in the emulsion have a volume-average diameter (D[4.3]) generally ranging from 10 nm to 1000 nm, preferably from 50 nm to 800 nm, more particularly from 100 nm to 600 nm and even more particularly from 200 nm to 500 nm. These particle sizes may be determined especially using a laser granulometer, for example the Malvern Mastersizer 2000 granulometer.

According to the invention, all the silicones can also be used in the form of emulsions or micro emulsions.

Preferably, the silicone compound(s) are chosen from the linear silicone block copolymers.

The total amount of the silicone compound(s) preferably ranges from 0.01% to 20% by weight, more preferentially from 0.1% to 15% by weight, even better still from 0.5% to 10% by weight, and even more particularly from 0.7% to 5% by weight, relative to the total weight of the composition.

The weight ratio of the total amount of polyurethane (active material) to the total amount of the silicone compound(s) present in the composition according to the invention preferably ranges from 0.1 to 5, more preferentially from 0.2 to 3, even better still from 0.5 to 3, even more particularly from 0.6 to 2.5.

The composition according to the present invention also comprises one or more clays.

Clays are well-known products which are described, for example, in the publication M in era l ogie des argiles [Mineralogy of Clays], S. Caillere, S. Henin and M. Rautureau, 2nd Edition, 1982, Masson.

Clays are silicates including a cation which can be chosen from calcium, magnesium, aluminium, sodium, potassium or lithium cations, and mixtures thereof.

As examples of clays that can be used according to the present invention, mention may be made of clays chosen from the smectite family such as montmorillonites, hectorites, bentonites, beidellites or saponites; the family of vermiculites, stevensite and chlorites; and mixtures thereof.

These clays may be of natural or synthetic origin. Clays that are cosmetically compatible and acceptable with keratin materials are preferably used.

Mention may be made, as clay which can be used according to the invention, of synthetic hectorites (also known as laponites), such as the products sold by Laporte under the names Laponite XLG, Laponite RD and Laponite RDS (these products are sodium magnesium silicates and in particular lithium magnesium sodium silicates); bentonites, such as the product sold under the name Bentone HC by Rheox; magnesium aluminium silicates, in particular hydrated, such as the product sold by Vanderbilt Company under the name Veegum Ultra, or calcium silicates and in particular that in synthetic form sold by the company under the name Micro-Cel C.

The clay(s) are preferably chosen from smectites, such as montmorillonite, bentonite, hectorite, attapulgite or sepiolite, and mixtures thereof. More particularly, the clay is a bentonite or a hectorite.

These clays may be modified with a chemical compound chosen from quaternary amines, tertiary amines, amine acetates, imidazolines, amine soaps, fatty sulfates, alkylaryl sulfonates and amine oxides, and mixtures thereof.

Mention may be made, as organophilic clays, of quatemium-l8 bentonites, such as those sold under the names Bentone 3, Bentone 38 and Bentone 38V by Rheox, Tixogel VP by United Catalyst and Claytone 34, Claytone 40 and Claytone XL by Southern Clay; stearalkonium bentonites, such as those sold under the names Bentone 27 by Rheox, Tixogel LG by United Catalyst and Claytone AF and Claytone APA by Southern Clay; and quatemium-l8/benzalkonium bentonites, such as those sold under the names Claytone HT and Claytone PS by Southern Clay.

The total amount of the clay(s), present in the composition according to the invention, preferably ranges from 0.01% to 10% by weight, more preferentially from 0.05% to 5% by weight, and better still from 0.1% to 1% by weight, relative to the total weight of the composition.

The weight ratio of the total amount of polyurethane (active material) to the total amount of the clay(s), present in the composition according to the invention, preferably ranges from 0.5 to 15, and more preferentially from 0.1 to 12.

The composition according to the present invention may optionally also comprise one or more colourant(s). The colorants can be chosen from pigments, in particular pearlescent agents. Preferably, the colorant is a pigment, in particular a pearlescent agent.

The term“pigment” is intended to mean white or coloured particles of any shape which are insoluble in the composition in which they are present.

The pigments that may be used are especially chosen from the organic and/or mineral pigments known in the art, especially those described in Kirk-Othmer’s Encyclopedia of Chemical Technology and in Ullmann’s Encyclopedia of Industrial Chemistry.

They can be natural, of natural origin, or not.

These pigments may be in pigment powder or paste form. They may be coated or uncoated.

The pigments may be chosen, for example, from mineral pigments, organic pigments, lakes, pigments with special effects, such as pearlescent agents or glitter flakes, and mixtures thereof.

The pigment may be a mineral pigment. The term“mineral pigment” is intended to mean any pigment that satisfies the definition in Ullmann’s encyclopaedia in the chapter on inorganic pigments. Mention may be made, among mineral pigments of use in the present invention, of ochres, such as red ochre (clay (in particular kaolinite) and iron hydroxide (for example haematite)), brown ochre (clay (in particular kaolinite) and limonite) or yellow ochre (clay (in particular kaolinite) and goethite); titanium dioxide, optionally surface-treated; zirconium or cerium oxides; zinc, (black, yellow or red) iron or chromium oxides; manganese violet, ultramarine blue, chromium hydrate and ferric blue; or metal powders, such as aluminium powder or copper powder.

Mention may also be made of alkaline earth metal carbonates (such as calcium carbonate or magnesium carbonate), silicon dioxide, quartz and any other compound used as inert filler in cosmetic compositions, provided that these compounds contribute colour or whiteness to the composition under the conditions under which they are employed.

The pigment may be an organic pigment. The term“organic pigment” is intended to mean any pigment that satisfies the definition in Ullmann’s encyclopaedia in the chapter on organic pigments.

The organic pigment may especially be chosen from nitroso, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, triphenylmethane, fluorane, phthalocyanine, metal-complex, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.

Use may also be made of any mineral or organic compound that is insoluble in the composition and standard in the cosmetics field, provided that these compounds give the composition colour or whiteness under the conditions under which they are used, for example guanine, which, according to the refractive index of the composition, is a pigment.

In particular, the white or coloured organic pigments can be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments codified in the Color Index under the references Cl 42090, 69800, 69825, 73000, 74100 and 74160, the yellow pigments codified in the Color Index under the references Cl 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000 and 47005, the green pigments codified in the Color Index under the references Cl 61565, 61570 and 74260, the orange pigments codified in the Color Index under the references

Cl 11725, 15510, 45370 and 71105, the red pigments codified in the Color Index under the references Cl 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915 and 75470, and the pigments obtained by oxidative polymerization of indole or phenol derivatives, as are described in Patent FR 2 679 771.

Mention may also be made, as example, of pigment pastes formed of organic pigment, such as the products sold by Hoechst under the names:

- Cosmenyl Y ellow IOG : Pigment Y ellow 3 (Cl 11710);

- Cosmenyl Yellow G: Pigment Yellow 1 (Cl 11680);

- Cosmenyl Orange GR: Pigment Orange 43 (Cl 71105);

- Cosmenyl Red R: Pigment Red 4 (Cl 12085);

- Carmin Cosmenyl FB: Pigment Red 5 (Cl 12490);

- Cosmenyl Violet RL: Pigment Violet 23 (Cl 51319);

- Cosmenyl Blue A2R: Pigment Blue 15.1 (Cl 74160);

- Cosmenyl Green GG: Pigment Green 7 (Cl 74260);

- Cosmenyl Black R: Pigment Black 7 (Cl 77266).

The pigments in accordance with the invention may also be in the form of composite pigments, as described in patent EP 1 184 426. These composite pigments may be composed especially of particles comprising a mineral core, at least one binder, which provides for the attachment of the organic pigments to the core, and at least one organic pigment which at least partially covers the core.

The organic pigment may also be a lake. The term“lake” is intended to mean dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use.

The inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate, calcium aluminium borosilicate and aluminium.

Mention may be made, among the dyes, of carminic acid. Mention may also be made of the dyes known under the following names: D&C Red 21 (Cl 45 380), D&C Orange 5 (Cl 45 370), D&C Red 27 (Cl 45 410), D&C Orange 10 (Cl 45 425), D&C Red 3 (Cl 45 430), D&C Red 4 (Cl 15 510), D&C Red 33 (Cl 17 200), D&C Yellow 5 (Cl 19 140), D&C Yellow 6 (Cl 15 985), D&C Green (Cl 61 570), D&C Yellow 1 O (Cl 77 002), D&C Green 3 (Cl 42 053), D&C Blue 1 (Cl 42 090).

Mention may be made, as examples of lakes, of the product known under the following name: D&C Red 7 (Cl 15 850:1).

The pigment may also be a pigment with special effects. The term“special effect pigments” is intended to mean pigments which generally create a coloured appearance (characterized by a certain shade, a certain vividness and a certain brightness) which is not uniform and which changes as a function of the conditions of observation (light, temperature, angles of observation, etc.). They thereby contrast with coloured pigments, which provide a conventional opaque, semi-transparent or transparent, uniform colour.

There exist several types of special effect pigments: those with a low refractive index, such as fluorescent, photochromic or thermochromic pigments, and those with a higher refractive index, such as pearlescent agents, interferential pigments or glitter.

Mention may be made, as examples of special effect pigments, of pearlescent pigments, such as mica covered with titanium or with bismuth oxychloride, coloured pearlescent pigments, such as mica covered with titanium and with iron oxides, mica covered with iron oxide, mica covered with titanium and in particular with ferric blue or chromium oxide or mica covered with titanium and with an organic pigment as defined above, and pearlescent pigments based on bismuth oxychloride. Mention may be made, as pearlescent pigments, of the following pearlescent agents: Cellini sold by Engelhard (mica-TiCh-lake), Prestige sold by Eckart (mica-TiCk), Prestige Bronze sold by Eckart (mica-Fe20 ₃ ) or Colorona sold by Merck (mica-Ti02-Fe20 ₃ ).

Mention may also be made of the gold-coloured pearlescent agents sold especially by the company Engelhard under the name Brilliant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); the bronze pearlescent agents sold especially by the company Merck under the name Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by the company Engelhard under the name Super bronze (Cloisonne); the orange pearlescent agents sold especially by the company Engelhard under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company Merck under the name Passion orange (Colorona) and Matte orange (17449) (Microna); the brown pearlescent agents sold especially by the company Engelhard under the name Nu- antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); the pearlescent agents with a coppery glint sold especially by the company Engelhard under the name Copper 340A (Timica); the pearlescent agents with a red glint sold especially by the company Merck under the name Sienna fine (17386) (Colorona); the pearlescent agents with a yellow glint sold especially by the company Engelhard under the name Yellow (4502) (Chromalite); the red pearlescent agents with a gold glint sold especially by the company Engelhard under the name Sunstone GO 12 (Gemtone); the pink pearlescent agents sold especially by the company Engelhard under the name Tan opale G005 (Gemtone); the black pearlescent agents with a gold glint sold especially by the company Engelhard under the name Nu antique bronze 240 AB (Timica), the blue pearlescent agents sold especially by the company Merck under the name Matte blue (17433) (Microna), the white pearlescent agents with a silvery glint sold especially by the company Merck under the name Xirona Silver, and the golden-green pink-orange pearlescent agents sold especially by the company Merck under the name Indian summer (Xirona), and mixtures thereof.

Still as examples of pearlescent agents, mention may also be made of particles comprising a borosilicate substrate coated with titanium oxide.

Particles comprising a glass substrate coated with titanium oxide are sold in particular under the name Metashine MC1080RY by the company Toyal.

Finally, examples of pearlescent agents that may also be mentioned include polyethylene terephthalate flakes, especially those sold by the company Meadowbrook Inventions under the name Silver 1P 0.004X0.004 (silver flakes). It is also possible to envisage multilayer pigments based on synthetic substrates, such as alumina, silica, calcium sodium borosilicate, calcium aluminium borosilicate and aluminium.

The special effect pigments can also be chosen from reflective particles, that is to say in particular particles having a size, a structure, in particular a thickness of the layer or layers of which it is composed and their physical and chemical nature, and a surface condition which allow them to reflect incident light. This reflection may, if appropriate, have an intensity sufficient to create, at the surface of the composition or mixture, when the latter is applied to the support to be made up, highlight points visible to the naked eye, that is to say more luminous points which contrast with their surroundings by appearing to sparkle.

The reflective particles can be selected so as not to detrimentally affect, to a significant extent, the colouring effect generated by the colouring agents which are combined with them and more particularly so as to optimize this effect in terms of colour rendition. They may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or coppery colour or glint.

These particles may have varied forms and may especially be in platelet or globular form, in particular in spherical form.

Irrespective of their form, the reflective particles may or may not have a multilayer structure, and, in the case of a multilayer structure, may have, for example, at least one layer of uniform thickness, especially of a reflective material.

When the reflective particles do not have a multilayer structure, they may be composed, for example, of metal oxides, especially titanium or iron oxides obtained synthetically.

When the reflective particles have a multilayer structure, they may comprise, for example, a natural or synthetic substrate, especially a synthetic substrate at least partially coated with at least one layer of a reflective material, especially of at least one metal or metallic material. The substrate may be made of one or more organic and/or mineral materials.

More particularly, it may be chosen from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, especially aluminosilicates and borosilicates, and synthetic mica, and mixtures thereof, this list not being limiting.

The reflective material may comprise a layer of metal or of a metallic material. Reflective particles are described especially in JP-A-09188830, JP-A- 10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

Again as an example of reflective particles comprising a mineral substrate coated with a layer of metal, mention may also be made of particles comprising a silver-coated borosilicate substrate.

Particles with a silver-coated glass substrate, in the form of platelets, are sold under the name Microglass Metashine REFSX 2025 PS by the company Toyal. Particles with a glass substrate coated with nickel/chromium/molybdenum alloy are sold under the name Crystal Star GF 550 and GF 2525 by this same company.

Use may also be made of particles comprising a metal substrate, such as silver, aluminium, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze or titanium, said substrate being coated with at least one layer of at least one metal oxide, such as titanium oxide, aluminium oxide, iron oxide, cerium oxide, chromium oxide, silicon oxides and mixtures thereof.

Examples that may be mentioned include aluminium powder, bronze powder or copper powder coated with S1O2 sold under the name Visionaire by the company Eckart.

Mention may also be made of pigments with an interference effect which are not attached to a substrate, such as liquid crystals (Helicones HC from Wacker) or interference holographic glitter flakes (Geometric Pigments or Spectra frx from Spectratek). Pigments with special effects also comprise fluorescent pigments, whether these are substances that are fluorescent in daylight or that produce an ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, sold, for example, by the company Quantum Dots Corporation.

Quantum dots are luminescent semiconductive nanoparticles capable of emitting, under light excitation, irradiation with a wavelength of between 400 nm and 700 nm. These nanoparticles are known from the literature. In particular, they may be synthesized according to the processes described, for example, in US 6 225 198 or US 5 990 479, in the publications cited therein and also in the following publications:

Dabboussi B.O. et ah, “(CdSe)ZnS core-shell quantum dots: synthesis and characterization of a size series of highly luminescent nanocrystallites”, Journal of Physical Chemistry B, vol. 101, 1997, pp. 9463-9475, and Peng, Xiaogang et al, “Epitaxial growth of highly luminescent CdSe/CdS core/shell nanocrystals with photostability and electronic accessibility”, Journal of the American Chemical Society, vol. 119, No. 30, pages 7019-7029.

The variety of pigments that may be used in the present invention makes it possible to obtain a wide range of colours, and also particular optical effects such as metallic effects or interference effects.

The size of the pigment used in the cosmetic composition according to the present invention is generally between 10 nm and 200 pm, preferably between 20 nm and 80 pm and more preferably between 30 nm and 50 pm.

The pigments may be dispersed in the product by means of a dispersant. The dispersant serves to protect the dispersed particles against agglomeration or flocculation. This dispersant may be a surfactant, an oligomer, a polymer or a mixture of several thereof, bearing one or more functionalities with strong affinity for the surface of the particles to be dispersed. In particular, they may become physically or chemically attached to the surface of the pigments. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, l2-hydroxystearic acid esters and C _H to C20 fatty acid esters of polyols such as glycerol or diglycerol are used, such as poly(l2-hydroxystearic acid) stearate with a molecular weight of approximately 750 g/mol, such as the product sold under the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel, or poly-hydroxystearic acid such as the product sold under the reference Arlacel P 100 by the company Uniqema, and mixtures thereof.

As other dispersants that may be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of poly condensed fatty acids, for instance Solsperse 17 000 sold by the company Avecia, and polydimethylsiloxane/oxypropylene mixtures such as those sold by the company Dow Coming under the references DC2-5185 and DC2-5225 C.

The pigments used in the cosmetic composition according to the invention may be surface-treated with an organic agent.

Thus, the pigments that have been surface-treated beforehand, which are useful in the context of the invention, are pigments that have totally or partially undergone a surface treatment of chemical, electronic, electrochemical, mechanochemical or mechanical nature, with an organic agent such as those described especially in Cosmetics and Toiletries, February 1990, Vol. 105, pages 53-64, before being dispersed in the composition in accordance with the invention. These organic agents may be chosen, for example, from waxes, for example camauba wax and beeswax; fatty acids, fatty alcohols and derivatives thereof, such as stearic acid, hydroxy stearic acid, stearyl alcohol, hydroxystearyl alcohol and lauric acid and derivatives thereof; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminium salts of fatty acids, for example aluminium stearate or laurate; metal alkoxides; polyethylene; (meth)acrylic polymers, for example polymethyl methacrylates; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds, for example silicones, polydimethylsiloxanes; organofluorine compounds, for example perfluoroalkyl ethers; fluorosilicone compounds.

The surface-treated pigments that are useful in the cosmetic composition according to the invention may also have been treated with a mixture of these compounds and/or may have undergone several surface treatments.

The surface-treated pigments that are useful in the context of the present invention may be prepared according to surface-treatment techniques that are well known to those skilled in the art, or may be commercially available in the required form.

Preferably, the surface-treated pigments are coated with an organic layer. The organic agent with which the pigments are treated may be deposited on the pigments by evaporation of solvent, chemical reaction between the molecules of the surface agent or creation of a covalent bond between the surface agent and the pigments.

The surface treatment may thus be performed, for example, by chemical reaction of a surface agent with the surface of the pigments and creation of a covalent bond between the surface agent and the pigments or the fillers. This method is notably described in the patent US 4,578,266.

An organic agent covalently bonded to the pigments will preferably be used.

The agent for the surface treatment may represent from 0.1% to 50% by weight, preferably from 0.5% to 30% by weight and even more preferentially from 1% to 10% by weight relative to the total weight of the surface-treated pigment.

Preferably, the surface treatments of the pigments are chosen from the following treatments:

- a PEG-silicone treatment, for instance the AQ surface treatment sold by LCW; - a methicone treatment, for instance the SI surface treatment sold by LCW;

- a dimethicone treatment, for instance the Co vasil 3.05 surface treatment sold by LCW;

- a dimethicone/trimethyl siloxysilicate treatment, for instance the Covasil 4.05 surface treatment sold by LCW;

- a magnesium myristate treatment, for instance the MM surface treatment sold by LCW;

- an aluminium dimyristate treatment, such as the MI surface treatment sold by Miyoshi;

- a perfluoropolymethylisopropyl ether treatment, for instance the FHC surface treatment sold by LCW;

- an isostearyl sebacate treatment, for instance the HS surface treatment sold by Miyoshi;

- a perfluoroalkyl phosphate treatment, for instance the PF surface treatment sold by Daito;

- an acrylate/dimethicone copolymer and perfluoroalkyl phosphate treatment, for instance the FSA surface treatment sold by Daito;

- a polymethylhydrogenosiloxane/perfluoroalkyl phosphate treatment, for instance the FS01 surface treatment sold by Daito;

- an acrylate/dimethicone copolymer treatment, for instance the ASC surface treatment sold by Daito;

- an isopropyl titanium triisostearate treatment, for instance the ITT surface treatment sold by Daito;

- an acrylate copolymer treatment, for instance the APD surface treatment sold by Daito;

- a perfluoroalkyl phosphate/isopropyl titanium triisostearate treatment, for instance the PF + ITT surface treatment sold by Daito.

Preferably, the pigment is chosen from mineral or mixed mineral-organic pigments.

Preferably, the pigment(s) are chosen from pearlescent agents, and more preferentially from white pearlescent pigments such as mica coated with titanium or with bismuth oxychloride, coloured pearlescent pigments such as titanium mica with iron oxides, titanium mica with ferric blue or with chromium oxide, titanium mica with an organic pigment, pearlescent pigments based on bismuth oxychloride, and mixtures thereof.

The total amount of the colorant(s), present in the composition according to the invention, preferably ranges from 0.005% to 5% by weight, more preferentially from 0.01% to 4% by weight, even better still from 0.02% to 2.5% by weight, and even more preferentially from 0.03% to 1% by weight, relative to the total weight of the composition.

The composition according to the present invention is aqueous. It preferably comprises water in a content of from 70% to 99% by weight, more preferentially from 75% to 98% by weight, better still from 80% to 97% by weight, and even more particularly from 85% to 95% by weight, relative to the total weight of the composition.

In addition to water, it may optionally comprise one or more organic solvents, or mixtures thereof.

Examples of organic solvents that may be mentioned include linear or branched C ₂ to C ₄ alkanols, such as ethanol and isopropanol; glycerol; polyols and polyol ethers, for instance 2-butoxyethanol, propylene glycol, hexylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and monoethyl ether, and also aromatic alcohols or ethers, such as benzyl alcohol or phenoxy ethanol, and mixtures thereof.

The composition according to the present invention may also optionally comprise one or more additives, different from the compounds of the invention and among which mention may be made of non-ionic, anionic, amphoteric or zwitterionic surfactants, and mixtures thereof, cationic, anionic, non-ionic or amphoteric polymers, or mixtures thereof, antidandruff agents, anti-seborrhoea agents, vitamins and provitamins including panthenol, sunscreens, sequestrants, plasticizers, solubilizers, acidifying agents, mineral or organic thickeners, especially polymeric thickeners, antioxidants, hydroxy acids, fragrances, preservatives and ceramides.

Of course, those skilled in the art will take care to select this or these optional additional compound(s) such that the advantageous properties intrinsically associated with the composition in accordance with the invention are not, or are not substantially, adversely affected by the envisaged addition(s).

The above additives may generally be present in an amount, for each of them, of between 0 and 20% by weight relative to the total weight of the composition. Treatment process

Another subject of the present invention is a process for treating keratin materials, especially keratin fibres, in particular human keratin fibres such as the hair, comprising a step of applying, to said keratin materials, a composition as defined above, optionally followed by a step of rinsing said keratin materials.

The composition according to the invention may be applied to dry or wet keratin materials, and in particular to wet keratin materials.

Preferably, the composition according to the invention is applied to wet keratin materials, preferably after applying a washing composition, for example of shampoo type. Said washing composition is advantageously rinsed off before applying the composition according to the invention.

Thus, the step of applying the composition according to the invention can be preceded by a step of washing the keratin materials, itself optionally followed by a rinsing step.

According to a first embodiment of the invention, the composition according to the invention is not rinsed off after application. In this embodiment, the process according to the invention may comprise a step of drying the keratin materials, just after the step of applying the composition according to the invention.

According to another embodiment of the invention, the composition according to the invention is rinsed off after application. In this embodiment, the process according to the invention can thus comprise, after the step of applying the composition according to the invention, a rinsing step, optionally followed by a step of drying the keratin materials.

In one variant of the invention, the process can also comprise a step of applying a conditioning composition (also called care composition), comprising for example at least one conditioning agent chosen from cationic surfactants, fatty alcohols, silicones, optionally amino silicones, cationic polymers and amphoteric polymers. According to this variant, the conditioning composition is preferably applied after the composition according to the invention as described above, and more preferentially after the composition according to the invention without intermediate rinsing. More preferably, the applying of the conditioning composition is followed by rinsing, and optionally by drying.

At the end of the process, the keratin materials may optionally be dried in the presence or absence of a heat source. Finally, the present invention relates to the use of a composition as described above, for the cosmetic treatment of, and in particular for caring for and/or conditioning, keratin materials, especially keratin fibres, in particular human keratin fibres such as the hair.

The examples that follow serve to illustrate the invention without, however, being limiting in nature.

EXAMPLES

Example 1 : cosmetic evaluations

2.1. Compositions tested

Comparative compositions (Bl) to (B6) and composition (C) according to the invention were prepared using the ingredients of which the contents, expressed as percentage by weight of active material, are mentioned in the table below.

2.2. Protocol

Each of the compositions thus obtained was applied to locks of sensitized wet hair, in a proportion of 0.37 g of composition per gram of hair.

After a leave-on time of 5 minutes, the locks were rinsed, wrung out and then disentangled with a comb.

The disentangling was evaluated by the ease with which the comb passed through the hair. For each composition, a score ranging from 0 to 5, in steps of 0.5, was assigned; the score 0 corresponding to an evaluation of“very poor”, that is to say no disentangling possible, and the score 5 corresponding to an evaluation of “excellent”, that is to say no resistance to disentangling.

The quality of the polymer deposit was evaluated by adding 0.03 g% of mica iron oxide pearlescent agent to each of the compositions mentioned above.

After treatment of the locks according to the protocol described above, the residual colouration on each of the locks is visually evaluated: the more visible the colouration of the locks, the greater the polymer deposit.

2.3. Results

The results obtained are given in the following table.

The results obtained above show that only composition (C) of the invention makes it possible to obtain both a very good level of disentangling and also a coating polymer deposit on the hair, demonstrated by a residual colour effect (the presence of pearlescent agent).

Although the cationic surfactant alone, composition (B2), makes it possible to obtain a good level of disentangling, its combination with the polyurethane, composition (B3), is not sufficient to achieve a satisfactory level of disentangling, in the absence of silicone and of clay.

Example 2 3.1. Composition tested

Composition (D) according to the invention was prepared using the ingredients of which the contents, expressed as percentage by weight of active material, are mentioned in the table below.

^ HMW 2220 non-ionic emulsion - Dow Corning

3.2. Procedure

Composition (D) thus obtained was compared to a conditioner composition (comprising in particular 1 g% of aminopropyltriethoxysilane, 1.6 g% of behentrimonium chloride and 4.2 g% of solid fatty substances) according to the following protocol. The two compositions were each applied by half head on 6 models with medium-sensitized fine hair, in a proportion of 6 g of composition per half head.

After a leave-on time of 5 min, the hair was rinsed and dried. The following conditioning properties: disentangling, smoothness, suppleness and coating were then evaluated.

The disentangling was evaluated using a comb, whereas the other properties were scored on feel. The smoothness was also evaluated visually.

For each composition, an expert assigned a score ranging from 0 to 5, in steps of 0.5; the score 0 corresponding to an evaluation of "very poor" concerning the criterion, and the score 5 corresponding to an evaluation of "excellent” concerning the criterion. 3.3. Results

The results of the cosmetic properties obtained are given in the following table (average value for 6 models).

The results obtained above show that the composition of the invention makes it possible to obtain cosmetic properties equivalent to those obtained with a conventional conditioner, without employing the usual ingredients of a conditioner.