BR112019020045B1 - COMPOSITION, PROCESS FOR COSMETIC TREATMENT AND USE OF THE COMPOSITION - Google Patents

Abstract

The present invention relates to a composition for dyeing keratin fibers, comprising at least (i) one or more copolymers derived from the polymerization of at least one monomer of crotonic acid or derivative of crotonic acid and at least two ester monomers different vinylic materials, (ii) one or more thickening polymers bearing (meth)acrylic acid unit(s), and (iii) one or more pigments. The invention also relates to a dyeing process in which said composition is applied to keratin fibres, the operation being optionally followed by drying. The composition makes it possible to obtain temporary dyeing with the advantage of forming a transfer-resistant deposit, leaving the treated fibers individualized, with a better cosmetic feel.

Description

[001] The present invention relates to a composition for dyeing keratin fibers, comprising at least one copolymer derived from the polymerization of at least one monomer of crotonic acid or derivative of crotonic acid and at least one monomer of vinyl ester, at least one thickening polymer carrying (meth)acrylic acid unit(s), and at least one pigment, and also to a dyeing process using said composition.

[002] In the field of dyeing keratin fibers, particularly human keratin fibers, it is already known practice to dye keratin fibers by various techniques using direct dyes or pigments for non-permanent dyeing, or dye precursors for permanent dyeing.

[003] There are essentially three types of hair dyeing processes: a) “permanent” dyeing, which has the function of promoting a substantial modification of the natural color and uses oxidation dyes that penetrate the hair fiber and form the dye through an oxidative condensation process; b) non-permanent, semi-permanent or direct dyeing that does not use the oxidative condensation process and that withstands four or five washes with shampoo; consists of dyeing the keratin fibers with dye compositions containing direct dyes. These dyes are colored and coloring molecules that have an affinity for keratin fibers; c) temporary dyeing, which promotes a modification of the hair's natural color that remains from one shampoo wash to the next and serves to intensify or correct a tone that has already been obtained. It can also be compared to a “makeup” process.

[004] For the latter type of dyeing, it is known practice to use colored polymers formed by grafting one or more dyes of azo, triphenylmethane, azine, indoamine or anthraquinone nature onto a polymeric chain. These colored polymers are not entirely satisfactory, especially in terms of the homogeneity of the obtained coloring and its resistance, not to mention the problems associated with its manufacture and especially with its reproducibility.

[005] Another dyeing method is to use pigments. Specifically, the use of pigment on the surface of keratin fibers generally makes it possible to achieve visible coloration on dark hair, as the surface pigment masks the fiber's natural color. The use of pigment for dyeing keratin fibers is described, for example, in patent application FR 2 741 530; when applied to keratin fibers, these compositions have the disadvantage of transferring, that is to say, of being at least partially deposited, leaving marks, on certain supports with which they may come into contact and particularly on clothing or on the skin. This results in mediocre persistence of the applied film, making it necessary to regularly repeat the application of the composition. Furthermore, the appearance of these unacceptable marks may discourage certain people from using this type of dye.

[006] Compositions for temporary hair dyeing and/or makeup may also result in a hair feeling that is non-cosmetic and/or unnatural; hair dyed in this way may, in particular, lack softness and/or manageability and/or individualization.

[007] There is therefore still a need to obtain compositions for the temporary dyeing of keratin materials, especially hair, which have the advantage of forming a transfer-resistant deposit, which, in particular, does not remain deposited, at least partially, on supports with which the compositions are brought into contact, such as the skin (in particular the hands and face) and/or clothing.

[008] The invention is directed at providing compositions that do not degrade keratin fibers, that do not affect their cosmetic properties, such as softness and malleability, that keep the hair strands clearly individualized and do not feel rough, while having , transfer resistance properties. Furthermore, the compositions according to the invention have good operational qualities, such as ease of application and location without running.

[009] This object is achieved with the present invention, an object of which is a composition for dyeing keratin fibers, especially human keratin fibers, such as hair, comprising at least one copolymer derived from the polymerization of at least one monomer of crotonic acid or crotonic acid derivative and at least two different vinyl ester monomers, at least one thickening polymer bearing (meth)acrylic acid unit(s) and at least one pigment.

[010] In addition, the presence of pigments or nacres within an aqueous gel can result in product stability problems; the reason for this is that these pigments and/or nacres are solid particles that are not dissolved in the final composition. As a result, they can interfere with the stability of said composition.

[011] The applicant has unexpectedly discovered that a keratin fiber dyeing composition comprising at least one copolymer derived from the polymerization of at least one crotonic acid monomer or crotonic acid derivative and at least two different vinyl ester monomers, at least at least one thickening polymer bearing (meth)acrylic acid unit(s), makes it possible to produce aqueous gels comprising pigments and/or nacres, said gels being additionally homogeneous and stable and capable of being applied easily with fingers or with any other support.

[012] An object of the invention is also a process for dyeing keratin fibers, especially human keratin fibers, such as hair, comprising applying to said fibers a composition as defined above.

[013] The term “at least one” means “one or more”.

[014] The term “comprising one” means “comprising at least one”, unless otherwise specified.

[015] An object of the present invention is therefore a composition for dyeing keratin fibers, especially human keratin fibers such as hair, comprising (i) one or more copolymers derived from the polymerization of at least one acidic monomer crotonic or crotonic acid derivative and at least two different vinyl ester monomers, (ii) one or more thickening polymers bearing (meth)acrylic acid unit(s) and (iii) one or more pigments.

DYE COMPOSITION

[016] The composition according to the invention is preferably a cosmetic composition for dyeing keratin fibers, in particular human keratin fibers, such as hair.

[017] It was observed that by using the dye composition according to the invention, it is possible to improve the individualization of the hair strands and also reduce transfer. The fibers also have a smoother feel, are softer and more pliable, and untangle more easily. Furthermore, this composition makes it possible to obtain a uniform and glossy gel with adequate viscosity for easy and localized application.

CROTONIC ACID COPOLYMERS

[018] The composition according to the invention comprises at least one copolymer derived from the polymerization of at least one monomer of crotonic acid or crotonic acid derivative and at least two different vinyl ester monomers.

[019] The copolymer according to the invention is selected from copolymers derived from the polymerization of at least one crotonic acid monomer and at least two different vinyl ester monomers.

[020] The term "crotonic acid derivative" preferably means a crotonic acid ester or a crotonic acid amide.

[021] The term "crotonic acid derivative" preferably means an ester or amide of crotonic acid, in particular: - (i) esters of crotonic acid of the formula CH3CH=CHCOOR'1 with R'1 representing a chain based on carbon and especially hydrocarbon-based (alkyl), linear, branched or cyclic, saturated or unsaturated, optionally aromatic (aryl, aralkyl or alkylaryl), containing 1 to 30 carbon atoms, optionally comprising one or more functions selected from -OH, -OR' with R' is C1-C6 alkyl (alkoxy), -CN, -X (halogen, especially Cl, F, Br or I); may be mentioned, for example, methyl crotonate and ethyl crotonate - (ii) the amides of crotonic acid of the formula CH3CH=CHCONR'2R"2 with R'2 and R"2, which may be identical or different, representing hydrogen or a carbon-based and especially hydrocarbon-based (alkyl) chain, straight, branched or cyclic, saturated or unsaturated, optionally aromatic, containing 1 to 30 carbon atoms, optionally comprising one or more functions selected from -OH, - OR' with R' is C1-C6 alkyl (alkoxy), -CN, -X (halogen, especially Cl, F, Br or I).

[022] The term "crotonic acid derivative" preferably means an ester or amide of crotonic acid, in particular: - (i) esters of crotonic acid of the formula CH3CH=CHCOOR'1 with R'1 representing a chain based on carbons and especially hydrocarbon-based, such as an alkyl, linear, branched or cyclic, saturated or unsaturated, optionally aromatic, such as an aryl, aralkyl or alkylaryl, containing 1 to 30 carbon atoms, optionally comprising one or more selected functions -OH, -OR' with R' is C1-C6 alkyl, such as an alkoxy, -CN, -X, such as a halogen, especially Cl, F, Br or I; may be mentioned, for example, methyl crotonate and ethyl crotonate, -(ii) the amides of crotonic acid of the formula CH3CH=CHCONR'2R"2 with R'2 and R"2, which may be identical or different, representing hydrogen or a carbon-based and especially hydrocarbon-based chain, such as an alkyl, straight, branched or cyclic, saturated or unsaturated, optionally aromatic, containing 1 to 30 carbon atoms, optionally comprising one or more functions selected from - OH, -OR' with R' is C1-C6 alkyl, such as an alkoxy, -CN, -X, such as a halogen, especially Cl, F, Br or I.

[023] The vinyl ester monomer(s) may be selected from the compounds of the formula CH2=CH-OCO-R'3 with R'3 representing a chain based on carbons and especially at hydrocarbon base, linear, branched or cyclic, saturated or unsaturated, optionally aromatic, containing 1 to 30 carbon atoms, optionally comprising one or more functions selected from -OH, -OR' with R' C1-C6 alkyl (alkoxy), -CN, -X (halogen, especially Cl, F, Br or I).

[024] Vinyl acetate, vinyl propionate, vinyl butyrate (or butanoate), vinyl ethylhexanoate, vinyl neononanoate, vinyl neododecanoate, vinyl neodecanoate, vinyl pivalate, vinyl cyclohexanoate may be mentioned in particular , vinyl benzoate, vinyl 4-tert-butylbenzoate and vinyl trifluoroacetate.

[025] The copolymer according to the invention is selected from copolymers derived from the polymerization of at least one crotonic acid monomer and at least two different vinyl ester monomers, said vinyl ester monomers being preferably selected from vinyl acetate, propionate vinyl, vinyl butyrate (or butanoate), vinyl ethylhexanoate, vinyl neononanoate, vinyl neododecanoate, vinyl neodecanoate, vinyl pivalate, vinyl cyclohexanoate, vinyl benzoate, vinyl 4-tert-butylbenzoate and vinyl trifluoroacetate, preferably vinyl acetate, vinyl propionate and vinyl neodecanoate, even better vinyl acetate and vinyl neodecanoate.

[026] More particularly, the copolymer according to the invention is selected from copolymers derived from the polymerization of crotonic acid, vinyl acetate and vinyl propionate, copolymers derived from the polymerization of crotonic acid, vinyl acetate and vinyl neodecanoate, and mixtures of the same.

[027] According to a particular embodiment, the copolymer of the composition according to the invention is a crotonic acid/vinyl acetate/vinyl neodecanoate terpolymer.

[028] The copolymers according to the invention may optionally comprise other monomers, such as allylic or methallyl esters, or vinyl ethers. These polymers can optionally be grafted or crosslinked.

[029] Such polymers are described, inter alia, in French patents Nos. 1,222,944, 1,580,545, 2,265,782, 2,265,781, 1,564,110 and 2,439,798. Commercial products that fall into this category are Resyn® products 28-2930 and 28-1310 sold by the Akzo Nobel company (INCI names VA copolymer / crotonates / vinyl decanoate and VA copolymer / crotonates, respectively). Mention should also be made of the products Luviset® CA 66 sold by the company BASF, Aristoflex® A60 sold by the company Clariant (INCI name copolymer VA / crotonates) and Mexomere® PW or PAM sold by the company Chimex (INCI name copolymer VA / butylbenzoate vinyl / crotonates).

[030] The total amount of the copolymer(s) of crotonic acid or crotonic acid derivative according to the invention may vary from 0.05% to 15% by weight relative to the weight of the composition, preferably from 0. 1% to 10% by weight relative to the weight of the composition, preferably from 1% to 5% by weight relative to the weight of the composition.

[031] Thickening polymers carrying (meth)acrylic acid unit(s).

[032] The composition according to the invention comprises at least one thickening polymer carrying unit(s) of acrylic acid and/or methacrylic acid. The polymer bearing unit(s) of acrylic acid and/or methacrylic acid according to the invention can be cross-linked. Preferably, the polymer carrying acrylic acid and/or methacrylic acid unit(s) according to the invention is cross-linked.

[033] According to the present invention, the term "thickening polymer" refers to a polymer which, by its presence at a concentration of 0.05% by weight, increases the viscosity of a composition in which it is introduced in at least 20 cps, preferably at least 50 cps, at room temperature (25 °C), atmospheric pressure and a shear rate of 1 s -1 (viscosity can be measured using a cone/ plate, a Haake R600 rheometer or similar).

[034] As indicated above, the composition contains one or more thickening polymers carrying (meth)acrylic acid unit(s). The thickening polymers bearing (meth)acrylic acid unit(s) may optionally be in salified form.

[035] In particular, the acrylic or methacrylic acid units may be in the form of alkali metal or ammonium acrylate or methacrylate.

[036] The thickening polymers carrying unit(s) of (meth)acrylic acid, according to the invention, can be anionic or amphoteric, preferably anionic.

[037] The thickening polymers carrying (meth)acrylic acid unit(s) are specially selected from: (a) acrylic associative polymers; (b) preferably cross-linked acrylic acid homopolymers; (c) cross-linked copolymers of (meth)acrylic acid and (C1-C6) alkyl acrylate; (d) homopolymers of ammonium acrylate or copolymers of ammonium acrylate and acrylamide.

[038] According to the invention, the term "associative polymer" means an amphiphilic polymer comprising both hydrophilic and hydrophobic units, in particular, comprising at least one C8-C30 fatty chain and at least one hydrophilic unit.

[039] Preferably the composition contains an acrylic acid homopolymer, which is preferably cross-linked. Polymers of this type have the INCI name Carbomer. a) acrylic associative polymers

[040] Acrylic associative polymers, according to the invention, that can be used are acrylic associative polymers carrying (meth)acrylic acid unit(s) selected from: - (i) anionic amphiphilic polymers carrying acid unit(s) (meth)acrylic comprising at least one hydrophilic unit and at least one fatty chain unit; - (ii) amphoteric amphiphilic polymers bearing (meth)acrylic acid unit(s) comprising at least one hydrophilic unit and at least one fatty chain unit, the fatty chains containing from 10 to 30 carbon atoms.

[041] In particular, the associative polymers bearing (meth)acrylic acid unit(s) may be selected from: - anionic amphiphilic polymers comprising at least one hydrophilic unit of the (meth)acrylic acid type and at least one hydrophobic ester unit of C10-C30 alkyl of the unsaturated carboxylic acid type; - amphoteric amphiphilic polymers comprising at least one hydrophilic unit of the (meth)acrylic acid type and containing at least one fatty chain, such as methacrylamidopropyltrimethylammonium chloride/acrylic acid/C10-C30 alkyl methacrylate copolymers, the alkyl radical being preferably a radical stearyl. b) homopolymers of preferably cross-linked acrylic acid.

[042] The polymer can be crosslinked with a crosslinking agent, in particular selected from pentaerythritol allyl ether, sucrose allyl ether or propylene allyl ether. Such polymers have the INCI name: Carbomer. Use may be made, for example, of polymers sold by the company Lubrizol under the names Carbopol 980 or 981, or Carbopol Ultrez 10, or by the company 3V under the names Synthalen K or Synthalen L or Synthalen M. c) acid cross-linked copolymers ( meth)acrylic and C1-C6 alkyl acrylate;

[043] Among the crosslinked copolymers of (meth)acrylic acid and C1-C6 alkyl acrylate that can be mentioned is the product sold under the name Viscoatex 538C by the company Coatex, which is a crosslinked copolymer of methacrylic acid and ethyl acrylate as an aqueous dispersion containing 38% active material, or the product sold under the name Aculyn 33 by the company Rohm & Haas, which is a cross-linked copolymer of acrylic acid and ethyl acrylate as an aqueous dispersion containing 28% active material. More particularly mention may be made of the methacrylic acid/ethyl acrylate cross-linked copolymer in the form of a 30% aqueous dispersion manufactured and sold under the name Carbopol Aqua SF-1 by the company Noveon. d) homopolymers of ammonium acrylate or copolymers of ammonium acrylate and acrylamide;

[044] Among the ammonium acrylate homopolymers that can be mentioned is the product sold under the name Microsap PAS 5193 by the company Hoechst.

[045] Among the ammonium acrylate and acrylamide copolymers that can be mentioned is the product sold under the name Bozepol C Nouveau or the PAS 5193 product sold by the company Hoechst (they are described and prepared in FR-2 416 723, US-2 798 053 and US-2 923 692).

[046] According to a particular embodiment of the invention, the composition comprises at least one cross-linked thickening polymer of acrylic and/or methacrylic acid.

[047] According to a particular embodiment of the invention, the composition comprises at least one thickening polymer carrying unit(s) of (meth)acrylic acid selected from cross-linked homopolymers of acrylic acid.

[048] According to the invention, the thickening polymer(s) carrying (meth)acrylic acid unit(s) may represent from 0.001% to 20% by weight, preferably from 0.01% to 10% by weight and more particularly from 0.1% to 5% by weight, even better from 0.4% to 2% by weight relative to the total weight of the final composition.

[049] Preferably, the ratio by weight of the total amount of copolymer(s) of crotonic acid or crotonic acid derivative, according to the invention, and the amount of thickening polymer carrying unit(s) of acid (met )acrylic is in the range from 0.1 to 15, more preferably from 1 to 10 and even better from 2 to 8.

PIGMENTS

[050] The composition comprises one or more pigments.

[051] The term "pigment" is understood to mean white or colored particles, of any shape, that are insoluble in the composition in which they are present.

[052] The pigments that can be used are specially selected from organic and/or mineral pigments known in the art, especially those described in Kirk-Othmer's Encyclopedia of Chemical Technology and Ullmann's Encyclopedia of Industrial Chemistry.

[053] They can be natural, of natural origin, or not.

[054] These pigments can be in the form of powder or pigment paste. They can be coated or uncoated.

[055] The pigments can be selected, for example, from mineral pigments, organic pigments, lacquers, pigments with special effects, such as nacres or glitter flakes, and mixtures thereof.

[056] The pigment may be a mineral pigment. The term "mineral pigment" means any pigment that meets the definition in Ullmann's encyclopedia in the chapter on inorganic pigments. Mention may be made, among mineral pigments used in the present invention, of ochres, such as reddish ocher (clay (in particular, kaolinite) and iron hydroxide (for example, hematite)), brownish ocher (clay (in particular, kaolinite) and limonite) or yellowish ocher (clay (in particular kaolinite) and goethite); titanium dioxide, optionally surface-treated; zirconium or cerium oxides; oxides of zinc, iron (black, yellow or red) or chromium; manganese violet, ultramarine blue, chromium hydrate and ferric blue; or metallic powders, such as aluminum powder or copper powder.

[057] Carbonates of alkaline earth metals (for example, calcium or magnesium), silicon dioxide, quartz and also any other compound used as an inert filler in cosmetic compositions may also be mentioned, provided that these compounds provide the composition with color or whiteness under the conditions under which they are used.

[058] The pigment may be an organic pigment. The term "organic pigment" means any pigment that meets the definition in Ullmann's encyclopedia in the chapter on organic pigments.

[059] The organic pigment can be specially selected from nitrous compounds, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, triphenylmethane, fluorane, phthalocyanine, metal complex, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo , dioxazine, triphenylmethane and quinophthalone.

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

[061] In particular, the white or colored organic pigments can be selected from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments coded in the Color Index under CI references 42090, 69800 , 69825, 73000, 74100, 74160, the yellow pigments coded in the Color Index under CI references 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments coded in the Color Index references CI 61565, 61570, 74260, the orange pigments coded in the color index under references CI 11725, 15510, 45370, 71105, red pigments coded in the color index under references CI 12085, 12120, 12420, 12490, 14700 , 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, pigments obtained by polymerization indole oxidant or phenolic derivatives as described in the FR 2 patent 679 771.

[062] Examples that may also be mentioned include pigment pastes of organic pigments, such as the products sold by the company Hoechst under the names: - Cosmenyl Yellow 10G: Pigment Yellow 3 (CI 11710); - Cosmenyl Yellow G: Pigment Yellow 1 (CI 11680); - Cosmenyl Orange GR: Pigment Orange 43 (CI 71105); - Cosmenyl Red R: Pigment Red 4 (CI 12085); - Carmine Cosmenyl FB: Pigment Red 5 (CI 12490); - Cosmenyl Violet RL: Pigment Violet 23 (CI 51319); - Cosmenyl Blue A2R: Pigment Blue 15.1 (CI 74160); - Cosmenyl Green GG: Pigment Green 7 (CI 74260); - Cosmenyl Black R: Pigment Black 7 (CI 77266).

[063] The pigments according to the invention can also be in the form of composite pigments, as described in patent EP 1 184 426. These composite pigments can be composed especially of particles comprising a mineral core, at least one binder, which provides the fixation of the organic pigments to the core, and at least one organic pigment that at least partially covers the core.

[064] The organic pigment can also be a lacquer. The term "lacquer" means dyes adsorbed onto insoluble particles, keeping the set thus obtained insoluble during use.

[065] The mineral substrates on which the dyes are adsorbed are, for example, alumina, silica, calcium and sodium borosilicate or calcium and aluminum and aluminum borosilicate.

[066] Among the dyes, carminic acid can be mentioned. Known dyes may also be mentioned under the following names: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green (CI 61 570) , D&C Yellow 10 (CI 77,002), D&C Green 3 (CI 42,053), D&C Blue 1 (CI 42,090).

[067] As examples of lacquers, the product known under the following name: D&C Red 7 (CI 15 850:1) can be mentioned.

[068] The pigment may also be a special effects pigment. The term “special effect pigments” means pigments that generally create a colored appearance (characterized by a certain hue, a certain vividness and a certain luminance level) that is not uniform and changes depending on the observation conditions (light, temperature, observation angles, etc.). They thus contrast with colored pigments that provide a standard uniform opaque, semi-transparent or transparent tone.

[069] There are several types of special effect pigments: those with a low refractive index, such as fluorescent or photochromic pigments, and those with a higher refractive index, such as nacres, interference pigments or glitter flakes.

[070] Examples of special effect pigments that can be mentioned include pearlescent pigments, such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments, such as mica coated with titanium and iron oxides, mica coated with oxides of iron, mica coated with titanium and, in particular, with ferric blue or chromium oxide, mica coated with titanium and with an organic pigment of the above type, and also pearlescent pigments based on bismuth oxychloride. Pearlescent pigments that may be mentioned include Cellini nacres sold by Engelhard (mica-TiO2-lacquer), Prestige sold by Eckart (mica-TiO2), Prestige Bronze sold by Eckart (mica-Fe2O3) and Colorona sold by Merck (mica-TiO2 -Fe2O3).

[071] Mention may be made of the gold-colored pearls sold especially by the Engelhard company under the names Brilliant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne) ; bronze pearls sold especially by the company Merck under the names Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by the company Engelhard under the name Super bronze (Cloisonne); orange nacres sold specially by the Engelhard company under the names Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the Merck company under the names Passion orange (Colorona) and Matte orange (17449) (Microna); the brown pearls sold specially by the Engelhard company under the names Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); mother-of-pearl with a coppery sheen sold specially by the Engelhard company under the name Copper 340A (Timica); mother-of-pearl with a reddish sheen sold especially by the Merck company under the name Sienna fine (17386) (Colorona); pearls with a yellowish sheen sold specially by the Engelhard company under the name Yellow (4502) (Chromalite); red mother-of-pearl with a golden sheen sold specially by the Engelhard company under the name Sunstone G012 (Gemtone); the pink pearls sold specially by the Engelhard company under the name Tan opale G005 (Gemtone); black mother-of-pearl with a golden sheen sold specially by the Engelhard company under the name Nu antique bronze 240 AB (Timica), blue mother-of-pearl sold especially by the Merck company under the name Matte blue (17433) (Microna), white mother-of-pearl with a golden sheen silver sold specially by the Merck company under the name Xirona Silver and golden orange-pink-green nacres sold specially by the Merck company under the name Indian summer (Xirona), and mixtures thereof.

[072] Still as examples of nacres, particles comprising a borosilicate substrate coated with titanium oxide can also be mentioned.

[073] The particles comprising a glassy substrate coated with titanium oxide are sold, in particular, under the name Metashine MC1080RY by the company Toyal.

[074] Finally, examples of nacres that may also be mentioned include polyethylene terephthalate flakes, especially those sold by Meadowbrook Inventions under the name Silver 1P 0.004X0.004 (silver flakes).

[075] It is possible to contemplate multilayer pigments based on synthetic substrates, such as alumina, silica, calcium and sodium borosilicate, calcium and aluminum borosilicate and aluminum.

[076] Special effect pigments can also be selected from reflective particles, that is, especially from particles whose size, structure, especially the thickness of the layer(s) from which they are produced and their physical and chemical nature and surface state, allow them to reflect incident light. This reflection can, if appropriate, have a sufficient intensity to create, on the surface of the composition or mixture, when the latter is applied to the substrate to be made up, highlights visible to the naked eye, i.e., brighter points that contrast with their nearby, seeming to glow.

[077] The reflective particles can be selected so as not to significantly alter the coloring effect generated by the coloring agents with which they are combined and, more particularly, so as to optimize this effect in terms of color reproduction. They may, more particularly, have a yellowish, pinkish, reddish, tan, orange, brownish, golden and/or coppery color or luster.

[078] These particles can have varied shapes and can, in particular, be platelet-shaped or globular, in particular, spherical in shape.

[079] Regardless of their shape, 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 .

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

[081] 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 a metal or metallic material. The substrate can be produced from one or more organic and/or mineral materials.

[082] More particularly, it can be selected from glasses, ceramics, graphite, metallic oxides, aluminas, silicas, silicates, especially aluminosilicates and borosilicates and synthetic mica, and mixtures thereof, and this list is not limiting.

[083] The reflective material may comprise a layer of metal or a metallic material.

[084] Reflective particles are described, in particular, in the documents.

[085] JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

[086] May also be mentioned, by way of example of reflective particles comprising a mineral substrate coated with a metal layer, particles comprising a borosilicate substrate coated with silver.

[087] The particles comprising a glassy substrate coated with silver, in the form of platelets, are sold under the name Microglass Metashine REFSX 2025 PS by Toyal. Particles with a glassy substrate coated with a nickel/chromium/molybdenum alloy are sold under the names Crystal Star GF 550 and GF 2525 by the same company.

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

[089] Examples that may be mentioned include aluminum powder, bronze powder or SiO2 coated copper powder sold under the name Visionaire by the company Eckart.

[090] Pigments with an interference effect that are not fixed to a substrate can also be mentioned, such as liquid crystals (Wacker Helicones HC) or interference holographic glitter (Geometric Pigments or Spectra f/x by Spectratek). Special effect pigments also comprise fluorescent pigments, whether 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 Quantum Dots Corporation.

[091] Quantum dots are luminescent semiconductor nanoparticles capable of emitting, under light excitation, irradiation with a wavelength between 400 nm and 700 nm. These nanoparticles are known from the literature. In particular, they can 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 al., “(CdSe)ZnS core-shell quantum dots: synthesis and characterization of a size series of highly luminescent nanocrystallites”, Journal of Physical Chemistry B, volume 101, 1997, pages 9463 to 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, volume 119, No. 30, pages 7019 to 7029.

[092] The variety of pigments that can be used in the present invention makes it possible to obtain a wide range of colors and also specific optical effects, such as metallic effects or interference effects.

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

[094] The pigments can be dispersed in the product using a dispersant.

[095] The dispersant serves to protect the dispersed particles against their agglomeration or flocculation. This dispersant can be a surfactant, an oligomer, a polymer or a mixture of several of them, supporting one or more functionalities with strong affinity with the surface of the particles to be dispersed. In particular, they can become physically or chemically attached to the surface of pigments. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, 12-hydroxystearic acid esters and C8 to C20 fatty acid esters of polyols such as glycerol or diglycerol are used, such as poly(12-hydroxystearic) acid stearate with a molecular weight of about 750 g/ mol, such as the product sold under the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipolyhydroxystearate (name CTFA) sold under the reference Dehymyls PGPH by the company Henkel or polyhydroxystearic acid, such as the product sold under the reference Arlacel P100 by the company Uniqema, and mixtures thereof.

[096] As other dispersants that can be used in the compositions of the invention, quaternary ammonium derivatives of polycondensate fatty acids can be mentioned, for example, Solsperse 17 000 sold by the company Avecia and mixtures of polydimethylsiloxane/oxypropylene, such as those sold by company Dow Corning under references DC25185 and DC2-5225 C.

[097] The pigments used in the cosmetic composition according to the invention can be superficially treated with an organic agent.

[098] Thus, pigments that have been previously surface treated, which are useful in the context of the invention, are pigments that have undergone, in whole or in part, a surface treatment of a chemical, electronic, electrochemical, mechanochemical or mechanical nature with an organic agent, such as as those described especially in Cosmetics and Toiletries, February 1990, volume 105, pages 53 to 64, before being dispersed in the composition according to the invention. Such organic agents can be selected, for example, from waxes, for example carnauba wax and beeswax; fatty acids, fatty alcohols and derivatives thereof, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol and lauric acid and derivatives thereof; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminum salts of fatty acids, for example aluminum 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.

[099] 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 various surface treatments.

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

[101] Preferably, surface-treated pigments are coated with an organic layer.

[102] The organic agent with which the pigments are treated can be deposited onto the pigments by solvent evaporation, chemical reaction between the surfacer molecules, or creation of a covalent bond between the surfacer and the pigments.

[103] Surface treatment can thus be carried out, for example, by chemically reacting a surfacer with the surface of the pigments and creating a covalent bond between the surfacer and the pigments or fillers. This method is especially described in US patent 4,578,266.

[104] Preferably, an organic agent covalently bound to the pigments will be used.

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

[106] Preferably, the surface treatments of the pigments are selected from the following treatments: - a PEG-silicone treatment, for example, the AQ surface treatment sold by LCW; - a methicone treatment, for example the SI surface treatment sold by LCW; - a dimethicone treatment, for example the Covasil 3.05 surface treatment sold by LCW; - a dimethicone/trimethylsiloxysilicate treatment, for example the Covasil 4.05 surface treatment sold by LCW; - a magnesium myristate treatment, for example the MM surface treatment sold by LCW; - an aluminum dimyristate treatment, such as the MI surface treatment sold by Miyoshi; - a perfluoropolymethylisopropyl ether treatment, for example the FHC surface treatment sold by LCW; - a treatment with isostearyl sebacate, for example the HS surface treatment sold by Miyoshi; - a perfluoroalkyl phosphate treatment, for example the PF surface treatment sold by Daito; - a treatment with acrylate/dimethicone copolymer and perfluoroalkyl phosphate, for example the FSA surface treatment sold by Daito; - a polymethylhydrogensiloxane/perfluoroalkyl phosphate treatment, for example the FS01 surface treatment sold by Daito; - a treatment with acrylate/dimethicone copolymer, for example the ASC surface treatment sold by Daito; - a titanium isopropyl triisostearate treatment, for example the ITT surface treatment sold by Daito; - an acrylate copolymer treatment, for example the APD surface treatment sold by Daito; - a perfluoroalkyl phosphate/titanium isopropyl triisostearate treatment, for example the PF + ITT surface treatment sold by Daito.

[107] Preferably, the pigment is selected from mixed mineral or mineral-organic pigments.

[108] The amount of pigment(s) may range from 0.01% to 30% by weight, more particularly from 0.05% to 20% by weight, preferably from 0.1% to 15% by weight and preferably from 1% to 10% by weight relative to the total weight of the composition.

[109] The composition of the invention may contain colored or colorant species other than the pigments according to the invention, such as direct dyes or dye precursors.

[110] The composition according to the invention advantageously comprises water, which may preferably be present in a content in the range of 20% to 98% by weight relative to the weight of the composition.

[111] The composition according to the invention may also comprise one or more fatty substances, preferably selected from silicones and non-silicone fatty substances that are liquid at 30 °C and atmospheric pressure, even better from silicones and triglyceride oils of vegetable origin .

[112] When the composition comprises one or more fatty substances, the total content of fatty substances may range from 0.01% to 20% by weight, preferably from 0.05% to 15% by weight and even better from 0 .1% to 10% by weight relative to the total weight of the composition.

ADDITIONS

[113] The compositions may also comprise at least one agent commonly used in cosmetics, for example selected from reducing agents, organic solvents, softeners, defoamers, moisturizers, UV screening agents, peptizers, solubilizers, fragrances, anionic, cationic surfactants, non-ionic or amphoteric, proteins and vitamins.

[114] The above additives are generally present in an amount for each of them between 0.01% and 20% by weight relative to the weight of the composition.

[115] It goes without saying that a person skilled in the art will take care to select this or these optional additives so that the advantageous properties intrinsically linked to the formation of the coating according to the invention are not, or are not substantially, negatively affected.

FORM OF PRESENTATION

[116] The composition according to the invention can especially be in the form of a suspension, a dispersion, a gel, an emulsion, especially an oil-in-water (O/W) or water-in-oil (W/O) emulsion , or a multiple emulsion (W/O/W or polyol/O/W or O/W/O), in the form of a cream, a mousse, a stick, a dispersion of vesicles, especially of ionic or non-ionic lipids , or a two-phase or multi-phase lotion. Preferably, the composition is in the form of a gel.

[117] A person skilled in the art can select the suitable presentation form, and also the method for preparing it, based on his general knowledge, taking into account firstly the nature of the constituents used, especially their solubility in the support, and , secondly, the intended application of the composition.

ORGANIC SOLVENTS

[118] The composition according to the invention may comprise one or more organic solvents.

[119] Examples of organic solvents that may be mentioned include lower C1-C4 alkanols such as ethanol and isopropanol; polyols and polyol ethers, for example 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether and diethylene glycol monoethyl ether and diethylene glycol monomethyl ether, and also aromatic alcohols, for example benzyl alcohol or phenoxyethanol, and mixtures thereof.

[120] Preferably, the composition according to the invention comprises one or more organic solvents.

[121] When they are present, the organic solvents are present in proportions, preferably even between 0.1% and 40% by weight approximately relative to the total weight of the dye composition, more preferably between 1% and 30 % by weight approximately and, even more particularly, including between 5% and 25% by weight relative to the total weight of the composition.

PROCESS

[122] The composition described above can be used on wet or dry keratin fibers, and also on any type of light or dark fibers, natural or dyed, permanent curl, lightened or relaxed.

[123] Application to the fibers can be carried out by any standard means, in particular using a comb, a fine brush, a coarse brush or the fingers.

[124] After application of the composition, the fibers can be allowed to dry naturally or they can be dried, for example, at a temperature greater than or equal to 30 °C. Drying, if carried out, can be carried out immediately after application. Preferably, if the fibers are dry, they are dried, in addition to providing heat, with an air flow.

[125] During drying, a mechanical action can be exerted on the locks, such as combing, brushing or fingering. This operation can similarly be carried out once the fibers have been dried, naturally or otherwise.

[126] The drying step of the process of the invention can be carried out with a column dryer, a hair dryer, a flat iron, a Climazon, etc.

[127] When the drying step is carried out with a column dryer or a hair dryer, the drying temperature is between 30 °C and 110 °C, and preferably between 50 and 90 °C.

[128] When the drying step is carried out with a flat iron, the drying temperature is between 110 and 220 °C, and preferably between 140 and 200 °C. EXAMPLES Example 1: Compositions (g AM/100 g)

PROTOCOL

[129] Composition A1 is applied to strands of yak hair at a rate of 1 g of composition per gram of strands.

[130] After application, the locks are combed, dried with a hairdryer, and then combed again.

RESULTS: “COSMETIC FEEL” PERFORMANCE

[131] Performance qualities in terms of cosmetic feel were evaluated on dry locks by five experts in a blind test.

[132] In 100% of the cases, experts judged that the A1 composition according to the invention provided smooth locks with clearly individualized hair strands, having a pleasant cosmetic feel, especially good softness, good manageability and absence of stickiness. Example 2: compositions (g AM/100 g)

PROTOCOL

[133] Composition A2, B2 or C2 is applied to strands of yak hair at a rate of 1 g of composition per gram of strands.

[134] The locks are dried with a hairdryer and then combed.

[135] The locks are then rubbed on a white cloth.

RESULTS: “TRANSFER RESISTANCE” PERFORMANCE

[136] The performance qualities in terms of transfer resistance were evaluated by five experts, in a blind test, who visually assessed the amount of pigment present in the white cloth after rubbing.

[137] In 100% of cases, experts judged that composition A2 according to the invention, compared to compositions B2 and C2, led to a much smaller amount of pigment(s) present in the cloth. Composition A according to the invention thus has better transfer resistance properties than comparative compositions B2 and C2. Example 3: Compositions in gel form (g AM/100 g)

RESULTS: “GEL APPEARANCE” PERFORMANCE

[138] In 100% of cases, experts judged that composition A3 of the invention, compared to compositions C3 and D3, led to the production of a uniform, glossy and consistent gel. Example 4: Compositions (g AM/100 g)

PROTOCOL

[139] Composition A4 and Composition E are applied to locks of yak hair at a rate of 1 g of composition per gram of lock.

[140] After application, the locks are combed, dried with a hairdryer, and then combed again.

RESULTS: PERFORMANCE IN TERMS OF COLOR

[141] Performance in terms of color homogeneity and intensity is evaluated on dry hair strands by 5 experts during a blind test.

[142] 100% of the experts noted that the hair strand treated with composition A4 according to the invention has a more intense and homogeneous color than comparative composition E.

Claims (14)

1. COMPOSITION, characterized in that it comprises (i) one or more copolymers derived from the polymerization of at least one crotonic acid monomer or crotonic acid derivative selected from crotonic acid esters or crotonic acid amides and at least two different vinyl ester monomers , (ii) one or more thickening polymers bearing (meth)acrylic acid unit(s) and (iii) one or more pigments. 2. COMPOSITION according to claim 1, characterized in that said at least one derivative of crotonic acid is selected from esters of crotonic acid of the formula CH3CH=CHCOOR'1, with R'1 representing a chain based on carbons and especially at hydrocarbon base, linear, branched or cyclic, saturated or unsaturated, optionally aromatic, containing 1 to 30 carbon atoms, optionally comprising one or more functions selected from -OH, -OR' with R' representing C1-C6 alkyl, -CN , a halogen, especially Cl, F, Br or I, such as methyl crotonate and ethyl crotonate. 3. COMPOSITION according to any one of claims 1 to 2, characterized in that said at least one derivative of crotonic acid is selected from amides of crotonic acid of the formula CH3CH=CHCONR'2R"2 with R'2 and R"2, which may be identical or different, representing hydrogen or a carbon-based and especially hydrocarbon-based chain, straight, branched or cyclic, saturated or unsaturated, optionally aromatic, containing 1 to 30 carbon atoms, optionally comprising one or more functions selected from -OH, -OR' with R' representing C1-C6 alkyl, -CN, a halogen, especially Cl, F, Br or I. 4. COMPOSITION according to any one of claims 1 to 3, characterized in that said vinyl ester monomer(s) is selected from vinyl acetate, vinyl propionate, vinyl, vinyl ethylhexanoate, vinyl neononanoate, vinyl neododecanoate, vinyl neodecanoate, vinyl pivalate, vinyl cyclohexanoate, vinyl benzoate, vinyl 4-tert-butylbenzoate and vinyl trifluoroacetate, preferably vinyl acetate vinyl, vinyl propionate and vinyl neodecanoate, even better vinyl acetate and vinyl neodecanoate. 5. COMPOSITION according to any one of claims 1 to 4, characterized in that said copolymer(s) is selected from copolymers derived from the polymerization of crotonic acid, vinyl acetate and propionate of vinyl, copolymers derived from the polymerization of crotonic acid, vinyl acetate and vinyl neodecanoate, and mixtures thereof. 6. COMPOSITION according to any one of claims 1 to 5, characterized in that the copolymer is a terpolymer of crotonic acid/vinyl acetate/vinyl neodecanoate. 7. COMPOSITION according to any one of claims 1 to 6, characterized in that said copolymer(s) also comprise(s) other monomers, such as allylic or methallyl esters or vinylic ethers. 8. COMPOSITION according to any one of claims 1 to 7, characterized by said crotonic acid copolymer derived from the polymerization of at least one crotonic acid monomer or crotonic acid derivative selected from crotonic acid esters or crotonic acid amides and at least one vinyl ester monomer, be present in an amount ranging from 0.05% to 15% by weight relative to the weight of the composition, preferably from 0.1% to 10% by weight relative to the weight of the composition, preferably from 1% to 5% by weight relative to the total weight of the composition. 9. COMPOSITION according to any one of Claims 1 to 8, characterized in that said thickening polymer(s) carrying unit(s) of acrylic acid(s) is(are) cross-linked. 10. COMPOSITION according to any one of claims 1 to 9, characterized in that said thickening polymer(s) carrying unit(s) of (meth)acrylic acid is(in) polymer(s) of crosslinked thickener(s) carrying acrylic acid unit(s), preferably crosslinked homopolymer(s) of acrylic acid. 11. COMPOSITION according to any one of claims 1 to 10, characterized in that said thickening polymer(s) carrying (meth)acrylic acid unit(s) are present in a total amount representing 0.001 % to 20% by weight, preferably from 0.01% to 10% by weight and more particularly from 0.1% to 5% by weight, even better from 0.4% to 2% by weight relative to the total weight of the final composition. 12. COMPOSITION according to any one of claims 1 to 11, characterized in that it comprises one or more fatty substances, preferably selected from silicones and non-silicone fatty substances that are liquid at 30 °C and atmospheric pressure, more preferably from silicones and triglyceride oils of vegetable origin. 13. PROCESS FOR COSMETIC TREATMENT, in particular for dyeing, keratin fibers, in particular human keratin fibers, such as hair, characterized in that the composition, as defined in any one of claims 1 to 12, is applied to said fibers. 14. USE OF THE COMPOSITION, as defined in any one of claims 1 to 12, characterized in that it is for the cosmetic treatment, in particular the dyeing, of keratin fibres, in particular human keratin fibres, such as hair.