FR2899807A1 - Cosmetic composition useful in the treatment of keratinous matters, preferably hair, e.g. hair perming, dying and bleaching, comprises a cyanoacrylate monomer, silica particles and an organic liquid solvent - Google Patents

Abstract

Cosmetic composition (A) comprises a cyanoacrylate monomer (I), silica particles having a size less than 30 mu m and an organic liquid solvent. Cosmetic composition (A) comprises a cyanoacrylate monomer (I) of formula (R1)(R2)C=C(CN)(COXR3a), silica particles having a size less than 30 mu m and an organic liquid solvent. X : NH, O or S, preferably O; R1, R2lower or non electron attractor (lower or non inductive-attractor) , preferably H; R3a1-20C, preferably 1-10C hydrocarbon (optionally containing N, O, S and optionally replaced by -ORa, -COORa, -CORa, -SHa, -SRa, -OH or halo) or a polymer residue obtained by radical polymerization, polycondensation or ring opening, preferably -CH(CH3)-(CH2)5-CH3, -CH2-CH(C2H5)-(CH2)3-CH3, -(CH2)5-CH(CH3)-CH3 or -(CH2)4-CH(C2H5)-CH3; and Ra1-10C alkyl. Independent claims are included for: (1) a process of treating keratinous matters, comprising applying (A) on the keratinous matters; (2) process of treatment of keratinous matters, such as hair, comprising applying a complete/permanent hair perming reducer, an oxidation dye, a bleach, shampoo or a hair styling or alkaline hair straightening product and applying (A); (3) process of treatment of keratinous matters, such as hair, comprising protecting the hair by application of (A), treating the hair by application of a complete/permanent hair perming reducer, an oxidation dye, a bleach, shampoo or a hair styling or alkaline hair straightening product and cleansing; (4) a kit comprising a first composition of (I) and optionally an anionic, radical and/or acid polymerization inhibitor and a second composition containing an organic solvent, the silica particles and optionally an acid, in a medium; and (5) a kit comprising a first anhydrous composition containing silica particle and an electrophilic monomer and a second composition containing a nucleophilic agent.

Description

COSMETIC COMPOSITION COMPRISING IN A COSMETIC MEDIUM AT LEAST ONE

  The present invention relates to novel compositions comprising silica particles, cyanoacrylate monomers and at least one liquid organic solvent for the cosmetic treatment of keratin materials, and in particular keratinous fibers such as the hair, as well as the use of new compositions for the cosmetic treatment of keratin materials. There are many styling products that can bring body, mass or volume to the hair. A disadvantage related to these products, most often based on film-forming polymers, lies in the fact that the cosmetic effect disappears from the first shampoo.

  It is conceivable to increase the remanence of the polymer deposit by directly effecting a radical polymerization of certain monomers in the hair. However, the treatments thus obtained are not very cosmetic and there is generally a strong degradation of the fiber. Hair so treated is difficult to disentangle.

  Furthermore, it is known from patent application FR 2 833 439 (OA 01452) hair treatment compositions from compositions comprising electrophilic monomers capable of polymerizing anionically directly on the hair. These monomers after polymerization make it possible to obtain perfectly sheathed hair. However, the cladding obtained does not have a satisfactory resistance compared to the different external aggressions that the hair can undergo. There is therefore a need to find new cosmetic compositions for bringing the body, mass and / or volume to the hair, and this in a sustainable manner, particularly in the face of shampoos and other external aggressions that can undergo the hair . Thus, the subject of the invention is a composition comprising in a cosmetic medium: a) at least one cyanoacrylate monomer; b) at least one silica particle, the primary size of which is less than 30 m; and c) at least one liquid organic solvent.

  The Applicant has more particularly found that by applying a composition based on such monomers and silica particles on the hair, it forms in situ a remanent coating. The polymer thus formed in situ by interfacial anionic polymerization is in the form of a homogeneous deposit and has excellent adhesion to hair. Such a composition when it is applied to keratinous fibers such as the hair makes it possible to obtain a cladding having improved resistance to external agents while maintaining perfectly individualized hair that can be easily capped. The styling properties provided to the fiber are persistent especially in shampoos. The subject of the invention is also the use for the treatment of keratin materials, and in particular keratinous fibers such as the hair, of the composition of the invention. It also relates to a process for the cosmetic treatment of keratin materials, and in particular keratin fibers such as the hair, using this composition. Its other object is a kit comprising a first composition containing at least one cyanoacrylate monomer, optionally at least one anionic and / or radical polymerization inhibitor and / or an acid; and a second composition containing at least one liquid organic solvent, a silica particle having a primary size of less than 30 μm, and optionally an acid.

  The cyanoacrylate monomer or monomers present in the composition of the invention are preferably chosen from the monomers of formula (I): ## STR1 ## in which: X denotes NH, S or O, R1 and R2 denote each independently of one another, a group with little or no electro-attractor (little or no inductive-attractor) such as: - a hydrogen atom; a saturated or unsaturated hydrocarbon group, linear, branched or cyclic, preferably containing from 1 to 20, more preferably from 1 to 10 carbon atoms, and optionally containing one or more nitrogen, oxygen or sulfur atoms, and optionally substituted with one or more groups chosen from -OR, -COOR, -COR, -SH, -SR, -OH, and the halogen atoms, with R denoting a saturated or unsaturated hydrocarbon group, linear, branched or cyclic , preferably comprising from 1 to 20, more preferably from 1 to 10 carbon atoms, and optionally containing one or more nitrogen, oxygen and sulfur atoms, and optionally substituted with one or more groups chosen from ûOR ', - COOR ', -COR', -SH, -SR ', -OH, the halogen atoms, and a polymer residue obtainable by radical polymerization, polycondensation or ring opening, with R' denoting a group C1-C10 alkyl; a modified or unsubstituted polyorganosiloxane residue; a polyoxyalkylene group; R '3 representing a hydrogen atom or a saturated or unsaturated hydrocarbon group, linear, branched or cyclic, preferably containing from 1 to 20, more preferably from 1 to 10 carbon atoms, and optionally containing one or more atoms nitrogen, oxygen, sulfur, and optionally substituted with one or more groups selected from --OR ', -COOR', - COR ', -SH, -SR', -OH, the halogen atoms, and a polymer residue obtainable by radical polymerization, polycondensation or ring opening, R 'denoting a C1-C10 alkyl group. By electro-attractor or inductive-attractor group (-I) is meant any group more electronegative than carbon. Reference can be made to PR Wells Prog. Phys. Org. Chem., Vol 6.11 (1968). By grouping little or no electro-attractor means any group whose electronegativity is less than or equal to that of carbon. 10 15

  The alkenyl or alkynyl groups preferably have 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms. As saturated or unsaturated hydrocarbon group, linear, branched or cyclic, preferably having 1 to 20 carbon atoms, there may be mentioned linear or branched alkyl, alkenyl or alkynyl groups, such as methyl, ethyl, n-butyl, tert butyl, isobutyl, pentyl, hexyl, octyl, butenyl or butynyl; cycloalkyl or aromatic groups. As the substituted hydrocarbon group, there may be mentioned, for example, hydroxyalkyl or polyhaloalkyl groups.

  As examples of unmodified polyorganosiloxane, there may be mentioned polyalkylsiloxanes such as polydimethylsiloxanes, polyarylsiloxanes such as polyphenylsiloxanes, polyarylalkylsiloxanes such as polymethylphenylsiloxanes. Among the modified polyorganosiloxanes, there may be mentioned polydimethylsiloxanes containing polyoxyalkylene and / or siloxy and / or silanol and / or amine and / or imine and / or fluoroalkyl groups. Among the polyoxyalkylene groups, there may be mentioned polyoxyethylene groups and polyoxypropylene groups preferably having 1 to 200 oxyalkylene units.

  Among the mono- or polyfluoroalkyl groups, mention may especially be made of groups such as - (CH 2) n - (CF 2) m-CF 3 or - (CH 2) n - (CF 2) m -CH 2 with n = 1 to 20 and m = 1 to 20. The substituents R 1 and R 2 may optionally be substituted with a group having a cosmetic activity. Particularly used cosmetic activities are obtained from groups with coloring functions, antioxidants, UV filters and conditioning. Examples of dye-functional groups that may be mentioned include azo, quinone, methine, cyanomethine and triarylmethane groups.

  By way of examples of an antioxidant-functional group, mention may especially be made of butylhydroxyanisole (BHA), butylhydroxytoluene (BHT) or vitamin E type groups. Examples of groups having a UV-screening function are, for example, benzophenone, cinnamate, benzoate, benzylidene camphor and dibenzoylmethane moieties. As examples of a group with a conditioning function, mention may be made in particular of cationic and fatty ester groups.

  Preferably R 1 and R 2 are hydrogen, R '3 is preferably a saturated hydrocarbon group having from 1 to 10 carbon atoms. Preferably, X denotes O. As compounds of formula (I), mention may be made of the monomers: a) belonging to the family of polyfluoroalkyl 2-cyanoacrylates such as: - the ester 2,2,3,3 2-cyano-2-propenoic acid tetrafluoropropyl derivative of formula (II): CN COOCH2CF2CHF2 or the 2,2,2-trifluoroethyl ester of 2-cyano-2-propenoic acid of formula (III) COOCH2CF3 b) alkyl or alkoxyalkyl 2-cyanoacrylates of formula (I) wherein R'3 represents a C1-C10 alkyl radical; C2-C10 alkenyl or (C1-C4) alkoxy (C1-C10) alkyl.

  Mention may be made more particularly of ethyl 2-cyanoacrylate, methyl 2-cyanoacrylate, n-propyl 2-cyanoacrylate, isopropyl 2-cyanoacrylate, tert-butyl 2-cyanoacrylate and 2-cyanoacrylate. of n-butyl, iso-butyl 2-cyanoacrylate, 3-methoxybutyl cyanoacrylate, n-decyl cyanoacrylate, hexyl 2-cyanoacrylate, 2-ethoxyethyl 2-cyanoacrylate, 2-cyanoacrylate 2-methoxyethyl 2-cyanoacrylate, 2-propoxyethyl 2-cyanoacrylate, n-octyl 2-cyanoacrylate, allyl 2-cyanoacrylate, methoxypropyl 2-cyanoacrylate, and cyanoacrylate; iso-amyl.

  In the context of the invention, it is preferred to use the monomers b). According to a preferred embodiment, the cyanoacrylate monomer or monomers are chosen from C 6 -C 10 alkyl or C 2 -C 10 alkenyl cyanoacrylates.

  Particularly preferred monomers are octyl cyanoacrylate of formula (IV) and their mixtures: CN ((IV) COOR'3 in which: R'3 = - (CH2) 7-CH3, - CH (CH3) - (CH2) ) 5-CH3, -CH2-CH (C2H5) - (CH2) 3-CH3, - (CH2) 5-CH (CH3) -CH3, - (CH2) 4-CH (C2H5) -CH3 The monomers used according to to the invention can be covalently attached to supports such as polymers, oligomers or dendrimers.The polymer or oligomer can be linear, branched, comb or block.The distribution of the monomers of the invention on the polymeric, oligomeric or dendritic structure may be random, in the terminal position or in the form of blocks The cyanoacrylate monomer is generally present in the composition between 0.1% and 80% by weight of the composition, preferably between 0. 2 % and 60% by weight of the composition.

  The silica particles may be chosen from hydrophilic silicas, hydrophobic silicas and mixtures thereof. Advantageously, the silica particle or particles have a number-average primary size of between 0.1 and 30 μm, preferably of between 0.2 and 20 μm and even more preferentially of between 0.5 and 15 μm. For the purposes of the present invention, the term "primary particle size" means the maximum dimension that can be measured between two diametrically opposite points of an individual particle.

  The size of the organic particles can be determined by transmission electron microscopy or from the measurement of the specific surface area by the BET method or from a laser particle size distribution. Silica in the present invention is understood to mean both pure hydrophilic or hydrophobic silicas, silica-coated particles and coated silica particles.

  These silicas are preferably amorphous and they may be of pyrogenic origin or of precipitated origin. They may be in pulverulent form or in aqueous dispersion. The pyrogenic hydrophilic silicas are obtained by pyrolysis in a continuous flame at 1000 ° C. of silicon tetrachloride (SiCl 4) in the presence of hydrogen and oxygen. The precipitated silicas are obtained by reaction of an acid with alkali silicate solutions, preferably sodium silicate. Hydrophilic silicas are sold by Degussa-Hüls under the name AEROSIL 90, AEROSIL 130, AEROSIL 150, AEROSIL 200, AEROSIL 300, AEROSIL 380, AEROSIL 0X50 silica, FK320DS silica; Asahi Glass under the name SUSPHERE H-31, SUSPHERE H-51, SUSPHERE H-121, SUSPHERE H-201, SUSPHERE L-31, SUSPHERE 30 H-51, SUSPHERE L-121, SUSPHERE L-201. It is also possible to use silica in aqueous dispersion, and for example a dispersion of colloidal silica, such as the product sold under the name BINDZIL 30/220 by the company Eka Chemicals, colloidal dispersion of amorphous silica (size: 14 nanometers) in water (30/70). The hydrophilic silica that may be used in the composition of the invention may also consist of a particle comprising a silica surface, for example a particle totally or partially covered with silica, in particular a mineral particle totally or partially covered with silica, such as silica beads containing titanium oxide, sold under the name TORAYCERAM S-IT by the company Toray; silica coated with titanium dioxide and coated with porous silica (85/5/10) (size: 0.6 p), sold under the name ACS-0050510 by the company SACI-CFPA; anatase titanium nano-oxide treated alumina and 40% silica in water (size: 60 nm, monodisperse), sold under the name MIRASUN TIW 60 by the company Rhodia Chimie CRA; anatase titanium nanooxide (60 nm) coated with silica / alumina / cerium IV 15/5/3 in a 32% aqueous dispersion, sold under the name MIRASUN TIW 160 by the company Rhodia Chimie CRA; anatase titanium nano-oxide treated alumina and silica (34 / 4.3 / 1.7) in a 40% aqueous dispersion, sold under the name Tioveil AQ-N by the company Uniqema; silica-coated titanium nano-oxide (66/33) (titanium dioxide granulometry: 30 nm, silica thickness: 4 nm), sold under the name MAXLIGHT TS-04 by Nichimen Europe PLC; and silica-coated titanium nano-oxide (80/20) (titanium dioxide granulometry: 30 nm, silica thickness: 2 nm) marketed under the name MAXLIGHT TS-042 by Nichimen Europe PLC.

  The amorphous hydrophobic silicas of pyrogenic origin are obtained from hydrophilic silicas. As described above, the latter are obtained by pyrolysis in continuous flame at 1000 C of silicon tetrachloride (SiCl4) in the presence of hydrogen and oxygen. They are then rendered hydrophobic by treatment with halogenated silanes, alkoxysilanes or silazanes. Hydrophobic silicas differ from hydrophilic starting silicas, inter alia, by a lower silanol group density and by a smaller water vapor adsorption. These silicas are marketed by: Degussa-Hüls under the name AEROSIL R202 silica, AEROSIL R805, AEROSIL R812, AEROSIL R972, AEROSIL 974; Asahi Glass under the name of SUSPHERE NP-30, SUSPHERE NP-100, SUSPHERE NP-200. The hydrophobic silica that may be used in the composition of the invention may also consist of a particle totally or partially covered with silica, in particular a mineral particle totally or partially covered with hydrophobic silica, such as pigments and metal oxides coated with silica. hydrophobic. On the other hand, the silica particles useful in the present invention can be surface treated with organic or inorganic compounds. Preferably, the surface treatments of the silica particles are chosen from: i) a PEG-silicone treatment such as the AQ surface treatment marketed by LCW; ii) a Chitosan treatment such as the CTS surface treatment marketed by LCW; iii) a triethoxycaprylylsilane treatment such as the surface treatment AS marketed by LCW; iv) a Methicone treatment such as the SI surface treatment marketed by LCW; v) a Dimethicone treatment such as the Covasil 3.05 surface treatment marketed by LCW; vi) a dimethicone / trimethylsiloxysilicate treatment such as the Covasil 4.05 surface treatment marketed by LCW; vii) a Lauroyl Lysine treatment such as the LL surface treatment marketed by LCW; viii) a Lauroyl Lysine Dimethicone treatment such as the LL / SI surface treatment marketed by LCW; ix) a magnesium Myristate treatment such as the MM surface treatment marketed by LCW; x) Aluminum Dimyristate treatment such as MI surface treatment marketed by Miyoshi; xi) a perfluoropolymethylisopropyl ether treatment such as the FHC surface treatment marketed by LCW; xii) Isostearyl Sebacate treatment such as the HS surface treatment marketed by Miyoshi; xiii) a Disodium Stearoyl Glutamate treatment such as the NAI surface treatment marketed by Miyoshi; xiv) a Dimethicone / Disodium Stearoyl Glutamate treatment such as the SA / NAI surface treatment marketed by Miyoshi; xv) Perfluoroalkyl Phosphate treatment such as the PF surface treatment marketed by Daito; xvi) an acrylate / dimethicone copolymer and perfluoroalkyl phosphate copolymer treatment such as the FSA surface treatment marketed by Daito; xvii) Polymethylhydrogen siloxane / Perfluoroalkyl phosphate treatment such as the FS01 surface treatment marketed by Daito; xviii) a Lauryl Lysine / Aluminum Tristearate treatment such as the LL-StAI surface treatment marketed by Daito; xix) Octyltriethylsilane treatment such as the OTS surface treatment marketed by Daito; xx) a Octyltriethylsilane / Perfluoroalkyl Phosphate treatment such as the FOTS surface treatment marketed by Daito; xxi) a Copolymer Acrylate / Dimethicone treatment such as the ASC surface treatment marketed by Daito; xxii) Isopropyl Titanium Triisostearate treatment such as the ITT surface treatment marketed by Daito; xxiii) Cellulose Microcrystalline and Carboxymethyl Cellulose treatment as the AC surface treatment marketed by Daito; xxiv) a Cellulose treatment such as the C2 surface treatment marketed by Daito; xxv) an Acrylate copolymer treatment such as the APD surface treatment marketed by Daito; el: xxvi) a Perfluoroalkyl Phosphate / Isopropyl Titanium Triisostearate treatment such as the PF + ITT surface treatment marketed by Daito. The silica particles are preferably constituted by particles of hydrophilic silica, more preferably the silicas sold under the names AEROSIL 100, AEROSIL 150, AEROSIL 200 and AEROSIL 300 (Degussa-Hüls company). The particles are also present in the composition in an amount of between 0.01% and 50% by weight of the composition, more preferably between 0.1% and 10% by weight of the composition. The medium of the compositions of the invention may contain, in addition to the liquid organic solvent or solvents, water. Preferably the medium is anhydrous, that is to say containing less than 1% by weight of water relative to the total weight of the composition. The cosmetic medium of the composition of the invention can be used homogeneous, be in the form of an emulsion or be encapsulated. The dispersed or continuous phase of the emulsion may then consist of water, aliphatic alcohols C 1 -C 4 or mixtures thereof. The capsules or microcapsules containing the composition of the invention may be dispersed in an anhydrous medium as defined above, water, C 1 -C 4 aliphatic alcohols or mixtures thereof.

  The medium of the compositions of the invention may contain at least one liquid organic solvent different from the cyanoacrylate monomer. The organic solvents are chosen from compounds that are liquid at a temperature of 25 ° C. and under a pressure of 760 mmHg.

  The organic solvent is for example selected from aromatic alcohols such as benzyl alcohol; liquid fatty alcohols, especially of C10-C30; modified or unmodified polyols such as glycerol, glycol, propylene glycol, dipropylene glycol, butylene glycol, butyl diglycol; volatile silicones such as cyclopentasiloxane, cyclohexasiloxane, polydimethylsiloxanes which may or may not be modified by alkyl and / or amine and / or imine and / or fluoroalkyl and / or carboxylic and / or betaine and / or quaternary ammonium functions, liquid modified polyclimethylsiloxanes, mineral, organic or vegetable oils, alkanes and more particularly C5 to C10 alkanes; liquid fatty acids, and liquid fatty esters and more particularly liquid benzoates or salicylates of liquid fatty alcohol.

  The organic solvent is preferably chosen from organic oils; silicones such as volatile silicones, silicone gums or silicone oils or not and mixtures thereof; mineral oils; vegetable oils such as olive, castor oil, rapeseed, copra, wheat germ, sweet almond, avocado, macadamia, apricot, safflower, bancoulier nut, camellina, tamanu, lemon or organic compounds such as C5-C10 alkanes, acetone, methyl ethyl ketone, esters of C1-C20 acids and C1-C8 alcohols such as methyl acetate, butyl acetate, ethyl acetate and isopropyl myristate, dimethoxyethane, diethoxyethane, C10-C30 liquid fatty alcohols such as oleic alcohol, fatty alcohol esters liquid C10-C30, such as C10-C30 fatty alcohol benzoates and mixtures thereof, polybutene oil, isononyl isononanoate, isostearyl malate, pentaerythrityl tetraisostearate, tridecyl, the mixture cyclopentasiloxane (14.7% by weight) / polydimethylsiloxane dihydroxylated in positions a and o (85.3% by weight), or their s mixtures.

  According to a preferred embodiment, the organic solvent is constituted by a silicone such as liquid polydimethylsiloxanes and liquid modified polydimethylsiloxanes, their viscosity at 25 c is between 0.1 cst and 1000 000cst and more preferably between 1 cst and 30 000cst.

  The following oils are preferably mentioned: the mixture of alpha-ornega-dihydroxylated polydimethylsiloxane / cyclopentadimethylsiloxane (14.7 / 85.3) marketed by Dow Corning under the name DC 1501 Fluid; the mixture of alpha-omega-dihydroxylated polydimethylsiloxane / polydimethylsiloxane marketed by Dow Corning under the name DC 1503 Fluid; the dimethicone / cyclopentadimethylsiloxane mixture marketed by Dow Corning under the name DC 1411 Fluid or that marketed by Bayer under the name SF1214; cyclopentadimethylsiloxane sold by Dow Corning under the name DC245 Fluid; And the respective mixtures of these oils.

  The organic solvent (s) of the composition generally represent from 0.01 to 99%, preferably from 50 to 99% by weight relative to the total weight of the composition.

  The cosmetic composition according to the invention may further comprise at least one pigment. The use of a pigment in the cosmetic composition according to the invention makes it possible to obtain visible dyes, in particular on dark hair since the surface pigment hides the natural color of the fiber.

  The composition according to the invention thus has the advantage of leading to colorations that have good resistance to various attacks that may occur in the hair, such as fats or shampoos. In addition, the cosmetic composition according to the invention makes it possible to lead to visible and highly chromatic colorations on a particularly dark keratin fiber without it being necessary to lighten or discolor the keratin fibers and, consequently, without any physical degradation of the keratin fibers. keratinous fibers.

  For the purposes of the present invention, the term "pigment" means any organic and / or mineral entity whose solubility in water is less than 0.01% at 20 ° C., preferably less than 0.0001%, and having an absorption between 350 and 700 nm, preferably absorption with maxirnum.

  The pigments used in the composition according to the invention may especially be chosen from organic and / or inorganic pigments known in the art, in particular those which are described in Kirk-Othmer's encyclopedia of chemical technology and in the encyclopedia of chemistry. Ullmann.

  These pigments can be in the form of powder or pigment paste. They can be coated or uncoated. The pigments according to the invention may for example be chosen from white or colored pigments, lacquers, special effect pigments such as nacres or flakes, and mixtures thereof.

  As examples of white or colored mineral pigments, mention may be made of titanium dioxide, treated or untreated on the surface, oxides of zirconium or cerium, iron or chromium oxides, manganese violet, blue ultramarine, chromium hydrate and ferric blue. For example, the following mineral pigments can be used: Ta2O5, Ti3O5, Ti2O: 3, TiO, ZrO2 mixed with TiO2, ZrO2, Nb2O5, CeO2, ZnS. By way of examples of white or colored organic pigments, mention may be made of nitroso, nitro, azo, xanthene, quinoline, anthraquinone and phthalocyanine compounds, of metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, quinophthalone. In particular, the white or colored organic pigments can be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, sorghum red, blue pigments codified in the color. Index under the references Cl 42090, 69800, 69825, 73000, 74100, 74160, the yellow pigments codified in the Color Index under the references Cl 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments coded in the Color Index under the references Cl 61565, 61570, 74260, the orange pigments coded in the Color Index under the references Cl 11725, 15510, 45370, 71105, the red pigments codified in the Color Index under the references CI 12085, 12120 , 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole derivatives , phenolic as they are dec FR 2 679 771. Organic pigment pigment pastes such as the products sold by HOECHST under the name: YELLOW COSMENYL 10G: Pigment YELLOW 3 (Cl 11710) can be used; YELLOW COSMENYL G: Pigment YELLOW 1 (CI 11680); ORANGE COSMENYL GR: ORANGE PIGMENT 43 (CI 71105); - COSMENYL RED R: Pigment RED 4 (Cl 12085); CARMIN COSMENYL FB: Pigment RED (Cl 12490); -VIOLET COSMENYL RL: Pigment VIOLET 23 (Cl 51319); - COSMENYL BLUE A2R: Pigment BLUE 15.1 (CI 74160); - GREEN COSMENYL GG: Pigment GREEN 7 (Cl 74260); - BLACK COSMENYL R: Pigment BLACK 7 (Cl 77266). The pigments according to 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 in particular of particles comprising an inorganic core, at least one binder for fixing the organic pigments on the core, and at least one organic pigment at least partially covering the core. By lacquer is meant dyes adsorbed on insoluble particles, the assembly thus obtained remaining insoluble during use. The inorganic substrates on which the dyes are adsorbed are, for example, alumina, calcium and sodium borosilicate or calcium and aluminum borosilicate, and aluminum. Among the organic dyes, mention may be made of cochineal carmine. As examples of lacquers, mention may be made of the products 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 7 (Cl 15,850: 1), D & C Red 4 (Cl 15,510), D & C Red. 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 10 (CI 77 002), D & C Green 3 (Cl 42 053), D & C Blue 1 (Cl 42 090). Pigments with special effects means pigments which generally create a colored appearance (characterized by a certain nuance, a certain liveliness and a certain clarity) which is non-uniform and changeable according to the conditions of observation (light, temperature , observation angles ...). They are therefore opposed to white or colored pigments that provide a uniform opaque, semi-transparent or conventional transparent tint.

  By way of examples of special effect pigments, mention may be made of white pearlescent pigments such as mica coated with titanium, or bismuth oxychloride, colored pearlescent pigments such as mica coated with titanium and with iron oxides. , mica coated with titanium and in particular ferric blue or chromium oxide, mica coated with titanium and an organic pigment as defined above, and pearlescent pigments based on bismuth oxychloride. As nacreous pigments, mention may be made of the nacres Cellini marketed by Engelhard (Mica-TiO2-lacquer), Prestige! marketed by Eckart (Mica-TiO2), Prestige Bronze marketed by Eckart (Mica-Fe2O3), Colorona marketed by Merck (Mica-TiO2-Fe2O3).

  Non-fixed interference-effect pigments may also be mentioned, such as liquid crystals (Wacker's Helicones HC) and holographic interference flakes (Geometric Pigments or Spectra f / x by Spectratek). Special effect pigments also include fluorescent pigments, whether they are fluorescent substances in the light of day or that produce an ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, marketed for example by the Quantum Dots Corporation. The quantum dots are luminescent conductive nanoparticles capable of emitting, under light excitation, radiation having a wavelength between 400 nm and 700 nm. These nanoparticles are known from the literature. In particular, they can be manufactured according to the methods described for example in US Pat. No. 6,225,198 or US 5,990,479, in the publications cited therein, as well as in the following publications: Dabboussi BO et al (CdSe) ZnS core quantum dots: synthesis and characterization of a large series of highly luminescent nanocrystallites. Journal of Phisical 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 Arnerican Chemical Society, vol 119, No. 30, pp 7019-7029. The variety of pigments that can be used in the present invention provides a rich palette of colors, as well as particular optical effects such as interferential metallic effects. According to a particular embodiment, the pigments are colored pigments. Colored pigment is understood to mean pigments other than white pigments. The size of the pigment useful in the context of the present invention is generally between 10 nm and 200 μm, preferably between 20 nm and 80 μm, and more preferably between 30 nm and 50 μm. The pigments can be coated with organic or inorganic compounds. The organic agent with which the pigments are treated can be deposited on the pigments by solvent evaporation, chemical reaction between the surfactant molecules or creation of a covalent bond between the surfactant and the pigments or the charges. The surface treatment in the sense of the present invention is such that a surface-treated pigment retains its intrinsic properties of pigment before treatment. The surface treatment can thus be carried out for example by chemical reaction of a surfactant with the surface of the pigments and creation of a covalent bond between the surfactant and the pigments. This method is especially described in US Pat. No. 4,578,266. Preferably, an organic agent bound to the pigments will be used in a covalent manner. The agent for the surface treatment may represent from 0.1 to 50% by weight of the total weight of the pigments or fillers treated on the surface, preferably from 0.5 to 30% by weight, and even more preferably from 1 to 10% by weight.

  Preferably, the surface treatments of the pigments are chosen from the following treatments: a PEG-silicone treatment such as the AQ surface treatment marketed by LCW; a Chitosan treatment such as the CTS surface treatment marketed by LCW; a Triethoxycaprylylsilane treatment such as the AS surface treatment marketed by LCW; a Methicone treatment such as the SI surface treatment marketed by LCW; a dimethicone treatment such as the Covasil 3.05 surface treatment marketed by LCW; a dimethicone / trimethylsiloxysilicate treatment such as the Covasil 4.05 surface treatment marketed by LCW; A Lauroyl Lysine treatment such as the LL surface treatment marketed by LCW; a Lauroyl Lysine Dimethicone treatment such as the LL / SI surface treatment marketed by LCW; a magnesium Myristate treatment such as the 20 MM surface treatment marketed by LCW; an aluminum dimyristate treatment such as the MI surface treatment marketed by Miyoshi; a perfluoropolymethylisopropyl ether treatment such as the FHC surface treatment marketed by LCW; An Isostearyl Sebacate treatment such as the HS surface treatment marketed by Miyoshi; a Disodium Stearoyl Glutamate treatment such as the NAI surface treatment marketed by Miyoshi; a Dimethicone / Disodium Stearoyl Glutamate treatment such as the SA / NAI surface treatment marketed by Miyoshi; a perfluoroalkyl phosphate treatment such as the PF surface treatment marketed by Daito; an acrylate / dimethicone copolymer and perfluoroalkyl phosphate copolymer treatment such as the FSA surface treatment marketed by Daito; a Polymethylhydrogen siloxane / perfluoroalkyl phosphate treatment such as the FS01 surface treatment marketed by Daito; a Lauryl Lysine / Aluminum Tristearate treatment such as the LL-StAl surface treatment marketed by Daito; Octyltriethylsilane treatment, such as the OTS surface treatment marketed by Daito, an octyltriethylsilane / perfluoroalkylphosphate treatment, such as the FOTS surface treatment marketed by Daito; an Acrylate / Dimethicone copolymer treatment such as the ASC surface treatment marketed by Daito; an Isopropyl Titanium Triisostearate treatment such as the ITT surface treatment marketed by Daito; a Cellulose Microcrystalline and Carboxymethyl Cellulose treatment, such as the AC surface treatment marketed by Daito; A Cellulose treatment such as the C2 surface treatment marketed by Daito, an Acrylate copolymer treatment such as the APD surface treatment marketed by Daito, a Perfluoroalkyl Phosphate / Isopropyl Titanium Triisostearate treatment, such as the PF + ITT surface treatment marketed by Daito. . The pigment or pigments are each generally present in the composition according to the invention in amounts generally between 0.05 and 50% of the total weight of the composition, preferably from 0.1 to 35%.

  Polymerization inhibitors, and more particularly anionic and / or radical polymerization inhibitors, may be introduced into the compositions in order to increase the stability of the composition over time. In a nonlimiting manner, mention may be made of the following polymerization inhibitors: sulfur dioxide, nitric oxide, boron trifluoride, hydroquinone and its derivatives such as hydroquinone monethyl ether, TBHQ, benzoquinone and its derivatives. derivatives such as duroquinone, catechol and its derivatives such as t-butyl catechol and methoxycatechol, anisole and its derivatives such as methoxyanisole or hydroxyanisole, pyrogallol and its derivatives, p-methoxyphenol, hydroxybutyl toluene, alkyl sulfates, alkyl sulfites, alkyl sulfones, alkyl sulfoxides, alkyl sulfides, mercaptans, 3-sulfonene and mixtures thereof. The alkyl groups preferably denote groups having 1 to 6 carbon atoms. It is also possible to use inorganic or organic acids as inhibitors. Thus, the cosmetic composition according to the invention may also comprise at least one mineral or organic acid, the latter having one or more carboxylic or sulphonic groups, having a pKa ranging from 0 to 6 such as phosphoric acid, hydrochloric acid, nitric acid, benzene or toluenesulfonic acid, sulfuric acid, carbonic acid, hydrofluoric acid, acetic acid, formic acid, propionic acid, benzoic acid, mono-, di- or trichloroacetic acids, salicylic acid and trifluoroacetic acid, octanoic acid, heptanoic acid and hexanoic acid.

  Preferably, acetic acid is used. The concentration of inhibitor in the cosmetic composition of the invention may be between 10 ppm and 30% by weight and more preferably between 10 ppm and 15% by weight relative to the total weight of the composition.

  The composition of the invention may comprise one or more cosmetic additives customary for the treatment of keratin materials. They can be chosen from this non-exhaustive list such as reducing agents, oxidizing agents, sequestering agents, softeners, defoamers, polymeric or non-polymeric thickeners, mineral or organic thickeners (such as benzylidene sorbitol). N-acylamino acids), moisturizing agents, charge dispersants, emollient agents, organic or inorganic bases, plasticizers, sunscreens, optical brighteners, direct or oxidation dyes, pigments, mineral fillers , clays, colloidal minerals, colloidal metals, quantum well semiconductor nanoparticles based on metals or silicon, a photo or thermochromic compound, nacres, pearlescent agents, perfumes, peptizers, preservatives, proteins, vitamins, anti-dandruff agents, anionic, cationic or amphoteric polymers fixing or not, non-polymeric conditioning agents such as cationic, anionic or amphoteric surfactants, oxyethylenated waxes or not, paraffins, C10-C30 fatty acids such as stearic acid, lauric acid, C10-C30 fatty amides such as lauric diethanolamide, C10-C30 fatty alcohol esters such as C10-C30 fatty alcohol benzoates and mixtures thereof. Preferably, the composition contains at least one dispersant. These agents may be optionally encapsulated. The capsule may be of the polycyanoacrylate type. A thruster may be integrated into the composition of the invention. The propellant consists of compressed or liquefied gases usually used for the preparation of aerosol compositions. Air, carbon dioxide, compressed nitrogen or a soluble gas such as dimethyl ether, halogenated (especially fluorinated) or non-halogenated hydrocarbons (butane, propane, isobutane) and mixtures thereof will preferably be used.

  The hair treatment method according to the invention consists in applying the composition described above to keratin materials, and in particular in the presence of a nucleophilic agent with or without heating. These two operations can also be performed after application of the composition. It is also possible to modulate the anionic polymerization kinetics by pre-impregnating the keratin materials with a nucleophilic agent. The nucleophilic agent can be used pure, in solution, in the form of an emulsion, or be encapsulated. To modulate the kinetics of anionic polymerization, it is also possible to increase the nucleophilicity of the fiber by chemical transformation of the keratinous material. By way of example, mention may be made of the reduction of di-sulphide bridges which partially comprise keratin in thiols before application of the composition of the invention. In a non-exhaustive manner, mention may be made, as reducing agents, of di-sulphide bridges, part of which consist of keratin, the following compounds: anhydrous sodium thiosulfate, sodium metabisulphite powder, thiourea, ammonium sulphite, thioglycolic acid , - thiolactic acid, - ammonium thiolactate, - glycerol mono-thioglycolate, - ammonium thioglycolate, - thioglycerol, - 2,5-dihydroxybenzoic acid, - diammonium di-thioglycolate, - strontium thioglycolate, - thioglycolate calcium, zinc -formosulfoxylate, isooctyl thioglycolate, dl-cysteine, monoethanolamine thioglycolate. To modulate anionic polymerization kinetics, and more specifically to reduce the polymerization rate of the monomers of the invention, it is possible to increase the viscosity of the composition. To do this, it is possible to add to the composition of the invention one or more polymers which have no reactivity with the monomers according to the invention. In this context, mention may be made in a non-exhaustive manner of poly (methyl methacrylate) (PMMA) or else copolymers based on cyanoacrylate as described in US Pat. No. 6,224,622.

  In order to improve inter alia the adhesion of the poly (cyanoacrylate) formed in situ, the fiber can be pretreated with all types of polymers. It is also possible to perform a hair treatment before application of the composition of the invention, such as a direct or oxidation coloring, a permanent or a hair straightener. The method of application of the compositions according to the invention may or may not be followed by rinsing. The compositions of the invention after application to the hair may be rinsed or not.

  The compositions may be in various galenic forms such as a lotion, an aerosol mousse, a spray, a conditioner or a shampoo, a gel or a wax. The compositions may be contained in a pump bottle, an aerosol spray.

  The treatment of the fiber can be a one-step process. In which case, the composition of the invention is applied to dry hair or previously moistened or shampooed. The hair is dried in the hair dryer, helmet or iron. A terminal shampoo may optionally be performed.

  The hair fiber can be pre-treated with at least one nucleophilic agent. When the composition according to the invention consists of two compositions, one comprising the silica particles according to the invention and the other comprising the cyanoacrylate monomer, then another embodiment of the process of the invention may be provided. The hair fiber may be pre-treated with the composition comprising the silica particles according to the invention. The hair can be dried. Then the second composition containing at least one cyanoacrylate monomer in a cosmetic solvent is applied to the hair. The hair is dried (hair dryer, helmet or iron). A terminal shampoo may be optionally performed.

  A particular method consists in combining the treatment according to the invention with treatments of the existing fiber such as the application of a perm reducer or a perm or an oxidation coloring or a discoloration or a shampoo or styling product or alkaline hair straightener. In this way the fiber is prepared to make the efficiency more important, by stripping the fiber and / or by etching the fiber as seen previously. In a second step, the composition of the invention is applied, the fiber being able to be previously treated with a nucleophilic agent. Another method consists in applying the treatment according to the invention before treatments of the fiber described above, capable of damaging the keratinous fibers. In this way, the fiber is protected during processing. It is then possible to remove the fiber, that is to say remove the sheathing resulting from the composition of the invention. The subject of the invention is also the use of the compositions described above for the cosmetic treatment of keratin materials, and in particular keratinous fibers such as the hair. The compositions may in particular be used for reinforcing keratin materials, and keratinous fibers, and in particular for providing volume and a particularly permanent cladding.

  Finally, the subject of the invention is a kit comprising a first composition containing at least one cyanoacrylate monomer, and optionally at least one anionic and / or radical and / or acidic polymerization inhibitor, and a second composition comprising at least one organic solvent. liquid, at least one silica particle and optionally an acid.

  According to one variant, the kit comprises a first anhydrous composition that comprises the silica particle (s) and the electrophilic monomer (s) and a second composition that comprises a nucleophilic agent.

  The following examples are intended to illustrate the invention, but are not limiting in nature.

  EXAMPLES Example 1 The following composition was produced poly dimethyl siloxane alpha-omega dihydroxy / 6.8 g cyclopentadimethylsiloxane (14.7 / 85.3) marketed by Dow Corning under the name DC 1501 Fluid cyclopentadimethylsiloxane marketed by Dow Corning under the name 91 , 2g name of DC245 Fluid Silica AEROSIL 200 1g Methylheptylcyanoacrylate Chemence lg 0.25g of this composition is applied to a lock of brown hair of 1g previously shampooed. After a pause of 15 minutes at room temperature, the wick is dried with a hair dryer for 3 minutes. 10 The hair is sheathed. This effect is still visible after several shampoos. EXAMPLE 2 The following composition is made of poly dimethyl siloxane alpha-omega dihydroxylated / 6.8 g cyclopentadimethylsiloxane (14.7 / 85.3) marketed by Dow Corning under the name DC 1501 Fluid cyclopentadimethylsiloxane marketed by Dow Corning under 91.1 g name of DC245 Fluid Silica AEROSIL 200 1g 245 OCTACARE DSP OL300 of Avécia * 0, lg Methylheptylcyanoacrylate of Chemence 1g * Dispersant marketed by AVECIA 0.25g of this composition is applied on a lock of brown hair of 1g previously shampooed. After standing for 15 minutes at room temperature, the wick is dried with a hair dryer for 3 minutes.

  The hair is sheathed. This effect is still visible after several shampoos. EXAMPLE 3 The following composition is made of poly dimethyl siloxane alpha-omega dihydroxy / 45 g cyclopentadimethylsiloxane (14.7 / 85.3) sold by Dow Corning under the name DC 1501 Fluid cyclopentadimethylsiloxane sold by Dow Corning under the name DC245 42g. Fluid Sunsphere H31 marketed by Asahi Glass 3g Methylheptylcyanoacrylate Chemence 10g 0.25g of this composition is applied to a lock of brown hair of 1g previously shampooed. After standing for 15 minutes at room temperature, the wick is dried with a hair dryer for 3 minutes.

  The hair is sheathed, This effect is still visible after several shampoos.

  EXAMPLE 4 The following composition is made of poly dimethyl siloxane alpha-omega dihydroxylated / 40g cyclopentadimethylsiloxane (14.7 / 85.3) sold by Dow Corning under the name DC 1501 Fluid cyclopentadimethylsiloxane marketed by Dow Corning under the name 37g DC245 Fluid Sunsphere H31 marketed by Asahi Glass 3g Nacre Mica-Iron Oxide Prestige Bronze marketed by Eckart 10 g Chemence Methylheptylcyanoacrylate 10g 0.5g of this composition is applied to a lock of hair brown lg previously shampooed. After a pause of 15 minutes at room temperature, the wick is dried with a hair dryer for 3 minutes. The hair is sheathed and colored. These effects are still visible after several shampoos.

Claims (18)

  1. Cosmetic composition comprising: a) at least one cyanoacrylate monomer of formula (I): ## STR1 ## in which: X denotes an oxygen or sulfur atom or an NH group; R 1 and R 2 each independently denote a group with little or no electro-attractor (little or no inductive-attractor) • R '3 denotes a hydrogen atom or a saturated or unsaturated hydrocarbon group, linear , branched or cyclic, preferably containing from 1 to 20, more preferably from 1 to 10 carbon atoms, and optionally containing one or more nitrogen, oxygen and sulfur atoms, and optionally: substituted with one or more groups chosen from -OR ', -COOR', -COR ', -SH, -SR', -OH, the halogen atoms and a polymer residue obtainable by radical polymerization or by polycondensation or by ring opening, R denoting a C1-C10 alkyl group; b) at least one silica particle whose size is less than 30 μm; and c) at least one liquid organic solvent.   2. Composition according to the preceding claim, characterized in that the cyanoacrylate monomer is of formula belonging to the family: i) either C 1 -C 20 polyfluoroalkyl 2-cyanoacrylates such as: -the ester of 2,2,3, 3-tetrafluoropropyl of 2-cyano-2-propenoic acid of formula (II): CN COOCH2CF2CHF2 20- or 2,2,2-trifluoroethyl ester of 2-cyano-2-propenoic acid of formula (III): CN (III) COOCH2CF3 ii) the alkyl or alkoxyalkyl 2-cyanoacrylate of formula (I) in which R'3 represents a C1-C10 alkyl radical; C2-C10 alkenyl or (C1-C4) alkoxy (C1-C10) alkyl.   3. Composition according to claim 1 characterized in that the cyanoacrylate monomer of formula (I) comprises R1 and R2 representing a hydrogen atom, X representing an oxygen atom and R'3 representing a linear C1-Clo alkyl group. or branched.   4. Composition according to the preceding claim characterized in that the cyanoacrylate monomer is of formula (IV) or mixtures thereof: CN (IV) COOR'3 wherein R'3 = - (CH2) 7-CH3, - CH (CH3) ) - (CH2) 5-CH3, -CH2-CH (C2H5) - (CH2) 3-CH3, - (CH2) 5-CH (CH3) -CH3, - (CH2) 4-CH (C2H5) -CH3.   5. Composition according to any one of the preceding claims, characterized in that the silica particle is hydrophilic.   6. Composition according to the preceding claim characterized in that the organic solvent is constituted by at least one volatile silicone.   7. Composition according to any one of the preceding claims, characterized in that the said composition is anhydrous.   8. Composition according to any one of the preceding claims, characterized in that it contains at least one acid.   9. Use of the composition as defined in any one of claims 1 to 8 for the treatment of keratin materials, and in particular keratin fibers such as the hair.   10. A method of treating keratin materials characterized in that it comprises the application on said keratinous materials of the composition 10 as defined in any one of claims 1 to 8.   11. Method according to the preceding claim characterized in that the composition of the invention is applied to dry keratin materials or previously moistened or shampooed.   12. The method of claim 10 characterized in that the composition of the invention is applied to the keratin materials followed by the application of a nucleophilic agent. 20   13. Method according to any one of claims 10 or 11 characterized in that the keratinous material, in particular the keratin fiber such as hair, may be pre-treated with at least one nucleophilic agent.   14. Method according to any one of claims 10 to 12 characterized in that the keratinous material, in particular the keratinous fiber such as hair, may be pretreated with at least one type of silica particle dispersed in a cosmetic solvent.   15. Process for treating keratinous material, in particular keratinous fiber such as hair, characterized in that in a first step, a complete permanent reducing agent or a permanent or an oxidation dyeing or a discoloration is applied to said keratinous material. or a shampoo or a styling product or an alkaline straightener and in a second step is carried out according to any one of claims 10 to 14. 15   16. A method of treating keratinous material, especially keratinous fiber such as hair, characterized in that i) in the first step said fiber is protected by a method according to any one of claims 11 to 14; ii) in the second step said fiber is treated in particular by the application of a permanent reducing agent or by the complete perm or by oxidation dyeing or alkaline stripping or straightening; and iii) in the third step said fiber is cleansed.   17. Kit comprising a first composition containing at least one cyanoacrylate monomer and optionally at least one anionic and / or radical and / or acidic polymerization inhibitor, and a second composition comprising in a cosmetically acceptable medium at least one liquid organic solvent, at least one silica particle and optionally an acid.   18. Kit comprising a first anhydrous composition containing at least one silica particle and at least one electrophilic monomer and a second composition containing at least one nucleophilic agent.