FR2891741A1 - Process useful for make-up or care of the keratinous matters other than hair, comprises applying a composition comprising an electrophilic monomer and solid particles that are treated on their surfaces e.g. with a silicone compound - Google Patents

Abstract

Process for make-up or care of the keratinous matters other than hair, comprises applying a composition comprising an electrophilic monomer and solid particles that are treated on their surfaces with a silicone compound, a fluorinated compound and/or a fluorosilicone compound.

Description

The subject of the present invention is a process for making up or caring for

  keratin materials other than hair such as skin, lips, nails and eyelashes, comprising applying to said keratin materials a composition comprising solid particles surface-treated with a silicone or fluoro compound, and at least one electrophilic monomer. The object of the present invention is to provide a makeup or care process comprising the application of a composition containing an electrophilic monomer, in particular an alkyl cyanoacrylate, which has a good stability over time. It is known to those skilled in the art that the polymerization of alkyl cyanoacrylates can be accelerated by pigments or fillers. By way of example, US Pat. No. 5,290,825 describes this phenomenon. In order to obtain stable cosmetic compositions over time, it is therefore necessary to seek a technical solution for inhibiting the reaction between alkyl cyanoacrylates and solid particles such as pigments and fillers. The Applicant has unexpectedly found that the surface treatment of these solid particles by particular compounds makes it possible to inhibit the polymerization reaction of the alkyl cyanoacrylates. It is more specifically the treatment with fluorinated compounds and / or silicone. The subject of the present invention is thus a method for making up or caring for keratinous materials other than the hair, comprising applying to said keratin materials a cosmetic composition comprising at least one electrophilic monomer, and solid particles surface-treated with a silicone compound. , a fluorinated compound, a fluoro-silicone compound, or a mixture thereof. Solid particles are understood to mean particles in the solid state at 25 ° C. and atmospheric pressure in said composition. The solid particles can be surface-treated with a compound that is itself solid or liquid. The solid particles treated at the surface may be chosen from: - pigments surface-treated with a silicone compound, a fluorinated compound, a fluoro-silicone compound, or a mixture thereof, the surface-treated fillers with a silicone compound, a compound fluoro, a fluoro-silicone compound, or a mixture thereof, and mixtures thereof. PIGMENTS In the context of the invention, the pigments that are not surface-treated have a solubility in water of less than 0.01% at 20 ° C., preferably less than 0.0001%, and an absorption between 350 and 700 nm, preferably an absorption with a maximum. The untreated surface pigment, hereinafter called pigment, may be an organic pigment. By organic pigment is meant any pigment that meets the definition of the Ullmann encyclopedia in the chapter on organic pigment. The organic pigment may especially be chosen from nitroso compounds, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, quinophthalone. The organic pigment (s) may be chosen for example from among 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 coded in the Color Index under the references Cl 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified 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 Cl 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 described in These pigments can also be in the form of composite pigments as described in patent EP 1 184 426. This composite pigment can be composed in particular of particles comprising an inorganic core, at least one binder ensuring fixing the organic pigments on the core, and at least one organic pigment at least partially covering the core. By way of example, mention may also be made of organic pigment pigment pastes such as the products sold by HOECHST under the name: YELLOW COSMENYL IOG: Pigment YELLOW 3 (Cl 11710) YELLOW COSMENYL G: Pigment YELLOW 1 (Cl 11680) ORANGE COSMENYL GR: Pigment ORANGE 43 (Cl 71105) RED COSMENYL R ": RED 4 Pigment (Cl 12085) 10 CARMIN COSMENYL FB: Pigment RED 5 (Cl 12490) VIOLET COSMENYL RL: Pigment VIOLET 23 (Cl 51319) COSMENYL BLUE A2R: BLUE Pigment 15.1 (Cl 74160) GREEN COSMENYL GG: GREEN Pigment 7 (Cl 74260) COSMENYL BLACK R Pigment BLACK 7 (Cl 77266) The pigment can also be a lacquer, lacquer is understood to mean the dyes adsorbed on particles The inorganic substrates on which the dyes are adsorbed are, for example, alumina, silica, calcium and sodium borosilicate or calcium borosilicate, which are insoluble. aluminum, and aluminum. organic, carmine of cochineal. 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 25 45 430), D & C Red 7 (Cl 15 850: 1), D & C Red 4 (Cl 15 510), D & C Red 33 (Cl 17,200), D & C Yellow 5 (Cl 19,140), D & C Yellow 6 (Cl 15,985), D & C Green (Cl 61,570), D & C Yellow 10 (Cl 77,002), D & C Green 3 (Cl 42,053), D & C Blue 1 (Cl 42,090). The pigment can also be a special effects pigment. By special effect pigments is meant 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 depending on the observation conditions (light, temperature, observation angles ...). They are therefore opposed to white or colored pigments that provide a uniform opaque, semi-transparent or conventional transparent tint. There are two types of special effect pigments, those with a low refractive index, such as fluorescent, photochromic or thermochromic pigments, and those with a higher refractive index, such as nacres or flakes. As special effect pigments, mention may be made of pearlescent pigments such as white pearlescent pigments such as mica coated with titanium, or bismuth oxychloride, colored pearlescent pigments such as titanium mica with iron oxides, titanium mica with in particular ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride. Special effect pigments also include fluorescent pigments, whether they are fluorescent substances in daylight or that produce ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments. The pigment may be a mineral pigment. By mineral pigment is meant any pigment that meets the Ullmann Encyclopedia definition in the inorganic pigment chapter. Mention may be made, among the mineral pigments useful in the present invention, of zirconium or cerium oxides, as well as oxides of iron or chromium, manganese violet, ultramarine blue, chromium hydrate and ferric blue, titanium dioxide. The following mineral pigments can also be used: Ta2O5, Ti3O5, Ti2O3, TiO, ZrO2 mixed with TiO2, ZrO2, Nb2O5, CeO2, ZnS.

  The pigment may also be a pearlescent pigment such as white pearlescent pigments, for example mica coated with titanium, or bismuth oxychloride, colored pearlescent pigments such as mica coated with titanium and iron oxides, coated mica 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. By way of example, mention may be made of Cellini pigments marketed by Engelhard (Mica-TiO2-lacquer), Prestige marketed by Eckart (Mica-TiO2), Colorona sold by Merck (Mica-TiO2-Fe2O3) In addition to mother-of-pearl mica support, it is possible to envisage multilayer pigments based on synthetic substrates such as alumina, silica, calcium and sodium borosilicate or calcium and aluminum borosilicate, and aluminum.

  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 surface-treated pigment or pigments are generally present in the composition in total amounts generally of between 0.05 and 50% of the total weight of the composition, preferably from 0.1 to 35%, preferably from 0.5 to 20%.

  Fillers The composition may contain at least one filler surface-treated with a silicone compound, a fluorinated compound, a fluoro-silicone compound, or a mixture thereof. By "filler" is meant an untreated surface filler which is a solid compound at room temperature and atmospheric pressure not chemically reactive with the various ingredients of the composition.

  This compound is further insoluble in these ingredients, even when these ingredients are brought to a temperature above room temperature. The fillers can be mineral or organic. The fillers may be particles of any form, in particular platelet, spherical or oblong, irrespective of their crystallographic form (for example sheet, cubic, hexagonal, orthorhombic). Among the fillers that can be used in the compositions according to the invention, mention may notably be made of talc, natural or synthetic mica, silica, kaolin, polyamide (nylon), poly-13-alanine and polyethylene powders, polymer powders of tetrafluoroethylene (Teflon), lauroyl-lysine, starch, boron nitride, acrylic acid polymer powders, - silicone resin microbeads (TOSHIBA TOSPEARLS, for example), - bismuth oxychlorides, precipitated calcium carbonate, magnesium carbonate and hydrocarbonate, hydroxyapatite. the hollow silica microspheres (such as the 'SILICA BEADS SB 700 / HA' or 'SILICA BEADS SB 700' from the company MAPRECOS, the 'SUNSPHERES H-33' and the 'SUNSPHERES H-51' from the company ASAHI GLASS), microspheres of acrylic polymers (such as those of crosslinked acrylate copolymer 'POLYTRAP 6603 ADSORBER' from the company RP SCHERRER, and those of polymethyl methacrylate 'MICROPEARL M 100' from the company SEPPIC), the powders polyurethane (such as the copolymer powder of hexamethylene diisocyanate and trimethylol hexyl lactone sold under the name PLASTIC POWDER D-400 by TOSHIKI), glass or ceramic microcapsules, metal soaps derived from organic acids carboxylic acids having from 8 to 22 carbon atoms, in particular from 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate, polymeric microcapsules, res or copolymers of acrylate or methyl methacrylate, or polyvinylidene chloride-acrylonitrile copolymers, like! ' EXPANCEL of EXPANCEL; elastomeric crosslinked organopolysiloxane powders, such as those sold under the name TREFIL POWDER E-506C by the company Dow Corning, and mixtures thereof. The surface-treated fillers may have an apparent diameter ranging from 0.01 to 150 m and better still from 0.5 to 150 m. An apparent diameter corresponds to the diameter of the circle in which the elementary particle is inscribed according to its smallest dimension (thickness for lamellae). The surface-treated filler or fillers are generally present in the composition in total amounts of between 0.05 and 95% of the total weight of the composition, preferably from 0.1 to 50%, preferably from 0.5 to 30%. %. SURFACE TREATMENT The pigments or fillers may be totally or partially surface-treated with a silicone-type compound, a fluorinated-type compound, a fluoro-silicone-type compound, or a mixture thereof.

  By silicone compound is meant a compound comprising at least one silicon atom. By fluorinated compound is meant a compound comprising at least one fluorine atom. By fluoro-silicone compound is meant a compound comprising at least one fluorine atom and at least one silicon atom.

  The pigments and surface-treated fillers may be prepared according to chemical, electronic, mechano-chemical or mechanical surface treatment techniques well known to those skilled in the art. Commercial products can also be used.

  The surfactant can be absorbed or adsorbed onto the solid particles by solvent evaporation, chemical reaction and creation of a covalent bond.

  According to one variant, the surface treatment consists of a coating of the pigments or fillers. The coating may comprise from 1 to 300% by weight of the weight of the untreated solid particles, for example from 5 to 200%, in particular from 10 to 100% by weight of the untreated solid particles. The coating may represent from 0.1 to 10% by weight, and in particular from 1 to 5% by weight of the total weight of the coated pigment.

  The coating may be carried out, for example, by adsorption of a liquid surface agent on the surface of the solid particles by simple stirring of the particles and said surfactant, optionally while hot, prior to the incorporation of the particles into the particles. other ingredients of the makeup or care composition.

  The coating can be carried out for example by chemical reaction of a surfactant with the surface of the solid particles and creation of a covalent bond between the surfactant and the particles. This method is described in particular in US Pat. No. 4,578,266.

  The chemical surface treatment may consist of diluting the surfactant in a volatile solvent, dispersing the solid particles in this mixture, then slowly evaporating the volatile solvent, so that the surfactant is deposited at the same time. surface of solid particles. SILICONE SURFACE AGENT Silicone surfactants may be selected from non-elastomeric organopolysiloxanes, silicone-acrylate copolymers, silicone resins, silicone elastomers, silane derivatives, and mixtures thereof.

  By organopolysiloxane compound is meant a compound having a structure comprising an alternation of silicon atoms and oxygen atoms and comprising organic radicals bonded to the silicon atoms. Silicone elastomers By elastomer is meant a flexible, deformable material having viscoelastic properties and in particular the consistency of a sponge or soft sphere. Its modulus of elasticity is such that this material resists deformation and has limited capacity for extension and contraction. This material is able to recover its original shape after stretching. This elastomer is formed of high molecular weight polymer chains whose mobility is limited by a uniform network of crosslinking points. The elastomer can be obtained by addition reaction crosslinking (A) of diorganopolysiloxane containing at least two hydrogens each bonded to a silicon, and (B) of diorganopolysiloxane having at least two silicon-bonded ethylenically unsaturated groups, especially in the presence (C) platinum catalyst, as for example described in the application EP-A-295886. Compound (A) may thus be chosen from trimethylsiloxy-terminated methylhydrogenpolysiloxanes, trimethylsiloxy-terminated dimethylsiloxanemethylhydrogensiloxane copolymers, and dimethylsiloxane-methylhydrogensiloxane cyclic copolymers.

  The diorganopolysiloxane (B) may be chosen from methylvinylpolysiloxanes, the methylvinylsiloxane-dimethylsiloxane copolymers, dimethylpolysiloxanes comprising dimethylvinylsiloxy endings, dimethylsiloxane-methylphenylsiloxane dimethylvinylsiloxy end groups, copolymers terminated dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane dimethylsiloxane copolymers, dimethylsiloxane-methylvinylsiloxane trimethylsiloxy end groups, trimethylsiloxy-terminated dimethylsiloxane-methylphenylsiloxane-methylvinylsiloxane copolymers, dimethylvinylsiloxy-terminated methyl (3,3,3-trifluoropropyl) polysiloxane, and dimethylvinylsiloxy-terminated dimethylsiloxane-methyl (3,3,3-trifluoropropyl) siloxane copolymers. As elastomers, those sold under the names "KSG-6", "KSG-15", "KSG-16", "KSG-18", "KSG-31", "KSG-32", "KSG- 33 "," KSG-41 "," KSG-42 "," KSG-43 "," KSG-44 "by the company Shin Etsu," DC 9040 "," DC9041 "," DC 9509 "," DC9505 ", "DC 9506" by Dow Corning, "GRANSIL" by Grant Industries, "SFE 839" by General Electric. The elastomer may be a polyoxyalkylene elastomer is obtained by addition reaction crosslinking (Al) of diorganopolysiloxane containing at least two hydrogens each bonded to a silicon, and (B1) of polyoxyalkylene having at least two ethylenically unsaturated groups, especially in the presence (Cl) platinum catalyst, as for example described in US5236986 and US5412004.

  Polyoxyalkylenated elastomers are described in particular in patents US5236986, US5412004, US5837793 and US5811487, the contents of which are incorporated by reference.

  As the polyoxyalkylene silicone elastomer, those sold under the names "KSG-21", "KSG-20", "KSG-30", "KSG-31", KSG-32 "," KSG-33 "," can be used. KSG-210, KSG-310, KSG-320, KSG-330, KSG-340, X-226146 by Shin Etsu, DC9010, DC9011 by the company Dow Corning The silicone elastomer may be a polyglycerolated elastomer such elastomers are described in particular in the patent application WO2004 / 024798.

  As polyglycerolated silicone elastomers, those sold under the names "KSG-710", "KSG-810", "KSG-820", "KSG-830", "KSG-840" by the company Shin Etsu can be used. Non-Elastomeric Organopolysiloxane Non-elastomeric organopolysiloxanes that may especially be mentioned include polydimethylsiloxanes, polymethylhydrogensiloxanes and polyalkoxydimethylsiloxanes.

  The alkoxy group may be represented by the radical RO- such that R represents methyl, ethyl, propyl, butyl or octyl, 2-phenylethyl, 2-phenylpropyl or 3,3,3-trifluoropropyl radicals, aryl radicals such as phenyl, tolyl, xylyl, or substituted aryl radicals such as phenylethyl.

  A method for surface treatment of pigments or fillers with a polymethylhydrogenosiloxane is to disperse the pigments or fillers in an organic solvent and then to add the silicone compound. By heating the mixture, covalent bonds are created between the silicone compound and the surface of the solid particle.

  Alkylsilanes and Alkoxysilanes Alkoxy functional silanes are described in particular by Witucki in silane primer, Chemistry and applications of alkoxy silanes, Journal of Coatings technology, 65, 822, pages 57-60, 1993 D.

  Alkoxysilanes such as alkyltriethoxysilanes and alkyltrimethoxysilanes sold under the references Silquest A-137 (OSI Specialties) and Prosil 9202 (PCR) can be used for the treatment of pigments or fillers.

  The use of alkylpolysiloxanes having a reactive end group such as alkoxy, hydroxy, halogen, amino or imino are described in JP 077-196946. They are also suitable for the treatment of pigments or fillers.

  Silicone-Acrylate Polymers Grafted silicone-acrylic polymers having a silicone backbone as described in US Patents 5,725,882, US 5,209,924, US 4,972,037, US 4,981,903, US 4,981,902, US 5,468 477, and in US Patents 5,219,560 and EP 0388,582 may be used.

  Other silicone-acrylate polymers may be silicone polymers having in their structure the following unit of formula (I): ## STR1 ## where G 1 (G 2), .TS-G 3 Gl (G 2) 7 SiG 4 in which the radicals G 1, which may be identical or different, represent hydrogen, a C 1 -C 10 alkyl radical or a phenyl radical; the radicals G2, which may be identical or different, represent a C1-C10 alkylene group; G3 represents a polymeric residue resulting from the (homo) polymerization of at least one ethylenically unsaturated anionic monomer; G4 represents a polymeric residue resulting from the (homo) polymerization of at least one hydrophobic monomer containing ethylenic unsaturation; m and n are 0 or 1; a is an integer ranging from 0 to 50; b is an integer which may range from 10 to 350, where c is an integer from 0 to 50; provided that one of the parameters a and c is different from 0. Preferably, the unit of formula (I) above has at least one, and even more preferably all, of the following characteristics: radicals G denote an alkyl radical, preferably the methyl radical; n is non-zero, and the radicals G 2 represent a divalent C 1 -C 3 radical, preferably a propylene radical; G3 represents a polymeric radical resulting from the (homo) polymerization of at least one monomer of the carboxylic acid type with ethylenic unsaturation, preferably acrylic acid and / or methacrylic acid; G4 represents a polymeric radical resulting from the (homo) polymerization of at least one monomer of the (C 1 -C 10) alkyl (meth) acrylate type, preferably of the isobutyl (meth) acrylate type or of methyl. Examples of silicone polymers corresponding to formula (I) are, in particular, polydimethylsiloxanes (PDMS) on which are grafted, via a thiopropylene-type connecting member, mixed polymeric units of the poly (meth) acrylic acid type. and of the poly (meth) acrylate type. Other examples of silicone polymers corresponding to formula (I) are, in particular, polydimethylsiloxanes (PDMS) on which are grafted, via a thiopropylene type connecting member, poly (meth) acrylate type polymer units. isobutyl.

  Silicone Resins By the term resin is meant a three-dimensional structure. In one embodiment, the silicone resin is selected from silsesquioxanes and siloxysilicates.

  In one embodiment, the silicone resin is selected from siloxysilicates, such as trimethylsiloxysilicates, which are represented by the following formula: [R 3 SiO 2] X (SiO 4, 2) y (M and Q units), wherein x and There may be values ranging from 50 to 80, and R is alkyl, such as methyl or an alkyl of two or more carbon atoms. The film-forming silicone resin may be selected, for example, from WACKER resins 803 and 804, available from WACKER SILICONE CORPORATION, and G.E. 1 170-002, available from GENERAL ELECTRIC. In another embodiment, the silicone resin is selected from silsesquioxanes which comprise units T: [RSiO312] t (units T), in which a value of up to several thousand and R represents an alkyl, such a methyl or an alkyl of two or more carbon atoms. In one embodiment, silsesquioxane is selected from polymethylsilsesquioxanes, which are silsesquioxanes such that R is a methyl group. Polymethylsilsesquioxanes may include, for example, TOSPEARLTM from TOSHIBA or KMP590 from SHIN-ETSU, BELSIL PMS MK (also referred to as MK resin), available from WACKER CHEMIE, KR-220L, available from SHIN-ETSU. . The KR-220L structure consists essentially of T (CH3SiO312) silicone units with Si-OH or silanol end units. There is no pattern D.

  By way of example of commercial references of pigments or fillers treated with a silicone compound, mention may be made of: Boron nitride / polymethylhydrogenosiloxane sold under the reference UHP 1107 by the company Carborundum, Red iron oxide / dimethicone sold under the reference SA-C 338075-10 by the company Miyoshi Kasei, a pigment obtained by treatment of DC Red 7 with a silicone compound, sold by the company Coletica under the reference Gransil GCM (which is a mixture of D4 and polysilicone 11), elastomeric cross-linked organopolysiloxane / silicone resin powders, such as those sold under the names "KSP-100", "KSP-101", "KSP-102", "KSP-103", KSP-100 104 "," KSP-105 "by SHIN ETSU.

  FLUORINATED SURFACE AGENT The fluorinated surfactants may be selected from perfluoroalkyl phosphates, perfluoropolyethers, polytetrafluoroethylene (PTFE) and perfluoroalkanes.

  Perfluoropolyethers are described in particular in patent application EP-A-486135 and sold under the trade names FOMBLIN by the company MONTEFLUOS. Perfluoroalkyl phosphates are in particular described in application JP H05-86984. The perfluoroalkyl phosphate-diethanol amines marketed by Asahi Glass under the reference AsahiGuard AG530 can be used. Among the linear perfluoroalkanes, mention may be made of perfluorocycloalkanes, perfluoro (alkylcycloalkanes), perfluoropolycycloalkanes, aromatic perfluorinated hydrocarbons (perfluoroarenes) and hydrocarbon-based perfluorinated hydrocarbon compounds comprising at least one heteroatom.

  Among the perfluoroalkanes, there may be mentioned the series of linear alkanes such as perfluorooctane, perfluorononane or perfluorodecane. Among the perfluorocycloalkanes and perfluoro (alkylcycloalkanes), mention may be made of perfluorodecalin sold under the name "FLUTEC PP5 GMP" by RHODIA, perfluoro (methyldecalin), perfluoro (C3-C5 alkylcyclohexanes) such as perfluoro ( butylcyclohexane).

  Among the perfluoropolycycloalkanes, mention may be made of bicyclo [3.3.1] nonane derivatives such as perfluorotrimethylbicyclo [3.3.1] nonane, derivatives of adamantane such as perfluorodimethyladamantane and perfluorinated derivatives of hydrogenated phenanthrene such as tetracosafluoro-tetradecahydrophenanthrene. .

  Among the perfluoroarenes, mention may be made of perfluorinated derivatives of naphthalene such as perfluoronaphthalene and perfluoromethyl-1-naphthalene.

  By way of example of commercial references of pigments and fillers treated with a fluorinated compound, mention may be made of: iron oxide / perfluoroalkyl phosphate sold under the reference PF 5 Yellow 601 by the company Daito Kasei, red iron oxide / perfluoroalkyl phosphate sold under the reference PF 5 Red R 516L by the company Daito Kasei, - black iron oxide / perfluoroalkyl phosphate sold under the reference PF 5 Black BL 100 by the company Daito Kasei, Titanium dioxide / perfluoroalkylphosphate sold under the reference PF 5 TiO 2 CR 50 by the company Daito Kasei, yellow iron oxide / perfluoropolymethylisopropylether sold under the reference Iron oxide yellow BF-25-3 by the company Toshiki, - DC Red 7 / perfluoropolymethylisopropyl ether sold under the reference D & C Red 7 FHC by the company Cardre Inc., 25 -The DC Red 6 / PTFE sold under the reference T 9506 by the company Warner Jenkinson, - boron nitride / perfluoroper hydrophenanthrene sold under the reference Boron nitride TBN12 by the company Saint Gobain Advanced Ceramics. FLUORO-SILICONE TREATMENT AGENT The fluoro-silicone compound may be chosen from perfluoroalkyl dimethicones, perfluoroalkyl silanes and perfluoroalkyl trialkoxysilanes.

  The term "perfluoroalkyl radical" means an alkyl radical in which all the hydrogen atoms have been replaced by fluorine atoms. Perfluoroalkyl silanes include LP-IT and LP-4T products marketed by Shin-Etsu Silicone. The perfluoroalkyl dimethicones may be represented by the following formula: ## STR2 ## in which: R represents a linear or branched divalent alkyl group having 1 to 6 carbon atoms, preferably a divalent methyl, ethyl, propyl or butyl group; represents a perfluoroalkyl radical, having 1 to 9 carbon atoms, preferably 1 to 4 carbon atoms, m is chosen from 0 to 150, preferably from 20 to 100, and n is chosen from 1 to 300, Preferably, from 1 to 100. By way of example of commercial references of pigment treated with a fluoro-silicone compound, mention may be made of titanium dioxide / fluorosilicone sold under the reference Fluorosil Titanium dioxide 100TA by Advanced 25 Dermaceuticals International Inc. ELECTROPHILIC MONOMER iH3 CH3 Tiù0 CH3 By electrophilic monomer is meant a monomer capable of polymerizing by anionic polymerization in the presence of a nucleophilic agent such as For example, hydroxyl ions (OH-) contained in water. By anionic polymerization is meant the mechanism defined in the "Advanced Organic Chemistry", Third Edition by Jerry March, pages 151 to 161. The electrophilic monomer (s) present in the composition of the invention are preferably selected from monomers of formula (I): ## STR1 ## wherein:

  R1 and R2 denote, 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, aromatic or aliphatic 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, sulfur, and optionally substituted with one or more groups selected from - OR, -OR, -COR, -SH, -SR, -OH, and halogen atoms, - polyorganosiloxane residue, modified or otherwise, a polyoxyalkylene group,

  R3 and R4 are each independently of one another an electron-withdrawing (or inductive-attracting) group preferably selected from -N (R) 3+, -S (R) 2+ groups, -SH2 +, -NH3 +, -NO2, -SO2R, -CN, -COOH, -COOR, -COSR, -CONH2, CONHR, -F, -Cl, -Br, -I, OR, -COR, -SH, - SR, -OH, linear or branched alkenyl groups, linear or branched alkynyl groups, C 1 -C 4 mono- or polyfluoroalkyl groups, aryl groups such as phenyl, or aryloxy groups such as phenoxyloxy,

  R denotes 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, sulfur, and optionally substituted with one or more groups selected from OR ', -COOR', -COR ', -SH, -SR', -OH, the halogen atoms, or a polymer residue obtainable by radical polymerization by polycondensation or by ring opening, R 'denotes a C 1 -C 6 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, we mean any group whose electronegativity is less than or equal to that of carbon. 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, there may be mentioned 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 electrophilic monomer (s) of formula (I) present in the composition of the invention may be chosen from: benzylidene malononitrile derivatives (A), 2- (4-chloro-benzylidene) malononitrile (Al) ethyl 2-cyano-3-phenyl acrylate (B) 1α, 2-cyano-3- (4-chloro-phenyl) acrylate (B1) described in Sayyah, J. Polymer Research, 2000, p. 97. CO2Et a CO2Et CN Cl Ph ~~ CN CN Ph ~ CN CN 20 (A) (B) - derivatives of methylidenemalonates such as 2-methylene-diethyl malonate (C) described by Hopff, Makromoleculare Chemie, 1961, p. 95, De Keyser, J. Pharm. Sci, 1991, p.67 and Klemarczyk, Polymer, 1998, p.173. CO2Et CO2Et (C) - ethyl 2-ethoxycarbonylmethyleneoxycarbonyl acrylate (D) described by Breton, Biomaterials, 1998, p.271 and Couvreur, Pharmaceutical Research, 1994, p.1270. 25,000 and the itaconate and itaconimide derivatives such as dimethyl itaconate (E) by Bachrach, European Polymer Journal, 1976, p.563. CO2Me ~ CO2Me (E) - the methyl α- (methylsulfonyl) acrylates (K), α- (methylsulfonyl) acrylates of ethyl (L), methyl α- (tert-butylsulfonyl) acrylates (M), tert-Butyl (N) tert-butyl (N) α- (tertbutylsulfonyl) acrylates α- (methylsulfonyl) acrylates, by O. Gipstein, J.Org.Chem, 1980, p.1486; and 1,1-bis- (Methylsulfonyl) ethylene (P), 1-acetyl-1-methylsulphonyl ethylene (Q), methyl (R), α-methylsulfonylacrylonitrile (S) a (methylsulfonyl) vinyl sulfonate (S) described in Shearer US2748050. SO2Me SO2Me SO2t-Bu SO2Me SO02t-Bu, CO2Me, CO2Et, CO2Me 'CO2t-Bu' CO2tBu (K) (L) (M) (N) (0) ME SO2Me SO2Me CN SO2 ~ SO 'COMe, SO3Me, SO2Me 2Me (P) (Q) (R) (S) O -t (D) Among the monomers of formula (I), preferred are the monomers of the cyanoacrylate family and their derivatives of formula (II): R1 C = NC = C R2 COXR'3 X denoting NH, S or O, R1 and R2 having the same meanings as above, preferably R1 and R2 representing a hydrogen atom, R'3 representing a hydrogen atom or R as defined in formula (I). Preferably, X denotes O. As compounds of formula (II), mention may be made of the monomers: a) belonging to the family of polyfluoroalkyl 2-cyanoacrylates such as: the 2,2,3,3-ester; tetrafluoropropyl of 2-cyano-2-propenoic acid of formula: ## STR1 ## wherein C 2 -C 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 2-cyano-2-propenoic compound of formula: C = N

CH2 = C (V) COO-CH2-CF3.

  b) alkyl or alkoxyalkyl 2-cyanoacrylates wherein R '3 represents a C 1 -C 10 alkyl radical or C 1 -C 4 alkoxy (C 1 -C 10) alkyl radical. 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-octyl 2-cyanoacrylate, 2-propoxyethyl 2-cyanoacrylate, n-octyl 2-cyanoacrylate and isoamyl cyanoacrylate. 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 cyanoacrylates. Particularly preferred monomers are octyl cyanoacrylates of formula (VI) and mixtures thereof: ## STR2 ## in which: R '3 = - (CH 2) 7 -CH 3 - CH (CH3) - (CH2) 5-CH3, -CH2-CH (C2H5) - (CH2) 3-CH3, - (CH2) 5-CH (CH3) -CH3, - (CH2) 4-CH (C2H5) CH3.

  The monomers used in accordance with the invention may be covalently attached to supports such as polymers, oligomers or dendrimers. The polymer or oligomer may be linear, branched, comb or block. The distribution of the monomers of the invention on the polymeric, oligomeric or dendritic structure may be statistical, in the terminal position or in block form. Other electrophilic monomers than those described above may also be used and be chosen from: N-butyl itaconimide (F), N- (4-tolyl) itaconimide (G), N- (2-ethylphenyl) itaconimide (H), N- (2,6-diethylphenyl) itaconimide (I) described by Wanatabe, J. Polymer Science: Part A: Polymer chemistry, 1994, p.2073. R = Bu (F), 4-tolyl (G), 2-ethylphenyl (H), 2,6-diethyphenyl (I) - the methyl vinyl sulfone (T) and phenyl vinyl sulfone (U) derivatives described by Boor, J. Polymer Science, 1971, p.249. SO2Me SO2Ph (T) (U) - the phenyl vinyl sulfoxide derivative (V) described by Kanga, Polymer preprints (ACS, Divison of Polymer Chemistry), 1987, p.322. se-Ph 1 O (V) - the 3-methyl-N- (phenylsulfonyl) -1-aza-1,3-butadiene derivative (W) described by Bonner, Polymer Bulletin, 1992, p.517. R 1 NSO 2 Ph (W) - acrylate and acrylamide derivatives such as: N-propyl-N- (3-triisopropoxysilylpropyl) acrylamide (X) and N-propyl-N- (3-5 triethoxysilylpropyl) acrylamide (Y) described by Kobayashi , Journal of Polymer Science, Part A: Polymer Chemistry, 2005, p.2754. Pr OiPr Pr Ot N ~~~~~~ O O (X) ^ 2-hydroxyethyl acrylate (Z) and 2-hydroxyethyl methacrylate (AA) described by Rozenberg, International Journal of Plastics Technology, 2003, p.17. N-Butyl acrylate (AB) described by Schmitt, Macromolecules, 2001, p.2115. Tert-butyl acrylate (AC) described by Ishizone, Macromolecules, 1999, p. 955. In the product of the invention, the amount of electrophilic monomers may be between 0.1 and 99% by weight of the total weight of the composition, preferably between 1 and 50%, preferably 3 to 40%. The electrophilic monomers can be synthesized according to the known methods described in the art. In particular, the cyanoacrylate monomers may be synthesized according to the teaching of US 3,527,224, US 3,591,767, US 3,667,472, US 3,995,641, US 4,035,334 and US 4,650,826.

  According to one embodiment, the electrophilic monomer, once deposited on the keratin materials, is intended to polymerize in contact with a nucleophilic agent such as water, to form an adherent film on the keratin materials.

  In the context of the invention, the electrophilic monomers are monomers capable of polymerizing anionically in the presence of a nucleophilic agent. The nucleophilic agents capable of initiating the anionic polymerization are systems known in themselves, capable of generating a carbanion in contact with a nucleophilic agent, such as the hydroxyl ions contained in water. By "carbanion" is meant the chemical species defined in Jerry March's "Advanced Organic Chemistry, Third Edition", page 141. The nucleophiles may be applied to the keratin materials via a composition distinct from the composition containing the electrophilic monomer. They can also be added to the composition of the invention at the time of use. The nucleophilic agent can be a molecular compound, an oligomer, a dendrimer or a polymer having nucleophilic functions. In a nonlimiting manner, the following functions may be mentioned as nucleophilic functions: R2N-, NH2, Ph3C-, R3C-, PhNH-, pyridine, ArS-, RCC-, RS-, SH-, RO-, R2NH, ArO-, N3, OH-, ArNH2, NH3, 1-, Br, C1-, RCOO-, SCN-, ROH, RSH, NCO-, CN-, NO3, CI04, H2O, Ph is phenyl; Ar represents an aryl group and R represents a C1-C10 alkyl group. In particular, the nucleophilic agent is water. The water may be provided by water naturally present on the surface of the keratin materials, by saliva, sweat, or by a composition which is applied to the keratin materials prior to the composition containing the electrophilic monomer. The water or the nucleophilic agent may also be provided by a composition which is applied to the composition containing the electrophilic monomer previously deposited on the keratin materials.

  The electrophilic monomer and the nucleophilic agent may thus be present in two separate compositions.

  The subject of the present invention is also a product comprising at least two cosmetically acceptable compositions, one corresponding to the composition containing the electrophilic monomer, and the surface-treated compound chosen from pigments, fillers and their mixtures, and the other containing the nucleophilic agent. The two compositions may be packaged separately or together in the same packaging article or in at least two separate packaging articles. Preferably, these compositions are packaged separately and advantageously in separate packaging articles.

  The invention also relates to a makeup kit containing the different compositions packaged separately and advantageously accompanied by appropriate application means. These means may be brushes, brushes, pens, pencils, felts, feathers, sponges, tubes and / or foam tips.

  The composition containing the electrophilic monomer and the surface-treated pigment or filler may be a base layer applied to the keratinous material and the composition containing the nucleophilic agent a top layer, or vice versa. It is possible to introduce, in the composition containing the electrophilic monomers or optionally into the composition containing the nucleophilic agent, polymerization inhibitors, and more particularly anionic and / or radical polymerization inhibitors, in order to increase the stability of the composition in the composition. the weather. In a nonlimiting manner, mention may be made of the following polymerization inhibitors: sulfur dioxide, nitric oxide, organic acids such as a sulphonic acid or phosphoric acid, acetic acid, lactone, trifluoride and the like. boron, hydroquinone and its derivatives such as hydroquinone monoethylether, tert-butylhydroquinone, benzoquinone and its 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 sulphates, alkyl sulphites, alkyl sulphones, alkyl sulphoxides, alkyl sulphides, mercaptans, and their mixtures. The alkyl groups preferably denote groups having 1 to 6 carbon atoms.

  The inhibitor concentration in a composition containing the electrophilic monomer may be between 10 ppm and 10%, and more preferably between 50 ppm and 5% by weight. The composition may also contain one or more polymers having no reactivity on the electrophilic monomers and capable of increasing the viscosity of the composition. The increase in viscosity makes it possible to reduce the polymerization speed of the electrophilic monomers. For this purpose, polymethyl methacrylate (PMMA) or cyanoacrylate-based copolymers as described in US Pat. No. 6,224,622 may be added to the composition of the invention and in a non-exhaustive manner.

  OILS The composition may contain at least one oil selected from volatile oils and / or non-volatile oils, and mixtures thereof.

  The term "volatile oil" means an oil having a non-zero vapor pressure, at ambient temperature and atmospheric pressure, in particular ranging from 0.13 Pa to 40 000 Pa (10-3 to 300 mmHg), in particular ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mm Hg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mm Hg). By "non-volatile oil" is meant an oil remaining on the skin or the keratin fiber at ambient temperature and atmospheric pressure for at least several hours and having in particular a vapor pressure of less than 10 -3 mmHg (0.13 Pa). .

  These oils may be hydrocarbon oils, silicone oils, fluorinated oils, or mixtures thereof. The volatile hydrocarbon oils may be chosen from hydrocarbon-based oils having 8 to 16 carbon atoms, and especially C8-C16 branched alkanes such as C8-C16 isoalkanes of petroleum origin (also known as isoparaffins), such as isododecane ( also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and for example the oils sold under the trade names Isopars' or permetyls, branched esters C8-C16 neopentanoate isohexyl, and mixtures thereof. Other volatile hydrocarbon oils such as petroleum distillates, especially those sold under the name Shell Solt by Shell, can also be used. Preferably, the volatile solvent is chosen from volatile hydrocarbon oils having from 8 to 16 carbon atoms and mixtures thereof.

  As volatile silicones, it is possible to use, for example, volatile linear or cyclic silicone oils, in particular those having a viscosity of 8 centistokes (8 10-6 m 2 / s), and having in particular 2 to 7 silicon atoms, these silicones possibly comprising alkyl or alkoxy groups having 1 to 10 carbon atoms. As volatile silicone oil that can be used in the invention, there may be mentioned in particular octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethylisiloxane, octamethyltrisiloxane and decamethyl tetrasiloxane, dodecamethylpentasiloxane and mixtures thereof.

  It is also possible to mention volatile alkyltrisiloxane linear oils of general formula (I): ## STR2 ## where R represents an alkyl group comprising from 2 to 4 carbon atoms and one of which or more than one hydrogen atom may be substituted by a fluorine or chlorine atom, Among the oils of the general formula (I), there may be mentioned: 3-butyl 1,1,1,3,5,5,5 -heptamethyl trisiloxane, 3-propyl-1,1,1,3,5,5,5-heptamethyltrisiloxane, and 3-ethyl-1,1,1,3,5,5,5-heptamethyltrisiloxane, corresponding to the oils of formula (I) for which R is a butyl group, a propyl group or an ethyl group respectively.Fluorinated volatile solvents such as nonafluoromethoxybutane or perfluoromethylcyclopentane may also be used.

  The composition may also comprise at least one non-volatile oil, and in particular chosen from non-volatile hydrocarbon and / or silicone and / or fluorinated oils. Non-volatile hydrocarbon oils that may be mentioned include: hydrocarbon-based oils of plant origin, such as esters of fatty acids and of glycerol, the fatty acids of which may have chain lengths varying from C4 to C24, the latter being linear or branched, saturated or unsaturated; these oils are in particular the oils of wheat germ, sunflower seed, grape seed, sesame, maize, apricot, castor, shea, avocado, olive, soya, oil sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, pumpkin, rapeseed, blackcurrant, evening primrose, millet , barley, quinoa, rye, safflower, bancoulier, passionflower, muscat rose; or the triglycerides of caprylic / capric acids, such as those sold by the company Stéarineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel, synthetic ethers having from 10 to 40 carbon atoms; branched-chain and / or unsaturated carbon-chain liquid fatty alcohols having from 12 to 26 carbon atoms, such as octyl dodecanol, isostearyl alcohol, oleic alcohol, 2-hexyldecanol, 2-butyloctanol 2-undecylpentadecanol; higher fatty acids such as oleic acid, linoleic acid, linolenic acid; - and their mixtures. According to one embodiment, the fatty phase contains an ester oil. This ester oil may be chosen from esters of monocarboxylic acids with monoalcohols and polyalcohols. Advantageously, said ester corresponds to the following formula (I): ## STR5 ## wherein R 1 represents a linear or branched alkyl radical of 1 to 40 carbon atoms, preferably 7 to 19 carbon atoms. carbon atoms, optionally comprising one or more ethylenic double bonds, and optionally substituted. R2 represents a linear or branched alkyl radical of 1 to 40 carbon atoms, preferably of 3 to 30 carbon atoms and better still of 3 to 20 carbon atoms, optionally comprising one or more ethylenic double bonds, and optionally substituted. The ester oil will be chosen, for example, from the following compounds isononyl isononanoate, cetostearyl octanoate, isopropyl myristate, 2-ethylhexyl palmitate, octyl stearate 2- dodecyl, octyl 2-dodecyl erucate, isostearyl isostearate.

  STRUCTURING AGENTS The composition may comprise at least one structuring agent of the oil or oils it contains chosen from: - semi-crystalline polymers, described for example in document EP 1396259, - mineral lipophilic gelling agents, such as optionally modified clays such as hectorites modified with a C10-C22 fatty acid ammonium chloride, such as hectorite modified with di-stearyl dimethyl ammonium chloride such as, for example, that marketed under the name Bentone 38V by ELEMENTIS society. It is also possible to mention the optionally hydrophobic fumed silica surface with a particle size of less than 1 μm. molecular organogelators, in particular those described in the "Specialist Surfactants" document, edited by D. Robb of 1997, p.209-263, chapter 8 of P. Terech, the European applications EP-A-1068854 and EP-A-1086945 or in application WO-A-02/47031. partially or totally crosslinked elastomeric organopolysiloxanes, of three-dimensional structure, such as those sold under the names KSG6, KSG16 and KSG18 by the company Shin-Etsu; polycondensates of polyamide type comprising at least one terminal carboxylic acid group esterified or amidified with at least one monohydric alcohol or a monoamine comprising from 12 to 30 linear and saturated carbon atoms, and in particular ethylene diamine / stearyl dilinoleate copolymers, such as the product sold under the name Uniclear 100 VG by the company ARIZONA CHEMICAL ; silicone polyamides of the polyorganosiloxane type such as those described in documents US-A-5,874,069, US-A-5,919,441, US-A-6,051,216 and US-A-5,981,680, for instance those sold under the reference Dow Corning 2 -8179 Gellant by the company Dow Corning; galactomannans containing from one to six, and in particular from two to four, hydroxyl groups per sac, substituted by a saturated or unsaturated alkyl chain, such as guar gum alkylated with C 1 -C 6 alkyl chains, and in particular C3-C3 and mixtures thereof;

  The product according to the invention may comprise at least one wax. The waxes that may be used in the compositions according to the invention are chosen from waxes, solid, at room temperature of animal, vegetable, mineral or synthetic origin, and mixtures thereof. Illustrative waxes suitable for the invention include hydrocarbon waxes such as beeswax, lanolin wax, and Chinese insect waxes; rice bran wax, Carnauba wax, Candelilla wax, Ouricury wax, Alfa wax, berry wax, shellac wax, Japanese wax and sumac wax; montan wax, orange and lemon waxes, microcrystalline waxes, paraffins and ozokerite; polyethylene waxes, waxes obtained by Fisher-Tropsch synthesis and waxy copolymers and their esters.

  There may also be mentioned waxes obtained by catalytic hydrogenation of animal or vegetable oils having linear or branched C8-C32 fatty chains. Among these, there may be mentioned isomerized jojoba oil such as trans isomerized partially hydrogenated jojoba oil manufactured or marketed by DESERT WHALE under the trade reference Iso-Jojoba-50, hydrogenated sunflower oil , hydrogenated castor oil, hydrogenated coconut oil, hydrogenated lanolin oil, and di- (1,1,1-trimethylolpropane) tetrastearate sold under the name Hest 2T-4S by the company HETERENE.

  Mention may also be made of silicone waxes and fluorinated waxes.

  The product according to the invention may comprise a wax content ranging from 0.01 to 20% by weight relative to the total weight of the composition, in particular it may contain from 0.1 to 15%. The product according to the invention may also comprise at least one pasty fatty substance. The pasty compound is advantageously chosen from: - Lanolin and its derivatives - Polymeric silicone compounds or not - Polymeric fluorinated compounds or non-vinyl polymers, in particular: • Homopolymers of olefins • Olefin copolymers • Homopolymers and hydrogenated diene copolymers • linear or branched oligomers, homo or copolymers of alkyl (meth) acrylates preferably having a C 8 -C 30 alkyl group • homo and copolymer oligomers of vinyl esters having C 8 alkyl groups -C30 homo- and copolymer oligomers of vinyl ethers having C 8 -C 30 alkyl groups; liposoluble polyethers resulting from the polyetherification between one or more C2-C100 diols, preferably C2-C50 diols; polyesters, and mixtures thereof. A preferred silicone and fluoro pasty compound is polymethyl trifluoropropyl methylalkyl dimethylsiloxane, manufactured under the name X22-1088 by SHIN ETSU.

  FILMOGENEOUS POLYMER According to one embodiment, the composition contains at least one polymer which may be chosen from film-forming polymers. Some film-forming polymers may be gelling agents.

  For the purposes of the invention, the term "polymer" means a compound having at least 2 repeating units, and preferably at least 3 repeating units.

  By "film-forming" polymer is meant a polymer capable of forming, by itself or in the presence of an auxiliary film-forming agent, a film which is macroscopically continuous on a support, in particular on keratin materials, and preferably a cohesive film and better still a film whose cohesion and mechanical properties are such that said film can be isolated from said support.

  The polymer may be present in the composition in a content ranging from 0.1% to 60% by weight, relative to the total weight of the composition, preferably ranging from 0.1% to 50% by weight, preferably ranging from 0.5 to 40% by weight, preferably ranging from 1% to 30% by weight, and more preferably ranging from 1% to 25% by weight.

  In one embodiment, the film-forming organic polymer is at least one polymer chosen from the group comprising: film-forming polymers that are soluble in an organic liquid medium, in particular liposoluble polymers, when the organic liquid medium comprises at least one oil; dispersible film-forming polymers in an organic solvent medium, in particular polymers in the form of nonaqueous dispersions of polymer particles, preferably dispersions in silicone or hydrocarbon oils; in one embodiment, the nonaqueous polymer dispersions comprise polymer particles stabilized on their surface by at least one stabilizing agent; film-forming polymers in the form of aqueous dispersions of polymer particles, often called latexes; in this case, the composition comprises an aqueous phase; water-soluble film-forming polymers; in this case, the composition comprises an aqueous phase.

  Among the film-forming polymers that can be used in the composition of the present invention, mention may be made of synthetic polymers, of free radical type or of polycondensate type, polymers of natural origin, and mixtures thereof. As film-forming polymer, mention may in particular be made of acrylic polymers, polyurethanes, polyesters, polyamides, polyureas, cellulose polymers such as nitrocellulose, silicone polymers, in particular silicone resins, silicone-grafted acrylic polymers, polyamide polymers and copolymers, polyisoprenes.

  The film-forming polymer may be chosen from the film-forming polymers described in application WO 04/028487, the contents of which are incorporated herein by reference.

  In particular, the film-forming polymer may be a crosslinked silicone compound as described in US 2003/0103918 and US 2003/0049216, the contents of which are incorporated by reference in the present application.

  Film-forming polymers are described in particular in the international patent application filed under PCT / FR03 / 02849, the contents of which are incorporated by reference.

  The film-forming polymer may be a film-forming linear ethylenic block polymer, advantageously free of styrene. More preferably, the sequenced polymer comprises less a first block and at least a second block having different glass transition temperatures (Tg), said first and second blocks being interconnected by an intermediate block comprising at least one constituent monomer of the first sequence and at least one constituent monomer of the second sequence.

  The film-forming polymer may also be in the form of a dispersion of particles, preferably solid, of an ethylenic polymer grafted into a liquid fatty phase. Such a dispersion is particularly described in the international patent application filed as PCT / FR / 03/03709, the contents of which are incorporated by reference.

  Advantageously, the grafted ethylenic polymer comprises an ethylenic skeleton insoluble in said liquid fatty phase, and side chains covalently bonded to said backbone and soluble in said dispersion medium.

  ADDITIVES The product of the invention may, in addition, contain one or more cosmetic or dermatological active agents such as those conventionally used. Active ingredients include moisturizers, vitamins, essential fatty acids, sphingolipids, sunscreens. These active agents are used in an amount customary for those skilled in the art and especially at concentrations of 0 to 20% and especially 0.001 to 15% of the total weight of the product.

  The product may furthermore comprise any other additive usually used in such compositions, antioxidants, perfumes, preservatives and essential oils.

  Of course those skilled in the art will take care to choose this or these optional additional compounds, and / or their amount, such that the advantageous properties of the product are not, or not substantially impaired by the addition envisaged.

  GALENIC / PACKAGING The composition may be in the form of a cast product and for example in the form of a stick or stick, or in the form of a cup used for direct contact or sponge. It may also be in the form of a soft paste or gel, cream more or less fluid, or liquid packed in a tube. The composition may be in any dosage form normally used for topical application. These galenics are in particular in the form of an oily solution, an oily gel, an oil dispersion in water by means of vesicles, the vesicles being located at the oil / water interface, or a powder. The composition can be fluid or solid. According to one embodiment, the composition containing the electrophilic monomer is in anhydrous form and contains less than 5% water, and even more preferably less than 1% water relative to the total weight of said composition. The composition may have the appearance of a lotion, a cream, an ointment, a soft paste, an ointment, a solid cast or molded and especially stick or cup, or compacted solid. The invention is illustrated in more detail in the following examples. Percentages are mass percentages. EXAMPLE 1: Evaluation of the stability of surface-treated pigments In order to measure the reaction rate of the octyl cyanoacrylate on each of the pigments referred to below, the following simplex mixture was formulated: 10% of the surface-treated pigment to test 30% octyl cyanoacrylate (commercial reference RITELOK CDN 1064 by the company Chemence) 60% cyclopentasiloxane (D5). Procedure: Each pigment is milled in the tri-cylinder in a fraction of D5. This dispersion is introduced into a flask and the balance of D5 and octyl cyanoacrylate are added. After incorporating all the ingredients into the vial, the vial is closed and shaken using a Bioblock test tube shaker positioned at 1800 rpm for 30 seconds. The end of the agitation corresponds to t = 0.

  The stability of each mixture is evaluated over time, noting with a spatula, when the simplex mixture changes consistency, relative to a reference composition containing: 10% of the surface-treated pigment to test 25 90% of cyclopentasiloxane (D5). The flasks are maintained during the evaluation in a thermostatically controlled room at 25 ° C. The mixture is estimated to be sufficiently stable when its consistency has not evolved under these conditions after 1 month.

  The results obtained are summarized in the table below: TABLE Time at which the mixture changes consistency Pigment / agent of Non Stearoyl Stearoyl Titanate Perfluoroalkylphosphate treated surface Glutamate Yellow iron oxide 7th day 5th day 7th day No change after 1 month Red iron oxide 7th day 10th day 2nd day No change after 1 month Titanium dioxide 6th day 6th day 9th day No change after 1 month References of surface-treated pigments used: - Yellow iron oxide no coating sold under the reference Sicovit Yellow E 172 by the company BASF 10 uncoated red iron oxide sold under the reference Sicomet brown ZP 3569 by the company BASF - uncoated titanium dioxide sold under the reference Hombitan Anatase FF Pharma by the Sachtleben company

  15-Yellow iron oxide / stearoyl aluminum glutamate sold under the reference NAI-C33-8073-10 by the company Miyoshi Kasei - red iron oxide / stearoyl aluminum glutamate sold under the reference NAI-C33-8075-10 by the company Miyoshi Kasei - Titanium dioxide / aluminum stearoyl glutamate sold under the reference NAI-20 C47-051-10 by the company Miyoshi Kasei - Yellow iron oxide / tri iso stearoyl isopropyl titanate sold under the reference BYO -1 2 by the company Kobo - red iron oxide / tri iso stearoyl isopropyl titanate sold under the reference 25 BRO-1 2 by the company Kobo5 - titanium dioxide / tri iso stearoyl isopropyl titanate sold under the reference BTD-401 by the company Kobo - yellow iron oxide / perfluoroalkyl phosphate sold under the reference PF 5 Yellow 601 by the company Daito Kasei - red iron oxide / perfluoroalkyl phosphate sold under the reference PF 5 Red R 516L by the company Daito Kasei Company - Titanium Dioxide / Phosphorus perfluoroalkyl ester sold under the reference PF 5 TiO 2 CR 50 by the company Daito Kasei.

EXAMPLE 2 Al Cyclopentasiloxane Weight Foundation 55.0 Cyclopentasiloxane 5.00 Yellow Iron Oxide / 1.43 Perfluoroalkyl Phosphate A2 Red Iron Oxide / 0.46 Perfluoroalkyl Phosphate Black Iron Oxide / Perfluoroalkyl Phosphate Titanium Dioxide / Perfluoroalkyl Phosphate 7.89 Octyl Cyanoacrylate sold under the reference 30.00 A3 Ritelok CDN 1064 by Chemence Company TOTAL 100% Procedure: Phase A2 is prepared by grinding the pigments with the three-roll and then mixed with phase Al using a stirrer.

Then the octyl cyanoacrylate is slowly added by homogenizing with a stirrer.

Claims (29)

  1. A process for making up or caring for keratinous materials other than the hair, consisting of the application of a cosmetic composition comprising at least one electrophilic monomer, and solid particles surface-treated with a silicone compound, a fluorinated compound, a fluorosilicone compound, or a mixture thereof.   2. The process as claimed in claim 1, in which the solid particles are chosen from: pigments surface-treated with a silicone compound, a fluorinated compound, a fluoro-silicone compound, or a mixture thereof; surface-treated fillers; with a silicone compound, a fluorinated compound, a fluoro-silicone compound, or a mixture thereof, and mixtures thereof.   3. The process as claimed in claim 2, in which the electrophilic monomer or monomers are monomers of formula (I): R 1 and R 2 each independently represent a group of little or no electro-attractor, and • R3 and R4 each denote, independently of each other, an electron-withdrawing group. 25   4. The method of claim 3 wherein the monomers of formula (I) are such that R1 and R2 independently represents a hydrogen atom; a saturated or unsaturated hydrocarbon group, linear, branched or cyclic, preferably containing from 1 to 20, and optionally containing one or more nitrogen, oxygen and sulfur atoms, and optionally substituted by one or more groups chosen from -OR, -COOR, -COR, -SH, -SR, -OH, and the halogen atoms; a modified or unsubstituted polyorganosiloxane residue; an R 1 R 3 R 2 R 4 (I) in which: polyoxyalkylene group, R denoting a saturated or unsaturated hydrocarbon group, linear, branched or cyclic, containing from 1 to 20, and optionally containing one or more nitrogen atoms, oxygen, sulfur, and optionally substituted with one or more groups selected from ùOR ', - COOR', -COR ', -SH, -SR', -OH, the halogen atoms, or a polymer residue, R'désignant a C 1 -C 6 alkyl group.   5. Process according to claim 3 or 4, in which the monomers of formula (I) are such that R3 and R4, independently, are chosen from the groups -N (R) 3+, -S (R) 2+, -SH2 +, -NH3 +, -NO2, -SO2R, -CN, -COOH, -COOR, -COSR, -CONHR, -CONH2, -F, -Cl, -Br, -I, OR, -COR, -SH, -SR, -OH, the linear or branched alkenyl groups, the linear or branched alkynyl groups, the mono- or polyfluoroalkyl groups in C1-C4, the aryl groups or the aryloxy groups, R denoting a saturated or unsaturated hydrocarbon group, linear, branched or cyclic , comprising from 1 to 20, and optionally containing one or more nitrogen, oxygen and sulfur atoms, and optionally substituted by one or more groups chosen from: ## STR5 ## SR ', -OH,, the halogen atoms, or a polymer residue, R' being a C1-C10 alkyl radical.   6. Method according to claim 3 or 4 wherein the monomers are cyanoacrylate monomers of formula: R1 C = NC = C R2 COXR'3 X denoting NH, S or O, R'3 being chosen from a hydrogen atom or R, R, R1 and R2 being as defined in claim 3.   7. Process according to any one of claims 3 to 6 wherein the electrophilic monomer is such that R1 and R2 represent a hydrogen atom.   8. Process according to any one of claims 6 to 7 wherein the cyanoacrylate monomers correspond to the formula R1 C = NC = C (III) R2 COOR'3 wherein R'3 represents a C1-C10 alkyl or alkoxy radical (C1-C4) (C1-C10) alkyl and R1 and R2 are as previously defined.   9. The method of claim 8 wherein R'3 is an alkyl radical comprising from 6 to 10 carbon atoms.   The process of claim 9 wherein R 1 and R 2 are hydrogen.   11. A process according to any one of the preceding claims wherein the electrophilic monomer is an alkyl cyanoacrylate of the formula CH 2 = C COO-R '3 wherein R' 3 = - (CH 2) 7 -CH 3 , -CH (CH3) - (CH2) 5-CH3, -CH2-CH (C2H5) - (CH2) 3-CH3, - (CH2) 5-CH (CH3) -CH3, 15- (CH2) 4- CH (C2H5) CH3.   12. Process according to any one of the preceding claims, in which the quantity of electrophilic monomers is between 0.1 and 80% by weight of the total weight of the composition.   13. Process according to any one of the preceding claims, in which the pigments are organic and chosen from nitroso, nitro, azo, xanthene, quinoline, anthraquinone and phthalocyanine type pigments, of the metal complex type, isoindolinone, isoindoline, quinacridone and perinone. , perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, quinophthalone. 10   The method according to any one of claims 1 to 12, wherein the pigment is a composite pigment composed of particles having 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.   The method of any one of claims 1 to 12, wherein the pigment is a lacquer consisting of an inorganic substrate selected from alumina, silica, sodium calcium borosilicate, calcium borosilicate, and aluminum, and the aluminum on which is adsorbed an organic dye.   16. The process as claimed in any one of claims 1 to 12, in which the pigment is a special-effect pigment chosen from pearlescent pigments, pigments with interferential effects not fixed on a substrate, fluorescent pigments or phosphorescent pigments. photochromic pigments, thermochromic pigments.   17. A process according to any one of claims 1 to 12, wherein the pigment is a pearlescent pigment selected from mica coated with titanium and iron oxides or chromium oxide, mica coated with titanium and titanium. an organic pigment, pearlescent pigments based on bismuth oxychloride.   18. Process according to any one of Claims 1 to 12, in which the pigment is inorganic and chosen from zirconium or cerium oxides, as well as iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate and ferric blue, titanium dioxide.   19. A method according to any one of the preceding claims wherein the surface-treated pigment is present at a concentration between 0.05 and 40% of the total weight of the composition.   20. Process according to any one of the preceding claims, in which the filler is chosen from talc, natural or synthetic mica, silica, kaolin, bismuth oxychlorides, precipitated calcium carbonate, carbonate and hydrochloric acid. magnesium carbonate, hydroxyapatite, hollow silica microspheres, microcapsules of glass or ceramics.   21. A process according to any one of claims 1 to 18 wherein the filler is selected from: polyamide, poly-13-alanine and polyethylene powders, tetrafluoroethylene polymer powders, lauroyl-lysine, starch, boron nitride, acrylic acid polymer powders, silicone resin microbeads, microspheres of acrylic polymers, such as those of crosslinked acrylate copolymer, and those of polymethyl methacrylate, polyurethane powders (such as the hexamethylene diisocyanate and trimethylol hexyl lactone copolymer powder, metal soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms, especially from 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate, microcapsules of polymers or copolymers of acrylate or methyl methacrylate, still further copolymers of vinylidene chloride and acrylonitrile; elastomeric crosslinked organopolysiloxane powders.   22. Method according to any one of the preceding claims wherein the filler has an apparent diameter ranging from 0.01 to 150 m and better still from 0.5 to 150 m.   23. A process according to any one of the preceding claims wherein the surface-treated filler is present in the composition in an amount of between 0.05 and 50%.   24. A method according to any one of the preceding claims wherein the silicone surfactant is selected from non-elastomeric organopolysiloxanes, silicone-acrylate copolymers, silicone resins, silicone elastomers, silane derivatives, and their derivatives. mixtures.   25. Process according to the preceding claim, in which the surface-treated pigment is chosen from red iron oxide / dimethicone, DC Red 7 / polysilicone 11, and mixtures thereof.   26. The process according to claim 23 wherein the surface-treated filler is boron nitride / polymethylhydrogensiloxane,   27. A process according to any one of claims 1 to 18 wherein the fluorinated surfactant is selected from perfluoroalkyl phosphates, perfluoropolyethers, polytetrafluoroethylene (PTFE) and perfluoroalkanes.   28. A process according to the preceding claim wherein the surface-treated pigment or filler is selected from yellow iron oxide / perfluoroalkyl phosphate, red iron oxide / perfluoroalkyl phosphate, black iron oxide / perfluoroalkyl phosphate, titanium dioxide / perfluoroalkyl phosphate, yellow iron oxide / perfluoropolymethylisopropyl ether, DC Red 7 / perfluoropolymethylisopropyl ether, DC Red 6 / PTFE, boron nitride / perfluoroperhydrophenanthrene, and mixtures thereof. 10 15   29. A method according to any one of claims 1 to 18, wherein the fluorosilicone surfactant is selected from perfluoroalkyl dimethicones, perfluoroalkyl silanes and perfluoroalkyl trialkoxysilanes.