FR2899801A1 - Cosmetic composition useful for hair dyeing, comprises polymerizable cyanoacrylate monomer, a suspension of metallic nanopartilces coated with organosulfur monolayer and a liquid organic solvent - Google Patents

Abstract

Cosmetic composition (A) for dyeing keratinous fibers, particularly hair, comprises polymerizable cyanoacrylate monomer (I), a suspension (II) of metallic nanopartilces coated with organosulfur monolayer and a liquid organic solvent (III). Independent claims are included for: (1) a process of coloring keratinous fibers such as hair, comprising applying (A) on the keratinous fibers; (2) process of treatment of keratinous matters, such as hair, comprising applying a (complete) hair perming reducer, an oxidation dye, a bleach, shampoo or a hair styling or alkaline hair straightening product and applying (A) before/after the application of the given composition; and (3) a device containing multiple compartments or a kit, comprising a first compartment comprising a composition of (I) and optionally an anionic/radical polymerization inhibitor in an organic solvent and a second compartment comprising a suspension of metallic nanoparticles coated with organosulfate monolayer in the organic solvent, where the nucleophilic agent is present in either of the two compartments or present in a third compartment.

Description

COSMETIC COMPOSITION COMPRISING AT LEAST ONE SUSPENSION OF

  The present invention relates to a cosmetic composition for the dyeing of keratinous fibers, such as human keratinous fibers, in particular hair, comprising at least one suspension of metal nanoparticles coated with a polyvinyl chloride. organosulfur mono-layer, at least one polymerizable cyanoacrylate monomer and at least one liquid organic solvent as well as a hair dyeing method using this composition and a compartment device. The patent application EP 1 064 918 describes the application, on the hair, of metal nanoparticles in suspension in a clear composition, in order to give the treated hair a shiny appearance. Deposition of the nanoparticles is described as a physico-chemical adsorption process which does not make it possible to obtain residual deposits, that is to say deposits resistant to elimination by shampoos. The applicant has discovered that it is possible to increase the remanence of metal nanoparticles on the surface of the hair and thus retain their cosmetic effect even after several shampoos, using not "bare" metal nanoparticles as described in EP 1 064 918 but "organomodified" nanoparticles, that is to say nanoparticles carrying on their surface organic groups. Such organomodified nanoparticles have indeed been synthesized and described, inter alia, in the following publications: • Synthesis and Characterization of Carboxylate Modified Gold-Nanoparticle Powders Dispersible in Water, Langmuir, 1999, 15, 1075 - 1082. • Comparative Study of Dodecanethiol- Derivatized Silver Nanoparticles Prepared in One-Phase and Two-Phase Systems, Langmuir, 1998, 14, 226 - 230. The metal nanoparticles described in these publications are characterized by the fact that they carry on their surface a monolayer of organosulfur compounds forming a a structure commonly referred to as "selfassembled monolayer" (see the article by A. Ulman, Chem Rev., 1997, 96, 1533).

  The Applicant has found that the metal particles thus "dressed" with a monolayer of organic compounds are significantly easier to handle and disperse in the various liquid solvents for the preparation of a cosmetic composition. In Application FR 2 838 052, the Applicant has disclosed the use of a suspension of organomodified metal nanoparticles carrying on their surface a self-assembled monolayer of organosulfur compounds, in a cosmetically acceptable medium, for coloring and / or fiber treatment. human keratin.

  When these compositions based on metal nanoparticles are used for hair dyeing, and more particularly are deposited on white hair, the colorations obtained vary from gray to black. However, it has been observed that this color transfers to the fingers or clothing and is resistant only to a few shampoos.

  Thus, there is a real need to develop hair coloring compositions based on metal nanoparticles resistant to shampoos. The Applicant has discovered that the combination of a suspension of nanoparticles described above with a polymerizable cyanoacrylate monomer in the presence of an organic liquid solvent made it possible to obtain a very cosmetic colored coating on the white hair by in situ polymerization of cyanoacrylate monomers. The hair is not glued together. This colored sheathing is residual to shampoos and the color does not transfer to fingers or clothes. Indeed, it is known from WO 03/053380 to use electrophilic monomers anionically polymerizing directly on the surface of the hair in the presence of a nucleophilic agent such as hydroxide ions (OH-) contained in the water to neutral pH. Thus, once deposited on the hair, these monomers form a polymer leading to a satisfactory conditioning. The Applicant has thus found that during the deposition of the composition on the hair, the metal nanoparticles were interlocked in the polymeric structure obtained following the in situ polymerization of the cyanoacrylate monomer, allowing good adhesion of the nanoparticles on the hair. The subject of the present invention is therefore a cosmetic composition for dyeing keratinous fibers, such as human keratinous fibers, in particular hair, comprising: at least one polymerizable cyanoacrylate monomer; at least one suspension of coated metal nanoparticles; an organosulfur mono-layer, and - at least one liquid organic solvent. The invention also relates to a hair dyeing method using the composition according to the invention. Another object of the invention is a multi-compartment device containing the composition according to the invention. Other objects of the invention will appear on reading the description and examples which follow. The polymerizable cyanoacrylate monomer or monomers present in the composition of the invention are preferably chosen from the monomers of formula (I): ## STR2 ## in which: X denotes NH, S or O, 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 linear or saturated hydrocarbon-based hydrocarbon group, branched or cyclic, preferably having from 1 to 20, more preferably from 1 to 10 carbon atoms, and optionally containing one or more nitrogen, oxygen, sulfur atoms, and optionally substituted with one or more groups selected from -OR, -COOR, -COR, -SH, -SR, -OH, and the halogen atoms, -a polyorganosiloxane residue which may or may not be modified, -a polyoxyalkylene group, R denotes a linear or branched, saturated or unsaturated hydrocarbon group; or cyclic, preferably having from 1 to 20, more preferably from 1 to 10 a carbon atoms, and optionally containing one or more nitrogen, oxygen, sulfur atoms, and optionally substituted with one or more groups selected from OROR ', - COOR', -COR ', -SH, -SR', OH, the halogen atoms, or a polymer residue obtainable by radical polymerization, by polycondensation or by ring opening, R 'denoting a C 1 -C 10 alkyl group. By electron-withdrawing or inductive grouping -tractor (-I) means 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. 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. As examples of dye-functional groups, there may be mentioned 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 with a UV-filtering functional group are, for example, groups benzophenones, cinnamates, benzoates, benzylidenecamphers and dibenzoylmethanes.

  As examples of a group with a conditioning function, mention may be made in particular of cationic and fatty ester groups. Preferably, R1 and R2 represent a hydrogen atom.

  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 of nitrogen, oxygen, sulfur, and optionally substituted with one or more groups selected from ùOR ', -COOR', -COR ', -SH, -SR', -OH, the halogen atoms, or a residue of polymer obtainable by radical polymerization, polycondensation or ring opening, R 'denoting a C 1 -C 10 alkyl group. Preferably, R' 3 is a saturated hydrocarbon group having from 1 to 10 carbon atoms or an alkenyl having 2 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 of the formula: (II) CN 25 COOCH 2 CF 2 CHF 2 or the 2,2,2-trifluoroethyl ester of 2-cyano-2-propenoic acid of formula: (III) CN 30 COOCH2CF3 b) Alkyl or alkoxyalkyl 2-cyanoacrylates

  (IV) R 1 CN> - (R 2 COOR '3 in which R' 3 represents a C 1 -C 10 alkyl 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 of 2-methoxyethyl, 2-methoxypropyl 2-cyanoacrylate, allyl 2-cyanoacrylate, 2-octyl 2-cyanoacrylate, 2-propoxyethyl 2-cyanoacrylate, n-octyl 2-cyanoacrylate 2 allyl cyanoacrylate, methoxypropyl 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 cyanoacrylate of formula V and mixtures thereof:

  (V) CN COOR'3 in which: R'3 = - (CH2) 7 -CH3,

CH (CH 3) - (CH 2) 5 -CH 3,

  CH 2 -CH (C 2 H 5) - (CH 2) 3 -CH 3, - (CH 2) 5 -CH (CH 3) -CH 3,

- (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. Preferably, the cyanoacrylate monomer is introduced into the composition between 0.1% and 80% by weight relative to the total weight of the composition; more preferably between 1% and 50% by weight, more preferably between 2% and 20% by weight relative to the total weight of the composition. The adjective "metallic" used in the present invention for describing organomodified nanoparticles means • that the nanoparticles are made of 100% of one or more metals in the elemental state, • or that the nanoparticles comprise a surface layer ( envelope) made of 100% of one or more metals in the elemental state, and which surrounds a core, or core, made of a different material. The metals forming the organomodified metal nanoparticles are preferably chosen from alkali metals, alkaline earth metals, transition metals, rare earth metals and alloys of these metals.

  It is preferred to use in particular aluminum, copper, cadmium, selenium, silver, gold, indium, iron, platinum, nickel, molybdenum, silicon, titanium, tungsten , antimony, palladium, zinc, tin and alloys of these metals, and among these especially gold, silver, palladium, platinum, cadmium, selenium and alloys of these metals. According to a preferred embodiment, the nanoparticles according to the invention consist of gold or silver. The residues of organosulfur compounds attached to the surface of the nanoparticles then correspond to formula (VI): ## STR2 ## (VI)

  with Z representing a spacer arm chosen from linear, branched or cyclic, saturated or unsaturated divalent C 1 -C 100 carbon chains, optionally interrupted by heteroatoms such as sulfur, oxygen, nitrogen, silicon or phosphorus; and optionally bearing one or more substituents such as hydroxyl, amine, thiol, carbamate, ether, acid, ester, amide, cyano or ureido groups, n represents an integer of 0 or 1, p represents an integer of 0, 1, 2 or 3, q represents an integer of 0 or 1, R4 represents a hydrogen atom, an alkyl group which may contain heteroatoms, a chlorine atom, a group of formula (VII, VIII or IX), or an alkylammonium group; With A representing a hydrogen atom or a group S03-, BB VIII With B representing a hydrogen atom or a fluorine atom, BX represents an atom O, NH, NR ", with R" an alkyl group which contain heteroatoms.

  Preferably, the nanoparticles are introduced into the composition between 0.01% and 80% by weight relative to the total weight of the composition; more preferably between 0.1 and 40% by weight relative to the total weight of the composition and even more preferably between 1 and 20% by weight relative to the total weight of the composition. By organic solvent is meant an organic substance capable of dissolving another substance without chemically modifying it. The medium of the compositions of the invention contains 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 modified or not by alkyl and / or amine and / or imine and / or fluoroalkyl and / or carboxylic and / or betaine and / or quaternary ammonium functions, liquid modified polydimethylsiloxanes; 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 liquid 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 trimelate, cyclopentasiloxane (14.7% by weight) / dihydroxylated polydimethylsiloxane at 85.3% by weight), or mixtures thereof. According to a preferred embodiment, the organic solvent is constituted by a silicone or a mixture of silicones such as liquid polydimethylsiloxanes and liquid modified polydimethylsiloxanes, the viscosity of the silicone and / or silicone mixture at 25 c is between 0.degree. .lcst and 1,000,000cst and more preferably between 1st and 30,000cst.

  The following oils are preferably: the mixture of alpha-omega-dihydroxylated polydimethylsiloxane / cyclopentadimethylsiloxane (14.7 / 85.3) sold by Dow Corning under the name DC 1501 Fluid; the mixture of alpha-omega-dihydroxy polydimethylsiloxane / polydimethylsiloxane sold 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 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 can 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. It is possible to introduce into the compositions polymerization inhibitors, and more particularly anionic and / or radical polymerization inhibitors, 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 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, 3-sulphonene 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 of between 0 and 6, such as phosphoric acid or 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 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 hydroxide ions contained in water at neutral pH. The term "carbanion" refers to the chemical species defined in Jerry March, Advanced Organic Chemistry, Third Edition, page 141. The nucleophilic agents may 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-, RC = C-, RS-, SH-, RO-, R2NH, ArO-, N3-, OH-, ArNH2, NH3, I-, Br-, Cl-, RCOO-, SCN-, ROH, RSH, NCO-, CN-, NO3-, ClO4-, H2O, etc. The composition according to the invention may contain pigments. In the context of the invention, the term "pigment" is understood to mean 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 a maximum. The pigments useful in the present invention are chosen from all the 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 Ullmann's encyclopedia of industrial chemistry. 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: Ta 2 O 5, Ti 3 O 5, Ti 2 O 3, TiO, ZrO 2 mixed with TiO 2, ZrO 2, Nb 2 O 5, CeO 2, 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 CI 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 in the patent FR 2 679 771. It is possible to use 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); - 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 (Cl 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 ensuring the fixation. 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, silica, calcium and sodium borosilicate or calcium and aluminum borosilicate, and aluminum. Among the organic dyes, mention may be made of cochineal carmine.

  By way of examples of lacquers, mention may be made of the products known under the following names: D & C Red 21 (CI 45 380), D & C Orange 5 (CI 45 370), D & C Red 27 (CI 45 410) ), D & C Orange 10 (CI 45,425), D & C Red 3 (CI 45,430), D & C Red 7 (CI 15,850: 1), D & C Red 4 (CI 15,510), D & C Red C Red 33 (CI 17,200), D & C Yellow 5 (CI 19,140), D & C Yellow 6 (CI 15,985), D & C Green (CI 61,570), D & C Yellow 10 (CI 77 002), D & C Green 3 (CI 42,053), D & C Blue 1 (CI 42,090). 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 Cellini nacres marketed by Engelhard (Mica-TiO2-lacquer), Prestige marketed by Eckart (Mica-TiO2), 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. Quantum dots are luminescent semiconductor nanoparticles capable of emitting, under light excitation, radiation having a wavelength of 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 American 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 m, preferably between 20 nm and 80 m, and more preferably between 30 nm and 50 m. 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%. The nacres and the composite pigments are preferably chosen. 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 molecules of the surfactant or creation of a covalent bond between the surfactant and the pigments or pigments. loads. The surface treatment can thus be carried out for example by chemical reaction of a surfactant with the surface of the pigments or fillers 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 covalently used. The agent for the surface treatment may represent from 0.1 to 50% by weight of the total weight of the surface-treated pigments, preferably from 0.5 to 30% by weight, and even more preferably from 1 to 10% by weight. weight. Preferably, the surface treatments of the pigments and fillers 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 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-StAI surface treatment marketed by Daito; an Octyltriethylsilane treatment such as the OTS surface treatment marketed by Daito; an Octyltriethylsilane / Perfluoroalkyl Phosphate 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 surface-treated pigment or pigments are generally present in the composition in total amounts generally of between 0.05 and 80% by weight of the total weight of the composition, preferably between 0.1 and 35% by weight, and even more preferably between 0.5 and 20% by weight. Preferably, the pigments are coated with perfluoroalkyl phosphates, acrylate / dimethicone copolymers and mixtures thereof. The compositions of the invention may also contain conventional cosmetic additives chosen from this non-exhaustive list such as reducing agents, oxidizing agents, sequestering agents, polymeric or non-polymeric thickening agents, moisturizing agents, emollient agents, organic bases or plastics, plasticizers, sunscreens, optical brighteners, oxidation dyes, mineral fillers, clays, colloidal minerals, colloidal metals, quantum well-based semiconductor nano-particles. metals or silicon, a photo or thermochromic compound, 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 surfactants.

  The formulations can be in various galenic forms such as a lotion, an aerosol mousse, a shampoo or a shampoo, a gel, a wax. The compositions may be contained in a pump bottle, an aerosol spray. The compositions of the invention after application to the hair may be rinsed or not. When the composition is contained in an aerosol, it may contain a propellant. 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.

  Another subject of the invention is processes using the composition according to the invention. Several methods of implementation are conceivable. In a first embodiment of the method of the invention, the treatment of the fiber can be a one-time process. The described composition optionally containing other cosmetic active agents is applied to dry or previously moistened or shampooed hair. The hair is then dried (hair dryer, helmet or iron). A terminal shampoo may be optionally performed.

  In a second embodiment of the method of the invention, the hair fiber may be pre-treated with at least one nucleophilic agent. The hair can be dried after pre-treatment. Then the composition according to the invention is applied to the hair. The hair is dried (hair dryer, helmet or iron). A terminal shampoo may be optionally performed. When the composition according to the invention consists of two compositions, one comprising the suspension of metal nanoparticles in a liquid organic solvent according to the invention and the other comprising the polymerizable cyanoacrylate monomer in a liquid organic solvent, then a third mode embodiment of the method of the invention may be provided. The hair fiber may be pre-treated with the composition comprising the suspension of metal nanoparticles according to the invention dispersed in a liquid organic solvent. The hair can be dried. Then the second composition containing at least one polymerizable cyanoacrylate monomer in a liquid organic solvent is applied to the hair. The hair is dried (hair dryer, helmet or iron). A terminal shampoo may be optionally performed.

  The dyeing process according to the invention can be used in the context of other treatments for keratinous fibers. Thus, the fiber is prepared to make the treatment more effective by stripping the fiber and / or by etching the fiber. In a fourth embodiment of the method of the invention, a permanent perm reducer or a permanent perm or an oxidation dyeing or a discoloration or a shampoo or a styling product or an alkaline hair straightener is applied in a first step. Then, in a second step, one of the processes described above is carried out.

  In a fifth embodiment of the process of the invention, the dyeing process according to the invention is carried out before existing fiber treatments. Thus, after having applied the composition of the invention according to one of the methods already described, a permanent reducing agent or a perm or an oxidation dyeing or an alkaline fading or bleaching is applied. The subject of the invention is also a kit comprising a first composition containing at least one polymerizable cyanoacrylate monomer as defined above and optionally at least one anionic and / or radical polymerization inhibitor in a liquid oragnic solvent, and a second composition containing in a liquid organic solvent at least one suspension of metal nanoparticles coated with an organosulfur mono-layer, the nucleophilic agent being in one or the other of the compartments or in a separate compartment.

  The examples which follow are intended to illustrate the invention, without being limiting in nature.

  EXAMPLES One skilled in the art can judge the amount of acid to add. This remark is valid for all the examples.

Example 1: One-time process

  The following composition is produced: poly dimethyl siloxane alpha-omega 44g dihydroxylated / cyclopentadimethylsiloxane (14.7 / 85.3) marketed by Dow Corning under the name DC 1501 Fluid cyclopentadimethylsiloxane 44g sold by Dow Corning under the name DC245 Fluid Nano- silver particles * 2g Acetic acid 0.2 g 10 g Chemence * Methylheptylcyanoacrylate Prepared according to publication: Langmuir 1999, 15, 1077 and coated with an organosulfur layer of the mercaptosuccinic acid type.

  0.2g of this composition is applied to a lock of white hair of 1g previously shampooed. After standing for 15 minutes at room temperature, the wick is dried with a hair dryer for 3 minutes. A terminal shampoo is performed. The hair has a gray color. They are soft and loose to the touch. There are no unpleasant residues. This color is still visible after several shampoos. Example 2: Two-step application

  The following compositions are produced: Composition A: poly-dimethyl siloxane alpha-omega 45g dihydroxylated / cyclopentadimethylsiloxane (14.7 / 85.3) marketed by Dow Corning under the name DC 1501 Fluid cyclopentadimethylsiloxane 45g marketed by Dow Corning under the name DC245 Fluid Acetic acid 0.2 g Methylheptylcyanoacrylate 10g Chemence Composition B H20 98g Silver nanoparticles * 2g * Prepared according to publication: Langmuir 1999, 15, 1077 and coated with an organosulfur layer of the mercaptosuccinic acid type.

  0.4 g of the composition B is applied to a lock of white hair of 1 g previously shampooed. After 15 minutes of pause at room temperature, the wick is dried. Then 0.2 g of the composition A is applied. After 15 minutes of pause at room temperature, the lock is dried with a hair dryer for 3 minutes. A final shampoo is performed. The hair has a gray color. They are soft and loose to the touch. There are no unpleasant residues5. This color is still visible after several shampoos. In a variation of this example, composition A is applied prior to composition B.

Claims (29)

  1. Cosmetic composition for the dyeing of keratinous fibers, in particular the hair comprising: at least one polymerizable cyanoacrylate monomer, at least one suspension of metal nanoparticles coated with an organosulfur mono-layer, at least one liquid organic solvent.   2. Cosmetic composition according to claim 1, characterized in that the cyanoacrylate monomer is chosen from the monomers of formula (I): ## STR5 ## wherein X denotes NH, S or O, R1 and R2 each denote, independently of one another, a little or no electro-attracting group (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 and sulfur atoms, and optionally substituted with one or more chosen groups among -OR, -COOR, -COR, -SH, -SR, -OH, and the halogen atoms, a polyorganosiloxane residue which may or may not be modified, a polyoxyalkylene group, R '3 denotes a saturated or unsaturated hydrocarbon group, linear, branched or cyclic, preferably having from 1 to 20, more preferably from 1 to 10 atoms of carbon, and optionally containing one or more nitrogen, oxygen, sulfur atoms, and optionally substituted with one or more groups selected from OROR ', - COOR', -COR ', -SH, -SR', - OH, the halogen atoms, or a polymer residue obtainable by radical polymerization, by polycondensation or by ring opening, R 'denoting a C 1 -C 10 alkyl group, R' 3 representing an atom of hydrogen 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 or sulfur atoms; and optionally substituted by 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 'denoting a C 1 -C 1 alkyl group 0.   3. Cosmetic composition according to claim 2, characterized in that the cyanoacrylate monomer is chosen from the monomers of formula (IV): R1> C R2 COOR '3 (IV) wherein R'3 represents a C1-C10 alkyl radical or (C 1 -C 4) alkoxy (C 1 -C 10) alkyl.   4. Cosmetic composition according to claim 3, characterized in that the cyanoacrylate monomer is chosen from 2-ethyl cyanoacrylate, methyl 2-cyanoacrylate, n-propyl 2-cyanoacrylate and isopropyl 2-cyanoacrylate. , tert-butyl 2-cyanoacrylate, n-butyl 2-cyanoacrylate, iso-butyl 2-cyanoacrylate, 3-methoxybutyl cyanoacrylate, n-decyl cyanoacrylate, hexyl 2-cyanoacrylate , 2-ethoxyethyl 2-cyanoacrylate, 2-methoxyethyl 2-cyanoacrylate, 2-octyl 2-cyanoacrylate, 2-propoxyethyl 2-cyanoacrylate, n-octyl 2-cyanoacrylate, cyanoacrylate, isoamyl, allyl 2-cyanoacrylate, methoxypropyl 2-cyanoacrylate, allyl cyanoacrylate 2-cyanoacrylate and methoxypropyl 2-cyanoacrylate.   5. Cosmetic composition according to claim 4, characterized in that the cyanoacrylate monomer is chosen from C6-C10 alkyl cyanoacrylates.   6. Cosmetic composition according to claim 5, characterized in that the cyanoacrylate monomer is chosen from the monomers octyl cyanoacrylates of formula (V) and their mixtures: CN COOR'3 (V) wherein R'3 = - (CH 2) 7-CH 3, -CH (CH 3) - (CH 2) 5 -CH 3, -CH 2 -CH (C 2 H 5) - (Cl-12) 3-Cl 13, - (CH 2) 5 -CH (CH 3) -CH 3, - (CH2) 4-CH (C2H5) CH3. 25   7. Cosmetic composition according to any one of the preceding claims, characterized in that the cyanoacrylate monomer or monomers are covalently attached to supports such as polymers, oligomers or dendrimers. 20 of the   8. Composition according to any one of the preceding claims, characterized in that the cyanoacrylate monomer is introduced into the composition between 0.1% and 80% by weight relative to the total weight of the composition, more preferably between 1% and 50%. % by weight relative to the total weight of the composition, more preferably between 2% and 20% by weight relative to the total weight of the composition.   9. Composition according to any one of the preceding claims, characterized in that the metals forming the organomodified metal nanoparticles are chosen from alkali metals, alkaline earth metals, transition metals, rare earth metals and aluminum alloys. these metals.   10. Composition according to claim 9, characterized in that the metals forming the organomodified metal nanoparticles are chosen from aluminum, copper, cadmium, selenium, silver, gold, indium, iron, platinum, nickel, molybdenum, silicon, titanium, tungsten, antimony, palladium, zinc, tin and the alloys of these metals, and among these, particularly gold, silver, palladium, platinum, cadmium, selenium and alloys of these metals.   11. Composition according to claim 10, characterized in that the metals forming the organomodified metal nanoparticles are gold or silver.   12. Composition according to any one of the preceding claims, characterized in that the metal nanoparticle coated with an organosulfur mono-layer comprises as residues of organosulfur compounds attached to its surface residues of formula (VI): -S-CH3- p (ZnCOXqR4) p (VI) with Z representing a spacer arm chosen from linear, branched or cyclic, saturated or unsaturated C 1 -C 100 carbonaceous chains, optionally interrupted by heteroatoms such as sulfur, oxygen, nitrogen, silicon or phosphorus, and optionally bearing one or more substituents such as hydroxyl groups, amines, thiols, carbamates, ethers, acids, esters, amides, cyano or ureido, n represents an integer of 0 or 1, p represents an integer of 0, 1, 2 or 3, q represents an integer of 0 or 1, R4 represents a hydrogen atom, an alkyl group which may contain heteroatoms, a chlorine atom, a group of formulas e (VII, VIII or IX), or an alkylammonium group, AA VII With A representing a hydrogen atom, or a group S03- VIII With B representing a hydrogen atom or a fluorine atom, X represents an atomant O , NH, NR ", with R" an alkyl group capable of containing heteroatoms.   13. Composition according to any one of the preceding claims, characterized in that the suspension of nanoparticles is introduced into the composition between 0.01% and 80% by weight, more preferably between 0.1 and 40% by weight. relative to the total weight of the composition.   14. Composition according to any one of the preceding claims, characterized in that it contains at least one polymerization inhibitor.   15. Composition according to the preceding claim, characterized in that the polymerization inhibitor is an inorganic or organic acid selected from 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, trifluoroacetic acid, octanoic acid, heptanoic acid and hexanoic acid.   16. Composition according to claim 15, characterized in that the polymerization inhibitor is acetic acid.   17. Composition according to any one of the preceding claims, characterized in that the content of polymerization inhibitor is between 10 ppm and 30% by weight relative to the total weight of the composition; more preferably between 10 ppm and 15% by weight relative to the total weight of the composition.   18. Cosmetic composition according to any one of the preceding claims, characterized in that the liquid organic solvent is chosen from aromatic alcohols, fatty alcohols, modified or unmodified polyols, volatile or non-volatile silicones, and mineral or organic oils. or vegetable, oxyethylenated waxes or not, paraffins, alkanes, fatty acids, fatty amides, fatty esters.   19. Cosmetic composition according to claim 16, characterized in that the solvent is a mixture of alpha-omega-dihydroxylated polydimethylsiloxane / cyclopenta dimethylsiloxane.   20. Composition according to any one of the preceding claims, characterized in that it is anhydrous.   21. Composition according to any one of the preceding claims, characterized in that it contains one or more inorganic or organic pigments, preferably nacres and composite pigments.   22. Composition according to any one of the preceding claims, characterized in that it contains usual cosmetic additives chosen from reducing agents, oxidizing agents, sequestering agents, polymeric or non-polymeric thickening agents, moisturizing agents, emollient agents. , organic or inorganic bases, plasticizers, sunscreens, optical brighteners, oxidation dyes, mineral fillers, clays, colloidal minerals, colloidal metals, well-type semiconductor nanoparticles quantum metals or silicon, a photo or thermochromic compound, 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 surfactants.   23. Composition according to any one of the preceding claims, characterized in that it is in the form of lotion, aerosol foam, a shampoo or a shampoo, a gel, a wax or is contained in a pump bottle or an aerosol spray.   24. Composition according to any one of the preceding claims, characterized in that the composition comprises at least one nucleophilic agent; said nucleophilic agent being mixed in the composition as defined in any one of the preceding claims or separately packaged.   25. Composition according to claim 24, characterized in that the nucleophilic agent is water.   26. A process for dyeing keratinous fibers, such as human fibers, in particular the hair, comprising applying to said keratinous fibers a composition as defined in any one of claims 1 to 25.   27. The method of dyeing according to claim 26, characterized in that prior to the application on said keratinous fibers of a composition as defined in any one of claims 1 to 21, the fibers undergo a pre-treatment with at least one nucleophilic agent as defined in claim 24 or 25.   28. The method of dyeing according to claim 26 or 27, characterized in that one applies a perm reducer or a complete perm or an oxidation dye or a dye or a shampoo or a styling product or an alkaline hair straightener, previously or following the application of the composition as defined in any one of claims 1 to 23.   29. A compartment device or kit, characterized in that the first comprising a first compartment, comprising a composition containing at least one polymerizable cyanoacrylate monomer as defined in any one of claims 1 to 7 and optionally at least one polymerization inhibitor. anionic and / or radical in a liquid organic solvent and a second compartment containing at least one suspension of metal nanoparticles coated with an organosulfur mono-layer in a liquid organic solvent; the nucleophilic agent possibly found in one of the two compartments mentioned above or possibly in a third compartment.