WO2007118807A2

WO2007118807A2 - Cosmetic composition comprising, in a cosmetic medium, at least one silica particle, at least one cyanoacrylate monomer and at least one liquid organic solvent

Info

Publication number: WO2007118807A2
Application number: PCT/EP2007/053392
Authority: WO
Inventors: Gaëlle Brun; Aude Livoreil; Gabin Vic
Original assignee: L'oréal
Priority date: 2006-04-13
Filing date: 2007-04-05
Publication date: 2007-10-25
Also published as: WO2007118807A3

Abstract

The present invention relates to novel compositions based on silica, on monomers which can be polymerized in situ, on a liquid organic solvent and on a cosmetically acceptable medium for the cosmetic treatment of keratinous substances and in particular of keratinous fibres, such as the hair, and to the use of novel compositions in the cosmetic treatment of keratinous substances and to a kit comprising the said composition.

Description

COSMETIC COMPOSITION COMPRISING, IN A COSMETIC MEDIUM, AT LEAST ONE SILICA PARTICLE, AT LEAST ONE CYANOACRYLATE MONOMER AND AT

LEAST ONE LIQUID ORGANIC SOLVENT

The present invention relates to novel compositions comprising silica particles, cyanoacrylate monomers and at least one liquid organic solvent for the cosmetic treatment of keratinous substances, and in particular keratinous fibres, such as the hair, and to the use of novel compositions for the cosmetic treatment of keratinous substances. There exist numerous styling products which make it possible to contribute body, bulk or volume to the hair. One disadvantage related to these products, generally based on film-forming polymers, lies in the fact that the cosmetic effect disappears from the first shampooing.

It is possible to envisage increasing the persistance of the deposited layer of polymers by directly carrying out a radical polymerization of certain monomers on the hair. However, the treatments thus obtained are not very cosmetic and great damage to the fibre is generally observed. The hair thus treated is difficult to disentangle.

Furthermore, Patent Application FR 2 833 489 discloses compositions for the treatment of the hair starting from compositions comprising electrophilic monomers capable of polymerizing anionically directly on the hair. These monomers, after polymerization, make it possible to obtain perfectly sheathed hairs. However, the sheathing obtained does not exhibit satisfactory strength with respect to the various external assaults to which hair may be subjected.

There thus exists a need to find novel cosmetic compositions which make it possible to contribute body, bulk and/or volume to the hair and this in a lasting fashion, in particular in the face of shampooing operations and other external assaults to which the hair may be subjected.

Thus, a subject-matter of the invention is a composition comprising, in a cosmetic medium: a) at least one cyanoacrylate monomer; b) at least one silica particle, the primary size of which is less than 30 μm; and c) at least one liquid organic solvent.

The Applicant Company has found more particularly that, on applying a composition based on such monomers and on silica particles to the hair, a persistent coating is formed in situ. The polymer thus formed in situ by interfacial anionic polymerization is present in the form of a homogeneous deposited layer and has excellent adhesion to hair.

Such a composition, when it is applied to keratinous fibres, such as the hair, makes it possible to obtain a sheathing exhibiting improved resistance to external agents while retaining completely separate hairs which can be styled without problem.

The styling properties contributed to the fibre are persistent, in particular towards shampooing operations.

Another subject-matter of the invention is the use of the composition of the invention in the treatment of keratinous substances and in particular of keratinous fibres, such as the hair.

Another subject-matter of the invention is a process for the cosmetic treatment of keratinous substances and in particular of keratinous fibres, such as the hair, employing this composition. Another subject-matter of the invention is a kit comprising a first composition comprising at least one cyanoacrylate monomer, optionally at least one anionic and/or radical polymerization inhibitor and/or an acid and a second composition comprising at least one liquid organic solvent, a silica particle, the primary size of which is less than

30 μm and optionally an acid. The cyanoacrylate monomer or monomers present in the composition of the invention are preferably chosen from the monomers of formula (I):

R1 CN

>=< ^{(l )}

R2 COXR'3 in which: • X denotes NH, S or O,

• R1 and R2 each denote, independently of one another, a group with little or no electron-withdrawing effect (with little or no inductive-withdrawing effect), such as : a hydrogen atom, - a saturated or unsaturated and linear, branched or cyclic hydrocarbon group preferably comprising from 1 to 20 carbon atoms, better still from 1 to 10 carbon atoms, and optionally comprising one or more nitrogen, oxygen or sulphur atoms and optionally substituted by one or more groups chosen from -OR, -COOR, - COR, -SH, -SR, -OH and halogen atoms, and with R denoting a saturated or unsaturated and linear, branched or cyclic hydrocarbon group preferably comprising from 1 to 20 carbon atoms, better still from 1 to 10 carbon atoms, and optionally comprising one or more nitrogen, oxygen or sulphur atoms and optionally substituted by one or more groups chosen from -OR', -COOR', -COR', -SH, -SR', -OH, halogen atoms, and a residue of a polymer which can be obtained by radical polymerization, by polycondensation or by ring opening, with R' denoting a C1-C10 alkyl group;

- a modified or unmodified polyorganosiloxane residue;

- a polyoxyalkylene group; • R'3 representing a hydrogen atom or a saturated or unsaturated and linear, branched or cyclic hydrocarbon group preferably comprising from 1 to 20 carbon atoms, better still from 1 to 10 carbon atoms, and optionally comprising one or more nitrogen, oxygen or sulphur atoms and optionally substituted by one or more groups chosen from -OR', -COOR', -COR', -SH, -SR', -OH, halogen atoms, and a residue of a polymer which can be obtained by radical polymerization, by polycondensation or by ring opening, R' denoting a C1-C10 alkyl group.

The term "electron-withdrawing group" or "inductive-withdrawing (-I) group" is understood to mean any group which is more electronegative than carbon. Reference may be made to the work PR Wells, Prog. Phys. Org. Chem., Vol. 6, 111 (1968).

The term "group with little or no electron-withdrawing effect" is understood to mean any group having an electronegativity less than or equal to that of carbon.

The alkenyl or alkynyl groups preferably have 2 to 20 carbon atoms, better still from 2 to 10 carbon atoms.

Mention may in particular be made, as saturated or unsaturated and linear, branched or cyclic hydrocarbon group preferably comprising from 1 to 20 carbon atoms, of linear or branched alkyl, alkenyl or alkynyl groups, such as methyl, ethyl, n-butyl, tert- butyl, isobutyl, pentyl, hexyl, octyl, butenyl or butynyl; cycloalkyl groups or aromatic groups.

Mention may be made, as substituted hydrocarbon group, for example, of hydroxyalkyl or polyhaloalkyl groups.

Mention may in particular be made, as examples of unmodified polyorganosiloxane, of polyalkylsiloxanes, such as polydimethylsiloxanes, polyarylsiloxanes, such as polyphenylsiloxanes, or polyarylalkylsiloxanes, such as polymethylphenylsiloxanes.

Mention may in particular be made, among modified polyorganosiloxanes, of polydimethylsiloxanes comprising polyoxyalkylene and/or siloxy and/or silanol and/or amine and/or imine and/or fluoroalkyl groups. Among polyoxyalkylene groups, mention may in particular be made of polyoxyethylene groups and polyoxypropylene groups preferably having 1 to 200 oxyalkylene units.

Mention may in particular be made, among mono- or polyfluoroalkyl groups, of groups such as -(CH₂)_n-(CF₂)_m-CF₃ or -(CH₂)_n-(CF₂)_m-CHF₂ where n = 1 to 20 and m = 1 to 20.

The R1 and R2 substituents can optionally be substituted by a group having a cosmetic activity. The cosmetic activities particularly used are obtained from groups with colouring, antioxidizing, UV-screening and conditioning functions.

Mention may in particular be made, as examples of a group with a colouring function, of azo, quinone, methine, cyanomethine or triarylmethane groups. Mention may in particular be made, as examples of a group with an antioxidizing functon, of groups of butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT) or vitamin E type.

Mention may in particular be made, as examples of a group with a UV- screening function, of groups of benzophenone, cinnamate, benzoate, benzylidenecamphor and dibenzoylmethane type.

Mention may in particular be made, as examples of a group with a conditioning function, of cationic groups and groups of fatty ester type.

Preferably, R1 and R2 represent a hydrogen atom.

Preferably, R'3 is a saturated hydrocarbon group comprising from 1 to 10 carbon atoms

Preferably, X denotes O.

Mention may be made, as compounds of formula (I), of the monomers: a) belonging to the family of the polyfluoroalkyl 2-cyanoacrylates, such as:

- the 2,2,3,3-tetrafluoropropyl ester of 2-cyano-2-propenoic acid of formula (II):

CN

(H) COOCH₂CF₂CHF₂

- or the 2,2,2-trifluoroethyl ester of 2-cyano-2-propenoic acid of formula (III):

b) alkyl or alkoxyalkyl 2-cyanoacrylates of formula (I) in which R'3 represents a Ci- Cio alkyl, C₂-Ci₀ alkenyl or (Ci-C₄)alkoxy(Ci-Ci₀)alkyl radical. Mention may more particularly be made of ethyl 2-cyanoacrylate, methyl

2-cyanoacrylate, n-propyl 2-cyanoacrylate, isopropyl 2-cyanoacrylate, tert-butyl 2- cyanoacrylate, n-butyl 2-cyanoacrylate, isobutyl 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, allyl 2-cyanoacrylate, methoxypropyl 2-cyanoacrylate and isoamyl cyanoacrylate.

In the context of the invention, it is preferable to use the monomers b). According to a preferred embodiment, the cyanoacrylate monomer or monomers are chosen from C6-C10 alkyl or C2-C10 alkenyl cyanoacrylates. The monomers which are particularly preferred are octyl cyanoacrylates of formula (IV) and their mixtures:

in which: R'3 = -(CH₂)Z-CH₃,

-CH(CH₃)-(CH₂)₅-CH₃, -CH₂-CH(C₂H₅)-(CH₂)3-CH₃,

-(CH₂)4-CH(C₂H₅)-CH₃.

The monomers used in accordance with the invention can be covalently attached to supports, such as polymers, oligomers or dendrimers. The polymer or oligomer can be linear, branched, of comb structure or of block structure. The distribution of the monomers of the invention over the polymer, oligomer or dendrimer structure can be random, in the end position or in the form of blocks.

The cyanoacrylate monomer is generally present in the composition between 0.1 % and 80% by weight of the composition, preferably between 0.2% and 60% by weight of the composition.

The silica particles can be chosen from hydrophilic silicas, hydrophobic silicas and their mixtures.

Advantageously, the silica particle or particles exhibit a number-average primary size of between 0.1 and 30 μm, preferably of between 0.2 and 20 μm and more preferably still of between 0.5 and 15 μm.

Within the meaning of the present invention, the term "particle primary size" is understood to mean the maximum dimension which it is possible to measure between two diametrically opposed points of an individual particle.

The size of the organic particles can be determined by transmission electron microscopy or from the measurement of the specific surface by the BET method or from laser particle sizing. The term "silica" is understood to mean, in the present invention, both pure hydrophilic or hydrophobic silicas and also particles coated with silica and coated silica particles.

These silicas are preferably amorphous and they can be of pyrogenic origin or of precipitated origin. They can be provided in pulverulent form or in aqueous dispersion.

Hydrophilic pyrogenic silicas are obtained by continuous flame pyrolysis at 1000⁰C of silicon tetrachloride (SiCI₄) in the presence of hydrogen and of oxygen. Precipitated silicas are obtained by reaction of an acid with solutions of alkali metal silicates, preferably sodium silicate.

Hydrophilic silicas are sold by:

- Degussa-Hϋls, under the name of Aerosil 90, Aerosil 130, Aerosil 150, Aerosil 200, Aerosil 300, Aerosil 380 or Aerosil OX50 silica, FK320DS silica;

- Asahi Glass, under the name of Susphere H-31 , Susphere H-51 , Susphere H- 121 , Susphere H-201 , Susphere L-31 , Susphere H-51 , Susphere L-121 or Susphere L-201.

Use may also be made of silica in aqueous dispersion and, for example, a colloidal silica dispersion, such as the product sold under the name Bindzil 30/220® by Eka Chemicals, a colloidal dispersion of amorphous silica (size: 14 nanometres) in water (30/70).

The hydrophilic silica which can be used in the composition of the invention can also consist of a particle comprising a silica surface, for example a particle completely or partially covered with silica, in particular an inorganic particle completely or partially covered with silica, such as silica beads comprising titanium oxide, sold under the name Torayceram S-IT® by Toray; silica coated with titanium dioxide and covered with porous silica (85/5/10) (size: 0.6 μm), sold under the name ACS-0050510® by SACI-CFPA; nano-scale anatase titanium oxide treated with alumina and silica at 40% in water (size: 60 nm, monodisperse), sold under the name Mirasun TIW by Rhodia Chemie CRA; nano-scale anatase titanium oxide (60 nm) coated with silica/alumina/cerium(IV) (15/5/3) as a 32% aqueous dispersion, sold under the name Mirasun TIW 160® by Rhodia Chemie CRA; nano-scale anatase titanium oxide treated with alumina and silica (34/4.3/1.7) as a 40% aqueous dispersion, sold under the name Tioveil AQ-N® by Uniqema; nano-scale titanium oxide coated with silica (66/33) (particle size of the titanium dioxide: 30 nm; silica thickness: 4 nm), sold under the name Maxlight TS-04® by Nichimen Europe pic; and nano-scale titanium oxide coated with silica (80/20) (titanium dioxide particle size: 30 nm; silica thickness: 2 nm), sold under the name Maxlight TS-042® by Nichimen Europe pic.

Amorphous hydrophobic silicas of pyrogenic origin are obtained from hydrophilic silicas. As described above, the latter are obtained by continuous flame pyrolysis at 1000⁰C of silicon tetrachloride (SiCI₄) in the presence of hydrogen and of oxygen. They are subsequently rendered hydrophobic by treatment with halogenated silanes, alkoxysilanes or silazanes. Hydrophobic silicas differ from the starting hydrophilic silicas, inter alia, in a lower density of silanol groups and in a smaller adsorption of water vapour. These silicas are sold by:

- Degussa-Hϋls, under the name of Aerosil R202, Aerosil R805, Aerosil R812, Aerosil R972 or Aerosil 974 silica; - Asahi Glass, under the name of Susphere NP-30, Susphere NP-100 or

Susphere NP-200.

The hydrophobic silica which can be used in the composition of the invention can also consist of a particle completely or partially covered with silica, in particular an inorganic particle completely or partially covered with hydrophobic silica, such as metal oxides and pigments covered with hydrophobic silica.

Furthermore, the silica particles of use in the present invention can be surface- treated, "coated', with organic or inorganic compounds. Preferably, the surface treatments of the silica particles are chosen from i) a PEG-Silicone treatment, such as the AQ surface treatment marketed by LCW; ii) a Chitosan treatment, such as the CTS surface treatment marketed by LCW; iii) a Triethoxycaprylylsilane treatment, such as the AS surface treatment marketed by LCW; iv) a Methicone treatment, such as the SI surface treatment marketed by LCW; v) a Dimethicone treatment, such as the Covasil 3.05 surface treatment marketed by LCW; vi) a Dimethicone/Trimethylsiloxysilicate treatment, such as the Covasil 4.05 surface treatment marketed by LCW; vii) a Lauroyl Lysine treatment, such as the LL surface treatment marketed by LCW; viii) a Lauroyl Lysine Dimethicone treatment, such as the LL/SI surface treatment marketed by LCW; ix) a Magnesium Myristate treatment, such as the MM surface treatment marketed by LCW; x) an Aluminium Dimyristate treatment, such as the Ml surface treatment marketed by Miyoshi; xi) a Perfluoropolymethylisopropyl ether treatment, such as the FHC surface treatment marketed by LCW; xii) an lsostearyl Sebacate treatment, such as the HS surface treatment marketed by Miyoshi; xiii) a Disodium Stearoyl Glutamate treatment, such as the NAI surface treatment marketed by Myoshi; xiv) a Dimethicone/Disodium Stearoyl Glutamate treatment, such as the SA/NAI surface treatment marketed by Miyoshi; xv) a Perfluoroalkyl Phosphate treatment, such as the PF surface treatment marketed by Daito; xvi) an Acrylate Copolymer/Dimethicone and Perfluoroalkyl Phosphate treatment, such as the FSA surface treatment marketed by Daito; xvii) a Polymethylhydrosiloxane/Perfluoroalkyl Phosphate treatment, such as the FS01 surface treatment marketed by Daito; xviii) a Lauroyl Lysine/Aluminium Tristearate treatment, such as the LL-StAI surface treatment marketed by Daito; xix) an Octyltriethylsilane treatment, such as the OTS surface treatment marketed by Daito; xx) an Octyltriethylsilane/Perfluoroalkyl Phosphate treatment, such as the FOTS surface treatment marketed by Daito; xxi) an Acrylate Copolymer/Dimethicone treatment, such as the ASC surface treatment marketed by Daito; xxii) an lsopropyl Titanium Triisostearate treatment, such as the ITT surface treatment marketed by Daito; xxiii) a Microcrystalline Cellulose and Carboxymethyl Cellulose treatment, such as the AC surface treatment marketed by Daito; xxiv) a Cellulose treatment, such as the C2 surface treatment marketed by Daito; xxv) an Acrylate Copolymer treatment, such as the APD surface treatment marketed by Daito; and xxvi) a Perfluoroalkyl Phosphate/lsopropyl Titanium Triisostearate treatment, such as the PF + ITT surface treatment marketed by Daito.

The silica particles are preferably composed of hydrophilic silica particles, more preferably the silicas sold under the names Aerosil 100®, Aerosil 150®, Aerosil 200® and Aerosil 300® (Degussa-Hϋls). The particles are also present in the composition in an amount of between 0.01 % and 50% by weight of the composition, more preferably between 0.1 and 10% by weight of the composition.

In addition to the liquid organic solvent or solvents, the medium of the compositions of the invention can comprise water. Preferably, the medium is anhydrous, that is to say comprising less than 1 % by weight of water with respect to the total weight of the composition.

The cosmetic medium of the composition of the invention can be used homogeneously, can be provided in the form of an emulsion or can be encapsulated. The dispersed or continuous phase of the emulsion can then be composed of water,

C1-C4 aliphatic alcohols or their mixtures. The capsules or microcapsules comprising the composition of the invention can be dispersed in an anhydrous medium as defined above, water, C1-C4 aliphatic alcohols or their mixtures.

The medium of the compositions of the invention can comprise at least one liquid organic solvent other than the cyanoacrylate monomer.

The organic solvents are chosen from compounds which are liquid at a temperature of 25°C and at 105 Pa (760 mmHg).

The organic solvent is chosen, for example, from aromatic alcohols, such as benzyl alcohol; liquid fatty alcohols, in particular C10-C30 fatty alcohols; modified or unmodified polyols, such as glycerol, glycol, propylene glycol, dipropylene glycol, butylene glycol or butyl diglycol; volatile silicones, such as cyclopentasiloxane, cyclohexasiloxane, polydimethylsiloxanes modified or unmodified by alkyl and/or amine and/or imine and/or fluoroalkyl and/or carboxyl and/or betaine and/or quaternary ammonium functional groups; 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 fatty alcohol benzoates or salicylates.

The organic solvent is preferably chosen from organic oils; silicones, such as volatile silicones, silicone gums or oils which are or are not aminated and their mixtures; mineral oils; vegetable oils, such as olive oil, castor oil, rapeseed oil, coconut oil, wheat germ oil, sweet almond oil, avocado oil, macadamia oil, apricot oil, safflower oil, candlenut oil, camelina oil, tamanu oil or lemon oil; or also organic compounds, such as C5-C10 alkanes, acetone, methyl ethyl ketone, liquid esters of C1-C20 acids and of d-Cβ alcohols, such as methyl acetate, butyl acetate, ethyl acetate and isopropyl myristate, dimethoxyethane, diethoxyethane, liquid C10-C30 fatty alcohols, such as oleyl alcohol, liquid C10-C30 fatty alcohol esters, such as C10-C30 fatty alcohol benzoates, and their mixtures; polybutene oil, isononyl isononanoate, isostearyl malate, pentaerythrityl tetraisostearate, tridecyl trimelate, the cyclopentasiloxane (14.7% by weight)/polydimethylsiloxane dihydroxylated in the α and ω positions (85.3% by weight) mixture, or their mixtures.

According to a preferred embodiment, the organic solvent is composed of a silicone such as liquid polydimethylsiloxanes and liquid modified polydimethylsiloxanes, the viscosity of which at 25°C is between 0.1 cSt and 1 000 000 cSt and more preferably between 1 cSt and 30 000 cSt.

Mention will preferably be made of the following oils: - the α,ω-dihydroxylated polydimethylsiloxane/cyclopentadimethylsiloxane

(14.7/85.3) mixture sold by Dow Corning under the name of DC 1501 Fluid;

- the α,ω-dihydroxylated polydimethylsiloxane/polydimethylsiloxane mixture sold by Dow Corning under the name of DC 1503 Fluid;

- the dimethicone/cyclopentadimethylsiloxane mixture sold by Dow Corning under the name of DC 1411 Fluid or that sold by Bayer under the name SF1214;

- the cyclopentadimethylsiloxane sold by Dow Corning under the name of DC245 Fluid; and the respective mixtures of these oils.

The organic solvent or solvents of the composition generally represent from

0.01 to 99% by weight, preferably from 50% to 99% by weight, with respect to the total weight of the composition.

The cosmetic composition according to the invention can additionally comprise at least one pigment.

The use of a pigment in the cosmetic composition in accordance with the invention makes it possible to obtain visible colourings, in particular on dark hair, since the surface pigment masks the natural colour of the fibre.

The composition in accordance with the invention thus exhibits the advantage of resulting in colourings which exhibit good resistance to the various assaults which the hair may be subjected to, such as fatty substances or shampoos.

Furthermore, the cosmetic composition according to the invention makes it possible to result in visible and highly chromatic colourings on a keratinous fibre, in particular a dark fibre, without it being necessary to lighten or bleach the keratinous fibres and consequently without physical damage to the keratinous fibres. Within the meaning of the present invention, the term "pigment" is understood to mean any organic and/or inorganic entity having a solublity in water of less than 0.01 % at 20⁰C, preferably at less than 0.0001 %, and exhibiting an absorption between 350 and 700 nm, preferably an absorption with a maximum. The pigments used in the composition according to the invention can be chosen in particular from known organic and/or inorganic pigments of 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 provided in the form of a powder or of a pigment paste. They can be coated or uncoated.

The pigments in accordance with the invention can, for example, be chosen from white or coloured pigments, lakes, special effect pigments, such as pearlescent agents or glitter, and their mixtures.

Mention may be made, as examples of white or coloured inorganic pigments, of titanium dioxide, which is or is not surface treated, zirconium or cerium oxides, iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate and ferric blue. For example, the following inorganic pigments can be used: Ta₂O₅, Ti₃O₅, Ti₂O₃,

TiO, ZrO₂ as a mixture with TiO₂, ZrO₂, Nb₂O₅, CeO₂, ZnS.

Mention may be made, as examples of white or coloured organic pigments, of nitroso, nitro, azo, xanthene, quinoline, anthraquinone or phthalocyanine compounds, compounds of metal complex type, or isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane or quinophthalone compounds.

In particulier, white or coloured organic pigments can be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, sorghum red, the blue pigments codified in the Color Index under the references Cl 42090,

69800, 69825, 73000, 74100 and 74160, the yellow pigments codified in the Color

Index under the references Cl 11680, 11710, 15985, 19140, 20040, 21100, 21108,

47000 and 47005, the green pigments codified in the Color Index under the references Cl 61565, 61570 and 74260, the orange pigments codified in the Color Index under the refences Cl 11725, 15510, 45370 and 71105, the red pigments codified in the Color

Index under the references Cl 12085, 12120, 12370, 12420, 12490, 14700, 15525,

15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410,

58000, 73360, 73915 and 75470, or the pigments obtained by oxidative polymerization of indole or phenol derivatives, as are described in Patent FR 2 679 771.

Use may be made of pigment pastes formed of organic pigment, such as the products sold by Hoechst under the name:

- Cosmenyl Yellow 1OG: Pigment Yellow 3 (Cl 11710);

- Cosmenyl Yellow G: Pigment Yellow 1 (Cl 11680); - Cosmenyl Orange GR: Pigment Orange 43 (Cl 71105); - Cosmenyl Red R: Pigment Red 4 (Cl 12085);

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

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

- Cosmenyl Blue A2R: Pigment Blue 15.1 (Cl 74160); - Cosmenyl Green GG: Pigment Green 7 (Cl 74260);

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

The pigments in accordance with the invention can also be in the form of composite pigments, as are described in Patent EP 1 184 426. These composite pigments can be composed in particular of particles comprising an inorganic core, at least one binder, which provides for the attachment of the organic pigments to the core, and at least one organic pigment which at least partially covers the core.

The term "lake" is understood to mean dyes adsorbed onto insoluble particles, the combination thus obtained remaining insoluble during use. The inorganic substrates onto which the dyes are adsorbed are, for example, alumina, calcium sodium borosilicate, calcium aluminium borosilicate and aluminium. Mention may be made, among organic dyes, of cochineal carmine.

Mention may be made, as examples of lakes, of the products known under the following names: D & C Red 21 (Cl 45 380), D & C Orange 5 (Cl 45 370), D & C Red 27 (Cl 45 410), D & C Orange 10 (Cl 45 425), D & C Red 3 (Cl 45 430), D & C Red 7 (Cl 15 850:1 ), D & C Red 4 (Cl 15 510), D & C Red 33 (Cl 17 200), D & C Yellow 5 (Cl 19 140), D & C Yellow 6 (Cl 15 985), D & C Green (Cl 61 570), D & C Yellow 1 O (Cl 77 002), D & C Green 3 (Cl 42 053) or D & C Blue 1 (Cl 42 090).

The term "special effect pigments" is understood to mean pigments which generally create a coloured appearance (characterized by a certain hue, a certain vividness and a certain lightness) which is not uniform and which changes as a function of the conditions of observation (light, temperature, angles of observation, and the like). They thereby contrast with white or coloured pigments, which provide a conventional opaque, semitransparent or transparent uniform colour.

Mention may be made, as examples of special effect pigments, of white pearlescent pigments, such as mica covered with titanium dioxide or with bismuth oxychloride, coloured pearlescent pigments, such as mica covered with titanium dioxide and with iron oxides, mica covered with titanium dioxide and in particular with ferric blue or with chromium oxide or mica covered with titanium dioxide and with an organic pigment as defined above, and pearlescent pigments based on bismuth oxychloride. Mention may be made, as pearlescent pigments, of the following pearlescent agents: Cellini sold by Engelhard (mica-Tiθ2-lake), Prestige sold by Eckart (mica-Tiθ2), Prestige Bronze sold by Eckart (mica-Fe2θ3) or Colorona sold by Merck

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

Quantum dots are luminescent semiconductor nanoparticles capable of emitting, under light excitation, radiation exhibiting 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 processes described, for example, in US 6 225 198 or US 5 990 479, in the publications which are cited therein and in the following publications: Dabboussi B. O. et al., "(CdSe)ZnS core-shell quantum dots: synthesis and characterisation of a size series of highly luminescent nanocristallites", Journal of Physical Chemistry B, vol. 101 , 1997, pp 9463-9475, and Peng, Xiaogang et al., "Epitaxial growth of highly luminescent CdSe/CdS core/shell nanocrystals with photostability and electronic accessibility", Journal of the American Chemical Society, vol. 119, No. 30, pp 7019-7029.

The variety of the pigments which can be used in the present invention makes it possible to obtain a rich palette of colours as well as specific optical effects, such as interference, metallic effects. According to a specific embodiment, the pigments are coloured pigments. The term "coloured pigments" is understood to mean pigments other than white pigments.

The size of the pigment of use in the context of the present invention is generally between 10 nm and 200 μm, preferably between 20 nm and 80 μm and more preferably between 30 nm and 50 μm.

The pigments can be coated with organic or inorganic compounds.

The organic agent with which the pigments are treated can be deposited on the pigments by evaporation of solvent, chemical reaction between the molecules of the surface agent or creation of a covalent bond between the surface agent and the pigments or fillers.

Within the meaning of the present invention, the surface treatment is such that a surface-treated pigment retains its intrinsic pretreatment pigment properties.

The surface treatment can thus be carried out, for example, by chemical reaction of a surface agent with the surface of the pigments and creation of a covalent bond between the surface agent and the pigments. This method is described in particular in Patent US 4 578 266.

Preferably, use will be made of an organic agent covalently bonded to the pigments. The agent for the surface treatment can represent from 0.1 to 50% by weight, preferably from 0.5 to 30% by weight and more preferably still from 1 to 10% by weight of the total weight of the surface-treated pigments or fillers.

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

- a PEG-Silicone treatment, such as the AQ surface treatment marketed by LCW;

- a Chitosan treatment, such as the CTS surface treatment marketed by LCW;

- a Triethoxycaprylylsilane treatment, such as the AS surface treatment sold 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 LL/SI surface treatment marketed by LCW; - a Magnesium Myristate treatment, such as the MM surface treatment marketed by LCW;

- an Aluminium Dimyristate treatment, such as the Ml surface treatment marketed by Miyoshi;

- a Perfluoropolymethylisopropyl ether treatment, such as the FHC surface treatment marketed by LCW;

- an lsostearyl 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 treatment, such as the FSA surface treatment marketed by Daito;

- a Polymethylhydrosiloxane/Perfluoroalkyl Phosphate treatment, such as the FS01 surface treatment marketed by Daito;

- a Lauroyl Lysine/Aluminium 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 lsopropyl Titanium Triisostearate treatment, such as the ITT surface treatment marketed by Daito;

- a Microcrystalline Cellulose and Carboxymethyl Cellulose treatment, such as the AC 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/lsopropyl Titanium Triisostearate treatment, such as PF + ITT surface treatment marketed by Daito.

The pigment or pigments are each generally present in the composition in accordance with the invention in amounts generally of between 0.05 and 50% of the total weight of the composition, preferably from 0.1 to 35%.

Polymerization inhibitors and more particularly anionic and/or radical polymerization inhibitors can be introduced into the compositions, in order to increase the stability of the composition over time. Mention may be made, in a nonlimiting way, of the following polymerization inhibitors: sulphur dioxide, nitric oxide, boron trifluoride, hydroquinone and its derivatives, such as hydroquinone monoethyl ether or TBHQ, benzoquinone and its derivatives, such as duroquinone, catechol and its derivatives, such as t-butylcatechol and methoxycatechol, anisole and its derivatives, such as methoxyanisole or hydroxyanisole, pyrogallol and its derivatives, p-methoxyphenol, hydroxybutyltoluene, alkyl sulphates, alkyl sulphites, alkyl sulphones, alkyl sulphoxides, alkyl sulphides, mercaptans, 3-sulphonene and their mixtures. The alkyl groups preferably denote groups having 1 to 6 carbon atoms.

Use may also be made, as inhibitor, of inorganic or organic acids. Thus, the cosmetic composition according to the invention can also comprise at least one inorganic or organic acid, the latter having one or more carboxyl or sulpho groups, exhibiting a pKa of between 0 and 6, such as phosphoric acid, hydrochloric acid, nitric acid, benzene- or toluenesulphonic acid, sulphuric acid, carbonic acid, hydrofluoric acid, acetic acid, formic acid, propionic acid, benzoic acid, mono-, di- or trichloroacetic acid, salicylic acid, 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 can be between 10 ppm and 30% by weight and more preferably between 10 ppm and 15% by weight, with respect to the total weight of the composition.

The composition of the invention can comprise one or more cosmetic additives conventional in the treatment of keratinous substances. They can be chosen from this nonexhaustive list, such as reducing agents, oxidizing agents, sequestering agents, softening agents, antifoaming agents, polymeric or nonpolymeric thickening agents, inorganic or organic thickening agents (such as benzylidinesorbitol or N-acylamino acids), moisturizing agents, dispersants for fillers, emollients, organic or inorganic bases, plasticizers, sunscreens, optical brightening agents, direct or oxidation dyes, pigments, inorganic fillers, clays, colloidal minerals, colloidal metals, nanoparticles of semiconductors of "quantum well" type based on metals or on silicon, a photo- or thermochromic compound, pearlescent agents, pearlizing agents, fragrances, peptizing agents, preservatives, proteins, vitamins, antidandruff agents, fixing or nonfixing anionic, cationic or amphoteric polymers, nonpolymeric conditioning agents, such as cationic, anionic or amphoteric surfactants, oxyethylenated or nonoxyethylenated waxes, paraffins, C10-C30 fatty acids, such as stearic acid or lauric acid, C10-C30 fatty amides, such as lauric acid diethanolamide, C10-C30 fatty alcohol esters, such as C10-C30 fatty alcohol benzoates, and their mixtures.

Preferably, the composition comprises at least one dispersant. These agents can optionally be encapsulated. The capsule can be of polycyanoacrylate type.

A propellant can be incorporated in the composition of the invention. The propellant is composed of the compressed or liquefied gases normally employed for the preparation of aerosol compositions. Use will preferably be made of air, carbon dioxide gas, compressed nitrogen or a soluble gas, such as dimethyl ether, halogenated (in particular fluorinated) or nonhalogenated hydrocarbons (butane, propane, isobutane) and their mixtures.

The process for the treatment of the hair in accordance with the invention consists in applying the composition described above to keratinous substances and in particular in the presence of a nucleophilic agent, with or without heating.

These two operations can also be carried out after application of the composition.

It is also possible to adjust the kinetics of polymerization by the anionic route by pre-impregnating the keratinous substances using a nucleophilic agent. The nucleophilic agent can be used pure, in solution or in the form of an emulsion or can be encapsulated. In order to adjust the kinetics of anionic polymerization, it is also possible to increase the nucleophilicity of the fibre by chemical conversion of the keratinous substance.

Mention may be made, by way of example, of the reduction of the disulphide bridges of which the keratin is partially composed to give thiols before application of the composition of the invention. Mention may be made, nonexhaustively, as reducing agents for the disulphide bridges of which the keratin is partially composed, of the following compounds:

- anhydrous sodium thiosulphate, - powdered sodium metabisulphite,

- thiourea,

- ammonium sulphite,

- thioglycolic acid,

- thiolactic acid, - ammonium thiolactate,

- glyceryl monothioglycolate,

- ammonium thioglycolate,

- thioglycerol,

- 2,5-dihydroxybenzoic acid, - diammonium dithioglycolate,

- strontium thioglycolate,

- calcium thioglycolate,

- zinc formaldehyde sulphoxylate,

- isooctyl thioglycolate, - d,l-cysteine

- monoethanolamine thioglycolate.

In order to adjust the kinetics of polymerization by the anionic route and more specifically to reduce the rate of polymerization of the monomers of the invention, it is possible to increase the viscosity of the composition. To do this, one or more polymers not exhibiting reactivity with regard to the monomers in accordance with the invention can be added to the composition of the invention. In this context, mention may be made, nonexhaustively, of poly(methyl methacrylate) (PMMA) or cyanoacrylate-based copolymers, such as are described in Patent US 6 224 622.

In order to improve, inter alia, the adhesion of the poly(cyanoacrylate) formed in situ, the fibre can be pretreated with any type of polymer. It is also possible to carry out a hair treatment before application of the composition of the invention, such as a direct or oxidation dyeing, a perming or a hair straightening. The process for the application of the compositions in accordance with the invention may or may not be followed by a rinsing operation. The compositions of the invention, after application to the hair, may or may not be rinsed out.

The compositions can be provided in various formulation forms, such as a lotion, an aerosol foam, a spray, a conditioner or a shampoo, a gel or a wax. The compositions can be present in a pump-action spray or an aerosol spray.

The treatment of the fibre can be a single-stage process, in which case the composition of the invention is applied to dry hair or hair moistened or treated with shampoo beforehand. The hair is dried with a hair dryer, hood dryer or iron. A final shampooing can optionally be carried out.

The hair fibre can be pretreated with at least one nucleophilic agent. When the composition according to the invention is composed of two compositions, one comprising the silica particles according to the invention and the other comprising the cyanoacrylate monomer, then another embodiment of the process of the invention can be provided. The hair fibre can be pretreated with the composition comprising the silica particles according to the invention. The hair can be dried. Then the second composition, comprising at least one cyanoacrylate monomer in a cosmetic solvent, is applied to the hair. The hair is dried (hair dryer, hood dryer or iron). A final shampooing can optionally be carried out. A specific process consists in combining the treatment according to the invention with existing treatments of the fibre, such as the application of a reducing agent for a permanent wave or of a permanent wave or of an oxidation dyeing or of a bleaching or of a shampooing or of a styling product or alkaline hair straightening.

In this way, the fibre is prepared, in order to increase the effectiveness, by stripping the fibre and/or by etching the fibre, as seen above. In a second stage, the composition of the invention is applied, it being possible for the fibre to be pretreated with a nucleophilic agent.

Another process consists in applying the treatment according to the invention before treatments, described above, of the fibre which are capable of damaging keratinous fibres. In this way, the fibre is protected during the treatment. Optionally, makeup can subsequently be removed from the fibre, that is to say the sheathing resulting from the composition of the invention can be removed.

Another subject-matter of the invention is the use of the compositions described above in the cosmetic treatment of keratinous substances and in particular keratinous fibres, such as the hair. The compositions can be used in particular for the strengthening of keratinous substances and keratinous fibres and in particular for contributing volume and a particularly persistent sheathing.

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

According to an alternative form, the kit comprises a first anhydrous composition which comprises the silica particle or particles and the electrophilic monomer or monomers and a second composition which comprises a nucleophilic agent.

The examples which follow are intended to illustrate the invention without, however, exhibiting a limiting nature.

EXAMPLES:

Example 1: The following composition is produced

0.25 g of this composition is applied to a lock of 1 g of chestnut hair treated with shampoo beforehand. After leaving for 15 min at ambient temperature, the lock is dried with a hair dryer for 3 min.

The individual hairs are sheathed. This effect is still visible after several shampooing operations. Example 2: The following composition is produced

^* Dispersant, sold by Avecia

The individual hairs are sheathed. This effect is still visible after several shampooing operations.

Example 3: The following composition is produced

The individual hairs are sheathed. This effect is still visible after several shampooing operations. Example 4: The following composition is produced

α,ω-Dihydroxylated polydimethylsiloxane/cyclopentadimethylsiloxane (14.7/85.3), sold by Dow Corning under the name of DC 1501 Fluid 4O g

Cyclopentadimethylsiloxane, sold by Dow Corning under the name of DC245 Fluid 37 g

Sunsphere H31 sold by Asahi Glass 3 g

Mica-iron oxide pearlescent agent, Prestige Bronze, sold by Eckart 1 O g Methylheptyl cyanoacrylate from Chemence 1 O g

0.5 g of this composition is applied to a lock of 1 g of chestnut hair treated with shampoo beforehand. After leaving for 15 min at ambient temperature, the lock is dried with a hair dryer for 3 min.

The individual hairs are sheathed and coloured. These effects are still visible after several shampooing operations.

Claims

1. Cosmetic composition comprising: a) at least one cyanoacrylate monomer of formula (I):

in which: • X denotes an oxygen or sulphur atom or an NH group ;

• R1 and R2 each denote, independently of one another, a group with little or no electron-withdrawing effect (with little or no inductive-withdrawing effect)

• R'3 denotes a hydrogen atom or a saturated or unsaturated and linear, branched or cyclic hydrocarbon group preferably comprising from 1 to 20 carbon atoms, better still from 1 to 10 carbon atoms, and optionally comprising one or more nitrogen, oxygen or sulphur atoms and optionally substituted by one or more groups chosen from -OR', -COOR', -COR', -SH, -SR', -OH, halogen atoms, and a residue of a polymer which can be obtained by radical polymerization or by polycondensation or by ring opening, R' denoting a C1-C10 alkyl group ; b) at least one silica particle, the size of which is less than 30 μm; and c) at least one liquid organic solvent ; with the proviso that when the cyanoacrylate monomer of formula (I) represents a methyl α-cyanocrylate, an ethyl α-cyanocrylate or an isobutyl α-cyanocrylate and the silica particle has a size of 1 μm, thus the liquid organic solvent cannot represent N,N- dimethyl-p-toluidine, hexane, or ethanol.

2. Composition according to the preceding claim, characterized in that the cyanoacrylate monomer is of formula belonging to the family: i) either of the C1-C20 polyfluoroalkyl 2-cyanoacrylates, such as : the 2,2,3,3-tetrafluoropropyl ester of 2-cyano-2-propenoic acid of formula

- or the 2,2,2-trifluoroethyl ester of 2-cyano-2-propenoic acid of formula

(III): CN

(III) COOCH₂CF₃ ii) or of the alkyl or alkoxyalkyl 2-cyanoacrylates of formula (I) in which R'3 represents a C1-C10 alkyl, C2-C10 alkenyl or (Ci-C4)alkoxy(Ci-Cio)alkyl radical.

3. Composition according to claim 1 , characterized in that the cyanoacrylate monomer of formula (I) comprises R1 and R2 representing a hydrogen atom, X representing an oxygen atom and R'3 representing a linear or branched C1-C10 alkyl group.

4. Composition according to the preceding claim, characterized in that the cyanoacrylate monomer is of formula (IV) or its mixtures:

in which: R'3 =-(CH₂)₇-CH₃,

-CH(CH₃)-(CH₂)5-CH₃, -CH₂-CH(C2H5)-(CH₂)3-CH3,

-(CH₂)4-CH(C₂H₅)-CH₃.

5. Composition according to any one of the preceding claims, characterized in that the silica particle is hydrophilic.

6. Composition according to the preceding claim, characterized in that the organic solvent is composed of at least one volatile silicone.

7. Composition according to any one of the preceding claims, characterized in that the said composition is anhydrous.

8. Composition according to any one of the preceding claims, characterized in that it comprises at least one acid.

9. Use of a composition comprising: a) at least one cyanoacrylate monomer of formula (I): in which:

• X denotes an oxygen or sulphur atom or an NH group;

• R1 and R2 each denote, independently of one another, a group with little or no electron-withdrawing effect (with little or no inductive-withdrawing effect);

• R'3 denotes a hydrogen atom or a saturated or unsaturated and linear, branched or cyclic hydrocarbon group preferably comprising from 1 to 20 carbon atoms, better still from 1 to 10 carbon atoms, and optionally comprising one or more nitrogen, oxygen or sulphur atoms and optionally substituted by one or more groups chosen from -OR', - COOR', -COR', -SH, -SR', -OH, halogen atoms, and a residue of a polymer which can be obtained by radical polymerization or by polycondensation or by ring opening, R' denoting a C1-C10 alkyl group; b) at least one silica particle, the size of which is less than 30 μm; and c) at least one liquid organic solvent ; in the treatment of keratinous substances and in particular of keratinous fibres, such as the hair.

10. Use according to the preceding claim characterized in that the composition comprising a cyanoacrylate monomer of formula belonging to the family : i) either of the C1-C20 polyfluoroalkyl 2-cyanoacrylates, such as : the 2,2,3,3-tetrafluoropropyl ester of 2-cyano-2-propenoic acid of formula

or the 2,2,2-trifluoroethyl ester of 2-cyano-2-propenoic acid of formula

ii) or of the alkyl or alkoxyalkyl 2-cyanoacrylates of formula (I) in which R'3 represents a C1-C10 alkyl, C₂-Ci₀ alkenyl or (Ci-C₄)alkoxy(Ci-Ci₀)alkyl radical.

11. Use according to either one of claims 9 and 10 characterized in that the composition comprising a cyanoacrylate monomer of formula (I) with R1 and R2 representing a hydrogen atom, X representing an oxygen atom and R'3 representing a linear or branched C1-C10 alkyl group.

12. Use according to any one of claims 9 to 11 characterized in that the composition comprising a cyanoacrylate monomer of formula (IV) or its mixtures:

CN

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

-CH(CH₃)-(CH₂)₅-CH₃, -CH₂-CH(C₂H₅)-(CH₂)3-CH₃,

-(CH₂)4-CH(C₂H₅)-CH₃.

13. Use according to any one of claims 9 to 12 characterized in that the composition comprising a hydrophilic silica particle.

14. Use according to any one of claims 9 to 13 characterized in that the composition comprising an organic solvent which is composed of at least one volatile silicone.

15. Use according to any one of claims 9 to 14 characterized in that the said composition is anhydrous.

16. Use according to any one of claims 9 to 15 characterized in that the composition comprising at least one acid.

17. Process for the treatment of keratinous substances, characterized in that it comprises the application to the said keratinous substances of the composition as defined in any one of claims 9 to 16.

18. Process according to the preceding claim, characterized in that the composition of the invention is applied to dry keratinous substances or keratinous substances moistened or treated with shampoo beforehand.

19. Process according to Claim 17, characterized in that the composition of the invention is applied to keratinous substances, followed by the application of a nucleophilic agent.

20. Process according to either one of claims 17 and 18, characterized in that the keratinous substance, in particular the keratinous fibre, such as the individual hair, can be pretreated with at least one nucleophilic agent.

21. Process according to any one of claims 17 to 19, characterized in that the keratinous substance, in particular the keratinous fibre, such as the individual hair, can be pretreated with at least one type of silica particle dispersed in a cosmetic solvent.

22. Process for the treatment of a keratinous substance, in particular a keratinous fibre, such as the individual hair, characterized in that, in a first step, a reducing agent for a full permanent wave or a permanent wave or an oxidation dyeing or a bleaching or a shampooing or a styling product or an alkaline hair straightening is applied to the said keratinous substance and, in a second step, the procedure according to any one of Claims 17 to 21 is carried out.

23. Process for the treatment of a keratinous substance, in particular the keratinous fibre, such as the individual hair, characterized in that i) in the first stage, the said fibre is protected by a process according to any one of claims 18 to 22; ii) in the second stage, the said fibre is treated, in particular by the application of a reducing agent for a permanent wave or with the full permanent wave or with the oxidation dyeing or the bleaching or the alkaline hair straightening; and iii), in the third stage, makeup is removed from the said fibre.

24. Kit, comprising a first composition comprising at least one cyanoacrylate monomer and optionally at least one anionic and/or radical polymerization inhibitor and/or acid and also a second composition comprising, in a cosmetically acceptable medium, at least one liquid organic solvent, at least one silica particle and optionally an acid.

25. Kit, comprising a first anhydrous composition comprising at least one silica particle and at least one electrophilic monomer and a second composition comprising at least one nucleophilic agent.