WO2010076489A2

WO2010076489A2 - Cosmetic composition containing a polyamine having diazirine groups and use thereof for photo-grafting pigments and/or micro- or nanoparticles

Info

Publication number: WO2010076489A2
Application number: PCT/FR2009/052549
Authority: WO
Inventors: Gabin Vic
Original assignee: L'oreal
Priority date: 2008-12-15
Filing date: 2009-12-15
Publication date: 2010-07-08
Also published as: WO2010076489A3

Abstract

The invention relates to a cosmetic composition that contains, in a cosmetically acceptable medium: one or more photo-activated compounds obtained from polyamine polymers, containing at least two -NH- and/or -N- amino units to which at least two photo-activated diazirine groups are covalently bonded; and b) one or more pigments and/or one or more micro- or nanoparticles.

Description

Cosmetic composition comprising a polvamine bearing diazirine groups and use for photo-grafting pigments and / or micro or nanoparticles

The invention relates to a cosmetic composition comprising a photoactivatable compound derived from a polyamine polymer to which are covalently bound at least two photoactivatable diazirine groups, and one or more pigments and / or one or more micro or nano particles. The invention also relates to the use of this composition for fixing pigments and / or micro or nanoparticles on keratin materials. The products used to fix cosmetic agents, in particular pigments and / or micro or nanoparticles, on keratin materials generally have the disadvantage of being eliminated very quickly during washing or during other treatments.

To overcome this drawback, it is generally sought to graft pigments and / or micro or nano particles on keratin materials.

The grafting of pigments on the keratin materials makes it possible to color the hair on the surface and thus to obtain a non-degrading coloration for the hair fiber.

The grafting of the micro or nanoparticles, on the surface on the keratin materials, makes it possible to obtain hair styling effects that are durable, soft or shiny depending on the nature of the micro or nanoparticles.

The grafting of pigments and / or micro or nano particles on the surface of the keratin materials is particularly difficult to achieve. Indeed, it must be done under mild conditions applicable in cosmetics, so as not to degrade the hair fiber. In addition, it is necessary to stabilize the pigments and / or the micro or nanoparticles in the possibly colored cosmetic composition while allowing it to be adsorbed on the surface of the hair before carrying out the grafting.

Document FR 2 839 446 discloses a photoactivatable cosmetic composition comprising a diazirine and a cosmetic active covalently bonded to form a diazirine-active compound. This photoactivatable composition is used to fix cosmetic active agents on keratin materials, using the diazirine compound which provides the bond between the cosmetic agent and the keratin materials.

FR 2 831 534 discloses a photoactivatable compound comprising a carrier molecule on which at least two photoactivatable functional groups are covalently bound. By means of the photoactivatable compound described in this document, the covalent grafting of the cosmetic active agents present in the medium on the keratinous material is provided.

Document WO 2006/018729 discloses polyamine polymers bearing photoactivatable diazirine groups that can be photo-grafted onto the surface of a substrate, for cosmetic use. FR 2 870 733 discloses a composition for dyeing keratinous fibers comprising a compound carrying an amine function, a pigment other than iron oxide, titanium oxide and silica, and a chemical coupling for the formation of amide bonds, this coupling agent being generally selected from carbodiimide derivatives. This composition makes it possible to obtain colorations which are visible on a dark support without it being necessary to lighten or discolour the fibers, and which have good resistance to shampooing. However, the application method generally requires several steps and the coupling agents used are not always perfectly safe. Moreover, this system does not easily allow localization of the effect.

There is therefore a need for a cosmetic composition which makes it possible to simply and safely fix pigments and / or micro or nanoparticles in a durable manner on the keratinous material, without degrading the keratinous material, this fixation being able to be easily located. The subject of the invention is therefore a cosmetic composition comprising, in a cosmetically acceptable medium: a) one or more photoactivatable compounds, obtained from polyamine polymers containing at least two amino units -NH- and / or -N- _; covalently bound at least two photoactivatable diazirine groups, and b) one or more pigments and / or one or more micro or nanoparticles.

The polyamine polymer (s) that can be used to obtain the photoactivatable compound (s) of the composition according to the invention may be linear, branched, hyperbranched or dendrimeric. Hyperbranched polymers are molecular constructs having a branched structure, usually around a heart. Their structure is generally devoid of symmetry: the basic units or monomers used for the construction of hyperbranched polymer may be of different types and their distribution is irregular. The branches of the polymer may be of different natures and lengths. The number of basic units, or monomers, may be different depending on the different branches. While being asymmetric, hyperbranched polymers may have: an extremely branched structure, around a heart; successive layers or generations of ramifications; a layer of terminal chains.

The hyperbranched polymers are generally derived from the polycondensation of one or more ABx monomers, A and B being reactive groups capable of reacting together, where x is an integer greater than or equal to 2, but other methods of preparation can be envisaged. The hyperbranched polymers are characterized by their degree of polymerization DP = 1 -b, where b is the percentage of non-terminal functional groups of B which have not reacted with an A group. The condensation being non-systematic, contrary to the synthesis. of dendrimers, the degree of polymerization is less than 100%. In the usual way, by the known synthetic methods, DP is between 15 and 90%.

It is also possible to react a terminal group T on the hyperbranched polymer to obtain a particular functionality at the end of chains. Several hyperbranched polymers can be associated with each other, by a covalent bond or another type of bond, through their terminal groups. Such polymers, called bridged polymers, come within the definition of hyperbranched polymers according to the present invention.

Dendrimers are highly branched polymers and oligomers with a well-defined chemical structure, and are said to be "perfect" hyperbranched polymers.

Generally, the dendrimers comprise a core, a predetermined number of generations of branches, or spindles, and terminal groups. Generations of spindles consist of structural units, which are identical for the same generation of spindles and which may be identical or different for different generations of spindles. Generations of spindles extend radially in a geometric progression from the heart. The terminal groups of a dendrimer of the N ^lθmθ generation are the terminal functional groups of the spindles of the N ^lθmθ generation or terminal generation. The definition of dendrimers given above includes molecules with symmetrical branches. It also includes non-symmetric branching molecules, such as, for example, dendrimers whose spindles are lysine groups, in which the branching of a spindle generation on the former is done on the amines α and ε of lysine, which leads to a difference in the length of the spindles of the different branches.

Star-filled polymers, or "dense star polymers," starburst polymers, rod-shaped dendrimers, or "rod-shaped dendrimers," are included in the present definition of dendrimers. The molecules denoted arborais and molecules in cascade also fall within the definition of the dendrimers according to the present invention.

Several dendrimers can be associated with each other by a covalent bond or other type of bond through their terminal groups to give entities known as "bridged dendrimers", "dendrimer aggregates" or "bridged dendrimer". ". Such entities are included in the definition of the dendrimers according to the present invention.

Dendrimers may be in the form of a set of molecules of the same generation, called monodisperse sets; they can also be in the form of sets of different generations, called polydisperses. The definition of the dendrimers according to the present invention includes monodisperse as well as polydisperse sets of dendrimers. The polyamine polymer (s) that may be used to form the photoactivatable compound (s) of the composition according to the invention may be chosen from:

the polyalkyleneimines, preferably the poly (C ₂ -C ₅ alkyleneimines),

polymers grafted with a (C ₂ -C ₅ ) alkyleneimine, preferably polymers grafted with ethyleneimine, better polyamidoamines, crosslinked or not, grafted with ethyleneimine,

copolymers based on aminoalkyl (Ci-C ₄ ) (meth) acrylate, preferably based on aminoethyl (meth) acrylate,

polyallylamines, polycondensates of at least one compound chosen from piperazine, 1 - (2-aminoethyl) piperazine, 1,4-bis (3-aminopropyl) piperazine and 1-alkyl (Ci-C). ₂₅ ) piperazine, 1,4-di (alkyl)

(Ci-C ₂₅₎₎ piperazine, 1 - (2-hydroxy (alkyl (C ₂ -C ₂₅₎₎₎ piperazine, lïmidazole the alkylimidazole -C _25, or mixtures thereof, with at least one compound selected from C ₆ -C ₂₂ alkylene dihalide, epihalohydrin and / or C ₈ -C ₂₂ bisepoxide,

the polymers containing in their structure at least 2 successive units of the same basic amino acid, the expression at least 2 units includes in particular at least 2, 3, 4, 5, 6, 7, 8, 9 and 10 units,

polyamidoamines; dendrimers containing primary amines in the terminal position.

Among the polyalkyleneimines that may be used in the composition according to the invention, mention may be made of polyethyleneimines and polypropyleneimines.

The polyethyleneimines (PEI) that can be used according to the invention generally have the following formula: - (CH ₂ -CH ₂ -NH) _n - where n is the average number of ethyleneimine units, n being between 5 and 10,000.

Homopolymers of ethyleneimine can be connected.

Of particular note are PEI-7 (n = 7), PEI-15 (n = 15), PEI-30 (n = 30), PEI-45 (n = 45), PEI-275 ( n = 275), PEI-700 (n = 700), PEI-1000 (n = 1000), PEI-1400 (n = 1400), PEI-1500 (n = 1500), PEI-1750 ( n = 1750), and PEI-2500 (n = 2500).

Polyethyleneimines are particularly described in the documents: "KIRK Othmer ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY" 3 ^èmθ edition, vol.20, 1982, p.214-216, and "Polyethyleneimine Prospective Application" HN Feigenbaum, Cosmetics & Toiletries, 108, 1993, p.73. The polyamine polymers that can be used to form the one or more photoactivatable compounds of the composition according to the invention can also be chosen from polymers grafted with a (C ₂ -C ₅ ) alkyleneimine, preferably polymers grafted with ethyleneimine, better polyamidoamines, crosslinked or not, grafted with ethyleneimine. The polyamidoamines can be prepared from polyalkylene polyamines chosen from those having from 3 to 10 carbon atoms, for example diethylene triamine, triethylene tetramine, dipropylene triamine, tripropylene tetramine and di-hexa methylene. triamine, amino-propyl-ethylene di-amine, bis-aminopropylethylene di-amine, and mixtures thereof, and from a monocarboxylic aliphatic acid.

As explained above, the polyamine polymer (s) may also be chosen from polycondensates of at least one compound selected from a) piperazine, 1 - (2-aminoethyl) piperazine, 1,4-bis (3-aminopropyl) piperazine), 1-alkyl (C1-C25) piperazine, 1,4-di (C1-C25 alkyl) piperazine, 1- (2-hydroxy (C ₂ -C 25) alkyl) piperazine, imidazole C ₁ -C ₂₅ alkylimidazole, or mixtures thereof, with at least one compound selected from b) C ₆ -C ₂₂ alkylene dihalide, epihalohydrin and / or C ₈ -C ₂₂ bisepoxide.

Advantageously, the constituent (s) of group a) and the constituent (s) of group b) are present in a molar ratio of between 1: 0.8 and 1: 1, 1.

A preferred polycondensate is, for example, the polycondensate of piperazine and imidazole with epihalohydrin.

Such polycondensates that can be used in the composition according to the invention are described in particular in US Pat. No. 6,025,322. The polyamine polymer (s) that may be used to form the photoactivatable compound (s) of the composition according to the invention may also be chosen from polymers containing in their structure at least 2 successive units of one and the same basic amino acid.

The at least one basic amino acid is preferably chosen from ornithine, asparagine, glutamine, lysine and arginine.

Said polyamine polymers containing at least 2 successive units of the same basic amino acid that can be used in the composition according to the invention generally contain 2 to 10,000 basic amino acid units.

Preferably, the polyamine polymer used to form the photoactivatable compound (s) is different from ovalbumin, albumin, keratin and collagen.

The polyamine polymer (s) constituting the photoactivatable compound (s) of the composition according to the invention may also be chosen from dendrimers containing terminal primary amines.

By dendrimers containing terminal primary amines is meant polymeric compounds consisting of a core and generation of base units, monomers or spindles, on which a terminal group T bearing a primary amine function has been grafted. .

Mention may be made, for example, of polyamidoamine dendrimers, such as those sold under the trade name STARBURST® PAMAM by the company DENDRITECH (block copolymers of ethylene diamine and of methyl acrylate), or those marketed under the commercial reference ASTROMOLS® (DAB) by the company DSM.

Preferably, the polyamines used to obtain the polymers of the invention are chosen from polyethylene imines (PEI), polylysines and polyallylamines. As explained above, at least two photoactivatable diazirine groups are covalently bound to said polyamine polymer.

By photoactivatable diazirine groups is meant diazirine groups capable of generating reactive species (carbenes, nitrenes, radical species, for example) by simple exposure to radiation of one or more wavelengths of between 200 and 450 nm, preferably 300 and 450 nm and even more preferably 300 and 380 nm. This exposure can be achieved by means of solar simulators, UV lamps or by simple action of solar radiation. These reactive species have the property of being able to be inserted nonselectively in numerous chemical bonds such as C-H, N-H, O-H, C-C, C =C, S-H, S≡C bonds, of the keratin material.

Preferably, the diazirine groups covalently bonded to the polyamine polymer are obtained by grafting onto the polyamine polymer a diazirine of formula:

wherein R ₁ is selected from the group consisting of a hydrogen atom, a linear alkyl radical of C ₁ to C ₁₀ or branched, an alkenyl C ₂ -C ₁₀ linear or branched alkynyl, C ₂ -C ₁₀ linear or branched, CF _3, CCI _3, CBr _3, NR ₃ ^+, SR ₂ ^+, SH ₂ ^+, NH ₃ ^+, NO _2, SO ₂ R, C≡N, COOH, F, Cl, Br, I, OR, COOR ', SO ₃ H, COR', SH, SR ', OH, where R' is a linear or branched C ₁ to C ₁₀ alkyl radical, Z is a single covalent bond or a spacer group which is a linear, branched or cyclic, saturated or unsaturated, C ₁ -C ₁₀ O, preferably C ₁ -C ₅₀ , carbon chain which may be interrupted by heteroatoms such as sulfur, oxygen, nitrogen, silicon or phosphorus and may also comprise one or more substituents such as hydroxyl groups, amines, thiols, carbamates, ethers, acids, esters, amides, cyano, ureido, Y represents a function selected from the group formed by alcohols, amines, thiols, thiosulfates, carboxylic acids and its derivatives such as anhydrides, acid chlorides, esters, acetals and hemi-acetals, aminals and hemi-amines, ketones, aldehydes, alpha-hydroxyketones, epoxidized alpha-haloketones, lactones, thiolactones, azalactones, isocyanates, thiocyanates, imines, imides (succinimides, glutimides), imidoesters, aziridines, imidates, oxazine and oxazoline, oxazinium and oxazolinium, halogens (fluorine, chlorine, iodine, bromine), chlorotriazines, chloropyrimidines, chloroquinoxalines, chlorobenzotriazoles, sulfonyl halides (X = F, Cl, I or Br); SO ₂ X, siloxanes, silanols, silanes, pyridyldithio, N-hydroxysuccinimide esters, activated or unactivated vinyls, including acrylonitriles, acrylic and methacrylic esters, crotonic acids and esters, cinnamic acids and esters, styrenes, butadienes, vinyl ethers, vinyl ketone, maleic esters, maleimides, vinyl sulfones, hydrazines, phenyl glyoxals, epoxies, Ar represents an aromatic ring selected from the group consisting of:

in which R ₂ , R ₃ , R ₄ and R ₅ represent, independently of one another, radicals chosen from the group formed by a hydrogen atom, a linear or branched C ₁ to C ₁₀ alkyl radical; , an alkenyl C ₂ -C ₁₀ linear or branched alkynyl, C ₂ -C ₁₀ linear or branched, CF _3, CCI _3, CBr _3, NR ₃ ⁺ SR _'2 ^+, SH ₂ ^+, NH ₃ ⁺ , NO ₂ , SO ₂ R ', CO, COOH, F, Cl, Br, I, OR, COOR', SO ₃ H, COR ', SH, SR', OH, where R 'is an alkyl radical linear or branched C ₁ -C ₁₀ .

A particularly preferred diazirine for forming diazirine groups on the polyamine polymer is 3- (4-Oxiranylphenyl) -3-trifluoromethyl-3H-diazirine of the following formula:

A method for synthesizing the compound (2) is described in the application WO 2006/0191 16. Another particularly preferred diazirine for forming diazirine groups on the polyamine polymer is the compound of the following formula:

(5)

The compound of formula (5) can be obtained by a method such as that described in M. Nassal, J. Am. Chem. Soc., 106, 7540-7545 (1984). A process for synthesizing polyamines carrying diazirine groups obtained from compounds (2) or (5) is described in application WO2006 / 018729.

The chemical reactions that are used to synthesize the photoactivatable compound present in the composition according to the invention depend on the Y groups and the complementary groups on the polyamine polymer, all the conventional chemical reactions that can be used. In a similar way, it is possible to protect the groups that one does not wish to see react. All conventional reactions of protection and de-protection of reactive functions can be used. According to a first preferred embodiment of the invention, the photoactivatable compound is a photoactivatable compound (10) comprising a unit of formula (3) and a unit of formula (A), and having a mean molecular mass of weight between 2,000 and 100,000:

Generally, the molar ratio of the unit of formula (3) to the unit of formula (A) is from 1: 50 to 1: 2.

According to a second preferred embodiment of the invention, the photoactivatable compound is a photoactivatable compound (1 1) comprising a unit of formula (4), a unit of formula (B) and a unit of formula (B). '), and having a weight average molecular weight of between 2,000 and 150,000:

Generally, the molar ratio of the unit of formula (4) and units of formula (B) and (B ') is between 1: 50 and 1: 2.

According to a third preferred embodiment of the invention, the photoactivatable compound is a photoactivatable compound (12) comprising a unit of formula (6), a unit of formula (C) and a unit of formula (C) , and having a weight average molecular weight of between 2,000 and 150,000:

Generally, the molar ratio of the unit of formula (6) and units of formula (C) and (C) is between 1: 50 and 1: 2.

According to a fourth preferred embodiment of the invention, the photoactivatable compound is a photoactivatable compound (13) comprising a unit of formula (7) and a unit of formula (A), and having an average molecular weight of weight between 2,000 and 100,000:

Generally, the molar ratio of the unit of formula (7) to the unit of formula (A) is from 1: 50 to 1: 2.

According to a fifth preferred embodiment of the invention, the photoactivatable compound is a photoactivatable compound (14) comprising a unit of formula (8), a unit of formula (B) and a unit of formula (B ') ), and having a weight average molecular weight of between 2,000 and 150,000:

Generally, the molar ratio of the unit of formula (8) and units of formulas (B) and (B ') is between 1: 50 and 1: 2.

According to a sixth preferred embodiment of the invention, the photoactivatable compound is a photoactivatable compound (15) comprising a unit of formula (9), a unit of formula (C) and a unit of formula (C) , and having a weight average molecular weight of between 2,000 and 150,000:

Generally, the molar ratio of the unit of formula (9) and units of formulas (C) and (C) is between 1: 50 and 1: 2. Generally, the photoactivatable compound (s) represent between 0.01% and

90% by weight of the total weight of the composition.

The photoactivatable compounds (10), (1 1) and (12) can be obtained by reacting the compound of formula (2) described above with a polyamine. If polyethyleneimine (PA) is used, the photoactivatable compound (10) is obtained. If polyallylamine hydrochloride (PB) is used, the photoactivatable compound (1 1) is obtained. If poly L-lysine hydrobromide (PC) is used, the photoactivatable compound (12) is obtained.

Polyethylene imine (PA), polyallylamine hydrochloride (PB), and poly L-lysine hydrobromide (PC) are commercial products available commercially. These products have at least one of the following repeating units.

Polyethylene imine

Polyallylamine hydrochloride

Poly L-lysine hydrobromide

The reaction between the compound of formula (2) and a polyamine can be carried out as follows. Generally, the epoxy groups, under heating, undergo a ring opening and generate 2-amino hydroxyl derivatives by a nucleophilic substitution reaction due to amines.

The photoactivatable compounds (10), (1 1) and (12) are produced by reacting each polyamine (PA), (PB) and (PC) and the compound of formula (2) in a solvent which is a mixture 1: 1 dimethylformaldehyde and water overnight at about 50 ° C in the dark. In the case where the polyamine compounds (PB) and (PC) are used, it is preferable to carry out the reaction in the presence of bases so as to neutralize the hydrochloride or the hydrobromide. Once the reaction is complete, the desired photoactivatable compound can be prepared by distilling off the solvent, dissolving the compound produced once more in water, and separating by exclusion / diffusion chromatography. Elution of the photoactivatable compound can be confirmed by measuring the absorption of light at 254 nm and 360 nm.

The photoactivatable compounds (13), (14) and (15) can be obtained by reacting the compound of formula (5) with a polyamine.

Generally, halogenated alkyl compounds and amines readily bind under heating in the presence of bases by a nucleophilic substitution reaction. By for example, the photoactivatable compound (13) is produced by reacting the compound of formula (5) with polyamine (PA) in a solvent which is a 1: 1 mixture of dimethylformaldehyde and water overnight in the presence of bases, at a temperature of approximately 50 ° C in the dark. The preparation can be made after the solvent has been distilled off, again redissolving these compounds in water, and separating them by exclusion / diffusion chromatography. Photoactivatable compounds (14) and (15) can also be obtained in a similar manner using polyamines (PB) or (PC) in place of polyamine (PA).

In the reaction scheme described below for the photoactivatable compound (13), a substituted phenyl group is attached to all amino groups, but in general in the polyamine compounds certain amino groups of the polyamine (PA) exist as free amino groups, i.e. as amino groups without attached phenyl group.

The diazirine groups of the photoactivatable compound (s) present in the composition according to the invention make it possible to graft the photoactivatable compound (s) onto the keratin materials. Under the effect of irradiation at a wavelength of between 200 and 450 nm, or under the effect of exposure to natural light, the diazirine groups react with the compounds constituting the keratin materials.

According to a first embodiment of the invention, by means of the one or more photoactivatable compounds present in the cosmetic composition according to the invention, the covalent grafting of the pigment or pigments and / or the micro or nanoparticles present is ensured. in the composition on the keratin material.

The grafting of the photoactivatable compound on the pigment and / or on the micro or nanoparticle on the one hand and on the keratin material on the other hand can be done in a single step, but it is also possible, if this procedure is desired , to previously graft the photoactivatable compound on the pigment and / or on the micro or nanoparticle then graft this association on keratin materials or graft the photoactivatable compound on keratin materials and graft this association on the pigment and / or on the micro or nanoparticle.

According to a second embodiment of the invention, the diazirine groups of the photoactivatable compound (s) present in the composition according to the invention form a crosslinked network grafted onto the surface of the keratin materials which traps the pigment (s) and / or the or the micro or nanoparticles.

As explained above, the cosmetic composition according to the invention may comprise one or more pigments. These pigments may be chosen from inorganic pigments, organic pigments, composite pigments, latex containing dyes, lacquers, and special effect pigments.

The pigment or pigments present in the composition according to the invention are chosen from all the organic and / or mineral pigments known in the art, in particular those which are described in Kirk-Othmer's encyclopedia of chemical technology and in the encyclopedia of Ullmann's industrial chemistry.

The pigment or pigments may be in the form of a powder or a pigment paste. They can be coated or uncoated.

The pigment or pigments present in the composition 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 inorganic 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 1 1680, 1 1710, 15985,

19140, 20040, 21 100, 21 108, 47000, 47005, the green pigments codified in the Color

Index under the references Cl 61565, 61570, 74260, the orange pigments codified in the Color Index under the references Cl 11725, 15510, 45370, 71 105, the red pigments codified in the Color Index under the references Cl 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole derivatives, phenolic as described in 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 (C1 1680);

ORANGE COSMENYL GR: Pigment ORANGE 43 (Cl 71 105);

- 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 pigment or pigments present in the composition 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 nucleus, at least a binder for fixing the organic pigments on the core, and at least one organic pigment at least partially covering the core.

Colored latex particles, especially latexes containing dyes such as polystyrene latex containing dyes, may also be used as pigment. These products are for example marketed by Merck under the trademark ESTAPOR® microspheres. 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. As examples of lacquers, mention may be made of the products known under the following names: D & C Red 21 (Cl 45 380), D & C Orange 5 (Cl 45 370), D & C Red 27 (Cl 45 410). ), D & C Orange 10 (Cl 45,425), D & C Red 3 (Cl 45,430), D & C Red 7 (Cl 15,850: 1), D & C Red 4 (Cl 15,510), D & C Red. C Red 33 (Cl 17,200), D & C Yellow 5 (Cl 19,140), D & C Yellow 6 (Cl 15,985), D & C Green (Cl 61,570), D & C Yellow 10 (Cl 77 002), D & C Green 3 (Cl 42 053), D & C Blue 1 (Cl 42 090).

Pigments with special effects means pigments which generally create a colored appearance (characterized by a certain nuance, a certain liveliness and a certain clarity) which is non-uniform and changeable according to the conditions of observation (light, temperature , observation angles ...). They are opposed by that even with white or colored pigments that provide a uniform, opaque, semi-transparent or classic transparent shade.

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 sold by Engelhard (Mica-TiO ₂ -laque), Prestige marketed by Eckart (MiCa-TiO ₂ ), Colorona marketed by Merck (Mica-TiO ₂ -Fe ₂ O ₃ ) .

It is also possible to mention interferential effect pigments not fixed on a substrate, such as liquid crystals (Wacker Helicones HC) or holographic interference flakes (Spectratek Geometry Pigments or Spectra f / x). 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 series of highly luminescent nanocrystallites "Journal of Physical Chemistry B, vol 101, 1997, pp 9463-9455 and Peng, Xiaogang et al," Epitaxial Growth of Highly Luminescent CdSe / CdS Core / nanocrystals shell with photostability and electronic accessibility "Journal of the American Chemical Society, vol 1 19, No. 30, pp 7019-7029.

The variety of pigments that may be present in the composition according to the invention makes it possible to obtain a rich palette of colors, as well as particular optical effects such as metallic, interferential effects.

According to a particular embodiment, the pigments are colored pigments. Colored pigment is understood to mean pigments other than white pigments.

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

As explained above, the cosmetic composition according to the invention may comprise one or more micro or nanoparticles. Nanoparticle means any particle insoluble in the medium whose elementary size is between 1 nm and 999 nm and microparticle any particle whose elementary size is between 1 micron and 300 microns.

Particle size means the distance between the two points furthest from the particle.

According to one embodiment of the invention, the micro or nano particles of the invention are not dyes or pigments, in that their use in cosmetic compositions does not give these compositions the property of being able to color the substrate on which they are used, for example keratinous fibers.

In the compositions of the invention, the micro- or nanoparticles may be inorganic, organic or mixed, and may be coated or grafted. The particles used in the compositions according to the invention can be dry or hydrated. The nanoparticles or microparticles that are suitable for the invention are described in the patent application EP 1 647 308.

For example, the nano or microparticles may have the objective of bringing volume to the hair. The combination use of the polyamine polymer of the invention and of micro or nanoparticles on the hair, by virtue of the particular grafting of the micro or nanoparticles onto the polyamine polymer and the grafting of the polyamine polymer onto the hair, makes it possible to obtain an effect cosmetic extended in time. In fact, the compositions of the invention make it possible in particular to increase the volume of the hair without modifying the shape or the feel of the hair, the whole being retentive to the shampoos.

In addition to the volume, certain particles also make it possible to bring the shine, the body, the mass and the optical effects remanently to the hair.

This nano- or microparticle may be in the form of a sphere, needles, flakes, platelets, tube, fiber, cube, prism or have an irregular shape. Non-limiting nano- or microparticles may be nano-or microfibrils, chips, latices, nanotubes, adhesive micro-objects, and expandable particles.

As indicated above, the particles may be inorganic, organic or mixed. The mineral particles can therefore be in particular:

- Metallic particles: Metal particles are particles formed exclusively by metals selected from 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 the alloys of these metals, and among these especially gold, silver, palladium, platinum, cadmium, selenium and alloys of these metals. These metal particles may be organomodified metal nanoparticles carrying on their surface a self-assembled monolayer of organosulfur compounds as described in the patent application FR 2838052.

- oxides. There may be mentioned oxides of titanium, zinc, cerium, zirconium, aluminum, bismuth oxychloride

carbides, nitrides, borides, sulphides and hydroxides.

inorganic salts. There may be mentioned barium sulfate, calcium carbonate, calcium sulfate, calcium phosphate, magnesium hydrocarbonate.

Among the mineral particles belonging to the species described above, there may also be mentioned clays, silicates, alumina, silica, kaolin, hydroxyapatite.

The particles can be organic as well.

When the particle is organic in nature, it is usually an organic polymer. This polymer must be in the vitreous state, that is to say have a glass transition temperature significantly higher than the ambient temperature or the temperature of use (for example the temperature of the human body), and / or must to be crosslinked.

The glass transition temperature of the organic polymers that can be used for the solid phase is preferably greater than 40 ° C., preferably greater than 60 ° C. and in particular between 80 ° C. and 200 ° C.

Among these polymers, non-exhaustive mention may be made of polystyrene, polyvinyl acetate, poly (α-methylstyrene), polyacrylamide, polyacrylonitrile and polyvinyl chloride. ), copolymers based on styrene and C 1 -C 4 alkyl (meth) acrylate, copolymers based on styrene and acrylamide, copolymers based on styrene and acrylonitrile, copolymers based on styrene and vinyl acetate, copolymers based on acrylamide and C 1 -C 4 alkyl (meth) acrylates, copolymers based on acrylonitrile and C 1 -C 4 alkyl (meth) acrylate, copolymers based on acrylonitrile and acrylamide, terpolymers based on styrene, acrylonitrile and acrylamide, poly (methyl methacrylate), poly (ethyl methacrylate), styrene / butadiene copolymers, styrene acrylic acid, styrene / vinylpyrrolidone and butadiene / acrylonitrile.

As non-limiting examples, mention may be made, as organic micro- or nanoparticles:

nylon powders, for example the one marketed under the name ORGASOL 2002 ED NAT COS by the company ATOCHEM,

polyethylene powders, for example the product marketed under the name "Coathylene HA 1681" by Plast Labor,

poly-β-alanine powders, polyfluorinated powders, especially of polytetrafluoroethylene, for example that marketed under the name "MP 1400" by the company Dupont de Nemours,

acrylic copolymer powders, such as those sold under the name Polytrap Q5 6603 by the company DOW CHEMICA,

polystyrene powders, such as those sold under the name "Polysphere 3000 SP" by the company PRESPERESE

- polyester powders,

expanded microspheres made of thermoplastic material, for example that marketed under the name "Expancel 551 DE" by Expancel,

silicone resin microbeads (Tospearls from Toshiba, for example),

metal soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate, sodium myristate, magnesium,

hydrophilic polymer powders, which are of synthetic origin, such as polyacrylates, for example the product sold under the name "MICROPEARL M 100" by the company MATSUMOTO,

acrylic polyamides, such as those marketed by ORIS, insoluble polyurethanes, such as the product sold under the name "Plastic Powder D 800" by the company TOSHNU,

the porous microspheres of cellulose,

microparticles or nanoparticles of PTFE (polytetrafluoroethylene),

polystyrene latex microbeads, optionally modified to include amine groups or COOH groups, for example sold under the name "LB-1, LB-3, LB-5, LB-6" by SIGMA.

The particles can be treated by coating or grafting. In particular, it is possible to obtain mixed inorganic / organic particles.

The particles may also be compounds which have been rendered hydrophilic by coating or chemical grafting using materials such as chitosan, titanium dioxide, silica or hydrophilic polymers, especially sulphonic polyesters or quaternary polyammonium.

It is also possible to choose hydrophobic pulverulent compounds, chosen from pulverulent compounds of both hydrophobic and hydrophilic nature. In the latter case, they are rendered hydrophobic by coating or chemical grafting by products such as silicones, amino acids, metal soaps, fluorinated derivatives, mineral oils, lecithin, isopropyl triisostearoyl titanate, polyethylene, collagen and its derivatives, polyacrylates.

By way of example, mention may be made of the silica microbeads coated with polymethylhydrogenosiloxane sold under the trade name "Silica SI SB" 700 "by Miyoshi or else the methicone coated sericite / hydrogenated egg oil sold under the trade name" Sericite SNI S100 "by Miyoshi.

The particles may be selected from the adhesive particles. The adhesive polymer can be immobilized on the surface of the particle by covalent chemical bonds (grafting) or by weak physicochemical interactions such as hydrophobic interaction, hydrogen bonds and van der Waals forces.

(adsorption).

The adhesive nature of an organic polymer is generally related to the glass transition temperature thereof. A necessary but not sufficient condition for a polymer to be adhesive is a glass transition temperature (Tg) significantly lower than the ambient temperature or the temperature of use. The organic adhesive polymers used for the preparation of the microobjects of the present invention preferably have a glass transition temperature of less than or equal to 10 ° C, preferably less than or equal to 0 ° C. The chemical nature of the adhesive organic polymers is not critical to the present invention as long as the polymer deposition exhibits the above tack and / or self-adhesive characteristics. These adhesive polymers may be crosslinked or not. To find concrete examples of adhesive polymers, reference may be made to the following applications describing adhesive particles or polymers: WO98 / 38969, FR 2833960 (cationic or amphoteric self-adhesive polyurethanes), FR 2833959 (cationic radical polymers or amphoteric self-adhesive polymers) .

The particles may also be chosen from nanotubes. The nanotubes may consist of at least one element belonging to groups NA, NIA, IVA, VA, VIII, IB, NB, INB, VIB and VIIB of the periodic table.

Nanotubes are nano-objects whose organization of atoms or molecules gives the nano-structure a tube shape. These nanotubes can be single-walled or multi-walled. The diameter of the nanotubes is conventionally between 1 and 300 nm and the length of the nanotubes is conventionally between 10 nm and 10 mm.

As examples of constituent elements of the nanotubes of the invention, mention may be made of carbon, silicon, tungsten, silver, gold, boron, zinc, platinum, magnesium, iron , cerium and aluminum.

Preferably, the nanotubes consist of at least one element belonging to group IVA, of the periodic table of elements. Even more preferentially, said element is carbon.

When one of the constituent elements of the nanotubes is carbon, said nanotubes may consist wholly or partially of organic molecules. By way of example of organic molecules, mention may be made of phospholipids diacetylenes, glutamates, long-chain diamides, glucophospholipids, alkylphenylglucopyranosides.

Preferably, the backbone of the nanotubes consists solely of carbon atoms. These carbon nano-forms are conventionally obtained by sublimation of graphite at very high temperature by means of an electric arc. The carbon nanotubes can be formed by a single plane of graphene; in this case they are said to single wall (Single Wall NanoTube SWNT in English). The winding of graphene planes can be zig-zag, niche or chiral. The nanotubes may also be constituted by several tubes "nested" into each other; in this case they are called multiwall nanotubes (Multi Wall NanoTube MWNT in English).

According to one embodiment of the invention, in order to obtain optimal exfoliation of the carbon nanotubes in the cosmetic medium in question, the surface of the nanotubes is functionalized. By the term "functionalized" is meant according to the invention the presence of functional groups that can interact physically or chemically with each other or with the external medium.

All reaction mechanisms can be used to functionalize the graphene planes constituting the carbon nanotubes. By way of example, the functionalization of carbon nanotubes can be carried out by a reaction mechanism of the nucleophilic substitution, electrophilic substitution, radical substitution, addition, elimination, rearrangement, oxidation, reduction, acid-base reaction, electrochemical reaction, or else photochemical reaction.

Among the functions that can be grafted onto the surface of the graphene planes constituting the carbon nanotube, mention may be made of carboxylic groups. Hydrophobic functions can also be grafted onto the surface of the graphene planes constituting the carbon nanotube. For example, the fluorination of carbon nanotubes described in the article "Fluorinated Single Wall Nanotubes", K.N. Kudin et al. (Rev. Phys., B63, 45413).

It is also possible to graft inorganic molecules such as alkoxysilanes (Nano Lett, vol 2, No. 4, 2002 pages 329 to 332).

Functionalization of graphene planes can be carried out in several steps, such as, for example, the functionalization of carbon nanotubes with fatty-chain amides, described in the article "Dissolution of Single Wall Carbon Nanotube", M.A. Hamon et al. (Adv, Mater 1999, 11, No. 10). This functionalization in several steps can also lead to the grafting of glucose (Nano Lett., Vol 2, No. 4, 2002 pages 369 to 373).

Functionalization of carbon nanotubes can be achieved by simple molecules, but also by oligomers, polymers or dendrimers. By way of example, mention may be made of the article "A New Purification Method for Single Wall Carbon Nanotubes", by M. Holzinger and CoII (Appl Physics A 70 (2000) 599), which describes grafting. of dendritic structures on the surface of the graphene planes constituting the carbon nanotube.

In addition to improving the dispersion of carbon nanotubes in the cosmetic media, the functionalization of the surface can also be carried out in order to increase the affinity of the carbon nanostructures for the keratin material. The improvement of the affinity between the nanotubes and the keratinous material induced by the functionalization of the graphene planes may be the result of the increase of Van der Waals-type interactions and / or the result of the appearance of hydrogen bonds and or ionic. Thus, the functional group or groups are capable of creating, with the keratin fibers, one or more chemical bonds chosen from the Van der Waals type interactions, the hydrogen bonds, the ionic bonds and the covalent bonds. In this context, mention may be made of the grafting of cationic molecules on the surface of carbon nanotubes, described in the article "Exohedral Sidewall Reactions of Single Walled Carbon Nanotubes in Molecular Nanostructures", M. Holzinger et ah (Proceeding of the Xllth International Winterschool on Electronic Properties of Novel Materials: Molecular Nanostructures, Kirchberg, Austria, March 2001). In the context of grafting of cationic molecules, it is also possible to mention the grafting of polyethyleneimine derivatives (Nano Lett., Vol 2, No. 3, 2002 pages 231 to 234) .The nanotubes may also be polymeric. the "nano-object" is a synthetic polymer "Synthetic polymer" as used herein means a polymer obtained by chemical or electrochemical synthesis (radical polymerization, polycondensation, ring opening polymerization, metathesis polymerization). can be done chemically or under the action of photochemical radiation such as under the action of UV or temperature.This polymer may be a homopolymer or a copolymer.

Homopolymers or copolymers derived from the radical polymerization of monomers comprising ethylenic, vinyl, allylic, (meth) acrylate and / or (meth) acrylamide and derivative units are particularly suitable for the invention. Thus, the vinyl / (meth) acrylate, vinyl / (meth) acrylamide, vinyl / (meth) acrylate / (meth) acrylamide, olefinic / vinyl and (meth) acrylate / (meth) acrylamide copolymers are suitable.

These nanotubes of polymers are described in particular in the following publications:

Nanotube formation from renewable resources via coiled nanofibers, G. John, M. Masuda, Y. Okada, K. Yase, T. Shimizu, Advanced Materials, 2001, 13, 715-718

- Bottom-up synthesis aged structural properties of self-assembled high-axial-ratio nanostructures, T; Shimizu, Macromol. Rapid Commun., 2002, 23, 31 1 -331 In nanoparticles, the metals present can be distributed homogeneously. The nanoparticles may also consist of a core consisting of one or more metals and one or more layers covering this core, consisting of one or more metals different from those constituting the heart. These nanoparticles are known in the literature in the form of core / shell nanoparticles.

The nanoparticles may also be covered with one or more additional organic and / or inorganic layers, preferably having an affinity for the hair. As an example of an organic layer, mention may be made of the layers obtained from polyethylene glycol, polyurethane, polyacrylic acid, polyvinylpyrrolidone or polyvinylcaprolactone.

As an inorganic layer, there may be mentioned by way of example, the layers obtained from alumina, silica or clay or a mixture of these materials. These layers can be obtained by sol-gel process from organosilane. These layers which are obtained by encapsulation of the nanoparticles can be made by various processes such as controlled precipitation, phase separation, emulsion polymerization, interfacial polycondensation, in situ polycondensation.

For further details, such encapsulation methods are described in "Microencapsulation Methods and Industrial Applications" (ISBN 0-8247-9703-5). The capsule may be formed by any inorganic compounds, more specifically by a metal oxide or an organometallic polymer and even more specifically by a metal oxide or an organometallic polymer obtained by sol-gel process, such as metal oxides or organometallic polymers synthesized by polycondensation. a single or a mixture of single or mixed alkoxy of silicon, aluminum, boron, lithium, magnesium, sodium, titanium and / or zirconium. For further details on the nature of precursors and reaction mechanisms, reference can be made to the book "Soi Gel Science" published by CJ Brinker and G.W. Scherer at Academic Press (ISBN 0-12-134970-5).

These additional layers can be covalently grafted or adsorbed on the surface of the nanoparticles.

According to a different embodiment, the nanoparticles may be incorporated in polymer microbeads, the polymer may be hydrophilic, hydrophobic, amphiphilic, ionic or nonionic.

The nanoparticles or micro-particles can also be chosen from nano- or microfibrils

By nano or microfibrils is meant particles as they can be described in the following publications:

Polymerization in nanometer-sized fibers: Molecular Packing Order and Polymerizability: M. Masuda, T. Hanada, Y. Okada, K. Yase, T. Shimizu, Macromolecules, 2000, 33, 9233-9238 - Organic supramolecula self-assembled materials stabilized by multiple hydrogen bonds, Shimizu T., Transactions of the Materials Research Society of Japan, 1999, 24, 3, 431-436

These fibrils may be natural, such as cellulose, protein, silk, or synthetic, such as polyamide.

The micro- or nanoparticles may also be chosen from the expandable particles, and in particular the compounds capable of swelling under the action of heat.

It can be in particular a compound that reacts, under the action of heat, to release a gas that is trapped in the matrix of the deposit.

The heat-swellable compound may also be in the form of heat-expandable particles. By the expression "thermally expandable particles" is meant more particularly particles capable of deforming and expanding with heat. For the purposes of the present invention, the particles may also be unexpanded thermodeformable particles. In this respect, they are distinguished from expanded particles which are precisely no longer subject to deformation under the action of heat, for example in the image of polyvinylidene / acrylonitrile particles marketed under the general name of "Expancel®" by the company AKZO NOBEL under the special references "Expancel® WE" or "DE".

These particles are capable of expanding under the action of a temperature generally greater than or equal to 45 ° C., in particular greater than or equal to 50 ° C., in particular greater than or equal to 60 ° C., more particularly greater than or equal to 70 ° C. In particular, it may be a temperature greater than or equal to 80 ° C, in particular greater than or equal to 85 ° C, more particularly greater than or equal to 90 ° C and up to 190-200 ° C. Advantageously, these particles are not sensitive to the presence of water.

In particular, the particles may be thermoplastics. The term "thermoplastic" denotes particles that are capable of deforming under the action of heat and retain their new shape, including after cooling, especially at room temperature.

The particles are generally hollow particles comprising a continuous envelope and at least one cavity.

The envelope of the particles is preferably flexible to lend itself to mechanical deformation. It generally comprises at least one homopolymer or copolymer polymer formed from ethylenically unsaturated monomers. Examples of such particles are described in particular in documents EP-A-56219 and EP-A-348.

372, EP-A-486,080, EP-A-320,473, EP-A-1,12,807 and US-A-3,615,972.

The monomers used may in particular be esters of methacrylic or acrylic acid, such as methyl acrylate and methacrylate, chloride vinylidene, acrylonitrile, styrene and its derivatives, butadiene and its derivatives, and mixtures thereof.

By way of nonlimiting representative of the polymers capable of composing the envelope of the particles, there may be mentioned polymers containing at least units derived from acrylate or methyl methacrylate, polymers comprising at least units derived from acrylonitrile, polymers containing at least units derived from acrylonitrile and methyl methacrylate, polymers comprising at least units derived from styrene and acrylonitrile, polymers comprising at least units derived from vinylidene chloride and acrylonitrile and polymers comprising at least units derived from vinylidene chloride chloride and vinyl chloride. In particular, said polymer may be chosen from vinylidene chloride / acrylonitrile / methyl methacrylate polymers, acrylonitrile / methyl methacrylate polymers and homopolymers of acrylonitrile.

The particles generally contain, within one or more cavities, at least one compound capable of manifesting, in response to heating at a temperature ranging from 45 ° C. to 200 ° C. and at a substantially constant pressure, a significant increase in its volume at room temperature.

The expression "significant increase in its volume" is understood to mean an increase of at least a factor of 30, in particular of at least a factor of 40 and more particularly of at least a factor of 50 of the occupied volume.

In general, the compound contained inside the cavity may be at ambient temperature a gaseous compound or a liquid compound having a vaporization temperature in the range of 45 ° C to 200 ° C, in particular in the range from 80 ° C to 200 ° C, and more particularly greater than or equal to 100 ° C.

According to a first variant, this compound is in the gaseous state in the particle and expands under the effect of heat. Among the compounds in the gaseous state, there may be mentioned air, nitrogen, hydrocarbons comprising 1, 2, 3 or 4 carbon atoms, especially butane, isobutane and mixtures thereof. According to a second variant, the compound contained in the cavity is a liquid compound as defined above. Among these compounds, mention may be made of hydrocarbons, especially containing from 5 to 15, in particular from 5 to 12 and more particularly from 5 to 10 carbon atoms. It may be in particular a compound selected from n-pentane, iso-pentane and neo-pentane. The expansion temperature of the particle depends both on the nature of the compound present in its cavity, and that of the polymer forming its envelope, and may in particular be from 45 to 200 ° C., and in particular be greater than or equal to 80 ° C and in particular greater than or equal to 100 ° C.

According to a particular embodiment, the unexpanded particles of the invention are spherical and have a particle size, expressed in diameter. "Effective" average weight D [0, 5], ranging from 0.5 microns to 200 microns, especially from 1 micron to 100 microns, in particular from 4 microns to 50 microns and more particularly from 5 microns to 40 microns.

The unexpanded particles used in the present invention generally have a density ranging from 500 kg / m ³ to 5000 kg / m ³ , in particular from 900 kg / m ³ to 3000 kg / m ³ , and more particularly from 900 kg / m ^3. m ³ at 2000 kg / m ³ .

As particles that can be used in the compositions of the invention, mention may be made, for example, of unexpanded microspheres of vinylidene chloride / acrylonitrile / methyl methacrylate copolymer, for instance those sold under the name "Expancel®" by the AKZO NOBEL company under the references 820DU 40 (10-16 μm) or 820 SL 40 (2-30 μm), and acrylonitrile / methyl methacrylate, for example those sold under the name "Expancel®" under the references 642 WU 40 (10-16 μm) or 051 DU 40 (9-15 μm). As particles that can also be used in the compositions according to the invention, mention may also be made of unexpanded microspheres of acrylonitrile homopolymer, for instance those sold under the name "Expancel 007W®" (5-25 μm), "Micropearl F-series®" by MATSUMOTO or "Ucelite®" by UCB.

The particles sold under the name "Expancel®" under the references cited above generally comprise in their cavity a compound in the gaseous state.

According to a particular embodiment, the particles used in the compositions according to the invention have a fiber form. By "fiber" it is necessary to understand an object of length L and of diameter D such that L is much greater than D, D being the diameter of the circle in which the section of the fiber is inscribed. In particular, the L / D ratio (or form factor) is chosen in the range from 3.5 to 2500, in particular from 5 to 500, and more particularly from 5 to 150. In particular, the fibers have a length of from 0.05 mm to 6 mm.

The pigment (s) and / or the micro or nanoparticle (s) present in the composition according to the invention generally represent from 0.01 to 50%, preferably from 0.1 to 20%, and more preferably from 0.1 to 10%. of the total weight of the composition.

In addition to the photoactivatable compound and the pigment and / or the micro- or nanoparticle, the cosmetic composition according to the invention may comprise one or more polymers other than the photo-activatable polyamine polymers as defined above. These polymers may be nonionic, cationic, anionic or amphoteric. The term "polymer" means all polymers that can be used in cosmetics, natural or synthetic, and in particular polymers obtained by radical polymerization or by polycondensation or by ring opening. These polymers can be linear, branched, star.

As natural polymers, the polysaccharides (for example dextrans, celluloses, starches, chitosan, pullulan, insulin, carrageenan, guar, alginates, xanthans, hyaluronic acid), proteins such as albumin, ovalbumin, keratin, collagen.

The natural polymers can be chemically modified, it is thus possible to introduce into the main chain of this natural polymer at least one group selected from hydroxyalkyl, carboxy, carboxyalkyl, amino, thio, aldehyde functions, epoxy.

The synthetic polymers can be homopolymers or copolymers.

Preferably polyurethanes, polyureas, polyethers, polyesters and polyamides will be used.

It may also be dendritic polymers or dendrimers as described by D. A. Tomalia et al, Angewandlte Chemie, Int. Engl. Ed., Vol. 29, No. 2, pp. 138-175. These dendrimers are molecular structures built around a generally versatile central pattern. Around this central motif, branched chain extension patterns are chained in concentric layers and according to a perfectly determined structure thus giving rise to symmetrical, monodisperse macromolecules having a well defined chemical and stereochemical structure.

It may also be dendritic polymers of the hyperbranched polymer type. Examples of polymers are described in patent applications WO 93 17 060 and WO 96 12754.

It may also be dendrons as defined in Article D. A. Tomalia.

These polymers may be substantive conditioning polymers, thickening polymers, fixing polymers, hydrophobic film-forming polymers.

Generally, the additional polymer or polymers present in the composition according to the invention represent between 0.01% and 90%, preferably from 0.1 to 20% and better still 0.1 to 10% by weight of the total weight of the composition. . The cosmetic composition according to the invention may also comprise one or more non-polymeric cosmetic active ingredients.

Generally, the cosmetic active agent (s) possibly present in the composition according to the invention are chosen from reducing agents, non-silicone fatty substances, plasticizers, silicones, softeners, anti-foam agents, moisturizing agents, filters UV, perfumes, anionic, cationic, nonionic or amphoteric surfactants, direct or oxidation dyes and pearlescent agents.

The subject of the invention is also a first cosmetic treatment method comprising a step of applying to the keratin materials a composition according to the invention, and a step of exposing said keratin materials to a radiation of one or more wavelengths between 300 and 450 nm, preferably between 300 and 380 nm, better between 350 and 380 nm, or in natural light.

This exposure can be done on the entire hair for example or be located at will on a previously defined surface area. According to a first embodiment, the method according to the invention may comprise, after the step of applying the composition according to the invention and before the step of exposure to radiation or natural light, a drying step hair, preferably by means of a hair dryer, a helmet or an iron.

According to a second embodiment, the first method according to the invention comprises, after the step of applying the composition according to the invention and before the step of exposure to radiation or natural light, a pre-drying step keratin materials, preferably by means of a hair dryer, and then a step of applying a heating flat iron or a curling iron.

The subject of the invention is also a second method of cosmetic treatment comprising the following steps:

- Application on the keratin materials of one or more photoactivatable compounds as defined above in a cosmetically acceptable medium,

- Application on the keratin materials of one or more pigments and / or one or more micro or nanoparticles as defined above in a cosmetically acceptable medium,

exposure of said keratin materials to radiation of one or more wavelengths between 300 and 450 nm, preferably between 300 and 380 nm, better still between 350 and 380 nm, or with natural light.

The second method according to the invention generally comprises a step of drying the keratin materials after the application of the photoactivatable compound and before the application of the pigment or pigments and / or the micro or nanoparticles.

According to a first embodiment, the second method according to the invention comprises a step of drying the keratin materials after the application of the pigment or pigments and / or the micro or nanoparticles and before the exposure of the keratin materials to the radiation. or in natural light.

According to a second embodiment, the second method according to the invention comprises after the step of applying the pigment (s) and / or the micro or nanoparticle (s) and before the step of exposure to radiation or light. natural, a step of pre-drying the keratin materials and then a step of applying a flat iron or a curling iron.

The first method according to the invention or the second method according to the invention may comprise a preliminary treatment step of the keratinous materials chosen from the group consisting of treatments using a reducing composition, and staining with oxidation dyes. , discolorations, alkaline straighteners, shampoos, styling treatments. The present invention is illustrated by the following examples.

EXAMPLES

A. Composition comprising pigments

The cosmetic composition A according to the invention is prepared comprising pigments whose formulation is as follows:

- red latex particles (reference ESTAPOR® DYED MICROSPHERES K035

RED 10% (g per 100 ml) reference 39523001 sold by the company Merck 5g

- polyethyleneimine-diazirine (10) at 1% (g per 100 ml) 5g

- H ₂ O 90g

Example 1

The cosmetic composition prepared above is applied to the gray hair at 90% white. The hair is then dried with a hair dryer and then irradiated at a wavelength of 365 nm (1000 mJ / cm ² ).

A durable grafting of the pigments on the hair is obtained. We then obtain hair colored red.

Example 2

The cosmetic composition prepared previously is applied to the hair. Then the hair is pre-dried in the hair dryer. Then we pass on the hair a flat iron at 180 ° C. The hair is then irradiated at a wavelength of 365 nm (1000 mJ / cm ² ).

A durable grafting of the pigments on the hair is obtained. The hair is then colored red.

B. Composition comprising nanoparticles

The cosmetic composition B according to the invention comprising nanoparticles whose formulation is as follows: latex particles (reference LB-3 at 10% in g per 100 ml) sold by SIGMA (size: 0.3 μm) 5g

- polyethyleneimine-diazirine (10) at 1% (g / 100 ml) 5g

- H ₂ O 90g

Example 3

The cosmetic composition prepared previously is applied to the hair.

The hair is then dried with a hair dryer and then irradiated at a wavelength of 365 nm (1000 mJ / cm ² ).

A durable grafting of the latex particles on the hair is obtained. This results in a volume-enhancing effect resistant to many shampoos.

Example 4

The cosmetic composition prepared previously is applied to the hair. Then the hair is pre-dried in the hair dryer. Then we pass on the hair a flat iron at 180 ° C.

The hair is then irradiated at a wavelength of 365 nm (1000 mJ / cm ² ). A durable grafting of the particles on the hair is obtained. This leads to a volume-enhancing effect resistant to many shampoos.

Claims

1. Cosmetic composition characterized in that it comprises, in a cosmetically acceptable medium: a) one or more photoactivatable compounds obtained from polyamine polymers, containing at least two -NH- and / or ^~ N- amino units _; covalently bound to at least two photoactivatable diazirine groups, and b) one or more pigments and / or one or more micro or nanoparticles.

2. Composition according to claim 1 characterized in that the polyamine polymer is chosen from:

the polyalkyleneimines, preferably the poly (C ₂ -C ₅ alkyleneimines),

copolymers based on aminoalkyl (CrC ₄ ) (meth) acrylate, preferably based on aminoethyl (meth) acrylate,

polyallylamines,

the polycondensates of at least one compound chosen from piperazine, 1 - (2-aminoethyl) piperazine, 1,4-bis (3-aminopropyl) piperazine), 1-alkyl (d-

C ₂₅₎ piperazine, 1, 4-di (alkyl (Ci-C ₂₅₎₎ piperazine, 1 - (2-hydroxy (alkyl (C ₂ -C ₂₅₎₎₎ piperazine, imidazole, alkylimidazole the -C ₂₅ or mixtures thereof with at least one compound selected from C ₆ -C ₂₂ alkylene dihalide, epihalohydrin and / or C ₈ -C ₂₂ bisepoxide, the polymers containing in their structure at least 2 successive units of the same basic amino acid,

polyamidoamines,

dendrimers containing primary amines in the terminal position.

3. Composition according to any one of the preceding claims, characterized in that the photoactivatable compounds are obtained from a polyamine chosen from polyethylene imines, polylysines and polyallylamines.

4. Composition according to any one of the preceding claims, characterized in that the diazirine groups are obtained by grafting onto the polyamine polymer a diazirine of formula:

wherein R ₁ is selected from the group consisting of a hydrogen atom, a linear alkyl radical of C ₁ to C ₁₀ or branched, an alkenyl C ₂ -C ₁₀ linear or branched alkynyl, C ₂ -C ₁₀ linear or branched, CF _3, CCI _3, CBr _3, NR _'3 ^+, SR' ₂ ^+, SH ₂ ^+, NH ₃ ^+, NO _2, SO ₂ R, C≡N, COOH, F, Cl, Br, I, OR, COOR ', SO ₃ H, COR', SH, SR ', OH, where R' is a linear or branched C ₁ to C ₁₀ alkyl radical, Z is a single covalent bond or a spacer group which is a linear, branched or cyclic, saturated or unsaturated, C ₁ -C ₁₀ O, preferably C ₁ -C ₅₀ , carbon chain which may be interrupted by heteroatoms such as sulfur, oxygen, nitrogen, silicon or phosphorus and may also include one or more substituents such as hydroxyl groups, amines, thiols, carbamates, ethers, acids, esters, amides, cyano, ureido,

Y represents a function selected from the group formed by alcohols, amines, thiols, thiosulfates, carboxylic acids and its derivatives such as anhydrides, acid chlorides, esters, acetals and hemi-acetals, aminals and hemi-amines, ketones, aldehydes, alpha-hydroxyketones, epoxidized alpha-haloketones, lactones, thiolactones, azalactones, isocyanates, thiocyanates, imines, imides (succinimides, glutimides), imidoesters, aziridines, imidates, oxazine and oxazoline, oxazinium and oxazolinium, halogens (fluorine, chlorine, iodine, bromine), chlorotriazines, chloropyrimidines, chloroquinoxalines, chlorobenzotriazoles, sulfonyl halides (X = F, Cl, I or Br); SO ₂ X, siloxanes, silanols, silanes, pyridyldithio, N-hydroxysuccinimide esters, activated or unactivated vinyls, including acrylonitriles, acrylic and methacrylic esters, crotonic acids and esters, cinnamic acids and esters, styrenes, butadienes, vinyl ethers, vinyl ketone, maleic esters, maleimides, vinyl sulfones, hydrazines, phenyl glyoxals, epoxies, Ar represents an aromatic ring selected from the group consisting of:

in which R ₂ , R ₃ , R 4 and R ₅ represent, independently of one another, radicals selected from the group consisting of a hydrogen atom, a linear or branched C ₁ to C ₁₀ alkyl radical, a alkenyl radical C ₂ -C ₁₀ linear or branched alkynyl, C ₂ -C ₁₀ linear or branched, CF _3, CCI _3, CBr _3, NR _'3 ^+, SR ₂ ^+, SH ₂ ^+, NH ₃ ^+, NO ₂ , SO ₂ R ', C≡N, COOH, F, Cl, Br, I, OR, COOR', SO ₃ H, COR ', SH, SR', OH, where R 'is a C-alkyl radical ₁ to ₁₀ linear or branched.

5. Composition according to any one of the preceding claims, characterized in that the photoactivatable compound comprises a unit of formula (3) and a unit of formula (A), and has a weight average molecular weight of between 2,000 and 100,000, and preferably, the molar ratio of the unit of formula (3) and the unit of formula (A) is between 1: 50 and 1: 2:

6. Composition according to any one of claims 1 to 4 characterized in that the photoactivatable compound comprises a unit of formula (4), a unit of formula (B) and a unit of formula (B '), and the average molecular weight of the photoactivatable compound by weight is between 2000 and 150 000 and preferably the molar ratio of the unit of formula (4) and units of formula (B) and (B ') is between 1: 50 and 1: 2:

7. Composition according to any one of claims 1 to 4 characterized in that the photoactivatable compound comprises a unit of formula (6), a unit of formula (C) and a unit of formula (C), and the mass average molecular weight of the photoactivatable compound by weight is between 2,000 and 150,000, and preferably the molar ratio of the unit of formula (6) and units of formulas (C) and (C) is between 1: 50 and 1: 2:

8. Composition according to any one of claims 1 to 4 characterized in that the photoactivatable compound comprises a unit of formula (7) and a unit of formula (A), and the average molecular weight of the photoactivatable compound in weight is between 2,000 and 100,000, and preferably the molar ratio of the unit of formula (7) and the unit of formula (A) is between 1: 50 and 1: 2:

9. Composition according to any one of claims 1 to 4 characterized in that the photoactivatable compound comprises a unit of formula (8), a unit of formula (B) and a unit of formula (B '), and the mass average molecular weight of the photoactivatable compound by weight is between 2000 and 150 000, and preferably the molar ratio of the unit of formula (8) and of units of formula (B) and (B ') is between 1: 50 and 1: 2:

10. Composition according to any one of claims 1 to 4 characterized in that the photoactivatable compound comprises a unit of formula (9), a unit of formula (C) and a unit of formula (C), and the mass average molecular weight of the photoactivatable compound by weight is between 2,000 and 150,000, and preferably the molar ratio of the unit of formula (9) and the units of formulas (C) and (C) is between 1:50 and 1: 2:

1. Composition according to any one of the preceding claims, characterized in that the photoactivatable compound (s) represent (s) between 0.01% and 90% by weight of the total weight of the composition.

A composition according to any one of the preceding claims, wherein the pigment is a mineral pigment, an organic pigment, a composite pigment, a latex containing dyes, a lacquer, a special effect pigment and / or the micro- or nanoparticle is mineral, organic or mixed, possibly coated or grafted.

13. Composition according to any one of the preceding claims characterized in that the pigment or pigments and / or the micro-or nanoparticles represent 0.01% to 50%, preferably 0.1 to 10%, by weight of the total weight of the composition.

14. Cosmetic treatment process characterized in that it comprises:

an application step on the keratin materials of a composition as defined in claims 1 to 13, and

a step of exposing said keratin materials to radiation of one or more wavelengths between 300 and 450 nm, preferably between 300 and 380 nm, better between 350 and 380 nm or in natural light and

optionally, after the step of applying the composition and before the step of exposure to radiation or natural light, a step of pre-drying the keratin materials, preferably by means of a hair dryer, then optionally a step of applying a heating flat iron or a curling iron.

15. Cosmetic treatment process comprising the following steps:

- Application on keratin materials of a photoactivatable compound as defined in any one of Claims 1 to 10 in a cosmetically acceptable medium,

- Application to the keratin materials of at least one pigment and / or at least one micro or nanoparticle as defined in claim 1 or 12 in a cosmetically acceptable medium,

exposure of said keratin materials to radiation of one or more wavelengths between 300 and 450 nm, preferably between

300 and 380 nm, better between 350 and 380 nm, or in natural light.