WO2002102333A1

WO2002102333A1 - Coated organic pigment and cosmetic composition containing said pigment

Info

Publication number: WO2002102333A1
Application number: PCT/FR2002/002098
Authority: WO
Inventors: Jean-Louis Mattei
Original assignee: L'oreal
Priority date: 2001-06-18
Filing date: 2002-06-18
Publication date: 2002-12-27
Also published as: FR2825917A1

Abstract

The invention relates to a method of preparing a coated organic pigment comprising the following steps, consisting in: a) preparing a mixture of: (i) a dispersion of an organic pigment in a liquid medium and (ii) a solution of a cross-linked organo-mineral hybrid material, said material (before hydrolysis) being obtained by sol-gel means from a premixture containing: (A) at least one metallic or metallo-organic compound and (B) at least one functionalised organic polymer or a precursor thereof, or at least one functionalised siliconised polymer or a precursor thereof, the latter being different from (A); b) bringing said mixture into contact with water. The invention also relates to a coated organic pigment obtained using said method and to a cosmetic composition containing one such coated organic pigment. Said invention is suitable for make-up for keratinous material.

Description

Coated organic pigment and cosmetic composition containing this pigment

The subject of the present invention is a process for the preparation of a coated organic pigment, a coated organic pigment obtained according to this process and a cosmetic composition comprising such a coated organic pigment. The invention also relates to a process for making up keratin materials using said composition. The makeup composition and method are suitable for keratin materials such as the skin, including the lips, hair, eyelashes, eyebrows and nails of humans. The composition is in particular in the form of makeup product, in particular nail polish, lip product, body makeup product, foundation, eyeshadow or blush, eyeliner, concealer, mascara. More specifically, this composition is in the form of nail polish.

The makeup compositions generally contain coloring materials to give the composition the desired color. The coloring matters can be mineral or organic pigments. These coloring matters are mixed in a wide variety of cosmetic supports which may in particular include water, solvents or oils. Very often, an ingredient in the composition can at least partially dissolve the organic pigment and this dissolution causes the pigment to become disgorged when it is applied to keratin materials, especially on the skin or the nails. Pigment bleeding can also be accentuated when the pigment comes into contact with sweat, sebum or tears. In particular for a lipstick, the disgorgement of the pigment causes the diffusion of the color in the micro-fine lines of the lips, making it difficult to remove makeup from the lips; for a nail polish, the bleeding of the pigment causes the diffusion of the color in the nail; for an eye makeup product such as a mascara or an eyeshadow, the bleeding of the pigment can cause the diffusion of color in the polymer of contact lenses, thus altering vision. Disgorgement of the organic pigment can also be caused when the pigment comes into contact with secretions such as sweat, sebum, and tears. These drawbacks can be mitigated by the use of organic lacquers which are organic pigments precipitated on a mineral support. However, the drawbacks mentioned above although mitigated remain.

It is known from the state of the art to coat organic pigments. For example, document EP-A-659069 describes the coating with cationic polymers to improve the adhesion of the pigment to keratin materials. However, such a coating is weakened in an aqueous medium and is therefore not suitable for preventing disgorgement of the pigment. In addition, certain cationic polymers are not transparent and can form a deposit on the pigment, altering or modifying the visible color of the pigment.

The aim of the present invention is therefore to propose a cosmetic composition comprising organic pigments which do not bleed after the application of the composition to keratin materials.

The applicant has discovered, surprisingly, that such a composition could be obtained by coating the organic pigments according to a process using an organo-mineral hybrid material. This process makes it possible to form a gangue around the organic pigment making it possible to isolate the organic pigment from the cosmetic support in which it can be formulated and thus to avoid dissolution, even partial, of the organic pigment in the medium of the composition or else during from contact with sweat, sebum or tears. The organic pigment thus coated does not bleed. After the composition has been applied to the keratin materials, the latter are not stained. In addition, the coating obtained by the process does not modify the visible color of the organic pigment and has good mechanical resistance, in particular a resistance to friction of the particles between them.

More specifically, the invention relates to a process for the preparation of a coated organic pigment comprising the following steps: a) a mixture is prepared (i) a dispersion of an organic pigment in a liquid medium, in particular an aqueous or alcoholic or oily medium, optionally in the presence of a dispersant,

(ii) and of a solution of a crosslinked organo-mineral hybrid material, said material (before hydrolysis) being obtained by sol-gel route from a premix comprising:

(A) at least one metallic or metallo-organic compound, and

(B) at least one functionalized organic polymer or a precursor thereof, or at least one functionalized silicone polymer or a precursor thereof, the latter being different from (A), b} said mixture is brought into contact with water when said dispersion of the organic pigment is a dispersion in an alcoholic or oily liquid medium.

The subject of the invention is also a coated organic pigment capable of being obtained according to the process as defined above.

Another subject of the invention is a cosmetic composition, in particular a nail varnish, comprising, in a cosmetically acceptable medium, at least one coated organic pigment as defined above.

The subject of the invention is also a process for making up keratin materials comprising the application to said keratin materials of a cosmetic composition as defined above.

The subject of the invention is also the use of a cosmetic composition comprising, in a cosmetically acceptable medium, a coated organic pigment as defined above to obtain a make-up which does not stain keratin materials.

The term “cosmetically acceptable medium” means a medium compatible with human keratin materials.

The organic particles intended to be coated can be for example: - cochineal carmine, - organic pigments of azo, anthraquinone, indigo, xanthenic, pyrenic, quinolinic, triphenylmethane, fluorane dyes;

- organic lakes or insoluble salts of sodium, potassium, calcium, barium, aluminum, zirconium, strontium, titanium, acid dyes such as azo, anthraquinone, indigo, xanthene, pyrene, quinolinic dyes , triphenylmethane, fluorane. These dyes generally contain at least one carboxylic or sulfonic acid group.

The organic lacquer can also be supported by any compatible support such as an inorganic support such as particles of alumina, clay, zirconia or metal oxides, in particular zinc oxide or titanium oxide, talc, calium carbonate, barium sulfate. Preferably, the mineral support is chosen from alumina, titanium oxide and barium sulfate. The organic lacquer can also be supported by a support such as colophane or aluminum benzoate.

Among the organic pigments, mention may be made of D&C Blue n ° 4, D&C Brown n ° 1,

D&C Green n ° 5, D&C Green n ° 6, D&C Orange n ° 4, D&C Orange n ° 5, D&C

Orange n ° 10, D&C Orange n ° 11, D&C Red n ° 6, D&C Red n ° 7, D&C Red n ° 17, D&C Red n ° 21, D&C Red n ° 22, D&C Red n ° 27, D&C Red n ° 28, D&C Red n ° 30,

D&C Red n ° 31, D&C Red n ° 33, D&C Red n ° 34, D&C Red n ° 36, D&C Violet n ° 2,

D&C Yellow n ° 7, D&C Yellow n ° 8, D&C Yellow n ° 10, D&C Yellow n ° 11, FD&C

Blue n ° 1, FD&C Green n ° 3, FD&C Red n ° 40, FD&C Yellow n ° 5, FD&C Yellow n ° 6.

Among the organic lacquers, mention may be made in particular of those known under the following names:

D & C Red n ° 2 Aluminum lake

D & C Red n ° 3 Aluminum lake D & C Red n ° 4 Aluminum lake

D & C Red n ° 6 Aluminum lake

D & C Red n ° 6 Barium lake

D & C Red n ° 6 Barium / Strontium lake

D & C Red n ° 6 Strontium lake D&C Red n ° 6 Potassium lake

D&C Red n ° 7 Aluminum lake

D&C Red n ° 7 Barium lake

D&C Red n ° 7 Calcium lake D&C Red n ° 7 Calcium / strontium lake

D&C Red n ° 7 Zirconium lake

D&C Red n ° 8 Sodium lake

D&C Red n ° 9 Aluminum lake

D&C Red n ° 9 Barium lake D&C Red n ° 9 Barium / Strontium lake

D&C Red n ° 9 Zirconium lake

D&C Red n ° 10 Sodium lake

D&C Red n ° 19 Aluminum lake

D&C Red n ° 19 Barium lake D&C Red n ° 19 Zirconium lake

D&C Red n ° 21 Aluminum lake

D&C Red n ° 21 Zirconium lake

D&C Red n ° 22 Aluminum lake

D&C Red n ° 27 Aluminum lake D&C Red n ° 27 Aluminum / Titanium / Zirconium lake

D&C Red n ° 27 Barium lake

D&C Red n ° 27 Calcium lake

D&C Red n ° 27 Zirconium lake

D&C Red n ° 28 Aluminum lake D&C Red n ° 30 lake

D&C Red n ° 31 Calcium lake

D&C Red n ° 33 Aluminum lake

D&C Red n ° 34 Calcium lake

D&C Red n ° 36 lake D&C Red n ° 40 Aluminum lake

D&C Blue n ° 1 Aluminum lake

D&C Green n ° 3 Aluminum lake

D&C Orange n ° 4 Aluminum lake

D&C Orange n ° 5 Aluminum lake D & C Orange n ° 5 Zirconium lake D & C Orange n ° 10 Aluminum lake D & C Orange n ° 17 Barium lake D & C Yellow n ° 5 Aluminum lake D & C Yellow n ° 5 Zirconium lake D & C Yellow n ° 6 Aluminum lake D & C Yellow n ° 7 Zirconium lake D & C Yellow n ° 10 Aluminum Lake FD & C Blue n ° 1 Aluminum lake FD & C Red n ° 4 Aluminum lake FD & C Red n ° 40 Aluminum lake FD & C Yellow n ° 5 Aluminum lake FD & C Yellow n ° 6 Aluminum lake

The chemical compounds corresponding to each of the organic pigments mentioned above are mentioned in the book “International Cosmetic Ingredient Dictionnary and Handbook”, Edition 1997, pages 371 to 386 and 524 to 528, published by “The Cosmetic, Toiletry, and Fragrance Association” , the content of which is incorporated into this application for reference.

The melanin pigments which can be used according to the invention are in particular: - the melanin pigments derived from natural or synthetic sources and which can be obtained: (A) by oxidation of at least one indolic or indolinic compound, or (B) by polymerization, oxidizing or enzymatic, of melanic precursors, or (C) by extraction of melanin from substances containing it, or (D) by culture of microorganisms. Such melanin pigments are described in particular in documents EP-A-518773, WO-A-93/13744 and WO-A-93/13745.

(A) The melanin pigments can, in the first place, be obtained by oxidation of at least one indolic compound chosen in particular from those corresponding to formula (I):

in which :

- Ri and R ₃ represent, independently of one another, a hydrogen atom or a C1-C4 alkyl group;

- R ₂ represents a hydrogen atom, a C1-C4 alkyl group, a carboxyl group or an alkoxy (Cι-C4) -carbonyl group;

- the substituents R ₄ to R7 each independently represent a hydrogen atom, a C1-C4 alkyl group, a -NHR ° or -OZ group, R ° denoting a hydrogen atom, a C2-C4 acyl group or C2-C4 hydroxyalkyl, Z denoting a hydrogen atom, a C2-C14 acyl group, a C1-C4 alkyl group, or a trimethylsilyl group,

- And R ₅ can also represent a halogen atom, it being understood that:

- at least one of the substituents R ₄ to R7 represents a group -OZ or -NHR °, one at most of the substituents R ₄ to R ₇ representing -NHR ° and two at most of the substituents R ₄ to R ₇ representing -OZ and, in the latter case, when Z represents a hydrogen atom, the two substituents representing -OH are R ₅ and

- and at least one of the substituents R ₄ to R ₇ represents a hydrogen atom, and in the case where only one of these substituents represents a hydrogen atom, only one of the substituents R ₄ to R ₇ then represents NHR ° or OZ, and the other substituents R ₄ to R ₇ then represent an ^" Cι-C4 alkyl group, or alternatively, if appropriate, for R ₅₎ a halogen atom; as well as the esters or the salts of Among these salts, mention will be made in particular of addition salts such as hydrochlorides, hydrobromides, sulfates and methanesulfonates, as well as the salts deriving from compounds for which R ₂ is a carboxylic group, such as the salts of alkali or alkaline earth, ammonium or amine metals, esters are for example phosphoric esters. The indole compounds of formula (I) above are, for example, from 4-hydroxyindole, 5-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxy-5-methoxyindole, 4-hydroxy- 5-ethoxyindole, 2-carboxy-5-hydroxyindole, 5-hydroxy-6-methoxyindole, 6-hydroxy-7-methoxyindole, 5-methoxy-6-hydroxyindole, 5,6-dihydroxyindole, N- methyl 5,6-dihydroxyindole, 2-methyl 5,6-dihydroxyindole, 3-methyl 5,6-dihydroxyindole, 2,3-dimethyl 5,6-dihydroxyindole, 2-carboxy 5,6-dihydroxyindole, 4-hydroxy 5-methyl indole, 2-carboxy 6-hydroxyindole, 6-hydroxy N-methylindole, 2-ethoxycarbonyl 5,6-dihydroxyindole, 4-hydroxy 7-methoxy 2,3-dimethyl indole, 4 -hydroxy 5-ethoxy N-methyl indole, 6-hydroxy 5-methoxy 2-methyl indole, 6-hydroxy 5-methoxy 2,3-dimethyl indole, 6-hydroxy 2-ethoxycarbonyl indole, 7-hydroxy 3 -methyl indole, 5-hydroxy 6-methoxy 2,3-dimethyl indole, 5-hydroxy 3-methyl indole, 5 -acetoxy 6-hydroxyindole, 5-hydroxy 2- ethoxycarbonylindole, 6-hydroxy 2-carboxy 5-methylindole, 6-hydroxy 2- ethoxycarbonyl 5-methoxyindole, 6-N-bhydroxyethylaminoindole, 4-aminoindole, 5 -aminoindole, 7-aminoindole, N-methyl 6-hydroxyethylaminoindole, 6-amino 2,3-dimethylindole, 6-amino 2, 3, 4,5-tetramethyl indole, 6-amino 2, 3, 4 -trimethylindole, 6-amino 2,3,5- trimethylindole, 6-amino 2,3,6-trimethylindole, 5,6-diacetoxyindole, 5-methoxy 6-acetoxyindole, 5,6-dimethoxyindole, 5,6-methylenedioxyindole, 5,6-trimethylsilyloxyindole, the phosphoric ester of 5,6-dihydroxyindole, 5,6-dibenzyloxyindole, and the addition salts of these compounds. One of the preferred compounds (I) is 5,6-dihydroxyindole.

The melanin pigments can also be obtained by oxidation of at least one indolinic compound chosen in particular from those corresponding to formula (II):

in which :

- Rio and R ₈ represent, independently of one another, a hydrogen atom or a C-1-C4 alkyl radical,

R ₉ represents a hydrogen atom, a C1-C4 alkyl radical, a carboxyl or alkoxy (CJ-C4) carbonyl group,

- R ₁₂ denotes a hydrogen atom, an alkyl radical in C1-C4, hydroxyl, alkoxy (C1-C4), amino or alkylamino in C- | -C- | o _> or halogen, - Ru indicates an atom of hydrogen, a hydroxyl, C1-C4 alkoxy or amino group, with the condition that at least one of the radicals Ru and R ₁ 2 denotes a hydroxyl, alkoxy or amino group, and with the condition that, when Ru denotes a group amino, R ₁₂ cannot denote an alkylamino radical, - Ru and R _{12 which} can also form a C- | -C2 alkylenedioxy group, when they are in positions 5 and 6, and their salts or esters.

The compounds corresponding to formula (II) are chosen in particular from the group consisting of 5,6-dihydroxyindoline, 6-hydroxyindoline, 5,6-methylenedioxyindoline, 7-methoxy 6-hydroxyindoline, 6,7-dihydroxyindoline , 5-hydroxy 4-methoxyindoline, 4,5-dihydroxyindoline, 5-methoxy 6-hydroxyindoline, 4-hydroxy 5-methoxyindoline, 5-hydroxy 6-methoxyindoline, 4,7-dihydroxyindoline, 6- aminoindoline, N-ethyl 4-hydroxyindoline, 1- ethyl 6-aminoindoline, 5,6-diaminoindoline, 1-methyl 6-aminoindoline, 2-methyl 6-aminoindoline, 3-methyl 6-aminoindoline, 2-methyl 5,6-diaminoindoline, 5-chloro 7-aminoindoline, 3-methyl 5,7-diaminoindoline, 5,7-diaminoindoline, 2-methyl 5,7-diaminoindoline, 7-aminoindoline, 2- methyl 7-aminoindoline, 4-aminoindoline, 4-amino 6-chioroindoline, 4-amino 6-iodoindoline, 4-amino 5-bromoindoline, there 4-amino 5-hydroxyindoline, 4-amino 7-hydroxyindoline, 4-amino 5-methoxyindoline, 4-amino 7-methoxyindoline, 5-aminoindoline, 2,3-dimethyl 5-aminoindoline, 1-methyl 5-aminoindoline, 2-methyl 5-aminoindoline, 5-N- (1-methylhexyl) aminoindoline, 5,6-dimethoxyindoline and 5,6-dihydroxy 2-carboxyindoline.

In the compounds of formula (II), the C1-C4 alkyl radicals preferably denote methyl, ethyl, propyl, isopropyl, butyl, isobutyl; the C 1 -C 6 radicals preferably denote methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 1-methylhexyl, 1-methylheptyl, 1-methyloctyl; alkoxy radicals preferably denote methoxy, ethoxy, propoxy or butoxy; halogen preferably means bromine, chlorine or iodine.

The salts of the compounds of formula (II) are, in particular, hydrochlorides, hydrobromides, sulfates, methanesulfonates or dices of alkali, alkaline-earth, ammonium or amine metals.

The oxidation of the indole compound of formula (I) or the indoline compound of formula (II) can be carried out in an aqueous medium or water-solvent (s), in air, optionally in the presence of an alkaline agent and / or a metal oxidation catalyst such as for example the cupric ion, as described in document ÈP-A-518773. In all cases, an insoluble oxidation product is formed.

(B) The melanin pigments can also come from the oxidative or enzymatic polymerization of melanic precursors, such as L-tyrosine, L-dopa, catechol and their derivatives.

(C) The melanin pigments can also come from the extraction of melanin from natural substances such as human hair or the ink of cephalopods (cuttlefish, octopuses), also known as sepiomelanin. These pigments can be purified and ground before use.

(D) The melanin pigments can also be obtained by culture of microorganisms producing melanin either naturally or by genetic modification. Methods of preparing such pigments are described, for example, in patent application WO-90,04029. The melanin pigment can also be in the form of a composite pigment. The melanin pigment can thus be present on the surface of a particulate filler, or incorporated into a particulate filler, mineral or organic, laminar or not lamellar, colored or not. For example, the composite pigment may result from the oxidation of at least one compound (I) or (II), in admixture with the particulate filler, in an essentially non-solvent medium for said filler, or also result from the polymerization oxidant of the melanic precursor on a particulate charge. The particulate filler can be any particulate filler used or usable in. cosmetic compositions, and having for example dimensions less than 100 μm.

Such particulate charges are for example non-lamellar mineral particles. The non-lamellar mineral particles used in this process are in particular inert mineral particles having a particle size of less than 20 micrometers. Such particles are in particular particles of calcium carbonate, silica or titanium oxide. Such composite melanin pigments, deposited on mineral fillers, as well as their preparation, are described in particular in patent application FR-2,618,069.

By a similar process, it is possible to prepare melanin pigments composite with colored mineral particles compatible with use in cosmetic products. The term “colored mineral particles” is used here to refer to non-white particles, in particular particles consisting of metal salts, insoluble in the cosmetic medium, such as those referenced in the Color Index under the chapter “Inorganic Coloring Matters” and bearing the numbers 77000 to 77947, other than white pigments.

The non-lamellar organic particles which can be used in the production of the composite pigments are particles of natural or synthetic, organic or inorganic polymers, compatible with use in cosmetics, for example having a molecular weight of between 5,000 and 5,000,000. Composite melanin pigments on such polymer particles, as well as their preparation, are described in European patent application No. 379,409. The lamellar particles which can be used in the production of composite pigments are mineral or organic particles which are in the form of sheets which may be laminated. These sheets are characterized by a thickness smaller than the largest dimension of the particles. For example, the ratio between the largest dimension and the thickness is between 2 and 100. The largest dimension is generally less than 50 micrometers. Such composite melanin pigments deposited on. lamellar charges are described, as well as their preparation, in European patent application No. 467,767.

The organo-mineral hybrid material, used in the present invention for the process making it possible to obtain said coated organic pigment, is known and has been described in particular in French patent application No. 97 04157 (corresponding application WO-A-98 / 44906). It is a material formed by mineral nanoparticles linked together by chains of organic or silicone polymers.

This material is obtained according to a so-called “sol-gel” process, that is to say a process involving partial or complete hydrolysis, then the condensation of the ingredients of a starting solution. The starting solution giving, after hydrolysis and condensation, the hybrid material used in the process of the present invention comprises:

(A) at least one metallic or metallo-organic compound, and

(B) at least one functionalized organic polymer or a precursor thereof, or at least one functionalized silicone polymer or a precursor thereof, the latter being different from (A).

In the present invention, the mixture of components (A) and (B) giving, after hydrolysis and condensation, said hybrid material preferably comprises at least one solvent (component (C)).

Component (A), when it is a metallic compound, can be chosen from: - the oxides of the transition metals from groups IB to VIIB or from the lanthanide group of the periodic table, - oxides of aluminum, boron, silicon or tin, and

- aluminum phosphates.

Preferred metal compounds which can be used in the present invention are chosen from the group formed by the oxides of the transition metals and include in particular titanium oxide, iron oxide and zirconium oxide.

This mineral component (A) must be reactive with respect to component (B) and allow the formation of covalent and / or physical bonds so as to form a three-dimensional network.

When it is a metallo-organic compound, component (A) can be chosen from the following three groups of compounds:

(1) the compounds corresponding to one of the following formulas:

(la) M (ORι) _n

(lb) RI HOR n. _!

(le) (OR ₁ ) _n- ι-MR "-M (OR ₁ ) n-ι

and R

(Id) M - (OR) _n _ ₂

R '

or :

M represents an atom of a transition metal from groups IB to VIIB of the periodic table of the elements or an atom of aluminum, boron, silicon or tin, preferably an atom of Si, Ti or Zr,

n is equal to the valence of M,

Ri represents a linear alkyl radical which can be branched in C1.30, preferably in Cι. ₆₎ R and R 'represent, independently of one another, a linear or branched alkyl group, a cycloalkyl group or a substituted or unsubstituted aryl group, said groups R and R' possibly being able to react or being able to carry a substituent capable of reacting with the functionalized organic or silicone polymer.

R "represents a linear or branched alkylene radical, cycloalkylene or arylene optionally substituted, which can react itself or which can carry a substituent capable of reacting with the functionalized organic or silicone polymer (B), such as those defined below:

(2) the coordination complexes of the compounds of formula (la) to (Id) above, corresponding to one of the following formulas:

(Ma) IVKOR nx (X) _x (llb) R-IV ORI LX (X) _X

(Island) (X) _x (ORι) n-ι-χM-R "-M- (OR ₁ ) _n -ι-χ (X) _x

R

(Hd) M - (OR) _n _ _{2 χ} (X) _χ ,

R '

where: M represents an atom of a transition metal from groups IB to VIIB of the periodic table of the elements or an atom of aluminum, boron, silicon or tin, preferably an atom of Ti or Zr,

X is a mono-coordinated or monodentate ligand comprising a nitrogen atom, a phosphorus atom, a sulfur atom or an oxygen atom, and which can carry a substance capable of reacting with said functionalized organic polymer or said functionalized silicone polymer (B ), such as those defined below:

x represents the number of ligands X, and n, R, Ri, R 'and R "are as defined for formulas (la) to (Id), and

(3) the chelation complexes corresponding to the following formula:

(III) M (OR ₁ ) _n-bx (X ') _x

in which :

M represents an atom of a transition metal from groups IB to VIIB of the periodic table of the elements or an aluminum, boron, silicon or tin atom, preferably a Ti or Zr atom,

X 'represents a chelating group or polydentate ligand comprising a nitrogen atom, a phosphorus atom, a sulfur atom and / or an oxygen atom, and which can carry a substituent capable of reacting with said functionalized organic polymer or said polymer functionalized silicone (B), such as those defined below:

b corresponds to the coordination valence of ligand X 'and is at least equal to 2,

x is equal to the number of ligands X ', and

Ri and n have the meanings indicated above for the formulas (la) to (Id).

In the description of the complexes of metallo-organic compounds above, the term “mono-coordinated or monodentate ligand” (X) is understood to mean a group comprising a single atom capable of binding to the central metallic atom. As examples of such ligands, mention may be made of carboxylic acids and ketones.

By chelating group (X ′) according to the present invention, is meant a polydentate ligand linked to a single central metal atom by more than one electron doublet donor atom. It is preferably chosen from β-diketones, β-ketoesters, β-ketoamines, α- and β-hydroxy acids, optionally β-hydroxylated amino acids, salicylic acid and derivatives thereof.

Mention may in particular be made of acetoxyethyl methacrylate, methyl α-hydroxymethacrylate, ε-N-methacryloyl-L-lysine, methacrylamino-4-salicylic acid and methacrylamino-5-salicylic acid. , acetoacetate, ethylacetoacetate and EDTA.

The component or components (A) described above are either in the form of colloidal particles or in the form of soluble compounds which, after hydrolysis and condensation, give nanometric particles. To be able to form the organo-mineral system used in the process of the present invention, the particles must establish connections with the organic or silicone polymers forming the component (B). For this they must be able to react and / or carry at least one group capable of reacting with these polymers. This group can be carried by one of the organic radicals R, R 'or R "or else by the ligand X or X' of the compounds described above under points (2) and (3).

The substituent capable of reacting with said functionalized organic or silicone polymer (B) is chosen in particular from ethylenically unsaturated radicals such as (meth) acrylic and vinyl groups, halogen, hydroxylated, carboxylated, thiol, epoxy, esters, amino, amido, amino acid, polypeptide, urethane, ureido, acetoacetate, ethylacetoacetate or a group derived from EDTA and derivatives thereof.

Examples of preferred metallo-organic components (A) of the present invention that may be mentioned include tetraethoxysilane, tetra-n-propyl orthotitanate, tetra- / so-propyl porthotitanate, tetra- / zirconate? -propyl, tetra- / so-propyl zirconate, methyltriethoxysilane, tetraethoxytitane, tetrabutoxytitane, triethoxyfer and triethoxytungsten. Metallo-organic compounds which are particularly advantageous for the process of the present invention are tetra- / so-propyl orthottanate, tetra- / 7-propyl porthotitanate, tetra- / so-propyl zirconate and tetra- zirconate / - propyl.

It is understood that the component (A) can be a mixture of two or more metallic and / or metallo-organic compounds.

For the preparation of the organo-mineral hybrid material used in the process of the present invention, the metal or metallo-organic compound (s) are mixed with at least one functionalized organic or silicone polymer, or with a precursor thereof.

The term “functionalized organic or silicone polymers” (component (B)) means organic or silicone polymers comprising at least two identical or different functions capable of reacting with the component (A).

The functionalized organic or silicone polymers involved in the preparation of the organomineral hybrid material used in the process of the present invention are chosen, for example, from:

(a) homopolymers and copolymers of alkyloxazoline;

(b) homopolymers and copolymers of (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, styrene-sulfonic acid, acrylamido-2-methylpropane-sulfonic acid, 2-sulfoethyl methacrylate, vinylsulfonic acid and / or vinylphosphonic acid;

(c) homopolymers of acrylic or methacrylic esters or amides and their copolymers with comonomers chosen from unsaturated carboxylic acids, sulfonic acids, phosphonic acids, vinyl esters and ethers, olefins, styrene, substituted styrenes, fluoro- or perfluoroolefins, perfluoroalkyl (meth) acrylates, fluorinated vinyl compounds and unsaturated organosilanes, organosiloxanes or organopolysiloxanes; (d) homopolymers and copolymers of vinyl alcohol,

(e) homopolymers of vinyl and / or allyl esters or amides and / or methalylics and their copolymers with comonomers chosen from unsaturated carboxylic acids, sulfonic acids, phosphonic acids, vinyl esters and ethers, olefins, styrene, substituted styrenes, fluoro- and perfluoroolefins, perfluoroalkyl (meth) acrylates, fluorinated vinyl compounds and unsaturated organosilanes, organosiloxanes or organopolysiloxanes;

(f) polyethers;

(g) polyesters;

(h) homo- and copolymers of olefins or of cycloolefins; (i) polyamides and polyesteramides; (j) polyurethanes and polyureas which may contain polyether, polyester and / or polyorganosiloxane blocks; (k) fluoropolymers;

(I) natural polymers and modified natural polymers (artificial polymers); (m) polyorganosiloxanes;

(n) polyorganophosphazenes;

(o) polysilanes - (SiR ^a R ^b -) _n , polycarbosilanes - (SiR ^a R ^b -CR ^c R ^d -) _n and polysilazanes - (- SiR ^a R ^b -NR ^c -) _n , and (p) mixtures of these polymers.

These polymers, when they do not in themselves contain functional groups capable of reacting with the component (A), can be functionalized in an additional step prior to mixing with the component (A).

Particularly advantageous polymers as components (B) of the organo-mineral hybrid materials used according to the present invention are polyhydimethylsiloxanes, preferably functionalized, and very particularly hydroxylated polydimethylsiloxanes, in particular PDMS-diol and PDMS-disilanol. Mention may also be made of PDMS carrying grafts of ethylene oxide and / or propylene oxide or of block polymers OE / OP-PDMS-OE / OP.

As an example of a silicone polymer precursor which can be used in the process of the present invention, mention may in particular be made of diethyldimethoxysilane.

The mixing ratio of the metallic or metallo-organic compound (A) to the organic or silicone polymer (B) in the organo-mineral hybrid material used according to the present invention depends on a large number of parameters such as the chemical nature of these two components, the type of cosmetic composition, the mode of use of the hybrid material (incorporation in or application to the cosmetic composition), the amount of solvent, the desired non-transfer properties, etc.

The metallic or metallo-organic component (A) is generally present in an amount of 1 to 99% by weight, preferably in an amount of 5 to 80% by weight, and very particularly in an amount of 10 to 70% by weight, based on the weight of the organomineral hybrid material.

The polymer component (B) is generally present in an amount of 1 to 99% by weight, preferably in an amount of 5 to 80% by weight, and very particularly in an amount of 10 to 70% by weight, relative to the weight of the hybrid material. organomineral.

The solvent (C) possibly present in the organo-mineral hybrid material can be volatile or non-volatile and can be chosen from alcohols, in particular aliphatic alcohols in Cι _-6 , linear or branched, volatile or non-volatile silicone oils, hydrocarbon oils, volatile or not, vegetable, mineral, synthetic or animal oils, or mixtures of these solvents. Mention may in particular be made of ethanol, cyclic or linear silicone oils containing from 4 to 12 silicon atoms, castor oil, apricot oil and parlameam oil.

The process for preparing the coated organic pigment according to the invention comprises the following steps: a) a mixture is prepared (i) a dispersion of an organic pigment in a liquid medium, in particular an aqueous or alcoholic or oily medium, optionally in the presence of a dispersant,

(ii) and a solution of a crosslinked organo-mineral hybrid material as described above, b) said mixture is brought into contact with water when said dispersion of the organic pigment is a dispersion in an alcoholic liquid medium or oily.

The mixture can be left to act at a temperature ranging from 10 ° C. to 30 ° C., in particular at ambient temperature (25 ° C.). The agitation of said mixture can last from 5 minutes to 1 hour. The product resulting from the contact of the organo-mineral hybrid material crosslinked with water is deposited on the organic pigment and coats the latter. The reaction medium can then be filtered or centrifuged and the collected filtrate is washed, in particular with water and then with a solvent capable of dissolving the residual uncoated organic pigment. After drying, a powder is obtained.

According to a first embodiment of the preparation process, an aqueous dispersion of the organic pigment (uncoated) is prepared, optionally in the presence of dispersant with mechanical stirring and optionally in the presence of ultrasound (to avoid the formation of agglomerates); a crosslinked organo-mineral hybrid material is prepared as described above and a solution of said material made with a solvent for this material (such as the solvent (C) mentioned above) is poured dropwise into the aqueous dispersion of the pigment. The contact of said crosslinked organo-mineral material with the water of the aqueous dispersion of the organic pigment forms a product which is deposited on the pigment and coats the latter.

According to a second embodiment of the preparation process, a solution of the crosslinked organo-mineral hybrid material is prepared as described above with a solvent for this material and the organic pigment is dispersed in this solution, optionally by adding a dispersant of said pigment. Then water in this solution is added dropwise. The contact of said organomineral material with water forms a product which is deposited on the pigment and coats the latter. In the process according to the invention, the final mixture, comprising the dispersion of organic pigment, the solution of the crosslinked organo-mineral hybrid material and water, is advantageously placed under effective stirring to prevent the formation of agglomerates and / or to disintegrate. agglomerates as they are formed. After reaction, a coated organic pigment powder is thus obtained. According to a particular mode of the process according to the invention, said final mixture can be treated with ultrasound in order to disaggregate the agglomerates which may form during the reaction.

The preparation of the coated pigment according to the process of the invention can be carried out in continuous mixing equipment which may include means for metering the constituents of the mixture to be produced, such as for example a twin-screw mixer-extruder.

The average size of the particles of coated organic pigment (particles obtained after grinding) can range from 0.1 μm to 500 μm, and preferably from 1 μm to 100 μm.

The content of the coating product in the coated organic pigment can range from 20% to 300% by weight, relative to the weight of organic pigment (uncoated), and preferably from 80% to 150% by weight.

The coated organic pigment may be present in the composition according to the invention in a content ranging from 0.1% to 99% by weight, relative to the total weight of the composition, preferably from 0.5% to 80% by weight , and better still from 1% to 60% by weight.

The composition according to the invention may be in the form of water-in-oil or oil-in-water emulsion, free or compacted powder, cast powder, solid stick, paste, organic or aqueous lotion.

The composition may further comprise other ingredients commonly used in cosmetic compositions. Such ingredients can be chosen among preservatives, perfumes, sunscreens, oils, waxes, thickeners, film-forming polymers, moisturizers, vitamins, proteins, ceramides, surfactants, antioxidants, free radical scavengers, solvents organic, water, mineral pigments. Of course, a person skilled in the art will take care to choose this or these optional additional compounds, and / or their quantity, in such a way that the advantageous properties of the composition according to the invention are not, or not substantially, affected by the addition. considered.

In particular, when the composition is a nail varnish, it may contain a film-forming polymer in a content ranging from −1% to 60% by weight, relative to the total weight of the composition, in an organic solvent medium or an aqueous medium. .

When the varnish comprises an organic solvent medium, the film-forming polymer can be chosen, in particular, from alkyd, acrylic and / or vinyl resins, polyurethanes and polyesters, celluloses and cellulose derivatives such as nitrocellulose, cellulose acetobutyrate and resins resulting from the condensation of formaldehyde with an arylsulfonamide, and mixtures thereof. In this case, the film-forming polymer is generally dissolved in the organic medium.

When the nail varnish comprises an aqueous medium, the polymer may be present in the form of particles of film-forming polymer dispersed in the aqueous medium.

Among the film-forming polymers which may be used, mention may be made of polyurethanes, for example anionics, polyesters-polyurethanes, polyether-polyurethanes, radical polymers in particular of acrylic, styrene and / or vinyl type, polyesters, resins alkyds, alone or as a mixture. The dispersion may also comprise an associative polymer of the polyurethane type or a natural gum such as xanthan gum. The film-forming polymer can be present in the composition according to the invention in a dry matter content ranging from 5% to 60% by weight, relative to the total weight of the composition, and better still from 10% to 40% by weight. .

As organic solvent which can be used in the invention, there may be mentioned:

- ketones liquid at room temperature such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone, acetone;

- Alcohols liquid at room temperature such as ethanol, isopropanol, diacetone alcohol, 2-butoxyethanol, cyclohexanol; - glycols which are liquid at room temperature such as ethylene glycol, propylene glycol, pentylene glycol, glycerol;

- Propylene glycol ethers which are liquid at room temperature such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol mono n-butyl ether; - short chain esters (having 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate, acetate isopentyl;

- ethers liquid at room temperature such as diethyl ether, dimethyl ether or dichlorodiethyl ether; - alkanes liquid at room temperature such as decane, heptane, dqdecane, cyclohexane;

- aromatic cyclic compounds which are liquid at room temperature such as toluene and xylene;

- aldehydes liquid at room temperature such as benzaldehyde, acetald _. éhyde

- their mixtures.

When the nail varnish comprises an organic solvent medium, the organic solvent may be present in a content ranging from 25 to 94.9% by weight, relative to the total weight of the composition, and preferably from 60% to 90% by weight. weight.

When the nail varnish according to the invention contains an aqueous medium, the latter can consist essentially of water or of a hydroalcoholic mixture comprising in particular C1-C5 monoalcohols or C2-C8 glycols. . The te- Neur in water in the composition in an aqueous medium can range from 25 to 94.9% by weight, relative to the total weight of the composition, and preferably from 60% to 90% by weight.

The invention is illustrated in more detail in the following examples.

Example 1:

a) Coated organic pigment:

A sol-gel composite material is first prepared by diluting 187.2 g of a PDMS-disilanol having a weight-average molar mass equal to 4000 with 84.9 g of ethanol. 280.8 g of a solution of 70% tetra-n-propyl zirconate in propanol are added to the mixture and the mixture is kept stirring for 24 hours to form the organo-mineral hybrid material.

100 g of an aqueous dispersion of organic pigment D&C Red n ° 30 to 30% in active material of organic pigment are placed with stirring. (D&C Red pigment n ° 30 is partially soluble in alcohol and completely soluble in acetone).

Then approximately 50 ml of the solution of the hybrid material prepared above (containing 47% by weight of organomineral hybrid material) are added dropwise until a solidification of the mixture is observed.

This mixture is then treated with ultrasound to disintegrate the agglomerates as they are formed, then ethyl alcohol is added to dilute the mixture twice, then left to stir overnight with magnetic stirring. The mixture is then filtered through Buchner and the residue is rinsed with distilled water (by washing this residue with ethanol or with acetone, it is found that the filtrate is not colored). After drying, the residue is sieved through a 160 μm sieve. An organic pigment powder coated with hybrid material is thus obtained.

b) Composition of nail polish: We prepared a nail polish having the following composition

- Nitrocellulose 10 g

- Plasticizers and resin 15 g

- Rheological agent 1.5 g

- Organic pigment coated in Example 1a) '10 g

- Ethyl acetate, butyl acetate qs 100 g

After applying the composition to the nails, a pink-colored makeup film was obtained. After removing makeup, we see that the nail is not stained.

Claims

1. Process for the preparation of a coated organic pigment comprising the following steps: a) a mixture is prepared

(i) a dispersion of an organic pigment in a liquid medium, in particular an aqueous or alcoholic or oily medium, optionally in the presence of a dispersant,

(A) at least one metallic or metallo-organic compound, and

(B) at least one functionalized organic polymer or a precursor thereof, or at least one functionalized silicone polymer or a precursor thereof, the latter being different from (A), b) said mixture is brought into contact with water when said dispersion of the organic pigment is a dispersion in an alcoholic or oily liquid medium.

2. Method according to claim 1, characterized in that the compound (A) is chosen from

(i) the transition metal oxides of groups IB to VIIB or of the lanantides group of the periodic table, (ii) oxides of aluminum, boron, silicon or tin, and (iii ) aluminum phosphates.

3. Method according to claim 1 or 2, characterized in that said compound (A) is chosen from titanium oxide, iron oxide and zirconium oxide.

4. Method according to any one of the preceding claims, characterized in that the said compound (A) is an organometallic compound chosen from:

(2) the compounds corresponding to one of the following formulas:

(la) M (ORι) _n (Ib) RM- (ORι) _n -ι (le) (OR ₁ ) _n . ₁ -MR "-M (OR ₁ ) _n -ι

or

n is equal to the valence of M,

Ri represents a linear or branched C-ι-30 alkyl radical, preferably C-i-β,

R and R 'represent, independently of one another, a linear or branched alkyl group, a cycloalkyl group or a substituted or unsubstituted aryl group, the said groups R and R' possibly being able to react or may carry a substituent capable of reacting with the functionalized organic or silicone polymer.

R "represents a linear or branched alkylene radical, cycloalkylene or arylene optionally substituted, which can react itself or which can carry a substituent capable of reacting with the functionalized organic or silicone polymer

(B),

^" (2) the coordination complexes of the compounds of formula (la) to (Id) above, corresponding to a request for the following formulas:

(llb) RM (ORι) _n -ι-χ (X) χ (Ile) (X) _x (OR1) _n .i- _x MR "-M- (OR ₁ ) n-ι-χ (X) x

or

M represents an atom of a transition metal from groups IB. to VIIB of the periodic table of the elements or an atom of aluminum, boron, silicon or tin, preferably an atom of Ti or Zr,

X is a mono-coordinated or monodentate ligand comprising a nitrogen atom, a phosphorus atom, a sulfur atom or an oxygen atom, and which can carry a substance capable of reacting with said functionalized organic polymer or said functionalized silicone polymer (B )

x represents the number of ligands X, and

n, R, R-i, R 'and R "are as defined for formulas (la) to (Id), and

(3) the chelation complexes corresponding to the following formula:

in which :

X 'represents a chelating group or polydentate ligand comprising a nitrogen atom, a phosphorus atom, a sulfur atom and / or an oxygen atom, and which can carry a substituent capable of reacting with said functionalized organic polymer or said polymer functionalized silicone (B),

b corresponds to the coordination valence of ligand X 'and is at least equal to 2, x is equal to the number of ligands X ', and

Ri and n have the meanings indicated above for the formulas (la) to (Id).

5. Method according to claim 4, characterized in that said substituent capable of reacting with said functionalized organic or silicone polymer (B), carried by the groups R, R 'or R "or by the ligands X or X' is chosen among the ethylenically unsaturated radicals, the halogenated, hydroxylated, carboxylated, thiols, epoxy, esters, amino, amido, amino acid, polypeptide, urethane, ureido, acetoacetate, ethylacetoacetate or an EDTA derivative group and derivatives of this one.

6. Method according to claim 4 or 5, characterized in that the mono-coordinated ligand X is chosen from carboxylic acids and ketones.

7. Method according to any one of claims 4 to 6, characterized in that the polydentate ligand X 'is chosen from β-diketones, β-ketoesters, β-ketoamines, α- and β-hydroxy acids, optionally β-hydroxylated amino acids, salicylic acid and derivatives thereof.

8. Method according to claim 7, characterized in that the polydentate ligand r

X 'is chosen from acetoxyethyl methacrylate, methyl α-hydroxymethacrylate, ε-N-methacryloyl-L-lysine, methacrylamino-4-salicylic acid and methacrylamino-5-salicylic acid.

9. Method according to any one of the preceding claims, characterized in that the said metallo-organic compound is chosen from the group formed by tetraethoxysilane, tetra orthotitanate - /? - propyl, tetra orthotitanate / so-propyl, tetra-? -propyl zirconate, tetra- / so-propyl zirconate, methyltriethoxysilane, tetraethoxytitane, tetrabutoxytitane, triethoxyfer and triethoxytungsten.

10. The method of claim 9, characterized in that said metallo-organic compound is tetra- / so-propyl orthotitanate, tetra-n-propyl orthotitanate, tetra- / so-propyl zirconate and tetra-n-propyl zirconate.

11. Method according to any one of the preceding claims, characterized in that the functionalized or silicone-based organic polymer. functionalized (B) is a homopolymer or a random, block and / or graft copolymer chosen from:

(a) homopolymers and copolymers of alkyloxazoline;

(c) homopolymers of acrylic or methacrylic esters or amides and their copolymers with comonomers chosen from unsaturated carboxylic acids, sulfonic acids, phosphonic acids, vinyl esters and ethers, olefins, styrene, styrenes substituted, fluoro- or perfluoro-olefins, perfluoroalkyl (meth) acrylates, fluorinated vinyl compounds and unsaturated organosilanes, organosiloxanes or organopolysiloxanes;

(d) homopolymers and copolymers of vinyl alcohol,

(f) polyethers;

(g) polyesters;

(h) homo- and copolymers of olefins or of cycloolefins; (ii) polyamides and polyesteramides;

(b) polyurethanes and polyureas which may contain polyether, polyester and / or polyorganosiloxane blocks. ;

(c) fluoropolymers; (d) natural polymers and modified natural polymers (artificial polymers);

(e) polyorganosiloxanes;

(f) polyorganophosphazenes;

(g) polysilanes - (SiR ^a R ^b -) _n , polycarbosilanes - (SiR ^a R ^b -CR ^c R ^d -) _n and polysilazanes - (- SiR ^a R ^b -NR ^c -) _n , and

(h) mixtures of these polymers.

12. Method according to any one of the preceding claims, characterized in that the said functionalized organic or silicone polymer is chosen from functionalized polydimethylsiloxanes.

13. Method according to any one of the preceding claims, characterized in that the said functionalized organic or silicone polymer is a hydroxylated polydimethylsiloxane.

14. Method according to any one of the preceding claims, characterized in that the mixture giving said crosslinked organo-mineral hybrid material also contains at least one solvent (component (C)).

15. The method of claim 14, characterized in that said solvent is chosen from alcohols, in particular aliphatic alcohols in ^• C-ι- ₆ , linear or branched, volatile or non-volatile silicone oils, volatile hydrocarbon oils or no, vegetable, mineral, synthetic or animal oils, or mixtures thereof.

16. Method according to any one of the preceding claims, characterized in that the metallic or metallo-organic component (A) is present in an amount of 1 to 99% by weight, preferably in an amount of 5 to 80% by weight , and all particularly at 10 to 70% by weight, based on the weight of the organomineral hybrid material.

17. Method according to any one of the preceding claims, characterized in that the polymer component (B) is generally present in an amount of 1 to 99% by weight, preferably in an amount of 5 to 80% by weight, and all particularly at 10 to 70% by weight, based on the weight of the organomineral hybrid material.

18. Method according to any one of the preceding claims, characterized in that the organic pigment is chosen from

- cochineal carmine,

- organic pigments of azo, anthraquinone, indigo, xanthene, pyrenic, quinolinic, triphenylmethane, fluorane dyes - organic lakes.

19. The method of claimlδ, characterized in that the lacquer is chosen from insoluble sodium, potassium, calcium, barium, aluminum, zirconium, strontium, titanium, azo organic dyes , anthraquinonics, indigoids, xanthenics, pyrenics, quinolinics, triphenylmethane, fluorane.

20. Method according to one of claims 18 or 19, characterized in that the organic lacquer is supported by an inorganic support.

21. The method as claimed in claim 20, characterized in that the mineral support is chosen from particles of clay, alumina, zirconia, metal oxides, in particular zinc oxide or titanium oxide, talc, calcium carbonate, barium sulfate.

22. Method according to any one of the preceding claims, characterized in that it comprises the following steps: a) an aqueous dispersion of the organic pigment is prepared; b) the solution is poured dropwise into the aqueous dispersion of the pigment of said material carried out with a solvent for this material.

23. The method of claim 22, characterized in that the aqueous dispersion of the organic pigment comprises a dispersant of said organic pigment. , ^' _

24. The method of claim 22 or 23, characterized in that the aqueous dispersion of the organic pigment is prepared with mechanical stirring, optionally in the presence of ultrasound.

25. Method according to any one of claims 1 to 21, characterized in that it comprises the following stages: a) a solution of the crosslinked organo-mineral hybrid material is prepared with a solvent for this material, b) it is dispersed in said solution of the crosslinked organo-mineral hybrid material, the organic pigment, c) water is added dropwise to this solution.

26. The method of claim 25, characterized in that said organic pigment is dispersed in said solution of the organo-mineral hybrid material crosslinked with a dispersant of said pigment.

27. Method according to any one of the preceding claims, characterized in that the mixture comprising the dispersion of organic pigment, the solution of the crosslinked organo-mineral hybrid material and water, is placed under effective stirring to prevent the formation of 'agglomerates and / or disaggregate agglomerates as they are formed.

28. The method of claim 27, characterized in that said mixture is treated with ultrasound.

29. Method according to any one of the preceding claims, characterized in that the method is carried out in continuous mixing equipment, such as for example a twin-screw mixer-extruder.

30. Coated organic pigment capable of being obtained according to the process according to any one of the preceding claims.

31. Coated organic pigment according to the preceding claim, characterized in that the content of said hybrid material in said coated organic pigment ranges from 20% to 300% by weight, relative to the total weight of said uncoated organic pigment, and preferably ranges from 80% to 150% by weight.

32. Cosmetic composition comprising, in a cosmetically acceptable medium, an organic pigment coated according to claim 30 or 31.

33. Composition according to claim 32, characterized in that the said coated organic pigment is present in a content ranging from 0.1% to 99% in

^• weight, relative to the total weight of the composition, preferably from 0.5% to 80% by weight, and better still from 1% to 60% by weight.

34. Composition according to one of claims 32 or 33, characterized in that it further comprises an additive chosen from the group formed by preservatives, perfumes, sunscreens, oils, waxes, thickeners, film-forming polymers, hydrating agents, vitamins, proteins, ceramides, surfactants, antioxidants, anti-free radical agents, organic solvents, water, mineral pigments.

35. Composition according to any one of claims 32 to 34, characterized in that it is in the form of nail polish, lip product, body makeup product, foundation, eyeshadow or blush, eyeliner, concealer, mascara.

36. Nail varnish comprising a composition according to any one of claims 32 to 34.

37. A process for making up keratin materials comprising the application to said keratin materials of a cosmetic composition according to any one of claims 32 to 35.

38. Use of a cosmetic composition according to any one of claims 32 to 36 to obtain a make-up which does not stain keratin materials.