FR2836633A1 - USE OF HYBRID COMPOUNDS AS ANTI-POLLUTANT AND ANTI-ADHERENT AGENTS, COMPOSITION FOR FLEXIBLE FILM - Google Patents

Abstract

Sol-gel composition for forming a coating on a keratinic substrate is produced by hydrolyzing an organometallic compound with water in the presence of a functionalized polymer and optionally an alcohol. The polymer makes up 10-95 wt.% of the composition.

Description

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Use of hybrid compounds as anti-polluting and non-sticking agents, flexible film composition
The present invention relates to the use of certain hybrid compounds as anti-pollutants and anti-adhesion agents, and more particularly with regard to particulate type pollutants such as particles produced by diesel engines, on the surface of the materials. keratin, especially skin and hair.

The invention also relates to a composition for flexible films containing these anti-pollutants.

 Particles produced by diesel engines are one of the major causes of urban pollution. These particles are generally carbon structures of variable size, containing many metals, anions and organic compounds. By depositing on the skin, they are responsible for the messy effect of the pollution and in addition are likely to release in the skin compounds adsorbed on their surface. Once released into the skin these compounds can cause many diseases or dermatological infections that can cause itching, change the visual appearance of the skin or cause discomfort.

 The present invention proposes the use of certain hybrid compounds, overcoming these disadvantages.

 In particular, the Applicant has surprisingly discovered that the application to the surface of the skin of certain hybrid materials developed by sol-gel can greatly reduce the adhesion of these particles to the surface of the skin. The result is a skin that remains unsalted following the application of particles produced by diesel engines. Having not been exposed to the adsorbed compounds on the surface of the particles, the skin remains clean and healthy.

 The subject of the present invention is therefore the use as an anti-pollutant of a composition intended to form a

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 coating, on a keratinous substrate, in a crosslinked hybrid material.

 The invention also relates to the use as an anti-adherent agent of such a composition.

 The invention also relates to a composition for obtaining a flexible film on the surface of keratin materials.

 Other objects of the invention will appear on reading the description and examples which follow.

 The subject of the invention is the use, as an anti-pollution agent, of a composition intended to form a coating, on a keratinous substrate, of a crosslinked hybrid material, said composition being obtained by the sol / gel process from the mixture: ) at least one organometallic compound, (b) at least one functionalized organic polymer or a precursor of said polymer, or at least one functionalized silicone polymer or a precursor of said polymer, the latter precursor being different (a), (c) an amount of water sufficient to hydrolyze the organometallic compound, and (d) optionally at least one alcohol, said coating being non-reversible.

 Functionalized expression is understood according to the invention as the presence of functional groups that can interact physically or chemically.

 The expression "non-reversible" means according to the invention that the hybrid material formed after application of the composition and evaporation of the solvent (s) retains its initial structure, that is to say that it is not not de-crosslinked after several washings with water.

 This non-reversibility of the hybrid material formed is essentially due to the fact that it has a high degree of crosslinking at a nanoscale and a very low surface energy.

 When the composition as defined above is applied to a keratinous substrate, a sol / gel reaction occurs, resulting, after evaporation of the solvent (s), in the formation of a

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 Hybrid material by polycondensation and crosslinking at the nanoscale.

 The crosslinked hybrid material thus formed can be of very varied structure. It may thus be in the form of a more or less dense network of chains of the inorganic polymer originating from the organometallic compound and chains of the organic or silicone polymer, these being connected to each other by physical, ionic and / or covalent bonds. .

 The hybrid material may also consist of inorganic nodules from the organometallic compound and chains of the organic or silicone polymer, the nodules being physically or chemically bonded to the chains of the organic or silicone polymer. Mineral nodules have a very small nanometric size, usually between 1 and 20 nanometers. These nodules can also take the form of aggregates or clusters.

 The invention also relates to the use as an anti-adherent agent of such a composition.

 The invention is particularly well adapted to prevent the adhesion of pollutants of a particular type to the surface of keratin materials, and in particular the skin.

dans lesquelles : The organometallic compound is preferably selected from the group consisting of: (1) chelated alkoxides having one of the following formulas:

in which :

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dans laquelle : M, Ri et n ont les mêmes significations que ci-dessus pour les formules (I), b représente le degré de complexation du ligand X, M represents a transition metal of groups 1b to 7b, of group 8 or of the group of lanthanides of the periodic table, aluminum, boron, silicon, tin, cerium or iron, n represents valence of the metal, R 1 and R 2 represent, independently of one another, a linear or branched C 1 -C 30, preferably C 1 -C 6, alkyl radical R and R 'present independently of one another; an alkyl radical, linear or branched, a cycloalkyl radical, a substituted or unsubstituted aryl radical, said radicals R and R 'being able to be substituted by groups capable of reacting with the organic or silicone polymer such as, for example, ethylenically unsaturated groups ( (meth) acrylic, vinyl), halogenated, hydroxylated, carboxylated, thiols, epoxy, esters, urethanes, ureas, amines, amino acids, polypeptides, said radicals R and R 'may additionally comprise a chosen cosmetically or dermatologically active group i, for example, from a dye group, a photochromic group, a group filtering UV-A radiation and / or UV / B radiation, an adhesion promoting group on keratin materials (such as, for example, amide groups, urethane groups). , ureas, hydroxyls, carboxyls, amino acids, polypeptides), a group facilitating make-up removal, a bactericidal group, a chelating group in particular capable of complexing multivalent cations, a hydroxy acid, a neurosuppressor, an anti-hair loss group, an antioxidant group, an anti-free radical group, or a vitamin-carrying group; (2) chelated alkoxides having the following formula:

in which: M, Ri and n have the same meanings as above for the formulas (I), b represents the degree of complexation of the ligand X,

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M- (Z), (IIIa) R-M- (Z) (IIIb) (Z) n-l-M-R" -M'- (Z) n-l (Ille) RR'-M- (Z) n-2 (IIId) dans lesquelles : - M, n, R, et R'ont la même signification que ci-dessus, - M et M', indépendamment l'un de l'autre, ont la même signification, - R"désigne-O-,-NR-,-S-ou un radical divalent hydrocarboné,

linéaire, cyclique ou ramifié, saturé ou insaturé, en Cl-C3., de préférence C2-C20, éventuellement substitué (par un substituant choisi dans la liste donnée pour R ou R') et/ou éventuellement interrompu ou substitué par 1 à 20 hétéroatomes choisis parmi 0, N, P et/ou S, pouvant comporter en outre un ou plusieurs groupes cosmétiquement actifs (comme R ou R'), avec R2 représentant un radical hydrocarboné, linéaire, cyclique ou ramifié, saturé ou insaturé, en C1-C30, de préférenceC2-C20, - Z représente, (indépendamment l'un de l'autre dans la formule (IIIc)), un atome d'halogène (chlore, iode, brome ou fluor) ; (4) les complexes répondant à l'une des formules (IVa), (IVb), (IVc) ou (IV d) suivantes : x is the number of complexing ligands, and X represents a ligand or a mono- or polydentate chelating group that can be covalently bonded to a group that is capable of reacting with the organic or silicone polymer, such as, for example, groups containing ethylenic unsaturation ((meth) ) acrylic, vinyl), halogenated groups, hydroxylated, carboxylated, thiol, epoxy, esters, amines, ureas, urethanes, acetoacetate group (ACAC) or a group derived from EDTA and its derivatives, said chelating group may also comprise a cosmetically or dermatologically active group such as those defined above; (3) metal halides corresponding to one of the following formulas (IIIa), (IIIb), (IIIc) or (IIId):

M- (Z), (IIIa) RM- (Z) (IIIb) (Z) nlMR "-M'- (Z) nl (IIl) RR'-M- (Z) n-2 (IIId) in which: - M, n, R, and R 'have the same meaning as above, - M and M', independently of each other, have the same meaning, - R "denotes -O-, - NR- , -S-or a divalent hydrocarbon radical,

linear, cyclic or branched, saturated or unsaturated, C1-C3., preferably C2-C20, optionally substituted (by a substituent selected from the list given for R or R ') and / or optionally interrupted or substituted with 1 to 20 heteroatoms chosen from O, N, P and / or S, which may additionally comprise one or more cosmetically active groups (such as R or R '), with R2 representing a hydrocarbon radical, linear, cyclic or branched, saturated or unsaturated, in C1 -C30, preferablyC2-C20; Z represents (independently of each other in formula (IIIc)), a halogen atom (chlorine, iodine, bromine or fluorine); (4) the complexes corresponding to one of the following formulas (IVa), (IVb), (IVc) or (IV d):

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(IVa) (lVb) M- (Z) n-xCX) x (IV a)

R-M (Z) ., (X), (IVb) (X), (Z),.,., M-R'-M'- (Z),n,l-x (X), (IVc) RR'-M- (Z),. (X), (IVd) dans lesquelles : - M, M', n, R, R', R", X, x et Z ont la même signification que cidessus.

(IVa) (IVb) M- (Z) n-xCX) x (IVa)

RM (Z)., (X), (IVb) (X), (Z),.,., M-R'-M'- (Z), n, lx (X), (IVc) RR'- M- (Z) ,. (X), (IVd) in which: - M, M ', n, R, R', R ", X, x and Z have the same meaning as above.

dans lesquelles M, X, R, R', Ri, n et x ont les mêmes significations que ci-desssus pour les formules (1) et (II). Among the compounds of formula (II) above, mention may be made especially of those corresponding to the following formulas (IIa) to (IId):

in which M, X, R, R ', R 1, n and x have the same meanings as above for formulas (1) and (II).

 The chelating group X may be chosen from carboxylic acids, s-ketones, n-diketones, s-keto esters, s-ketoamines, α- and β-hydroxy acids, and preferably ss-hydroxylated amino acids. salicylic acid and its derivatives. Acetoacetoxyethyl methacrylate, methyl alpha-hydroxymethyl methacrylate, e-N-methacryloyl-L-lysine and methacrylamino-4- or -5-salicylic acid may be mentioned in particular.

 Particularly preferred organometallic compounds include tetraethoxysilane, tetraisopropylorthotitanate, tetrapropylzirconate, methyltriethoxysilane, titanium tetraethoxide, titanium tetrabutoxide, tungsten triethoxide.

 The functionalized organic or silicone polymer of the composition of the sol / gel type according to the invention may be of the random, sequence and / or grafted type, and is preferably chosen from the group consisting of:

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 (a) alkyloxazoline homopolymers and copolymers such as poly (2-ethyl-2-oxazoline); (b) homopolymers and copolymers resulting from the copolymerization of (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, styrene sulfonic acid, acrylamido-2-methylpropanesulphonic acid, 2-sulfoethyl methacrylate, vinylsulfonic acid and vinylphosphonic acid; (c) homopolymers of acrylic or methacrylic esters or amides and their copolymers comprising monomers chosen from unsaturated carboxylic, sulphonic or phosphonic acids, vinyl esters or ethers, olefins, styrene, substituted styrenes such as hydroxystyrene, fluoro or perfluoroolefins, perfluoroalkyl (meth) acrylates, fluorinated vinyl compounds such as fluorinated vinyl ethers and unsaturated organosilanes, organosiloxanes or organopolysiloxanes; (d) homopolymers and copolymers of vinyl alcohol; (e) homopolymers of vinyl and / or allyl and / or methallyl esters or amides and their copolymers with monomers chosen from unsaturated carboxylic, sulphonic or phosphonic acids, vinyl esters or ethers, olefins, styrene and substituted styrenes such as hydroxystyrene, fluoro or perfluoroolefins, perfluoroalkyl meth (acrylates), fluorinated vinyl compounds such as fluorinated vinyl ethers and unsaturated organosilanes, organosiloxanes or organopolysiloxanes; (f) polyethers such as homopolymers and copolymers of methylene oxide, ethylene oxide, propylene oxide or tetarmethylene oxide;

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 (g) aromatic and / or aliphatic polyesters and ring-opening polyesters such as poly (caprolactone), polylactide, polyglycolide and copolymers thereof; (h) homo-and copolyolefins and homo-and copolycycloolefins such as polyethylenes, ethylene / vinyl acetate, ethylene / α-olefin, ethylene / cycloolefin, ethylene / (meth) acrylic ester and homo- and copolymers polypropylene, polybutene, polyisobutene and polynorbornene; (i) polyamides, polyesteramides and polyetheramides; (j) polyurethanes and polyureas which may comprise polyether, polyester and / or polyorganosiloxane blocks, optionally carrying fluorinated groups; (k) fluorinated polymers such as the products sold by Ausimont under the name Fomblin (perfluoropolyether); (1) natural polymers and modified natural polymers such as ether derivatives and / or cellulose or starch esters, polysaccharides, glycosaminoglucans and oligosaccharides, natural gums such as hydroxyalkyl guar gums such as hydroxypropylated gums , hydroxypropylated guar gums with carboxylic or quaternized functions, locust bean gum, xanthan gum, carrageenans, pectins, alginates, polypeptides or proteins such as collagen, elastin, gelatin or keratin ; (m) polyorganosiloxanes such as polydimethylsiloxanes, polymethylphenylsiloxanes, polyphenylsiloxanes, polyorganosiloxanes substituted laterally or at the chain end with amino acid groups, polyoxyethylene chains, amino or polyamino groups, hydroxy groups, acid groups

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 carboxylic, alkyl chains, vinyl or acrylic grafts or blocks, fluorinated or perfluorinated grafts or blocks; (n) polyorganophosphazenes; (o) polysilanes, polycarbosilanes or polysilazanes; and (p) their mixtures.

 According to a particular embodiment, the hydrocarbon homo-and copolymers as enumerated above can be sequenced and / or grafted with polysiloxane chains.

 The organic or silicone polymers listed may also comprise a cosmetically or dermatologically active group such as those listed above.

 If, among the organic or silicone polymers listed above, some are not functionalized, they can be either by reaction within the composition itself such as for example the polyorganosiloxanes, or by prior reaction by the usual methods before the formation of the composition.

 Among the particularly preferred organic or silicone polymers, there may be mentioned poly (2-ethyl-2-oxazoline), vinyl acetate / 4-tert-butylbenzoate / crotonic acid copolymer (65/25/10%), polydimethylsiloxane diols, polyethylene glycol, polyvinyl alcohol or polyvinylpyrrolidone.

 The amount of water present in the composition should be, as indicated above, such that it can allow the hydrolysis of the organometallic compound. Its pH, which can be acidic or basic (from 1 to 12), will depend on the nature of the organometallic compound present in the composition.

 Thus, when an alkyl titanate or alkyl zirconate is used as the organometallic compound, the pH of the water is acidic, preferably less than or equal to 3.

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 The alcohol, when present, is preferably selected from lower linear or branched (21-C6) aliphatic alcohols, such as ethanol or isopropanol.

 The weight ratio of the organometallic compound to the organic or silicone polymer may be between about 9: 1 and 1: 9, and preferably between 8: 2 and 2: 8.

 When the composition contains a precursor of the organic or silicone polymer, it is essentially one or more monomers capable of leading to an organic or silicone polymer functionalized by polymerization of unsaturated double bonds or by polycondensation during the application of the composition .

 The polymerization can be initiated conventionally thermally in the presence of conventional radical initiators, by UV irradiation, by electron beams ionically (cationic or anionic) or by any known method of polymerization.

 Although this particular embodiment can be implemented, it is nevertheless preferable, for practical reasons, to use a functionalized organic or silicone polymer already formed.

ou non, des filtres solaires UV-A et/ou UV-B, des enzymes, des amincissants, des hydratants, des vitamines, des a-hydroxyacides. According to a particular embodiment of the invention, the composition may contain cosmetic or dermatological active ingredients which, during the formation of the hybrid material, will be included in the matrix of said material. Among these various active agents, mention may be made, for example, of dyes, organic or inorganic pigments, which are colored

or not, UV-A and / or UV-B sunscreens, enzymes, slimming agents, moisturizers, vitamins, α-hydroxy acids.

 Furthermore, the composition may also contain various additives customary in cosmetics and dermatology, provided however that these additives can not interfere with the other constituents of the composition.

 The present invention also relates to a release composition, which, when applied to the keratinous material, and

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 especially the skin, does not pull on it, leaving it thus particularly flexible.

 This composition, intended to form a coating, on a keratinous substrate, of a crosslinked hybrid material, said composition being of the sol / gel type, is obtained by mixing: (a) at least one organometallic compound, (b) d at least one functionalized organic polymer or a precursor of said polymer, or at least one functionalized silicone polymer or a precursor of said polymer, the latter precursor being different from (a), (c) an amount of water sufficient to hydrolyze the organometallic compound, and (d) optionally at least one alcohol, said coating being non-reversible, the polymer being further present in the composition at levels of between 10 and 95% of the total weight of the the composition, preferably between 50 and 95% of the total weight of the composition, and more preferably between 60 and 90% of the total weight of the composition.

 The organometallic compound may be present in the composition at contents of between 1 and 90% of the total weight of the composition, preferably between 5 and 50% of the total weight of the composition, and even more preferably between 10 and 30% by weight. total of the composition.

 Of course, this composition can also be used as an anti-pollution agent or as a release agent. The organometallic compound, the organic or silicone polymer, the pH of the water, the proportions of the inorganic phase / organic phase and the alcohol can be chosen from those seen above.

 The following examples are intended to illustrate the invention without being limiting in nature.

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 EXAMPLE 1 Hybrid compound prepared by the sol-gel route Tetraisopropyl orthotitanate (Ti (Oipr) 4 (Fluka reference 87560) 5.97 g Polydimethylsiloxane-disilanol (PDMS-disilanol) (ABCR reference DMS-S12) 3.82 g - Ethanol 1 The PDMS-diol is diluted in ethanol, then the (Ti (Oipr) 4 'is stirred for 30 minutes and the hybrid compound is ready for use.

 EXAMPLE 2 Hybrid compound prepared by sol-gel tetrapropyl zirconate (Zr (Onpr) 4 (Fluka reference 96595) 70% in propanol 7.02g Polydimethylsiloxane-disilanol (PDMS-disilanol) (ABCR reference DMS-S21) 2 73 g Absolute ethanol reference Prolabo Normapur 1.40 g The PDMS-diol is diluted in ethanol and the (Zr (Onpr) 4 is then added.

 Stir 30 minutes. The hybrid compound is ready to be used.

Evaluation of the anti-adherent effect
The anti-adherence effect of the hybrid compounds with respect to diesel particles (NIST reference SRM1640) deposited on the surface of a reconstructed skin model (Episkin) is evaluated in vitro.

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'dépôt en excès de particules diesel (1, 5 mg par peau) * élimination de l'excès par retournement de la nacelle # séchage pendant 10 minutes sous hotte à flux laminaire La détermination de la surface recouverte par les particules est faite

2 par analyse de l'image. la surface recouverte est exprimée en mm2. The experimental protocol is as follows: # application of the concentration compound 2 l / cm2 topically (or the reference product (sebum) at 2 mg / cm2) * drying for two hours in a laminar flow hood

excess deposition of diesel particles (1, 5 mg per skin) * elimination of the excess by overturning of the nacelle # drying for 10 minutes under laminar flow hood The determination of the surface covered by the particles is made

2 by image analysis. the surface covered is expressed in mm2.

Results The results obtained are recorded in the following table.

<Tb>
<tb> Product <SEP> Surface <SEP> coated <SEP> Effect <SEP> non-stick
<tb> (mm
<tb> Example <SEP> 1 <SEP> 3 ~ 2 <SEP> Very <SEP> large
<tb> Example <SEP> 2 <SEP> 2 ~ 1 <SEP> Very <SEP> large
<tb> Sebum <SEP> 47 <SEP>: <SEP> t2 <SEP> Null
<tb> Cream <SEP> of <SEP> day <SEP> of <SEP> 502 <SEP> Nil
<tb> commerce
<Tb>

Claims (34)

1. Use as an anti-pollutant of a composition intended to form a coating, on a keratinous substrate, of a crosslinked hybrid material, said composition being obtained by the sol / gel process from the mixture of: (a) from least one organometallic compound, (b) at least one functionalized organic polymer or a precursor of said polymer, or at least one functionalized silicone polymer or a precursor of said polymer, the latter precursor being different from (a) (c) an amount of water sufficient to hydrolyze the organometallic compound, and (d) optionally at least one alcohol, said coating being of the non-reversible type.  2. Use as an anti-adherent agent of the composition defined in claim 1.  3. Use according to claim 1 or 2, to prevent the adhesion of particulate type pollutants on the surface of keratin materials, including the skin.  4. Use according to any one of the preceding claims, characterized in that the organometallic compound is chosen from the group consisting of: (1) the chelated alkoxides corresponding to one of the following formulas:

 in which : <Desc / Clms Page number 15> R-M- (Z) n-1 (IIIb) M- (Z), (IIIa)  in which: M, R 1 and n have the same meanings as above for the formulas (I), b represents the degree of complexation of the ligand X, x is the number of complexing ligands, and X represents a ligand or a chelating group mono-or polydentate that can be covalently bonded to a group that is capable of reacting with the organic or silicone polymer such as, for example, ethylenically unsaturated groups ((meth) acrylic, vinyl), halogenated, hydroxylated, carboxylated, thiol or epoxy groups; esters, amines, ureas, urethanes, acetoacetate group (ACAC) or a group derived from EDTA and its derivatives, said chelating group may also comprise a cosmetically or dermatologically active group; (3) metal halides corresponding to one of the following formulas (IIIl), (IIIb), (IIIc) or (IIId):

 M represents a transition metal of groups 1b to 7b, of group 8 or of the group of lanthanides of the periodic table, aluminum, boron, silicon, tin, cerium or iron, n represents valence of the metal, R 1 and R represent, independently of one another, a linear or branched C 1 -C 30, preferably C 1 -C 6, alkyl, R and R 'present, independently of one another a linear or branched alkyl radical, a cycloalkyl radical, an aryl radical which may or may not be substituted, and which radicals R and R 'may be substituted with groups which are capable of reacting with the organic or silicone polymer and which may also comprise a cosmetically or cosmetically group; dermatologically active; (2) chelated alkoxides having the following formula: <Desc / Clms Page number 16> RR'-M- (Z) n-x, (X), (IV d) in which: M, M ', n, R, R', R ", X, x and Z have the same meaning as above.  (X) x (Z) M-R "-M'- (Z) (X), (IVc) (IVC)

R-M- (Z)., (X) x (IVb) M- (Z) n-x (X) x (IVa)  (Z) -MR "M'- (Z) (IIIc) RR'-M- (Z) n-2 (IIId) (IIID) in which: - M, n, R, and R 'have the same meaning as above, - M and M ', independently of one another, have the same meaning, - R "denotes -O-, -NR-, -S- or a divalent hydrocarbon radical, linear, cyclic or branched , saturated or unsaturated, C1-C30, preferably C2-C20, optionally substituted (with a substituent chosen from the list given for R or R ') and / or optionally interrupted or substituted with 1 to 20 heteroatoms chosen from 0, N , P and / or S, which may further comprise one or more cosmetically active groups (such as R or R '), with R2 representing a hydrocarbon radical, linear, cyclic or branched, saturated or unsaturated, C 1 -C 4, of preferably C2-C20; Z represents, (independently of one another in formula (IIIc)), a halogen atom (chlorine, iodine, bromine or fluorine); (4) the complexes corresponding to one of the following formulas (IVa), (IVb), (IVc) or (IVd):

 5. Use according to claim 4, characterized in that the chelated alkoxides of formula (II) correspond to one of the following formulas:

<Desc / Clms Page number 17>  in which: M, X, R, R ', R 1, n and x have the same meanings as those given for formulas (I) and (II) of claim 4.

 6. Use according to claim 4 or 5, characterized in that the radicals R and R 'are substituted by a group selected from ethylenically unsaturated groups, halogenated groups, hydroxylated, carboxylated, thiols, epoxies, esters, amines, acids. amino and polypeptides.  7. Use according to any one of claims 4 to 6, characterized in that the chelating group X is covalently bound to a group capable of reacting with the organic or silicone polymer, selected from ethylenically unsaturated groups, the groups halogenated, hydroxylated, carboxylated, thiols, epoxy esters, amides, urethanes and ureas.  8. Use according to any one of claims 4 to 7, characterized in that the chelating group X is selected from carboxylic acids, ss-ketones, (3-diketones, ss-ketoesters, ss-ketoamines, the - and ss-hydroxyacids optionally ss-hydroxylated, salicylic acid and its derivatives.  9. Use according to any one of the preceding claims, characterized in that the organometallic compound is selected from the group consisting of tetraethoxysilane, tetraisopropylorthotitanate, tetrapropylzirconate, methyltriethoxysilane, titanium tetraethoxide, titanium tetrabutoxide, triethoxide of iron and tungsten triethoxide.  10. Use according to any one of the preceding claims, characterized in that the functionalized organic or silicone polymer is random, sequenced and / or grafted and is selected from the group consisting of: <Desc / Clms Page number 18>  (a) alkyloxazoline homopolymers and copolymers; (b) homopolymers and copolymers of monomers chosen from (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, styrene sulphonic acid, acrylamido-2-methylpropanesulphonic acid, 2-sulfoethyl methacrylate, vinylsulfonic acid and vinylphosphonic acid; (c) homopolymers of acrylic or methacrylic esters or amides and their copolymers comprising monomers chosen from unsaturated carboxylic, sulphonic or phosphonic acids, vinyl esters or 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 and / or methallyl esters or amides and their copolymers with monomers chosen from unsaturated carboxylic, sulphonic or phosphonic acids, vinyl esters or ethers, olefins, styrene and substituted styrenes, fluoro or perfluoroolefins, perfluoroalkyl meth (acrylates), fluorinated vinyl compounds and unsaturated organosilanes, organosiloxanes or organopolysiloxanes; (f) polyethers; (g) polyesters; (h) homo-and copolyolefins or cyclohefins; (i) polyamides, polyesteramides and polyetheramides; <Desc / Clms Page number 19>  (j) polyurethanes and polyureas which may comprise polyether, polyester and / or polyorganosiloxane blocks; (k) fluoropolymers; (1) natural polymers and modified natural polymers; (m) polyorganosiloxanes; (n) polyorganophosphazenes; (o) polysilanes, polycarbosilanes or polysilazanes; and (p) their mixtures.  11. Use according to claim 10, characterized in that the organic or silicone polymer is selected from the group consisting of poly (2-ethyl-2-oxazoline), vinyl acetate copolymer / 4-terbobutyl vinyl benzoate / crotonic acid ( 65/25/10%), polydimethylsiloxane diols, polyethylene glycol, polyamyl alcohol and polyvinylpyrrolidone.  12. Use according to any one of the preceding claims, characterized in that the pH of the water is between 1 and 12.  13. Use according to claim 12, characterized in that when the organometallic compound is an alkyltitanate or alkylzirconate, the pH of the water is less than or equal to 3.  14. Use according to any one of the preceding claims, characterized in that the alcohol is a lower aliphatic alcohol, linear or branched C1-C6.  15. Use according to any one of claims 1 to 11, characterized in that the weight ratio of the compound <Desc / Clms Page number 20>  organometallic to the organic or silicone polymer is between 9: 1 and 1: 9, preferably between 8: 2 and 2: 8.  16. Use according to any one of the preceding claims, characterized in that the composition also contains at least one cosmetic or dermatological active agent chosen from the group consisting of dyes, organic or inorganic pigments, colored or not, and sunscreens. UV-A and / or UV-B, enzymes, slimming agents, moisturizers, vitamins and α-hydroxy acids.  17. Use according to any one of the preceding claims, characterized in that it further contains at least one additive customary in cosmetics or dermatology. 90% of the total weight of the composition.  18. A composition for forming a coating, on a keratinous substrate, of a crosslinked hybrid material, said composition being of the sol / gel type and being obtained by the mixture of: (a) at least one organometallic compound, (b) d at least one functionalized organic polymer or a precursor of said polymer, or at least one functionalized silicone polymer or a precursor of said polymer, the latter precursor being different from (a), (c) an amount of water sufficient to hydrolyze the organometallic compound, and (d) optionally at least one alcohol, said coating being of the non-reversible type, the polymer being further present in the composition at contents of between 10 and 95% by weight total of the composition, preferably between 50 and 95% of the total weight of the composition, and more preferably between 60 and  19. Composition according to claim 18, characterized in that the organometallic compound is present in the composition at contents of between 1 and 90% of the total weight of the composition, preferably between 5 and 50%, and more preferably between 10 and 50%. and 30%. <Desc / Clms Page number 21>  20. Composition according to claim 18 or 19, characterized in that the organometallic compound is chosen from the group consisting of: (1) chelated alkoxides corresponding to one of the following formulas:

 in which: M represents a transition metal of groups 1b to 7b, of group 8 or of the group of lanthanides of the periodic table, aluminum, boron, silicon, tin, cerium or iron, represents the valence of the metal, R 1 and R 2 represent, independently of one another, a linear or branched C 1 -C 30, preferably C 6 -C 6, alkyl radical, R and R 'represent, independently one of the other, an alkyl radical, linear or branched, a cycloalkyl radical, a substituted or unsubstituted aryl radical, said radicals R and R 'may be substituted by groups capable of reacting with the organic or silicone polymer and may further comprise a cosmetically or dermatologically active group; (2) chelated alkoxides having the following formula:

 in which: M, Ri and n have the same meanings as above for formulas (1), b represents the degree of complexation of ligand X, x is the number of complexing ligands, and X represents a ligand or a mono- or polydentate chelating group capable of being covalently bound to a group likely to <Desc / Clms Page number 22> R-M- (Z)., (X), (IVb) (X) x (Z) n-1-xM-R '' - M '- (Z) n-1-x (X) x (IVc) M- (Z) n-x (X) x (IVa)  R "denotes -O-, -NR-, -S- or a linear, cyclic or branched, saturated or unsaturated, C 1 -C 3, preferably C 2 -C 20, divalent hydrocarbon radical which is optionally substituted (by a substituent selected from the list given for R or R ') and / or optionally interrupted or substituted with 1 to 20 heteroatoms selected from O, N, P and / or S, which may further comprise one or more cosmetically active groups (such as R or R). with R2 being a linear, cyclic or branched, saturated or unsaturated, C1-C30 hydrocarbon radical, preferably C-Co- - Z is (independently of each other in formula (IIIc) ), a halogen atom (chlorine, iodine, bromine or fluorine); (4) the complexes corresponding to one of the following formulas (IVa), (IVb), (IVc) or (IVd):

 (Z) -MR "-M'- (Z) (IIIc) RR'-M- (Z) n-2 (IIId) in which: M, n, R, and R 'have the same meaning as above; - M and M ', independently of each other, have the same meaning,

R-M- (Z) (IIIb) M- (Z), (IIIa)  react with the organic or silicone polymer such as for example ethylenically unsaturated groups ((meth) acrylic, vinyl), halogenated groups, hydroxylated, carboxylated, thiols, epoxies, esters, amines, ureas, urethanes, the acetoacetate group (ACAC ) or a group derived from EDTA and its derivatives, said chelating group possibly also comprising a cosmetically or dermatologically active group; (3) metal halides corresponding to one of the following formulas (IIIl), (IIIb), (IIIc) or (IIId): <Desc / Clms Page number 23> RR'-M- (Z)., (X) x (IVd) in which: - M, M ', n, R, R', R ", X, x and Z have the same meaning as above.  21. The composition as claimed in claim 20, characterized in that the chelated alkoxides of formula (II) correspond to one of the following formulas:

 in which : M, X, R, R ', R1, n and x have the same meanings as those given for formulas (1) and (II) of claim 3.  22. A composition according to claim 20 or 21, characterized in that the radicals R and R 'are substituted with a group selected from ethylenically unsaturated groups, halogenated groups, hydroxylated, carboxylated, thiols, epoxies, esters, amines, acids. amino and polypeptides.  23. A composition according to any one of claims 20 to 22, characterized in that the chelating group X is covalently bound to a group capable of reacting with the organic or silicone polymer selected from ethylenically unsaturated groups, the groups halogenated, hydroxylated, carboxylated, thiols, epoxy esters, amides, urethanes and ureas.  24. The composition according to claim 20, wherein the chelating group X is chosen from carboxylic acids, <Desc / Clms Page number 24>  β-ketoamines, optionally hydroxylated α- and β-hydroxy acids, salicylic acid and its derivatives.  25. Composition according to any one of claims 18 to 24, characterized in that the organometallic compound is selected from the group consisting of tetraethoxysilane, tetraisopropylorthotitanate, tetrapropylzirconate, methyltriethoxysilane, titanium tetraethoxide, titanium tetrabutoxide, iron triethoxide and tungsten triethoxide.  26. Composition according to any one of claims 18 to 25, characterized in that the functionalized organic or silicone polymer is of the random, sequence and / or grafted type and is chosen from the group consisting of: (a) homopolymers and alkyloxazoline copolymers; (b) homopolymers and copolymers of monomers chosen from (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, styrene sulphonic acid, acrylamido-2-methylpropanesulphonic acid, 2-sulfoethyl methacrylate, vinylsulfonic acid and vinylphosphonic acid; (c) homopolymers of acrylic or methacrylic esters or amides and their copolymers comprising monomers chosen from unsaturated carboxylic, sulphonic or phosphonic acids, vinyl esters or 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 and / or methallyl esters or amides and their copolymers with selected monomers <Desc / Clms Page number 25>  of the unsaturated carboxylic, sulphonic or phosphonic acids, vinyl esters or ethers, olefins, styrene and substituted styrenes, fluoro or perfluoroolefins, perfluoroalkyl meth (acrylates), fluorinated vinyl compounds and organosilanes, organosiloxanes or unsaturated organopolysiloxanes; (f) polyethers; (g) polyesters; (h) homo-and copolyolefins or cyclohefins; (i) polyamides, polyesteramides and polyetheramides; (j) polyurethanes and polyureas which may comprise polyether, polyester and / or polyorganosiloxane blocks; (k) fluoropolymers; (1) natural polymers and modified natural polymers; (m) polyorganosiloxanes; (n) polyorganophosphazenes; (o) polysilanes, polycarbosilanes or polysilazanes; and (p) their mixtures.  27. Composition according to claim 26, characterized in that the organic or silicone polymer is selected from the group consisting of poly (2-ethyl-2-oxazoline), vinyl acetate copolymer / 4-tert-butyl vinyl benzoate / acid crotonic (65/25/10%), polydimethylsiloxane diols, polyethylene glycol, polyamyl alcohol and polyvinylpyrrolidone. <Desc / Clms Page number 26>  28. Composition according to any one of claims 18 to 27, characterized in that the pH of the water is between 1 and 12.  29. Composition according to any one of claims 18 to 28, characterized in that when the organometallic compound is an alkyltitanate or alkylzirconate, the pH of the water is less than or equal to 3.  30. Composition according to any one of claims 18 to 29, characterized in that the alcohol is a lower aliphatic alcohol, linear or branched, C1-c6.  31. Composition according to any one of claims 18 to 30, characterized in that the weight ratio of the organometallic compound to the organic or silicone polymer is between 9: 1 and 1: 9, preferably between 8: 2 and 2: 8.  32. Composition according to any one of claims 18 to 31, characterized in that the composition also contains at least one cosmetic or dermatological active agent selected from the group consisting of dyes, organic or inorganic pigments, colored or not, UV-A and / or UV-B sunscreens, enzymes, slimming agents, moisturizers, vitamins and oc-hydroxy acids.  33. Composition according to any one of claims 18 to 32, characterized in that it further contains at least one additive customary in cosmetics or dermatology.  34. Use as an anti-pollutant or anti-adherent agent of a composition according to any one of claims 18 to 33.