EP0971685A1

EP0971685A1 - Cosmetic or dermatological composition forming, on a keratin substrate, a film in cross-linked hybrid material

Info

Publication number: EP0971685A1
Application number: EP98917304A
Authority: EP
Inventors: Jean Mondet; Francis Xavier Quinn; Clément Sanchez
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 1997-04-04
Filing date: 1998-04-03
Publication date: 2000-01-19
Also published as: PL336001A1; CA2284904A1; IL132108A0; AU717355B2; AU7055398A; BR9808454A; WO1998044906A1; RU2179842C2; JP4006028B2; HUP0002337A2; KR20010005970A; CN1251519A; AU717355C; JP2000510167A; US6352699B1

Abstract

The invention concerns a cosmetic or dermatological composition designed for forming a film, on a keratin substrate, in cross-linked hybrid material. Said composition is of the sol/gel type and is obtained by mixing: (a) at least an organometallic compound; (b) at least a functionalised organic polymer or said polymer precursor, or at least a functionalised silicone polymer or said polymer precursor, the latter precursor being different from (a); (c) a sufficient amount of water for hydrolysing the organometallic compound; and (d) optionally at least an alcohol; said film being non-reversible.

Description

Cosmetic or dermatological composition forming, on a keratinous substrate, a coating of a crosslinked hybrid material.

The present invention relates to a cosmetic or dermatological composition intended to form on a keratinous substrate, after drying, a film-forming coating in a crosslinked hybrid material, as well as its use in particular in the field of hair products, make-up products and skin care products.

By the expression "keratinous substrate" is meant according to the invention not only the hair, the eyelashes, the eyebrows and the nails, but also the skin. The formation of a film on a keratinous substrate is generally carried out in the cosmetic and dermatological fields by the use of various types of polymers in solution or in dispersion. After drying and depending on the nature of the polymer, films are obtained having mechanical and cosmetic characteristics specific to the intended use.

While numerous studies have so far focused on a wide variety of organic film-forming polymers intended in particular for hair compositions or for nail varnish compositions, very few studies have however focused on organic-inorganic polymers or also called materials. hybrids.

Indeed, the first studies result from an article by F. Sardo, American Cosmetics and Perfumeries, Vol. 87, 43-46 (1972) which describes, as a hair fixative, compositions containing copolymers of organic titanate and of dimethylsilicone, these being obtained by polymerization reaction of the silicone and of the organic titanate in the presence of water, and evaporation of the alcohol formed. However, it has been found that these organic-inorganic copolymers had the disadvantage of being neither soluble nor dispersible in alcohols, in particular in ethanol. Indeed, these have been found to be soluble only in non-cosmetic solvents such as aliphatic, aromatic and chlorinated hydrocarbons, and in particular in 1, 1, 1-trichloroethane. It is further indicated in this article that these organic-inorganic polymers have the major drawback of not being able to be removed, even after several washes, due to their very strong adhesion to the hair. It has also been described in patent US Pat. 'an aminoalkylalkoxysilane and from 0.005 to 1.5% by weight of an organic titanate and then to put the hair in the desired shape. According to this process, it is particularly recommended to keep the isopropanol solution away from any humidity.

In addition, unlike the article by F. SARDO, it is specified that this process only leads to temporary shaping of the hair and therefore therefore has a reversible character.

Patent EP-113 992 has also described a process for simultaneously fixing and conditioning the hair using a composition, stable in the absence of moisture, containing (A) a siloxane oligomer having at least a nitrogen-hydrogen bond and (B) an anhydrous additive, easily hydrolyzable, chosen from titanates, zirconates, vanadates, germanates and their mixtures. As in the article by F. SARDO, the solvent for the composition is an aliphatic hydrocarbon or an aliphatic halohydrocarbon, preferably 1,1,1-trichloroethane. After application of the composition to the hair, the hair is placed in a humid atmosphere in order to cause crosslinking of the siloxane oligomer and the easily hydrolyzable anhydrous additive. The crosslinked film formed on the hair is described in this patent as also being reversible, that is to say that after washing even with water, the hair loses its initial shape, this reversibility phenomenon being supposed to be due to de-crosslinking.

It follows from the analysis of this state of the art that no valid solution has been proposed in order to achieve by a process, simple in its implementation, the formation of a film of a hybrid material having a character non-reversible, by a sol / gel reaction in situ, from a stable or easy to apply cosmetic or dermatological composition.

It is indeed important in certain cosmetic applications, in particular in the treatment of hair and very particularly of the nails, to be able to obtain a film having good adhesion and being capable of withstanding numerous washes over time without its properties being affected. .

An object of the present invention is therefore to provide a composition for fixing and / or coloring the hair which, in a single application, after rapid drying, can lead to a long-lasting hold and / or coloring effect which can withstand washing and even after several shampoos without affecting the properties conferred on the hair.

Another object of the present invention is to provide an eyelash makeup composition such as a mascara, leading, after drying, to good coverage and coloring of the eyelashes while resisting water and ambient humidity. Another object of the present invention is to provide a composition of nail varnish, colored or colorless, giving rise to a film having excellent gloss, good surface hardness, good mechanical properties, in particular impact resistance (absence of flaking) and being remanent to washes with water, detergents and common organic cosmetic solvents.

Finally, another object of the present invention is to provide a composition for caring for or treating the skin with a view to giving it a protective and caring effect giving rise to an invisible film which can withstand dry rubbing, washing and detergents.

The present invention therefore relates to a cosmetic or dermatological composition intended to form a coating, on a keratinous substrate, in a crosslinked hybrid material characterized in that the said composition is of the sol / gel type and is obtained by mixing:

(a) at least one organometallic (or metallo-organic) 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.

By the expression "functionalized" is meant according to the invention the presence of functional groups which can interact physically or chemically.

By the term "non-reversible", it should be understood 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 de-crosslinked after several washes with water.

This non-reversibility of the hybrid material formed according to the invention is essentially due to the fact that it has a high degree of crosslinking on a nanometric scale and a very low surface energy. When the composition as defined above is applied to a keratinous substrate, a sol / gel reaction takes place, leading, after evaporation of the solvent (s), to the formation of a hybrid material by polycondensation and cross-linking at the nanoscale.

The crosslinked hybrid material thus formed can be of very varied structure. It can thus be in the form of a more or less dense network of chains of the inorganic polymer coming from the organometallic compound and chains of the organic or silicone polymer, these being linked together by physical, ionic and / or covalent bonds. . The hybrid material can also consist of mineral nodules originating from the organometallic compound and chains of the organic or silicone polymer, the nodules being linked physically or chemically to the chains of the organic or silicone polymer. The mineral nodules have a very small nanometric size, generally between 1 and 20 nanometers. These nodules can also take the form of aggregates or clusters. The organometallic compound of the composition of the sol / gel type according to the invention can be chosen from the group consisting of:

(i) the oxides of the transition metals of groups lb to 7b, of group 8 or of the lanthanide group of the periodic table,

(ii) oxides of aluminum, boron, silicon, tin, titanium, cerium or tungsten, and (iii) aluminum phosphates.

Preferably, the organometallic compound is chosen from the group consisting of:

(1) alkylsilanes, alkyltitanates or alkylzirconates corresponding to one of the following formulas: M-fOR _j ) ,, (la)

R-NrfOR.) _N _. (Ib) (O .- ^ zïM-RM O -) ^. ( the )

R ^

M- OR _α ) _n _, (Id)

R in which: M represents Si, Ti or Zr, n represents the valence of the metal,

R1 represents a linear or branched C1 radical _. -C ₃₀ , preferably in Cι-C ₆ ,

R and R ', independently of each other, represent an alkyl radical, linear or branched, a cycloalkyl radical, an aryl radical substituted or not, 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 ((meth) acrylic, vinyl, etc.) groups, halogen, hydroxylated, carboxylated, thiols, epoxy, esters, urethanes, ureas, amines, amino acids groups, polypeptides, etc., said radicals R and R ′ being able to comprise in addition a cosmetically or dermatologically active group chosen, for example, from a coloring group, a photochromic group, a group filtering UV-A radiation and / or radiation UV-B, an adhesion promoter group on keratin materials (amide, urethane, urea, hydroxyl, carboxyl, amino acid or polypeptide groups), a group facilitating make-up removal, a bactericidal group e, a chelating group in particular which can complex multivalent cations, a hydroxy acid, a neurosuppressant, an anti-hair loss group, an antioxidant group, an anti-free radical group, or a vitamin-carrying group; and

(2) chelated alkylsilanes, alkyltitanates or alkylzirconates corresponding to 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, x is the number of complexing ligands, and

X represents a ligand or a chelating group mono- or polydentate which can be covalently linked to a group capable of reacting with the organic or silicone polymer such as for example ethylenically unsaturated groups ((meth) acrylic, vinyl), halogen groups , hydroxylated, carboxylated, thiols, epoxy, esters, amines, ureas, urethanes, the acetoacetate group (ACAC) or a group deriving from EDTA and its derivatives, said chelating group possibly also comprising a cosmetically or dermatologically active group such as those defined above.

Among the compounds of formula (II) above, one can very particularly mention those corresponding to the following formulas (IIIa) to (IIId):

(Xτ-fOR ₁ -7 ^ 7 _: MRM- R ₁ t7 ^ X) _x (II le)

in which :

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

The chelating groups X can be chosen from carboxylic acids, β-ketones, β-diketones, β-ketoesters, β-ketoamines, α- and β-hydroxy acids, preferably β-hydroxylated amino acids, the salicylic acid and its derivatives. Mention may in particular be made of acetoacetoxyethylmethacrylate, methyl α-hydroxymethacylate, ε-N-methacryloyl-L-lysine, methacrylamino-4- or -5-salicylic acid. Among the organometallic compounds which are particularly preferred according to the invention, mention may in particular be made of tetraethoxysilane, tetraisopropylorthotitanate, tetrapropylzirconate, methyltriethoxysilane, titanium tetraethoxide, titanium tetrabutoxide, iron triethoxide or tungsten triethoxide.

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

(a) homopoly er and copolymers of alkyloxazoline 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-methyl-propane acid sulfonic, 2-sulfoethyl methacrylate, vinyl sulfonic acid and vinyl phosphonic acid;

(c) homopolymers of acrylic or methacrylic esters or amides and their copolymers with monomers chosen from unsaturated carboxylic, sulphonic or phosphonic acids, vinyl esters or ethers, olefins, styrene, substituted styrenes such as l 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 esters or amides and / or methallylics 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, (meth) acrylates of perfluoroalkyl, 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 tetramethylene oxide;

(g) aromatic and / or aliphatic polyesters and polyesters obtained by opening rings such as poly (caprolactone), polylactide, polyglycolide and their copolymers;

(h) homo- and copolyolefins and homo- and copolycyloolefins 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 contain polyether, polyester and / or polyorganosiloxane blocks, optionally carrying fluorinated groups;

(k) fluoropolymers such as the products sold by Ausimont under the name of "Fomblin ^® "(perfluoropolyether); (1) natural polymers and modified natural polymers such as ethers and / or esters of cellulose or starch derivatives, polysaccharides, glycosaminoglucans and oligosaccharides, natural gums such as hydroxyalkylated guar gums such as those hydroxypropylated , 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 end of the chain by amino acid groups, polyoxyethylene chains, amino or polyamino groups, hydroxy groups, carboxylic acid groups, alkyl chains, vinyl or acrylic grafts or sequences, fluorinated or perfluorinated grafts or sequences; (n) polyorganophosphazenes; (o) polysilanes, polycarbosilanes or polysilazanes; and (p) mixtures thereof.

According to a particular embodiment, the homo and hydrocarbon copolymers as listed above can be block and / or grafted by polysiloxane chains. The organic or silicone polymers can also contain a cosmetically or dermatologically active group such as those listed above.

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

Among the organic or silicone polymers which are particularly preferred according to the invention, mention may in particular be made of poly (2-ethyl-2-oxazoline), the vinyl acetate / 4-tert-butyl benzoate / crotonic acid copolymer (65/25/10 %), polydimethylsiloxane-diols, polyethylene glycol, polyvinyl alcohol or polyvinylpyrrolidone.

The amount of water present in the composition according to the invention must 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.

The alcohol, when present, is preferably chosen from lower aliphatic alcohols, linear or branched, Cι-C ₆ , such as ethanol or 1 isopropanol.

According to the invention, the weight ratio of the organometallic compound to the organic or silicone polymer is generally between approximately 9: 1 and 1: 9 and preferably between 8: 2 and 2: 8.

These ratios are relatively broad because, in certain cosmetic or dermatological applications, the mineral phase of the hybrid material will have to be preponderant compared to the organic phase or vice versa. Thus, when the composition is intended for capillary use for maintaining and / or coloring the hair, the mineral phase of the hybrid material is generally between 10 and 99%, and preferably between 20 and 75%. In makeup products such as mascaras, the mineral phase is generally between 10 and 99%, and preferably between 30 and 90%.

In nail varnishes, colorless or colored, the mineral phase of the hybrid material is generally between 50 and 99%, and preferably between 60 and 90%. Finally, when the composition is intended for application to the skin as an anti-wrinkle, the mineral phase is generally between 5 and 99%, and preferably between 10 and 70%.

When the composition according to the invention contains a precursor of the organic polymer or silicone, it is essentially one or more monomers capable of leading to an organic polymer or silicone 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 primers, by irradiation with UV radiation, by electron beams by ionic pathway (cationic or anionic) or by any known method of polymerization.

Although this particular embodiment can be implemented according to the invention, it is nevertheless preferred, for practical reasons, to use an organic polymer or functionalized silicone already formed. According to a particular embodiment of the invention, the composition can contain cosmetic or dermatological active agents which, during the formation of the hybrid material, will be included in the matrix of said material. Among these various active agents, there may be mentioned for example dyes, organic or inorganic pigments, colored or not, sun filters UV-A and / or UV-B, enzymes, slimming agents, moisturizers, vitamins, α -hydroxyacids, etc.

Furthermore, the compositions according to the invention may also contain various additives customary in cosmetics and in dermatology, provided however that these additives cannot interfere with the other constituents of the composition.

The composition according to the invention as defined above can be used as a hair product, in particular for maintaining or shaping the hairstyle. It can also add color to the hair and / or provide protection against the effects of UV radiation while providing hold or fixing properties.

Indeed, as has been specified above, the crosslinked hybrid material, during its formation, can include various active agents such as organic or mineral pigments and / or UV filters.

The hair composition is preferably in the form of a lotion for styling or brushing, or in the form of a gel. When the composition is in the form of a lotion, this can be packaged in a spray bottle, in a pump-action bottle or even in an aerosol container in the presence of a conventional cosmetic propellant in order to obtain either a spray or a foam.

The composition according to the invention can also be used as a product for caring for, treating or protecting the skin, in particular as a long-lasting sunscreen product insofar as the coating of crosslinked hybrid material has good resistance to water and sea baths. According to this embodiment, the crosslinked hybrid material contains, included, one or more UV filters.

The composition according to the invention may also be an eye makeup product such as a mascara or an eyeliner, or a nail product such as a colored nail varnish for making up the nails, or a colorless base or nail care varnish.

When the composition is in the form of an eye makeup product or a colored nail varnish, the organic and / or mineral pigments are also in the state included in the crosslinked hybrid material.

The present invention also relates to the use of the composition according to the invention in a method of treating the hair, with a view to maintaining and / or coloring it.

According to one embodiment of this method, a composition according to the invention is applied to the hair, preferably in the form of a spray, either using a pump bottle or using an aerosol. After spraying all over the hair, the composition is left to act until the solvent (s) has evaporated, optionally drying.

The hair can be put into the desired shape either before application or immediately after.

The drying time can be variable and depends on the nature of the composition applied to the hair.

If deformation means are used, these are then eliminated. The hair, after combing, is shiny and has a beautiful wave. Even after several washes with water and using shampoos, the initial waviness of the hair is retained. This demonstrates the irreversible nature of the attachment by adhesion of the hybrid material to the surface of the hair.

When the composition contains at least one hair dye and / or pigment, it may happen to be included in the hybrid material during the sol / gel reaction on the hair so that the coloring imparted to the hair is not found. be modified by washing with water or using successive shampoos. Another object of the present invention is the use of the composition as defined above in a process for making up the eyelashes.

According to this method, a sufficient amount of the composition is applied using a mascara brush, by carefully smoothing the eyelashes. After a variable drying time depending on the composition, the eyelashes have a shiny appearance, the makeup having good resistance to water and ambient humidity.

Another object of the invention is the use of the composition as defined above, in a process for making up or caring for the nails.

According to this method, a thin layer of the composition of the invention is applied to the surface of the nails, using a brush, which may be colorless or colored. The nails are left to dry for a variable period of time depending on the nature of the composition and it is found that the coating film deposited on the nails has excellent gloss and good surface hardness. In addition, this film is resistant to washing with water, detergents and organic solvents customary in cosmetics. When the varnish composition according to the invention contains at least one dye and / or pigment, this can be included in the hybrid coating material so that there is no variation in color over time if the coloring substance is soluble in water or in common organic solvents.

Finally, another object of the invention is the use of the composition as defined above in a process for treating or caring for the skin and more particularly in an anti-wrinkle process.

According to this process, the composition according to the invention is carefully applied to the parts of the skin where it is desired to obtain an attenuation of the wrinkles in particular present around the eyes. The composition can be applied by any suitable means in a thin layer and leads, after evaporation of the solvent (s), to the formation of an invisible transparent film exerting a tightening effect visually dissipating wrinkles. We will now give, by way of illustration, several examples of compositions according to the invention and of implementation thereof.

EXAMPLES

EXAMPLE 1 Nail Polish

A nail varnish according to the invention is obtained by mixing the following ingredients:

- Tetraethoxysilane 53.4%

- Poly (2-ethyl-2-oxazoline) in 50% solution in ethanol ... 19.0%

- Absolute ethanol 11.8%

- Water (pH = 1) 9.2% - Iron oxide / propylene glycol (50/50) 4.6%

- Titanium oxide / propylene glycol (50/50) 2.0 = 6

This nail varnish is obtained by mixing tetraethoxysilane in absolute ethanol and adding water brought to pH = 1 (addition of hydrochloric acid).

After having allowed to react for 30 minutes with stirring, the poly (2-ethyl-2-oxazolme) is added in 50% solution in ethanol and the stirring is continued for 15 minutes. Finally, the iron oxide is added to the propylene glycol and the stirring is continued for 30 minutes and, finally, the titanium oxide is added to the propylene glycol, still stirring for approximately 30 minutes.

A varnish is thus obtained which is easily applied to the surface of the nails and leads, after drying, to the formation of a homogeneous, shiny film having excellent persistence with water, detergents and also with alcohol.

It also has excellent scratch resistance.

EXAMPLE 2 Nail Polish

A nail varnish according to the invention is obtained using the following ingredients:

- Tetraisopropylorthotitanate 33.9%

- Polydimethylsiloxane-diol 41.4%

- Absolute ethanol 18.3 -ό

- Water (pH = 1) 0.4% - Iron oxide / propylene glycol (50/50) 4.0 t

- Titanium oxide / propylene glycol (50/50) 2%

This varnish is obtained according to the same procedure as that described above in Example 1 and carried out by application on the surface of the nails with a homogeneous and shiny film which also exhibits excellent remanence with water, detergents and alcohol.

EXAMPLE 3 Colored Fixing Composition for the Hair

This composition is prepared as follows:

10.4 g of diethoxydimethoxysilane are diluted in 4.6 g of ethanol and then 0.6 g of water is added at pH = 1 (addition of hydrochloric acid). After stirring (approximately 1 minute), 14 g of tetrapropyl zirconate in 70% solution in propanol are added, then 5.2 g of polydimethylsiloxane-diol (average molecular weight = 550). After stirring for 30 minutes, 0.15 g of Rhodamme 101 diluted in 1 g of ethanol is added to the solution. The dry extract of the solution is then brought to 25% by addition of a volatile silicone oil (D5 from the Company

Dow Corning). 2.5 g of the α-ω hydroxy / oxo silicone (viscosity 6500 is) from the Dow Corning company are then added.

The final solution obtained is then packaged in a container suitable for spraying on the hair.

After spraying and drying the hair, it is observed that it has a natural feel and is uniformly colored and shiny.

Even after several washes with water or with a shampoo, the initial coloring of the hair persists.

EXAMPLE 4: Mascara

A composition in the form of a mascara is obtained using the following ingredients:

- Tetraethoxysilane 28.9 *

- Methyltπethoxysilane 28.9% - Poly (2-ethyl-2-oxazolme) in 50% solution in ethanol 9.4%

- Absolute ethanol 13.9%

- Water (pH = 1) 9.45% - Iron oxide / propylene glycol (50/50) 9.45%

This mascara is obtained by mixing tetraethoxysilane, methyltriethoxysilane and absolute ethanol to which the water brought to pH = 1 is then added (addition of hydrochloric acid). The reaction medium is left to react for 30 minutes with stirring and then the poly (2-ethyl-2-oxazolme) is added in 50% solution in ethanol and the stirring is continued for approximately 15 minutes. Then iron oxide is added to the propylene glycol and the stirring is continued for 30 minutes. This mascara, by application using a brush to the eyelashes, leads, after evaporation of the volatile components, to the formation of a film, homogeneous, shiny and remanent with water.

EXAMPLE 5: Anti-wrinkle composition

This anti-wrinkle composition according to the invention is obtained from the following ingredients:

- Tetraisopropylorthotitanate 20.2% - Polydimethylsiloxane-diol 27.7 -B

- D ethoxydimethylsilane 47.2%

- Absolute ethanol 8.0%

- Water (pH = 1) 0.9%

This anti-wrinkle composition is obtained by diluting the diethoxydimethylsilane in 80% of ethanol and then adding the water brought to pH = 1 (addition of hydrochloric acid) and stirring for about 1 minute.

The tetraisopropylorthotitanate is then added under stirring and finally add the polydimethylsiloxane-diol with stirring for about 30 minutes.

A fluid composition is thus obtained which, when applied in the form of a thin layer on the wrinkles surrounding the eyes, leads, after evaporation of the volatile components, to the formation of a transparent and invisible film which exerts a tightening effect (effect stretching) thus noticeably reducing wrinkles around the eyes.

EXAMPLE 6 Hair-fixing composition

This composition is prepared as follows:

10.4 g of tretraethoxysilane are diluted in 2.3 g of ethanol and then 2 g of deionized water and 2.5 ml of IN HCl are added. After stirring and homogenization, 3.85 g of a 30% alcoholic solution of the vinyl acetate / vinyl 4-tert-butyl benzoate / crotonic acid copolymer are added.

(65/25/10% by weight) of molecular weight at the top of the GPC peak equal to 110,000 (described in FR-A-2439798) and neutralized with 2-amino-2-methylpropanol. 20 g of ethanol are then added for final dilution, and the mixture is stirred.

The final solution obtained is then packaged in a pump bottle and its vaporization is then carried out on hair previously shaped. After drying, the hair is shiny, detangles easily and has a nice wavy shape.

The hair, even after several washes using a shampoo consisting of 15% sodium lauryl ether sulfate and 3% cocoylbetaine and rinsing with water retain the initial shape which had been given to them and remain shiny.

Claims

1. Cosmetic or dermatological composition intended to form a coating, on a keratinous substrate, of a crosslinked hybrid material, characterized in that the said composition is of the sol / gel type and is obtained by mixing:

(a) 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 from (a),

(c) an amount of water sufficient to hydrolyze the organometallic compound, and

2. Composition according to claim 1, characterized in that the organometallic compound is chosen from the group consisting of:

(ii) oxides of aluminum, boron, silicon, tin, titanium, cerium or tungsten, and

(iii) phosphates.

3. Composition according to claim 1 or 2, characterized in that the organometallic compound is chosen from the group consisting of:

(1) alkylsilanes, alkyltitanates or alkylzirconates corresponding to one of the following formulas: M-rOR-) _n (la)

R-NKOR-) „_., (Ib)

(OR _f ) - ^ _τ MRM-tOR ₁ ) _rι _ ₁ (le)

in which: M represents Si, Ti or Zr, n represents the valence of the metal,

Ri represents a linear or branched alkyl radical, in Cι-C ₀ , preferably in Cι-C ₆ ,

R and R ', independently of one another, represent an alkyl radical, linear or branched, a cycloalkyl radical, an aryl radical substituted or not, said radicals R and R' being able to be substituted by groups capable of reacting with the organic or silicone polymer and which may additionally comprise a cosmetically or dermatologically active group; and (2) chelated alkylsilanes, alkyltitanates or alkylzirconates corresponding to the following formula: in which :

M, R 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 which can be covalently linked to a group capable of reacting with the organic or silicone polymer such as, for example, ethylenically unsaturated ((meth) acrylic, vinyl) groups, halogen, hydroxylated, carboxylated, thiol, epoxy, ester groups, amines, ureas, urethanes, the acetoacetate group (ACAC) or a group deriving from EDTA and its derivatives, said chelating group possibly also comprising a cosmetically or dermatologically active group.

4. Composition according to claim 3, characterized in that the chelated alkylsilanes, alkyltitanates or alkylzirconates correspond to one of the following formulas: M-tOR.t ^ r-tX) _(IIIa)

RM (OR _: - ^ X). _(IIIb) R ^

^" ^ ₇ rf O ¹ R ₁ ^ ₁ ⁽⁾ (I Hd)

R in which:

M, X, R, R ', Ri, n and x have the same meanings as those given for formulas (I) and (II) of claim 3.

5. Composition according to claim 3 or 4, characterized in that the radicals R and R ′ are substituted by a group chosen from ethylenically unsaturated groups, halogen, hydroxylated, carboxylated, thiol, epoxy, ester, amino groups, amino acids and polypeptides.

6. Composition according to any one of claims 3 to 5, characterized in that the chelating group is covalently linked to a group capable of reacting with the organic or silicone polymer, chosen from among the ethylenically unsaturated groups, the groups halogens, hydroxylated, carboxylated, thiols, epoxy, esters, amides, urethanes and ureas.

7. Composition according to any one of claims 3 to 6, characterized in that the chelating group X is chosen from carboxylic acids, β-ketones, β-diketones, β-ketoesters, β-ketoamines, α- and β- hydroxy acids optionally β-hydroxylated, salicylic acid and its derivatives.

8. Composition according to any one of claims 1 to 7, characterized in that the organometallic compound is chosen from the group consisting of tetraethoxysilane, tetraisopropylorthotitanate, tetrapropylzirconate, methyltriethoxysilane, tetraethoxide of titanium, tetrabutoxide of titanium , iron triethoxide and tungsten triethoxide.

9. Composition according to Claim 1, characterized in that the functionalized organic polymer or silicone is of the random, block and / or grafted type and is chosen from the group made up of:

(a) homopolymers and copolymers of alkyloxazoline;

(b) homopolymers and copolymers of monomers chosen from (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, styrene sulfonic acid, acrylamido-2-methyl-propane acid sulfonic, 2-sulfoethyl methacrylate, vinyl sulfonic acid and vinyl phosphonic acid;

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

(f) polyethers;

(g) polyesters;

(h) homo- and copolyolefins or cycloolefins; (i) polyamides and polyesteramides; (j) polyurethanes and polyureas which may contain 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.

10. Composition according to Claim 9, characterized in that the organic or silicone polymer is chosen from the group consisting of poly (2-ethyl-2-oxazoline), the vinyl acetate / vinyl 4-tert-butyl benzoate / crotonic acid (65/25/10%), polydimethylsiloxane-diols, polyethylene glycol, polyamyl alcohol and polyvinylpyrrolidone.

11. Composition according to claim 1, characterized in that the pH of the water is preferably between 1 and 12.

12. Composition according to claim 11, characterized in that when the organometallic compound is an alkyltitanate or alkylzirconate, the pH of the water is less than or equal to 3.

13. Composition according to claim 1, characterized in that the alcohol is a lower aliphatic alcohol, linear or branched, C _! -C ₆ .

14. Composition according to any one of claims 1 to 10, characterized in that the weight ratio of the organometallic compound to the organic polymer or silicone is generally between 9: 1 and 9: 1, and preferably between 8: 2 and 2: 8.

15. Composition according to any one of the preceding claims, characterized in that it also contains at least one cosmetic or dermatological active agent chosen from the group consisting of dyes, organic or mineral pigments, colored or not, filters UV-A and / or UV-B sunscreen, enzymes, slimming agents, moisturizers, vitamins and α-hydroxy acids.

16. Composition according to any one of the preceding claims, characterized in that it also contains at least one usual additive in cosmetics or dermatology.

17. A method for maintaining and / or coloring the hair, characterized in that it consists in applying by spraying onto the whole of the hair a composition according to any one of claims 1 to 16 and which is then leaves the composition to act until the solvent (s) has evaporated.

18. The method of claim 17 for coloring hair, characterized in that said composition contains at least one dye and / or pigment.

19. Method according to claims 17 and 18, characterized in that after having left the composition to act, the hair is dried.

20. Method for making up the eyelashes, characterized in that it consists in applying to the eyelashes, using a mascara brush, a sufficient amount of a composition according to any one of claims 1 to 16 and that the composition is left to act and dry by evaporation of the solvent (s).

21. A method of making up or caring for the nails, characterized in that it consists in applying to the surface of the nails, using a brush, a layer of the composition according to any one of claims 1 to 16 and the composition is then left to act until the solvent (s) has evaporated.

22. Method according to claim 20 or 21, characterized in that said composition contains at least one dye and / or pigment.

23. A method of treating or caring for wrinkles of the skin, characterized in that it consists in applying to the parts of the skin to be treated a thin layer of a composition according to any one of claims 1 to 16, and allowing the composition to act until the solvent (s) has evaporated.