FR2842419A1 - A method of broadening the UV absorption spectrum of an organic UVA filter used in cosmetic composition to protect against solar radiation by immobilizing it in a matrix produced by sol-gel from a silicon alkoxide and a surfactant - Google Patents

Abstract

A method of broadening the absorption spectrum of an organic UV filter active at least in UVA by immobilizing it in a matrix produced by the sol-gel route from a mixture of one or more silicon alkoxides, one or more surfactants and water. Independent claims are included for a method of sol-gel preparation of a material containing an organic UVA filter by mixing the filter, a silicon alkoxide, a surfactant and water in sufficient quantity for the partial or total hydrolysis of the silicon alkoxide and its condensation in the absence of organic solvent, for the material produced by the method and for a cosmetic and/or dermatological composition comprising the material.

Description

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METHOD FOR WIDENING THE SPECTRUM
OF UV ABSORPTION OF A UV-A SOLAR FILTER AND MATERIAL OBTAINED BY SOIL-GEL CONTAINING SAID
FILTERED
The present invention relates to a method for widening the absorption spectrum of UV rays of an organic sunscreen active at least in the wavelength range 320-400 nm, to a method for preparing a material containing said organic sunscreen, to a material capable of being obtained by said preparation process and to a cosmetic and / or dermatological composition containing such a material.

 We know that light radiations of wavelengths between 280 nm and 400 nm allow browning of the human epidermis and that rays of wavelengths between 280 nm and 320 nm, known under the name of UV -B, cause erythema and skin burns which can affect the development of natural tanning; this UV-B radiation must therefore be filtered.

 It is also known that UV-A rays, of wavelengths between 320 and 400 nm, which cause browning of the skin, are capable of inducing an alteration thereof, in particular in the case of skin sensitive or skin continuously exposed to solar radiation. UV-A rays are more penetrating than UV-B rays and cause in particular a loss of elasticity in the skin and the appearance of wrinkles, leading to premature aging.

They promote the initiation of the erythematous reaction or amplify this reaction in certain subjects and can even be the cause of phototoxic or photoallergic reactions. It is therefore desirable to also filter UV-A radiation, and in particular long UV-A radiation.

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 Thus, in order to ensure protection of the skin and keratin materials against UV radiation, sunscreen compositions generally comprising filters active in UV-A and filters active in UV-B are used.

 The Applicant has surprisingly discovered that the immobilization of an organic sunscreen active at least in UVA, in a matrix produced by the sol-gel route from at least one silicon alkoxide, at least one surfactant and water, led to the production of a material with a long UVB-UVA plateau absorption spectrum of UV rays. Such a material having the behavior of a broadband filter, has the advantage of absorbing UV rays over a wide range of wavelengths ranging from 280 to 400 nm.

 This material therefore has a better protective effect over a wider range of wavelengths than the sun filters used as such.

 Other advantageous properties are also obtained with this new solar material. In particular, the material and the compositions comprising it are film-forming, impart a pleasant feel and exhibit very good persistence with water, pure or saline, and with polar and non-polar cosmetic oils.

 The present invention therefore relates to a method of broadening the absorption spectrum of an organic sunscreen active at least in UV-A, in the wavelength range from 280 to 400 nm.

 The present invention also relates to a process for the preparation by sol-gel route of a material containing such an organic sunscreen active at least in UV-A.

 Another object consists of a material capable of being obtained from the preparation process according to the invention.

 The present invention also relates to a cosmetic and / or dermatological composition comprising such a material.

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 Other objects, characteristics, aspects and advantages of the invention will appear even more clearly on reading the description and the various examples which follow.

 The method for broadening the UV absorption spectrum of an organic sunscreen active at least in UV-A, according to the present invention, consists in immobilizing said filter in a matrix produced by sol-gel route from at least one silicon alkoxide, at least one surfactant and water.

 The expression organic sunscreen active at least in UV-A means any filter in the form of a simple molecule, dimer, oligomer or polymer, having absorption properties in UV-A, that is to say in the wavelength range from 320 to 400 nm, and which may have absorption properties in UV-B (280-320 nm).

Among the organic sunscreens active at least in UVA, which can be used according to the invention, there may be mentioned in particular: (1) dibenzoylmethanes such as - 2-methyldibenzoylmethane, - 4-methyldibenzoylmethane, - 4-isopropyldibenzoylmethane or Isopropyl Dibenzoylmethane, sold under the name "EUSOLEX # 8020" by MERCK, - 4-tert-butyldibenzoylmethane, - 2,4-dimethyldibenzoylmethane, - 2,5-dimethyldibenzoylmethane, - 4, 4'-diisopropyldibenzoylmethane, - 4,4'-dimethoxydibenzoylmethane, - 4-tert-butyl-4'-methoxydibenzoylmethane or Butyl Methoxy- dibenzoylmethane, sold in particular under the trade name "PARSOL 1789" by HOFFMANN-LA
ROCHE, - 2-methyl-5-isopropyl-4'-methoxydibenzoylmethane, - 2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane, - 2,4-dimethyl-4'-methoxydibenzoylmethane,

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 - 2,6-dimethyl-4-tert-butyl-4'-methoxydibenzoylmethane.

dans laquelle : RI et R3, identiques ou différents, représentent un atome d'hydrogène, un atome d'halogène, un groupe OH, un groupe alkyle saturé ou non, linéaire ou ramifié en C1-C10, un groupe alcoxy saturé ou non, linéaire ou ramifié en C1-C10, ou un groupe HS03 ; R4 représente un atome d'hydrogène ou HS03 ; R2 représente un groupe hydroxy ; groupe OR5 où R5 représen- te un groupe alkyle, saturé ou insaturé, linéaire ou ramifié en CIC10 ; ou bien un groupe de structure suivante :

dans laquelle R6 représente un atome d'hydrogène ou HS03 ; ou bien un groupe de formule suivante : Mention may also be made of other dibenzoylmethanes such as those described in documents FR 2 509 723 and FR 2 526 658, or also silanes or polyorganosiloxanes with dibenzoylmethane group (s) such as, for example, those described in application EP 0 383,655; (2) benzylidene-camphors active in UV-A such as those of formula (I) below:

in which: RI and R3, identical or different, represent a hydrogen atom, a halogen atom, an OH group, a saturated or unsaturated, linear or branched C1-C10 alkyl group, a saturated or unsaturated alkoxy group, linear or branched in C1-C10, or a group HS03; R4 represents a hydrogen atom or HS03; R2 represents a hydroxy group; group OR5 where R5 represents an alkyl group, saturated or unsaturated, linear or branched in CIC10; or a group with the following structure:

in which R6 represents a hydrogen atom or HS03; or a group of the following formula:

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ou bien un groupe de formule suivante :

dans lesquelles :
Z représente un atome d'oxygène ou un groupe -NH- ; R7, R8, R9 et R10, identiques ou différents, représentent un atome d'hydrogène, un atome d'halogène, un groupe OH, un groupe alky- le, saturé ou non, linéaire ou ramifié en C1-C10 ; un groupe al- coxy, saturé ou non, linéaire ou ramifié en CI-CI, ou un groupe
HS03.

or a group of the following formula:

in which :
Z represents an oxygen atom or a group -NH-; R7, R8, R9 and R10, identical or different, represent a hydrogen atom, a halogen atom, an OH group, an alkyl group, saturated or unsaturated, linear or branched C1-C10; an alkoxy group, saturated or not, linear or branched in CI-CI, or a group
HS03.

As an example of benzylidene-camphor active in UV-A, there may be mentioned, Terephthalylidene Dicamphor
Sulfonic Acid marketed under the name MEXORYL SX by
CHIMEX.

Mention may also be made of silanes or polyorganosiloxanes containing benzylidene-camphor group (s) such as, for example, those described in applications EP 0 335 777, EP 0 370 867, EP 0 507 692 and
EP 0 712 855; (3) benzimidazoles or benzoxazoles active in UV-A such as those of formula (II) below:

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dans laquelle : W représente un atome d'oxygène ou un groupe-NH- ; R11 représente un atome d'hydrogène ou HS03 ; R12 représente un groupe alcoxy, linéaire ou ramifié, comportant de 1 à 10 atomes de carbone environ ou un groupe de formule suivante :

dans laquelle :
Y représente un atome d'oxygène ou un groupe-NH- ; et
R13 représente un atome d'hydrogène ou HS03.

in which: W represents an oxygen atom or a group -NH-; R11 represents a hydrogen atom or HS03; R12 represents an alkoxy group, linear or branched, comprising from 1 to 10 carbon atoms approximately or a group of the following formula:

in which :
Y represents an oxygen atom or an NH- group; and
R13 represents a hydrogen atom or HS03.

 Mention may also be made of benzimidazoles or benzoxazoles such as those described in EP 0 944 624 as well as silanes or polyorganosiloxanes with group (s) or benzoxazole such as those described in EP 0 921 126; (4) bis (benzoazolyls) such as those described in patent applications EP0669323 and WO 02/39972, and in patent US2463264.

Examples that may be mentioned include Disodium Phenyl
Dibenzimidazole Tetra-sulfonate sold under the trade name
NEO HELIOPAN AP by HAARMANN AND REIMER.

Mention may also be made of silanes or polyorganosiloxanes containing bis (benzoazolyl) group (s) such as those described in the application.
EP 1,028,120;

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dans laquelle : R14 représente un atome d'hydrogène ou un groupe alkyle, saturé ou non, linéaire ou ramifié en C1-C10 ; R15 et R16, identiques ou différents, représentent un atome d'hydrogène, un atome d'halogène, un groupe OH, un groupe alkyle, saturé ou non, linéaire ou ramifié en C1-C10 ; un groupe alcoxy, saturé ou non, linéaire ou ramifié en C1-C10 ; ou un groupe HSO3 ; R17 représente un atome d'hydrogène, OH, un groupe alkyle, saturé ou non, linéaire ou ramifié en C1-C10 ou un groupe alcoxy, saturé ou non, linéaire ou ramifié en C1-C10 ; R18 représente OH, un atome d'hydrogène ou un groupe alkyle, saturé ou non, linéaire ou ramifié en C1-C10. (5) benzophenones such as those of formula (III) below:

in which: R14 represents a hydrogen atom or an alkyl group, saturated or not, linear or branched in C1-C10; R15 and R16, identical or different, represent a hydrogen atom, a halogen atom, an OH group, an alkyl group, saturated or unsaturated, linear or branched C1-C10; a linear or branched C1-C10 alkoxy group, saturated or not; or an HSO3 group; R17 represents a hydrogen atom, OH, an alkyl group, saturated or not, linear or branched in C1-C10 or an alkoxy group, saturated or not, linear or branched in C1-C10; R18 represents OH, a hydrogen atom or an alkyl group, saturated or not, linear or branched in C1-C10.

As other benzophenones, mention may also be made of silanes or polyorganosiloxanes with group (s) such as those described in documents EP-A-0 389 377, FR-A-2 657 351 and EP-A-0 655 453, and the Amino 2-hydroxybenzophenones such as those described in patent applications EP 1 046 391 and DE 10012408.

Examples of benzophenones are as follows: - Benzophenone-1 sold under the trade name UVINUL #
400 by BASF, - Benzophenone-2 sold under the trade name UVINUL # D-
50 by BASF,

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- Benzophenone-3 or Oxybenzone sold under the trade name UVINUL # M-40 by BASF, - Benzophenone-4 sold under the trade name UVINUL #
MS-40 by BASF, - Benzophenone-5, - Benzophenone-6 sold under the trade name HELISORB #
11 by NORQUAY, - Benzophenone-8 sold under the trade name SPECTRA- SORB # UV-24 by AMERICAN CYANAMID, - Benzophenone-9 sold under the trade name UVINUL
DS-49 by BASF, - Benzophenone-12, and - 2- (4-diethylamino-2-hydroxybenzoyl) benzoate n-hexyl.

(6) anthranilates such as Menthyl Anthranilate sold under the trade name NEO HELIOPAN MA by HAARMAN AND
REIMER; (7) imidazolines such as Ethylhexyl Dimethoxybenzylidene
Dioxoimidazoline Propionate; (8) bis-resorcinyl-triazines active at least in UV-A, such as those described in patent applications EP 0 775 698 and
EP 0 878 469. Mention may in particular be made, by way of example, of Anisotriazine sold under the trade name TINOSORB S by CIBA GEIGY; (9) benzalmalonates, and in particular those described in EP 350 386, s-triazines with group (s) such as those described in applications EP 0 507 691 and EP 0 790 243, such as 2,4,6-tris - (4'-aminobenzalmalonate diisobutyl) -s-triazine.
Mention may also be made of silanes or polyorganosiloxanes containing benzalmalonate group (s) such as those described in patent applications EP 0 392 882 or EP 0 709 080, and in particular the

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polyorganosiloxane with benzalmalonate functions sold under the trade name PARSOL SLX by HOFFMANN LA ROCHE; (10) benzotriazoles active at least in UV-A, such as s-triazines with benzotriazole group (s) described, for example, in patent applications EP 0 841 341 and EP 0 944 624, or derivatives methylene-bis (hydroxyphenyl) benzotriazole such as those described in US Patents 5,237,071, US 5,166,355, GB2303549,
DE19726184 and EP 0 893 119, for example: - Methylene bis-Benzotriazolyl Tetramethylbutylphenol sold in solid form under the trade name MIXXIM # BB / 100 by FAIRMOUNT CHEMICAL or in micronized form in aqueous dispersion under the trade name TINOSORB # M by
CIBA SPECIALTY CHEMICALS.

Mention may also be made of silanes or polyorganosiloxanes containing benzotriazole group (s) such as those cited in patent applications EP 0 392 883, EP 0 660 701 and more particularly: - Drometrizole Trisiloxane sold under the trade name MEXORYL # XL, as well as those cited in patent applications EP 0 708 108,
EP 0 711 778 and EP 0 771 779; (11) silanes or polyorganosiloxanes with group (s) such as those described in patent application EP 0 842 938; and (12) silanes or polyorganosiloxanes comprising at least one cinnamonitrile function with an alkylene or alkyleneoxy group, such as those described in patent application EP 0 716 089.

 The organic sunscreens active at least in the preferred UV-A are chosen from the following compounds: - Butyl Methoxydibenzoylmethane, - Terephthalylidene Dicamphor Sulfonic Acid, - Disodium Phenyl Dibenzimidazole Tetra-sulfonate,

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 - Benzophenone-3, - Benzophenone-4, - Benzophenone-5, - 2- (4-diethylamino-2-hydroxybenzoyl) benzoate n-hexyle, - Anisotriazine, - 2,4,6-tris- (4'- diisobutyl amino benzalmalonate) -s- triazine, - Drometrizole Trisiloxane, and - Methylene bis-Benzotriazolyl Tetramethylbutylphenol.

 Even more preferred organic sunscreens active at least in UV-A are the following UV-A filters: - Butyl Methoxydibenzoylmethane, - Anisotriazine, and - diisobutyl 2,4,6-tris- (4'-aminobenzalmalonate) -s- triazine.

 The organic filter active at least in UV-A more particularly preferred in the invention is Butyl Methoxydibenzoylmethane (PARSOL 1789).

The silicon alkoxides used in the process according to the present invention are in particular chosen from those corresponding to the following formulas: Si (ORa) 4 (I) R-Si (ORa) 3 (II) (RaO) 3-Si-R "- If (ORa) 3 (III)
R-Si (ORa) 2 (IV)
R 'in which:
Ra represents a linear or branched alkyl group, C1-30, preferably C1-6;
R and R ', independently of one another, represent a linear or branched alkyl group, a cycloalkyl group, an aryl group substituted or not, the said groups R and R' possibly comprising in addition a cosmetically or dermatologically group active;

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R "represents a linear or branched alkylene group, a cycloalkylene group, a substituted or unsubstituted arylene group, said group R" possibly comprising in addition a cosmetically or dermatologically active group.

 Among the cosmetically or dermatologically active groups which can be carried by the groups R, R ′ and R ", there may be mentioned, for example, a coloring group, a photochromic group, a group promoting adhesion to keratin materials as groups such as phoshates, phosphonates, phosphonic acid, amide, urethane, ureido, hydroxy, carboxy, thiol, amino acid or polypeptide, an anti-free radical group or a vitamin-carrying group.

 Among the silicon alkoxides defined above, very particularly preferred are tetraethoxysilane and methyltriethoxysilane.

 The surfactants used in the process according to the present invention are preferably nonionic. They are chosen in particular from alcohols, alkylphenols or polyethoxylated, polypropoxylated or polyglycerolated fatty acids with a fatty chain comprising from 6 to 32 carbon atoms, preferably from 8 to 18 carbon atoms, the number of ethylene oxide groups or propylene oxide being between 2 and 100, preferably between 2 and 50 and the number of glycerol groups being between 2 and 30.

 By way of example, mention may be made of polyethoxylated 4- (1,1,3,3-tetramethylbutyl) phenol sold under the name of Triton X100 by Union Carbide.

 Mention may also be made, as nonionic surfactants, of copolymers of ethylene and propylene oxides, of amphiphilic block polymers of molecular weights 1000 to 100,000, for example, poly (methyl methacrylate) / polyethylene glycol; condensates of ethylene and propylene oxides on fatty alcohols; polyethoxylated fatty amides preferably having 2 to 30 moles of ethylene oxide; polyglycerolated fatty amides preferably comprising 1 to 5 glycerol groups and in particular 1.5 to 4; polyethoxylated fatty amines preferably having 2 to 30 moles of ethylene oxide;

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 fatty acid esters of sorbitan ethoxylated with 2 to 30 moles of ethylene oxide; sucrose fatty acid esters, polyethylene glycol fatty acid esters, alkylpolyglucosides, carbamate or amide derivatives of N-alkylglucamines, aldobionamides, amine oxides such as oxides of alkylamines or N- acylamidopropyl morpholine.

 In a particular embodiment of the invention, a polyethoxylated alkylphenol is used such as polyethoxylated 4- (1,1,3,3-tetramethylbutyl) phenol sold under the name of Triton @ X100 by Union Carbide associated with a filter derived from dibenzoylmethane such as PARSOL # 1789.

 Another subject of the invention consists in a process for the preparation, by sol-gel route, of a material containing an active organic sunscreen at least in UV-A, which consists in mixing at least one active organic sunscreen at least in UV-A, at least one surfactant, at least one silicon alkoxide and water in an amount sufficient for the partial or total hydrolysis of the alkoxide and its condensation, in the absence of solvent organic.

 The organic sunscreens active at least in UV-A, the surfactants, the silicon alkoxides and the water used in said preparation process are as described above.

 We will choose for a given organic sunscreen, active at least in UV-A, the starting components, that is to say the surfactants and the silicon alkoxides, as well as their amounts and the amount of water of so that said filter is homogeneously dispersed in the final material.

 Said sunscreens are used in particular in the process of the present invention in an amount preferably ranging from 0.1% to 20% by weight, better still from 0.5 to 10% by weight relative to the weight of the alkoxide. silicon.

 The amount of surfactant used in the context of the invention depends on the solubility of the surfactant in the alkoxide / water mixture.

 It is such that the weight ratio of the surfactant to the alkoxide of

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 silicon is in particular between 0.01 and 99, and preferably between 1 and 60.

 Water is used in an amount sufficient for the total or partial hydrolysis of the silicon alkoxide and its condensation. This amount is between 0.01 and 99% by weight, preferably between 1 and 50% by weight relative to the total weight of the silicon alkoxide.

 The water preferably comprises a cosmetically acceptable mineral or organic acid, and more particularly hydrochloric acid, nitric acid, sulfuric acid or acetic acid. In the context of the present invention, it is preferred to use hydrochloric acid.

 The pH of the hydrolysis water is preferably in the range from 1 to 4, more preferably from 1 to 2.

 This process makes it possible to obtain a final material having an absorption spectrum of UV rays of the UVB-UVA plateau type. This final material has a wider absorption band than said organic sunscreen used as such.

 A preferred embodiment of the process of the invention consists in adding to the mixture of at least one surfactant, preferably nonionic, and of a sunscreen active at least in UV-A, firstly an alkoxide of silicon, and secondly water containing a mineral or organic acid, cosmetically acceptable.

 The invention also relates to the material containing said filter, capable of being obtained according to the preparation process described above.

 An additional object of the present invention is a cosmetic and / or dermatological composition comprising, in a cosmetically and / or dermatologically acceptable medium, an effective amount of at least one material containing an organic sunscreen active at least in UV-A , capable of being obtained according to the process for the preparation of the present invention.

 The term “cosmetically and / or dermatologically acceptable medium” means a medium compatible with all the materials

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 keratin such as the skin, hair, nails, eyelashes and eyebrows, lips and any other area of the body and face.

 This cosmetic and / or dermatological composition comprises said material in an effective amount ranging from 1% by weight to 99% by weight, preferably from 1% by weight to 60% by weight, relative to the total weight of the composition.

 Preferably, the material according to the invention is dried and ground, and added in the form of particles in a cosmetic and / or dermatological composition. The average particle size depends on the type of grinding method and the equipment used, and is preferably in the range of 0.1 to 50 m, more preferably 0.1 to 20 lira, and even more preferably from 0.1 to 10 m.

The cosmetic and / or dermatological compositions according to the present invention may also contain one or more complementary organic sunscreens which are not active in UV-A, chosen in particular from cinnamic acid derivatives; salicylic derivatives; camphor derivatives not active in UV-A; derivatives of B, B'-diphenylacrylate; triazine derivatives not active in UV-A; benzimidazole derivatives not active in UV-A; p-aminobenzoic acid derivatives (PABA); filter hydrocarbon polymers and filter silicones which are not active in UV-A; and alkylstyrene derivatives.

The cosmetic and / or dermatological compositions according to the invention may also contain pigments or else nano-pigments (average size of the primary particles: generally between
5 nm and 100 nm, preferably between 10 and 50 nm) of coated or uncoated metal oxides, such as, for example, nanopigments of titanium oxide (amorphous or crystallized in rutile form and / or anatase), of iron , zinc, zirconium or cerium which are all well-known photoprotective agents. Conventional coating agents are moreover alumina and / or aluminum stearate. Such nanopigments of metal oxides, coated or uncoated, are in particular described in patent applications EP-A-0 518 772 and EP-A-0 518 773.

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 The compositions according to the invention can also contain agents for tanning and / or artificial browning of the skin (self-tanning agents) such as, for example, dihydroxyacetone (DHA).

 The compositions in accordance with the present invention may also comprise conventional cosmetic adjuvants, in particular chosen from fatty substances, organic solvents, ionic or nonionic thickeners, softeners, antioxidants, anti-free radical agents, opacifiers, stabilizers, emollients, silicones, α-hydroxy acids, anti-foaming agents, hydrating agents, vitamins, insect repellents, perfumes, preservatives, anionic, cationic, amphoteric or nonionic surfactants , anti-inflammatory drugs, substance P antagonists, fillers, sequestrants, polymers, propellants, basifying or acidifying agents, dyes or any other ingredient usually used in the cosmetic and / or dermatological field, in particular for the manufacture of sunscreen compositions in the form of emulsions, and their mixtures.

 The fatty substances can consist of an oil or a wax or their mixtures. By oil is meant a compound which is liquid at room temperature. The term “wax” is intended to mean a compound which is solid or substantially solid at room temperature, and whose melting point is generally greater than 35 C. They also include fatty acids, fatty alcohols and fatty acid esters, linear or cyclic such as the benzoic, trimellitic and hydroxy-benzoic acid derivatives.

 As oils, mention may be made of mineral oils (petrolatum); vegetable (sweet almond oil, macadamia oil, blackcurrant seed, jojoba); synthetics such as perhydrosqualene, alcohols, acids or fatty esters (such as the benzoate of C12-C15 alcohols sold under the name "Finsolv TN" by the company Finetex, octyl palmitate, lanolate isopropyl, triglycerides including those of capric / caprylic acids), fatty or ethoxylated or propoxylated esters and ethers; silicone (cyclomethicone preferably with 4 or 5 atoms of

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 silicon, polydimethylsiloxane or PDMS) or fluorinated, polyalkylenes.

 As waxy compounds, there may be mentioned paraffin, carnauba wax, beeswax, hydrogenated castor oil.

 Among the organic solvents, mention may be made of lower alcohols and polyols.

 The thickeners can be chosen in particular from crosslinked polyacrylic acids, guar gums and modified or unmodified celluloses such as hydroxypropylated guar gum, methylhydroxyethylcellulose, hydroxypropylmethylcellulose and silicone gums such as, for example, a derivative of polydimethylsiloxane.

 The cosmetic and / or dermatological compositions according to the invention can be prepared according to techniques well known to those skilled in the art, in particular those intended for the preparation of emulsions of oil-in-water or water-in-type. oil.

 These cosmetic and / or dermatological compositions may be in particular in the form of a simple or complex emulsion (O / W, W / O, O / W / O or W / O / W) such as a cream, a milk, or in the form of a gel or a cream gel, powder, solid stick and optionally be packaged as an aerosol and be in the form of foam or spray.

 When it is an emulsion, the aqueous phase thereof may comprise a nonionic vesicular dispersion prepared according to known methods (Bangham, Standish and Watkins, J. Mol. Biol.

 13, 238 (1965), FR 2 315 991 e FR 2 416 008).

 The cosmetic and / or dermatological composition according to the invention can be used as a protective composition for keratin materials such as the skin, hair, nails, lips, eyelashes or eyebrows, against ultraviolet rays, such as sunscreen composition or as a makeup product.

 When the cosmetic composition according to the invention is used for protecting the skin against UV rays or as an antisun composition, it may be in the form of a suspension or a dispersion in solvents or fatty substances, under

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 form of nonionic vesicular dispersion, or emulsion, preferably, of the oil-in-water type, such as a cream or a milk, or in the form of an ointment, gel, cream gel, solid stick, powder, stick, aerosol foam or spray.

 When the cosmetic composition according to the invention is used for protecting the hair, it can be in the form of a shampoo, lotion, gel, emulsion, nonionic vesicular dispersion, and can constitute, for example, a composition to rinse, to apply before or after shampoo, before or after coloring or bleaching, before, during or after permanent or straightening, a styling or treating lotion or gel, a lotion or gel for brushing or setting, composition for perming or straightening, coloring or bleaching the hair.

 When the cosmetic composition according to the invention is used as a makeup product for the eyelashes, the eyebrows or the skin, such as an epidermis treatment cream, foundation, lipstick stick, eyeshadow, blush cheeks, mascara or "liner" also called "eyeliner", it can be in solid or pasty, anhydrous or aqueous form, like emulsions of oil-in-water or water-in-oil type, non vesicular dispersions ionic or dispersions.

 The following examples are given by way of illustration of the present invention.

Example 1
A material is prepared by the sol-gel route from the following ingredients:

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 Tetraethoxysilane (TEOS) (1) 5.0 g Water (0.1 N HCl) 0.9 g Triton @ X-100 0.75 g Parsol 1789 0.25 g (1) Sold by the company Fluka.

 Parsol 1789 is dispersed in Triton @ X-100 while heating at 40 ° C. for 30 minutes. TEOS is then added to the dispersion, with stirring at room temperature. Then, acidified water is added dropwise. The whole is stirred for 24 hours at room temperature. A ready-to-use material is obtained.

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Example 2
A material is prepared by the sol-gel route from the following ingredients:
Tetraethoxysilane (TEOS) 5.0 g Water (HCI 0, 1 N) 0.87 g
Poly (methyl methacrylate) block copolymer / 0.75 g polyethylene glycol (Molecular weights 1000/1000) (1)
2,4,6-tris (4'-aminobenzalmalonate diisobutyl) -s- 0.25 g triazine (1) Sold under the trade name ME 10-10 by the company Goldschmidt
2,4,6-tris- (4'-aminobenzalmalonate diisobutyl) -s-triazine is added to the surfactant ME 10-10 while heating for 20 minutes. Then add the TEOS. The homogeneous mixture obtained is left under stirring for 15 minutes at room temperature, then the acidified water is added and the whole is stirred for 2 hours. A ready-to-use material is obtained.

Example 3
A material is prepared by the sol-gel route from the following ingredients:
Tetraethoxysilane (TEOS) 5.0 g
Water (HCI 0, 1 N) 0.9 g
Poly (methyl methacrylate) block copolymer / 1.0 g polyethylene glycol (Molecular weights 1000/1000) (1)
Anisotriazine (2) 0.25 g (1) sold under the trade name ME 10-10 by the company Goldschmidt (2) sold under the trade name TINOSORB # S by CIBA GEIGY

<Desc / Clms Page number 20>

Tinosorb S is added to the ME 10-10 surfactant while heating for 20 minutes. TEOS is then added and the homogeneous mixture is left stirring for 15 minutes at room temperature. Then add the acidified water and stir for 2 hours. A ready-to-use material is obtained.

Measurement of the UV absorption spectra of the materials of examples 1, 2 and 3
The materials are deposited on glass plates (microscope slides). After evaporation of the volatile components of the mixture, films are obtained. The drying time of the films is rapid, that is to say between 1 and 3 minutes. The material is nevertheless left as is at room temperature for 24 hours, before measurement.

 By measuring the optical density of the films thus obtained, UV absorption spectra of the plate type are obtained for the three materials according to the invention of Examples 1,2 and 3. The spectra M1, M2 and M3, of the respective materials of the Examples 1,2 and 3 are shown respectively in Figures 1, 2 and 3 attached.

 Also shown in each Figure is the UV absorption spectrum of the filter alone, i.e. Parsol # 1789 (F1) in Figure 1, 2,4,6-tris- (4'-aminobenzalmalonate from diisobutyl) -s-triazine (F2) in Figure 2 and Tinosorb # S (F3) in Figure 3.

Claims (30)

 1. Method for broadening the UV absorption spectrum of an organic sunscreen active at least in UV-A, characterized in that it consists in immobilizing said filter in a matrix produced by sol-gel route from of a mixture of at least one silicon alkoxide, at least one surfactant and water.  2. Method according to claim 1, characterized in that the organic solar filter is chosen from: (1) dibenzoylmethanes, and silanes and polyorganosiloxanes with group (s) dibenzoylmethane; (2) benzylidene-camphors, and silanes and polyorganosiloxanes with benzylidene-camphor group (s); (3) benzimidazoles or benzoxazoles, and silanes and polyorganosiloxanes with group (s) or benzoxazole; (4) bis (benzoazolyls), silanes and polyorganosiloxanes containing group (s) bis (benzoazolyl); (5) benzophenones, silanes and polyorganosiloxanes containing benzophenone group (s), and amino 2-hydroxybenzophenones; (6) anthranilates; (7) imidazolines; (8) bis-resorcinyl-triazines; (9) benzalmalonates, s-triazines with group (s) and silanes and polyorganosiloxanes with group (10) benzotriazoles, s-triazines with group (s) and silanes and polyorganosiloxanes with group (s) (11) silanes or polyorganosiloxanes with group (s) and (12) silanes or polyorganosiloxanes comprising at least one cinnamonitrile function with alkylene or alkyleneoxy group.  3. Method according to claim 2, characterized in that the organic sunscreen active at least in UV-A is chosen from: - Butyl Methoxydibenzoylmethane, - Terephthalylidene Dicamphor Sulfonic Acid, <Desc / Clms Page number 22>  - Disodium Phenyl Dibenzimidazole Tetra-sulfonate, - Benzophenone-3, - Benzophenone-4, - Benzophenone-5, - n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate, - Anisotriazine, - 2,4 , 6-tris (4'-aminobenzalmalonate diisobutyl) -s-triazine, - Drometrizole Trisiloxane, and - Methylene bis-Benzotriazolyl Tetramethylbutylphenol.  4. Method according to claim 3, characterized in that the organic sunscreen active at least in UV-A is chosen from: - Butyl Methoxydibenzoylmethane, - Anisotriazine, and - 2,4,6-tris- (4 ' -isobutylaminobenzalmalonate) -s- triazine 5. Method according to claim 4, characterized in that the organic sunscreen active at least in UV-A is Butyl Methoxydibenzoylmethane.  6. Method according to any one of the preceding claims, characterized in that the silicon alkoxide is chosen from the compounds of the following formulas: Si (ORa) 4 (I) R-Si (ORa) 3 (II) (RaO ) 3-Si-R "-Si (ORa) 3 (III) Ri (ORa) 2 (IV) R 'in which: Ra represents a linear or branched, C1-30 alkyl group; R and R ′, independently of one another, represent a linear or branched alkyl group, a cycloalkyl group, an aryl group which may or may not be substituted, said groups R and R 'may additionally contain a cosmetically or dermatologically group active; <Desc / Clms Page number 23> R "represents a linear or branched alkylene group, a cycloalkylene group, a substituted or unsubstituted arylene group, said group R" possibly comprising in addition a cosmetically or dermatologically active group.  7. Method according to claim 6, characterized in that the silicon alkoxide is tetraethoxysilane or methyltriethoxysilane.  8. Method according to any one of the preceding claims, characterized in that the surfactant is a nonionic surfactant chosen from alcohols, alkylphenols or polyethoxylated, polypropoxylated or polyglycerolated fatty acids with a fatty chain comprising from 6 to 32 atoms of carbon, the number of ethylene oxide or propylene oxide groups being between 2 and 100 and the number of glycerol groups being between 2 and 30; copolymers of ethylene and propylene oxides; amphiphilic block polymers with molecular weights 1000 to 100,000; condensates of ethylene and propylene oxides on fatty alcohols; polyethoxylated fatty amides; polyglycerolated fatty amides preferably comprising 1 to 5 glycerol groups; polyethoxylated fatty amines; esters of sorbitan fatty acids ethoxylated with 2 to 30 moles of ethylene oxide; sucrose fatty acid esters, polyethylene glycol fatty acid esters, alkylpolyglucosides, carbamate or amide derivatives of N-alkylglucamines, aldobionamides and amine oxides.  9. Method according to claim any one of the preceding claims, characterized in that one uses a polyethoxylated alkylphenol associated with a filter derived from dibenzoylmethane.  10. A process for the preparation by sol-gel route of a material containing an organic sunscreen active at least in UV-A, characterized in that it consists in mixing at least one active organic sunscreen at least in the UV-A, at least one silicon alkoxide, at least one surfactant and water in an amount sufficient for the partial or total hydrolysis of the silicon alkoxide and its condensation, in the absence of organic solvent. <Desc / Clms Page number 24>  11. Preparation process according to claim 10, characterized in that the organic sunscreen active at least in UV-A is chosen from: (1) dibenzoylmethanes, and silanes and polyorganosiloxanes with dibenzoylmethane group (s); (2) benzylidene-camphors, and silanes and polyorganosiloxanes with benzylidene-camphor group (s); (3) benzimidazoles or benzoxazoles, and silanes and polyorganosiloxanes with group (s) or benzoxazole; (4) bis (benzoazolyls), silanes and polyorganosiloxanes containing group (s) bis (benzoazolyl); (5) benzophenones, silanes and polyorganosiloxanes containing benzophenone group (s), and amino 2-hydroxybenzophenones; (6) anthranilates; (7) imidazolines; (8) bis-resorcinyl-triazines; (9) benzalmalonates, s-triazines with group (s) and silanes and polyorganosiloxanes with group (10) benzotriazoles, s-triazines with group (s) and silanes and polyorganosiloxanes with group (s) ( 11) silanes or polyorganosiloxanes with group (s) and (12) silanes or polyorganosiloxanes comprising at least one cinnamonitrile function with alkylene or alkyleneoxy group.  12. Preparation process according to claim 11, characterized in that the organic sunscreen active at least in UV-A is chosen from: - Butyl Methoxydibenzoylmethane, - Terephthalylidene Dicamphor Sulfonic Acid, - Disodium Phenyl Dibenzimidazole Tetra-sulfonate, - Benzophenone-3, - Benzophenone-4, - Benzophenone-5, - n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate, - Anisotriazine, <Desc / Clms Page number 25>  - 2,4,6-tris- (4'-aminobenzalmalonate diisobutyl) -s-triazine, - Drometrizole Trisiloxane, and - Methylene bis-Benzotriazolyl Tetramethylbutylphenol.  13. Preparation process according to claim 12, characterized in that the organic sunscreen active at least in UV-A is chosen from: - Butyl Methoxydibenzoylmethane, - Anisotriazine, and - 2,4,6-tris- ( Diisobutyl 4'-aminobenzalmalonate) -s- triazine.  14. Preparation process according to claim 13, characterized in that the organic sunscreen active at least in UV-A is Butyl Methoxydibenzoylmethane.  15. Preparation process according to any one of claims 10 to 14, characterized in that the organic sunscreen active at least in UV-A is present in an amount ranging from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight relative to the weight of the silicon alkoxide.  16. Preparation process according to any one of claims 10 to 15, characterized in that the silicon alkoxide is chosen from the compounds of the following formulas: Si (ORa) 4 (I) R-Si (ORa) 3 ( II) (RaO) 3-Si-R "-Si (ORa) 3 (III) Ri (ORa) 2 (IV) R 'in which: Ra represents a linear or branched alkyl group, in CI-30, R and R ′, independently of one another, represent a linear or branched alkyl group, a cycloalkyl group, an aryl group which may or may not be substituted, said groups R and R 'may additionally contain a cosmetically or dermatologically group active; <Desc / Clms Page number 26> R "represents a linear or branched alkylene group, a cycloalkylene group, a substituted or unsubstituted arylene group, said group R" possibly comprising in addition a cosmetically or dermatologically active group.  17. Preparation process according to claim 16, characterized in that the silicon alkoxide is tetraethoxysilane or methyltriethoxysilane.  18. A method of preparation according to any one of claims 10 to 17, characterized in that the surfactant is a nonionic surfactant chosen from alcohols, alkylphenols or polyethoxylated, polypropoxylated or polyglycerolated fatty acids, with fatty chain comprising of 6 32 carbon atoms, the number of ethylene oxide or propylene oxide groups being between 2 and 100 and the number of glycerol groups being between 2 and 30; copolymers of ethylene and propylene oxides; amphiphilic block polymers with molecular weights 1000 to 100,000; condensates of ethylene and propylene oxides on fatty alcohols; polyethoxylated fatty amides; polyglycerolated fatty amides preferably comprising 1 to 5 glycerol groups; polyethoxylated fatty amines; fatty acid esters of sorbitane ethoxylated with 2 to 30 moles of ethylene oxide; sucrose fatty acid esters, polyethylene glycol fatty acid esters, alkylpolyglucosides, carbamate or amide derivatives of N-alkylglucamines, aldobionamides and amine oxides.  19. A method according to claim any one of claims 10 to 18, characterized in that one uses a polyethoxylated alkylphenol associated with a filter derived from dibenzoylmethane.  20. Preparation process according to any one of claims 10 to 19, characterized in that the weight ratio of the surfactant to the silicon alkoxide is between 0.01 and 99, and preferably between 1 and 60. <Desc / Clms Page number 27>  21. Preparation process according to any one of claims 10 to 20, characterized in that the water contains a cosmetically acceptable mineral or organic acid.  22. Preparation process according to any one of claims 10 to 21, characterized in that the pH of the water of the hydrolysis is in the range from 1 to 4, preferably from 1 to 2.  23. Preparation process according to any one of claims 10 to 22, characterized in that one adds to the mixture of at least one surfactant, preferably nonionic, and of an active sunscreen at least in the UV-A, firstly a silicon alkoxide, and secondly water containing a mineral or organic acid, cosmetically acceptable.  24. Material capable of being obtained by the process according to any one of claims 10 to 23.  25. Cosmetic and / or dermatological composition comprising, in a cosmetically and / or dermatologically acceptable medium, an effective amount of at least one material according to claim 24.  26. Composition according to claim 25, characterized in that the material is present in an amount from 1 to 99% by weight, preferably from 1 to 60% by weight, relative to the total weight of the composition.  27. Composition according to claim 25 or 26, characterized in that it also contains one or more complementary organic sunscreens which are not active in UV-A chosen from cinnamic acid derivatives; salicylic derivatives; camphor derivatives not active in UV-A; derivatives of ss, ss'-diph nylacrylate; triazine derivatives not active in UV-A; benzimidazole derivatives not active in UV-A; p-aminobenzoic acid derivatives (PABA); filter hydrocarbon polymers and filter silicones which are not active in UV-A; and alkylstyrene derivatives.  28. Composition according to any one of claims 25 to 27, characterized in that it further comprises pigments or nanopigments of metal oxides coated or not. <Desc / Clms Page number 28>  29. Composition according to any one of claims 25 to 28, characterized in that it comprises cosmetic adjuvants chosen from fatty substances, organic solvents, ionic or nonionic thickeners, softeners, antioxidants, anti agents -free radicals, opacifiers, stabilizers, emollients, silicones, α-hydroxy acids, anti-foaming agents, hydrating agents, vitamins, insect repellents, perfumes, preservatives, anionic surfactants , cationic, amphoteric or nonionic, anti-inflammatory drugs, substance P antagonists, fillers, sequestrants, polymers, propellants, basifying or acidifying agents, dyes and their mixtures.  30. Composition according to any one of claims 25 to 29, characterized in that it is in the form of an emulsion, simple or complex, or in the form of a gel or a gel-cream, powder, solid stick, or in the form of foam or spray.