FR2801209A1 - Cosmetic or dermatological composition comprises aqueous phase(s), oil phase(s), a UV photoprotective system and mono- or poly-carboxylic naphthalene acid(s) - Google Patents

Abstract

Cosmetic or dermatological composition comprises aqueous phase(s), oil phase(s), a UV photoprotective system and mono- or poly-carboxylic naphthalene acid(s). An Independent claim is also included for the use of the composition for cosmetic/dermatological purpose.

Description

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EMULSIONS WITHOUT EMULSIFYING FILTERS CONTAINING AT LEAST ONE
The subject of the present invention is a cosmetic or dermatological emulsion without emulsifier that can be used for the photoprotection of the skin and / or the hair, characterized in that it comprises: (a) at least one an aqueous phase and (b) at least one fatty phase; (c) at least one photoprotective system capable of filtering UV rays and (d) at least one naphthalene mono- or polycarboxylic acid derivative.

 The invention also relates to its uses for the manufacture of cosmetic or dermatological compositions for the photoprotection of the skin or hair.

 It is known that the luminous radiations of wavelengths between 280 nm and 400 nm allow the browning of the human epidermis, and that the wavelength rays more particularly between 280 and 320 nm, known by the name of UV-B, cause erythema and skin burns that can affect the development of natural tanning. For these reasons as well as for aesthetic reasons, there is a constant demand for means of control of this natural tan to thereby control the color of the skin; it is therefore necessary to filter this UV-B radiation.

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, especially in the case of a skin sensitive or skin continuously exposed to solar radiation. UV-A rays cause in particular a loss of elasticity of the skin and the appearance of wrinkles leading to premature cutaneous aging. They promote the triggering of the erythematous reaction or amplify this reaction in some subjects and may even be the cause of phototoxic or photoallergic reactions. Thus, for aesthetic and cosmetic reasons such as the preservation of the natural elasticity of the skin for example, more and more people wish to control the effect of UV-A on their skin. It is therefore desirable to also filter the UV-A radiation.

Numerous cosmetic compositions intended for the photoprotection (UV-A and / or UV-B) of the skin have been proposed to date.

These antisolar compositions are quite often in the form of an emulsion, of the oil-in-water type (ie a cosmetically and / or dermatologically acceptable support consisting of an aqueous dispersant continuous phase and a discontinuous phase. dispersed fatty) or water-in-oil (aqueous phase dispersed in a continuous fat phase), which contains, in various concentrations, one or more conventional organic filters, lipophilic and / or and / or mineral nanopigments of metal oxides, capable of selectively absorbing the harmful UV radiation, these filters (and their amounts) being selected according to the desired sun protection factor (the sun protection factor (SPF) expressed mathematically by the ratio of the irradiation time required for reach the erythematogenic threshold with the UV filter at the time necessary to reach the erythematogenic threshold without UV filter). In such emulsions, the hydrophilic filters are present in the aqueous phase and the lipophilic filters are present in the fatty phase.

The oil-in-water emulsions are, in general, more appreciated by the consumer than the water-in-oil emulsions, in particular because of their feel.

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 pleasant (near the water) and their presentation in the form of milk or non-fat cream; however, they also lose their effectiveness in UV protection when they come into contact with water; in fact, hydrophilic filters tend to disappear with water, by swimming in the sea or in the pool, in the shower or when practicing water sports; thus, the sunscreen compositions which contain them, alone or in combination with the lipophilic filters, no longer provide the initial protection sought, provided that the substrate (skin or hair) to which they have been applied comes into contact with the water.

It is possible to provide antisolar compositions having improved water resistance by using water-in-oil emulsions. Indeed, a hydrophilic filter is more persistent with water in a water-in-oil emulsion than with water-in-oil emulsions. 'in an oil-in-water emulsion. However, as indicated above, such compositions are not yet entirely satisfactory insofar as they leave after application an impression of fat particularly unpleasant for the user Thus, the need still remains to be able to have antisolar compositions providing the skin and / or the hair effective, stable and water-resistant sunscreen (persistence with water) and whose cosmetic performance would be comparable to those obtained with conventional oil / water emulsions.

 The Applicant has surprisingly and unexpectedly discovered that emulsifier-free emulsions containing the combination of a mono- or polycarboxylic naphthalene acid derivative and a photoprotective system capable of filtering UV rays in said emulsions not only allowed to obtain sunscreen compositions whose cosmetic performance was comparable to those generally obtained with a conventional sunscreen composition in the form of oil / water emulsion but also had good stability and improved water retention.

These discoveries are at the origin of the present invention.

The present invention relates to a cosmetic or dermatological emulsion without emulsifier, usable for photoprotection of the skin and / or hair, characterized in that it comprises: (a) at least one aqueous phase and (b) at least a fatty phase; (c) at least one photoprotective system capable of filtering UV rays and (d) at least one naphthalene mono- or polycarboxylic acid derivative.

By cosmetic or dermatological emulsion, within the meaning of the present invention and in the text that follows, is meant any emulsion whose aqueous phase and the fatty phase consist of cosmetically or dermatologically acceptable substances for topical application to human keratin materials including the skin, hair, eyelashes, eyebrows, lips, nails or mucous membranes.

By emulsion without emulsifier, within the meaning of the present invention and in the text which follows, is meant any oil-in-water emulsion (consisting of an aqueous dispersant continuous phase and a dispersed fat discontinuous phase) or any water-emulsion emulsion. in-oil (consisting of a continuous dispersant fatty phase and an aqueous dispersed discontinuous phase) containing no conventional emulsifying surfactant.

A photoprotective system capable of filtering UV rays means any system consisting of one or more organic compounds and / or mineral compounds filtering UVA and / or UV-B radiation.

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The subject of the present invention is also the use of an emulsifier emulsion as defined above for the manufacture of cosmetic compositions for the protection of the skin and / or the hair against ultraviolet radiation, in particular solar radiation.

dans laquelle : A, identiques ou différents, désignent un groupe OR' ; un groupe NR2R3 ou un cation M x est un nombre de 1 à 8 ; y est un nombre de 0 à 7 avec x+y < 8 ; B, identiques ou différents, désignent hydrogène, OR' ; un groupe NR2R3 ou un groupe - (C=O)R1;
R1, R2, R3, identiques ou différents, désignent hydrogène ; un alkyle en C1-C30, linéaire ou ramifié acyclique ou cyclique, éventuellement interrompu par un ou plusieurs hétéroatomes et éventuellement substitué par un ou plusieurs groupements B différents d'hydrogène ; un alcényle en C2-C30, linéaire ou ramifié acyclique ou cyclique, éventuellement interrompu par un ou plusieurs hétéroatomes (tels que 0, S, N) et éventuellement substitué par un ou plusieurs groupements B différents d'hydrogène ; un groupement aryle, aralkyle ou alkylaryle en C6-C3o , éventuellement substitué par un ou plusieurs groupements B différents d'hydrogène ; un hétérocycle en C3-C12, éventuellement substitué par un ou plusieurs groupements B différents d'hydrogène ; un halogène (tel que fluor, brome ou chlore) ; un groupe nitrile ; un groupe amino ; un groupe nitro ;un groupe cyano ; un groupe SO3H ou S03M ; un groupement comportant au moins un atome de silicium ; M représente un cation de métal alcalin, de métal alcalino-terreux, un groupe ammonium ou un reste d'amine ou d'alcanolamine quaternisée. Other characteristics, aspects and advantages of the present invention will appear on reading the detailed description which follows. The naphthalene mono- or polycarboxylic acid derivatives according to the invention may be chosen from compounds comprising at least one pattern corresponding to the following structure:

wherein: A, the same or different, denote a group OR '; an NR 2 R 3 group or a cation M x is a number from 1 to 8; y is a number from 0 to 7 with x + y <8; B, identical or different, denote hydrogen, OR '; an NR2R3 group or a - (C = O) R1 group;
R1, R2, R3, which may be identical or different, denote hydrogen; an acyclic or cyclic linear or branched C1-C30 alkyl, optionally interrupted by one or more heteroatoms and optionally substituted with one or more different B groups of hydrogen; C 2 -C 30 alkenyl, linear or branched acyclic or cyclic, optionally interrupted by one or more heteroatoms (such as O, S, N) and optionally substituted with one or more different groups B of hydrogen; a C 6 -C 30 aryl, aralkyl or alkylaryl group, optionally substituted with one or more different B groups of hydrogen; a C3-C12 heterocycle, optionally substituted with one or more different B groups of hydrogen; a halogen (such as fluorine, bromine or chlorine); a nitrile group; an amino group; a nitro group; a cyano group; a group SO3H or SO3M; a group comprising at least one silicon atom; M represents an alkali metal, alkaline earth metal cation, an ammonium group or a quaternized amine or alkanolamine residue.

Among the compounds of formula (I) known in the prior art and usable in accordance with the invention, mention may be made of: (1) mono- or polycarboxylic naphthalene acids and their salts, such as: 1-naphthalene carboxylic acid (available from ALDRICH-catologue 1999-2000); 2-naphthalene carboxylic acid (available from ALDRICH); 1-hydroxy-2-naphthalene carboxylic acid (available from ALDRICH); 2-hydroxy-1-naphthalene carboxylic acid (available from ALDRICH);

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 3-hydroxy-2-naphthalene carboxylic acid (available from ALDRICH); 6-hydroxy-2-naphthalene carboxylic acid (available from ALDRICH); 1,4-naphthalene dicarboxylic acid (available from ALDRICH); 2,3-naphthalene dicarboxylic acid (available from ALDRICH); 2,6-naphthalene dicarboxylic acid (available from ALDRICH) 2,6-naphthalene dicarboxylic acid 1,3-naphthalene dicarboxylic acid 1,2-naphthalene dicarboxylic acid 1-acid 5-Naphthalene dicarboxylic acid - 1,6-naphthalene dicarboxylic acid - 1,7-naphthalene dicarboxylic acid - 2,7-naphthalene dicarboxylic acid - Potassium salt of 4-sulpho-1,8 -naphthalene dicarboxylic acid - 1,2,3-naphthalene tricarboxylic acid - 1,2,3-naphthalene tricarboxylic acid - 1,2,4-naphthalene tricarboxylic acid - 1,2,5-naphthalene acid tricarboxylic acid - 1,2,6-naphthalene tricarboxylic acid - 1,2,7-naphthalene tricarboxylic acid - 1,2,8-naphthalene tricarboxylic acid - 1,3,5-naphthalene tricarboxylic acid - 1,3,7-naphthalene tricarboxylic acid - 1,3,8-naphthalene tricarboxylic acid - 1,4,5-naphthalene tricarboxylic acid - 1,4,6-2-naphthalene tricarboxylic acid - 2,3,5-naphthalene tricarboxylic acid ue - 2,3,6-naphthalene tricarboxylic acid - 1,4,5,8-naphthalene tetracarboxylic acid (available from ALDRICH) - 1,2,3,4-naphthalene tetracarboxylic acid - acid 1,2,5,8-naphthalene tetracarboxylic acid - 1,3,6,8-naphthalene tetracarboxylic acid - 1,4,5,8-naphthalene tetracarboxylic acid - 2,3,6,7- naphthalene tetracarboxylic acid (2) mono- or polyesters of mono- or polycarboxylic naphthalene acid such as - 2,3-naphthalene dicarboxylic acid dimethyl ester - 2,3-naphthalene dicarboxylic acid dimethyl ester - Methyl ester 2-naphthalene carboxylic acid (available from ALDRICH) (3) mono- or polyamides of mono- or polycarboxylic naphthalene acid such as the diamide of 2,3-naphthalene dicarboxylic acid.

More particularly, the naphthalene dicarboxylic acid derivatives containing glycols and alcohols sold under the trade name HALLBRITE TQ by the company C.P. HALL will be used more particularly.

The naphthalene mono- or polycarboxylic acid derivatives according to the invention are generally present in the compositions according to the invention at a total concentration of between approximately 0.1 and 20% by weight, and preferably between 0.5 and 10. % by weight, relative to the total weight of the composition.

The emulsifier-free emulsions according to the present invention preferably contain at least one crosslinked polymer of at least one non-associative ethylenically unsaturated monomer and / or an associative polymer.

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By associative polymer, within the meaning of the present invention and in the text that follows, is meant any amphiphilic polymer having in its structure at least one fatty chain and at least one hydrophilic portion.

 Among the non-associative crosslinked polymers of at least one ethylenically unsaturated monomer, in accordance with the invention, mention may be made in particular of: (i) crosslinked homopolymers or copolymers of at least one ethylenically unsaturated monomer with a sulphonic function, under free form or partially or totally salified; (ii) crosslinked copolymers of at least one ethylenically unsaturated monomer containing a carboxylic acid function, in free form or partially or totally salified form; or an ester or amide derivative, (iii) cross-linked homopolymers or copolymers of at least one cationic ethylenic unsaturation monomer of the ester or amide type.

 The sulfonic acid-functional monomers are chosen in particular from 2-acrylamido-2-methylpropanesulphonic acid and its salts.

The carboxylic acid functional monomers are chosen in particular from acrylic acid, methacrylic acid and their salts. Their esters are generally chosen from those of (meth) acrylic acid and C 1 -C 30 alcohols. Their amides are generally chosen from those of (meth) acrylic acid and C 1 -C 30 amines and more particularly methacrylamide and / or acrylamide
The cationic monomers of the ester or amide type are preferably chosen from ammonium (meth) acrylate, dialkylaminoalkyl (meth) acrylates, in particular dimethylaminoethylmethacrylate; dialkylaminoalkyl (meth) acrylamides and their quaternary or acidic salts; the alkyl radicals preferably being C 1 -C 4. The non-associative crosslinked polymers of the invention comprise at least one ethylenically unsaturated polyunsaturating crosslinking agent which is preferably chosen from divinylbenzene; tetraallyloxyethane; diallylic ether; polyglyceryl polyallyl ethers; allyl ethers of alcohols of the sugar series such as erythritol, pentaerythritol, arabitol, sorbitol or glucose; methylene-bis-acrylamide, ethylene glycol di- (methyl) acrylate, di- (meth) acrylamide, cyano-methylacrylate, vinyloxyethyl- (meth) acrylate or their metal salts.

Among the crosslinked non-associative homopolymers or copolymers of at least one ethylenically unsaturated monomer with a sulfonic function, neutralized to at least 90%, mention may be made more particularly of cross-linked homopolymers of 2-acrylamido-2-methyl-propane acid. sulphonic acid, neutralized to at least 90%, such as those described in the application
EP-A-0815828 (forming an integral part of the content of the description).

 crosslinked copolymers of 2-acrylamido-2-methyl-propanesulfonic acid and acrylamide, partially or totally neutralized (with a base such as sodium hydroxide, potassium hydroxide or an amine) as described in document EP-A -503 853 (forming part of the content of the description) and more particularly in Example 1.

Among the crosslinked non-associative homopolymers or copolymers of at least one cationic ethylenic unsaturation monomer of the ester or amide type, it is possible in particular to use (1) ammonium acrylate homopolymers or acrylate copolymers of ammonium and acrylamide such as the product sold under the name BOZEPOL C

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 NEW or the product PAS 5193 sold by HOECHST (they are described and prepared in FR 2 416 723, USP2798053 and USP 2 923 692); (2) homopolymers of dimethylaminoethyl methacrylate quaternized with methyl chloride such as the products sold under the names SALCARE 95 and SALCARE 96 by the company Allied Colloids or the copolymers of dimethylaminoethyl methacrylate quaternized by methyl chloride and acrylamide such as the SALCARE SC92 product sold by ALLIED COLLOIDS or the PAS 5194 product sold by HOECHST (they are described and prepared in EP-A-395 282). The associative polymers according to the present invention may be anionic, nonionic or cationic or amphoteric.

dans laquelle R' désigne H ou CH3, D désigne le radical éthylèneoxy, n est nul ou désigne un entier allant de 1 à 100, R désigne un radical hydrocarboné choisi parmi les radicaux alkyl, arylalkyle, aryle, alkylaryle, cycloalkyle, comprenant 8 à 30 atomes de carbone, de préférence 10 à 24, et plus particulièrement encore de 12 à 18 atomes de carbone Un motif de formule (11) plus particulièrement préféré selon la présente invention est un motif dans lequel R' désigne H, n est égal à 10, et R désigne un radical stéaryl (C18) Des polymères amphiphiles anioniques de ce type sont décrits et préparés, selon un procédé de polymérisation en émulsion, dans le brevet EP-0 216 479. Among the associative anionic polymers, mention may be made of those comprising at least one hydrophilic unit, and at least one fatty-chain allyl ether unit, more particularly from those whose hydrophilic unit is constituted by an ethylenic unsaturated anionic monomer, more particularly by a vinyl carboxylic acid and very particularly with an acrylic acid, a methacrylic acid or their mixtures, and whose fatty-chain allyl ether unit corresponds to the following monomer of formula (II):

in which R 'denotes H or CH3, D denotes the ethyleneoxy radical, n is nil or denotes an integer ranging from 1 to 100, R denotes a hydrocarbon radical chosen from alkyl, arylalkyl, aryl, alkylaryl and cycloalkyl radicals, comprising 8 to 30 carbon atoms, preferably 10 to 24, and more particularly 12 to 18 carbon atoms A unit of formula (11) more particularly preferred according to the present invention is a unit in which R 'denotes H, n is equal to 10, and R denotes a stearyl radical (C18) Anionic amphiphilic polymers of this type are described and prepared, according to an emulsion polymerization process, in patent EP-0 216 479.

Among these associative anionic polymers, polymers formed from 20 to 60% by weight of acrylic acid and / or methacrylic acid, from 5 to 60% by weight of (meth) acrylates, are particularly preferred according to the invention. from lower alkyls, from 2 to 50% by weight of fatty-chain allyl ether of formula (II), and from 0 to 1% by weight of a crosslinking agent which is a well-known copolymerizable polyethylenic unsaturated monomer, such as diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate, and methylenebisacrylamide.

Among these, the crosslinked terpolymers of methacrylic acid, ethyl acrylate, polyethylene glycol (10 EO) and stearyl alcohol (Steareth 10) are particularly preferred, in particular those sold by the company ALLIED COLLOIDS under the names SALCARE SC 80 and SALCARE SC90 which are 30% aqueous emulsions of a crosslinked terpolymer of methacrylic acid, ethyl acrylate and steareth-10-allyl ether (40/50/10).

Among the associative anionic polymers, mention may also be made of anionic polymers comprising at least one hydrophilic unit of the olefinic unsaturated carboxylic acid type, and at least one hydrophobic unit exclusively of the (C 10 -C 30) alkyl ester of unsaturated carboxylic acid type.

Preferably, these polymers are chosen from those whose hydrophilic unit of unsaturated olefinic carboxylic acid type corresponds to the following monomer of formula (III):

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dans laquelle, R1 désigne H ou CH3 ou C2H5, c'est-à-dire des motifs acide acrylique, acide méthacrylique ou acide éthacrylique, et dont le motif hydrophobe de type ester d'alkyle (C10-C30) d'acide carboxylique insaturé correspond au monomère de formule (III) suivante

dans laquelle, R2 désigne H ou CH3 ou C2H5 (c'est-à-dire des motifs acrylates, méthacrylates ou éthacrylates) et de préférence H (motifs acrylates) ou CH3 (motifs méthacrylates), R3 désignant un radical alkyle en C10-C30, et de préférence en C12-C22.

in which, R1 denotes H or CH3 or C2H5, that is to say units acrylic acid, methacrylic acid or ethacrylic acid, and whose hydrophobic unit of the alkyl ester (C10-C30) unsaturated carboxylic acid type corresponds to the monomer of formula (III) below

in which, R2 denotes H or CH3 or C2H5 (that is to say acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH3 (methacrylate units), R3 denotes a C10-C30 alkyl radical; and preferably C12-C22.

Alkyl (C 10 -C 30) esters of unsaturated carboxylic acids according to the invention include, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate.

Anionic polymers of this type are, for example, described and prepared according to US Pat. Nos. 3,915,921 and 4,509,949.

dans laquelle R2 désigne H ou CH3, R3 désignant un radical alkyle ayant de 12 à 22 atomes de carbone, (iii) et un agent réticulant, qui est un monomère insaturé polyéthylénique copolymérisable bien connu, comme le phtalate de diallyle, le (méth)acrylate d'allyl, le divinylbenzène, le diméthacrylate de (poly)éthylèneglycol, et le méthylène-bis-acrylamide. Among this type of associative anionic polymers, there will be used more particularly polymers formed from a monomer mixture comprising: (i) essentially acrylic acid, (ii) an ester of formula (IV) below:

wherein R2 denotes H or CH3, R3 denotes an alkyl radical having from 12 to 22 carbon atoms, (iii) and a crosslinking agent, which is a well-known copolymerizable polyethylenic unsaturated monomer, such as diallyl phthalate, (meth) allyl acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate, and methylene-bis-acrylamide.

Among this type of associative anionic polymers, use will more particularly be made of 95 to 60% by weight of acrylic acid (hydrophilic unit), 4 to 40% by weight of C10-C30 alkyl acrylate (hydrophobic unit). and 0 to 6% by weight of crosslinking polymerizable monomer, or those consisting of 98 to 96% by weight of acrylic acid (hydrophilic unit), 1 to 4% by weight of C 10 -C 30 alkyl acrylate ( hydrophobic pattern), and 0.1 to 0.6% by weight of crosslinking polymerizable monomer such as those described above.

Among said polymers above, the products sold by the company Goodrich under the trade names Pemulen TR1, Pemulen TR2 and Carbopol 1382, and even more preferentially Pemulen TR1, and the product sold by the company, are particularly preferred according to the present invention. SE PP IC company under the name COATEX SX.

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Among the associative anionic polymers, mention may also be made of terpolymers of maleic anhydride / α-olefin C30-C38 / alkyl maleate such as the product (maleic anhydride copolymer / [alpha] -olefin C30-C38 / maleate d isopropyl) sold under the name PERFORMA V 1608 by the company NEWPHASE TECHNOLOGIES Among the associative anionic polymers, there may be mentioned acrylic terpolymers comprising: (a) about 20% to 70% by weight of an unsaturated carboxylic acid [alpha ], ss-monoethylenic (b) about 20 to 80% by weight of a non-surfactant [alpha], ss-monoethylenic unsaturated monomer other than (a) (c) about 0.5 to 60% by weight a nonionic mono-urethane which is the reaction product of a monohydric surfactant with a monoethylenically unsaturated monoisocyanate such as those described in the patent application EP-A-0173109 and more particularly that described in US Pat. example 3 namely an aci terpolymer of methacrylic / methyl acrylate / dimethyl metaisopropenyl benzyl icocyanate of ethoxylated behenyl alcohol (400E) in a 25% aqueous dispersion.

The nonionic associative polymers used according to the invention are preferably chosen from: (1) celluloses modified with groups comprising at least one fatty chain; By way of example, mention may be made of: hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably CS-C22, such as the product NATROSOL PLUS GRADE 330 CS (alkyls in C16) sold by AQUALON, or the product BERMOCOLL EHM 100 sold by BEROL NOBEL, - those modified with polyalkylene glycol ether alkylphenol groups, such as the product AMERCELL POLYMER HM-1500 (polyethylene glycol (15) nonyl phenol ether) sold by the company Amerchol.

(2) hydroxypropyl guars modified with groups comprising at least one fatty chain such as the product ESAFLOR HM 22 (C22 alkyl chain) sold by LAMBERTI, the products RE210-18 (C14 alkyl chain) and RE205-1 ( C20 alkyl chain) sold by the company Rhone-Poulenc (3) polyether polyurethanes comprising in their chain, both hydrophilic sequences of mostly polyoxyethylenated nature and hydrophobic sequences which may be aliphatic sequences alone and / or sequences cycloaliphatic and / or aromatic.

(4) copolymers of vinyl pyrrolidone and hydrophobic fatty-chain monomers; by way of example, mention may be made of: the products ANTARON V216 or GANEX V216 (vinylpyrrolidone / hexadecene copolymer) sold by the company I.S.P.

 products ANTARON V220 or GANEX V220 (vinylpyrrolidone / eicosene copolymer) sold by the company I.S.P.

(5) copolymers of C 1 -C 6 alkyl methacrylates or acrylates and amphiphilic monomers comprising at least one fatty chain, such as, for example, the oxyethylenated methyl acrylate / stearyl acrylate copolymer sold by GOLDSCHMIDT under the name ANTIL 208

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 (6) copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers comprising at least one fatty chain, such as, for example, polyethylene glycol methacrylate / lauryl methacrylate copolymer.

 Preferably, the polyether polyurethanes comprise at least two hydrocarbon-based lipophilic chains having from C6 to C30 carbon atoms, separated by a hydrophilic sequence, the hydrocarbon chains may be pendant chains or chains at the end of the hydrophilic sequence. In particular, it is possible that one or more pendant chains are provided. In addition, the polymer may comprise a hydrocarbon chain at one end or at both ends of a hydrophilic block.

 The polyether polyurethanes may be multiblocked, in particular in the form of a triblock. The hydrophobic sequences may be at each end of the chain (for example: hydrophilic central block triblock copolymer) or distributed at both the ends and in the chain (multiblock copolymer for example). These same polymers may also be graft or star.

 Preferably, the associative nonionic polyurethane polyethers are triblock copolymers whose hydrophilic sequence is a polyoxyethylenated chain comprising from 50 to 1000 oxyethylenated groups. In nonionic polyurethane polyethers, there is a urethane bond between the hydrophilic blocks, hence the origin. by name.

 By extension also appear among the associative nonionic polyurethane polyethers, those whose hydrophilic sequences are linked by other chemical bonds to the lipophilic sequences.

As examples of associative nonionic polyurethane polyethers that may be used in the invention, mention may be made of the polymer C16-OE120-C16 sold by the company Servo Delden (under the name SER-AD FX1100, molecule with urethane function and molecular weight weight average of 1300), EO being an oxyethylenated unit. As an associative polymer, it is also possible to use also the urea-functional Rheolate 205 sold by the company Rheox or else the Rheolate 208, 204 or 212; as well as Acrysol RM 184, Aculyn 44 and Aculyn 46 from RHOM & HAAS.

Mention may also be made of the product ELFACOS T210 with a C12-14 alkyl chain and the product ELFACOS T212 with a C18 alkyl chain from AKZO.

The product DW 1206B from RHOM & HAAS comprising a C20 alkyl chain and a urethane linkage, sold at 20% solids content in water, may also be used.

It is also possible to use solutions or dispersions of these polymers, in particular in water or in an aqueous-alcoholic medium. For example, such polymers include SER-AD FX1010 and SER-AD 1035 sold by the company HULS. Rheolate 255, Rheolate 278 and Rheolate 244 sold by Rheox. The product DW 1206F and DW 1206J can also be used.

The polyurethanes that can be used in the invention are in particular those described in the article by G Fonnum, J. Bakke and Fk. Hansen - Colloid Polym Sci 271, 380389 (1993).

The cationic associative polymers used in the present invention are preferably chosen from quaternized cellulose derivatives and polyacrylates with amide side groups.

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 The quaternized cellulose derivatives are, in particular, quaternized celluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups containing at least 8 carbon atoms, or mixtures thereof, quaternized hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups containing at least 8 carbon atoms, or mixtures thereof.

The polyacrylates with amino side groups, quaternized or otherwise, have, for example, hydrophobic groups of the steareth type (stearyl alcohol polyoxyethylenated (20)).

The alkyl radicals borne by the above quaternized celluloses or hydroxyethylcelluloses preferably contain from 8 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups. It can be indicated as examples of C8 fatty chain quaternized alkylhydroxyethylcelluloses. -C30, the products QUATRISOFT LM 200, QUATRISOFT LM-X 529-18-A, QUATRISOFT LM-X 529-18B (C12 alkyl) and QUATRISOFT LM-X 529-8 (C18 alkyl) marketed by the company AMERCHOL and the products CRODACEL QM, CRODACEL QL (C12 alkyl) and CRODACEL QS (C18 alkyl) marketed by the company CRODA.

Examples of aminated side chain polyacrylates include polymers 8781-121B or 9492-103 from the company National Starch.

dans lesquelles R4 et R5, identiques ou différents, représentent un atome d'hydrogène ou un radical méthyle, R6, R7 et R8, identiques ou différents, représente un radical alkyle linéaire ou ramifié ayant de 1 à 30 atomes de carbone, Z représente un groupe NH ou un atome d'oxygène, n est un nombre entier de 2 à 5, E- est un anion issu d'un acide organique ou minéral, tel qu'un anion méthosulfate ou un halogénure tel que chlorure ou bromure. Among the amphoteric associative polymers of the invention, mention may be made of amphoteric polymers, crosslinked or non-crosslinked, branched or non-branched, obtainable by the copolymerization of 1) at least one monomer of formula (Va) or ( Vb)

in which R4 and R5, which may be identical or different, represent a hydrogen atom or a methyl radical, R6, R7 and R8, which may be identical or different, represents a linear or branched alkyl radical having from 1 to 30 carbon atoms, Z represents a NH group or an oxygen atom, n is an integer from 2 to 5, E- is an anion derived from an organic or inorganic acid, such as a methosulphate anion or a halide such as chloride or bromide.

2) at least one monomer of formula (VI):

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dans laquelle Rg et R10, identiques ou différents, représentent un atome d'hydrogène ou un radical méthyle; Z1 représente un groupe OH ou un groupe NHC(CH3)2CH2SO3H ; 3) d'au moins un monomère de formule (VI) :

dans laquelle Rg et R10, identiques ou différents, représentent un atome d'hydrogène ou un radical méthyle, X désigne un atome d'oxygène ou d'azote et R11 désigne un radical alkyle linéaire ou ramifié ayant de 1 à 30 atomes de carbone; 4) éventuellement au moins un agent de réticulation ou de branchement , l'un au moins des monomères de formule (Va), (Vb) ou (VII) comportant au moins une chaîne grasse ayant de 8 à 30 atomes de carbone et lesdits composés des monomères de formule (Va), (Vb), (VI) et (VII) pouvant être quatemisés par exemple par un halogénure d'alkyle en C1C4 ou un sulfate de dialkyle en C1-C4 .

in which R 8 and R 10, which may be identical or different, represent a hydrogen atom or a methyl radical; Z1 represents an OH group or an NHC (CH3) 2CH2SO3H group; 3) at least one monomer of formula (VI):

in which R 8 and R 10, which may be identical or different, represent a hydrogen atom or a methyl radical, X denotes an oxygen or nitrogen atom and R 11 denotes a linear or branched alkyl radical having from 1 to 30 carbon atoms; 4) optionally at least one crosslinking or branching agent, at least one of the monomers of formula (Va), (Vb) or (VII) comprising at least one fatty chain having from 8 to 30 carbon atoms and said compounds monomers of formula (Va), (Vb), (VI) and (VII) may be quaternized for example by a C1-C4 alkyl halide or a C1-C4 dialkyl sulphate.

The monomers of formula (Va) and (Vb) of the present invention are preferably chosen from the group consisting of: dimethylaminoethylmethacrylate, dimethylaminoethylacrylate, diethylaminoethylmethacrylate, diethylaminoethylacrylate, dimethylaminopropylmethacrylate, dimethylaminopropylacrylate, dimethylaminopropylmethacrylamide, dimethylaminopropylacrylamide "optionally quaternized for example by a C1-C4 alkyl halide or a C1-C4 dialkyl sulphate.

More particularly, the monomer of formula (Va) is chosen from acrylamidopropyltrimethylammonium chloride and methacrylamidopropyltrimethylammonium chloride.

The compounds of formula (VI) of the present invention are preferably selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, 2-methylcrotonic acid, 2- acrylamido-2-methylpropanesulphonic acid and 2-methacrylamido-2-methylpropanesulphonic acid. More particularly, the monomer of formula (VI) is acrylic acid.

The monomers of formula (VII) of the present invention are preferably chosen from the group consisting of C12-C22 and more particularly C16-C18 alkyl acrylates or methacrylates.

The crosslinking or branching agent is preferably chosen from N, N'methylene bis-acrylamide, triallyl methyl ammonium chloride, allyl methacrylate, n-methylolacrylamide, polyethylene glycol dimethacrylate, dimethacrylate and the like. ethylene glycol, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate and allylsucrose.

The polymers according to the invention may also contain other monomers such as nonionic monomers and in particular such as C1-C4 alkyl acrylates or methacrylates.

<Desc / Clms Page number 12>

The ratio of the number of cationic charges / anionic charges in these amphoteric polymers is preferably equal to about 1. The weight average molecular weight of the amphoteric associative polymers has a weight average molecular mass of greater than 500, preferably of between 10,000 and 10,000,000. and even more preferentially between 100000 and 8000000.

Preferably, the amphoteric associative polymers of the invention contain from 1 to 99 mole%, more preferably from 20 to 95 mole% and even more preferably from 25 to 75 mole% of compound (s) formula (Va) or (Vb). They also preferably contain from 1 to 80 mole%, more preferably from 5 to 80 mole% and even more preferably from 25 to 75 mole% of compound (s) formula (VI). The content of compound (s) of formula (VII) is preferably between 0.1 and 70 mol%, more preferably between 1 and 50 mol% and even more preferably between 1 and 10 mol%. The crosslinking or branching agent when it is present is preferably between 0.0001 and 1 mol% and even more preferably between 0.0001 and 0.1 mol%. Preferably, the molar ratio between the at least one compound of formulas (Va) or (Vb) and the compound (s) of formula (VI) vary from 20:80 to 95: 5 and more preferably from 25:75 to 75:25. The associative amphoteric polymers according to the invention are for example described in the patent application WO9844012.

The amphoteric polymers which are particularly preferred according to the invention are chosen from acrylic acid / acrylamidopropyltrimethylammonium chloride / stearyl methacrylate copolymers. The polymers in accordance with the invention are generally present in the antisolar compositions according to the invention at a concentration (expressed as active MA) between 0.01 and 10% by weight, and preferably between 0.1 and 5% by weight, relative to the total weight of the composition The photoprotective system according to the invention may contain one or more organic filters active in UVA and / or UVB (absorbers), water-soluble, fat-soluble or in the form of insoluble particles in both phases of the emulsion. These organic filters may be chosen in particular from cinnamic derivatives; dibenzoylmethane derivatives; salicylic derivatives, camphor derivatives; triazine derivatives such as those described in patent applications US 4367390, EP863145, EP517104, EP570838, EP796851, EP775698, EP878469 and EP 933376, the benzophenone derivatives; ss, ss'-diphenylacrylate derivatives, benzimidazole derivatives; bis-benzoazolyl derivatives such as those described in patents EP-A-0669323 and US 2,463,264; bis-hydroxyphenolbenzotriazole derivatives such as those described in US Pat. No. 5,237,071, US 5,166,355, GB-A-2,303,549, DE 197,266 and EP-A-893,119; p-aminobenzoic acid derivatives; the hydrocarbon filter polymers and the screening silicones such as those described in particular in the application WO-93/04665.

Examples of sunscreens that are active in the UV-A and / or UV-B range include p-aminobenzoic acid, oxyethylenated p-aminobenzoate (25mol), 2-ethylhexyl p-dimethylaminobenzoate,

<Desc / Clms Page number 13>

la 2,4,6-tris-[ p-(2'-éthylhexyl-1'-oxycarbonyl)anilino)-1,3,5-triazine, la 2-[p-(tertiobutylamido)anilino)-4,6-bis-[(p-(2'-éthylhexyl-1'-oxycarbonyl)anilino)-1,3,5- triazine, la 2,4-bis {[4-2-éthyl-hexyloxy)]-2-hydroxy]-phenyl}-6-(4-méthoxy-phenyl)-1,3,5-triazine ; le polymère de N-(2 et 4)-[(2-oxobom-3-ylidèn)méthyl] benzyl]-acrylamide, l'acide 1,4-bis-benzimidazolyl-phénylen-3,3',5,5'-tétrasulfonique et ses sels solubles

le 2,2' -méthylène-bis-[6-(2H-benzotriazol-2-yl)-4-( 1,1 ,3,3-tétraméthylbutyl)phénol], le composé (2,2'-méthylène-bis-[6-(2H-benzotriazol-2-yl)-4-(methyl)phénol], les polyorganosiloxanes à fonction benzalmalonate les polyorganosiloxanes à fonction benzotriazole tel que le Drometrizole Trisiloxane. ethyl p-aminobenzoate N-oxypropylenated glycerol p-aminobenzoate, homomenthyl salicylate, 2-ethylhexyl salicylate, triethanolamine salicylate, 4-isopropylbenzyl salicylate, 4-tert-butyl-4 methoxy dibenzoylmethane, 4-isopropyl dibenzoylmethane, 2-ethylhexyl 4-methoxy cinnamate, methyl diisopropyl cinnamate, isoamyl 4-methoxy cinnamate, diethanolamine 4-methoxy cinnamate, anthranilate menthyl, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, ethyl-2-cyano-3,3'-diphenylacrylate, 2-phenylbenzimidazole 5-sulfonic acid and its salts, 3- (4'-trimethylammonium) -benzyliden-bornan-2-on-methylsulfate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 2,4-dihydroxybenzophenone, 2,2 4,4'-Tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, aci α- (2-oxobom-3-ylidene) -tolyl-4-sulfonic acid and its soluble salts 3- (4'-sulfo) benzyliden-bornan-2-one and its soluble salts, 3- (4'-methylbenzylidene) ) -d, l-camphor, 3-benzylidene-d, 1-camphor, benzene 1,4-di (3-methylidene-10-camphosulfonic acid) and its soluble salts, urocanic acid,

2,4,6-tris- [p- (2'-ethylhexyl-1'-oxycarbonyl) anilino) -1,3,5-triazine, 2- [p- (tert-butylamido) anilino) -4,6- bis - [(p- (2'-ethylhexyl-1'-oxycarbonyl) anilino) -1,3,5-triazine, 2,4-bis {[4-2-ethylhexyloxy]] - 2-hydroxy] phenyl-6- (4-methoxy-phenyl) -1,3,5-triazine; N- (2 and 4) - [(2-oxobom-3-ylidene) methyl] benzyl] -acrylamide polymer, 1,4-bis-benzimidazolyl-phenyl-3,3 ', 5,5' -tetrasulfonic acid and its soluble salts

2,2 '-methylene-bis- [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], the compound (2,2'-methylenebis) [6- (2H-benzotriazol-2-yl) -4- (methyl) phenol], the benzalmalonate functional polyorganosiloxanes, the benzotriazole functional polyorganosiloxanes such as Drometrizole Trisiloxane.

The photoprotective system according to the invention may also contain pigments or even nanopigments (average size of the primary particles: generally between 5 nm and 100 nm, preferably between 10 nm and 50 nm) of metal oxides coated or not for example nanopigments of titanium oxide (amorphous or crystallized in rutile and / or anatase form), iron, zinc, zirconium or cerium which are all UV photoprotective agents well known per se 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-0518772 and EP-A-0518773.

Another subject of the invention consists of cosmetic or dermatological compositions characterized in that it comprises at least one emulsion as defined above.

<Desc / Clms Page number 14>

The compositions of the invention may furthermore comprise conventional cosmetic adjuvants, chosen especially from fatty substances, organic solvents, thickeners, softeners, opacifiers, stabilizers, emollients, antifoaming agents, moisturizing agents, perfumes, preservatives, polymers, fillers, sequestering agents, propellants, alkalizing or acidifying agents or any other ingredient usually used in cosmetics, in particular for the manufacture of sunscreen compositions in the form of emulsions.

The fatty substances may consist of an oil or a wax or mixtures thereof, and they also include fatty acids, fatty alcohols and fatty acid esters. The oils may be chosen from animal, vegetable, mineral or synthetic oils. and especially from liquid petroleum jelly, paraffin oil, silicone oils, volatile or not, isoparaffins, polyolefins, fluorinated and perfluorinated oils. Similarly, the waxes can be chosen from animal, fossil, vegetable, mineral or synthetic waxes known per se.

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

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

Of course, those skilled in the art will take care to choose this or these optional additional compounds and / or their amounts in such a way that the advantageous properties, in particular the persistence with water, stability, intrinsically attached to the emulsions according to the invention are not, or not substantially, altered by the addition or additions envisaged.

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

These compositions may be in particular in the form of an emulsion, simple or complex (O / W, W / O, O / W / H or W / O / W) such as cream, milk, gel or gel cream, powder, solid stick and optionally be packaged in aerosol and be in the form of foam or spray. Their aqueous phase may comprise a nonionic vesicular dispersion prepared according to known methods (Bangham, Standish and Watkins, Mol Mol, 13, 238 (1965), FR2315991 and FR2416008).

The cosmetic composition of the invention may be used as a composition for protecting the human epidermis or the hair against ultraviolet rays, as an antisolar composition or as a makeup product. When the cosmetic composition according to the invention is used for the protection of the human epidermis against UV rays, or as an antisolar composition, it may be in the form of a suspension or dispersion in solvents or of fatty substances, in the form of a nonionic vesicular dispersion or in the form of an emulsion, preferably of the type oil-in-water, such as cream or milk, in the form of 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 against UV rays, it may be in the form of a shampoo, a lotion, a gel, an emulsion or a nonionic vesicle dispersion and may constitute, for example, a composition. rinse, apply before or after shampoo, before or after

<Desc / Clms Page number 15>

 staining or discoloration, before, during or after permanent or straightening, a styling or treating lotion or gel, a lotion or a gel for blow-drying or setting, a composition of permanent or straightening, coloring or bleaching of the hair .

When the composition is used as a makeup product for eyelashes, eyebrows or skin, such as epidermis cream, foundation, lipstick stick, eyeshadow, blush, mascara or liner also called "eyeliner", it can be in solid or pasty, anhydrous or aqueous form, such as oil-in-water or water-in-oil emulsions, nonionic vesicular dispersions or suspensions As an indication, for antisolar formulations that comply According to the invention, which have an oil-in-water emulsion type support, the aqueous phase (comprising in particular the hydrophilic filters) generally represents from 50 to 95% by weight, preferably from 70 to 90% by weight, relative to the entire formulation, the oily phase (including in particular the lipophilic filters) from 5 to 50% by weight, preferably from 10 to 30% by weight, relative to the entire formulation.

As indicated at the beginning of the description, another object of the present invention resides in the use of an emulsion according to the invention for the manufacture of cosmetic compositions for the protection of the skin and / or the hair against ultraviolet radiation, especially solar radiation.

Another object of the present invention resides in the use of an emulsifier emulsion containing at least one naphthalene mono- or polycarboxylic acid derivative as a support for the preparation of a photoprotective cosmetic or dermatological composition containing at least one photoprotective system. capable of filtering UV rays in order to improve the water resistance of its filtering power (water retention).

A concrete example, but in no way limiting, illustrating the invention, will now be given

<Desc / Clms Page number 16>

<Tb>
<tb> COMPOSITION <SEP>%
<tb> in <SEP> weight
<tb> Benzoate <SEP> of alcohols <SEP> in <SEP> C <SEP> 12 / C <SEP> 15 <SEP> 10
<tb> (WITCONOL <SEP> TN <SEP> -WITCO) <SEP> ~~~~~~~~
<tb> Methylene <SEP> bis- (tetramethylbutyl <SEP> hydroxyphenyl <SEP> benzotriazole) <SEP> 25
<tb> Octocrylene <SEP> (Uvinul <SEP> N539-BASF) <SEP> 5
<tb> Butylmethoxy <SEP> dibenzoylmethane <SEP> (Parsol <SEP> 1789-HOFFMANN <SEP> LAROCHE) <SEP> 2
<tb> Copolymer <SEP> acid <SEP> acrylic <SEP> / <SEP> alkyl acrylate <SEP>(SEP> C10 <SEP>: C30 <SEP>) <SEP> crosslinked <SEP> 0. <SEP> 75
<tb>(<SEP> PEMULEN <SEP> TR1 <SEP> - <SEP> GOODRICH <SEP> @
<tb> Oxide <SEP> of <SEP> titanium <SEP> 3
<tb> (TITANIUM <SEP> DIOXIDE <SEP> MT100 <SEP> TV <SEP> - <SEP> TAYCA <SEP>) <SEP>
<tb> EDTA <SEP> 0.1 <SEP>
<tb> Derivative <SEP> of acid <SEP> naphthalene <SEP> dicarboxylic acid <SEP> to <SEP> termination <SEP> glycol <SEP> and <SEP> alcohol <SEP> 4
<tb> (proposed <SEP> under <SEP> the <SEP> name <SEP> HALLBRITE <SEP> TQ <SEP> by <SEP> the <SEP> company <SEP> CP
<tb> HALL)
<Tb>

Acide benzène 1,4-di(3-méthylidène-10-camphosuifonique) 0.5

Benzene 1,4-di (3-methylidene-10-camphosulphonic acid) 0.5

<Tb>
<tb> (Mexoryl <SEP> SX-CHIMEX)
<tb> Triethanolamine <SEP> qs <SEP> pH <SEP> = 7
<tb> Glycerine <SEP> 5
<tb> Conservatives
<tb> Demineralized water <SEP><SEP> qsp <SEP> 100
<Tb>

Claims (36)

1. cosmetic or dermatological emulsion without emulsifier, usable for the photoprotection of the skin and / or hair, characterized in that it comprises: a) at least one aqueous phase and b) at least one fatty phase; c) at least one photoprotective system capable of filtering UV rays; d) at least one naphthalene mono- or polycarboxylic acid derivative. 2. Emulsion according to claim 1, wherein the naphthalene mono- or poly-carboxylic acid derivative (s) are chosen from compounds comprising at least one unit corresponding to the following structure:

 in which: A, identical or different, denote a group OR1; an NR 2 R 3 group or a cation M x is a number from 1 to 8; y is a number from 0 to 7 with x + y # 8; B, identical or different, denote hydrogen, OR,; an NR2R3 group or a - (C = O) R1 group; R1, R2, R3, which may be identical or different, denote hydrogen; an acyclic or cyclic linear or branched C1-C30 alkyl, optionally interrupted by one or more heteroatoms and optionally substituted with one or more different B groups of hydrogen; C 2 -C 30 alkenyl, linear or branched acyclic or cyclic, optionally interrupted by one or more heteroatoms (such as O, S, N) and optionally substituted with one or more different groups B of hydrogen; a C 6 -C 30 aryl, aralkyl or alkylaryl group, optionally substituted with one or more different B groups of hydrogen; a C3-C12 heterocycle, optionally substituted with one or more different B groups of hydrogen; a halogen (such as fluorine, bromine or chlorine); a nitrile group; an amino group; a nitro group; a cyano group; group S03H or S03M; a group comprising at least one silicon atom; M represents an alkali metal, alkaline earth metal cation, an ammonium group or a quaternized amine or alkanolamine residue. An emulsion according to claim 1 or 2, wherein the naphthalene mono or polycarboxylic acid derivative (s) is selected from the group consisting of: (1) mono- or polycarboxylic naphthalene acids and their salts; (2) mono- or polyesters of mono- or polycarboxylic naphthalene acid and their salts; (3) mono or polyamides of mono- or polycarboxylic naphthalene acid and their salts; diamide of 2,3-naphthalene dicarboxylic acid and their salts. <Desc / Clms Page number 18> 4. Emulsion according to any one of claims 1 to 3, wherein the naphthalene mono- or polycarboxylic acid derivative (s) are derivatives of naphthalene dicarboxylic acid endowed with glycols and alcohols.  5. Emulsion according to any one of claims 1 to 3, wherein the naphthalene mono- or polycarboxylic acid derivative (s) present in the compositions according to the invention at a total concentration of between 0.1 and 20% by weight. about weight, and preferably between 0.5 and 10% by weight, relative to the total weight of the composition.  6. Emulsion according to any one of claims 1 to 4, wherein the UV filter (s) of the hydroxyphenylbenzotriazole derivative type are siliconized or hydrocarbon-based.  7. Emulsion according to any one of claims 1 to 6, characterized in that it comprises at least one non-associative crosslinked polymer of at least one ethylenically unsaturated monomer and / or an associative polymer.  An emulsion according to claim 7, wherein the non-associative crosslinked polymer of at least one ethylenically unsaturated monomer is selected from the group consisting of: (i) crosslinked homopolymers or copolymers of at least one ethylenically unsaturated monomer with sulphonic function, in free form or partially or totally salified; (ii) crosslinked copolymers of at least one ethylenically unsaturated monomer containing a carboxylic acid function, in free form or partially or totally salified form; an ester or amide derivative; (iii) crosslinked homopolymers or copolymers of at least one cationic ethylenic unsaturation monomer of the ester or amide type; (iv) their mixtures.  9. Emulsion according to claim 8, wherein the non-associative crosslinked homopolymers or copolymers of at least one ethylenically unsaturated monomer containing a sulfonic function are chosen from the group consisting of: - crosslinked homopolymers of 2-acrylamido-2-acid; methyl propanesulfonic acid, neutralized to at least 90%; crosslinked copolymers of 2-acrylamido-2-methyl-propanesulfonic acid and acrylamide partially or completely neutralized.  An emulsion according to claim 8, wherein the non-associative crosslinked homopolymers or copolymers of at least one cationic ethylenic unsaturation monomer of the ester or amide type are selected from: (1) ammonium acrylate homopolymers or copolymers ammonium acrylate acrylamide; (2) homopolymers of dimethylaminoethyl methacrylate quaternized with methyl chloride or copolymers of dimethylaminoethyl methacrylate quaternized with methyl chloride. Emulsion according to claim 7, wherein the associative polymer is anionic, nonionic, cationic or amphoteric. 12. Emulsion according to claim 11, wherein the associative anionic polymers are chosen from those comprising at least one hydrophilic unit and at least one fatty-chain allyl ether unit. <Desc / Clms Page number 19>  13. The emulsion according to claim 12, wherein the associative anionic polymers are chosen from those whose hydrophilic unit consists of at least one vinyl carboxylic acid and whose fatty-chain allyl ether unit corresponds to the following monomer of formula (II). :

 in which R 'denotes H or CH3, D denotes the ethyleneoxy radical, n is nil or denotes an integer ranging from 1 to 100, R denotes a hydrocarbon radical chosen from alkyl, arylalkyl, aryl, alkylaryl and cycloalkyl radicals, comprising 8 to 30 carbon atoms, preferably 10 to 24, and more particularly 12 to 18 carbon atoms. An emulsion according to claim 13, wherein the hydrophilic unit is acrylic acid, methacrylic acid or mixtures thereof. The emulsion of claim 4 or 5 wherein R 'is H, n is 10, and R denotes a stearyl radical (C18). 16. Emulsion according to any one of claims 13 to 15, wherein the associative anionic polymers are chosen from polymers formed from 20 to 60% by weight of acrylic acid and / or methacrylic acid, from 5 to 60 % by weight of lower alkyl (meth) acrylates, from 2 to 50% by weight of fatty-chain allyl ether of formula (II), and from 0 to 1% by weight of a crosslinking agent. An emulsion according to claim 16, wherein the associative anionic polymer is selected from crosslinked terpolymers of methacrylic acid, ethyl acrylate, polyethylene glycol (10 EO) stearyl alcohol ether (Steareth 10). Emulsion according to Claim 11, in which the associative anionic polymer is chosen from anionic polymers comprising at least one hydrophilic unit of the olefinic unsaturated carboxylic acid type, and at least one hydrophobic unit exclusively of the (C 10 -C 30) alkyl ester type. unsaturated carboxylic acid. 19. Emulsion according to claim 9, wherein the hydrophilic unit of olefinic unsaturated carboxylic acid type corresponds to the following monomer of formula (III):

 wherein R 1 is H or CH 3 or C 2 H 5, i.e., acrylic acid, methacrylic acid or ethacrylic acid units, and wherein the hydrophobic unit of the (C 10 -C 30) alkyl ester of unsaturated carboxylic acid corresponds to the monomer of formula (IV) below

 wherein R2 is H or CH3 or C2Hs; R3 denotes a C1-C30 alkyl radical, and preferably a C12-C22-20 radical. The emulsion according to claim 19, wherein the alkyl (C 10 -C 30) alkyl esters of unsaturated carboxylic acids are chosen from lauryl acrylate. , stearyl acrylate, <Desc / Clms Page number 20>  decyl acrylate, isodecyl acrylate, dodecyl acrylate, and the corresponding methacrylates. An emulsion according to any one of claims 18 to 20, wherein the anionic polymer is formed from a monomer mixture comprising: (i) essentially acrylic acid, (ii) an ester of formula (IV) next :

 wherein R2 is H or CH3, R3 is an alkyl radical having 12 to 22 carbon atoms, and iii is a crosslinking agent. 22. Emulsion according to any one of claims 18 to 21, wherein the associative anionic polymer is formed from a monomer mixture comprising from 95 to 60% by weight of acrylic acid, 4 to 40% by weight of C10-C30 alkyl acrylate, and 0 to 6% by weight of crosslinking polymerizable monomer, 23. Emulsion according to any of claims 18 to 21, wherein the associative anionic polymer is formed from a monomer mixture. comprising from 98 to 96% by weight of acrylic acid, 1 to 4% by weight of C 10 -C 30 alkyl acrylate, and from 0.1 to 0.6% by weight of polymerizable crosslinking monomer 24 Emulsion according to claim 11 wherein the nonionic associative polymers are selected from: (1) celluloses modified with moieties having at least one fatty chain; (2) hydroxypropyl guars modified with groups comprising at least one fatty chain; (3) polyether polyurethanes comprising in their chain, both hydrophilic sequences and hydrophobic sequences which may be aliphatic sequences alone and / or cycloaliphatic and / or aromatic sequences; (4) copolymers of vinyl pyrrolidone and hydrophobic fatty-chain monomers; (5) copolymers of C 1 -C 6 alkyl methacrylates or acrylates and amphiphilic monomers comprising at least one fatty chain; (6) copolymers of hydrophilic methacrylates or acrylates and hydrophobic monomers comprising at least one fatty chain. 25. Emulsion according to claim 24, wherein the celluloses modified with groups comprising at least one fatty chain are chosen from: hydroxyethylcelluloses modified with groups comprising at least one fatty chain such as alkyl, arylalkyl or alkylaryl groups, or their mixtures, and in which the alkyl groups are preferably C8-C22, - hydroxyethylcelluloses modified with alkyl phenol polyalkylene glycol ether groups. 26. Emulsion according to claim 24, wherein the copolymers of vinyl pyrrolidone and hydrophobic fatty-chain monomers are chosen from: vinylpyrrolidone / hexadecene copolymers; vinylpyrrolidone / eicosene copolymers. <Desc / Clms Page number 21> An emulsion according to claim 24, wherein the C 1 -C 6 alkyl methacrylate or acrylate copolymer and amphiphilic monomer having at least one fatty chain is a methyl acrylate / oxyethylenated stearyl acrylate copolymer. 28. Emulsion according to claim 24, wherein the copolymer of hydrophilic methacrylate or acrylate and of hydrophobic monomer comprising at least one fatty chain is a polyethylene glycol methacrylate / lauryl methacrylate copolymer. 30. The emulsion according to claim 11, wherein the nonionic associative polyether polyurethanes comprise in their chain polyoxyethylene hydrophilic blocks. The emulsion according to claim 30, wherein the nonionic associative polyether polyurethanes comprise at least two hydrophobic hydrocarbon chains having from C6 to C30 atoms. carbon, separated by a hydrophilic sequence, the hydrocarbon chains may be pendant chains or chains at the end of hydrophilic sequence. An emulsion according to any one of claims 30 to 31, wherein the nonionic associative polyether polyurethanes are multiblocked and preferably triblocked. 33. Emulsion according to any one of claims 30 to 32, wherein the nonionic associative polyether polyurethanes are graft or star. 34. Emulsion according to any one of claims 30 to 33, wherein the nonionic associative polyether polyurethanes are chosen from triblock copolymers whose hydrophilic sequence is a polyoxyethylenated chain comprising from 50 to 1000 oxyethylenated groups. 35. The emulsion according to claim 11, wherein the cationic associative polymers are chosen from quaternized cellulose derivatives and polyacrylates with amine side groups. 36. The emulsion according to claim 35, wherein the quaternized cellulose derivatives are chosen from: quaternized celluloses modified with groups comprising at least one fatty chain, preferably chosen from alkyl, arylalkyl and alkylaryl groups containing at least 8 carbon atoms; carbon, preferably from 8 to 30 carbon atoms; or mixtures thereof; quaternized hydroxyethylcelluloses modified with groups having at least one fatty chain, such as alkyl, arylalkyl, alkylaryl groups having at least 8 carbon atoms, preferably 8 to 30 carbon atoms; or mixtures thereof. 37. The emulsion according to claim 35, wherein the polyacrylates with amino side groups, whether quaternized or not, have hydrophobic groups of the steareth- (polyoxyethylenated stearyl alcohol (20)) type. 38. Emulsion according to claim 11, wherein the amphoteric associative polymers are chosen from amphoteric polymers crosslinked or non-crosslinked, branched or unconnected, obtainable by the copolymerization 1) of at least one monomer of formula (Va) or (Vb): <Desc / Clms Page number 22>

 in which R4 and R5, which may be identical or different, represent a hydrogen atom or a methyl radical, R6, R7 and R8, which may be identical or different, represents a linear or branched alkyl radical having from 1 to 30 carbon atoms, Z represents a NH group or an oxygen atom, n is an integer from 2 to 5, E- is an anion derived from an organic or inorganic acid, such as a methosulphate anion or a halide such as chloride or bromide. 2) at least one monomer of formula (VI):

 in which R 8 and R 10, which may be identical or different, represent a hydrogen atom or a methyl radical; Z1 represents an OH group or an NHC (CH3) 2CH2SO3H group; 3) of at least one monomer of formula (VII):

 in which R9 and R10, which are identical or different, represent a hydrogen atom or a methyl radical, X denotes an oxygen or nitrogen atom and R11 denotes a linear or branched alkyl radical having from 1 to 30 carbon atoms; 4) optionally at least one crosslinking agent or branching agent; at least one of the monomers of formula (Va), (Vb) or (VII) comprising at least one fatty chain having from 8 to 30 carbon atoms and said compounds of the monomers of formula (Va), (Vb), ( VI) and (VII) may be quaternized, for example, with a C1-C4 alkyl halide or a C1-C4 dialkyl sulphate. 39. An emulsion according to any one of claims 7 to 38, in which the associative or non-associative polymer or polymers are generally present at a concentration ranging from 0.05 to 15% by weight, and preferably from 0.1 to 5% by weight, relative to the total weight of the composition. Emulsion according to any one of claims 1 to 39, characterized in that the photoprotective system comprises one or more organic filters active in the UV-A and / or UV-B, water-soluble, liposoluble or in the form of insoluble particles in the phases of the emulsion. <Desc / Clms Page number 23> 41. Emulsion according to claim 40, characterized in that said complementary organic filters are selected from cinnamic derivatives, salicylic derivatives, camphor derivatives; triazine derivatives; triazole derivatives; dibenzoymethane derivatives; benzophenone derivatives; derivatives of ss, ss'diphenylacrylate, benzimidazole derivatives; bis-benzoazolyl derivatives; bis-hydroxyphenylbenzotriazole derivatives; p-aminobenzoic acid derivatives; the hydrocarbon polymers filters and silicones filters. 42. Emulsion according to any one of claims 1 to 41, characterized in that the photoprotective system comprises one or more pigments or nanopigments of metal oxides, coated or uncoated. 43. Emulsion according to claim 42, characterized in that said pigments or nanopigments are selected from titanium oxides, zinc, iron, zirconium, cerium and mixtures thereof, coated or uncoated. 44. Cosmetic or dermatological composition, intended for the photoprotection of the skin and / or the hair, characterized in that it comprises at least in a cosmetically acceptable support an emulsion as defined in any one of Claims 1 to 43. . 45. Composition according to claim 44, characterized in that it further comprises at least one agent for tanning and / or artificial browning of the skin. 46. Composition according to any one of claims 44 to 45, characterized in that it further comprises at least one adjuvant selected from fatty substances, organic solvents, thickeners, softeners, opacifiers, stabilizers, emollients, anti-foam agents, moisturizing agents, perfumes, preservatives, polymers, sequestering agents, propellants, alkalizing or acidifying agents. 47. A composition according to any one of claims 44 to 46, characterized in that it is a protective composition of the human epidermis or an antisolar composition and that it is in the form of a non-ionic vesicle dispersion, an emulsion, in particular an oil-in-water emulsion, a cream, a milk, a gel, a cream gel, a suspension , a dispersion, a powder, a solid stick, a mousse or a spray. A composition according to any one of claims 44 to 47, characterized in that it is an eyelash, eyebrow or skin makeup composition and is in solid or pasty, anhydrous or aqueous form, an emulsion, a suspension or a dispersion. 49. A composition according to any one of claims 44 to 47, characterized in that it is a composition for the protection of the hair against ultraviolet rays and that it is in the form of a shampoo, lotion, gel, emulsion, nonionic vesicular dispersion Use of the emulsion defined in any one of claims 1 to 43 for the manufacture of cosmetic compositions for protection skin and / or hair against ultraviolet radiation, especially solar radiation <Desc / Clms Page number 24>  Use as a carrier of an emulsion-free emulsion containing at least one mono- or polycarboxylic naphthalene acid derivative for the preparation of a photoprotective cosmetic or dermatological composition containing at least one photoprotective system capable of filtering UV radiation with a view to improve the water resistance of its filtering power (water retention).