FR2781369A1 - Cosmetic sun screen composition for photoprotection of skin and hair comprising benzene 1,4-di(3-methylidene-10-camphosulfonic acid) as primary filter and an N-substituted benzazole derivative as secondary filter - Google Patents

Abstract

A cosmetic solar protection composition for photoprotecting skin and hair comprises benzene 1,4-di(3-methylidene-10-camphosulfonic acid) as primary filter and an N-substituted benzazole derivative as secondary filter having a synergistic effect. A cosmetic composition for topical application, especially for photoprotection of skin and hair, comprises, in a cosmetic medium: (1) benzene 1,4-di(3-methylidene-10-camphosulfonic acid) (I), optionally in partially or completely neutralized form, as primary filter; and (2) an N-substituted benzazole derivative of formula (II) as secondary filter. X = S, NH, NR<1> or O; R<1> = 1-20 C alkyl, 2-20 C alkenyl, 3-15 C cycloalkyl, 6-12 C aryl, (6-12 C)ar-(1-6 C)alkyl or 5-12 C heteroaryl (all optionally substituted by at least one 1-6 C alkyl, 1-16 C alkoxy, 6-12 C aryloxy, amino, OH, CONR<2>R<3>, COOR<4> or Si(OR<7>)3 ; R<2>, R<3> = H or 1-6 C alkyl; R<4> = H, 1-16 C alkyl, 6-12 C aryl, or a radical R<5>-O(CH2-CH(R<6>)-O)n-CH2CH(R<6>)-; R<5>, R<7> = 1-4 C alkyl; R<6> = H or methyl; n = 0-4; and R<8> - R<15> = H, amino, nitro or R<1>. The primary and secondary filter compounds are present in relative proportions giving a synergistic improvement in solar protection factor, and the composition containing no organic UV filters of the dibenzoylmethane, 1,3,5-triazine or cinnamic acid types.

Description

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ANTI-SUN COSMETIC COMPOSITIONS BASED ON A MIXTURE
SYNERGIC OF FILTERS AND USES The present invention relates to novel cosmetic compositions for topical use more particularly intended for the photoprotection of the skin and / or the hair against ultraviolet radiation (compositions hereinafter referred to more simply as sunscreen compositions), as well as their use. in the above-mentioned cosmetic application. More precisely still, it relates to sunscreen compositions comprising, in a cosmetically acceptable support, a combination of at least two specific filters, namely on the one hand benzene 1,4-di (3-methylidene-10camphosulfonic acid) and , on the other hand, a particular N-substituted benzazole derivative, these two filters being present in proportions suitable for obtaining a synergistic effect in terms of the protection indices conferred.

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

It is also known that UV-A rays, with wavelengths between 320 and 400 nm, which cause the skin to brown, are liable to induce an alteration of the latter, in particular in the case of a skin. sensitive or skin continuously exposed to sunlight. UV-A rays in particular cause a loss of elasticity in the skin and the appearance of wrinkles leading to premature aging. They promote the onset of the erythematous reaction or amplify this reaction in certain subjects and can even be the cause of photo-toxic or photoallergic reactions. It is therefore desirable to filter UV-A radiation as well.

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

These sunscreen compositions are quite often in the form of an emulsion of oil-in-water type (that is to say a cosmetically acceptable carrier consisting of a continuous aqueous dispersing phase and an oily dispersed discontinuous phase) which contains , at various concentrations, one or more conventional organic filters, lipophilic and / or hydrophilic, capable of selectively absorbing harmful UV radiation, these filters (and their quantities) being selected according to the desired protection index (the protection index (IP) expressed mathematically as the ratio of the irradiation time necessary to reach the erythematogenic threshold with the UV filter to the time necessary to reach the erythematogenic threshold without UV filter).

Now, following extensive research carried out in the field of photoprotection mentioned above, the Applicant has discovered, unexpectedly and surprisingly, that the combination, in proportions within well-defined limits, of two sun filters particular and already known per se in the state of the art, made it possible, due to a remarkable synergistic effect, to obtain sunscreen compositions exhibiting markedly improved protection indices, and in any case greatly superior to those which can be obtained either with one or the other of the filters used alone,

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or again with associations simultaneously containing the two filters but in reports outside the scope of the invention.

This discovery is the basis of the present invention.

Thus, in accordance with one of the objects of the present invention, there are now proposed new cosmetic compositions, in particular sunscreen, which are essentially characterized in that they comprise, in a cosmetically acceptable carrier, (i) of benzene 1,4-di (3-methylidene-10camphosulfonic acid), optionally in partially or totally neutralized form, as a first filter, and (ii) a particular N-substituted benzazole derivative as a second filter; said first and second filters being present in said compositions in a proportion producing synergistic activity and said composition not containing an organic UV filter of the dibenzoylmethane type, or an organic UV filter of the type derived from 1,3,5-triazine, or of a filter Organic UV of the type derived from cinnamic acid.

A subject of the present invention is also the use of such compositions as, or for the manufacture of, cosmetic compositions intended for the protection of the skin and / or the hair against ultraviolet radiation, in particular solar radiation.

Yet another object of the present invention lies in a cosmetic treatment process for protecting the skin and / or hair against ultraviolet radiation, in particular solar radiation, and which essentially consists in applying to the latter an effective amount of a composition in accordance with the invention.

Other characteristics, aspects and advantages of the present invention will become apparent on reading the detailed description which follows.

dans laquelle A désigne un atome d'hydrogène, un métal alcalin ou encore un radical NH(R)3+ dans lequel les radicaux R, qui peuvent être identiques ou différents, désignent un atome d'hydrogène, un radical alkyle ou hydroxyalkyle en C,-C4 ou encore un groupement Mn+/n, Mn+ désignant un cation métallique polyvalent dans lequel n est égal à 2 ou 3 ou 4, Mn+ désignant de préférence un cation métallique choisi parmi Ca2+, Zn2+, Mg2+, Ba2+, Al3+ et Zr4+ Il est bien entendu que les composés de formule (I) cidessus peuvent donner lieu à l'isomère "cis-trans" autour d'une ou plusieurs double(s) liaison(s) et que tous les isomères rentrent dans le cadre de la présente invention. Benzene 1,4-di (3-methylidene-10-camphosulfonic acid) and its various salts, described in particular in patent applications FR-A-2528420 and FR-A-2639347, are filters already known per se ( so-called broadband filters) capable of absorbing ultraviolet rays with wavelengths of between 280 and 400 nm, with absorption maxima of between 320 and 400 nm, in particular around 345 nm. These filters correspond to the following general formula (I):

in which A denotes a hydrogen atom, an alkali metal or else an NH (R) 3+ radical in which the radicals R, which may be identical or different, denote a hydrogen atom, an alkyl or hydroxyalkyl radical in C , -C4 or else an Mn + / n group, Mn + denoting a polyvalent metal cation in which n is equal to 2 or 3 or 4, Mn + preferably denoting a metal cation chosen from Ca2 +, Zn2 +, Mg2 +, Ba2 +, Al3 + and Zr4 + II It is of course understood that the compounds of formula (I) above can give rise to the "cis-trans" isomer around one or more double bond (s) and that all the isomers come within the scope of the present invention.

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Benzene 1,4-di (3-methylidene-10-camphosulfonic acid) and or one of its various salts is generally present in the filtering compositions according to the invention at a total concentration ranging from 0.1 to 15% by weight approximately, and preferably from 0.2 to 10% by weight approximately, relative to the total weight of the composition.

dans laquelle : - X désigne S, NH, NR1 ou O ;

- R' désigne alkyle en C1-CZO' alcényle en C2-C2., cycloalkyle en C3-C1S' aryle en CS-C1z, (Cs-C,2)ar-(C,-Cs)alkyle, hétaryle en CÇC12' lesdits radicaux pouvant être substitués par au moins un alkyle en C,-C6, un alcoxy en C1-C1S' un aryloxy en C6-C,z, un groupe amino, un hydroxy, un radical CONR2R3, COOR4 ou Si(OR')3 ; - R2et R3, indépendamment l'un de l'autre, désignent hydrogène ou un alkyle en C1-C6 ; - R4 désigne hydrogène, alkyle en C1-C16, aryle en C6-C12 ou le radical de

structure : RS-O(CHZ-CH(R6)-O) CHzCH(Rs)- ; - R5 désigne un alkyle en C1-C4 ; - R6 désigne hydrogène ou méthyle ; -R7 désigne un alkyle en C1-C4 - n est un entier de 0 à 4 ; - les radicaux R8 à R15, indépendamment les uns des autres, désignent hydrogène, amino, nitro ou R1 ; Les dérivés de benzazole N-substitués de formule (II) de l'invention sont des filtres déjà connus en soi (filtres dits à large bande) capables en effet d'absorber les rayons ultraviolets de longueur d'ondes comprises entre 280 nm et 400 nm, avec des maxima d'absorption compris entre 310 nm et 400 nm, en particulier aux alentours de 345 nm. Ils sont décrits et préparés selon les synthèses indiquées dans la demande de brevet EP-A- 0843 995 (faisant partie intégrante du contenu de la description). The N-substituted benzazole derivatives in accordance with the present invention correspond to the following formula (II):

in which: - X denotes S, NH, NR1 or O;

- R 'denotes alkyl in C1-CZO' alkenyl in C2-C2., Cycloalkyl in C3-C1S 'aryl in CS-C1z, (Cs-C, 2) ar- (C, -Cs) alkyl, hetaryl in CÇC12' said radicals possibly being substituted by at least one C, -C6 alkyl, a C1-C1S 'alkoxy, a C6-C, z aryloxy, an amino group, a hydroxy, a CONR2R3, COOR4 or Si (OR') radical 3; - R2and R3, independently of one another, denote hydrogen or a C1-C6 alkyl; - R4 denotes hydrogen, C1-C16 alkyl, C6-C12 aryl or the radical of

structure: RS-O (CHZ-CH (R6) -O) CHzCH (Rs) -; - R5 denotes a C1-C4 alkyl; - R6 denotes hydrogen or methyl; -R7 denotes a C1-C4 alkyl - n is an integer from 0 to 4; - the radicals R8 to R15, independently of one another, denote hydrogen, amino, nitro or R1; The N-substituted benzazole derivatives of formula (II) of the invention are filters already known per se (so-called broadband filters) capable in fact of absorbing ultraviolet rays with wavelengths between 280 nm and 400 nm. nm, with absorption maxima between 310 nm and 400 nm, in particular around 345 nm. They are described and prepared according to the syntheses indicated in patent application EP-A-0843 995 (forming an integral part of the content of the description).

Among the preferred compounds of formula (II), mention may be made of those in which R1 denotes C5-C20 and particularly C5-C12 alkyl and more particularly 2-ethylhexyl.

(C,-C4)alcoxycarbonyl(C1-C3)alkyle. Among the particularly preferred compounds of formula (II), mention may be made of those where X denotes 0 or S and R1 denotes C4-C12 alkyl, cyclohexyl-C1-C6 alkyl, benzyl or

(C, -C4) alkoxycarbonyl (C1-C3) alkyl.

Mention may also be made of those where X denotes NR1 and R 'denotes C4 C, 2 alkyl, cyclohexyl (C, -C6) alkyl, benzyl, C: -C12 aryl, (C, -C4) alkoxy-carbonyl (C , -C3) alkyl. As examples of compounds of formula (II) which can be used, mention may be made of: (1) benzoxazole derivatives such as: 2- (1-n-pentylbenzimidazol-2-yl) -benzoxazole; 2- [1- (3-methylbutyl) benzymidazol-2-yl] -benzoxazole;

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le 2-(1-(2-éthylhexyl))benzimidazol-2-yl)-benzothiazole ; le 2-(1-propènylbenzimidazol-2-yl)-benzothiazole ; le 2-[1-(3-méthylbutyl)benzimidazol-2-yl]-benzothiazole ; (3 ) les dérivés de 2,2'-bis-benzimidazole tels que : le 2,2'-bis-(1-n-pentylbenzimidazole) ; le 1,1'-dipentyl-5-méthoxy-2,2'-bis-benzimidazole ; le 1,1'-dipentyl-6-méthoxy-2,2'-bis-benzimidazole ; le 1,1'-dipropyl-5,5'-diméthyl-2,2'-bis-benzimidazole ; le 1,1'-dipropyl-6,6'-diméthyl-2,2'-bis-benzimidazole. 2- (1-n-octylbenzimidazol-2-yl) -benzoxazole; 2- (1- (2-ethylhexyl)) benzimidazol-2-yl) -benzoxazole; 2- (1-n-dodecylbenzimidazol-2-yl) -benzoxazole; 2- [1- (ethoxycarbonylmethyl) benzymidazol-2-yl] -benzoxazole; 2- [1- (3-cyclohexylpropyl) benzymidazol-2-yl] -benzoxazole; 2- (1-Benzylbenzimidazol-2-yl) -benzoxazole; (2) benzothiazole derivatives such as:

2- (1- (2-ethylhexyl)) benzimidazol-2-yl) -benzothiazole; 2- (1-propenylbenzimidazol-2-yl) -benzothiazole; 2- [1- (3-methylbutyl) benzimidazol-2-yl] -benzothiazole; (3) 2,2'-bis-benzimidazole derivatives such as: 2,2'-bis- (1-n-pentylbenzimidazole); 1,1'-dipentyl-5-methoxy-2,2'-bis-benzimidazole;1,1'-dipentyl-6-methoxy-2,2'-bis-benzimidazole;1,1'-Dipropyl-5,5'-dimethyl-2,2'-bis-benzimidazole;1,1'-Dipropyl-6,6'-dimethyl-2,2'-bis-benzimidazole.

The organic filter (s) of formula (II) are generally present in the filtering compositions according to the invention at a total concentration of between 0.1 and 15% by weight approximately, and preferably between 0.2 and 10% by weight approximately , relative to the total weight of the composition.

As indicated above, according to an essential characteristic of the present invention, these two compounds should both be present in the final composition in a respective proportion such as a synergistic effect at the level of the protection index conferred by the. resulting association, is obtained in a notable, substantial and significant manner.

In addition, and in general, it will be noted that the concentrations and ratios of compounds of formula (I) and of formula (II) as defined above are chosen such that the sun protection index of the final composition or preferably at least 2.

Finally, still according to a preferred embodiment of the present invention, the cosmetically acceptable support in which the various organic filters of formula (1) and of formula (II) as defined above are contained, is an emulsion of oil-in type. -water.

benzophénone, les dérivés de ,[3'-diphénylacrylate, les dérivés de l'acide p- aminobenzoïque, les polymères filtres et silicones filtres décrits dans la demande WO-93/04665. D'autres exemples de filtres organiques sont donnés dans la demande de brevet EP-A-0487404. The sunscreen cosmetic compositions according to the invention can of course contain one or more complementary sun filters active in UVA and / or UVB (absorbers), hydrophilic or lipophilic, other of course than the two filters mentioned above. These additional filters can in particular be chosen from salicylic derivatives, camphor derivatives, benzotriazole derivatives,

benzophenone, [3'-diphenylacrylate derivatives, p-aminobenzoic acid derivatives, filter polymers and filter silicones described in application WO-93/04665. Other examples of organic filters are given in patent application EP-A-0487404.

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As examples of complementary sun filters active in UV-A and / or UV-B, there may be mentioned: p-aminobenzoic acid, oxyethylenated p-aminobenzoate (25mol), 2-ethylhexyl p-dimethylaminobenzoate , N-oxypropylene ethyl p-aminobenzoate, glycerol p-aminobenzoate, homomenthyl salicylate, 2-ethylhexyl salicylate, triethanolamine salicylate, 4-isopropylbenzyl salicylate, menthyl anthranilate, 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, urocanic acid, 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, 3- (4'-sulfo) benzylidèn-boman-2-one and se s salts, 2,4,6-trianilino- (p-carbo-2'ethylhexyl-1 'oxy) -1, 3,5-triazine, the disodium salt of phenylen-bis-benzimidazyl-tetrasulfonic acid, polymer of N- (2 and 4) - [(2-oxoborn-3-ylidèn) methyl] benzyl] -acrylamide, polyorganosiloxanes with a malonate function.

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

The cosmetic compositions 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 and 50 nm) of coated or uncoated metal oxides, for example nanopigments of titanium oxide (amorphous or crystallized in rutile and / or anatase form), iron, zinc, zirconium or cerium which are all photoprotective agents well known per se acting by physical blocking (reflection and / or diffusion) of UV radiation. Conventional coating agents are moreover alumina and / or aluminum stearate. Such metallic oxide nanopigments, coated or uncoated, are in particular described in patent applications EP-A-0518772 and EP-A-0518773.

The compositions of the invention can also comprise conventional cosmetic adjuvants in particular chosen from fatty substances, organic solvents, thickeners, softeners, antioxidants, opacifiers, stabilizers, emollients, hydroxy acids, anti- mousse, moisturizers, vitamins, perfumes, preservatives, surfactants, fillers, sequestering agents, polymers, propellants, alkalinizing or acidifying agents, colorants, or any other

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ingredient usually used in cosmetics, in particular for the manufacture of sunscreen compositions in the form of emulsions The fatty substances can consist of an oil or a wax or their mixtures, and they also include fatty acids, fatty alcohols and esters of 'Fatty acids. The oils can be chosen from animal, vegetable, mineral or synthetic oils and in particular from petrolatum oil, paraffin oil, silicone oils, volatile or not, isoparaffins, poly-a-olefins, fluorinated and perfluorinated oils. Likewise, 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 thickeners can be chosen in particular from crosslinked acrylic acid homopolymers, guar gums and celluloses modified or not, such as hydroxypropylated guar gum, methylhydroxyethylcellulose, hydroxypropylmethyl cellulose or else hydroxyethylcellulose.

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 remanence in water, the photoprotection spectrum, intrinsically attached to the 'binary association in accordance with the invention are not, or substantially not, altered by the addition (s) envisaged.

The compositions of 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-oil type.

This composition can be in particular in the form of an emulsion, simple or complex (O / W, W / O, O / W / O or W / O / W) such as a cream, a milk, a gel or a gel cream, 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 2315991 and FR 2416008).

The cosmetic composition of the invention can be used as a composition for protecting the human epidermis or the hair against ultraviolet rays, as an anti-sun composition or as a make-up product.

When the cosmetic composition according to the invention is used for the protection of the human epidermis against UV rays, or as an anti-sun composition, it can be in the form of a suspension or of a dispersion in solvents or fatty substances, in the form of nonionic vesicular dispersion or else in the form of an emulsion, preferably of the oil-in-water type, such as a cream or a milk, 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 the protection of the hair, it can be in the form of a shampoo, a lotion, a gel, an emulsion, a nonionic vesicular dispersion and can constitute, for example, a composition with

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rinse, to apply before or after shampooing, before or after coloring or bleaching, before, during or after perm or defnsage, a styling or treating lotion or gel, a lotion or a gel for brushing or styling, a composition perming or straightening, coloring or bleaching of the hair.

When the composition is used as a make-up product for the eyelashes, the eyebrows or the skin, such as an epidermis treatment cream, foundation, lipstick stick, eye shadow, blush, mascara or liner also called "eye liner", 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 else suspensions.

As an indication, for the sunscreen formulations in accordance with the invention which have a carrier of oil-in-water emulsion type, the aqueous phase (comprising in particular the hydrophilic filters) generally represents from 50 to 95% by weight, preferably from 70% by weight. at 90% by weight, relative to the whole of the formulation, the oily phase (comprising in particular the lipophilic filters) from 5 to 50% by weight, preferably from 10 to 30% by weight, relative to the whole of the formulation, and the (co) emulsifier (s) from 0.5 to 20% by weight, preferably from 2 to 10% by weight, relative to the entire formulation.

As indicated at the beginning of the description, another object of the present invention lies in a process for the cosmetic treatment of the skin or the hair intended to protect them against the effects of UV rays, consisting in applying thereto an effective amount of a cosmetic composition as defined above.

Concrete, but in no way limiting, examples illustrating the invention will now be given. The amounts indicated are expressed in% by weight.

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<tb>

Examples <SEP> Ex1 <SEP> Ex2 <SEP> Ex3
<tb> (excluding <SEP> (excluding <SEP> (invention)
<tb> invention) <SEP> invention)
<tb> Glycerol <SEP> 4 <SEP> 4 <SEP> 4
<tb> Triethanolamine <SEP> 0. <SEP> 65 <SEP> 0. <SEP> 65 <SEP> 0. <SEP> 65
<tb> Demineralised <SEP> water <SEP> 62. <SEP> 55 <SEP> 62. <SEP> 55 <SEP> 62. <SEP> 55
<tb> Cetyl alcohol <SEP><SEP> 0.5 <SEP> 0.5 <SEP> 0. <SEP> 5
<tb><SEP> silicone oil <SEP> 350 <SEP> cst <SEP> (1) <SEP> 0.5 <SEP> 0.5 <SEP> 0. <SEP> 5
<tb> Mixture <SEP> p-hydroxybenzoates <SEP> / phenoxy-2 <SEP> 1 <SEP> 1 <SEP> 1
<tb> ethanol, <SEP> (2)
<tb> Stearic acid <SEP><SEP> 2. <SEP> 5 <SEP> 2. <SEP> 5 <SEP> 2.5
<tb> Mono / distearate <SEP> of <SEP> glycerol / <SEP> stearate <SEP> PEG <SEP> 1 <SEP> 1 <SEP> 1
<tb> (100), <SEP> (3)
<tb> Hydroxypropyl <SEP> methyl <SEP> cellulose <SEP> 0. <SEP> 1 <SEP> 0. <SEP> 1 <SEP> 0.1
<tb>

j 2-(1-isooctylbenzimidazole-2-yl)benzothiazole 5 - 2.5

j 2- (1-isooctylbenzimidazol-2-yl) benzothiazole 5 - 2.5

<tb>
<tb> Acid <SEP> benzene <SEP> 1,4-di (3-methylidene-10- <SEP> 2.5
<tb> camphulphonic)
<tb> Cyclopenta <SEP> dimethylsiloxane, <SEP> (4) <SEP> 2 <SEP> 2 <SEP> 2
<tb> Benzoate <SEP> of alcohols <SEP> (5) <SEP> 20 <SEP> 20 <SEP> 20
<tb> Copolymer <SEP> acid <SEP> acrylic <SEP> @ <SEP> alkyl acrylate <SEP>, <SEP> 0. <SEP> 2 <SEP> 0.2 <SEP> 0.2
<tb> (6)
<tb>

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(1) DC 200 Fluid from Dow-Cormng, (2) Phenonip from Nipa, (3) Arlacel 165 from ICI, (4) DC 245 Fluid from Dow-Corning, (5) Witconol TN from Witco, (6) Pemulen TR1 de Goodrich For each of these formulations, the sun protection factor (SPF) which was attached to it was then determined. This was determined using the in vitro method described by BL DIFFEY et al. in J. Soc. Cosmet. Chem. 40-127-133 (1989); this method consists in determining the monochromatic protection factors every 5 nm in a range of wavelengths from 290 to 400 nm and in calculating from them the sun protection factor according to a given mathematical equation. The results (mean value corresponding to three tests) are grouped together in the table below:

<tb>
<tb> Compositions <SEP> Ex1 <SEP> Ex2 <SEP> Ex3
<tb> (excluding <SEP> (excluding <SEP> (invention)
<tb> invention) <SEP> invention)
<tb> SPF <SEP> 7.91.2 <SEP> 6.8 <SEP> 1 <SEP> 20.6 <SEP> 3.4 <SEP>
<tb>

Claims (21)

structure: RS-O (CHz-CH (Rs) -O) CHZCH (R6) -; - R5 denotes a C1-C4 alkyl; - R6 denotes hydrogen or methyl; - R7 denotes a C1-C4 alkyl - n is an integer from 0 to 4; - the radicals R8 to R15, independently of one another, denote hydrogen, amino, nitro or R1; said first and second filters being present in said compositions in a proportion producing a synergistic activity in terms of sun protection indices and said composition not containing an organic UV filter of the dibenzoylmethane type, of the type derived from 1,3,5-triazine nor of organic UV filter of the type derived from cinnamic acid.

(CC, Z) ar- (C-C6) alkyl, Cs-C12 hetaryl, said radicals possibly being substituted by at least one C1-C6 alkyl, C1-C6 alkoxy, C6-C12 aryloxy, amino group, a hydroxy, a CONR2R3, COOR4 or Si (OR ') 3 radical; - R2 and R3, independently of one another, denote hydrogen or a C1-C6 alkyl: - R4 denotes hydrogen, C1-C16 alkyl, C6-C12 aryl or the radical of

in which: - X denotes S, NH, NR1 or 0; - R1 denotes C1-C20 alkyl, C2-C20 alkenyl, C3-C15 cycloalkyl, C6-C12 aryl,

CLAIMS 1. Cosmetic composition for topical use, in particular for the photoprotection of the skin and / or the hair, characterized in that it comprises, in a cosmetically acceptable carrier: (i) benzene 1,4- acid di (3-methylidene-10-camphorsulfonic acid), optionally in partially or totally neutralized form, as a first filter, (ii) and as a second filter, at least one N-substituted benzazole derivative corresponding to formula (II ) next : 2. Composition according to Claim 1, characterized in that the compound of formula (II) is chosen from those where R1 denotes C5-C20 and particularly C5C12 alkyl and more particularly 2-ethylhexyl. 3. Composition according to Claim 1, characterized in that the compound of formula (II) is chosen from those where X denotes 0 or S and R1 denotes C4-C12 alkyl, cy-

Clohexyl C1-C6 alkyl, benzyl or (CrC4) alkoxy-carbonyl (CrC3) alkyl. 4. Composition according to Claim 1, characterized in that the compound of formula (II) is chosen from those where X denotes NR1 and R1 denotes C4-C12 alkyl, cyclo-

C 1 -C 6 hexylalkyl, benzyl, C6-C12 aryl, (C1-C4) alkoxy-carbonyl (CI-C3) alkyl. 5. Composition according to Claim 1, characterized in that the compound of formula (II) is chosen from: 2- (1-n-pentylbenzimidazol-2-yl) -benzoxazole; <Desc / Clms Page number 10> 1,1'-dipentyl-5-methoxy-2,2'-bis-benzimidazole; 1,1'-dipentyl-6-methoxy-2,2'-bis-benzimidazole; 1,1'-Dipropyl-5,5'-dimethyl-2,2'-bis-benzimidazole; 1,1'-di pro pyl-6,6'-d im ethyl-2,2'-bi s-b e nzi mi d azole. 6. Composition according to any one of the preceding claims, characterized in that the concentration of filter of formula (II) is between 0.1 and 15% by weight relative to the total weight of the composition.

2- [1- (3-methylbutyl) benzymidazol-2-yl] -benzoxazole; 2- (1-n-octylbenzimidazol-2-yl) -benzoxazole; 2- (1- (2-ethylhexyl)) benzimidazol-2-yl) -benzoxazole; 2- (1-n-dodecylbenzimidazol-2-yl) -benzoxazole; 2- [1- (ethoxycarbonylmethyl) benzymidazol-2-yl] -benzoxazole; 2- [1- (3-cyclohexylpropyl) benzymidazol-2-yl] -benzoxazole; 2- (1-Benzylbenzimidazol-2-yl) -benzoxazole; 2,2'bis- (1-n-pentylbenzimidazole). 2- (1- (2-ethylhexyl)) benzimidazol-2-yl) -benzothiazole; 2- (1-Propenylbenzimidazol-2-yl) -benzothiazole; 2- [1- (3-methylbutyl) benzimidazol-2-yl] -benzothiazole; 2,2'-bis- (1-n-pentylbenzimidazole); 7. Composition according to Claim 6, characterized in that the said concentration is between 0.2 and 10% by weight relative to the total weight of the composition. 8. Composition according to any one of the preceding claims, characterized in that the benzene 1,4-di (3-methylidene-10-camphosulfonic acid) and its salts corresponds to the following formula (I):

in which D denotes a hydrogen atom, an alkali metal or else an NH (R25) 3+ radical in which the radicals R25, which may be identical or different, denote a hydrogen atom, an alkyl or hydroxyalkyl radical in C1 -C4 or else an Mn + / n group, Mn + denoting a polyvalent metal cation in which n is equal to 2 or 3 or 4, Mn + preferably denoting a metal cation chosen from Ca2 +, Zn2 +, Mg2 +, Ba2 +, A13 + and Zr4 +. 9. Composition according to any one of the preceding claims, characterized in that the benzene 1,4-di (3-methylidene-10-camphosulfonic acid), or one of its salts is generally present in a total concentration. between 0.1 and 15% by weight approximately relative to the total weight of the composition. 10. The composition of claim 9, wherein the concentration is between 0.2 and 10% by weight approximately, relative to the total weight of the composition. 11. Composition according to any one of the preceding claims, characterized in that the said cosmetically acceptable support is in the form of an emulsion of oil-in-water type. <Desc / Clms Page number 11> 12. Composition according to any one of the preceding claims, characterized in that it further comprises one or more complementary organic filters active in UV-A and / or UV-B, hydrophilic or lipophilic, different from said first and second filters. 13. Composition according to Claim 12, characterized in that said additional organic filters are chosen from salicylic derivatives, camphor derivatives, benzotriazole derivatives, p, p-diphenylacrylate derivatives, p acid derivatives. -aminobenzoic acid, filter polymers and filter silicones. 14. Composition according to any one of the preceding claims, characterized in that it further comprises, as additional UV photoprotective agents, pigments or nanopigments of metal oxides, coated or not. 15. Composition according to Claim 14, characterized in that said pigments or nanopigments are chosen from oxides of titanium, zinc, iron, zirconium, cerium and their mixtures, coated or not. 16. Composition according to any one of claims 1 to 15, characterized in that it further comprises at least one agent for artificial tanning and / or browning of the skin. 17. Composition according to any one of claims 1 to 16, characterized in that it further comprises at least one adjuvant chosen from fatty substances, organic solvents, thickeners, softeners, antioxidants, opacifiers, stabilizers, emollients, hydroxy acids, anti-foaming agents, moisturizing agents, vitamins, perfumes, preservatives, surfactants, fillers, sequestering agents, polymers, propellants, alkalinizing or acidifying agents, dyes. 18. Composition according to any one of claims 1 to 17, characterized in that it is a protective composition for the human epidermis or an antisun composition and that it is in the form of a nonionic vesicular dispersion, of an emulsion, in particular of an emulsion of oil-in-water type, of a cream, of a milk, of a gel, of a cream gel, of a suspension , a dispersion, a powder, a solid stick, a foam or a spray. 19. Composition according to any one of claims 1 to 17, characterized in that it is a makeup composition for the eyelashes, the eyebrows or the skin and that it is in solid or pasty form. , anhydrous or aqueous, of an emulsion, a suspension or a dispersion. 20. Composition according to any one of claims 1 to 17, characterized in that it is a composition intended for protecting the hair against ultraviolet rays and that it is in the form of a shampoo, lotion, gel, emulsion, nonionic vesicular dispersion. 21. Use of the composition defined in any one of claims 1 to 20 for the manufacture of cosmetic compositions for protecting the skin and / or the hair against ultraviolet radiation, in particular solar radiation.