MXPA98007286A - Photoprotector compositions comprising a benzlidene alcanfor and / or a dibenzoylmethane and / or a triazine and a dialkyl tartrate; uses in cosmet - Google Patents

Abstract

The present invention relates to new cosmetic and / or dermatological compositions intended for the protection of the skin and / or hair against UV radiation, in particular solar radiation. More precisely, the invention relates to new cosmetic and / or dermatological compositions having an improved sun protection factor and comprising, in a cosmetically and / or dermatologically acceptable support, at least one dialkyl tartrate and at least one photoprotective system capable of to filter the UV radiation, consisting of at least one UV filter of the type derived from benzylidene camphor and / or by at least one UV filter of the type derived from dibenzoylmethane and / or from at least one UV filter of the triazi-derived type

Description

PHOTOPROTECTIVE COMPOSITIONS COMPRISING A BENCILIDENE ALCANFOR AND / OR A DIBENZOYLMETHANE AND / OR A TRIAZINE AND A DIALKYL TARTRATE; UTILIZATIONS IN COSMETICS FIELD OF THE INVENTION The present invention relates to new cosmetic and / or dermatological compositions intended for the protection of the skin and / or hair against UV radiation, in particular solar radiation. More precisely, the invention relates to new cosmetic and / or dermatological compositions comprising at least one UV filter of the dibenzoyl ethane type and / or a UV filter of the type derived from benzylidene camphor and / or at least one UV filter of the derivative type. of triazine having an improved sun protection factor and comprising, in a cosmetically and / or dermatologically acceptable support, at least one dialkyl tartrate, linear or branched.

BACKGROUND OF THE INVENTION It is known that light radiations with wavelengths between 280 nm and 400 nm allow tanning of the human epidermis and that radiation REF .: 28348 with wavelengths between 280 nm and 320 nm, known as UV-B, cause erythema and skin burns that can impair the development of natural tanning; this UV-B radiation, therefore, must be filtered. It is also known that UV-A radiations, with wavelengths comprised between 320 nm and 400 nm that cause tanning of the skin, are susceptible to induce an alteration of this, particularly in the case of sensitive skin or skin. of a skin continually exposed to solar radiation. UV-A radiation causes, in particular, a loss of elasticity of the skin and the appearance of wrinkles that lead to premature aging. They favor the triggering of the erythematous reaction or amplify this reaction in some subjects and may even be the origin of phototoxic or photo-allergic reactions. It is therefore desirable to also filter the UV-A radiation. Numerous cosmetic compositions intended for photoprotection (UV-A and / or UV-B) of the skin have been proposed up to now. These sunscreen compositions are often often in the form of an oil-in-water type emulsion (ie a cosmetically acceptable support consisting of a continuous aqueous dispersing phase and a dispersed dispersed oil phase) containing, in 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 Protection Index sought (the protection index (IP) that is expressed mathematically by the ratio of the irradiation time necessary to reach the erythematogenic limit with the UV filter with respect to the time necessary to reach the erythematogenic limit without UV filter). However, as a consequence of important investigations carried out in the field of photoprotection mentioned above, the Applicant has now discovered, unexpectedly and surprisingly, that it is possible to obtain antisun compositions with improved protection rates by associating a di-alkyl tartrate. with and more particularly of C12-C15 with a photoprotective system consisting of at least one UV filter of the type derived from benzylidene camphor and / or a UV filter of the tip dibenzoylmethane and / or at least one UV filter of the tip triazine derivative, in any case higher than those that can be obtained with a photoprotector system only of this class. This property is all the more surprising when known in the prior art, particularly in the 3rd application 096/40047, cosmetic or pharmaceutical compositions containing alpha-hydroxy acid esters, particularly diethyl tartrate in the presence of conventional UV filters and more particularly in the application EP-A-635,250 sunscreen lipogels using C? 2-C13 dialkyl tartrates and UV filters of the cinnamic type or benzophenone. Photoprotective compositions are also known based on 2, 4,6-tris [p- (2'-ethylhexyl-1-oxycarbonyl) -anilino] -1,3,5-triazine (sold under the trade name "UVINUL T150" by the company BASF) in which the dialkyl esters of α, β-dihydroxylated carboxylic acid are used only to solubilize the triazine or to improve the solubilization of this particular UV filter. The Applicant has unexpectedly observed that the Protection Index was not improved by using a dialkyl tartrate in association with a photoprotector system according to the prior art which does not contain those of the invention and which is constituted by other types of classic UV filters such such as cinnamic derivatives or benzophenone. This discovery forms the basis of the present invention.

DESCRIPTION OF THE INVENTION Thus, according to a first object of the present invention, new compositions are proposed, more particularly intended for the protection of the skin and / or hair against ultraviolet radiation, characterized in that they comprise, in a cosmetically acceptable support , at least: (a) a photoresist system capable of filtering UV radiation, consisting of at least one UV filter of the type derived from benzylidene camphor and / or at least one UV filter of the type derived from dibenzoylmethane and / or at least a UV filter of the triazine derivative type, (b) a linear or branched dialkyl tartrate preferably having 1 to 16 carbon atoms / said composition does not contain 2,4,6-tris [p- (2'-e-hexhexyl-1'-oxycarbonyl) anilino] -1,3, 5-triazine. According to the invention, it is meant to designate in a general way a photoresist system capable of filtering UV radiation, any compound or any combination of compounds that, by means of known mechanisms in the absorption and / or reflection and / or diffusion of UV radiation -A and / or UV-B, allows to prevent, or at least limit, the contact of said radiation with a surface (skin, hair), on which this or these compounds have been applied. In other words, these compounds can be UV absorbing photoprotective organic filters or (nano) mineral pigments, diffusers and / or UV reflectors, as well as their mixtures. Another object of the present invention also resides in the use of a dialkyl tartrate in one or even the manufacture of a cosmetic or dermatological composition intended for the protection of the skin and / or hair against ultraviolet radiation, of the type that comprises a photoresist system capable of filtering UV radiation, consisting of at least one UV filter of the type derived from benzylidene camphor and / or at least one UV filter of the dibenzoylmethane type and / or at least one UV filter of the type derived from triazine, to increase the sun protection factor. Another object of the present invention also resides in a cosmetic treatment method for the protection of the skin and / or hair against ultraviolet radiation, in particular solar radiation, and which essentially consists in applying an effective amount of ultraviolet radiation to the latter. a composition according to the invention. Other features, advantages aspects of the present invention will appear on reading the detailed description that follows. Mention may be made, as dialkyl tartrates, of the linear compounds, of which the alkyl radicals are C1-C4, such as the dimethyl, diethyl or dipropyl tartrates. Preference will be given to diethyl tartrate. Particularly preferred dialkyl tartrates according to the present invention respond to the following structure: where R denotes a group of formula: CH2) m-CH3 CH where p is 0 ° 1; n equals 12 or 13 when p is equal to 0 and m + n equals 8 or 9 when p equals 1. More linear C 1 2-C13 dialkyl tartrates such as those sold under the name of COSMACOL ETI by the Company ENICHEM AUGUST INDUSTRÍALE as well as the linear di-alkyl tartrates of Cu-Ci5 such as those sold under the name of COSMACOL ETL by the same Company. The di-alkyl tartrates are used in the compositions according to the invention in concentrations preferably ranging from 0.1 to 10% by weight, based on the total weight of the composition and more particularly between 0.2 and 5% by weight. The dibenzoylmethane derivatives considered by the present invention are products already well known per se and described particularly in documents FR-A-2 326 405, FR-A-2,440,933 and EP-A-0 114 607, documents whose teachings are, as regards the definition of these products, which are included as a reference in the present description. Among the dibenzoylmethane derivatives more particularly considered by the present invention, there may be mentioned, in a non-limiting manner: - 2-methyldibenzoylmethane, - 4-methyldibenzoyl-methane, - 4-isopropyldibenzoylmethane, - 4-tert-butyldibenzoylmethane, - 2,4-dimethyldibenzoylmethane, - 2 , 5-dimethyldibenzoylmethane - 4, A '-diisopropyldibenzoylmethane, - 4-tert-butyl-4'-methoxydibenzoylmethane, - 2-methyl-5-isopropyl-4'-methoxydibenzoylmethane, - 2-methyl-5-tert -butyl-4 '-methoxydibenzoylmethane, - 2,4-dimethyl-4'-methoxydibenzoylmethane, - 2,6-dimethyl-4-tert-butyl-4'r-methoxydibenzoylmethane. Among the dibenzoylmethane derivatives mentioned above, it is very particularly preferred, according to the present invention, to use 4-tert-butyl-4'-methoxydibenzoylmethane, particularly that proposed for sale under the trade name "PARSOL 1789" by the company Givaudan , answering this filter to the formula developed (I) below: Another preferred dibenzoylmethane derivative according to the present invention is 4-isopropyldibenzoylmethane, a filter sold under the name "EUSOLEX 8020" by the Merck society, and that responds to the developed formula (II) next: O The benzylidene camphor derivatives considered by the present invention are already well known products. Mention may be made, by way of example, of the following compounds: 3-benzylidene camphor; 4-methyl-benzylidene camphor; - 3 (4 '-trimethyl-ammonium benzylidene) -camphor methyl sulfate; benzylidene camphor sulfonic acid and its salts; - 3- (3 '-sulfo-4' -methyl benzylidene) camphor; - polyacrylamino-methyl benzylidene camphor; Mention may also be made of diorganopolysiloxanes with a benzylidene camphor function, such as those described in patent EP-B-0 355 777, as well as short chain, linear or cyclic diorganosiloxanes or benzylidene camphor functional triorganosilanes such as those described in the EP patent. B-0 712 855; fully including these documents, as regards the definition of these products, by way of reference in the present description. Mention may also be made of benzene l, 4-di (3-methylidene-10-camphorsulfonic acid) and its various salts, described in particular in patent applications FR-A-2,528,420 and FR-A-2,639 347, are already known per se (so-called broadband filters) capable, in effect, of absorbing ultraviolet radiation with wavelengths between 280 nm and 400 nm, with absorption maxima between 320 nm and 400 nm, in particular in the close to 345 nm. These filters respond to the following general formula (III): (lll) wherein B designates a hydrogen atom, an alkali metal or also an NH (R) 3 radical in which the radicals R, which may be identical or different, designate a hydrogen atom, an alkyl or hydroxyalkyl radical of Cj- C4 0 also a group Mn + / n, designating M * «+, a metal cation, polyvalent in which n is equal to 2 or 3 or 4 designated Mn + preferably a metal cation selected from Ca2, Zn2 +, Mg2 +, Ba2 +, Al3 + and Zr4 +. It is understood that the compounds of formula (III) indicated above can give rise to the "cis-trans" isomer around one or more double (s) bond (s) and that all isomers fall within the framework of the present invention.

Very particularly, 4-methylbenzylidene camphor, which is a liposoluble filter known per se, absorbs UV-B radiation and sold in particular under the trade name "EUSOLEX 6300" by the Merck Company or "PARSOL 5000" by the company GIVAUDAN, will be used. . This product responds to the following formula (IV) As the triazine derivative, 2, 4,6-tris [p-2'-ethylhexyl-1'-oxycarbonyl) anilinol-1,3,5-triazine will be used more particularly. This filter is known per se, active against UV-B radiation and is presented under a solid form, which is sold in particular under the trade name "UVINUL T 150" by the BASF Company. This product corresponds to the following formula (V): O II H- < ) -C-OR (V) in which R denotes a 2-ethylhexyl radical. As triazine derivatives, it will also be possible to use those described in patent application FR-A-2,744,721 which correspond to the following formula (VI) (SAW) wherein Ri, Ri 'and Ri ", which may be identical or different, are chosen from the following monovalent radicals of formulas (1) or (2): (1) (2) in which: - R2 and R2 ', which may be identical or different, designate a linear or branched C1-C3 alkyl radical, R3 designates a hydrogen atom, a linear C1-C4 alkyl radical or branched or an alkoxy radical of C1-C4, - R4 denotes a linear or branched C1-C12 alkyl radical, - Xi represents a hydrogen atom or a phenyl radical optionally substituted by a halogen or by an alkyl radical of -C4 or by a radical C1-C12 alkoxy C4 Among the compounds of formula (VI), the following compounds can be mentioned more particularly: 2, 4, 6-tris (diethylamino-amino benzalmalonate) -striazine, - 2,4,6-tris (4'-amino-benzalmalonate diisopropyl) - s-triazine, - 2, 4, 6-t- «Ls (4 '-amino benzalmalonate dimethyl) -s- triazine, 2, 4, 6-tris (ethyl a-cyano-4-aminocinnamate) -s- triazine. It is also possible to use other triazine derivatives such as those described in patent applications EP-A-0517104, EP-A-0570838, EP-A-0796851; these documents are, as far as the definition of these products themselves, totally included as references in the present description. The photoprotective systems according to the invention may additionally contain, in addition to one or more additional organic UV absorbers, different from the benzylidene camphor derivatives, the dibenzoylmethane derivatives and the triazine derivatives, or one or more pigments and / or nanopigmentos minerals, or also mixtures between these. The additional organic UV filters which can be used in the antisun compositions according to the invention are conventional sunscreens, which are UV-A and / or UV-B active, hydrophilic or lipophilic. By way of example, these filters can be chosen, alone b in a mixture, between 2-phenylbenzimidazole-5-sulfonic acid and its salts, cinnamic derivatives, salicylic derivatives, benzophenone derivatives, derivatives of β, β -diphenylacrylate, the p-aminobenzoic acid derivatives, the menthyl anthranilate, the polymeric filters and the silicone filters described in the application WO-93-04665. Other examples of organic filters are given in the patent application EP-A-0487404. The photoprotective system according to the invention is generally present in the compositions according to the invention in a content ranging from 0.1% to 30%, preferably from 0.5 to 15%, by weight, relative to the total weight of the composition. A second category of additional photoprotective agents that can be used in the compositions according to the invention is that of the pigments. Preferably, nanopigments are used (average size of the primary particles: generally between 5 nm and 100 nm, preferably between 10 and 50 nm) metal oxide minerals coated or not, such as, for example, titanium oxide nanopigments (amorphous or crystallized in the form of rutile and / or anatase), iron, zinc, zirconium or cerium which are all well-known photoprotective agents that act by physical blocking (reflection and / or diffusion) of UV radiation . Classical coating agents, on the other hand, are alumina and / or aluminum stearate or even silicones. Such nanopigments of metal oxides, coated or uncoated, are described in particular in patent applications EP-A-0518 772 and EP-A-0518,773, The mineral (s) (nano) pigments may be present in the compositions according to the invention with a content comprised between 0.1% and 30%, preferably between 0.5 and 10%, by weight, relative to the total weight of the composition. The other constituents that can enter into the formulation of the compositions considered by the invention, in particular the oils, the waxy compounds, the cosmetic and / or dermatological active agents, are those that are conventionally used in the cosmetic and / or dermatological field. By oil, a liquid compound is understood at room temperature. By wax, it is meant a solid or substantially solid compound at room temperature, and whose melting point is generally higher than 35 ° C. As oils, mineral oils can be cited (Vaseline); vegetables (sweet almond, acadamia, gooseberry, jojoba oil); synthetics such as perhydrosqualene, alcohols, acids or fatty esters (octyl palmitate, isopropyl lanolate, triglycerides of which capric / caprylic acids), esters and oxyethylenated or oxypropylenated fatty ethers; silicone (cyclomethicone, polydimethylsiloxanes or PDMS) or fluorinated, the polyalkylenes.

As waxy compounds, mention may be made of paraffin wax, carnauba wax, beeswax, hydrogenated castor oil. The compositions according to the invention can also contain anti-free radical agents, antioxidants, vitamins such as vitamins E and C, the a-hydroxy acids. The compositions according to the invention can also contain artificial tanning and / or toasting agents of the skin (self-tanning agents), such as, for example, dihydroxyacetone (DHA). The compositions considered by the present invention can also contain various ingredients conventionally used in the cosmetic, dermatological or dermopharmaceutical field such as coloring matters, solvents (water, alcohols, ...), preservatives, perfumes, moisturizing active agents, agents powders, bactericidal agents and / or odor absorbers. Of course, the person skilled in the art will take care to choose the one or any additional compounds mentioned above and / or their amounts in such a way that the advantageous properties intrinsically related to the association [photoresist system + C12-C15 alkyl tartrate] according to The invention is not, or substantially, altered by the addition (s) considered. The compositions having to do with the invention can be prepared according to techniques well known to those skilled in the art, in particular those intended for the preparation of aqueous continuous phase dispersions such as oil-in-water type emulsions, gels and the gels-creams. This composition can be present in particular in the form of an emulsion, simple or complex (H / E, E / H, H / E / H or E / H / E) such as a cream, a milk, or in the form of a gel or of a cream gel, of powder, of solid stick and possibly be conditioned in aerosol and presented in the form of foam or spray. By way of indication, for the antisun formulations according to the invention which have an aqueous continuous-phase dispersion-type support, such as oil-in-water emulsions and gel-creams, the aqueous phase (which particularly comprises hydrophilic filters) generally represents 50 to 95% by weight, preferably from 70 to 90% in. weight, in relation to the formulation as a whole, the oily phase (which particularly comprises the lipophilic filters) of 5 to 50% by weight, preferably 10 to 30% by weight, relative to the formulation as a whole, with respect to the formulation set. Preferably, the compositions according to the invention are in the form of gel creams. Concrete, but by no means limiting, examples illustrating the invention will be given below. In all the following examples, the amounts are expressed in% by weight relative to the total weight of the composition.

EXAMPLE 1: An antisun formulation A according to the invention was prepared in the form of an oil-in-water emulsion and containing: Phase 1: 4- (tert-butyl) A '-methoxy dibenzoylmethane ("PARSOL 1789" ) 2 g a-cyano-β, 2-ethylhexyl β-diphenylacrylate ("UVINUL N 539") 10 g 2, 4,6-tris [p-2'-ethylhexyl-1'-oxycarbonyl) ani- nyl] -l, 3,5-triazine ("UVINUL T 150") by the company BASF '2 g Nanopigment of titanium oxide sold under the name "MT100T" by Tayca 3 g C14-C15 di-alkyl tartrate ("COSMACOL ETL") 1 g Isohexadecane 5 g Phase 2: Polyacrylic acid neutralized by NaOH sold under the trade name "PNC 400" for 3V 0.55 g Dimethicone copolyol 0.65 g Phase 3: Benzene 1, -di (3-methylidene-10-camphosulphonic acid) i g Triethanolamine acid is pH 7 Phase 4: Moisturizing agents 4 g Xanthan gum 0.5 g Preservatives is Purified water is 100 g A comparative antisun formulation A '(outside the invention) was then prepared, with identical support to that of Formulation A but not containing C 14 -C 15 dialkyl tartrate. For each of the compositions A and ', the sun protection factor (SPF) was then determined in the range of the UV-A and UV-B radiation that was related to it. This was determined using an in vivo method on 5 subjects by means of a solar simulator equipped with a XENON MULTIPORT WG 320 lamp and 6 optical fibers that were placed at the level of the skin.- The energy flow was controlled in each irradiation by means of of a UV radiation meter model 3D-600. Each antisun emulsion was applied with a fingernail on a regular basis on the back of each subject at a rate of 2 mg / cm2 or 0.096 g for a 48 cm2 area. The irradiation was performed 15 minutes after the application of each emulsion. The UV exposure was carried out in a constant time and the irradiation time was chosen according to the erythematous limit of the subject and the presumed protection factor of each filter composition tested. It was determined for each filter composition A or A ', the average protection index (IP) that was expressed mathematically by the ratio of the irradiation time necessary to reach the erythematous limit with the composition with respect to the time necessary to reach the erythematous limit without the filtering composition. The results are indicated in the following table (I): Table (I) These results clearly show that the contribution of a C14-C15 di-alkyl tartrate to a photoresist system comprising at least one UV filter of the dibenzoylmethane derivative type and a UV filter of the benzylidene camphor derivative type makes it possible to significantly increase its power photoprotector.

EXAMPLE 2: An antisun formulation B according to the invention was prepared in the form of an oil-in-water emulsion and containing: Phase 1: 4- (tert.-butyl) A '-methoxy dibenzoylmethane (PARS 1789 2, 5 g - 2-ethylhexyl α-cyano-β, β-diphenylacrylate ("UVINUL N 539") 10 g Di-alkyl tartrate of C? -C? S ("COSMACOL ETL") 1 g Stearyl acid 0.5 g Stearic acid 1 g Dimeticone 1 g - Benzoate of C] 2-Ci5 alcohols sold under the trade name "Finsolv TN" by the Company Finetex 2 g Mixture of glyceryl stearate / stearate PEG-100 sold under the name of ARLACEL 165 by ICI 1.5 g - Triethanolamine 0.3 g Preservatives is Phase 2: Polyacrylic acid sold under the trade name "Carbopol 980" by Goodrich 0.2 g Triethanolamine 0.2 g Phase 3: Potassium Cetyl Phosphate ("AMPHISOL K" by GI AUDAN) i g Phase 4 Moisturizing agents 15 g Preservatives is Phase 5: Cyclomethicone 10 g Stage 6: - 1,4-di (3-methylidene-10-camphosulphonic) benzene acid. 1 g Triethanolamine is pH 7 Purified water is 100 g A comparative antisun formulation B 'was then prepared, with the same support as Formulation B but without containing di-C 1 4-C 1 alkyl divalent tartrate. For each of the compositions B and B, the sun protection factor (SPF) that was related to it was then determined. For each of the compositions B and B ', the sun protection factor (SPF) that was related to it was then determined. This was determined using the in vitro method described by B.L. DIFFEY et al. in J. Soc. Cos et. Chem. 40-127-133 (1989); this method consists in determining the monochromatic protection factors every 5 nm in a range of wavelengths between 290 and 400 nm and in calculating from them the sun protection factor according to a given mathematical equation. The results (average value corresponding to five tests) are indicated in the table (II) given below: Table (II) These results clearly show that the contribution of a di-alkyl tartrate of C? -C15 to a photoresist system comprising at least one UV filter of the dibenzoylmethane derivative type and a UV filter of the benzylidene camphor derivative type makes it possible to significantly increase its power photoprotector.

EXAMPLE 3: An antisun formulation C according to the invention was prepared in the form of an oil-in-water type emulsion and containing: Stage 1: - 4- (tert.-butyl) A '-methoxy dibenzoylmethane ("PARSOL 1789") 5 g - Stearyl acid 0.5 g - Stearic acid 1 g - Dimeticone 1 g - Di-alkyl tartrate of C? 2-C? 3 ("COSMACOL ETI") 1 g - Benzoate of alcohols of C12-C15, sold under the trade name "Finsolv TN", by the Society Finetex 2 g - Mix of glyceryl stearate / stearate PEG-100 sold under the name of ARLACEL 165 by ICI 1.5 g - Triethanolamine 0.3 g Preservatives is Phase 2: - Polyacrylic acid sold under the trade name "Carbopol 980" by Goodrich 0.2 g - Triethanolamine 0.2 g Phase 3: - Potassium potassium phosphate ("AMPHISOL K" from GIVAUDAN) i g Phase 4: - Moisturizing agents 15 g - Preservatives is Phase 5: - Cyclomethicone 10 g Phase 6: - Triethanolamine is pH 7 - Purified water -, it is 100 g A comparative antisun formulation C was then prepared, having the same support as formulation C but not containing C12-C13 di-alkyl tartrate. For each of the compositions C and C, the sun protection factor (SPF) that was related to it was then determined. This was determined using the method described in example 2. The results (average value corresponding to five tests) are indicated in the table (III) given below.

Table (III): These results clearly show that the contribution of a di-alkyl tartrate of C? 2-C? 3 to a photoresist system comprising a UV filter of the type derived from dibenzoylmethane allows to significantly increase its photoprotective power. Equivalent results are obtained using diethyl tartrate (C2) or a di-alkyl tartrate of 2-Ci3 as the COSMACOL ETI product instead of the COSMACOL product. ETL.

EXAMPLE 4: An antisun formulation D according to the invention was prepared with the same composition as that of example 3 but containing instead of the UV filter of the type derived from dibenzoylmethane, 6% by weight of 4-methylbenzylidene camphor "EUSOLEX 6300" from Merck and as dialkyl tartrate, the COSMACOL ETL product of C? 4-C15. A comparative DI antisun formulation was then prepared, of identical support as formulation D but not containing di-alkyl tartrate. For each of the compositions D and D ', the sun protection factor (SPF) that was related to it was then determined. This was determined using the method described in example 2. The results (average value corresponding to five tests) are indicated in the table (IV) given below Table (IV): These results clearly show that the contribution of a di-alkyl tartrate of C? 4-Ci5, to a photoprotective system constituted by a UV filter of the type derived from benzylidene camphor allows to significantly increase its photoprotective power. Equivalent results were obtained using diethyl tartrate (C2) or a di-alkyl 2-C13 tartrate as the COSMACOL ETI product instead of the COSMACOL ETL product.

EXAMPLE 5: An antisun formulation E according to the invention was prepared with the same composition as that of example 4 but containing instead of the UV filter of the benzylidene camphor derivative type, 5% by weight of the 2,4,6-tris [ p- (2'-ethylhexyl-1 '-oxycarbonyl) anilinol-1,3,5-triazine PUVINUL T 150"from the company BASF.) A comparative antisun formulation E' was then prepared, with the same support as for the formulation E but without containing di-alkyl tartrate, it was subsequently determined for each of the compositions E and E ', the sun protection factor (SPF) that was related to it, this was determined using the method described in example 2. results (average value corresponding to five tests) are indicated in the table (V) given below Table (V): These results clearly show that the contribution of a C14-C15 di-alkyl tartrate to a photoprotective system constituted by a UV filter of the triazine derivative type makes it possible to significantly increase its photoprotective power. Equivalent results were obtained using diethyl tartrate (C2) or a C12-C13 dialkyl tartrate as the COSMACOL ETI product instead of the COSMACOL ETL product.

EXAMPLE 6 (comparative): An antisun formulation F (not forming part of the invention) was prepared in the form of an oil-in-water type emulsion with the same composition as that of example 4 but containing instead of UV filter of the benzylidene camphor derivative type, 9% by weight of 2-ethylhexyl p-methoxycinnamate ("PARSOL MCX" from Givaudan). A comparative antisun formulation F was then prepared, giving the same support as formulation F but not containing di-C14-C15 alkyl tartrate. For each of the compositions F and F ', the sun protection factor (SPF) that was related to it was then determined. This was determined using the method described in example 1. The results (average value corresponding to five tests) are indicated in the table (VI) given below: Table (VI): These results clearly show that the contribution of a di-alkyl tartrate of 4-C15 to a photoprotective system constituted by a UV filter of the type derived from cinnamic acid does not allow to significantly increase its photoprotective power.

EXAMPLE 7 (comparative): An antisun formulation G (not forming part of the invention) was prepared in the form of an oil-in-water type emulsion with the same composition as that of example 4, but containing instead of the filter UV of the type derived from benzylidene camphor, 6% by weight of 3-benzophenone ("UVINUL M40" from BASF). Next, a comparative antisun formulation G 'was prepared, with the same support as that of formulation G but without containing di-C4-C? -alkyl tartrate. For each of the compositions G and G ', the sun protection factor (SPF) that was related to it was then determined. This was determined using the method described in example 2. The results (average value corresponding to five tests) are indicated in the table (VII) given below: Table (VII) These results clearly show that the contribution of a C12-C15 di-alkyl tartrate to a photoprotective system constituted by a UV filter of the benzophenone type does not allow to significantly increase its photoprotective power.

EXAMPLE 8 (comparative): An antisun formulation H (not forming part of the invention) was prepared in the form of an oil-in-water type emulsion with the same composition as in example 4 but containing instead of UV filter of the type derived from benzylidene camphor, 9% by weight of 2-ethylhexyl p-methoxycinnamate ("PARSOL MCX" from Givaudan) and 1% by weight of di-ethyl tartrate instead of COSMACOL ETL. A comparative antisun formulation H 'was then prepared, with the same support as formulation H but without containing diethyl tartrate. For each of the compositions H and H ', the sun protection factor (SPF) that was related to it was then determined. This was determined using the method described in example 2. The results (mean value corresponding to five tests) are indicated in the table (VIII) given below: Table (VII) These results clearly show that the contribution of diethyl tartrate to a photoprotective system constituted by a UV filter of the cinnamic type does not allow to increase its photoprotective power.

It is noted that in relation to this date the best method known by the applicant to carry out the aforementioned invention, is that which is clear from the manufacture of the objects to which it refers.

Having described the invention as above, the content of the following is claimed as property

Claims (24)

1. Composition intended for the protection of the skin and / or hair against ultraviolet radiation, characterized in that it comprises, in a cosmetically acceptable support, at least: (a) a photoprotective system capable of filtering UV radiation, constituted by at least a UV filter of the benzylidene camphor derivative type and / or of at least one UV filter of the dibenzoylmethane derivative type and / or of at least one UV filter of the triazine derivative type; (b) a linear or branched dialkyl tartrate, preferably having 1 to 16 carbon atoms; said composition does not contain 2, 4,6-tris [p- (2'-ethylhexyl-1'-oxycarbonyl) anilino] -1,3,5-triazine.

2. Composition according to claim 1, characterized in that the dialkyl tartrate is chosen from the dialkyl tartrates of Ci-Ciß.

3. Composition according to claim 1 or 2, characterized in that the dialkyl tartrate is chosen from the dialkyl tartrates of C1-C4.

Composition according to any one of claims 1 to 3, characterized in that the dialkyl tartrate is diethyl tartrate.

5. Composition according to claim 1 or 2, characterized in that the dialkyl tartrate responds to the following structure: CH3- CH3- (CH2) n- (R) p-CH, -O-C: O in which R designates a group of formula where p is 0 or 1; n equals 12 or 13 when p equals 0 and + n equals 8 or 9 when p equals 1.

6. Composition according to any one of claims 1 to 6, characterized in that the di-alkyl tartrate is used at a concentration ranging between 0.1 and 10% by weight relative to the total weight of the composition and more particularly between the 0.2 and 5% by weight.

7. Composition according to any one of claims 1 to 6, characterized in that the dibenzoylmethane derivative is chosen from the group consisting of: - 2-methyldibenzoylmethane, - 4-methyldibenzoylmethane, - 4-isopropyldibenzoylmethane, - 4-tert-butyldibenzoylmethane , - 2,4-dimethyldibenzoylmethane, - 2,5-dimethyldibenzoylmethane, - 4,4'-diisopropyldibenzoylmethane, - 4-tert-butyl-4'-methoxydibenzoylmethane, - 2-methyl-5-isopropyl-4 '-methoxydibenzoylmethane, - 2-methyl-5-tert-butyl-4f-methoxydibenzoylmethane, - 2,4-dimethyl-4'-methoxydibenzoylmethane, - 2,6-dimethyl-4-tert-butyl-4'- methoxydibenzoylmethane.

8. Composition according to any one of claims 1 to 7, characterized in that the dibenzoylmethane derivative is 4-tert-butyl-4'-methoxydibenzoylmethane.

9. Composition according to any one of claims 1 to 7, characterized in that the dibenzoylmethane derivative is 4-isopropyldibenzoylmethane.

10. Composition according to any one of claims 1 to 9, characterized in that the benzylidene camphor derivative is selected from the group consisting of: - 3-benzylidene camphor; 4-methyl-benzylidene camphor; - 3 (4 '-trimethyl-ammonium benzylidene) -camphor methyl sulfate; - benzylidene camphor sulfonic acid and its salts; - 3 (3 '-sulfo-4' -methyl benzylidene) camphor; - the polyacrylamino-methyl benzylidene camphor.

11. Composition according to any one of claims 1 to 9, characterized in that the benzylidene derivative is chosen from the group consisting of: diorganopolysiloxanes of. . benzylidene camphor function; the diorganosiloxanes of short, linear or cyclic chains; - the triorganosilanes of benzylidene camphor function.

12. Composition according to any one of claims 1 to 9, characterized in that the benzylidene derivative corresponds to the following general formula (III): wherein B designates a hydrogen atom, an alkali metal or also an NH (R) 3+ radical in which the radicals R, which may be identical or different, designate a hydrogen atom, an alkyl or hydroxyalkyl radical of C ? -C or also a group Mn + / n, designating Mn + a polyvalent metal cation in which n is equal to 2 or 3 or 4, M preferably designating a metal cation selected from Ca2 +, Zn2 +, Mg2 +, Ba2 +, Al3 + and Zr + as well as their isomers.

13. Composition according to any one of claims 1 to 10, characterized in that the benzylidene camphor derivative is 4-methylbenzylidene camphor.

14. Composition according to any one of claims 1 to 13, characterized in that the triazine derivative corresponds to the following formula (VI): (VI) in which: Ri, Rj 'and Ri ", which may be identical or different, are chosen from the following monovalent radicals of formulas (1) or (2): (2) in which - R2 and R2 ', which may be identical or different, designate a linear or branched C1-C3 alkyl radical, R3 designates a hydrogen atom, a linear or branched C1-C4 alkyl radical or an alkoxy radical of C1-C4. - R 4 denotes a linear or branched C 1 -C 12 alkyl radical, - X i represents a hydrogen atom or a phenyl radical optionally substituted by a halogen or by a C 1 -C 4 alkyl radical or by a C 1 -C 4 alkoxy radical.

15. Composition according to claim 14, characterized in that the triazine derivative is chosen from: 2,4,6-tris (4'-amino benzalmalonate diethyl) -striazine, 2,4,6-tris (4 '- diisopropyl amino benzalmalonate) - s-triazine, 2,4,6-tris (4'-amino benzalmalonate dimethyl) -striazine, - 2,4,6-tris (a-cyano-4-aminocinamate ethyl) -s- triazine.

16. Composition according to any one of Claims 1 to 15, characterized in that the photoresist system also contains one or more additional organic UV absorbers other than the benzylidene camphor derivatives, the dibenzoylmethane derivatives and the triazine derivatives, one or more pigments and / or mineral nanopigments or mixtures among them.

17. Composition according to claim 16, characterized in that the additional organic UV filters are chosen, alone or as a mixture, between 2-phenylbenzimidazole-5-sulfonic acid and its salts, cinnamic derivatives, salicylic derivatives, benzophenone derivatives, ß, β-diphenylacrylate derivatives, p-aminobenzoic acid derivatives, menthyl anthranilate, filter polymers and filter silicones.

18. Composition according to any one of claims 1 to 17, characterized in that the photoprotective system is present in said composition at a concentration ranging between 0.1% and 30% and preferably between 0.5 to 15%, and 'n-weight, in relation to the total weight of the composition.

19. Composition according to any one of Claims 1 to 18, characterized in that the photoprotective system also comprises, as complementary light-protecting agents, pigments or nanopigments of metal oxides, whether coated or not, capable of physically blocking, by diffusion and / or reflection, the UV radiation.

20. Composition according to claim 19, characterized in that the said pigments or nanopigments are chosen from the oxides of titanium, zinc, iron, zirconium, cerium and their mixtures, coated or not.

21. Composition according to any one of claims 1 to 20, characterized in that it also comprises at least one agent for tanning and / or artificially toasting the skin.

22. Composition according to any one of claims 1 to 21, characterized in that it is in the form of an aqueous continuous phase dispersion.

23. Composition according to-. Claim 22, characterized in that it is in the form of a cream gel.

24. Use of a dialkyl tartrate as defined in any one of claims 1 to 3, for the manufacture of a composition intended for the protection of the skin and / or hair against ultraviolet radiation, of the type comprising, a photoprotector system capable of filtering the UV radiation, consisting of at least one UV filter of the type derived from benzylidene camphor and / or at least one UV filter of the dibenzoylmethane type, to increase the sun protection factor. PHOTOPROTECTOR COMPOSITIONS COMPRISING A BENCILIDEN ALCANFOR AND / OR A DIBENZOYLMETHANE AND / OR A TRIAZINE AND A DIALKYL TARTRATE; USES IN COSMETICS SUMMARY OF THE INVENTION The present invention relates to new cosmetic and / or dermatological compositions intended for the protection of the skin and / or hair against UV radiation, in particular solar radiation. More precisely, the invention relates to new cosmetic and / or dermatological compositions having an improved sun protection factor and comprising, in a cosmetically and / or dermatologically acceptable support, at least one dialkyl tartrate and at least one photoprotective system capable of to filter the UV radiation, consisting of at least one UV filter of the type derived from benzylidene camphor and / or at least one UV filter of the type derived from dibenzoylmethane and / or from at least one UV filter of the triazine derivative type.