FR2949324A1 - Composition, useful e.g. for the cosmetic treatment of e.g. skin, comprises UV filter system in a support, where the UV filter system comprises dibenzoylmethane derivative, proline ester compound and siliceous-s-triazine compound - Google Patents

Abstract

Composition (A) comprises: at least one UV filter system in a support, where the UV filter system comprises (i) at least one dibenzoylmethane derivative; (ii) at least one proline ester compound (I); and (iii) at least one siliceous-s-triazine compound (II) or its tautomeric forms containing silane units and organosiloxane groups. Composition (A) comprises: at least one UV filter system in a support, where the UV filter system comprises (i) at least one dibenzoylmethane derivative; (ii) at least one proline ester compound of formula (I); and (iii) at least one siliceous-s-triazine compound of formula (D-Si(R) a1-O (3-a 1)/2) (II) or its tautomeric forms containing silane units of formula (-A-(Si)(R) a1(O) 3-a1/2), and organosiloxane group of formula (R b-Si(O) 4-b/2). R 1>0>H or 1-5C alkyl; R 2>0>8-30C alkyl; R : 1-30C alkyl optionally halogenated or unsaturated, 6-12C aryl, 1-10C alkoxy, OH or trimethylsilyloxy; a1 : 0-3; D : s-triazine group of formula (III); X : O or NR 3>; R 3>H or 1-5C alkyl; R 1>1-30C alkyl (optionally unsaturated and containing silicon atom), 5-20C cycloalkyl (optionally substituted by 1-3 1-4C alkyl group), or group of formula (-(CH 2CHR 4>-O) m1R 5>) or (-CH 2CH(OH)CH 2-O-R 6>); R 4>H or CH 3, where the group (C=O)XR 1>may be ortho, meta or para to the amino group; R 5>H or 1-8C alkyl; R 6>H or 4-8C alkyl; m1 : 2-20; n1 : 0-2; either R 2>OH, 1-8C alkyl, or 1-8C alkoxy; or R 2>R 2>1 or 2C alkylidene dioxy group; A : methylene, -[CHSi(CH 3) 3]-, ethylene or group of formula (-Z-CHW 1>-CH 2-) (IV), (-Z-CHCH 3-) (V), (-Z-CH=CH-) (VI), or (-Z-CH(=CH 2)-) (VII); b : 1-3; Z : 1-10C alkylene diradical (optionally substituted by OH or O and optionally containing amino group); and W 1>H, OH or optionally saturated 1-8C alkyl. An independent claim is included for method for improving chemical stability, against UV radiation, of at least one dibenzoylmethane derivative comprising combining dibenzoylmethane derivative, at least one caprolactam derivative (I), and at least one siliceous-s-triazine compound (II). [Image] [Image].

Description

COMPOSITION CONTAINING A DIBENZOYLMETHANE FILTER, A PROLINE DERIVATIVE ESTER AND A SILICATED S-TRIAZINE; METHOD FOR PHOTOSTABILIZING THE DIBENZOYLMETHANE FILTER

The present invention relates to a cosmetic composition containing the combination of i) at least one filter of the dibenzoylmethane derivative type, ii) at least one particular proline ester derivative of formula (I) and iii) of at least one silicon-substituted s-triazine substituted with at least two aminobenzoate or aminobenzamide groups of formula (II). It also relates to a method of photostabilization with respect to the radiation of at least one filter of the dibenzoylmethane-derived type by a quantity effective of at least one particular proline ester derivative of formula (I) which will be given the following definition and at least one siliconized s-triazine is substituted by at least two aminobenzoate or aminobenzamide groups of formula (II) defined below.

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 under the name 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 controlling this natural tan so as to 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 initiation 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.

In order to protect the skin and the keratin materials against UV radiation, antisolar compositions comprising UV-B active and UV-B organic screening agents are generally used. Most of these filters are fat soluble.

In this respect, a particularly interesting family of UV-A filters currently consists of the dibenzoylmethane derivatives, and especially 4-tert-butyl-4'-methoxydibenzoylmethane, which in fact have a high intrinsic absorption capacity. These dibenzoylmethane derivatives, which are now products that are well known per se as active filters in UV-A, are described in particular in French patent applications FR-A-2326405 and FR-A-2440933, as well as in US Pat. European Patent Application EP-A-0114607; 4-tert-butyl-4'-methoxydibenzoyl methane is also currently offered for sale under the trade name PARSOL 1789 by DSM NUTRITIONAL PRODUCTS.

Unfortunately, it turns out that the dibenzoylmethane derivatives are relatively sensitive products to ultraviolet radiation (especially UV-A), that is to say, more precisely, that they have an unfortunate tendency to degrade more or less rapidly under the action of the latter. Thus, this substantial lack of photochemical stability of the dibenzoylmethane derivatives with respect to the ultraviolet radiation to which they are inherently intended to be subjected, does not allow to guarantee a constant protection during prolonged solar exposure, so that repeated applications at intervals of Regular and close times must be performed by the user to achieve effective protection of the skin against UV rays.

It is known that in EP717982 the amide compounds have a light stabilizing effect on the dibenzoylmethane derivatives and more particularly the N, N-disubstituted amidated oils such as the N, N-diethyl-3-methylbenzamide compound of structure: product sold under the trade name R3535 by the company Merck. These amidated oils have been described in particular in application US2007141014 as solvents in cosmetic formulations of poorly soluble agents in oils such as UV filters, flavone derivatives, chromone derivatives, aryloximes and parabens. However, this stabilization is obtained in the presence of 20 to 30% of the latter compound, which has a high solvent power for all the raw materials involved in making the formulations, which has the consequence of destabilizing the compositions. rendering the compositions containing such an association unfit for use.

Also known in US Pat. No. 6,528,068 are sunscreen compositions comprising amidated oils which are neutral N-acylamino acid esters comprising a linear or branched C6-C22 long chain acyl group such as Isopropyl Lauroyl Sarcosinate ( ELDEW SL 205 of AJINOMOTO) H3 O or ethyl N-butyl, N-acetyl aminopropionate of formula: associated with organic UV filters hardly soluble in the oils usually used in the solar formulations. The combination of these amidated oils with a dibenzoylmethane derivative such as 4-tert-butyl-4'-methoxydibenzoylmethane does not provide a fully satisfactory photostability of dibenzoylmethane.

EP1891079 has also been proposed to improve the photostability of dibenzoylmethane type UVA filters by siliconized strazine derivatives substituted with at least two aminobenzoate or aminobenzamide groups. The combination of one of these triazines alone with a dibenzoylmethane derivative such as 4-tert-butyl-4'-methoxydibenzoylmethane does not provide a fully satisfactory dibenzoylmethane photostability.

The photostabilisation of the dibenzoylmethane derivatives with respect to UV radiation thus constitutes, to date, a problem which has not yet been solved in a completely satisfactory manner.

However, the Applicant has now surprisingly found that by combining the dibenzoylmethane derivatives mentioned above a particular proline ester derivative of formula (I) and a siliconized s-triazine substituted with at least two aminobenzoate groups. or aminobenzamides of formula (II) it was possible to substantially further improve the photochemical stability (or photostability) of these same dibenzoylmethane derivatives and their effectiveness in UV-A compared with the amidated compounds of the prior art and with respect to the s-triazines of the prior art without the disadvantages listed below.

This discovery is the basis of the present invention. Thus, according to one of the objects of the present invention, there is now proposed a composition comprising in a cosmetically acceptable support at least one UV filtering system, characterized in that it comprises: 3s (i) at least one derivative of dibenzoylmethane and (ii) at least one particular proline ester derivative of formula (I) which will be defined hereinafter (iii) at least one siliconized s-triazine of formula (II), the definition of which will be given below. Another object of the invention also relates to a process for improving the chemical stability with respect to UV radiation of at least one dibenzoylmethane derivative comprising associating with said dibenzoylmethane derivative an effective amount of at least one derivative. particular proline ester of formula (I) 45 which will be given the following definitions and at least one s-triazine silicon substituted by at least two aminobenzoates or aminobenzamide groups of formula (II), the definition of which will be given below.

Other features, aspects and advantages of the invention will become apparent upon reading the following detailed description.

By "cosmetically acceptable" is meant compatible with the skin and / or its integuments, which has a pleasant color, smell and feel and which does not generate unacceptable discomfort (tingling, tightness, redness), which are likely to divert the consumer to use this composition.

An effective amount is understood to mean an amount sufficient to obtain a significant and significant improvement in the photostability of the dibenzoylmethane derivative (s) in the cosmetic composition. This minimum amount of the particular pyrrolidone derivative of formula (I) and the siliciated s-triazine of formula (II), which may vary depending on the nature of the support selected for the composition, can be determined without any difficulty by means of a test. conventional photostability measurement, such as that given in the examples below.

The proline ester derivatives according to the invention are chosen from those corresponding to the following general formula (I): in which: R 1 denotes hydrogen or a linear or branched C 1 -C 5 alkyl radical; R2 denotes a linear or branched C8-C30 alkyl radical; Any enantiomeric form is also included in the general formula (I).

Among the compounds of formula (I), the following compounds (a) to (h) will be used more particularly: (a) RN = 4931-70-8 (b) RN = 4261-80-7 O NH 0 (c) (d) RN = 37673-23-7 RN = 22794-26-9 RN = 37673-37-3 where RN = 104148-11-0 RN = 104148-07-4 s The proline ester compounds of formula (I) ) are known per se and can be prepared according to the processes described in the literature, and more particularly by esterifying 2-pyrrolidone-5-carboxylic acid (also called pyroglutamic acid) with a solvent-free alcohol and without the addition of a catalyst. and microwaves according to the patent application FR 2833260 or io well by biotransformation of the same pyroglutamic acid in the presence of an alcohol and Novosym 435 according to the application EP 1642891. The proline ester compounds of formula (I) are from preferably present in the composition according to the invention in a content ranging from 0.1% to 40% by weight, based on the total weight of the composition, and preferably ranging from 0.1 to 30% by weight.

Among the derivatives of dibenzoylmethane, there may be mentioned, but not limited to: 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane, dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4'-diisopropyldibenzoylmethane, 4,4'-dimethoxydibenzoylmethane, 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'-methoxydibenzoylmethane.

Among the dibenzoylmethane derivatives mentioned above, use will be made particularly of 4- (tert-butyl) -4'-methoxy dibenzoylmethane or butyl methoxy dibenzoylmethane, offered for sale under the trade name "PARSOL 1789" by the company DSM NUTRITIONAL PRODUCTS; this filter corresponds to the following formula: OMe The dibenzoylmethane derivative (s) may be present in the compositions in accordance with the invention at contents which preferably vary from 0.01 to 10% by weight and more preferably from 0.1 to 10% by weight. 6% by weight relative to the total weight of the composition.

The s-triazine silicon compounds according to the present invention have the following general formula (II) or one of its tautomeric forms: (D) ù (S0 (3-a) I2 (I1) (R) a in which R, which are identical or different, represent a linear or branched and optionally halogenated or unsaturated C 1 -C 30 alkyl radical, a C 6 -C 12 aryl radical, a C 1 -C 10 alkoxy radical, a hydroxyl radical or the trimethylsilyloxy group; = 0 to 3 - the group (D) denotes a s-triazine compound of formula (III) below: ## STR2 ## where X represents -O- or -NR 3 -, with R 3 which represents hydrogen or a C 1 -C 5 alkyl radical; R 1 represents a linear or branched and optionally unsaturated C 1 -C 30 alkyl radical which may contain a silicon atom or a C 5 -C 20 cycloalkyl group, optionally substituted with From 1 to 3 linear or branched C1-C4 alkyl radicals, the group ## STR2 ## R4 represents hydrogen or methyl; the group (C = O) XR1 may be in the ortho, meta or para position of the amino group; - R5 represents hydrogen or a C1-C8 alkyl group; -R6 represent hydrogen or a C4-C8 alkyl group; M is an integer ranging from 2 to 20, n = 0 to 2, R 2, which may be identical or different, represent a hydroxyl radical, a linear or branched C 1 -C 8 alkyl radical or a C 1 -C 4 alkoxy radical; C8, two adjacent R2s of the same aromatic ring may together form an alkylidene dioxy group in which the alkylidene group contains 1 or 2 carbon atoms, - A is a divalent radical selected from methylene, - [CH (Si (CH3) 3] -, ethylene or a group corresponding to one of the following formulas (IV), (V), (VI) or (VII): (Z) ùCHùCH₂-- (IV)

Wherein Z is a linear or branched C1-C10 alkylene diradical, saturated or unsaturated, and wherein Z is a C 1 -C 10 alkylene diradical, linear or branched, saturated or unsaturated; , optionally substituted by a hydroxyl radical or oxygen and possibly containing an amino group, W represents a hydrogen atom, a hydroxyl radical or a linear or branched, saturated or unsaturated C1-C8 alkyl radical; in addition to the units of formula -A - (Si) (R) a (O) (3a) I2, the organosiloxane may comprise units of formula: (R) b- (Si) (O) {4_b3,2 where R has the same meaning as above and b = 1, 2 or 3;

It should be noted that the derivatives of formula (II) can be used in their tautomeric forms and more particularly in the tautomeric form of formula (II ') below:

Wherein (D ') denotes an s-triazine compound of the following formula (III'): ## STR1 ## wherein The preferred s-triazine derivatives are those for which in the formula s (III) or (III ') at least one, and even more preferably all, the following characteristics are fulfilled: R is methyl, a = 1 or 2, X is O, R1 is a C4-05 radical n = 0, the (C = O) group XR1 is in the para position opposite amino group, Z = -CH2-, W = H. Preferably, the s-triazine compounds of the invention are represented by the following formulas (Ila), (Ilb) or (Ilc): R7 R7 (IIa) (B) ù SiiO-SiiO R7 R7 R7 R7-SiiO + Siu (B) (D) R7 R7 R7 WhereSi] t [WhereSi u R7 (D) (IIc) (D) -Si (R8) In which: - (D) corresponds to formula (III) as defined above, - R7, which are identical or different, are chosen from linear or branched C1-C20 alkyl radicals, phenyl radicals; 3,3,3-trifluoropropyl and trimethylsilyloxy or the hydroxyl radical, 30-R8, which may be identical or different, are chosen from linear and branched C1-C20 alkyl and alkenyl radicals, and hydroxy or phenyl radicals, - (B) ), which are identical or different, are chosen from the radicals R7 and the radical (D), r is an integer between 0 and 200 inclusive, 20 - s is an integer ranging from 0 to 50 and if s = 0, at least one of the two symbols (B) denotes (D), - u is an integer ranging from 1 to 10, - t is an integer ranging from 0 to 10, provided that t + u is equal to or greater than 3 as well as their tautomeric forms.

The linear diorganosiloxanes of formula (IIa) are particularly preferred.

The linear or cyclic diorganosiloxanes of formula (IIa) or (IIb) falling within the scope of the present invention are random oligomers or polymers preferably having at least one, and even more preferably all, of the following characteristics: R7 is the methyl radical or the hydroxyl radical B is preferably methyl (in the case of linear compounds of formula is (Va)),

By way of examples of compounds of formula (II) which are particularly preferred, mention may be made of the following compounds of formulas (1) to (26) and also their tautomeric forms: ## STR1 ## If Si (NH) Si (NH) Si (Si) Si SiNHN (NH) (Si), Si

INP --- Si.o Si HN, NH (13) (14) HN N NH (15) (16) SiO, SiO, SiHNNNO (17) embedded image O Si (19) N OH HO (20) / Si Si

5.L - (21) (22) O Nj 'N NHkNNH 1 Sil O ~

S

O Si / 1 HN N NH YYN N HN O NH O (23) NH NN NH N ~ - / - L-0 + 1-0 1 1 NH Si-NH NH ~ N NH (24) r stat = 8 ## STR1 ## where: ## STR1 ## and ## STR1 ## will be used more particularly the compounds chosen from ethyl 2,4-bis (4'-aminobenzoate) -6 - [(3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -s -triazine of formula (2), If NP jSi.O, Si - 2,4-bis (isopropyl 4'-aminobenzoate) -6 - [(3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl propyl) amino] -s-triazine of formula (4) io s - 2,4-bis (n-butyl 4-aminobenzoate) -6 - [(3- {1,3,3,3-tetramethyl) 1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -s-triazine of formula (5) (5) - 2,4-bis (isobutyl 4'-aminobenzoate) -6 - [(3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -s-triazine of formula (6)

## STR1 ## wherein 2,4-bis (4'-aminobenzoate) - 6 - [(3- {1,3,3 , 3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -s-triazine of formula (10). More particularly, n-butyl 2,4-bis (4'-aminobenzoate) -6 - [(3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino will be used more particularly. ] s-triazine of formula (5): If i0

Of the triazine compounds of formula (II) and their tautomeric forms, some are known and have been described in patents EP 0841341 and FR 2886143. Among the compounds of formula (II) and their tautomeric forms, the products of formulas (1 ), (3), (4), (7), (8), (9), (10), (11), (12) and (13) and (25) are new and constitute another object of the invention. 'invention.

The compounds of formula (II) can be obtained according to the reaction scheme below: ## STR1 ## where R, R1, R2, A, X, n and a are as defined above and Y is halogen, especially chlorine or bromine.

The order of introduction of the reagents can be indifferently, 2 equivalents of the derivative of formula (VIII) followed by an equivalent of the derivative of formula (IX) (lane 1) or 1 equivalent of the derivative of formula (IX) followed of 2 equivalents of the derivative of formula (VIII) (Route 2).

The above reactions may be carried out optionally in the presence of a solvent (for example: THF, acetone / water for the first step of Route 2); toluene, xylene, 2-butanone or ethyl acetate for the first step of Route I), at a temperature between 0 ° C and 200 ° C, more particularly between 0 ° C and 20 ° C for the first step of Lane II and between 50 and 120 ° C for the first step of Route 1 and in the presence or absence of a scavenging base of the formed acid (for example: sodium bicarbonate, sodium carbonate, aqueous sodium hydroxide, triethylamine or pyridine). They can also be carried out in microwaves in the presence or absence of a solvent (for example: toluene, xylene or ethyl acetate) or in the presence or absence of 10% of graphite, at a temperature of 50 to 150 ° C. at a power of 50-150 Watts for a period of 10 to 30 minutes.

Be it channels 1 or 2, the steps can be chained in the same reactor without isolation of the intermediate derivatives formed. The compounds of formula (VIII), some of which are commercially available, can be obtained from a number of methods from the corresponding nitrobenzoyl chloride by reaction with the corresponding amine and reduction of the nitro benzoate obtained (by autoclave with 50% Raney nickel per example) as described in EP 0570838; or by a (preferred) method of transesterifying ethyl (commercial) para-aminobenzoate with the corresponding alcohol in the presence of a catalytic amount of dibutyltin diacetate with removal of the formed ethanol.

The compositions in accordance with the invention may comprise, in addition to other water-soluble or liposoluble, or otherwise insoluble UVA and / or UVB UV-screening agents in the commonly used cosmetic solvents.

Of course, those skilled in the art will take care to choose the optional additional filters and / or their amounts in such a way that the advantageous properties intrinsically attached to the compositions according to the invention are not, or not substantially, altered by the addition or additions envisaged in particular the improvement of the photostability of the dibenzoylmethane derivative.

The complementary organic screening agents are chosen in particular from anthranilates; cinnamic derivatives; salicylic derivatives, camphor derivatives; benzophenone derivatives; R, R-diphenylacrylate derivatives; triazine derivatives other than those of formula (II); benzotriazole derivatives; benzalmalonate derivatives including those cited in US5624663; benzimidazole derivatives; imidazolines; the bis-benzoazolyl derivatives as described in patents EP669323 and US is 2,463,264; p-aminobenzoic acid derivatives (PABA); methylene bis- (hydroxyphenylbenzotriazole) derivatives as described in US5,237,071, US 5,166,355, GB2303549, DE 197 26 184 and EP893119; benzoxazole derivatives as described in patent applications EP0832642, EP1027883, EP1300137 and DE10162844; filter polymers and screening silicones such as those described in particular in application WO-93/04665; dimers derived from α-alkylstyrene such as those described in patent application DE19855649; 4,4-diarylbutadienes as described in applications EP0967200, DE19746654, DE19755649, EP-A-1008586, EP1133980 and EP133981; merocyanine derivatives such as those described in WO04006878, WO05058269 and WO06032741 and mixtures thereof.

Examples of organic UV filters that may be mentioned are those designated below under their INCI name: para-aminobenzoic acid derivatives: PABA, Ethyl PABA, Ethyl Dihydroxypropyl PABA, Ethylhexyl Dimethyl PABA sold in particular under the name ESCALOL 507 by ISP, Glyceryl PABA, PEG-25 PABA sold under the name UVINUL P25 by BASF,

Salicylic Derivatives: Homosalate sold under the name Eusolex HMS by Rona / EM Industries, Ethylhexyl Salicylate sold under the name NEO HELIOPAN OS by Haarmann and REIMER, Dipropylene glycol salicylate sold under the name DIPSAL by SCHER, TEA 4s Salicylate, sold under the name NEO HELIOPAN TS by Haarmann and REIMER,

Cinnamic derivatives: Ethylhexyl methoxycinnamate sold in particular under the trade name 50 PARSOL MCX by DSM NUTRITIONAL PRODUCTS, Isopropyl Methoxy cinnamate, Isoamyl Methoxy cinnamate sold under the trade name NEO HELIOPAN E 1000 by SYMRISE, Cinoxate, DEA Methoxycinnamate, Diisopropyl Methylcinnamate, Glyceryl Ethylhexanoate Dimethoxycinnamate

Derivatives of 13,13-diphenylacrylate: Octocrylene sold in particular under the trade name UVINUL N539 by BASF, Etocrylene, sold in particular under the trade name UVINUL N35 by BASF,

Benzophenone derivatives: Benzophenone-1 sold under the trade name UVINUL 400 by BASF, Benzophenone-2 sold under the trade name UVINUL D50 by BASF Benzophenone-3 or Oxybenzone, sold under the trade name UVINUL M40 by BASF, Benzophenone- 4 sold under the trade name UVINUL MS40 by BASF, Benzophenone-5 Benzophenone-6 sold under the trade name Helisorb 11 by Norquay Benzophenone-8 sold under the trade name Spectra-Sorb UV-24 by American Cyanamid 25 Benzophenone-9 sold under the trade name Trade name UVINUL DS-49 by BASF, Benzophenone-12 2- (4-diethylamino-2-hydroxybenzoyl) -N-hexyl benzoate sold under the trade name UVINUL A + or as a mixture with octylmethoxycinnamate under the trade name UVINUL A + B by BASF, Derivatives of benzylidene camphor: 3-Benzylidene camphor manufactured under the name MEXORYL SD by CHIMEX, 4-Methylbenzylidene camphor sold under the name EUSOLEX 6300 by MERCK, 35 Benzylidene Campho Sulfonic Acid manufactured under the name MEXORYL SL by CHIMEX, Camphor Benzalkonium Methosulfate manufactured under the name MEXORYL SO by CHIMEX, Terephthalylidene Dicamphor Sulfonic Acid manufactured under the name MEXORYL 40 SX by CHIMEX, Polyacrylamidomethyl Benzylidene Camphor manufactured under the name MEXORYL SW by CHIMEX,

Derivatives of phenyl benzimidazole: 45 Phenylbenzimidazole Sulfonic Acid sold in particular under the trade name Eusolex 232 by Merck, Disodium Phenyl Dibenzimidazole Tetrasulfonate sold under the trade name NEO HELIOPAN AP by SYMRISE, 50 Derivatives of phenyl benzotriazole: 30 Drometrizole Trisiloxane sold under the name Silatrizole by Rhodia Chimie, methylene bis-benzotriazolyl tetramethylbutylphenol, sold in solid form under the trade name MIXXIM BB / 100 by FAIRMOUNT CHEMICAL or in micronized form in aqueous dispersion under the trade name TINOSORB M by CIBA SPECIALTY CHEMICALS,

Triazine derivatives: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine sold under the trade name TINOSORB S by CIBA GEIGY, Ethylhexyl triazone sold in particular under the trade name UVINUL T150 by BASF, Diethylhexyl butamido triazone sold under the trade name UVASORB HEB by SIGMA 3V, 2, 4,6-tris- (4'-amino benzalmalonate diisobutyl) -s-triazine, is 2,4,6-tris (4'-amino benzalmalonate dineopentyl) -s-triazine, 2,4-bis (4 ') dineopentyl amino benzalmalonate) -6- (n-butyl 4'-aminobenzoate) -s-triazine symmetrical triazine filters described in US Pat. No. 6,225,467, WO2004 / 085412 (see compounds 6 and 9) or Symetrical Triazine Derivatives IP.COM Journal, IP.COM Inc. WEST HENRIETTA, NY, US (September 20, 2004) including 2,4,6-tris (biphenyl) -1,3,5-triazines (especially 2,4 , 6-tris (biphenyl-4-yl-1,3,5-triazine) and 2,4,6-tris (terphenyl) -1,3,5-triazine which is incorporated in the applications of Beiersdorf WO06 / 035000 , WO06 / 034982, WO06 / 034991, WO06 / 035007, WO2006 / 034992, WO2006 / 034985.

Anthranilic Derivatives: Menthyl Anthranilate sold under the trade name NEO HELIOPAN MA by SYMRISE, Imidazoline Derivatives: Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate,

Derivatives of benzalmalonate: Di-neopentyl 4'-methoxybenzalmalonate Polyorganosiloxane with benzalmalonate functions such as Polysilicone-15 sold under the trade name PARSOL SLX by DSM NUTRITIONAL PRODUCTS

40 Derivatives of 4,4-diarvlbutadiene: 1,1-dicarboxy (2,2'-dimethylpropyl) -4,4-diphenylbutadiene

Benzoxazole derivatives: 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino] -6- (2-ethylhexyl) -4-imino-1,3,5-triazine sold under the name Uvasorb K2A by Sigma 3V and mixtures thereof.

The preferred complementary organic screening agents are chosen from ethylhexyl methoxycinnamate 50 homosalate ethylhexyl salicylate, octocrylene, phenylbenzimidazole sulphonic acid, benzophenone-3, benzophenone-4, benzophenone-5, 2- (4-diethylamino-2-hydroxybenzoyl) benzoate. hexyl. 4-Methylbenzylidene camphor, Terephthalylidene Dicamphor Sulfonic Acid, Disodium Phenyl Dibenzimidazole Tetrasulfonate, Ethylhexyl Triazone, Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine Diethylhexyl Butamido Triazone, 2,4,6-tris (biphenyl-4-yl-1,3,5- triazine 2,4,6-tris (dineopentyl 4'-amino benzalmalonate) -s-triazine 2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazine, 2,4-bis ( Dineopentyl 4'-amino benzalmalonate) -6- (N-Butyl 4-aminobenzoate) -s-triazine Methylene bis-Benzotriazolyl Tetramethylbutylphenol, Drometrizole Trisiloxane Polysilicone-15 Di-neopentyl 4'-methoxybenzalmalonate 1,1-dicarboxy (2, 2'-dimethyl-propyl) -4,4-diphenylbutadiene 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) -imino] -6- (2-ethylhexyl) - imino-1,3,5-triazine and mixtures thereof.

The complementary inorganic filters are chosen from coated or uncoated metallic oxide pigments, the average size of the primary particles of which is preferably between 5 nm and 100 nm (preferably between 10 nm and 50 nm), for example dye pigments. 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. The pigments may be coated or uncoated.

The coated pigments are pigments which have undergone one or more surface treatments of chemical, electronic, mechanochemical and / or mechanical nature with compounds as described, for example, in Cosmetics & Toiletries, February 1990, Vol. 105, p. 53-64, such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminum salts of fatty acids, metal alkoxides (titanium or aluminum), polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.

In a known manner, the silicones are organosilicon polymers or oligomers with a linear or cyclic, branched or crosslinked structure, of variable molecular weight, obtained by polymerization and / or polycondensation of suitably functionalized silanes, and essentially constituted by a repetition of main motifs in which the silicon atoms are connected to each other by oxygen atoms (siloxane bond), optionally substituted hydrocarbon radicals being directly bonded via a carbon atom to said silicon atoms.

The term "silicones" also includes the silanes necessary for their preparation, in particular alkyl silanes.

The silicones used for coating the pigments suitable for the present invention are preferably selected from the group containing alkyl silanes, polydialkylsiloxanes, and polyalkylhydrogensiloxanes. More preferably still, the silicones are selected from the group containing octyl trimethyl silane, polydimethylsiloxanes and polymethylhydrosiloxanes.

Of course, the metal oxide pigments before their treatment with silicones, may have been treated with other surfactants, in particular with cerium oxide, alumina, silica, Aluminum, silicon compounds, or mixtures thereof.

The coated pigments are more particularly titanium oxides coated with: - silica such as the product "Sunveil" from the company IKEDA and the product "Eusolex T-AVO" from the company MERCK 25 - silica and iron oxide such as that the product "SUNVEIL F" from the company IKEDA, - silica and alumina such as the products "MICROTITANIUM DIOXIDE MT 500 SA" and "MICROTITANIUM DIOXIDE MT 100 SA" from the company TAYCA, "TIOVEIL" from the company TIOXIDE and Mirasun TiW 60 from Rhodia, 30-alumina such as the products "TIPAQUE TTO-55 (B)" and "TIPAQUE TTO-55 (A)" from ISHIHARA, and "UVT 14/4" of the company KEMIRA, - aluminum alumina and stearate such as the product "MICROTITANIUM DIOXIDE MT 100 TV, MT 100 TX, MT 100 Z, MT-01 from TAYCA, the products" Solaveil CT-10 W "," Solaveil CT 100 "and" Solaveil CT 200 "from the company UNIQEMA, - silica, alumina and alginic acid such as the product" MT-100 AQ "from the company TAYCA, - alumina and aluminum laurate such as the product "MICROTITANIUM DIOXIDE MT 100 S" from TAYCA, 40 - iron oxide and iron stearate such as the product "MICROTITANIUM DIOXIDE MT 100 F" from the TAYCA company, - zinc oxide and zinc stearate such as the product "BR351" from the company TAYCA, - silica and alumina and treated with a silicone such as the products 45 "MICROTITANIUM DIOXIDE MT 600 SAS" "MICROTITANIUM DIOXIDE MT 500 SAS" or "MICROTITANIUM DIOXIDE MT 100 SAS" from TAYCA, - silica, alumina, aluminum stearate and treated with a silicone such as the product "STT-30-DS" the company TITAN KOGYO, - silica and treated with a silicone such as the product "UV-TITAN X 195" 50 KEMIRA company, or the product SMT-100 WRS TAYCA company. of alumina and treated with a silicone such as the products "TIPAQUE TTO-55 (S)" from ISHIHARA, or "UV TITAN M 262" from KEMIRA, of triethanolamine such as the product "STT-65- S "of the company TITAN KOGYO, s - stearic acid such as the product" TIPAQUE TTO-55 (C) "from the company ISHIHARA, - sodium hexametaphosphate such as the product" MICROTITANIUM DIOXIDE MT 150 W "of the company TAYCA.

Other titanium oxide pigments treated with a silicone are preferably TiO 2 treated with octyl trimethyl silane and whose average elementary particle size is between 25 and 40 nm, such as that sold under the trade name " T 805 "by the company Degussa Silices, the TiO 2 treated with a polydimethylsiloxane and whose average particle size is elementary is 21 nm such as that sold under the trade name" 70250 Carder UF TiO2SI3 "by the CARDRE company, TiO2 anatase / rutile treated with a polydimethylhydrogensiloxane and whose average elementary particle size is 25 nm such as that sold under the trade name "MICRO TITANIUM DIOXIDE USP GRADE 20 HYDROPHOBIC" by the company COLOR TECHNIQUES.

The uncoated titanium oxide pigments are for example sold by the company Tayca under the trade names "MICROTITANIUM DIOXIDE MT 500 B" or "MICROTITANIUM DIOXIDE MT600 B", by the company DEGUSSA under the name "P 25", by the company WACKHER under the name "transparent titanium oxide PW", by the company MIYOSHI KASEI under the name "UFTR", by the company TOMEN under the name "ITS" and by the company TIOXIDE under the name "TIOVEIL AQ". The uncoated zinc oxide pigments are, for example, those sold under the name "Z-cote" by the company Sunsmart; those marketed under the name "Nanox" by Elementis; those marketed under the name "Nanogard WCD 2025" by Nanophase Technologies;

The coated zinc oxide pigments are, for example, those marketed under the name Z-COTE HP1 by Sunsmart (dimethicone-coated ZnO); 40 - those sold under the name "Zinc Oxide CS-5" by the company Toshibi (ZnO coated with polymethylhydrogenosiloxane); those marketed under the name "Nanogard Zinc Oxide FN" by Nanophase Technologies (as a 40% dispersion in Finsolv TN, C12-C15 alcohol benzoate); 45 - those sold under the name "DAITOPERSION ZN-30" and "DAITOPERSION Zn-50" by the company Daito (dispersions in cyclopolymethylsiloxane / polydimethylsiloxane oxyethylenated, containing 30% or 50% of zinc nano-oxides coated with silica and the polymethylhydrogensiloxane); those marketed under the name "NFD Ultrafine ZnO" by the company Daikin (ZnO coated with perfluoroalkyl phosphate and a copolymer based on perfluoroalkylethyl dispersed in cyclopentasiloxane); those marketed under the name "SPD-Z1" by the company Shin-Etsu s (ZnO coated with silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane); those marketed under the name "Escalol Z100" by the company ISP (ZnO treated alumina and dispersed in the mixture methoxycinnamate ethylhexyl / copolymer PVP-hexadecene / methicone); - those sold under the name "Fuji ZnO-SMS-10" by Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane); those marketed under the name "Nanox Gel TN" by Elementis (ZnO dispersed at 55% in C12-C15 alcohols benzoate with hydroxystearic acid polycondensate). The uncoated cerium oxide pigments are sold for example under the name "COLLOIDAL CERIUM OXIDE" by the company RHONE POULENC.

Uncoated iron oxide pigments are for example sold by the company ARNAUD under the names "NANOGARD WCD 2002 (FE 45B)", "NANOGARD IRON FE 45 BL AQ", "NANOGARD FE 45R AQ," NANOGARD WCD 2006 (FE 45R) ", or by the company MITSUBISHI under the name" TY-220 "The coated iron oxide pigments are for example sold by ARNAUD under the names" NANOGARD WCD 2008 (FE 45B FN) " , "NANOGARD WCD 2009 (FE 45B 556)", "NANOGARD FE 45 BL 345", "NANOGARD FE 45 BL", or by BASF under the name 30 "TRANSPARENT IRON OXIDE".

Mention may also be made of mixtures of metal oxides, in particular of titanium dioxide and cerium dioxide, of which the titanium dioxide / cerium-coated cerium-aluminum alloy mixture, sold by IKEDA under the name "SUNVEIL" A ", as well as the mixture of titanium dioxide and zinc dioxide coated with alumina, silica and silicone such as the product" M 261 "sold by the company KEMIRA or coated with alumina, silica and glycerin such as the product "M 211" sold by KEMIRA.

The additional UV filters are generally present in the compositions according to the invention in proportions ranging from 0.01% to 20% by weight relative to the total weight of the composition, and preferably ranging from 0.1% to 10% by weight. relative to the total weight of the composition.

The aqueous compositions in accordance with the present invention may furthermore comprise conventional cosmetic adjuvants, chosen in particular from fatty substances, organic solvents, ionic or nonionic, hydrophilic or lipophilic thickeners, softeners, humectants, opacifiers and stabilizers. , emollients, silicones, anti-foam agents, perfumes, preservatives, anionic, cationic, nonionic, zwitterionic or amphoteric surfactants, actives, fillers, polymers, propellants, basifying agents or acidifying agents or any other ingredient usually used in the cosmetic and / or dermatological field.

The fatty substances may consist of an oil or a wax other than the apolar waxes as defined above or mixtures thereof. By oil is meant a liquid compound at room temperature. By wax is meant a compound that is solid or substantially solid at room temperature and whose melting point is generally greater than 35 ° C. As oils, there may be mentioned mineral oils (paraffin); vegetable (sweet almond oil, macadamia oil, blackcurrant seed oil, jojoba oil); synthetic compounds such as perhydrosqualene, alcohols, fatty amides (such as isopropyl lauroyl sarcosinate sold under the name Eldew SL-205 by the company Ajinomoto), fatty acids or esters such as the benzoate of C 12 alcohols. C15 sold under the trade name Finsolv TN or Witconol TN by the company WITCO, 2-ethylphenyl benzoate as the commercial product sold under the name X-TEND 226 by the company ISP, octyl palmitate, isopropyl lanolate triglycerides, including those of capric / caprylic acids, dicaprylyl carbonate sold under the name Cetiol CC by Cognis), oxyethylenated or oxypropylenated esters and fatty ethers; silicone oils (cyclomethicone, polydimethylsiloxane or PDMS) or fluorinated oils, polyalkylenes, trialkyl trimellitates such as tridecyl trimellitate. As wax compounds, mention may be made of carnauba wax, beeswax, hydrogenated castor oil, polyethylene waxes and polymethylene waxes, such as that sold under the name Cirebelle 303 by the company SASOL. Among the organic solvents, mention may be made of lower alcohols and polyols. These can be selected from glycols and glycol ethers such as ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol or diethylene glycol. As hydrophilic thickeners, mention may be made of carboxyvinyl polymers such as Carbopols (Carbomers) and Pemulen (acrylate / C10-C30-alkylacrylate copolymer); polyacrylamides, for example crosslinked copolymers sold under the names Sepigel 305 (CTFA name: polyacrylamide / C13-14 isoparaffin / Laureth 7) or Simulgel 600 (CTFA name: acrylamide / sodium acryloyldimethyltaurate copolymer / isohexadecane / polysorbate 80) by the company Seppic; polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid, optionally crosslinked and / or neutralized, such as poly (2-acrylamido-2-methylpropanesulfonic acid) marketed by Hoechst under the trade name Hostacerin AMPS (CTFA name : ammonium polyacryloyldimethyltaurate or SIMULGEL 800 sold by the company SEPPIC (CTFA name: sodium polyacryolyldimethyltaurate / polysorbate 80 / sorbitan oleate); copolymers of 2-acrylamido-2-methylpropane sulfonic acid and hydroxyethyl acrylate such as SIMULGEL NS and SEPINOV EMT 10 sold by the company SEPPIC, cellulose derivatives such as hydroxyethylcellulose, polysaccharides and especially gums such as Xanthan gum, water-soluble or water-dispersible silicone derivatives such as acrylic silicones, polyether silicones and polyesters. cationic silicones and mixtures thereof.

As lipophilic thickeners, mention may be made of synthetic polymers such as poly C 10 -C 30 alkyl acrylates sold under the name INTELIMER IPA 13-1 and INTELIMER IPA 13-6 by the company Landec or modified clays such as hectorite and its derivatives, such as the products marketed under the name of Bentone.

Of course, one skilled in the art will take care to choose the optional additional compound (s) mentioned above and / or their amounts in such a way that the advantageous properties intrinsically attached to the compositions in accordance with the invention are not, or substantially not, altered by the addition or additions envisaged, including the improvement of the photostability of the dibenzoylmethane derivative.

The compositions according to the invention can be prepared according to the techniques well known to those skilled in the art. They 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 or cream gel ; in the form of an aqueous gel; in the form of a lotion. They may optionally be packaged in aerosol and be in the form of foam or spray.

Preferably, the compositions according to the invention are in the form of an oil-in-water or water-in-oil emulsion.

The emulsification processes that can be used are of the pale or helix type, rotor-stator and HHP.

It is also possible, by HHP (between 50 and 800b), to obtain stable dispersions with drop sizes up to 100 nm. The emulsions generally contain at least one emulsifier chosen from amphoteric, anionic, cationic or nonionic emulsifiers, used alone or as a mixture. The emulsifiers are suitably selected according to the emulsion to be obtained (W / O or O / W). Exemplary emulsifying surfactants for the preparation of W / O emulsions include, for example, alkyl esters or ethers of sorbitan, glycerol or sugars; silicone surfactants such as dimethicone copolyols such as the mixture of cyclomethicone and dimethicone copolyol, sold under the name DC 5225 C by Dow Corning, and alkyl dimethicone copolyols such as Laurylmethicone copolyol sold under the name "Dow Corning" 5200 Formulation Aid "by Dow Corning; Cetyl dimethicone copolyol such as the product sold under the name Abil EM 90R by the company Goldschmidt and the mixture of cetyl dimethicone 50 copolyol, polyglycerol isostearate (4 moles) and hexyl laurate sold under the name ABIL WE 09 by the company Goldschmidt. One or more coemulsifiers may also be added, which advantageously may be selected from the group consisting of alkylated polyol esters.

As alkylated esters of polyol, there may be mentioned polyethylene glycol esters such as PEG-30 dipolyhydroxystearate such as the product sold under the name Arlacel P135 by the company ICI.

Examples of glycerol and / or sorbitan esters that may be mentioned are polyglycerol isostearate, such as the product sold under the name Isolan GI 34 by the company Goldschmidt; sorbitan isostearate, such as the product sold under the name Arlacel 987 by the company ICI; sorbitan isostearate and glycerol, such as the product sold under the name Arlacel 986 by the company ICI, and mixtures thereof. Examples of O / W emulsions which may be mentioned as emulsifiers are nonionic emulsifiers such as oxyalkylenated (more particularly polyoxyethylenated) fatty acid esters of glycerol; oxyalkylenated fatty acid and sorbitan esters; oxyalkylenated fatty acid esters (oxyethylenated and / or oxypropylenated) such as PEG-100 Stearate / Glyceryl Stearate sold, for example, by the company ICI under the name Arlacel 165; oxyalkylenated fatty alcohol ethers (oxyethylenated and / or oxypropylenated); sugar esters such as sucrose stearate; the fatty alcohol and sugar ethers, in particular the alkylpolyglucosides (APG) such as decylglucoside and laurylglucoside marketed, for example, by Henkel under the respective names Plantaren 2000 and Plantaren 1200, cetostearylglucoside optionally mixed with alcohol; cetostearyl, marketed for example under the name Montanov 68 by the company Seppic, under the name Tegocare CG90 by the company Goldschmidt and under the name Emulgade KE3302 by Henkel, as well as arachidyl glucoside, for example in the form of the mixture of arachidic and behenic alcohols and arachidylglucoside sold under the name Montanov 202 by the company Seppic. According to a particular embodiment of the invention, the mixture of the alkylpolyglucoside as defined above with the corresponding fatty alcohol may be in the form of a self-emulsifying composition, as described for example in the document WO -A-92/06778.

In the case of an emulsion, the aqueous phase thereof may comprise a nonionic vesicle dispersion prepared by known methods (Bangham, Standish and Watkins, J. Mol Biol 13, 238 (1965)). , FR 2 315 991 and FR 2 416 008).

The compositions according to the invention find their application in a large number of treatments, in particular cosmetics, of the skin, lips and hair, including the scalp, in particular for the protection and / or care of the skin, lips and / or hair, and / or for makeup of the skin and / or lips.

Another object of the present invention is constituted by the use of the compositions according to the invention as defined above for the manufacture of products for the cosmetic treatment of the skin, lips, nails, hair, eyelashes, eyebrows and / or scalp, including skincare products, sunscreen products and make-up products.

The cosmetic compositions according to the invention may for example be used as a makeup product.

The cosmetic compositions according to the invention may, for example, be used as care product and / or sun protection for the face and / or body of liquid to semi-liquid consistency, such as milks, more or less creamy creams. , gel-creams, pasta. They may optionally be packaged in an aerosol and be in the form of foam or spray.

The compositions according to the invention in the form of vaporizable fluid lotions according to the invention are applied to the skin or the hair in the form of fine particles by means of pressurizing devices. The devices according to the invention are well known to those skilled in the art and include non-aerosol pumps or "atomizers", aerosol containers comprising a propellant as well as aerosol pumps using compressed air as a propellant. These are described in US Pat. Nos. 4,077,441 and 4,850,517 (which forms an integral part of the content of the description). The aerosol-conditioned compositions according to the invention generally contain conventional propellants such as, for example, hydrofluorinated compounds, dichlorodifluoromethane, difluoroethane, dimethyl ether, isobutane, n-butane, propane and trichlorofluoromethane. They are preferably present in amounts ranging from 15 to 50% by weight relative to the total weight of the composition.

The compositions according to the invention may also comprise, in addition, additional cosmetic and dermatological active ingredients. Among the active ingredients, mention may be made of: vitamins (A, C, E, K, PP) and their derivatives or precursors, alone or in mixtures, anti-glycation agents; 40 - soothing agents, - NO-synthase inhibitors; agents stimulating the synthesis of dermal or epidermal macromolecules and / or preventing their degradation; agents stimulating the proliferation of fibroblasts; 4s - agents stimulating the proliferation of keratinocytes; - muscle relaxants; tensors, mattifying agents, keratolytic agents, desquamating agents; - Moisturizing agents such as polyols such as glycerin, butylene glycol, propylene glycol. anti-inflammatory agents; agents acting on the energetic metabolism of cells; - insect repellents - antagonists of substances P or CRGP. - anti-hair loss and / or hair regrowth agents - anti-wrinkle agents. Of course, those skilled in the art will take care to choose the optional additional compound (s) mentioned above and / or their amounts in such a way that the advantageous properties intrinsically attached to the compositions in accordance with the invention are not, or substantially not, altered by the addition or additions envisaged. Those skilled in the art will choose the active agent (s) for the desired effect on the skin, hair, eyelashes, eyebrows, nails.

The composition may furthermore comprise at least one ingredient such as fillers with a blooming effect or agents promoting the natural coloration of the skin, intended to complete the biological effect of these active ingredients or provide an immediate visual anti-aging effect.

For the care and / or makeup of oily skin, those skilled in the art will preferably choose at least one active agent selected from desquamating agents, sebo-regulating or anti-seborrhoeic agents, astringent agents.

OTHER ADDITIONAL INGREDIENTS

The composition may further comprise at least one additional ingredient to complement the biological effect of these assets or provide an immediate visual effect; mention may in particular be made of matting agents, blooming fillers, fluorescent agents, agents which promote the naturally rosy coloration of the skin and abrasive or exfoliating fillers. To complement and / or optimize the effects conferred by the cosmetic active agents and / or dermatological cited above on keratin materials, it may be advantageous to incorporate in the compositions of the invention other additional ingredients.

In particular, these additional ingredients may confer an immediate visual effect that will be relayed by the biological effect of the assets mentioned above. They can also, through a mechanical action (eg abrasvies), amplify the effect of the biological assets mentioned above.

Thus, the composition according to the invention may also comprise at least one agent chosen from matting agents, fillers with a blooming effect, agents promoting the naturally rosy coloration of the skin, abrasive fillers or exfoliating agents, and mixtures thereof. 40 45 50 Mattifying agents

By "matting agent" is meant agents intended to make the skin visibly duller, less glossy. The matting effect of the agent and / or of the composition containing it can in particular be evaluated using a gonioreflectometer, by measuring the ratio R between the specular reflection and the diffuse reflection. A value of R less than or equal to 2 generally reflects a matting effect. The matting agent may especially be chosen from a rice starch or a corn starch INCI name: ZEA MAYS (CORN) STARCH as in particular the product sold under the trade name FARMAL CS 3650 PLUS 036500 by National Starch, kaolinite, talc, an extract of pumpkin seeds, cellulose microbeads, vegetable fibers, synthetic fibers, in particular polyamides, microspheres of expanded acrylic copolymers, polyamide powders, silica powders, polytetrafluoroethylene powders silicone resin powders, acrylic polymer powders, wax powders, polyethylene powders, elastomeric crosslinked organopolysiloxane powders coated with silicone resin, talc / titanium dioxide / alumina / composite powders silica, mixed amorphous silicate powders, silicate particles and in particular mixed silicate, and mixtures thereof.

Examples of matting agents that may be mentioned include: rice or maize starch, in particular starch octenyl succinate aluminum sold under the name Dry Flo by the company National Starch, kaolinite; Silicas; - talc; an extract of pumpkin seeds as marketed under the name Curbilene by the company Indena; cellulose microbeads as described in patent application EP 1 562 562; - fibers, such as silk, cotton, wool, flax, cellulose fibers extracted from wood, vegetables or algae, polyamide (nylon), modified cellulose, poly-p-phenylene terephtamide acrylic, polyolefin, glass, silica, aramid, carbon, Teflon, insoluble collagen, polyesters, polyvinyl chloride or vinylidene, polyvinyl alcohol, polyacrylonitrile, chitosan, polyurethane, polyethylene phthalate, fibers formed from a mixture of polymers, synthetic resorbable fibers, and mixtures thereof described in patent application EP 1 151 742; Microspheres of expanded acrylic copolymers such as those sold by EXPANCEL under the names EXPANCEL 551; optical effect fillers as described in patent application FR 2 869 796, in particular: 305-polyamide powders (Nylon), such as for example Arkema's Orgasol type 12 nylon particles having a mean size of 10 microns and a refractive index of 1.54, silica powders, for example Silica beads SB150 from Miyoshi's average size 5 microns and refractive index 1.45, - polytetrafluoroethylene powders, such as PTFE ceridust 9205F Clariant of average size 8 microns and refractive index 1.36, - silicone resin powders as GE Silicone Silicon resin Tospearl 145A having a mean size of 4.5 microns and a refractive index of 1.41, the powders of acrylic copolymers, in particular of methyl poly (meth) acrylate, such as particles PMM A Jurymer MBI of Nihon Junyoki of average size 8 microns and refractive index 1.49, or the particles Micropearl M100 and F 80 ED of the company Matsumoto Yushi-Seiyaku, - the wax powders like the particles Paraffin wax microease 114S of 15 micropowders having a mean size of 7 microns and a refractive index of 1.54, polyethylene powders, especially comprising at least one ethylene / acrylic acid copolymer, and in particular consisting of ethylene / acrylic acid copolymers such as the Flobeads EA particles. 209 of Sumitomo (average size 10 microns and refractive index 1.48), elastomeric crosslinked organopolysiloxane powders coated with silicone resin, in particular silsesquioxane resin, as described for example in US Pat. No. 5,538 793. Such elastomer powders are sold under the names "KSP-100", "KSP-101", "KSP-102", "KSP-103", "KSP-104", "KSP-105" by the 25 company SHIN ETSU, and - the powder comp Talc osites / titanium dioxide / alumina / silica, such as those sold under the name Coverleaf AR-80 by Catalyst & Chemicals, - mixtures thereof, - absorbing and / or adsorbent sebum compounds as described in the application for Patent FR 2 869 796. Mention may in particular be made of: silica powders, such as, for example, the porous silica microspheres sold under the name "Silica Beads SB-700" marketed by the company MYOSHI, the "SUNSPHERE H51", "SUNSPHERE" H33 ", 35" SUNSPHERE H53 "marketed by ASAHI GLASS; the polydimethylsiloxane-coated amorphous silica microspheres sold under the name "SA SUNSPHERE H-33" and "SA SUNSPHERE H-53" marketed by ASAHI GLASS; amorphous mixed silicate powders, in particular aluminum and magnesium, such as, for example, that marketed under the name "NEUSILIN UFL2" by the company Sumitomo. polyamide powders (nylon), such as, for example, "Orgasol 4000" marketed by Arkema, and acrylic polymer powders, in particular of polymethyl methacrylate, such as for example the "COVABEAD LH85" marketed by the company WACKHERR company; polymethyl methacrylate / ethylene glycol dimethacrylate, such as, for example, "DOW CORNING 5640 MICROSPONGE SKIN OIL ADSORBER" marketed by Dow Corning, or "Ganzpearl GMP-0820" marketed by 50 Ganz Chemical; allyl polymethacrylate / ethylene glycol dimethacrylate, such as, for example, "POLY-PORE L200" or "POLY-PORE E200" marketed by AMCOL; ethylene glycol dimethacrylate / lauryl methacrylate copolymer, such as, for example, the "POLYTRAP 6603" sold by the company Dow Corning; silicate particles, such as alumina silicate; mixed silicate particles, such as: magnesium aluminum silicate particles, such as saponite or magnesium aluminum silicate, hydrated with sodium sulphate sold under the trade name Sumecton® by the company io Kunimine; the magnesium silicate complex, hydroxyethylcellulose, black cumin oil, squash oil and phospholipids or MatipureO from Lucas Meyer, and their mixtures. As preferred matting agents, it is possible to use, according to the invention, an extract of pumpkin seeds, a starch of rice or maize, kaolinite, silicas, talc, polyamide powders, polyethylene powders, powders of acrylic copolymers, expanded acrylic copolymer microspheres, silicone resin microbeads, mixed silicate particles and mixtures thereof. 20 Chargers with a flutter effect

These fillers can be any material capable of modifying the wrinkles by its intrinsic physical properties and of masking them. These fillers may in particular modify the wrinkles by a tightening effect, a camouflaging effect, or a blurring effect.

As a filler, the following compounds can be exemplified: - porous silica microparticles, for example Myochi's Silica Beads 30 SB 150 and SB 700 with an average size of 5 μm and Asahi's SUNSPHERESO series H Glass, such as H33, H51 with a size of 3.5 and 5 μm respectively, the hollow hemispherical particles of silicone resins, such as NLK 500, NLK 506 and NLK 510 from Takemoto Oil and Fat, described in particular in EP-A-1579849. silicone resin powders such as, for example, SILICON Resin TospearI 0.15 A DE GE silicone of average size of 4.5 μm. powders of acrylic copolymers, in particular of methyl poly (meth) acrylate, for example PMMA Jurimer MBIO particles of Nihon 40 Junyoki with an average size of 8 μm, the hollow spheres of PMMA sold under the name COVABEADO LH 85 by the company Wackherr and expanded vinylidene / acrylonitrile / methylene methacrylate microspheres sold under the name ExpanceI0. wax powders such as paraffin wax microloase O 114S particles of 45 micropowders of average size of 7 μm. polyethylene powders in particular comprising at least one ethylene / acrylic acid copolymer, for example the FLOBEADSO EA 209 E from Sumimoto with an average size of 10 μm. crosslinked elastomeric organopolysiloxane powders coated with silicone resin, especially silsesquioxane under the name KSP 100, KSP 1010, KSP 102, KSP 103, KSP 104 and KSP 105 by the company Shin Etsu. talc / dioxide or titanium / alumina / silica composite powders such as for example Coverleaf AR 800 from Catalyst & Chemical. talc, mica, kaolin, lauryl glycine, starch powders crosslinked with octyanyl succinate anhydride, boron nitride, polytetrafluoroethylene powders, precipitated calcium carbonate, hydrocarbon carbonate, magnesium, barium sulfate, hydroxyapatite, calcium silicate, cerium dioxide and microcapsules of glass or ceramics. synthetic or natural hydrophilic or hydrophobic fibers, mineral or organic fibers such as silk, cotton, wool, flax, cellulose extracted especially from wood, vegetables or algae, polyamide (nylon), modified cellulose, poly-p-phenylene terephtamide, acrylic, polyolefin, glass, silica, aramid, carbon, polytetrafluoroethylene (Teflon), insoluble collagen, polyesters, polyvinyl chloride or vinylidene , polyvinyl alcohol, polyacrylonitrile, chitosan, polyurethane, polyethylene phthalate, fibers formed from a mixture of polymers, resorbable synthetic fibers, and mixtures thereof described in patent application EP 1 151 742. - spherical elastomeric crosslinked silicones such as Trefil E-505C or E-506 C from Dow Corning. abrasive fillers which, by a mechanical effect, provide a smoothing of the cutaneous microrelief, such as abrasive silica, for example abrasive SPO from Semanez or powders of nuts or shells (apricot, walnut, for example from Cosmetochem).

The fillers having an effect on the signs of aging are chosen in particular from porous silica microparticles, hollow hemispherical silicone particles, silicone resin powders, acrylic copolymer powders, polyethylene powders, powders of crosslinked elastomeric organopolysiloxanes coated with silicone resin, talc / titanium dioxide / alumina / silica composite powders, precipitated calcium carbonate, magnesium hydrocarbonate carbonate, barium sulfate, hydroxyapatite, silicate calcium, cerium dioxide and microcapsules of glass or ceramics, silk fibers, cotton, and mixtures thereof.

40 The load can be a soft focus load.

By soft-focus charge, we mean a charge which in addition gives transparency to the complexion and a fuzzy effect. Preferably, the soft-focus charges have an average particle size of less than or equal to 15 microns. These 45 particles can be of any shape and in particular be spherical or nonspherical. More preferably, these fillers are nonspherical. The soft-focus fillers may be chosen from silica and silicate powders, in particular alumina powders, polymethyl methacrylate (PMMA) powders, talc, silica / TiO 2 or silica / zinc oxide composites, powders 50 of polyethylene, starch powders, polyamide powders, styrene / acrylic copolymer powders, silicone elastomers, and mixtures thereof.

In particular, mention may be made of talc with a mean size of less than or equal to 3 microns, for example talc with a mean size of 1.8 microns and in particular that sold under the trade name Talc P3 by the company Nippon Talc, nylon 12 powder, in particular that sold under the name Orgasol 2002 Extra D Nat Cos by the company Atochem, silica particles treated on the surface with a mineral wax 1 to 2% (INCI name: hydrated silica (and) paraffin) such as those marketed by Degussa, amorphous silica microspheres, such as those sold under the name Sunsphere for example reference H-53 by Asahi Glass, and silica micro-beads such as those sold under the name SB-700 or SB-150 by the company Miyoshi, this list is not limited to.

The concentration of these fillers having an effect on the signs of aging in the compositions according to the invention may be between 0.1 and 40%, or even between 0.1 and 20% by weight relative to the total weight of the composition. Aqents favoring the naturally rosy coloration of the skin.

A self-tanning agent, that is to say an agent which, applied on the skin, in particular on the face, makes it possible to obtain a tanning effect of a more or less similar appearance to that which may result from a prolonged exposure to the sun (natural tanning) or under a UV lamp; an additional coloring agent, that is to say any compound having a particular affinity for the skin enabling it to confer on the latter a durable, non-covering coloration (ie not having a tendency to opacify the skin ) and which is eliminated with neither water nor with the aid of a solvent, and which is resistant to both rubbing and washing with a solution containing surfactants. Such durable coloration is therefore distinguished from the superficial and temporary coloration provided for example by a makeup pigment; and their mixtures.

Examples of self-tanning agents that may be mentioned include: dihydoxyacetone (DHA), erythrulose, and the combination of a catalytic system formed of: salts and oxides of manganese and / or zinc, and alkaline hydrogen carbonates and or alkaline earth.

The self-tanning agents are generally chosen from mono or polycarbonyl compounds such as, for example, isatin, alloxane, ninhydrin, glyceraldehyde, mesotartaric aldehyde, glutaraldehyde, erythrulose, pyrazolin-4 derivatives, 5-diones as described in patent application FR 2 466 492 and WO 97/35842, dihydroxyacetone (DHA), 4,4-dihydroxypyrazolin-5-ones derivatives as described in patent application EP 903 342 DHA will preferably be used.

DHA may be used in free form and / or encapsulated for example in lipid vesicles such as liposomes, in particular described in application WO 97/25970.

In general, the self-tanning agent is present in an amount ranging from 0.01 to 20% by weight, and preferably in an amount of between 0.1 and 10% of the total weight of the composition.

It is also possible to use other dyes which make it possible to modify the color produced by the self-tanning agent.

These dyes may be chosen from synthetic direct dyes or natural dyes.

These dyes may be chosen, for example, from red or orange dyes of the fluoran type such as those described in the patent application FR2840806. Mention may be made, for example, of the following dyes: tetrabromofluorescein or eosin known under the name CTFA: Cl 45380 or Red 21 phloxine B known under the name CTFA: Cl 45410 or Red 27 diiodofluorescein known under the name CTFA Cl 45425 or Orange 10; Dibromofluorescein known under the name CTFA: Cl 45370 or Orange 5. - the sodium salt of tetrabromofluorescein known under the name CTFA: Cl 45380 (Na knows) or Red 22 - the sodium salt of phloxine B known under the CTFA name: Cl 45410 (Na knows) or Red 28 - the sodium salt of diiodofluorescein known as CTFA: Cl 45425 (Na knows) or Orange 11; Erythrosine known under the name CTFA: Cl 45430 or Acid Red 51. Phloxine known under the name CTFA: Cl 45405 or Acid Red 98.

These dyes may also be chosen from antraquinones, caramel, carmine, charcoal black, azulene blue, methoxalene, trioxalene, guajazulene, chamuzulene, bengal rose, cosine 10B, cyanosine, daphinin.

These dyes may also be chosen from indole derivatives such as the monohydroxyindoles as described in the patent FR2651126 (ie: 4-, 5-, 6- or 7-hydroxyindole) or the dihydroxyindoles as described in the EP-patent. B-0425324 (ie: 5,6-dihydroxyindole, 2-methyl-5,6-dihydroxyindole, 3-methyl-5,6-dihydroxyindole, 2,3-dimethyl-5,6-dihydroxyindole); 45 Abrasive agents or exfoliating agents

As exfoliation agents that can be used in rinsed compositions according to the invention, mention may be made, for example, of exfoliant or scrubbing particles 50 of mineral, vegetable or organic origin. Thus, for example, beads or polyethylene powder, nylon powder, polyvinyl chloride powder, pumice, crushed apricot kernels or nut shells can be used. sawdust, glass beads, alumina, and mixtures thereof. Exfogreen of Solabia (bamboo extract), extracts of strawberry akenes (Greentech strawberry Akenes), peach stone powder, apricot kernel powder, and finally the field of vegetable powders with abrasive effect include the cranberry powder.

As abrasive fillers or preferred exfoliant agents according to the invention, mention may be made of peach kernel powder, apricot kernel powder, cranberry kernel powder, strawberry achene extracts, bamboo extracts. .

The examples which follow serve to illustrate the invention without however being limiting in nature. In these examples, the amounts of the ingredients compositions are given in% by weight relative to the total weight of the composition.

EXAMPLES OF SYNTHESES: EXAMPLE 1 Preparation of methyl 2,4-bis (4'-diylamino benzoate) -6 - {[1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxyldisiloxanyllpropyl-3-ylamino} In a reactor under nitrogen bubbling, methylparaminobenzoate (9.2 g, 0.0609 mol), 2- butanone (40 ml) and potassium carbonate (4.21 g) dissolved in 57 ml of water. The mixture was cooled to 0-5 ° C. and cyanuric chloride (5.61 g, 0.0304 mol) dissolved in 88 ml of 2-butanone was added dropwise over 1 hour. The mixture is heated at 70 ° C. for 6 hours; the methyl 2,4-bis (4'-diylamino benzoate) -6-chloro-s-triazine formed is not isolated. To the reaction mixture was added 2.56 g of sodium bicarbonate and 1-amino-1,3,3,3-tetramethyl-1- [(trimethylsilyl) oxy] disiloxanyl was then added dropwise over 1 hour. ] -3-propane (8.51 g, 0.0304 mol). After cooling, the two phases are separated and the organic phase is washed with water and dried. 2-butanone is removed under reduced pressure. The paste obtained is purified by passage over a silica column (eluent: Heptane / EtOAc 8: 2). The clean fractions of the derivative of Example 1 (3.53 g, yield: 18%) are thus recovered in the form of a beige powder: s Melting point: 144-145 ° C., UV (Ethanol): X max = 311 nm, El% = 1268.

EXAMPLE 2 Preparation of ethyl 2,4-bis (4'-diylamino benzoate) -6 - {[1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxyldisiloxanyllpropyl-3-ylamino} -sio triazine (Route I): (2) In a reactor bubbled with nitrogen, ethyl paraben aminobenzoate (6.05 g, 0.0366 mol), 2-butanone (30 ml) and the potassium carbonate (2.53 g) dissolved in 38 ml of water. The mixture is cooled to 0-5 ° C. and cyanuric chloride (3.38 g, 0.0183 mol), dissolved in 68 ml of 2-butanone, is added dropwise over 1 hour. The mixture is heated at 70 ° C. for 6 hours; the ethyl 2,4-bis (4'-diylamino benzoate) -6-chloro-s-triazine formed is not isolated and is reacted in the next step.

1.54 g of sodium bicarbonate are added to the reaction mixture, then 1-amino [1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl is added dropwise over 1 hour. 3-propane (5.12 g, 0.0183 mol). It is maintained at 70 ° C. for 4 hours. After cooling, the two phases are separated and the organic phase is washed with water and dried. 2-butanone is removed under reduced pressure. The paste obtained is crystallized in heptane. The product of Example 2 (8.8 g, Yield 70%) is thus obtained in the form of light beige crystals: Melting point: 134-135 ° C., UV (Ethanol): X max = 311 nm, El% = 1186.

EXAMPLE 3 Preparation of ethyl 2,4-bis (4'-divamino benzoate) -6-fi, 3,3,3-tetramethyl-1 - ((trimethylsilyl) oxyldisiloxanyl) -propyl-3-ylamino} -striazine (Lane II): HNNyNHN1 * N NH First Step: Preparation of 2,4-dichloro-6- {[1,3,3,3-tetramethyl-1- (trimethylsilyl) oxyldisiloxanyllpropyl-3-ylamino} -s-triazine:

To a solution of cyanuric chloride (25 g, 0.135 mole) in 250 ml of acetone is added dropwise at 0 ° C 1-amino [1,3,3,3-tetramethyl-1- [ (trimethylsilyl) oxy] disiloxanyl] -3-propane (41.7 g, 0.149 mol) and a solution of sodium bicarbonate (11.4 g, 0.135 mol) in 120 ml of water so that the pH is between 3 and 6.5. At the end of the introduction, the pH is 6.5. The stirring is then maintained for 1 hour 30 minutes at 10 ° C. and then left at laboratory temperature. The precipitate formed is filtered, washed with water, drained and dried. 55.2 g (yield: 95%) of the expected derivative are obtained in the form of a white powder (mp: 59 ° C.).

Second Step: Preparation of the Derivative of Example 3: The mixture of the above product (2.1 g, 0.005 mole) and ethyl para-amino benzoate (1.65 g, 0.01 mole) in suspension in 20 ml of toluene is refluxed for 1 hour 30 minutes. It is cooled and hot heptane is added to the resin obtained. After trituration, filtration and drying, 2.3 g (Yield: 67%) of the derivative of Example 3 are obtained in the form of a white powder: Melting point: 126 ° -128 ° C., UV (Ethanol): X max = 311 nm, El% = 1147.

EXAMPLE 4 Preparation of n-propyl-2,4-bis (4'-divamino benzoate) -6- (1,3,3,3-tetramethyl-1-yl) (trimethylsilyl) oxyldisiloxane] propyl-3-ylamino} -s- triazine (Route II): n-propyl para-aminobenzoate (3.35 g, 0.0187 mol) dissolved in 15 ml of ethyl acetate is introduced into a reactor. 1.5 ml of pyridine dissolved in 10 ml of ethyl acetate are added thereto. The reaction mixture was heated to 70 ° C under an argon atmosphere and then the product of the first step of Example 3 (4 g, 0.0094 moles) was added. It is left at 70 ° C. for 2 hours. The dark red solution is cooled and washed with saturated sodium chloride solutions and then with water. After drying of the organic phase, the paste obtained is crystallized in heptane. The product of Example 4 (2.3 g, yield: 34%) is thus obtained in the form of light beige crystals: Melting point: 109-110 ° C., UV (Ethanol): X max = 311 nm, El % = 1228.

EXAMPLE 5: Preparation of Isopropyl 2,4-bis (4'-divamino benzoate) -6- (1,3,3,3-tetramethyl) -1- (trimethylsilyl) oxyldisiloxane-3-propyl-3-ylamino} -striazine ( Route II): (4) Isopropyl para-aminobenzoate (10.05 g, 0.0561 mol) dissolved in 40 ml of ethyl acetate is charged to a reactor. 4.54 ml of pyridine dissolved in 15 ml of ethyl acetate are added. The reaction mixture is heated to 70 ° C under an Argon atmosphere and then the product of the first step of Example 3 (12 g, 0.0281 mole) is added. It is left at 70 ° C. for 2 hours. The dark red solution is cooled and washed with saturated sodium chloride solutions and then with water. After drying of the organic phase, the paste obtained is purified by chromatography on a silica column (eluent: heptane / EtOAc 8: 2) crystallized in heptane. The product of Example 5 (10.8 g, Yield: 54%) is thus obtained in the form of a light beige powder: Melting point: 68-70 ° C., UV (Ethanol): X max = 311 nm, El% EXAMPLE 6 Preparation of n-butyl 2,4-bis (4'-diylamino benzoate) -6- (1,3,3,3-tetramethyl) -1- (trimethylsilyl) oxyldisiloxanylpropyl-3-ylamino } -striazine (Route II): If INP 15 (5)

Under nitrogen sparging, the product obtained in the first step of Example 3 (16.74 g, 0.0391 mol), n-butyl para-amino benzoate (15 g, 0.0776 mol) and Potassium carbonate (5.36 g, 0.0388 mol) was suspended in 170 ml of toluene and refluxed for 1 hour 20 minutes. The reaction mixture is cooled and 150 ml of dichloromethane are added thereto. The minerals are filtered. The filtrate is washed with bicarbonate water and then twice with water. After drying of the organic phase and evaporation of the solvents, a white powder is obtained. After recrystallization from 1: 15 EtOAc / Heptane, 20.1 g (Yield: 69%) of the derivative of Example 6 was obtained as a white powder: m.p .: 111-113 ° C, UV (Ethanol): λmax = 312 nm, El / / o = 1360. EXAMPLE 7 Preparation of 2,4-bis (4'-divlamino benzoate of isobutyl) -6-fi 1,3,3,3- tetramethyl-1 -f (trimethylsilyl) oxyldisiloxanepropyl-3-ylamino} -striazine (Lane I): ## STR1 ##

In a reactor bubbled with nitrogen, isobutyl paraaminobenzoate (10.39 g, 0.0538 mol), 2-butanone (72 ml) and potassium carbonate (3.72 g) dissolved in 57 ml of water. The mixture was cooled to 0-5 ° C. and cyanuric chloride (4.96 g, 0.0269 mol) dissolved in 68 ml of 2-butanone was added dropwise over 1 hour and 30 minutes. The mixture is heated at 70 ° C. for 17 hours; the isobutyl 2,4-bis (4'-diylamino benzoate) -6-chloro-striazine formed is not isolated. To the reaction mixture was added 2.26 g of sodium bicarbonate, and then the product of the first step of Example 2a (7.52 g, 0.0269 mol) was run dropwise over 1 hour. After cooling, the two phases are separated and the organic phase is washed with water and dried. 2-butanone is removed under reduced pressure. The paste obtained is chromatographed on a column of silica (eluent: Heptane / EtOAc 8: 2). The product of Example 7 (5.2 g, Yield 26%) is thus obtained in the form of light beige crystals: Melting point: 66-67 ° C, UV (Ethanol): X max = 311 nm, El% = 1150.

EXAMPLE 8 Preparation of 2- (4'-methylamino-benzoate) -4- (4 "-N-butylamino benzoate) -6 - {[1,3,3,3-tetramethyl-1- (trimethylsilyl) ) (modified lane I): (7) In a nitrogen bubbled reactor, tert-butyl para-aminobenzoate (1 g, 0.00517 mol) was solubilized in 10 g. ml of ethyl acetate, pyridine (836 μl) dissolved in 5 ml of ethyl acetate is added, the mixture is heated to 70 ° C. and a solution of the derivative of the first is dripped in 30 minutes. step of Example 2a (2.21 g, 0.00517 mol) in 15 ml of ethyl acetate is left at 70 ° C for 2 hours and then a solution of paraaminobenzoate (0.98 g, 0.00517 mole) dissolved in 5 ml of ethyl acetate, the mixture is heated at 70 ° C. for 2 hours and the organic phase is washed with saturated sodium chloride solution and then cooled. The paste obtained is chromatographed Silica column (eluent: Heptane / EtOAc 8: 2). The product of Example 8 (1.52 g, yield 30%) is thus obtained in the form of light beige crystals: Melting point: 111-113 ° C., UV (Ethanol): X max = 311 nm, El% EXAMPLE 9 Preparation of tert-butyl-2,4-bis (4'-diylamino benzoate) -6411,3,3,3-tetramethyl-1- (trimethylsilyl) oxyldisiloxanylpropyl-3-ylamino} -s-triazine (Way II): \, sii INP ~ si. In a nitrogen bubbled reactor, tert-butyl para-aminobenzoate (3.62 g, 0.00189 mol) is solubilized in 15 ml of ethyl acetate. Pyridine (1.5 ml) dissolved in 10 ml of ethyl acetate is added. The mixture is heated to 70 ° C. and a solution of the derivative of the first step of Example 3 (4 g, 0.00936 mol) in 15 ml of ethyl acetate is run dropwise over 30 minutes. It is left at 70 ° C. for 2 hours. After cooling, the organic phase is washed with a saturated solution of sodium chloride, then with water and dried. The paste obtained is chromatographed on a column of silica (eluent: Heptane / EtOAc 8: 2). The clean fractions of the product of Example 9 (3.94 g, Yield 42%) are thus obtained in the form of a white powder: Melting point: 78-79 ° C., UV (ethanol): X max = 311 nm, El% = 1321.

EXAMPLE 10 Preparation of n-pentyl-2,4-bis (4'-diylamino benzoate) -64111,3,3,3-tetramethyl-1- (trimethylsilyl) oxyldisiloxanylpropyl-3-ylamino) -s-triazine ( Lane I): N-pentyl paraaminobenzoate (40 g, 0.0193 mol), 2-butanone (200 ml) and potassium carbonate (13, respectively) were introduced successively into a reactor bubbling with nitrogen. 34 g) dissolved in 116 ml of water. The mixture is cooled to 0-5 ° C. and cyanuric chloride (17.8 g, 0.0965 mol) dissolved in 68 ml of 2-butanone is added dropwise over 1 hour and 30 minutes. The mixture is heated at 70 ° C. for 17 hours; the n-pentyl 2,4-bis (4'-diylamino benzoate) -6-chloro-s-triazine formed is not isolated. To the reaction mixture was added 8.11 g of sodium bicarbonate, then the product of the first step of Example 2a (27 g, 0.00965 mole) was run dropwise over 1 hour. Heating is maintained at 70 ° C for 4 hours. After cooling, the two phases are separated and the organic phase is washed with water and dried. 2-butanone is removed under reduced pressure. The yellow-orange solid obtained is chromatographed on a column of silica (eluent: Heptane / EtOAc 9: 1). The product of Example 10 (3.79 g, Yield 51%) is thus obtained in the form of light beige crystals: mp: 94 ° -95 ° C., is UV (Ethanol): λmax = 311 nm, El% = 1265 .

EXAMPLE 11 Preparation of (1,1,3,3-tetramethylbutyl) 1-6- {1,3,3,3-tetramethyl-1-1 (trimethylsilyl) oxyldisiloxanylpropyl) -2,4-bis (4-diethylamino) benzamide 3-ylamino} -s-triazine: First step: preparation of 4-nitro-N- (tert-octyl) benzamide:

In a reactor, tert-octyl amine (51.7 g, 0.4 mole) and triethylamine (61.2 ml, 0.44 mole) were charged to 260 ml of dichloroethane. The mixture is heated to 70 ° C. and 4-nitrobenzoyl chloride (77.9 g, 0.42 mol) is then added in 50 minutes in small portions. Refluxed for 4 hours. The reaction mixture is poured into ice water; it is extracted with dichloromethane, dried and the solvent evaporated. The beige precipitate obtained is recrystallized from a mixture of isopropyl ether and ethanol (ratio 10: 1). After drying under vacuum, 84.6 g (yield 76%) of 4-nitro-N- (tert-octyl) benzamide is obtained in the form of an off-white powder and used as it is in the next step.

Second step: preparation of 4-amino-N- (tert-octyl) benzamide:

In a 500 ml hydrogenator, the product of the preceding step (30 g, 0.108 mol) dissolved in 200 ml of ethyl acetate is hydrogenated in the presence of 4.8 g of 10% palladium on 50% carbon. % water as catalyst 40 (hydrogen pressure: 8-10 bar) at a temperature of 70-75 ° C for 1 hour and 15 minutes. After filtration, concentration of the solvent and drying under vacuum, 20.4 g (yield: 76%) of 4-amino-N- (tert-octyl) benzamide are obtained in the form of a light yellow powder and used as such in the aqueous solution. 'next step. Third Step: Preparation of the Derivative of Example 4: In a CEM Discover Microwave, the mixture of the product of the first stage of the product is heated for 20 minutes at a temperature of 115 ° C. and at a power of 150 watts. Example 3 (1 g, 2.3x10-3 mol), the product of the previous step (1.16 g, 4.6x10-3 mol) and sodium bicarbonate (0.39 g, 4.6x10-3 mol) ) in 10 ml of dry toluene. Dichloromethane is added to the reaction mixture and washed with saturated sodium chloride solution and then twice with water. After drying of the organic phase and evaporation of the solvents, a light yellow oil is obtained. After purification on a silica column (eluent: Heptane / EtOAc 70: 30), the clean fractions of the derivative of Example 11 (0.9 g, Yield: 45%) are recovered in the form of white flakes: UV (Ethanol ): X max = 302 nm, El% = 775.

EXAMPLE 12 Preparation of Methyltrimethylsilyl (-3,3,3,3-tetramethyl-1-yl) (trimethylsilyl) oxyldisiloxanylpropyl-3-ylamino) -2,3-bis (4'-diylamino benzoate) -s- triazine: SiSi First step: preparation of methyltrimethylsilyl 4-aminobenzoate

In a reactor, chloromethyltrimethylsilyl (38.5 g, 0.314 mol) is added dropwise at 80 ° C. to the heterogeneous mixture of para-amino benzoic acid potassium salt (50 g, 0.285 mol) in 350 ml. of DMF. Refluxed for 3 hours. After cooling, the salts are filtered and the DMF is evaporated. The residue is taken up in dichloromethane, dried and the solvent evaporated. The oil obtained is purified by distillation. The fractions which distil at 189 ° C. are recovered under a vacuum of 0.6 mbar. The oil crystallises. 50.4 g (yield: 79%) of methyltrimethylsilyl 4-aminobenzoate are obtained in the form of a white powder and used as such in the next step. Second step: preparation of the derivative of Example 12:

Under nitrogen sparge, the mixture of the product of the first step of Example 3 (2.1 g, 4.9 × 10 -3 mol) and the derivative of the preceding step (2.19 g, 10 9 × 10 -3 mol) in 40 ml of toluene is refluxed for 5 hours. Cool and evaporate the solvent. The residue is taken up in dichloromethane, dried and the solvent evaporated. 3 g (yield: 76%) of the derivative of Example 12 are obtained in the form of a pale yellow gum: UV (Ethanol): X max = 311 nm, El% = 907.

EXAMPLE 13 Preparation of n-hexyl-2,4-bis (4'-diylamino benzoate) -6411,3,3,3-tetramethyl-1- (trimethylsilyl) oxyldisiloxanylpropyl-3-ylamino) -s-triazine (Lane II): In an argon bubbling reactor, n-hexyl para-aminobenzoate (19.32 g, 0.0904 mol) is solubilized in 50 ml of ethyl acetate. Pyridine (7.3 ml) dissolved in 15 ml of ethyl acetate is added. Heated to 70 ° C and dripped in 30 minutes a solution of the derivative of the first step of Example 3 (19.32 g, 0.0452 mol) in 50 ml of ethyl acetate. It is left at 70 ° C. for 2 hours. After cooling, the organic phase is washed with a saturated solution of sodium chloride, then with water and dried. The paste obtained is chromatographed on a column of silica (eluent: Heptane / EtOAc 9: 1). The clean fractions of the product of Example 13 (12.4 g, yield 34%) are thus obtained in the form of a white powder: Melting point: 40-41 ° C., UV (Ethanol): X max = 311 nm , El% = 1371. EXAMPLE 14: Preparation of Cyclohexyl (2,4-bis (4'-divamino benzoate) -6- {1,3,3,3-tetramethyl-1-yl (trimethylsilyl) oxyldisiloxanvllpropyl) -3 In a reactor under argon bubbling, cyclohexyl para-aminobenzoate (20 g, 0.0912 moles) was solubilized in 50 ml of ethyl acetate. Pyridine (7.4 ml) dissolved in 15 ml of ethyl acetate is added. The solution of the first step derivative of Example 3 (19.5 g, 0.0456 mol) in 50 ml of ethyl acetate was heated to 70 ° C and dripped in 30 minutes. It is left at 70 ° C. for 2 hours. After cooling, the organic phase is washed with a saturated solution of sodium chloride, then with water and dried. The paste obtained is chromatographed on a column of silica (eluent: Heptane / EtOAc 8: 2). The clean fractions of the product of Example 14 (31.8 g, yield 82%) are thus obtained in the form of a beige powder: Melting point: 74-75 ° C., UV (Ethanol): X max = 311 EXAMPLE 15 Preparation of 2,2-bis (4'-divlamino benzoic acid) -6- {1,3,3,3-tetramethyl-1-yl (trimethylsilyl) oxyldisiloxane] propyl-3 -vlamino} -s-triazine (Lane II): \, ùsi INP --Si. In an argon bubbling reactor, 2-ethyl hexyl para-aminobenzoate (20 g, 0.0802 mol) is solubilized in 50 ml of ethyl acetate. Pyridine (6.5 ml) dissolved in 15 ml of ethyl acetate is added. The mixture is heated to 70 ° C. and a solution of the derivative of the first step of Example 3 (17.2 g, 0.0401 mol) in 50 ml of ethyl acetate is run in dropwise over 30 minutes. It is left at 70 ° C. for 2 hours. After cooling, the organic phase is washed with a saturated solution of sodium chloride, then with water and dried. The paste obtained is chromatographed on a column of silica (eluent: Heptane / EtOAc 8: 2). The clean fractions of the product of Example 15 (14.4 g, yield 42%) are thus obtained in the form of a pale brown wax: UV (Ethanol): X max = 311 nm, El% = 1450.

EXAMPLE 16 Preparation of 2,4-bis (2'-hydroxy-4'-diylamino benzoate 2-ethylhexyl) -6- {1,3,3,3-tetramethyl-1-io 1 (trimethylsilyl) ) Oxyldisiloxanyllpropyl-3-ylamino} -s-triazine (Lane II): Under nitrogen sparge, a mixture of ethyl 2-hexyl 2-hydroxy-4-aminobenzoate (1.4 g, 5.57 × 10- 3 mol) and the product of the first step of Example 3 (1.19 g, 2.78x10-3 mol) in 10 ml of toluene is refluxed for 5 hours. Cool and evaporate the solvent. The residue is chromatographed on a silica column (eluent: Heptane / EtOAc 9/1). 1.58 g (yield: 64%) of the eigenfractions of the derivative of Example 16 are obtained in the form of a white paste: UV (Ethanol): = 300 nm, E1% = 480 X max = 325 nm, E1% = 709.

EXAMPLE 17 Preparation of 4-Butylcarbonyl) phenylamino) -6- ({3-diethoxy (methyl) silylpropyl} amino) -3,5-triazin-2-ylamino} benzoate butyl (Lane I) ): First step: preparation of n-butyl 2,4-bis- (4'-diylamino benzoate) -6-chloro-s-triazine:

To a solution of cyanuric chloride (54.36 g, 0.295 mole) in 500 ml of dioxane and 50 ml of water was added dropwise at 5 ° C simultaneously n-butyl para-aminobenzoate (113.94). g, 0.59 moles) and potassium carbonate solution (40.68 g, 0.295 moles) in 50 ml of water so that the pH is between 3 and 6.5. It is maintained for 1 hour 30 minutes at 5 ° C. A precipitate is formed in the medium corresponding to the monosubstituted s-triazine. The mixture is gradually heated to 70 ° C. and the second equivalent of potassium carbonate (40.68 g, 0.295 moles) in 50 ml of water is added. Stirring is then maintained for 5 hours at 70 ° C. Cool and filter the reaction mixture. The precipitate formed is washed with water, drained and dried. After recrystallization from dioxane / water, 52.5 g (yield: 36%) of the first recrystallization stream of n-butyl 2,4-bis (4'-diylamino benzoate) were obtained after drying under vacuum. -chloro-s-triazine as a white powder.

Second step: preparation of the compound of Example 17

Under nitrogen sparging, the heterogeneous mixture of the product of the preceding step (20 g, 0.04 mol) and aminopropyl diethoxy methyl silane (15.37 g, 0.08 mol) was gradually heated to 70 ° C. After one hour, the mixture is cooled, dichloromethane is added and the organic phase is washed 3 times with water. After drying of the organic phase and evaporation of the solvents, then by recrystallization from heptane the derivative of Example 17 (21 g, yield 80%) in the form of a white solid UV (Ethanol): Xmax = 311 nm, El% = 1197.

EXAMPLES 18 and 19: Preparation of the derivatives: butyl 4- (4- {[4- (butoxycarbonyl) phenyl] amino} -6- {f3- (1-hydroxy-1,3,3,3-tetramethyldisiloxanyl) propyllamino} -1 4,4'- {[6- [(3-dihydroxy (methyl) silylpropyl} amino} -1,3,5-triazine-2,4-diylldiimino} dibutyl, 3,5-triazin-2-yl) aminolbenzoate and dibutyl; (obtained by acid treatment of the derivative of Example 5): ## STR1 ## to the derivative of Example 6 (10 g, 0.013 mol) solubilized in 500 ml of the 80:20 ethanol / isopropanol mixture, 160 ml of 0.1 N hydrochloric acid and 340 ml of the 80:20 ethanol / isopropanol mixture are added. The mixture is stirred at room temperature for 5 hours. This solution is neutralized with 0.4% sodium hydroxide to a pH of 7. 1 liter of water is added and the solution is freeze-dried. The freeze-dried batches are pooled to give 6.5 g of a light beige powder which contains in relative percentages by HPLC about 28% of the derivative of Example 18 and about 10% of the derivative of Example 19. This powder was fractionated by centrifugal partition chromatography (with two-phase systems composed of heptane, ethyl acetate, methanol and water in various proportions) to give 0.58 g of the derivative of Example 18 in the form of a powder white: UV (Ethanol): Xmax = 312 nm, El% = 1228 and 0.42 g of the derivative of Example 19 in the form of a white powder.

EXAMPLE 20 Preparation of Butyl 4 - ({4 - {[4- (butoxycarbonyl) phenyllamino} -6 - [(2- {1,3,3,3-tetramethyl-1-yl (trimethylsilyl) oxyldisiloxanyl} propyl) aminol-1,3,5-triazin-2-yl} amino) benzoate:

Step 1: Preparation of 4,6-dichloro-N- (2- {1,3,3,3-tetramethyl-1-f (trimethylsilyl) oxyldisiloxanyl} propyl) -1.3 5-triazin-2-amine:

To a solution of cyanuric chloride (32.5 g, 0.176 mol) in 180 ml of acetone is added dropwise at 0 ° C a mixture of 15/85 of 2- {1,3,3,3- tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propan-1-amine and 3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propan-1-amine (49, 3 g, 0.176 mol) and sodium bicarbonate solution (14.8 g, 0.176 mol) in 210 ml of water so that the pH is between 4 and 5.8. At the end of the introduction, the pH is 5.3. The stirring is then maintained for 1 hour 30 minutes at 10 ° C. and then left at laboratory temperature. The precipitate formed is filtered, washed with water, drained and dried. 72.4 g (yield: 96%) of the isomeric derivatives in the ratio 15/85 are obtained in the form of a white powder (mp: 59 ° C.). 20 g of this mixture was fractionated by centrifugal partition chromatography (biphasic system: Heptane / Acetonitrile / Water 50: 49: 1) to give 2.0 g of 4,6-dichloro-N- (2- {1, 3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) -1,3,5-triazin-2-amine employed as such in the following step: Step 2: Preparation of the derivative of the example 20:

The preceding product (2 g, 0.0047 mol) is solubilized in 18 ml of toluene. Pyridine (0.8 ml, 0.009 mol) and n-butyl para-amino benzoate (1.8 g, 0.009 mol) were added thereto. The mixture is heated at 70 ° C. with stirring for 3 hours. The solution is cooled and poured onto a bed of silica and the cake is rinsed with 80 ml of toluene. After evaporation of the solvent, the brownish beige solid obtained is crystallized in 30 ml of heptane. 2.2 g (yield 63%) of the derivative of Example 20 is thus obtained in the form of a light beige powder: melting point: 149-151 ° C., UV (Ethanol): X max = 312 nm, El% = 955.

EXAMPLE 21 Preparation of the compound (23): embedded image in the derivative of Example 6 (1 g, 0.0013 mol) solubilized in 50 ml of the ethanol / isopropanol mixture in the 80:20 ratio, 25 ml of 1N hydrochloric acid is added. The mixture is stirred at room temperature for 4 hours. This solution is neutralized with 35% sodium hydroxide to a pH of 7. The solvents are evaporated under vacuum. 0.8 g of a light beige powder is obtained which contains, in relative percentage by HPLC, approximately 37% of the derivative of Example 21. This powder was fractionated by centrifugal partition chromatography (with two-phase system composed of heptane, ethyl acetate, methanol and water) to give 0.18 g of the derivative of Example 21 as a white powder: UV (Ethanol): X max = 312 nm, El% = 1109.

EXAMPLE 22 Preparation of the Compound (24) ## STR1 ## ## STR1 ##

s First step: preparation of n-butyl 2,4-bis (4'-diylamino benzoate) -6-chloro-s-triazine:

To a solution of cyanuric chloride (54.36 g, 0.295 mole) in 500 ml of dioxane and 50 ml of water was added dropwise at 5 ° C simultaneously n-butyl parabino-benzoate (113 g). 94 g, 0.59 mol) and a solution of potassium carbonate (40.68 g, 0.295 mol) in 50 ml of water so that the pH is between 3 and 6.5. It is maintained for 1 hour 30 minutes at 5 ° C. A precipitate is formed in the medium corresponding to the monosubstituted s-triazine. The mixture is gradually heated to 70 ° C. and the second equivalent of potassium is carbonate (40.68 g, 0.295 mole) in 50 ml of water is added. Stirring is then maintained for 5 hours at 70 ° C. Cool and filter the reaction mixture. The precipitate formed is washed with water, drained and dried. After recrystallization from dioxane / water, 52.5 g (yield: 36%) of the first recrystallization stream of 2,4-bis (4'-diylamino-n-butyl benzoate) are obtained after drying under vacuum. -chloro-s-triazine as a white powder.

Second step: preparation of the derivative of Example 22:

Under nitrogen sparging, a mixture of the above product (2 g, 4x10-3 mol), aminopropyl terminated polydimethylsiloxane (DMS-A-11 from Gelest) (2.13 g, 2x10-3 mol) and pyridine (0.32 ml, 4x10-3 mol) in 40 ml of toluene is heated at 70 ° C for 5 hours. It is cooled, dichloromethane is added and the organic phase is washed 3 times with water. After drying of the organic phase and evaporation of the solvents, a brown oil is obtained. After treatment with black in hot ethanol and filtration on celite, 3.3 g (yield: 70%) of the derivative of Example 22 is obtained in the form of a light brown gum: UV (Ethanol): X max = 311 nm, El% = 916.

EXAMPLE 23 Preparation of 2,4-bis (diylamino benzoate dodecyl) -6411,3,3,3-tetramethyl-1- (trimethylsilyl) oxyldisiloxanyllpropyl-3-ylamino) -s-triazine (Lane II) : (25)

First step: preparation of dodecyl para-aminobenzoate

A mixture of ethyl para-aminobenzoate (33.8 g, mole), n-dodecanol (114.84 ml, mole), catalyst (dibutyl tin diacetate: 544 μL) was heated at 170 ° C. 48 hours (the ethanol formed is removed by distillation). The reaction mixture changes from colorless to orange. Under a vacuum of about 20 mmHg, the mixture is heated for 6 hours at 100 ° C. The reaction mixture changes from orange to red. The mixture is then heated to 120 ° C. to remove excess lauryl alcohol. The reddish brown viscous oil is crystallized from methanol. After filtration, washing the cake with cold methanol and drying in vacuo docecyl para-aminobenzoate (52.77 g, Yield 84%) as a pale yellow powder and used as it in the step Next: Second Step: Preparation of the Derivative of Example 23:

Under argon sweeping and stirring, the product of the first step of Example 3 (20 g, mole) solubilized in ethyl acetate, 5.3 ml of pyridine dissolved in 'ethyl acetate. The mixture is heated to 70 ° C. and the dodecyl para-amino benzoate of the previous step (14 g, mole) is added in portions over 10 minutes. The reaction mixture is left at this temperature for 3 hours. The red / black reaction mixture is cooled and washed twice with saturated sodium chloride solution and then with water and then suspended in 20 ml of toluene is refluxed for 1 hour 30 minutes. Cooled and added to the resin obtained hot heptane. After trituration, filtration and drying, 2.3 g (yield: 67%) of the derivative of Example 23 are obtained in the form of a pale brown wax: Melting point: 134-135 ° C., UV (Ethanol) Λmax = 311 nm, El / / o = 838.

EXAMPLE 24 Preparation of compound (26): ## STR1 ## of the product of Example 17 (1 g, 1.53x10-3 mol), decamethylcyclopentasiloxane (D5 (0.57 g, 1.53x10-3 mol), hexamethyldisiloxane (MM) (0.062 g, 0.38x10) mole) and concentrated hydrochloric acid (0.1 ml) is stirred vigorously in a mixture of 10 ml of toluene and 1 ml of water, and the mixture is gradually heated to 70 ° C. and left at this temperature for 2 hours. After cooling to room temperature and dilution with water, the whole is filtered off The precipitate obtained is washed with water and dried to give 0.56 g of a white powder of the derivative of Example 24: UV (Ethanol): Xmax = 311 nm, El% = 892. 15 PHOTOSTABILITY TESTS

The photostabilizing effect of the combination of a proline ester derivative of formula (I) and a siliconized s-triazine derivative substituted with two aminobenzoate groups of formula (II) in accordance with US Pat. invention with respect to the dibenzoylmethane derivative: Butyl Methoxy Dibenzoylmethane (avobenzone), sold for sale under the trade name "PARSOL 1789" by Roche Vitamins.

The light stabilizing effect of the combination of a proline ester derivative of formula (I) and a siliconized s-triazine derivative substituted with two aminobenzoate groups of formula (II) was also compared with each derived alone (Comparative Examples 1 and 2)

30 PRINCIPLE OF THE METHOD:

The percentage loss of dibenzoylmethane derivative induced by exposure to a solar simulator of a formula spread in films of thickness close to 20 μm is measured. The evaluation is made by HPLC analysis of the filter in solution, after extraction of the films, by comparing irradiated and non-irradiated samples.

s MATERIAL AND METHOD:

Solar simulator: Oriel 1000W device with a 4-inch output, with 81017 filter and dichroic mirror. The samples are exposed in a horizontal position. UV-meter: OSRAM CENTRA device equipped with 2 reading heads, one for UVA and the other for UVB. The UV meter simulator assembly is calibrated annually by spectroradiometry.

Irradiance measurements made at the beginning and at the end of the exposure by placing the read heads at the position of the sample.

The irradiances are: 0.35 - 0.45mW / cm2 in UVB 20 16-18mW / cm2 inUVA

Residual Butyl Methoxy Dibenzoylmethane is measured by chromatography: HPLC chain with diode array detector.

25 COMMON SUPPORT

The compounds of formula (I) and (II) are introduced into the common carrier defined above in the presence of 1% Butyl Methoxydibenzoylmethane of composition: Phase Name Quantity per 100g C12-C ~ 5 alkyl benzoate 10 Cetearyl alcohol and cetearyl glucoside 7.5 Butyl Methoxy 1 Dibenzoylmethane Grasse Derivative 10% proline ester formula (I) Derivative of s-triazine silicon substituted by two groups 0/0 aminobenzoates of formula (II) Aqueous Pure glycerine 5 Water gsp100 IMPLEMENTATION OF TESTS OF PHOTOSTABILITY

About 20 mg of each test formula is spread over a 10 cm 2 surface on a frosted side of a fused silica disk. The exact amount is determined by weighing.

3 films are exposed to the solar simulator and 3 others serve as a control.

The samples are exposed 3 by 3 in the light of the solar simulator for a time sufficient to deliver a UVA dose equal to 12J corrected for the sensitivity of the UV meter corresponding to the degradation of approximately 50% of Butyl Methoxy Dibenzoylmethane (avobenzone) in the absence of photoprotective agent.

At the end of the exposure, each support disk is introduced into a 600 ml jar with 10 ml of a suitable solvent (in general EtOH); the whole is placed for 5 minutes in an ultrasonic tank.

The solution is then transferred to vials adapted to the support 20 compatible with the HPLC analysis apparatus used.

The analytical conditions can be adjusted according to the tested active.

The calculation of the losses is made from the averages obtained on the irradiated and non-irradiated samples, as described below:

TABLE I Examples Silicon S-triazine proline ester derivative of formula (I) formula (II) Example 10% of compound (a) none comparative 1 Example no 5% of compound (5) comparative 2 Example 1 10% of compound ( a) 5% of compound (5) (invention) It is observed that the combination of the proline ester derivative of formula (I) and the siliconized striazine of formula (II) in example 1 of the invention leads to a light stabilizing effect vis-à-vis the dibenzoylmethane derivative significantly greater than that obtained with the proline ester derivative of formula (I) alone or with the s-3s silicon triazine of formula (II) alone.

Claims (13)

REVENDICATIONS1. Composition comprising in a cosmetically acceptable support at least one UV filtering system, characterized in that it comprises: (i) at least one dibenzoylmethane derivative and (ii) at least one proline ester derivative of the following formula (I) O in which: R1 denotes hydrogen or a C1-C5 alkyl radical, linear or branched; R2 denotes a linear or branched C8-C30 alkyl radical; (iii) at least one silicon s-triazine of the following general formula (II) or one of its tautomeric forms: in which - R, identical or different, represent a linear or branched and optionally halogenated C 1 -C 30 alkyl radical; unsaturated, C 6 -C 12 aryl radical, C 1 -C 10 alkoxy radical, hydroxy radical or trimethylsilyloxy group; -a-0A3; the group (D) denotes an s-triazine compound of the following formula (III): ## STR2 ## where X represents -O (0) - (SiiO (3-a) 12 (II) (R) O- or -NR 3 -, with R 3 representing hydrogen or a C 1 -C 5 alkyl radical, R 1 represents a linear or branched and optionally unsaturated C 1 -C 30 alkyl radical which may contain a silicon atom, a group C 5 -C 20 cycloalkyl, optionally substituted with 1 to 3 linear or branched C 1 -C 4 alkyl radicals, the - (CH 2 CHR 4 --O) m R 5 group or the -CH 2 -CH (OH) -CH 2 -O-R 6 group, R 4 represents hydrogen or methyl, the group (C = O) XR may be in the ortho, meta or para position of the amino group; R 5 represents hydrogen or a C 1 -C 8 alkyl group; R 6 represent hydrogen or a C4-C8 alkyl group, s - m is an integer ranging from 2 to 20, -n = 0 to 2, - R2, which may be identical or different, represent a hydroxyl radical or a C1-C8 alkyl radical; , linear or branched, an alkox radical C 1 -C 8, two adjacent R 2 of the same aromatic ring which together can form an alkylidene dioxy group in which the alkylidene group contains 1 or 2 carbon atoms, - A is a divalent radical chosen from methylene, - [CH ( If (CH 3) 3) -, ethylene or a group corresponding to one of the following formulas (IV), (V), (VI) or (VII): (Z) ù CH ù CH 2 ù (IV) ( Z CH (V) CH 3 (Z) ùCH = CH (VI) IIH 2. Wherein Z is a linear or branched, saturated or unsaturated C1-C10 alkylene diradical optionally substituted with a hydroxyl radical or oxygen and optionally containing an amino group; W represents a hydrogen atom, a hydroxyl radical or a linear or branched, saturated or unsaturated C 1 -C 8 alkyl radical; in addition to the units of formula -A- (Si) (R) a (O) (3-a) / 2, the organosiloxane may comprise units of formula: (R) b- (Si) (O) (4 -b) Where R has the same meaning as above and b = 1, 2 or 3; 2. Composition according to claim 1, wherein the praline ester derivative of formula (I) is chosen from the following compounds (a) to (h): ## STR2 ## 3. Composition according to claim 1 or 2, wherein the dibenzoylmethane derivative is the 4- (tert-butyl) -4'-methoxy dibenzoylmethane or butyl methoxy dibenzoylmethane of the following formula: ## STR2 ## A composition according to any one of claims 1 to 3, wherein the s-triazine is selected from which at least one, and even more preferably all, of the following characteristics are fulfilled: R is methyl, a = 1 or 2, X is O, RI is a C4-05 n-0 radical, 20 group (C = O) XR1 is in position para to the amino group, Z = -CH2-, W = H. 5. A composition according to any one of claims 1 to 4, wherein the siliconized s-triazine has one of the following formulas (IIa), (lib) or (IIc): R7 R7 R7 R7 (Ila) (B) Wherein (B) R7R7 (D) R7R7R7R7SerII (wherein R7 (D) (D) -Si (R8) 3 in which: - (D) corresponds to formula (III) ) as defined in claim 1, R7, which are identical or different, are chosen from linear or branched C1-C20 alkyl, phenyl, 3,3,3-trifluoropropyl and trimethylsilyloxy radicals or the hydroxyl-R8 radical, identical or different, are chosen from linear and branched C 1 -C 20 alkyl and alkenyl radicals, the hydroxyl or phenyl radicals, - (B), which may be identical or different, are chosen from radicals R 7 and radical (D), and is an integer from 0 to 200 inclusive, - s is an integer from 0 to 50 and if s = 0, at least one of the two symbols (B) denotes (D), - u is an integer allan t is 1 to 10, t is an integer from 0 to 10, with the proviso that t + u is equal to or greater than 3 and their tautomeric forms. as well as their tautomeric forms. The composition of claim 5 wherein the siliconized s-triazine is selected from. 2,4-bis (ethyl 4'-aminobenzoate) -6 - [(3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -s -triazine of formula (2), 60- 2,4-bis (isopropyl 4'-aminobenzoate) -6 - [(3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] ] disiloxanyl} propyl) amino] -s-triazine of formula (4) NNHNN (4) -N-2,4-bis (n-butyl 4-aminobenzoate) - [- (3- 1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -s-triazine of the formula (5) NH (5) 1 - 2,4-bis (4'- isobutyl aminobenzoate) -6 - [(3 - {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -s-triazine of formula (6) (6) neopentyl 2,4-bis (4'-aminobenzoate) -6 - [(3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -s- triazine of formula (10). The composition of claim 6, wherein the siliconized s-triazine is n-butyl 2,4-bis (4-aminobenzoate) -6 - [(3- {1,3,3,3-tetramethyl-1 [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] s-triazine of formula (5) (5) 8. Composition according to any one of claims 1 to 7, characterized in that it. contains in addition to other water-soluble or fat-soluble organic or inorganic filters in UV-A and / or UV-B or insoluble in commonly used cosmetic solvents. 9. Composition according to claim 8, wherein the complementary organic screening agents are chosen from anthranilates; cinnamic derivatives; salicylic derivatives, camphor derivatives; benzophenone derivatives; [3,3-diphenylacrylate derivatives; triazine derivatives other than those of formula (II); benzotriazole derivatives; benzalmalonate derivatives; benzimidazole derivatives; imidazolines; the bis-benzoazolyl derivatives; p-aminobenzoic acid derivatives (PABA); methylene bis (hydroxyphenyl benzotriazole) derivatives; benzoxazole derivatives; filter polymers and silicone filters; dimers derived from α-alkylstyrene; 4,4-diarylbutadienes; merocyanine derivatives and mixtures thereof. 15 10. Composition according to Claim 9, characterized in that the organic UV screening agent (s) is (are) chosen from the following compounds: Ethylhexyl Methoxycinnamate Homosalate Ethylhexyl Salicylate, Octocrylene, Phenylbenzimidazole Sulfonic Acid, Benzophenone-3, Benzophenone-4, Benzophenone-5 N-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate. 4-Methylbenzylidene camphor, Terephthalylidene Dicamphor Sulfonic Acid, Disodium Phenyl Dibenzimidazole Tetra-Sulfonate, Ethylhexyl Triazone, Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine Diethylhexyl Butamido Triazone, 2,4,6-Tris (Biphenyl-4-yl-1,3,5- triazine 2,4,6-tris (dineopentyl 4'-amino benzalmalonate) -s-triazine 2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazine, 2,4-bis ( Dineopentyl 4'-amino benzalmalonate) -6- (N-Butyl 4-aminobenzoate) -s-triazine Methylene bis-Benzotriazolyl Tetramethylbutylphenol, Drometrizole Trisiloxane Polysilicone-15 Di-neopentyl 4'-methoxybenzalmalonate 1,1-dicarboxy (2, 2'-dimethyl-propyl) -4,4-diphenylbutadiene 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino] -6- (2-ethylhexyl) imino -1,3,5-triazine and mixtures thereof. 11. Composition according to the. claim 8, characterized in that the complementary inorganic filters are metallic oxide pigments, coated or not. 12. Composition according to any one of claims 1 to 11, characterized in that it is in the form of an oil-in-water emulsion or water-in oil. s 13. Process for improving the chemical stability with respect to the UV radiation of at least one dibenzoylmethane derivative as defined in any one of the preceding claims, characterized by the fact that said dibenzoylmethane derivative is effective combination of at least one praline ester derivative of formula (I) and at least one siliconized s-triazine of ~ o formula (II) as defined in the preceding claims.