FR2908988A1 - Photostabilization of a dibenzoylmethane derivative against UV radiation, useful e.g. for the manufacture of makeup products, by combining with silicated s-triazine compound and bis(resorcinyl) triazine compound - Google Patents

Abstract

Process for photostabilization of a dibenzoylmethane derivative against UV radiation, comprises combining a silicated s-triazine compound (I) or its tautomer forms, substituted by two aminobenzoate or aminobenzamide and a bis(resorcinyl) triazine compound, with the dibenzoylmethane derivative. Process for photostabilization of a dibenzoylmethane derivative against UV radiation, comprises combining a silicated s-triazine compound of formula (D)-Si((R)a)-O(3-a)/2 (I) or its tautomer forms, substituted by two aminobenzoate or aminobenzamide and a bis(resorcinyl) triazine compound, with the dibenzoylmethane derivative. R : 1-30C alkyl (optionally halogenated or unsaturated), 6-12C aryl, 1-10C alkoxy or trimethylsilyloxy, preferably -CH3; a : 0-3, preferably 1-2; D : s-triazine compound of formula (II); X : -O- (preferred) or -NR3-; R3H or 1-5C alkyl; R11-20C alkyl (optionally unsaturated and optionally containing Si) or 5-20C cycloalkyl (optionally substituted by 1-3 substituents of 1-4C alkyl, -(CH2CHR4-O)mR5 or -CH2-CH(OH)-CH2-O-R6), preferably 4-5C alkyl, where the group (C=O)XR1 may be in ortho, meta or para position to the amino groups, preferably in para position; R4H or CH3; R5H or 1-8C alkyl; R6H or 4-8C alkyl; m : 2-20; n : 0-2, preferably 0; either R2OH, 1-8C alkyl or 1-8C alkoxy; or R2R21-2C alkylidene dioxy; A : methylene, -CH(Si(CH3)3)-, ethylene, -Z-CH(W1)-CH2-, -Z-CH=CH- or -Z-C=CH2-; Z : 1-10C alkylene diradical (optionally substituted by OH or O and optionally containing amino group), preferably -CH2-; and W1H (preferred), OH or 1-8C alkyl. An independent claim is included for the composition comprises a filtering system in a support, comprising UV filter of dibenzoylmethane derivative, (I) and a bis(resorcinyl)triazine compound. [Image].

Description

PHOTOSTABILIZATION OF A DIBENZOYLMETHANE BY A SILICOUS S-TRIAZINE AND

  SUBSTITUTED BY TWO AMINOBENZOATE OR AMINOBENZAMIDE GROUPS AND A BIS-RESORCINYLTRIAZINE; The present invention relates to a process for photostabilizing the UV radiation of at least one dibenzoylmethane derivative by the combination of at least one siliconized s-triazine and substituted with two groups. BACKGROUND OF THE INVENTION aminobenzoates or aminobenzamides of particular formula (I) and at least one bis-resorcinyl triazine compound. It also relates to novel compositions, in particular cosmetic compositions for topical use containing the combination of a dibenzoylmethane derivative of a siliconized s-triazine and substituted by two aminobenzoate or aminobenzamide groups of the formula (I) and a bis-resorcinyl triazine compound. 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 control of this natural tan to thereby control the color of the skin; it is therefore necessary to filter this UV-B radiation. It is also known that UV-A rays of wavelengths between 320 and 400 nm, which cause browning of the skin, are capable of inducing an alteration thereof, especially in the case of a skin sensitive or skin continuously exposed to solar radiation. UV-A rays cause in particular a loss of elasticity of the skin and the appearance of wrinkles leading to premature cutaneous aging. They promote the triggering of the erythematous reaction or amplify this reaction in some subjects and may even be the cause of phototoxic or photoallergic reactions. Thus, for aesthetic and cosmetic reasons such as the preservation of the natural elasticity of the skin for example, more and more people wish to control the effect of UV-A on their skin. It is therefore desirable to also filter the UV-A radiation. In order to provide skin and keratin protection against UV radiation, antisolar compositions comprising UV-B active and UV-B active organic screening agents are generally used. In this respect, a particularly interesting family of UV-A filters currently consists of the dibenzoylmethane derivatives, and in particular 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 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 the company ROCHE VITAMINS. Unfortunately, it is found that the dibenzoylmethane derivatives are relatively sensitive to ultraviolet radiation (especially UV-A), that is to say, they degrade more or less quickly under the action of the latter. Thus, this substantial lack of photochemical stability with respect to the ultraviolet radiation to which they are inherently intended to be subjected, does not ensure a constant protection during prolonged sun exposure. Several means of photostabilization of dibenzoylmethane derivatives are known to date. Thus, it is known in patent application EP514491 that the alkyl derivatives R, Rdiphenylacrylate or α-cyano [3, [3'-diphenylacrylate substantially improves the photostability of the dibenzoylmethane derivatives. Unfortunately, although these filters have a good efficiency vis-à-vis the improved photostability of dibenzoylmethane derivatives, they nonetheless have a low UV-B absorbency. Another particularly interesting family of filters is the bis-rescorcinyl triazine compounds such as those described and prepared according to the syntheses indicated in patent applications EP-A-0775 698. These are products that are well known per se as active filters in UV-B and UV-A. 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine or bis-ethylhexyloxyphenol methoxyphenyl triazine is particularly known. under the trade name TINOSORB S by CIBA. It is also known in patent application EP1280505 that Bis-ethylhexyloxyphenol methoxyphenyl triazine alone enhances the photostability of dibenzoylmethane derivatives. Unfortunately, if this filter has a high UV-B absorbing capacity, it nevertheless has a limited effectiveness with regard to improving the photostability of the dibenzoylmethane derivatives. The good photostabilization of the dibenzoylmethane derivatives with respect to UV radiation, combined with a good protective efficacy in the UVB in order to be able to provide complete and effective protection of the skin against the aggressions related to the exposure to UV radiation is, to date, a problem that has not yet been solved in a completely satisfactory manner.

  Now, the Applicant has now surprisingly discovered that a particular family of s-triazine compounds which are siliconized and substituted by two aminobenzoate or aminobenzamide groups, active in the UV-B of formula (I) (which can be will further define in detail) associated with a bis-resorcinyl triazine compound allowed on the one hand to substantially improve the photochemical stability (or photostability) of the dibenzoylmethane derivatives and on the other hand to ensure a good protective efficacy in UV-B. In addition, these same particular s-triazine compounds of formula (I) are photostable even in the presence of a dibenzoylmethane derivative.

  Silica means a compound comprising in its structure at least one diorganosiloxane group or a silane group. These findings are the basis of the present invention.  Thus, in accordance with one of the objects of the present invention, there is now provided a method for improving the stability of at least one derivative of dibenzoylmethane with respect to UV radiation by combining said dibenzoylmethane derivative with at least one s-triazine compound of formula (I) or one of its tautomeric forms which will be given the following definition and at least one bis-resorcinyl triazine compound.  Another subject of the invention also relates to a composition comprising in a cosmetically acceptable support at least one UV filtering system, characterized in that it comprises at least: (a) at least one UV filter of the dibenzoylmethane type and (b) at least one s-triazine silicate compound substituted with two aminobenzoate or aminobenzamide groups of formula (I) which will be defined hereinafter or one of its tautomeric forms, (c) at least one bis-resorcinyl compound triazine.  Finally, another subject of the present invention is the use of at least one siliconized striazine compound substituted by two aminobenzoate or aminobenzamide groups of formula (I) or one of its tautomeric forms, the definition of which will be given below and of at least one bis-resorcinyl triazine compound in a composition comprising in a physiologically acceptable carrier at least one dibenzoylmethane derivative for the purpose of improving the UV stability of said dibenzoylmethane derivative.  Other features, aspects and advantages of the invention will be apparent from the following detailed description.  In the remainder of the present description, the term "UV radiation filtering system" is understood to mean a UV radiation filtering agent consisting of either a single organic or mineral compound filtering the UV radiation or a mixture of several organic or inorganic radiation-filtering compounds. UV, for example a mixture comprising a UVA filter and a UVB filter.  The silicon-substituted silicon compounds substituted with two aminobenzoate or aminobenzamide groups according to the invention have the following general formula (I) or one of its tautomeric forms: (D) ù (Sii-O (3-a) Embedded image in which - R, which may be identical or different, represents a linear or branched and optionally halogenated or unsaturated C 1 -C 30 alkyl radical, a C 6 -C 12 aryl radical or a C 1 -C 12 alkoxy radical; C10 or trimethylsilyloxy group; a = 0-3; group D denotes an s-triazine compound of formula (II) below: represents hydrogen or a C1-C5 alkyl radical; 5 -R1 represents a linear or branched and optionally unsaturated C1-C20 alkyl radical which may contain a silicon atom or an optionally substituted C5-C20 cycloalkyl group; by 1 to 3 linear or branched C1-C4 alkyl radicals, the group û (CH2CHR4-O) mR5 or grou CH 2 -CH (OH) -CH 2 -O-R 6, -R 4 represents hydrogen or methyl; the group (C = O) XR, which 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 alkyl group; -C8, - m is an integer ranging from 2 to 20, - n = 0 to 2, 15 - R2, identical or different, represent a hydroxyl radical, a linear or branched C1-C8 alkyl radical, an alkoxy radical; C1-C8, two adjacent R2 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 ( CH 3) 3] -, ethylene or a group corresponding to one of the following formulas (III), (IV) or (V): (Z) ùCH ùCH2 W (Z) ù CH = CH (IV) IIH2 (Z) - C (V) in which: Z is a linear or branched, saturated or unsaturated C1-C10 alkylene diradical, optionally substituted by a hydroxyl radical or oxygen, and Optionally containing an amino group, -W represents a hydrogen atom, a hydroxyl radical or a linear or branched C1-C8 alkyl radical, saturated or unsaturated. It should be noted that the derivatives of formula (I) may be used in their tautomeric forms, and more particularly in the tautomeric form of the following formula (I '): ## STR3 ## wherein the group (I') D 'denotes an s-triazine compound of formula (II') below: In addition to the units of formula -Au (Si) (R) a (O) (3_ay2, the organosiloxane may comprise units of formula (R) ) b- (Si) (O) (4_by2 in which: R has the same meaning as in formula (I), b = 1.2 or 3.  The preferred s-triazine derivatives are those for which in formula (II) or (II ') at least one, and even more preferably all, the following characteristics are met: R is methyl, a = 1 or 2, X is O, R, is a C4-05 n = 0 radical, the (C = O) XR group is in the para position with respect to the amino group, Z = -CH2-, W = H.  Preferably, the s-triazine compounds of the invention are represented by the following formulas (Ia), (Ib) or (Ic): R7 R7 R7 R7 (Ia) (B) SiO + Si (SiO) Si (Si) B) R7 R7 (D) R7 R7 R7 WhereSi * WhereSi R7 (D) (D) -Si (R8) 3 in which: - (D) corresponds to formula (II) as defined above, NH) = And R 7, which may be identical or different, are chosen from linear or branched C 1 -C 20 alkyl, phenyl, 3,3,3-trifluoropropyl and trimethylsilyloxy radicals or the hydroxyl-R 8 radical, which may be identical or different. different, are chosen from linear and branched C 1 -C 20 alkyl and alkenyl radicals, the hydroxyl or phenyl radicals, 5 - (B), which are identical or different, are chosen from the radicals R 7 and the radical (D), r is a 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 ranging from 1 to 10, 10 t is an integer ranging from 0 to 10, it being understood that t + u is equal to or greater than 3 and their tautomeric forms.  The linear diorganosiloxanes of formula (Ia) are particularly preferred.  The linear or cyclic diorganosiloxanes of formula (Ia) or (Ib) 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 is preferably methyl (in the case of linear compounds of formula (Ia)). By way of examples of compounds of formula (I) that are particularly preferred, mention may be made of compounds of formulas (a) to (m) as well as their tautomeric forms: NH Where Si (a) Si-- (b) NH Os c Si-- (d) NH O Si Si (f) NH \ Where Si (e) 7 O . ~.  S; ## STR1 ## where / if O \ N OH / Si Si (i) (j), OH ## STR2 ## In particular, the compound 2,4-dihydroxypropionic acid will be used. bis (n-butyl 4'-diylamino benzoate) -6 - {[1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl] propyl-3-ylamino} -s-triazine ( b): (m) wherein R, R 1, R 2, A, n and a are as defined above and Y is halogen, especially chlorine or bromine.  The order of introduction of the reagents may be indifferently, 2 equivalents of the derivative of formula (VI) followed by an equivalent of the derivative of formula (VII) (lane 1) or 1 equivalent of the derivative of formula (VII) followed 2 equivalents of the derivative of formula (VI) (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, toluene, xylene or 1,2-dichloroethane for the second step), at a temperature of between 0 ° C. and 200 ° C., more particularly between 0 ° C. and 20 ° C. for the first step and between 50 ° and 120 ° C. for the second step and in the presence or absence of a scavenger base of the acid formed (for example: bicarbonate sodium, 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 1,2-dichloroethane) 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.  When a is 1-3 and R is alkoxy, the polymerizations of the alkoxysilane monomeric derivatives can be carried out by conventional methods of silicone chemistry.  The preparation of the aminated derivatives of benzoic acid of formula (VI) is described in particular in FR 2151503.  As amino derivatives of benzoic acid that are particularly suitable for the preparation of the compounds according to the invention, mention may be made of butyl 4-amino benzoate and pentyl 4-amino benzoate.  The compounds of below: ## STR5 ## wherein formula (VII) can be obtained from Dow Corning Toray Silicone Co, Ldt such as those of a, w-diamino structure such as BY16-853 (viscosity: 30, NH2 equivalent: 650) or BY16-853B (viscosity: 80; NH 2: 2200) or those of pendent group structure such as BY16-828 (viscosity: 120, NH2 equivalent: 3500) or BY16-850 (viscosity: 1100, NH2 equivalent: 4000); Aminomethyltrimethylsilane sold by Gelest and bis (trimethylsilyl) methylamine (RN 134340-00-4).  The s-triazine compounds of formula (I) according to the invention are preferably present in the compositions in accordance with the invention at contents ranging from 0.01% to 20% by weight and more preferably from 0.1% to 10%. and even more preferably from 0.1 to 6% by weight relative to the total weight of the composition.  The bis-resorcinyl triazine compounds according to the invention are preferably chosen from the compounds corresponding to the following formula (VIII): ## STR2 ## in which: R 9 and R 10, identical or different, represent a linear or branched C1-C30 alkyl radical, a C2-C30 alkenyl radical, linear or branched, a radical A-(Si) (R) aO (3_ay2 with A, R and a having the have the same meanings as in formula (I) defined above, with the proviso that when R9 and R10 both denote a group ûA- (Si) (R) aO (3_ay2 then a = 1; following formulas (IX) or (X): wherein R 11 represents hydrogen, a C 1 -C 20 alkyl, the radical - (CH 2 CHR 13 --O) p R 12 or the radical of formula - CH 2 -CH (OH) -CH 2 -O-T1, -R12 represents hydrogen, a C1-C29 alkyl or a radical of formula - (CH2) pO-T1, - R13 is hydrogen or methyl, - T1 is hydrogen or a C1-C6 alkyl In the formulas (VIII), (IX) and / or (X) described above: the alkyl radicals are linear or branched and may be chosen for example from methyl, ethyl, n-propyl, isopropyl, n-butyl, dry. butyl, tert. butyl, amyl, isoamyl, tert. amyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl; the alkenyl radicals may be chosen for example from allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct 2-enyl, n-dodec-2-enyl, iso-dodecenyl, n-octadec-4-enyl; The bis-resorcinyl triazine derivatives of formula (VIII) of the invention are already known per se filters.  They are described and prepared according to the syntheses indicated in patent applications EP-A-0775 698.  By way of examples of compounds of formula (VIII) that may be used, mention may be made of: 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl} -6- (4) -methoxy-phenyl) -1,3,5-triazine; 2,4-bis {[4- (3- (2-propyloxy) -2-hydroxy-propyloxy) -2-hydroxy] -phenyl} -6 (4-methoxyphenyl) -1,3,5-triazine; 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl} -6- [4- (2-methoxyethyl-carboxyl) -20-phenylamino] -1,3,5- triazine; 2,4-bis {[4-tris (trimethylsilyloxy-silylpropyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5triazine; 2,4-bis {[4- (2 "-methylpropenyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine; 2,4-bis; {[4- (1 ', 1', 1 ', 3', 5 ', 5', 5'-heptamethyltrisiloxy-2 "-methylpropyloxy) -2-hydroxy] -phenyl] -6- (4-methoxyphenyl) - 1,3,5-triazine.  2,4-bis {[4- (3- (2-propyloxy) -2-hydroxy-propyloxy] -2-hydroxy] -phenyl} -6 - [(4-ethylcarboxyl) phenylamino] -1,3 5-triazine; 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl} -6- (1-methylpyrrol-2-yl) -1,3,5- triazine.  The more preferred bis-resorcinyl triazine derivative compound according to the invention will be 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxy) compound. phenyl) -1,3,5-triazine (INCI name: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine sold under the trade name TINOSORB S by CIBA GEIGY, The bis-resorcinyl triazine compounds are preferably present in the compositions according to the invention according to contents ranging from 0.01 to 20% by weight and more preferably from 0.1 to 10% and even more preferentially from 0.1 to 6% by weight relative to the total weight of the composition.  Among the dibenzoylmethane derivatives in accordance with the invention, mention may be made in particular, but not limited to: 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, 45-isopropyldibenzoylmethane, 4-tert. benzyldibenzoylmethane, 2,4-dimethyldibenzoylmethane, 2,5-dimethyldibenzoylmethane, 4,4'-diisopropyldibenzoylmethane, 50-4,4'-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 in particular be made of 4-isopropyl-dibenzoylmethane, sold under the name "Eusolex 8020" by Merck, and having the following formula: It is particularly preferred to use 4- (ter. butyl) 4'-methoxy dibenzoylmethane or Butyl Methoxy Dibenzoylmethane, offered for sale under the trade name "PARSOL 1789" by Roche Vitamins; this filter has 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 20% by weight and more preferably from 0.1. 10% by weight and even more preferably from 0.1 to 6% by weight relative to the total weight of the composition.  According to the present invention, the combination consisting of the silicon triazine derivative (s) of formula (I) and the bis-resorcinyl triazine compound will be used in a sufficient amount to obtain a significant and significant improvement in the photostability of the dibenzoylmethane derivative in a given composition.  This minimum amount of light-stabilizing agent to be used may vary according to the amount of dibenzoylmethane present initially in the composition and according to the nature of the cosmetically acceptable support selected for the composition.  It can be determined without any difficulty by means of a conventional photostability measurement test.  The compositions according to the invention are generally suitable for topical application to the skin and therefore generally comprise a physiologically acceptable medium, that is to say compatible with the skin and / or its integuments (hair, eyelashes, eyebrows, nails ).  It is preferably a cosmetically acceptable medium, that is to say which has a pleasant color, odor and feel and which does not generate unacceptable discomfort (tingling, tightness, redness), which is susceptible to divert the consumer from using this composition.  The compositions in accordance with the invention may comprise, in addition to other complementary organic or inorganic UV filters 40 active in the UVA and / or UVB.  Of course, one 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.  The complementary organic photoprotective agents are in particular chosen from anthranilates; cinnamic derivatives; salicylic derivatives, camphor derivatives; benzophenone derivatives; 13,13-diphenylacrylate derivatives; benzalmalonate derivatives; benzimidazole derivatives; imidazolines; bis-benzoazolyl derivatives as described in patents EP669323 and US 2,463,264; p-aminobenzoic acid derivatives (PABA); benzoxazole derivatives as described in patent applications EP0832642, EP1027883, EP1300137 and DE10162844; filter polymers and silicone filters such as those described in particular in the 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 and mixtures thereof.  As examples of complementary organic photoprotective agents, mention may be made of those referred to below under the name INCI: Paraben 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 Salicylate, sold under the name Neo Heliopan TS by Haarmann and Reimer, cinnamic derivatives: Ethylhexyl Methoxycinnamate sold in particular under the trade name Parsol 40 MCX by Hoffmann La Roche, Isopropyl Methoxy Cinnamate Isoamyl Methoxy cinnamate sold under the trade name NEO HELIOPAN E 1000 by HAARMANN and REIMER, Cinoxate, 45 DEA Methoxycinnam ate, - 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, 50 2908988 Derivatives of benzophenone: Benzophenone -1 sold under the trade name UVINUL 400 by BASF, Benzophenone-2 sold under the trade name UVINUL D50 by BASF 5 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 Benzophenone-9 sold under the trade name UVINUL DS-49 by BASF, Benzophenone-12 Derivatives of benzylidene camphor: 3-Benzylidene camphor manufactured under the name MEXORYL SD by CHIMEX, 4-Methylbenzylidene c amphor sold under the name Eusolex 6300 by Merck, Benzylidene Camphor Sulfonic Acid manufactured under the name Mexoryl SL by 20 Chimex, Camphor Benzalkonium Methosulfate manufactured under the name Mexoryl SO by Chimex, Polyacrylamidomethyl Benzylidene Camphor manufactured under the name MEXORYL SW by CHIMEX, 25 Derivatives phenyl benzimidazole: 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 Haarmann and Reimer, anthranilic derivatives: Menthyl anthranilate sold under the trade name commercial NEO HELIOPAN MA by Haarmann and REIMER, Imidazoline derivatives: 40 Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate, Derivatives of benzalmalonate: Polyorganosiloxane with benzalmalonate functions such as Polysilicone-15 sold under the trade name PARSOL SLX by HOFFMANN LA ROCHE Derivative 4,4-Diarylbutadiene: -1,1-dicarboxy (2,2'-dimethyl-propyl) -4,4-diphenylbutadiene. Benzoxazole derivatives: 2,4-bis- [5-1 (dimethylpropyl) benzoxazole] 2-yl- (4-phenyl) imino] -6 (2-ethylhexyl) imino-1,3,5-triazine sold as Uvasorb K2A by Sigma 3V and mixtures thereof.  The preferred complementary organic photoprotective agents are chosen from ethylhexyl methoxycinnamate homosalate ethylhexyl salicylate, octocrylene, phenylbenzimidazole sulphonic acid, benzophenone-3, benzophenone-4, benzophenone-5,4-methylbenzylidene camphor, disodium phenyl dibenzimidazole tetrasulfonate, Polysilicone-15 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 photoprotective agents are chosen from coated or uncoated metal oxide pigments (average size of the primary particles: generally between 5 nm and 100 nm, preferably between 10 nm and 50 nm), for example oxide pigments. titanium (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 can 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 repeating major motifs in which the silicon atoms are connected to each other by oxygen atoms (siloxane linkage), 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.  Even more preferentially, the silicones are chosen from the group containing octyl trimethyl silane, polydimethylsiloxanes and polymethylhydro-genosiloxanes.  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, compounds of 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 TAVO" from the company Merck 10 - silica and iron oxide such as 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, - alumina such as the products "TIPAQUE TTO-55 (B)" and "TIPAQUE TTO-55 (A)" from the company ISHIHARA, and "UVT 14/4" from the KEMIRA company, - 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 20 TAYCA, - d alumina and aluminum laurate such as the product "MICROTITANIUM DIOXIDE MT 100 S" from the company TAYCA, iron oxide and iron stearate such as the product "MICROTITANIUM DIOXIDE MT 100 F" from the company TAYCA 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 "MICROTITANIUM DIOXIDE MT 600 SAS", " MICROTITANIUM DIOXIDE MT 500 SAS "or" MICROTITANIUM DIOXIDE MT 100 SAS "from the company TAYCA, silica, alumina, aluminum stearate and treated with a silicone such as the product" STT-30-DS "from the company TITAN KOGYO, - silica and treated with a silicone such as the product "UV-TITAN X 195" Kemira company, or the product SMT-100 WRS TAYCA society.  of alumina and treated with a silicone such as the products "TIPAQUE TTO-55 (S)" from the company ISHIHARA, or "UV TITAN M 262" from the company KEMIRA, 35 of triethanolamine such as the product "STT-65 - S "of the company TITAN KOGYO, - stearic acid such as the product" TIPAQUE TTO-55 (C) "from 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 having an average particle size of between 25 and 40 nm, such as that sold under the trade name " T 805 "by the company Degussa Silices, TiO 2 treated with a polydimethylsiloxane and whose average elementary particle size is 21 nm, such as that sold under the trade name" 70250 Cardre UF Ti02S13 "by CARDRE, 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 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 "titanium oxide 2908988 16 transparent 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 marketed 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); those marketed 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); 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 Shin-Etsu (ZnO coated with silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane); those marketed under the name "Escalol Z100" by ISP (ZnO treated with alumina and dispersed in the ethylhexyl methoxycinnamate / PVP-hexadecene / methicone copolymer mixture); those marketed under the name "Fuji ZnO-SMS-10" by the company 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).  Uncoated cerium oxide pigments are sold for example under the name "COLLOIDAL CERIUM OXIDE" by the company RHONE POULENC.  Uncoated iron oxide nanopigments 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 the company ARNAUD 45 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 the company BASF under the name "OXIDE OF CLEAR IRON".  Mention may also be made of mixtures of metal oxides, in particular titanium dioxide and cerium dioxide, including the titanium dioxide and cerium-coated cerium dioxide equivalent mixture, sold by the company 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 2908988 17 or coated with alumina, silica and glycerine such as the product "M 211" sold by the company Kemira.  The additional photoprotective agents 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 compositions according to the invention may also contain agents for tanning and / or artificial browning of the skin (self-tanning agents), and more particularly dihydroxyacetone (DHA).  They are preferably present in amounts 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 especially from fatty substances, organic solvents, ionic or nonionic thickeners, 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, alkalizing 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 their mixtures.  By oil is meant a liquid compound at room temperature.  By wax is meant a compound which is solid or substantially solid at ambient 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 such as perhydrosqualene, alcohols, acids or fatty esters such as the benzoate of C12-C15 alcohols sold under the trade name Finsolv TN or Witconol TN by the company WITCO, the octyl palmitate, the lanolate of isopropyl, 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.  As waxy 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.  The latter may be chosen 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 such as crosslinked copolymers sold under the names Sepigel 305 (name C. T. F. AT.  : polyacrylamide / C13-14 isoparaffin / Laureth 7) or Simulgel 600 (name C. T. F. AT.  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-methylpropanesulphonic acid) marketed by the company Hoechst under the trademark Hostacerin AMPS (name CTFA: ammonium polyacryloyldimethyl taurate or SIMULGEL 800 sold by the company SEPPIC (CTFA name: sodium polyacryolyldimethyl taurate / polysorbate 80 / sorbitan oleate); copolymers of 2-acrylamido-2-methylpropanesulfonic 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, and mixtures thereof.  As lipophilic thickeners, mention may be made of synthetic polymers such as poly C, O-C30 alkyl acrylates sold under the name INTELIMER IPA 13-1 and INTELI MER IPA 13-6 by the company Landec, or modified clays such as hectorite and its derivatives, such as the products marketed under the Bentone name.  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-pollution agents and / or anti-radical agents; depigmenting agents and / or pro-pigmenting agents; Anti-glycation agents; the soothing agents; the NO-synthase inhibitors; agents stimulating the synthesis of dermal or epidermal macromolecules and / or preventing their degradation; Agents stimulating the proliferation of fibroblasts; agents stimulating the proliferation of keratinocytes; - muscle relaxants; tensing agents, mattifying agents, keratolytic agents, desquamating agents; the moisturizing agents; anti-inflammatory agents; agents acting on the energetic metabolism of cells, insect repellents - P-substance antagonists or CRGPs.  - 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.  The compositions according to the invention may be prepared according to 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 an 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 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).  The emulsions may also contain other types of gelling or thickening polymer stabilizers.  As emulsifying surfactants that may be used for the preparation of W / O emulsions, mention may be made, for example, of alkyl esters or ethers of sorbitan, of glycerol or of 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 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, mention may in particular be made of 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 the PEG-100 Stearate / Glyceryl Stearate mixture marketed for example by the

  ICI company under the name Arlacel 165; oxyalkylenated fatty alcohol ethers (oxyethylenated and / or oxypropylenated); sugar esters such as sucrose stearate; fatty alcohol and sugar ethers, especially alkylpolyglucosides (APG) such as decylglucoside and laurylglucoside sold, for example, by Henkel under the respective names Plantaren 2000 and Plantaren 1200, cetostearylglucoside 40 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 a mixture of arachidic and behenic alcohols and 45 arachidylglucoside sold under the name Montanov 202 by the company Seppic. According to one 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 WO- A-92/06778.

Among the other emulsion stabilizers, the polymers of isophthalic acid or of sulphoisophthalic acid, and in particular the phthalate / sulphoisophthalate / glycol copolymers, for example the copolymer of diethylene glycol / phthalate / isophthalate / 1,4, will be used more particularly. cyclohexane dimethanol (INCI name: Polyester-5) sold under the name "Eastman AQ polymer" (AQ35S, AQ38S, AQ55S, AQ48 Ultra) by the company Eastman Chemical. In the case of an emulsion, the aqueous phase thereof may comprise a nonionic vesicular 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 a care product and / or sun protection for the face and / or body of liquid to semi-liquid consistency, such as milks, more or less smooth creams. , gel-creams, pasta. They may optionally be packaged in 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 present preferably in amounts ranging from 15 to 50% by weight relative to the total weight of the composition.

Concrete, but not limiting, examples illustrating the invention will now be given.

EXAMPLES OF SYNTHESIS: EXAMPLE 1 Preparation of Ethyl 2,4-bis (4'-divamino benzoate) -6- (1,3,3,3-tetramethyl) -1- (trimethylsilyl) oxyldisiloxanepropyl-3-yl vlamino} -s-triazine: 21 (a) First step: preparation of 2,4-dichloro-6 - {[1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl] propyl-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 of such 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 1: 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. Cooled and added to the resin obtained hot heptane. After trituration, filtration and drying, 2.3 g (yield: 67%) of the derivative of Example 1 is obtained in the form of a white powder: mp: 106 ° -108 ° C., UV (Ethanol): X max = 311 nm, El% = 1147.

EXAMPLE 2 Preparation of n-butyl (N-butyl) -2,4-bis (4'-divamino benzoate) -6- (1,3,3,3-tetramethyl) -1 - [(trimethylsilyl) oxy] disiloxane] propyl] -3 By nitrogen sparging, the mixture of the product of the first step of Example 1 (16.74 g, 0.0391 mole), n-butyl para-amino benzoate was reacted. (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 a 1: 15 EtOAc / Heptane mixture, 20.1 g (yield: 69%) of the derivative of Example 2 in the form of a white powder are obtained: Mp: 111-113 ° C., UV (Ethanol ): Xmax = 312 nm, El% = 1055. EXAMPLE 3: Preparation of n-pentyl 2,4-bis (4'-divlamino benzoate) -6 - {[1,3,3,3-tetramethyl-1- [(trimethylsilyl) oxy] disiloxane] propyl-3-ylamino} -s-triazine: In a CEM Discover microwave, the mixture of the product of the product was heated for 20 minutes at a temperature of 115 ° C. and at a power of 150 watts. the first step of Example 1 (1 g, 2.3x10-3 mol), n-pentyl para-amino benzoate (0.97 g, 4.6x10-3 mol) and sodium bicarbonate (0, 39 g, 4.6x10-3 mol) in 15 ml of 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 transparent oil is obtained. After purification on a silica column (eluent: Heptane / EtOAc 85:15), the clean fractions of the derivative of Example 3 (0.9 g, yield: 50%) are recovered in the form of a white powder: UV (Ethanol): Xmax = 312 nm, El% = 1008. EXAMPLE 4: Preparation of (1,1,3,3-tetramethylbutyl) -6- {[1,3] 2,4-bisf4'-divlamino benzamide 3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxane] propyl-3-ylamino} -s-triazine: NH \ (b) O.. ## STR1 ## where (S) Step 1: Preparation of 4-nitro-N- (tert-octyl) benzamide: In a reactor, tert-octyl amine (51.7 g) is introduced. g, 0.4 mole) and triethylamine (61.2 ml, 0.44 mole) in 260 ml of dichloroethane. The mixture is heated to 70 ° C. and then 4-nitrobenzoyl chloride (77.9 g, 0.42 mol) is added in the course of 50 minutes in small portions. Refluxed for 4 hours. The reaction mixture is poured onto 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- (tertoctyl) 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, 4-nitro-N- (tert-octyl) benzamide (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 charcoal at 50% of water as a catalyst (hydrogen pressure: 8-10 bar) at a temperature of 70.degree. 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 step 15 of the product is heated for 20 minutes at a temperature of 115 ° C. and 150 Watt. Example 1 (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 3 (0.9 g, Yield: 45%) are recovered in the form of white flakes: UV (Ethanol ): Xmax = 302 nm, El% = 775. EXAMPLE 5 Preparation of 2,4-bis (4'-divlamino benzoate of methyltrimethylsilyl) -6- {f1,3,3,3-tetramethyl-1-f (trimethylsilyl) oxyldisiloxanylpropyl-3-ylamino) -s-triazine: Step 1: Preparation of Methyltrimethylsilyl 4-aminobenzoate Chloromethyltrimethylsilyl (38.5 g, 0.314 mole) was added dropwise at 80 ° C. to a chloromethyltrimethylsilyl mixture to the heterogeneous mixture. potassium salt of para-amino benzoic acid (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 distill at 189 ° C. under a vacuum of 0.6 mbar are recovered. The oil crystallises. 50.4 g (yield: 79%) of the derivative of Example 5 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 5: Under a nitrogen sparge, the mixture of the product of the first step of Example 1 (2.1 g, 4.9 × 10 -3 mol) and the derivative of The preceding step (2.19 g, 9.8 × 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 5 are obtained in the form of a pale yellow gum: UV (Ethanol): X max = 311 nm, El% = 907. EXAMPLE 6: Preparation of 2,4- bis (2'-hydroxy-4'-divamino benzoate, 2-ethylhexyl) -6 - {[1,3,3,3-tetramethyl-1-yl (trimethylsilyl) oxy} disiloxane] propyl-3-vinylamine Using a nitrogen sparge, a mixture of 2-ethyl-2-hexyl 2-hydroxy-4-aminobenzoate (1.4 g, 5.57 × 10 -3 mole) and the product of the first stage of the reaction were added. Example 1 (1.19 g, 2.78x103 mol) in 10 ml of toluene is refluxed for 5 hours. It is cooled and the solvent is evaporated. The residue is chromatographed on a silica column (eluent: Heptane / EtOAc 9/1). 1.58 g (yield: 64%) of the clean fractions of the derivative of Example 6 are obtained in the form of a white paste: UV (Ethanol): = 300 nm, El% = 480 X max = 325 nm, El% = 709.

EXAMPLE 7 Preparation of the Statistical Derivative of Formula (Ia, III): R1 = n-butyl, X = O, n = O, B = A, W = H, Z = CH2, R7 = CH3, s = 0, R = 8, 1: ## STR2 ## First step: preparation of the 2,4 -bis (4'-n-butyl 4-divamino benzoate) -6-chlorostriazine: To a solution of cyanuric chloride (54.36 g, 0.295 moles) in 500 ml of dioxane and 50 ml of water, n-Butyl para-amino benzoate (113.94 g, 0.59 mol) and a solution of potassium carbonate (40.68 g, 0.295 mol) in 50 ml of water are added dropwise simultaneously at 5 ° C. 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 which corresponds to monosubstituted s-triazine. The mixture is gradually heated to 70 ° C. and the second equivalent of potassium carbonate (40.68 g, 0.295 mole) in 50 ml of water is added. The stirring is then maintained for 5 hours at 70 ° C. The mixture is cooled and the reaction mixture is filtered. 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) are obtained after drying under vacuum. chlorostriazine in the form of a white powder. Second Step: Preparation of the Derivative of Example 7: Under nitrogen sparge, 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 7 is obtained in the form of a light brown gum: UV (Ethanol): Xmax = 311 nm, El% = 916.

EXAMPLE 8 Preparation of 4-Butyl-4- (4-butoxycarbonyl) phenylaminol-6 - ({3-ethylethoxy (methyl) silvylpropylamino) -1,3,5-triazin-2-yl] aminolbenzoate: NH 2 0 ## STR2 ## When sparging with nitrogen, the heterogeneous mixture of the product of the first step of Example 7 (20 g, 0.04 mole) and aminopropyl diethoxy methyl silane (15.37 g , 08 mol) is gradually heated to 70 ° C. After 1 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 21 g (yield 80%) of a white solid of the derivative of Example 8: UV (Ethanol): X max = 311 nm, El% = 1197.

EXAMPLE 9 Preparation of the Statistical Derivative of Formula (1a, III) Obtained by Polymerization of the Derivative of Example (8) with D5 + MM: R1 = n-butyl, X = O, n = O, W = H, a = 1, b = 2, R = CH 3, Z = CH 2: -Si-O 2 O-O] O -NH 4 NH 4 Nitrogen bubbled, the heterogeneous mixture of the product of the example 8 (1 g, 1.53x10-3 mol), decamethylcyclopentasiloxane (D5) (0.57 g, 1.53x10-3 mol), hexamethyldisiloxane (MM) (0.062 g, 0.38 × 10 -3 mol) and concentrated hydrochloric acid (0.1 ml) is stirred vigorously in a mixture of 10 ml of toluene and 1 ml of water. It 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. The precipitate obtained is washed with water and dried. There is thus obtained 0.56 g of a white powder of the derivative of Example 9: UV (Ethanol): X max = 311 nm, El% = 892. EXAMPLES 10a and 10b: Preparation of the derivatives: butyl 4-f ( 4- {4- (Butoxycarbonyl) phenyl] amino} -6- {[3- (1-hydroxy-1,3,3,3-tetramethyldisiloxanyl) propyllamino} -1,3,5-triazin-2-yl) aminolbenzoate and dibutyl 4,4 '- {[6- [(3-dihydroxy (methyl) silyl] propyl} amino) -1,3,5-triazine-2,4-divylimino} dibenzoate obtained by acid treatment of the derivative of Example (2): (h) 10a = (j) 10b = (k) To the derivative of Example 2 (10 g, 0.013 mol) solubilized in 500 ml of the mixture ethanol / isopropanol in the ratio 80:20, 160 ml of acid are added. 0.1N hydrochloric acid and 340 ml of the 80:20 ethanol / isopropanol mixture. 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 lyophilized 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 10a and about 10% of the derivative of Example 10b. This powder was fractionated by centrifugal partition chromatography (with biphasic systems composed of heptane, ethyl acetate, methanol and water in various proportions) to give 0.58 g of the derivative of Example 10a under white powder form: UV (Ethanol): Xmax = 312 nm, El% = 1228 and 0.42 g of the derivative of Example 10b in the form of a white powder.

EXAMPLE 11 Preparation of Butyl 4 - ({4 - {[4- (butoxycarbonyl) phenylamino} -6- (2- {1,3,3,3-tetramethyl-1-trimethylsilyl) oxyldisiloxanepropyl) aminol-1,3,5-triazin-2-ylamino) benzoate and ethyl 2,4-bis (4'-divamino benzoate) -6- (1, 3, 3, 3-tetramethyl-1) (trimethylsilyl) oxyldisiloxanepropyl-3-ylamino} -s-triazine: ## STR2 ## to a solution of cyanuric chloride (19.8 g, 0.11 mol) and lutidine (11.5 g, 0.11 mol) in 100 ml of ethyl acetate is added dropwise at 0 C in 30 minutes a 7/93 mixture of 2- {1,3,3,3 1-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propan-1-amine and 3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propan-1-amine g, 0.11 mol). The mixture is left stirring at 0 ° C. for 30 minutes, then at 10 ° C. for 30 minutes and finally at 20 ° C. for 30 minutes. Pyridine (17.4 g, 0.22 mol) and n-butyl para-amino benzoate (41.4 g, 0.22 mol) are then added and the mixture is heated at 70 ° C. for 3 hours. After cooling the reaction mixture, it is washed with twice 100 ml of a saturated solution of sodium chloride. This organic phase is passed over a bed of silica and the cake rinsed with 80 ml of ethyl acetate. This organic phase is dried over sodium sulfate and the solvents evaporated. The residue obtained is crystallized in heptane. 50.2 g of a pale yellow solid are thus obtained. This solid was recrystallized from 98: 2 Heptane / EtOAc to give 49 g (Yield: 60%) of the 7:93 mixture of the two isomers of Example 11 as a white powder: mp: 165-167 C, UV (Ethanol): X max = 312 nm, El% = 1040.

EXAMPLE 12: Preparation of the 50:50 mixture of butyl 4 - ({4- (4-butoxycarbonyl) phenylamino} -6- (2- (1,3,3,3-tetramethyl) -1- (trimethylsilyl) oxyldisiloxanepropyl) aminol-1,3,5-triazin-2-ylamino) benzoate and ethyl 2,4-bis (4'-divamino benzoate) -6- (1, 3, 3, 3-tetramethyl-1) (trimethylsilyl) oxyldisiloxanepropyl-3-ylamino} -s-triazine: ## STR2 ## ## STR2 ## ## STR2 ## N 50 50 First step: preparation of the 50: 50 mixture of 4,6-dichloro-N- (2- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) -1, 3,5-triazin-2-amine and 4,6-dichloro-N- (3 - {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} 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 15/85 mixture 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-yl 1-amine (49.3 g, 0.176 mol) and a solution of sodium bicarbonate (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 expected isomeric derivatives in the ratio 15/85 are obtained in the form of a white powder (mp: 59 ° C.). Fractionation of 20 g of the above mixture on 2 successive chromatographic columns of silica (eluent Heptane / EtOAc 95: 5) was carried out. It was possible to obtain 3.54 g of the 50:50 isomeric mixture and used as such in the next step.

Second Step: Preparation of the Derivative of Example 12: The mixture of the above product (3 g, 0.007 mole), n-butyl para-amino benzoate (2.7 g, 0.014 mole) and sodium bicarbonate ( 1.18 g, 0.014 mol) suspended in 30 ml of toluene is heated at 70 ° C. for 5 hours. Cool and add dichloromethane. After 2 washes with water, the organic phase is dried over sodium sulfate and the solvents evaporated. The residue obtained is crystallized from a 50: 5 Heptane / EtOAc mixture. The precipitate is then purified by chromatographic column of silica (eluent: CH 2 Cl 2 / EtOAc 95: 5) to obtain 3.7 g (yield: 71%) of the 50:50 mixture of the 2 isomers of Example 12 in the form of a white powder: Mp: 165-167 ° C., UV (Ethanol): X max = 312 nm, El% = 1149. EXAMPLE 13 Preparation of the derivative of formula (1a, III): R 1 = n-butyl, X = O, n = 0, B = CH3, W = H, Z = CH2, R7 = CH3, s = 1, r = 0: 2908988 (I) ## STR2 ## First step : Preparation of 4,6-dichloro-N- (2- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) -1,3,5-triazin-2-amine: The 15:85 isomeric mixture of the first step of the synthesis of Example 12 was fractionated by centrifugal partition chromatography (biphasic system: heptane / acetonitrile / water 50: 49: 1) to give 2.0 g of 6-dichloro-N- (2- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) -1,3,5-triazin-2-amine, as it is used in the next step: Second Step: preparation of the derivative of Example 13: The preceding product (2 g, 0.0047 mol) is solubilized in 18 ml of toluene. Pyridine (0.8 ml, 0.009 mole) and n-butyl para-amino benzoate (1.8 g, 0.009 mole) 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 brown beige solid obtained is crystallized in 30 ml of heptane. 2.2 g (yield 63%) of the derivative of Example 13 is thus obtained in the form of a light beige powder: Mp: 149-151 ° C., UV (Ethanol): X max = 312 nm, El% = 955.

EXAMPLE 14 Preparation of the derivative of formula (Ia, III): R1 = n-butyl, X = O, n = 0, B = CH3, W = H, Z = CH2, R7 = CH3, s = 2, r = 0: NH N NH HO Si-O-ii, Si, O (m) / HNNNYNH 5 Au derivative of Example 2 (1 g, 0.0013 mol) solubilized in 50 ml of the ethanol mixture / isopropanol in the ratio 80:20, 25m1 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 14. 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 14 in the form of a white powder: UV (Ethanol): X max = 312 nm, El% = 1109. FORMULATION EXAMPLES EXAMPLE 17 EXAMPLE 15 EXAMPLE 13 EXAMPLE 13 EXAMPLE 13 S-TRIAZINE Compound of Example 13 3-Triazine Compound of Example 2 3-Triazine Compound of Example 3 Butylmethoxydibenzoylmethane 2 2 2 (PARSOL 1789) Bis-Ethylhexyloxyphenol Methoxyphenyl 3 3 Triazine (Tinosorb S) C12-15 alkyl benzoate 15 Cetyl alcohol 0.5 0.5 0.5 Stearic acid 1.5 1.5 1.5 Glyceryl mono-stearate mixture / 1 1 PEG stearate (100 0E) Mixture of cetylstearyl glucoside and 2 2 2 of cetyl alcohols, stearyl Dimethicone 0.50 0.50 0.50 Triet hanolamine 0.45 0.45 0.45 Preservative 1 1 1 Titanium dioxide 5 Phase B Glycerol 5 5 5 Complexing 0.1 0.1 0.1 Phenyl ketyl phosphate 1 1 1 Water qs 100G qs 100G qs 100G Phase C Xanthan Gum 0.2 0.2 0.2 Acid Copolymer 0.2 0.2 0.2 acrylic / stearyl methacrylate Iso-Hexadecane 1 1 1 Cyclopentasiloxane 1 Phase D Triethanolamine qsp pH qsp pH qsp pH 2908988 Procedure Heating the fatty phase (A) at 70 ° C. The aqueous phase (B) is heated in the final beaker. Phase (C) is prepared: dispersion of the powders in the oil. With Rotor Stator stirring, the fatty phase is emulsified in the aqueous phase. The phase (C) is introduced with faster stirring and is then stirred slowly until it returns to ambient temperature. We neutralize (D) and then condition. 33 10

Claims (29)

  1. A process for photostabilization with respect to the UV radiation of at least one dibenzoylmethane derivative, characterized in that it consists in associating with said dibenzoylmethane derivative (a) at least one siliconized s-trazine substituted with two groups aminobenzoates or aminobenzamides of the following formula (I) or one of its tautomeric forms: ## STR2 ## in which - R, which may be identical or different, represent a radical C1-C30 alkyl, linear or branched and optionally halogenated or unsaturated, a C6-C12 aryl radical, a C1-C10 alkoxy radical or the trimethylsilyloxy group; a = 0 to 3; the group D denotes an s-triazine compound of the following formula (II): wherein X represents -O- or -NR 3 -, with R 3 representing hydrogen or a C 1 -C 5 alkyl radical; RI represents a linear or branched and optionally unsaturated C 1 -C 20 alkyl radical which may contain a silicon atom, a g C 5 -C 20 cycloalkyl ring, optionally substituted with 1 to 3 linear or branched C 1 -C 4 alkyl radicals, the group - (CH 2 CHR 4 --O) m R 5 or the group --CH 2 --CH (OH) - CH 2 --O - R 6, - 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 8 alkoxy radical; , two adjacent R 2 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 (CH 3) 3 ethylene or a group corresponding to one of the following formulas (III), (IV) or (V): ## STR2 ## where (CH) CH (IV) IIH2 ù (Z) where C (V) in which: Z is a linear or branched, saturated or unsaturated C 1 -C 10 alkylene diradical, optionally substituted by a hydroxyl radical or oxygen and may be optionally containing an amino group, - W represents a hydrogen atom, a hydroxyl radical or a linear or branched, saturated or unsaturated C1-C8 alkyl radical, (b) at least one bis-resorcinyl triazine compound.   2. The process according to claim 1, wherein the compound of formula (I) is in the tautomeric form of the following formula (I '): (D') ù (SI) ùO (3 a) / 2 (1 (R) a wherein the group D 'denotes a s-triazine compound of the following formula (II'): ## STR3 ##   3. Process according to claim 1 or 2, wherein the compound of formula (I) additionally comprises units of formula (R) b- (Si) (O) (4_by2) in which: R has the same meaning as in formula (I), b = 1.2 or 3. 5   4. Method according to claim 3, wherein the compounds of formula (I) are chosen from those for which at least one, and even more preferably all, of the following characteristics are fulfilled: R is methyl, 10 a = 1 or 2, X is O, R1 is a C405 radical n = 0, the group (C = O) XR1 is in the para position with respect to the amino group, Z = -CH2-, W = H.   5. Process according to any one of claims 1 to 4, wherein the compounds of formula (I) are chosen from those corresponding to one of formulas (la), (Ib) or (Ic): R7 R 7 7 (la) (B) ùSiùOù [ùSiùO R7R7R7R7r SiiO Sii (B) (D) R7R7R7SiSiSiuuR7 (D) (Ic) (D) -Si (R8) 3 in which: - ( D) corresponds to formula (II) as defined in the preceding claims; R7, which may be identical or different, are chosen from linear or branched C1-C20 alkyl, phenyl and 3,3,3-trifluoropropyl and trimethylsilyloxy alkyl radicals; or the hydroxyl radical - R8, which may be identical or different, are chosen from linear and branched C1-C20 alkyl and alkenyl radicals, the hydroxyl or phenyl radicals, - (B), which may be identical or different, and are chosen from the radicals R7 and the radical (D), r is an integer between 0 and 200 inclusive, 35 - 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 from 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. 40   6. Process according to claim 5, wherein the compounds of formula (Ia) or (Ib) are random oligomers or polymers having at least one, and even more preferably all, of the following characteristics: R7 is the radical methyl or the hydroxy radical; 45 - B is preferably methyl. 25 2908988 37   7. Process according to claim 6, wherein the compound of formula (I) is chosen from the following compounds of formulas (a) to (m) and their tautomeric forms: ## STR5 ## , i N (b) Where Si (Si) (c) (d) N NH \ Where Si (e) If ## EQU1 ## Where / if O \ N OH / Si Si (i) (j) 2908988 38% Si O HN N NH ---- Si (k) (1) 1n HN N. "N 2908988 39   8. Process according to claim 7, wherein the compound of formula (I) is the compound 2,4-bis (4'-diylamino benzoate n-butyl) -6 - {[1,3,3,3-tetramethyl- 1 - [(trimethylsilyl) oxy] disiloxanyl] propyl-3-ylamino} -s-triazine of structure (b): NH (b)   9. Process according to any one of the preceding claims, wherein the bisresorcinyl triazine compound is chosen from the compounds corresponding to the following formula (VIII): ## STR2 ## in which: R9 and R19, which may be identical or different, represent a linear or branched C1-C30 alkyl radical, a linear or branched C2-C30 alkenyl radical, a radical ùA- (Si) (R) aO (3_a), 2 with A, R and a having the same meanings as in formula (I) defined above, with the proviso that when R 9 and R 10 both denote a group ùA- (Si) (R) aO (3_ay 2 then a = 1 E is the radical of the following formulas (IX) or (X): OR 11 NHCOOR 12 (X) in which: R11 represents hydrogen, a C1-C20 alkyl, the radical - (CH2CHR13-O) p R12 or the radical of formula -CH2-CH (OH) -CH2-O-T1, -R12 represents hydrogen, a C1-C29 alkyl or a radical of formula 25 - (CH2) pO-T1, - R13 is hydrogen or methyl, - T1 is h ydrogen or C1-C8 alkyl, - o = 1-16, - p = 1-4. 2908988 40   10. The method of claim 9, wherein the bis-resorcinyl triazine compound of formula (VIII) is selected from the following compounds: - 2,4-bis {[4- (2-ethyl-hexyloxy) -2-hydroxy] phenyl-6- (4-methoxy-phenyl) -1,3,5-triazine; 2,4-bis {[4- (3- (2-propyloxy) -2-hydroxy-propyloxy) -2-hydroxy] -phenyl} -6 (4-methoxyphenyl) -1,3,5-triazine; 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl} -6- [4- (2-methoxyethyl-carboxyl) -phenylamino] -1,3,5-triazine ; 2,4-bis {[4-tris (trimethylsiloxy-silylpropyloxy) -2-hydroxy] -phenyl} -6 (4-methoxyphenyl) -1,3,5-triazine; 2,4-bis {[4- (2 "-methylpropenyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine; [4- (1 ', 1', 1 ', 3', 5 ', 5', 5'-heptamethyltrisiloxy-2 "-methylpropyloxy) -2-hydroxy] phenyl] -6- (4-methoxyphenyl) - 1,3,5-triazine. 2,4-bis {[4- (3- (2-propyloxy) -2-hydroxy-propyloxy] -2-hydroxy] -phenyl} -6 - [(4-ethylcarboxyl) phenylamino] -1,3 5-triazine; 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] -phenyl} -6- (1-methylpyrrol-2-yl) -1,3,5- triazine 20   The process according to claim 10, wherein the bis-resorcinyl triazine compound of formula (VIII) is 2,4-bis {[4- (2-ethyl-hexyloxy) -2-hydroxy] -phenyl} -6- (4-methoxyphenyl) -1,3,5-triazine.   12. Process according to any one of claims 1 to 11, wherein the dibenzoylmethane derivative is chosen from: 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert-butyldibenzoylmethane, 2,4-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.   The process according to claim 10, wherein the dibenzoylmethane derivative is 4- (tert.-butyl) -4'-methoxydibenzoylmethane or Butyl Methoxy Dibenzoylmethane.   14. Composition comprising at least, in a physiologically acceptable support, a filter system, characterized in that it comprises: (a) at least one UV filter of the dibenzoylmethane derivative type as defined in the preceding claims and (b) at least one s-triazine silicate compound substituted with two aminobenzoate or aminobenzamide groups of formula (I) or one of its tautomeric forms as defined in the preceding claims, (c) at least one bis-resorcinyl triazine compound as defined in the preceding claims. 41 2908988   15. A composition according to claim 14, wherein the compound (s) of formula (I) is (are) present at levels ranging from 0.01 to 20% by weight and more preferably from 0.1. 10% by weight and more preferably from 0.1 to 6% by weight relative to the total weight of the composition.   16. Composition according to claim 14 or 15, wherein the bis-resorcinyl triazine compound (s) is (are) present at levels ranging from 0.01 to 20% by weight and more preferably from 0, 1 to 10% by weight and more preferably from 0.1 to 6% by weight relative to the total weight of the composition.   17. Composition according to any one of claims 14 to 16, wherein the dibenzoylmethane derivative (s) are present at levels ranging from 0.01 to 20% by weight and more preferably from 0.1 to 10% by weight and more. preferably from 0.1 to 6% by weight relative to the total weight of the composition.   18. Composition according to any one of claims 14 to 17, characterized in that it additionally contains other organic or inorganic photoprotective agents active in the UV-A and / or UV-B. 20   19. The composition of claim 18, wherein the complementary organic photoprotective agents are selected from anthranilates; cinnamic derivatives; salicylic derivatives, camphor derivatives; benzophenone derivatives; [3, 3-diphenylacrylate; triazine derivatives other than those defined in the preceding claims; benzalmalonate derivatives; benzimidazole derivatives; imidazolines; bis-benzoazolyl derivatives; paminobenzoic acid derivatives (PABA); benzoxazole derivatives; filter polymers and silicone filters; dimers derived from α-alkylstyrene; 4,4-diarylbutadienes and mixtures thereof.   20. Composition according to Claim 19, 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- 5,4-Methylbenzylidene camphor, Disodium Phenyl Dibenzimidazole Tetra-sulfonate, Polysilicone-1,1-dicarboxy (2,2'-dimethyl-propyl) -4,4-diphenylbutadiene 2,4-bis- [5-I] ( dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino) -6- (2-ethylhexyl) imino-1,3,5-triazine 45 and mixtures thereof.   21. Composition according to claim 18, characterized in that the complementary inorganic photoprotective agents are metal oxide pigments, treated or not.   22. Composition according to Claim 21, characterized in that the said pigments are chosen from titanium, zinc, iron, zirconium and cerium oxides and their mixtures, whether or not treated. 5 10 15 50 2908988 42   23. Composition according to any one of claims 14 to 22, characterized in that it further comprises at least one agent for tanning and / or artificial browning of the skin. 5   24. Composition according to any one of claims 14 to 23, characterized in that it further comprises at least one adjuvant chosen from fatty substances, organic solvents, ionic or nonionic thickeners, hydrophilic or lipophilic, softeners, humectants, opacifiers, stabilizers, emollients, silicones, anti-foam agents, perfumes, preservatives, anionic, cationic, nonionic, zwitterionic or amphoteric surfactants, actives, fillers, polymers, propellants, alkalizing or acidifying agents   25. Composition according to any one of claims 14 to 20, characterized in that it is in the form of an oil-in-water or water-in-oil emulsion. 15   26. Use of a composition as defined in any one of claims 14 to 25 for the manufacture of products for the cosmetic treatment of the skin, lips, nails, hair, eyelashes, eyebrows and / or scalp 20   27. Use of a composition as defined in any one of claims 14 to 25 for the manufacture of care products for the skin, lips, nails, hair and / or scalp.   28. Use of a composition as defined in any one of claims 14 to 25 for the manufacture of make-up products.   29. Use of the combination of at least one compound of formula (I) or one of its tautomeric forms as defined in the preceding claims and at least one bis-resorcinyl triazine compound as defined in the claims in a composition comprising, in a physiologically acceptable carrier, at least one derivative of dibenzoylmethane as defined in any one of the preceding claims, for the purpose of improving the UV stability of said derivative of dibenzoylmethane. 35