FR2949341A1 - Composition, useful as e.g. makeup products, comprises UV filter system, which comprises siliceous-s-triazine compound substituted by two alkylaminobenzoates and lipophilic merocyanine filter, in medium - Google Patents

Abstract

Composition (A) comprises: at least one UV filter system, in a medium, where the UV filter system comprises: (i) at least one siliceous-s-triazine compound (I) substituted by at least two alkylaminobenzoates, where (I) contains silane units and organosiloxane; and (ii) at least one lipophilic merocyanine filter. Composition (A) comprises: at least one UV filter system, in a medium, where the UV filter system comprises: (i) at least one siliceous-s-triazine compound of formula (D-Si(R) a-O (3-a) /2) (I) substituted by at least two alkylaminobenzoates, where (I) contains silane units of formula (-A-(Si)(R) a(O) 3-a/2), and organosiloxane group of formula (R b-Si(O) 4-b/2); and (ii) at least one lipophilic merocyanine filter. R : 1-2C alkyl, phenyl, 1-2C alkoxy, OH or trimethylsilyloxy; a : 1-3; D : s-triazine group of formula (II); R 11-10C alkyl (optionally unsaturated and containing 5-6C cycloalkyl group), where the COOR 1>group is in ortho, meta or para to the amino group; R 2H, OH, 1-4C alkyl, or methoxy; A : methylene or group of formula (-Z-CHW 1>-CH 2-) (III), (-Z-CHCH 3-) (IV), (-Z-CH=CH-) (V), or (-Z-CH(=CH 2)-) (VI); b : 1-3; Z : 1-3C alkylene biradical; and W 1>H, OH or 1-3C alkyl. [Image].

Description

COMPOSITION CONTAINING SILICIE S-TRIAZINE SUBSTITUTED WITH AT LEAST TWO ALKYLAMINOBENZOATE GROUPS AND LIPOPHILIC MEROCYANINE UV FILTER

The present invention relates to a composition comprising in a cosmetically acceptable support at least one UV filtering system, characterized in that it comprises: (i) at least one siliconized s-triazine of formula (I) substituted with at least two groups alkylaminobenzoates; (ii) at least one lipophilic merocyanine UV filter.

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, particularly in the case of sensitive skin or skin continuously exposed to solar radiation. The UV-A rays in particular cause 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 desire 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 employed.

These antisolar compositions are quite often in the form of an oil-in-water emulsion (ie a cosmetically acceptable carrier consisting of an aqueous dispersant continuous phase and an oily dispersed discontinuous phase) which contains, at various concentrations, one or more conventional organic filters, lipophilic and / or hydrophilic, capable of selectively absorbing harmful UV radiation, these filters (and their amounts) being selected according to the desired protection index ( the protection index (IP) expressed mathematically by the ratio of the exposure time necessary to reach the erythematogenic threshold with the UV filter at the time necessary to reach the erythematous threshold without UV filter). UV-B filters of particular interest and widely used to date are the non-siliceous 1,3,5-triazine lipophilic type filters. They are described in patent applications EP-A-0517104, EP-A-0570838, EP-A-796851 and EPA-0775698. In particular, the 2,4,6-tris [p- (2'-ethylhexyl-1-oxycarbonyl) anilino] -1,3,5-triazine derivative sold in particular under the trade name Uvinul T150 is known from the company BASF. These lipophilic filters active in the UVB have the disadvantage of being solid at room temperature. Their use in solar compositions induces formulation constraints, with the need to identify solvents allowing them to be solubilized correctly.

Other useful UV-B filters used in solar compositions today are alkyl [3, [3'-diphenylacrylate or α-cyano- [3, 3'-diphenylacrylate; Examples include 2-ethylhexyl α-cyano- (3, 3'-diphenylacrylate, also called octocrylene, which is commercially available and sold in particular under the name "UVINUL N 539" by BASF. They can be easily formulated but their filtering properties are relatively low, which results in high use concentrations to obtain an advantageous level of UV-filtration. "Cinnamate derivatives such as ethyl-2-4-methoxycinnamate. hexyl or isoamyl 4-methoxycinnamate are good solvents for UV filters which are difficult to dissolve in oils and have good photoprotection properties in the UVB These cinnamate derivatives have the disadvantage of having insufficient photostability and of disturbing the photostability of the complete filter systems into which they are introduced.

It thus appears necessary to have a system that broadly filters the UVA and UVB radiation, which is easy to use in solar compositions without the disadvantages mentioned above, ie to obtain a UVA and UVB filtering system which is photostable, of high protection index and having good solubility in the solar formulations.

The applicant has discovered that the combination of two particular sunscreens makes it possible to obtain sunscreen compositions with significantly improved protection indices, and in any case higher than those which can be obtained with either one of the two sunscreens. filters used alone.

However, the Applicant has now discovered, surprisingly, that by combining at least one lipophilic merocyanine UV filter with a siliconized s-triazine substituted with at least two alkylaminobenzoate groups of formula (I) which will be defined later. it was possible to obtain a filter system broadly UVA and UVB radiation, easy to implement in solar compositions without the disadvantages mentioned above. The sunscreen compositions containing such a combination of organic UV filters also have good persistence with water, perspiration and washes and good persistence over time. 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 medium at least one UV filtering system, characterized in that it comprises: (i) at least one s -triazine silicon of formula (I) substituted with at least two alkylaminobenzoate groups; (ii) at least one lipophilic merocyanine filter. Other characteristics, aspects and advantages of the invention will appear on reading the detailed description which follows. By "cosmetically acceptable" is meant compatible with the skin and / or its integuments, which has a pleasant color, odor and feel and which does not generate unacceptable discomfort (tingling, tightness, redness), which can divert the consumer to use this composition. In the remainder of the present description, the term "UV-lipophilic filter" is understood to mean any UV radiation filtering agent capable of being completely dissolved in the molecular state in a fatty phase, for example an emulsion, or else being solubilized under colloidal form (for example in micellar form) in a fatty phase. The s-triazine silicon compounds according to the present invention have the following general formula (I) or one of its tautomeric forms: (D) - (SiO (3-a) / 2 ~~~ 1 (R) in which - R, which may be identical or different, represent a C1-C2 alkyl radical, a phenyl radical, a C1-C2 alkoxy radical, a hydroxyl radical or the trimethylsilyloxy group, - a = 1 to 3; of formula -Au (Si) (R) a (O) (3_a), 2, the organosiloxane may comprise units of formula: (R) b- (Si) (O) (4_b), 2 in which: R has the same meaning as in formula (I), b = 1, 2 or 3; group (D) denotes an s-triazine compound of the following formula (II): ## STR2 ## - ^^ ~ N (II) NH where - RI, identical or different, represent a linear or branched and optionally unsaturated C 1 -C 10 alkyl radical which may contain a C 5 -C 6 cycloalkyl group, - the group (C = O) OR1 can be in the ortho, meta or para position of the group amino, - R2, identical or different, represent hydrogen, a hydroxyl radical, a linear or branched C1-C4 alkyl radical, a methoxy radical, A is a divalent radical chosen from methylene or a group corresponding to one of following formulas (III), (IV), (V) or (VI): ## STR3 ## where: ## STR2 ## c (VI) in which: Z is a C 1 -C 3 alkylene diradical; W is a hydrogen atom, a hydroxyl radical or a C 1 -C 3 alkyl radical;

It should be noted that the derivatives of formula (I) can be used in their tautomeric forms and more particularly in the tautomeric form of the following formula (I '): (D') ù (Si) O (3-a) / 2 (I (R) a) in which the group (D ') denotes an s-triazine compound of the following formula (II'):

In the formulas (II) and (II ') as defined above, the alkyl radicals may be linear or branched and chosen in particular from methyl, ethyl, n-propyl or isopropyl radicals. n-butyl, isobutyl, tert-butyl, n-amyl, isoamyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl and tert-octyl. The particularly preferred alkyl radical is the butyl radical.

The preferred s-triazine derivatives are those for which in the formula (II) or (II ') at least one, and even more preferably all, the following characteristics are fulfilled: R is methyl, a = 1 or 2, RI is a C1-C8 radical, Z = -CH2-, is W = H, the (C = O) OR1 group is in the para position of the amino group.

Preferably, the s-triazine compounds of the invention are represented by the following formulas (la, (Ib) or (Ic): R 7 R 7 (la) (B) SiO 2 + SiO 4 R 7 R 7 R 7 R 7 R 7 SiùO + Siù (B) (D) R7 R7 R7 WhereSi] t [WhereSi uR7 (D) (Ic) (D) -Si (R8) 3 in which: - (D) corresponds to formula (XV) as defined above, R7, which may be 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, which may be identical or different, are chosen from linear and branched C 1 -C 20 alkyl and alkenyl radicals, the hydroxyl or phenyl radicals, - (B), which are identical or different, and are chosen from the radicals R 7 and the radical (D), r is a whole number between 0 and 200 inclusive, - s is an integer from 0 to 50 and if s = 0, at least one of the two symbols (B) is (D), - u is an integer from 1 to 10, - t is an integer e being 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 preferably having at least one, and even more preferably all, of the following characteristics: R is the methyl radical, the C 1 -C 2 alkoxy radical or the hydroxyl radical, B is preferably methyl (in the case of linear compounds of formula (Ia)),

By way of examples of particularly preferred compounds of formula (I), mention will be made of the compounds of formulas (1) to (26) below, as well as their tautomeric forms: INP / sl, o, sl HNN NH II -Si NH ( 1) NH 4 NH (4) (NPP) Si (5) Si (n) Si (n) Si (n) Si (Si) O (Si) O (Si) Si (Si) O (Si) Si (Si) O (Si) SiO (Si) Si (15) (16) O (17) NH (NH) SiN (NH) SiN (NH 2) Si (N) O (Si) N SiH (21) (22) 10 HN NN I 1 NH N NH LIù Sil ~ O 1 SiùOiSi / 1 HN N NH N ÍN NH (23) NH N j N `) -NH Si-O + Si-O N \ - f 1 L 1 O NH 0 Siù NH NH N = (/ N NH (24) r stat = 8.1 OO (25) s ~ siiO ~ SiiO] r [SiiO-S

## STR2 ## and more particularly compounds such as ethyl 2,4-bis (4'-aminobenzoate) -6 - [(3 - {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -s-triazine of formula (2), 2,4-bis (4'-aminobenzoate) isopropyl) -6 - [(3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -s-triazine of formula (4), 2,4-bis; (N-Butyl 4'-aminobenzoate) -6 - [(3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -s-triazine of the formula (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) and 2,4-bis (4'-aminobenzoate neopentyl) - 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} propy l) amino] s-triazine of formula (5):

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

The compounds of formula (I) can be obtained according to reaction scheme 5 below: Y

NO R1 + 2 YNY + H2NiA SY0 (3a) I2 (R) a (VIII) NH2 i0 (1) + 3 HY where R, R1, R2, A, X, n and a are as defined above and Y represents halogen, especially chlorine or bromine. The order of introduction of the reagents can be indifferently, 2 equivalents of the derivative of formula (VII) followed by one equivalent of the derivative of formula (VIII) (lane 1) or 1 equivalent of the derivative of formula (VIII) followed by 2 equivalents of the derivative of formula (VII) (Route 2). The above reactions can 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 preferably between 0 ° C and 20 ° C for the first step of Route II and between 50 and 120 ° C for the first step of Route 1 and in the presence or absence of a sensing base of the acid formed (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.

Whether lanes 1 or 2, the steps can be chained in the same reactor without isolation of the intermediate derivatives formed.

The compounds of formula (VII), some of which are commercial, 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 (in an 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 triazine derivatives of formula (I) according to the invention are preferably present in the compositions in accordance with the invention at contents of 0.01 to 20% by weight and more preferably of 0.1 to 10% and more preferably from 0.1 to 6% by weight relative to the total weight of the composition. Among the lipophilic merocyanines that can be used in accordance with the present invention, there may be mentioned compounds corresponding to one of the following general formulas (IXa) and (IXb): ## STR2 ## In which: R 'and R2, which are identical or different, represent H, a C1-C22 alkyl radical and which may contain a silicon atom or a C3-C8 cycloalkyl radical, a C 6 -C 20 aryl radical, it being understood that only one of R ', R 2 is H and R' and R 2 together with nitrogen may form a ring containing the - (CH 2) 6 - group, uninterrupted or interrupted by -O-, -S-, -NH- or by -NR5-, -R3, R4, which are identical or different, represent a carboxyl group, -COOR5, -CONHR5, -COR5, -CONR5R6, -CN or SO2R5, -R5 , identical or different, represent a C1-C22 alkyl radical and which may contain a silicon atom, a C3-C8 cycloalkyl radical or a C6-C20 aryl radical; R6 is hydrogen or a rad C1-C20 alkyl, - Z1 is a - (CH2) I group uninterrupted or interrupted by -O-, -S-, -NH- or by -N R6-, 30 - g is 1-7, - I is 1-4, - o is 1-4, with the proviso that (i) when o = 2, R 'or R5 is an alkyl diradical or R' and R2 together with 2 to 35 nitrogen atoms form a divalent radical - ( CH2) g-, (ii) when o = 3, R 'or R5 is a trivalent radical, (iii) when o = 4, R' or R5 is a tetravalent radical, (iv) R 'and R2 are not simultaneously a hydrogen atom.

The compounds of formula (IXa) that are particularly preferred are those for which the following conditions are met: R1 and R2, which are identical or different, denote a C1-C12 alkyl radical or a C5 cycloalkyl radical; R3 is a COOR5 or CN group; R4 is SO2R5 or COOR5; R 5 denotes a C 1 -C 12 alkyl radical o is equal to 1 or 2. The compounds of formulas (IXa) and (IXb) may be present in the isomeric forms E, E-, E, Z- or Z, Z- .

By way of examples of compounds of formula (IXa) which are particularly preferred, mention may be made of the products of formulas (27) to (41) below: (20) RN = 69641-64-1 (28) RN = 329729- 94-4 (32) RN = 69641-76-5 where O = S = O (29) RN = 98835-90-6 where o (31) RN = 615285-47-7 0 = 6 = 0 " N = O = S = OO (33) (34) RN = 69641-75-4 (36) RN = 69486-81-3 (35) RN = 68452-64-2 (37) (38) ) RN = 69641-75-4 (39) RN = 942408-05-1 NO (40) (41) By way of examples of compounds of formula (IXb) which are particularly preferred, mention will be made of the products of formulas (42) to (47): (42) NNN (44) RN = 110186-47-5 (45) RN = 923271-36-7 ovo N oo N (46) RN = 923271-35-6 (47) The syntheses of derivatives of formulas (IXa) and (IXb) are described in US Patents 2186608, US 3723154, US 4045229, US 4195999, US 4749643, EP 0127819, EP 0210409, WO 2004/006878 and IPCOM000022279D.

A second family of UV filters of merocyanines according to the present invention consists of the compounds corresponding to the following general formula (X): (D 1) (Si O (3-a) / 2 (X) (R ') a in which - R and a have the same meaning as in the formula (I) defined above, - the group (D1) denotes a compound derived from merocyanine of the following formulas (XIa), (XIb) and (XIc): O 1 RN w (X1) q Y1 2 R 0 = S = 0 R4 p (XIa) 0 = S = 0 R4 Y (Y 0 IN \ \ (X1) q R2 p (XIb) R3 N1 R2 O = S = O R4 p (XIc) in which: X1 = represents -O-, -NR6-, -R1, R2, R3, R4, R5 and R6 having the same definitions as in the formulas (IXa) and (IXb) indicated above, - p = 1 or 2, - q = O or 1, - Y1 is a divalent C1-C5 alkyl radical optionally substituted with C1-C4 alkyl radicals and / or containing -O-, -S- atoms, or by a 20 group ùNR6,

In addition to the units of the formula (Ai) (Si) (R) a (O) (3-a), 2, the organosiloxane may have units of the formula: (R) b- (Si) (O) (4-b) ), 2 in which R and b have the same meaning as in formula (I); Preferably, the compounds of formula (X) are represented by the following formulas (Xa), (Xb) or (Xc): (Xa) R7 R7 II (B ') SiO + SiuO R7 R7R7 R7 1 SiO ] Siù (B ') (D1) R7 R7 Si (D1) u R7 WhereSi] t [o-R7 (Xb) (Xc) (D1) -Si (R8) 3

in which: R7, R8, r, s, t and u have the same meaning as in formulas (Ia), (Ib) and (Ic) as defined above; - (D ') corresponds to the formulas (Xla), (Xlb) and (Xlc) as defined above, - (B'), which are identical or different, are chosen from the radicals R7 and the radical is (D ').

Y 'is more particularly a group of atoms whose result lies in the formation of an oxazolidine ring, a pyrrolidine ring, a thiazolidine ring or an indoline bicycle. The compounds of the formulas (Xa), (Xb) and (Xc) may be present in the isomeric forms E, E-, E, Z- or Z, Z-.

Examples of compounds of formula (Xa) which are particularly preferred are the products of the following formulas (48) to (53): ## STR2 ## 19 2949341 6i_ ~ If O Si o 16 [If O ~ Si 6 / (50) O (51) --Si / O SI / o psi o 5 ONH ,, OS \ NS * OO 0 (52) (53) A As an example of compounds of formula (Xb) that are particularly preferred, mention may be made of the mixture of compounds of formulas (54) below: ## STR1 ##

By way of examples of compounds of formula (Xc) which are particularly preferred, mention may be made of the compounds of formulas (55) to (62) below: ## STR2 ## O ~ OS OiN ~ OOSO (57) (56) / ùSiùO - SiO ~ s L SiùO + Si-NO (58) \, -siO ~ O 0 IO jsi3O ~ Si, + ~ Si_O ~ Si ~ / N \ S ## STR2 ## wherein R 1 is O, O, O, O, O, O, O, O, OH, O, O, O, O, O, O, O, O, O, O, O, O, OH (Xb) can be prepared according to a method described in US Patents 4045229 and US 4195999.

The derivatives of formulas (Xa) and (Xc) may be prepared according to a method described in patent WO 0020388.

Among the lipophilic merocyanines described above, the following compounds will be used more particularly:

H Oy-Si S% O J O 22 O 0 = s = 0 (29) (33) Y N W O N O

N (37) (38) N (39) RN = 942408-05-1 N II NH (45) RN = 923271-36-7 N (44) RN = 110186-47-5 S .-- 0 'Si 0 '1 /

0-0 (48) The lipophilic merocyanine filter or filters in accordance with the invention may be present in the compositions according to the invention at a concentration of between 0.1 and 15%, preferably between 0.2 and 10%, in weight relative to the total weight of the composition.

The compositions in accordance with the invention may comprise, in addition to other, additional lipid-soluble or insoluble UVA and / or UVB active organic or inorganic UV-screening agents as well as water-soluble UVB filters in the commonly used cosmetic solvents.

Of course, one skilled in the art will take care to choose the optional additional filters and / or their amounts so that the advantageous properties intrinsically attached to the compositions according to the invention are not, or not substantially impaired by the addition or additions envisaged.

The additional organic screening agents are especially chosen from dibenzoylmethane derivatives; anthranilates; cinnamic derivatives; salicylic derivatives, camphor derivatives; benzophenone derivatives; 13,13-diphenylacrylate derivatives; triazine derivatives other than those of formula (I); benzalmalonate derivatives including those cited in US5624663; benzimidazole derivatives; imidazolines; p-aminobenzoic acid derivatives (PABA); benzotriazole derivatives; methylene bis (hydroxyphenyl benzotriazole) 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 and mixtures thereof.

Examples of organic UV filters are those referred to below under their INCI name:

Derivatives of dibenzoylmethane Butyl Methoxy Dibenzoylmethane, offered for sale under the trade name 40 "PARSOL 1789" by the company DSM NUTRITIONAL PRODUCTS

Derivatives of para-aminobenzoic acid: PABA, Ethyl PABA, Ethyl Dihydroxypropyl PABA, Ethylhexyl Dimethyl PABA sold in particular under the name Escalol 507 by ISP, Glyceryl PABA, 50 PEG-25 PABA sold under the name Uvinul P25 by BASF, Derivatives Salicylics: Homosalate sold under the name Eusolex HMS by Rona / EM Industries, Ethylhexyl Salicylate sold under the name NEO HELIOPAN OS by SYMRISE, Dipropylene glycol salicylate sold under the name DIPSAL by SCHER, TEA Salicylate, sold under the name NEO HELIOPAN TS by SYMRISE ,

Cinnamic derivatives: io Ethylhexyl Methoxycinnamate sold in particular under the trade name 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 1,3,13-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 30 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 35 American Cyanamid Benzophenone-9 sold under the trade name UVINUL DS-49 by BASF, Benzophenone-12 2- (4) n-hexyl diethylamino-2-hydroxybenzoyl) 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 45 MERCK, Benzylidene Camphor 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 SX by CHIMEX, Polyacrylamidomethyl Benzylidene Camphor manufactured under the name MEXORYL SW by CHIMEX, Derivatives of 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 SYMRISE,

Benzotriazole derivatives: Methylene bis-benzotriazolyl tetramethylbutylphenol, sold in solid form under the tradename MIXXIM BB / 100 by FAIRMOUNT CHEMICAL or in micronized form as an 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, 25 2 4,6-tris- (4'-amino benzalmalonate diisobutyl) -s-triazine, 2,4,6-tris (4'-amino benzalmalonate dineopentyl) -s-triazine, 2,4-bis (4 ') dineopentylamino benzalmalonate) -6- (n-butyl 4'-aminobenzoate) -s-triazine triazine symmetrical 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 , 35 WO 06/034982, WO06 / 034991, WO06 / 035007, WO2006 / 034992, WO2006 / 034985.

Anthranilic Derivatives: Menthyl anthranilate sold under the trade name NEO 40 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 50 Derivatives of 4,4-diarvlbutadiene: 1,1-dicarboxy (2,2 N'-dimethyl-propyl) -4,4-diphenylbutadiene

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

The preferred organic complementary filters are chosen from Ethylhexyl Methoxycinnamate Homosalate Ethylhexyl Salicylate, Octocrylene, Butyl Methoxy Dibenzoylmethane is Terephthalylidene Dicamphor Sulfonic Acid Disodium Phenyl Dibenzimidazole Tetrasulfonate Phenylbenzimidazole Sulfonic Acid, Benzophenone-3 2- (4-diethylamino-2-hydroxybenzoyl) n-hexyl benzoate 4-Methylbenzylidene camphor, 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- (4'-amino benzalmalonate diisobutyl) -s-triazine, 2,4-bis (4'-amino benzalmalonate dineopentyl) ) -6- (N-Butyl 4-aminobenzoate) -s-triazine Methylene bis-Benzotriazolyl Tetramethylbutylphenol, Polysilicone-15 Di-neopentyl 4'-methoxybenzalmalonate 1,1-dicarboxy (2,2'-dimethyl-propyl) -4 4-diphenylbutadiene 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-y 1- (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazine and mixtures thereof.

The complementary inorganic filters are chosen from coated or uncoated metal 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 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 a chemical, electronic, mechanochemical and / or mechanical nature with compounds as described for example in Cosmetics & 50 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. Even more preferentially, the silicones are chosen from the group containing octyl trimethyl silane, polydimethylsiloxanes and polymethylhydrogensiloxanes. Of course, the metal oxide pigments before being treated 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 - silica and iron oxide such as that the product "SUNVEIL F" 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" of the company TIOXIDE, and Mirasun TiW 60 from Rhodia, - alumina such as the products "TIPAQUE TTO-55 (B)" and "TIPAQUE TTO-55 40 (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 the company TAYCA, the products Solaveil CT-10 W "," Solaveil CT 100 "and" Solaveil CT 200 "from the company UNIQEMA, 45 - 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, iron oxide and iron stearate such as the product "MICROTITANIUM 50 DIOXIDE MT 100 F", the company TAYCA, - zinc oxide and zinc stearate such as the product "BR351" from TAYCA, - silica and alumina and treated with a silicone such as the products "MICROTITANIUM DIOXIDE MT 600 SAS" "MICROTITANIUM DIOXIDE MT s 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 "from the company TITAN KOGYO - silica and treated with a silicone such as the product" UV-TITAN X 195 "KEMIRA society, or the product SMT-100 WRS TAYCA society. - Alumina and treated with a silicone such as the products "TIPAQUE TTO-55 (S)" ISHIHARA company, or "UV TITAN M 262" KEMIRA company, triethanolamine such as the product "STT-65 -S "from the company TITAN KOGYO, - stearic acid such as the product" TIPAQUE TTO-55 (C) "of the company ISHIHARA, - sodium hexametaphosphate such as the product" MICROTITANIUM DIOXIDE MT 150 W " from 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 TiO2SI3 "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 "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".

Non-coated 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); 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 marketed 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); is - those sold under the name "Escalol Z100" by the company ISP (ZnO treated alumina and dispersed in the mixture methoxycinnamate ethylhexyl / PVP-hexadecene copolymer / methicone); 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).

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 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 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 45 such as the product" M 261 "sold by the company KEMIRA or coated with alumina, with silica and with glycerin such as the product "M 211" sold by the company 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. relative to the total weight of the composition.

The aqueous compositions in accordance with the present invention may further comprise conventional cosmetic adjuvants, chosen especially 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, alkalinizing 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 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 benzoate of C12 alcohols. C15 sold under the trade name Finsoly 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.

Organic solvents include 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 50: acrylamide / sodium acryloyldimethyltaurate copolymer / isohexadecane / polysorbate 80) by the company Seppic; polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid, optionally cross-linked and / or neutralized, such as poly (2-acrylamido-2-methylpropanesulphonic acid) marketed by Hoechst under the trademark Hostacerin AMPS (CTFA name: 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-methylpropanesulphonic acid and hydroxyethyl acrylate such as SIMULGEL NS and SEPINOV 10 EMT 10 marketed 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 cationic silicones and mixtures thereof As lipophilic thickeners mention may be made of synthetic polymers such as the 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, as the products marketed under the names of Bentone.

Of course, those skilled in the art will take care to choose the optional additional compound or compounds mentioned above and / or their amounts in such a way that the advantageous properties intrinsically attached to the compositions according to 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.

Emulsification processes that can be used are pale or helical, rotor-stator and HHP.

In order to obtain stable emulsions with a low level of polymer (oil / polymer ratio> 25), it is possible to disperse in the concentrated phase and then to dilute the dispersion with the rest of the aqueous phase. 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).

As emulsifying surfactants that can 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 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. It is also possible to add one or more co-emulsifiers, which advantageously can be chosen from the group comprising the alkylated polyol esters.

Polyol alkyl esters that may especially be mentioned include 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 company ICI under the name Arlacel 165; oxyalkylenated fatty alcohol ethers (oxyethylenated and / or oxypropylene); 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 names Plantaren 2000 and Plantaren 1200 respectively, 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 arachidylglucoside sold under the name Montanov 202 by 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. 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 and aerosol pumps using compressed air as a propellant. These are described in US Patents 4,077,441 and US 4,850,517 (forming 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.

The compositions according to the invention may also comprise, in addition to the additional 45 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; the soothing agents; the NO-synthase inhibitors; agents stimulating the synthesis of dermal or epidermal macromolecules and / or preventing their degradation; s - agents stimulating the proliferation of fibroblasts; agents stimulating the proliferation of keratinocytes; - muscle relaxants; tensing agents, mattifying agents, keratolytic agents, desquamating agents; - Moisturizing agents such as polyols such as glycerin, butylene glycol, propylene glycol. anti-inflammatory agents; is - agents acting on the energetic metabolism of cells, - insect repellants - 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, impaired by the 25 or additions considered.

The skilled person will choose the active agent (s) depending on the desired effect on the skin, hair, eyelashes, eyebrows, nails.

The composition may also comprise at least one ingredient such as blooming fillers or agents promoting the natural coloration of the skin, intended to supplement the biological effect of these active ingredients or to 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, and astringent agents.

ADDITIONAL INGREDIENTS The composition may further comprise at least one additional ingredient intended to complement the biological effect of these actives or to provide an immediate visual effect; mention may in particular be made of matting agents, fillers with a blooming effect, fluorescent agents, agents which promote the naturally rosy coloration of the skin and abrasive or exfoliating fillers.

In order to complement and / or optimize the effects conferred by the cosmetic and / or dermatological active agents mentioned above on keratin materials, it may be advantageous to incorporate other additional ingredients into the compositions of the invention.

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 (ex: abrasvies), amplify the effect of the biological assets mentioned above.

Thus, the composition according to the invention may further 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.

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 20 2 generally reflects a matting effect.

The matting agent may in particular 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 25 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 / silica composite powders mixed amorphous silicate powders, silicate particles, and especially mixed silicate particles, 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 , in 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 blend of polymers, resorbable synthetic fibers, and mixtures thereof described in EP 1 151 742; microspheres of expanded acrylic copolymers such as those sold by EXPANCEL under the trade names EXPANCEL 551, fillers with an optical effect as described in patent application FR 2 869 796, in particular: 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 the Miyoshi size Silica beads SB150. average 5 microns and refractive index 1.45, - powders of polytetrafluoroethylene, such as PTFE ceridust 9205F Clariant average size 8 microns and refractive index 1.36, - the silicone resin powders as the Silicon resin Tospearl 145A of GE Silicone of average size 4.5 microns and refractive index 1.41, the powders of acrylic copolymers, in particular of poly (meth) acrylate, such as PMMA particles J urymer MBI from Nihon Junyoki with an average size of 8 microns and a refractive index of 1.49, or the Micropearl M100 and F 80 ED0 particles from the company Matsumoto Yushi-Seiyaku, - wax powders such as paraffin wax microease 114S particles from 25 micropowders having a mean size of 7 microns and a refractive index of 1.54, polyethylene powders, in particular comprising at least one ethylene / acrylic acid copolymer, and in particular consisting of ethylene / acrylic acid copolymers such as the Flobeads EA 209 particles. 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 US Pat. company SHIN ETSU, and - the powders composi talc / titanium dioxide / alumina / silica, such as those sold under the name Coverleaf® AR-80 by the company 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 ", 45" SUNSPHERE H53 "marketed by ASAHI GLASS; the polydimethylsiloxane-coated amorphous silica microspheres sold under the name "SA SUNSPHEREO H-33" and "SA SUNSPHEREO H-53" marketed by the company 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 (nylon) powders, such as for example "ORGASOL 4000" marketed by Arkema, and acrylic polymer powders, in particular polymethyl methacrylate, such as for example "COVABEAD LH85" marketed by the WACKHERR company; polymethyl methacrylate / ethylene glycol dimethacrylate, such as, for example, "DOW CORNING 5640 MICROSPONGEO SKIN OIL ADSORBER" marketed by Dow Corning, or "Ganzpearl GMP-0820" marketed by 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" marketed from 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 a sodium sulphate sold under the trade name Sumecton® by the company Kunimine; the magnesium silicate complex, hydroxyethylcellulose, black cumin oil, pumpkin oil and phospholipids or Matipure® from Lucas Meyer, and mixtures thereof. As preferred matting agents, it is possible to use, according to the invention, an extract of pumpkin seeds, a rice or maize starch, kaolinite, silicas, talc, polyamide powders, polyethylene powders and copolymer powders. acrylics, expanded acrylic copolymer microspheres, silicone resin microbeads, mixed silicate particles, and mixtures thereof.

Chargers with a flutter effect

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

The following compounds can be exemplified by the filler: - porous silica microparticles, for example Myochi's Silica Beads 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, and 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 Tospearl 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 instance PMMA Jurimer MBIO particles of Nihon 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 the expanded vinylidene / acrylonitrile / methylene methacrylate microspheres sold under the name ExpanceI0. - Wax powders such as paraffin wax microlase 114S micropowders particles of average size of 7pm. polyethylene powders, especially comprising at least one ethylene / acrylic acid copolymer, for example the FLOBEADSO EA 209 E from Sumimoto, with an average size of 10 μm. the crosslinked elastomeric organopolysiloxane powders coated with silicone resin, in particular silsesquioxane under the name KSP 100, is 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 80 from Catalyst & Chemical. talc, mica, kaolin, lauryl glycine, starch powders crosslinked with octyanyl succinate anhydride, boron nitride, polytetrafluoroethylene powders, precipitated calcium carbonate, carbonate of hydrocarbonate magnesium, barium sulfate, hydroxyapatite, calcium silicate, cerium dioxide and glass or ceramic microcapsules. Synthetic or natural hydrophilic or hydrophobic fibers, mineral or organic such as fibers of silk, cotton, wool, flax, cellulose extracted in particular 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, synthetic resorbable fibers, and mixtures thereof described in patent application EP 1 151 742. 35 crosslinked elastomeric spherical 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 Abrasif SPO from Semanez or walnut or shell powders (apricot, walnuts, 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.

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 particles may be of any shape and in particular be spherical or non-spherical. 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 / TiO2 or silica / zinc oxide composites, polyethylene powders starch powders, polyamide powders, styrene / acrylic copolymer powders, silicone elastomers, and mixtures thereof.

In particular, mention may be made of talc of average size in a number less than or equal to 3 microns, for example talc of average size in number of 1.8 micron 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 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 of reference H-53 by Asahi Glass, and silica micro-beads such as those sold under the name denomination SB-700 or SB-150 by the company Miyoshi, this list not being limiting. 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. .

35 Ages promoting naturally rosy skin coloration These include:

a self-tanning agent, that is to say an agent which, applied on the skin, especially 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 give 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 momentary coloration provided for example by a makeup pigment; 50 and mixtures thereof. Examples of self-tanning agents that may be mentioned include: dihydoxyacetone (DHA), erythrulose, and the combination of a catalytic system consisting of: salts and oxides of manganese and / or zinc, and alkaline hydrogenocarbonates 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 is 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.

Other dyes that can modify the color produced by the self-tanning agent can also be used.

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 tetrabromofluoroscéine known under the name CTFA: Cl 40 45380 (Na sait) 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; 45 - Erythrosine known as CTFA: Cl 45430 or Acid Red 51. - Phloxine known as 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, daphinine.

These dyes may also be chosen from indole derivatives such as monohydroxyindoles as described in the patent FR2651126 (ie: 4-, 5-, 6- or 7-hydroxyindole) or the di-hydroxyindoles 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);

io Abrasive loads or exfoliating agents

As exfoliating agents that may be used in rinsed compositions according to the invention, mention may be made, for example, of exfoliant or scrubbing particles 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.

Preferred abrasive fillers or exfoliation agents according to the invention are 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 composition ingredients are given in% by weight based on the total weight of the composition.

EXAMPLES OF TRIAZINE SYNTHESIS OF FORMULA (I):

EXAMPLE 1: Preparation of methyl 2,4-bis (4'-diylamino benzoate) -6- {1,3,3,3-tetramethyl-1- (trimethylsilyl) oxyldisiloxanylpropyl-3-ylamino} -straprine Lane I): (1)

In a reactor bubbled with nitrogen, methyl paraaminobenzoate (9.2 g, 0.0609 mol), 2-butanone (40 ml) and potassium carbonate (4.21 g) dissolved in 57 ml of water. The mixture is cooled to 0-5 ° C. and the cyanuric chloride (5.61 g, 0.0304 mol) dissolved in 88 ml of 2-butanone is introduced 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: 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} -striazine (lane I): (2) In a reactor bubbled with nitrogen, ethyl paraaminobenzoate (6.05 g, 0.0366 mol), 2-butanone ( 30 ml) and potassium carbonate (2.53 g) dissolved in 38 ml of water. The mixture is cooled to 0-5 ° C. and the 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 and 1-amino [1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl is then 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'-diylamino benzoate) -6-fi, 3,3,3-tetramethyl-1 - [(trimethylsilyl) oxyldisiloxanyllpropyl-3-ylamino] -straprine ( Lane II): HN.NyNH N1 * N NH 25 (2)

First Step: Preparation of 2,4-dichloro-6- {[1,3,3,3-tetramethyl-1- (trimethylsilyl) oxyldisiloxanylpropyl-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'-diylamino benzoate) -6411,3,3,3-tetramethyl-1- (trimethylsilyl) oxyldisiloxanylpropyl-3-ylamino) -s-triazine ( Lane II): 20 (3)

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'-diylamino benzoate) -6-fi 1,3,3,3-tetramethyl-1- (trimethylsilyl) oxyldisiloxanylpropyl-3-ylamino) -straprine ( Lane II): (4)

Isopropyl para-aminobenzoate (10.05 g, 0.0561 mol) dissolved in 40 ml of ethyl acetate is introduced into 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 mol) 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 the organic phase, the paste obtained is purified by chromatography on a column of silica (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., is UV (Ethanol): X max = 311 nm, El % = 1155.

EXAMPLE 6 Preparation of n-Butyl 2,4-bis (4'-diylamino benzoate) -6- {1,3,3,3-tetramethyl-1 (trimethylsilyl) oxyldisiloxanyllpropyl-3-ylamino} -s-2o triazine (Route II): Under nitrogen sparge, 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) are suspended in 170 ml of toluene and heated under reflux 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 EtOAc / Heptane 1: 15, 20.1 g (yield: 69%) of the derivative of Example 6 is obtained in the form of a white powder: Melting point: 111-113 ° C., UV (Ethanol): X max = 312 nm, El% = 1360.

EXAMPLE 7 Preparation of Isobutyl-2,4-bis (4'-diylamino benzoate) -6-fi, 3,3,3-tetramethyl-1 - ((trimethylsilyl) oxyldisiloxanylpropyl-3-ylamino} -s-15 triazine (lane I): ## STR2 ## In a nitrogen-bubbled reactor, isobutyl para-aminobenzoate (10.39 g, 0.0538 mol) is introduced successively. 2-butanone (72 ml) and potassium carbonate (3.72 g) dissolved in 57 ml of water. The mixture is cooled to 0-5 ° C. and the cyanuric chloride (4.96 g, 0.0269 mol) dissolved in 68 ml of 2-butanone is introduced 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-s-triazine formed is not isolated. 2.26 g of sodium bicarbonate are added to the reaction mixture, and then the product of the first step of Example 2a (7.52 g, 0.0269 mol) is added 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 methyl 2- (4'-methylaminoazoate) -4- (4-tert-butylamino benzoate) -6- (1, 3, 3, 3-tetramethyl) (trimethylsilyl) oxyldisiloxanylpropyl-3-ylamino} -s-triazine (modified lane I): (7) In a nitrogen bubbled reactor, tert-butyl para-aminobenzoate was solubilized (1 g, 0.00517 moles ) in 10 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 sodium derivative is dripped in the course of 30 minutes. the first 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 para- aminobenzoate ( 0.98 g, 0.00517 mole) dissolved in 5 ml of ethyl acetate, and heating continued at 70 ° C. 2 hours After cooling, the organic phase is washed with saturated sodium chloride solution, then with water and dried. The paste obtained is chromatographed on a column of silica (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 (13.34) are successively introduced into a reactor bubbling with nitrogen. 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., UV (ethanol): λmax = 311 nm, El% = 1265 .

EXAMPLE 11 Preparation of (1,1,3,3-tetramethylbutyl) -6- {1,3,3,3-tetramethyl-1-2o-1 (trimethylsilyl) oxyldisiloxanylpropyl) -2,4-bis-4-diylamino benzamide -3-ylamino} -s-triazine: NH /

where / NH NH Step 1: 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 carbon at room temperature. 50% water as catalyst (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 mole) 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 is 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 (4-diylamino benzoate) -6- {1,3,3,3-tetramethyl-1-1 (trimethylsilyl) oxyldisiloxanylpropyl-3-ylamino} -2-bis (4'-diylamino benzoate) -s- triazine: \ / -Si NH

OS / Si (12) First step: preparation of methyltrimethylsilyl 4-aminobenzoate: Chloromethyltrimethylsilyl (38.5 g, 0.314 mol) is added dropwise at 80 ° C. to the heterogeneous mixture of the potassium salt. 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 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 a 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 previous step (2.19 g, 9.8x10-3 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 is 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 ( II): In a argon bubbling reactor, n-hexyl para-aminobenzoate (19.32 g, 0.0904 mol) was 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) oxyldisiloxane] propyl-3-ylamino} -s-triazine (Route II): In a reactor bubbled with argon, 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 cyclohexyl (2,4-bis (4'-divamino benzoate) -6- {1,3,3,3-tetramethyl-1-yl (trimethylsilyl) oxyldisiloxane] propyl-3-yl -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 ethyl-2-hexyl) -6- {1,3,3,3-tetramethyl-1-1 (trimethylsilyl) ) Oxyldisiloxanyllpropyl-3-ylamino} -s-triazine (Lane II): Under nitrogen sparge, a mixture of 2-ethylhexyl 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 pure fractions 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 . (17) EXAMPLE 17: Preparation of 4-But {1- [4- [4- (butoxycarbonyl) phenyl] amino} -6 - ({3-diethoxy (methyl) silylpropyl} amino) -3,5-triazin-2-yl] amino} benzoate (Route 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 mol) in 500 ml of dioxane and 50 ml of water is 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 which corresponds 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 mol) is added in 50 ml of water. 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 previous step (20 g, 0.04 mol) and aminopropyl diethoxy methyl silane (15.37 g 0.084 mol) is progressively 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, the derivative of Example 17 (21 g, yield 80%) is obtained after drying of the organic phase in the form of a white solid UV (Ethanol): X max = 311 nm, El% = 1197. EXAMPLES 18 and 19: Preparation of the derivatives: butyl 4-f- (4- {4- (butoxycarbonyl) phenyl] amino} -6- {f- (1-hydroxy-1,3,3, 3-tetramethyldisiloxanyl) propyllamino} -1,3,5-triazin-2-yl) aminolbenzoate and dibutyl 4,4 '- {f6 - ({3-dihydroxy (methyl) silyllpropyl} amino) -1,3,5-triazine -2,4-s diylldiimino} dibenzoate (obtained by acid treatment of the derivative of Example 5): ## STR2 ## Si (21) / ~ / Au derived from Example 6 (10 g, 0.013 mol) Solubilized in 500 ml of the 80:20 mixture of ethanol / isopropanol, 160 ml of 0.1 N hydrochloric acid and 340 ml of the 80:20 mixture of ethanol / isopropanol 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 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 18 and about 10% of the derivative of Example 19. This powder has 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 white powder: UV (Ethanol): X max = 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) phenylamino} -6 - [(2- {1,3,3,3-tetramethyl-1-1 (trimethylsilyl) oxyldisiloxane} propyl) aminol-1,3,5-triazin-2-yl) amino) benzoate:

/ -Si O

O HNyNyNH / NH (22) O First step: 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 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-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 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:

Second Step: Preparation of the Derivative of Example 20: The foregoing product (2 g, 0.0047 moles) was 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) are 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% = EXAMPLE 21: Preparation of the compound (23): ## STR5 ## To the derivative of Example 6 (1 g, 0.0013 mol) solubilized in 50 ml of the ethanol / mixture. isopropanol in the ratio 80:20, 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 a biphasic system composed of heptane, d ethyl acetate, methanol and water) to give 0.18 g of the derivative of Example 21 in the form of a white powder: UV (Ethanol): X max = 312 nm, El% = 1109.

EXAMPLE 22 Preparation of the Compound (24) ## STR2 ## N = (N N -NH, -ii-O + ii -O + L-NH - (N)

## STR1 ## 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, n-butyl para-amino benzoate (113.94 g) was added dropwise at 5 ° C. 0.59 moles) and a solution of potassium carbonate (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 mol) is added in 50 ml of water. 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) are obtained after drying under vacuum. chloro-s-triazine as a white powder. Second Step: Preparation of the Derivative of Example 22

Under nitrogen bubbling, 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 / O = 916.

EXAMPLE 23 Preparation of 2,4-bis (3,3,3-tetramethyl-1H-trimethylsilyl) oxyldisiloxanylpropyl-3-ylamino) -s-triazine 2,4-bis (4'-diylamino benzoate) (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 for 48 hours. 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 the excess lauric alcohol. The reddish brown viscous oil is crystallized from methanol. After filtration, the cake is washed with cold methanol and dried under a vacuum, the para-aminobenzoate of dodecyl (52.77 g, Yield 84%) as a pale yellow powder and used as it is in next step :

Second Step: Preparation of the Derivative of Example 23: Under argon sweeping and with stirring, the product of the first step of Example 3 (20 g, mole) solubilized in ethyl acetate is added, 5.3 ml of pyridine in solution in ethyl acetate. The mixture is heated to 70 ° C. and the dodecyl para-amino benzoate of the preceding 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) : X max = 311 nm, El% = 838.

EXAMPLE 24 Preparation of Compound (26)

~ siiiO ~ siiiO] r [SiùO-S NH N "/ N HN NNH (26) r stat = 9 and s stat = 1.8

Under nitrogen sparging, the heterogeneous mixture of the product of Example 17 (1 25 g, 1.53 × 10 -3 mol), decamethylcyclopentasiloxane (D5 (0.57 g, 1.53 × 10 -3 mol), hexamethyldisiloxane (MM) (0.062g, 0.38x10-mole) and concentrated hydrochloric acid (0.1ml) is stirred vigorously in a mixture of 10ml of toluene and 1ml of water, 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 to give 0.56 g of a powder. white of the derivative of Example 24 UV (Ethanol): Xmax = 311 nm, El% = 892.

II / EXAMPLES OF THE SYNTHESIS OF THE MEROCYANINE FAMILY: EXAMPLE 25 Preparation of the compound of formula (33): (33) First step: Preparation of 2-ethyl-1-hexylphenylsulphonylacetate

In a reactor bubbled with argon, phenylsulfonic acid (50 g, 0.25 mole) was solubilized in 500 ml of anhydrous acetonitrile. Ethyl-2-hexanol (42.45 ml, 0.275 mole) is added. The reaction mixture is cooled to about 4.degree. C. and N, N-dicyclohexylcarbodiimide (51.5 g, 0.25 mol) is added. Triethylamine (35 ml, 0.25 mol) is then added. A white precipitate is formed. The mixture is allowed to warm to room temperature and refluxed for 15 hours. The reaction mixture is allowed to cool and the formed salts are filtered off. The filtrate is concentrated under vacuum. The residue is taken up in dichloromethane. Wash 3 times with water and dry over sodium sulfate. After filtration and evaporation of the solvent, an orange-yellow oil is obtained which is purified by passage through silica.

70.3 g (yield 90%) of 2-ethyl-1-hexylphenylsulphonylacetate are thus obtained in the form of a yellow oil and used as such in the third step. Second step: Preparation of (2E) -3- (diethylamino) prop-2-enal:

In a reactor, propargyl alcohol (9.81 g, 0.173 mol) and diethylamine (16 g, 0.218 mol) are solubilized in 500 ml of toluene. Activated manganese dioxide (51.26 g, 0.6 moles) was added by 30 plots. The mixture is heated at 50 ° C. for 5 hours. Filtered hot. The toluene solution containing (2E) -3- (diethylamino) prop-2-enal is used as it is in the next step.

Step 3: Preparation of the compound of Example 25: To the above toluene solution was added the derivative of the first step (64.9 g, 0.208 mol) and a portion of the catalyst (4.31 ml of diethylamine + 2). 37 ml of acetic acid). The reaction mixture is heated under reflux (with removal of water using a Dean Stark) for 3 hours. A second portion of catalyst identical to the previous one is added and the reaction mixture is left reflux for 3 hours. This operation is renewed twice more. After returning to the temperature of the laboratory, 500 ml of dichloromethane are added. Wash twice with saturated sodium bicarbonate solution followed by washing with water. The organic phase is separated, dried over sodium sulfate. After removing the solvent and drying, a dark brown viscous oil is obtained. After purification on a silica bed, 35 μg (yield: 40%) of the clean fractions of the derivative of Example 25 are thus obtained in the form of a very viscous yellow-orange oil: UV (Ethanol): X max = 372 nm, El % = 1605.

This product kept in the fridge crystallized; recrystallized from heptane, the derivative of Example 25 is obtained in the form of a yellow powder: mp 45 ° -47 ° C.

EXAMPLE 26 Preparation of the compound of formula (37): o (37)

First step: Preparation of (2E) -3- (diethylamino) prop-2-enal:

In a reactor, propargyl alcohol (6.81 g, 0.126 mol) and diethylamine (14.5 mL, 0.28 mol) were solubilized in 90 mL of toluene. Activated manganese dioxide (34.5 g, 0.397 mole) was added by pinching. It is heated at 52 ° C. for 12 hours. Filtered hot. The toluene solution containing (2E) -3- (diethylamino) prop-2-enal is used as it is in the next step.

Second step: Preparation of the compound of Example 26:

To the above toluene solution was added n-octyl cyanoacetate (23 g, 0.125 mol) and the catalyst (1.2 ml diethylamine + 0.667 ml acetic acid). The reaction mixture is refluxed (with removal of water with a Dean Stark) for 5 hours and 30 minutes. After returning to the temperature of the laboratory, 500 ml of dichloromethane are added. Wash once with saturated sodium bicarbonate solution followed by washing with water. The organic phase is separated, dried over sodium sulfate. After removing the solvent and drying, a viscous brown red oil is obtained. After purification by passage through a column of silica (gradient eluent: Heptane / EtOAc 90:10 to 80:20), 26 g (yield: 72%) of the eigenfunctions of the derivative of Example 26 in the form of orange flakes are obtained: UV (Ethanol): λmax = 381 nm, El% = 2274. EXAMPLE 27: Preparation of the compound of formula (38) ONWO II N (38) First step: Preparation of (2E) -3- (diethylamino) prop -2-enal:

In a reactor, propargyl alcohol (18.4 g, 0.328 mol) and diethylamine (30 g, 0.41 mol) are solubilized in 250 ml of toluene. Activated manganese dioxide (72.6 g, 0.835 moles) was added by a pinch. The mixture is heated at 50 ° C. for 5 hours. Filtered hot. The toluene solution containing (2E) -3- (diethylamino) prop-2-enal is used as it is in the next step.

Second step: Preparation of the compound of Example 28

To the above toluene solution was added 2-ethylhexyl cyanoacetate (61.5 g, 0.312 mol) and 10 ml of diethylamine. The reaction mixture is heated under reflux (with removal of water using a Dean Stark) for 3 hours. After returning to the temperature of the laboratory, 500 ml of dichloromethane are added. Wash twice with saturated sodium bicarbonate solution followed by washing with water. The organic phase is separated, dried over sodium sulfate. After removing the solvent and drying, an orange viscous oil is obtained. After purification on a silica bed, 33.5 g (yield: 35%) of the clean fractions of the derivative of Example 28 are thus obtained in the form of a very viscous yellow-orange oil: UV (Ethanol): X max = 381 nm, El ° / o = 2240.

EXAMPLE 28 Preparation of the compound of formula (39) NNN (39) NR = 942408-05-1 First step: Preparation of (2E) -3-bis (2-ethylhexyl) aminolprop-2-enal: In a reactor, solubilized propargyl alcohol (5.79 g, 0.103 mol) and di- (ethyl-2-hexyl) amine (30 g, 0.124 mol) in 150 ml of toluene. Activated manganese dioxide (30.54 g, 0.351 mole) was added by pinching. It is heated at 95 ° C for 5 hours. It is allowed to return to the temperature of the laboratory and filters the solution. The toluene solution containing (2E) -3- [bis (2-ethylhexyl) amino] prop-2-enal is used as it is in the next step.

Second Step: Preparation of the compound of Example 28

To the above toluene solution was added malonitrile (2.54 g, 0.0384 mol) and 1 ml of piperidine. The reaction mixture is heated under reflux (with removal of water using a Dean Stark) for 3 hours. After returning to the temperature of the laboratory, 300 ml of dichloromethane are added. Wash twice with saturated sodium bicarbonate solution followed by washing with water. The organic phase is separated, dried over sodium sulfate. After removing the solvent and drying, a dark brown viscous oil is obtained. After purification on a silica bed, 16.3 g (yield: 46%) of the clean fractions of the derivative of Example 28 are obtained in the form of a very viscous yellow-orange oil: UV (Ethanol): X max = 380 nm, El% = 1892.

EXAMPLE 29 Preparation of the compound of formula (44): (44) RN = 110186-47-5 First step: Preparation of 3-f (2-ethylhexyl) aminol-5,5-dimethylcyclohex-2-en-1-one In a reactor, 5,5-dimethylcyclohexane-1,3-dione (10 g, 0.0713 mole) and ethyl-2-hexylamine (9.22 g, 0.0713 mole) were solubilized. in 75 ml of toluene. Refluxed for 4 hours and 30 minutes. It is allowed to return to the temperature of the laboratory and the solvent is evaporated under vacuum. A yellow oil is obtained which is solubilized under heat in a minimum of cyclohexane. Put in the fridge, the product precipitates. After filtration and drying, 15.6 g (87% yield) of 3 - [(2-ethylhexyl) amino] -5,5-dimethylcyclohex-2-en-1-one are obtained, which is used as such in the next step.

Second step: Preparation of the compound of Example 29:

In a reactor, the mixture of the product of the preceding step (2 g, 7.64 × 10 -3 mol) with dimethylsulphate (1.06 g, 8.4 × 10 -3) is gradually heated to 100 ° C. for 40 minutes. mole). The temperature is brought to 60 ° C. and the solution of malonitrile (0.504 g, 7.64 × 10 -3 moles) in 3 ml of isopropanol and 1.17 ml of triethylamine is poured in over 5 minutes. The reaction mixture is refluxed for 1 hour and 30 minutes. Cool in an ice-water bath and pour water until precipitation. The precipitate obtained is filtered, rinsed with water and dried under vacuum. There is thus obtained 2.12 g (yield: 92%) of the derivative of Example 29 in the form of a yellow powder: UV (ethanol): X max = 382 nm, El% = 1765. X max = 369 nm (shoulder ), El% = 1400.

EXAMPLE 30 Preparation of the compound of formula (45): N (45) NR = 923271-36-7 First step: Preparation of 3-bis (2-ethylhexyl) aminolcyclohex-2-en-1-one:

In a reactor, cyclohexanedione (8.97 g, 0.08 mol) was stirred in 15 ml of toluene. To the resulting pasty heterogeneous mixture at about 8 ° C with stirring was added dropwise Bis-ethyl-2-hexylamine (19.44 g, 0.08 mol). Refluxed for 12 hours. It is allowed to return to the temperature of the laboratory and the solvent is evaporated under vacuum. 26 g of a brown oil are obtained. Since the amine has not completely reacted, it is partly removed by birch distillation (150 ° C. under 0.05 mbar). The residue (18.6 g) is a viscous dark oil. After purification on a column of silica (eluent Heptane / EtOAc 60:40), 5.46 g (yield: 20%) of the clean fractions of 3- [bis (2-ethylhexyl) amino] cyclohex-2-en are obtained. 1-one, which is used as is in the next step. Second step: Preparation of the compound of Example 30:

In a reactor, the mixture of the product of the preceding step (2 g, 4.6 × 10 -3 mol) was gradually heated to 100 ° C. for 40 minutes and then refluxed for 12 hours with dimethylsulphate (0.63 g). g, 5x10-3 mol). The temperature is reduced to 60 ° C. and the solution of malonitrile (0.304 g, 4.6 × 10 -3 mol) in 3 ml of isopropanol and 0.51 ml of triethylamine is poured in over 5 minutes. The reaction mixture is refluxed for 1 hour and 30 minutes. The solvents are removed in vacuo and the residue is taken up in dichloromethane. It is washed 2 times with water. The organic phase is dried and the solvent is evaporated under vacuum. After purification on a column of silica (eluent CH 2 Cl 2 / MeOH 90:10), 1.09 g (yield: 62%) of the clean fractions of the derivative of Example 30 are obtained in the form of a light brown oil: UV ( Ethanol): Xmax = 395 nm, El% = 1657. 40 Xmax = 380 nm (shoulder), El% = 1225. EXAMPLE 31: Preparation of the compound of formula (48):

O, Si O_Si O-O First step: Preparation of 2-methylprop-2-en-1-yl (phenylsulphonyl) acetate:

In an argon bubbling reactor, phenylsulfonic acid (25 g, 0.125 moles) was solubilized in 250 ml of anhydrous acetonitrile. Methallyl alcohol (11.55 ml, 0.137 mole) is added. The reaction mixture was cooled to about 4 ° C and N, N-dicyclohexylcarbodiimide (25.76 g, 0.125 mole) was added maintaining the temperature below 30 ° C with an ice-water bath. Triethylamine (17.5 ml, 0.125 mole) is then added. Allowed to warm to room temperature and concentrated in vacuo. The residue is taken up in dichloromethane. The organic phase is washed with a solution of bicarbonate and then twice with water. It is dried over sodium sulphate. After filtration and evaporation of the solvent, the brown oil obtained is passed over a bed of silica (eluent: dichloromethane). 23.75 g (yield 75%) of 2-methylprop-2-en-1-yl (phenylsulphonyl) acetate are thus obtained in the form of a colorless oil and used as such in the third step.

Second step: Preparation of (2E) -3- (diethylamino) prop-2-enal:

In a reactor, propargyl alcohol (5.21 g, 0.093 mol) and diethylamine (8.5 g, 0.116 mol) were solubilized in 100 ml of toluene. Activated manganese dioxide (27.5 g, 0.316 mol) was added by a pinch. The mixture is heated at 95 ° C. for 5 hours. It is allowed to return to the temperature of the laboratory and filters the solution. The toluene solution containing (2E) -3- (diethylamino) prop-2-enal is used as it is in the next step.

Third step: Preparation of 2-methylprop-2-en-1-yl (2E, 4E) -5- (diethylamino) -2- (phenylsulfonyl) penta-2,4-dienoate:

To the above toluene solution is added the 2-methylprop-2-en-1-yl (phenylsulphonyl) acetate obtained in the first step (22.45 g, 0.088 mol) and the catalyst: a mixture of piperidine (0.41 g). ml) and acetic acid (0.52 ml). The reaction mixture is heated under reflux (with removal of water using a Dean Stark) for 2 hours. The operation of adding the same amount of catalyst is repeated 3 times with heating for 2 hours at each operation. After returning to the temperature of the laboratory, 500 ml of dichloromethane are added. Wash twice with saturated sodium bicarbonate solution followed by washing with water. The organic phase is separated, dried over sodium sulfate. After removing the solvent and drying, an orange viscous oil is obtained. After purification on a silica bed, 15.5 g (yield: 47%) of the 2-methylprop-2-en-1-yl (2E, 4E) -5- (diethylamino) -2- (phenylsulfonyl) penta-2,4-dienoate as a very viscous yellow-orange oil and used as it is in the following step:

Fourth step: Preparation of the compound of Example 31

The preceding product (13 g, 0.0358 mol) is melted at 95 ° C. The catalyst (10-11 wt.% Complex of Pt sileolease 21093: 8.38 l) is added thereto, followed by dropwise heptamethyltrisiloxane (7.96 g, 0.0358 mol) in 3 hours while gradually lowering the temperature. from the reaction mixture of 95 ° C to 55 ° C. The reaction mixture is heated at 55 ° C for a further 8 hours. After cooling, the brown orange oil obtained is purified by passage through a column of silica (gradient eluent: Heptane / EtOAc 80:20 to 70:30). 16.6 g (yield: 55%) of the clean fractions of the derivative of Example 31 are thus obtained in the form of an orange-yellow viscous oil. Melting point 55-58 ° C. UV (ethanol): λmax = 373 nm, El% = 1445.

This product kept in the fridge crystallized; recrystallized from heptane, the derivative of Example 31 is obtained in the form of a yellow powder: mp 40.degree.-45.degree. EXAMPLE 32 Preparation of the compound of formula (51): First step: Preparation of 2-methylprop-2-en-1-yl (2E, 4E) -5-facetyl (phenyl) aminol-2- (phenylsulfonyl) penta-2 , 4-dienoate:

85-90 ° C is heated in 5 ml of 3-anilinoacrolein aniline acetic anhydride (12.15 g, 0.04 mole) and the product of the first step of Example 32 (12.2 g, 0.048 moles) for 2 hours 30 minutes. The acetic anhydride is evaporated to dryness under reduced pressure. The orange-brown oil obtained is purified by a chromatographic column of silica (eluent: AcOEt / Heptane 20:80 then gradient up to 30: 70. 6.85 g of clean fractions (yield: 40%) of methyl-5 are recovered. - [allyl (methyl) amino] -2 - [(4-methylphenyl) sulfonyl] penta-2,4-dienoate as a pale yellow oil and used as is in the next step.

Second step: Preparation of 2-methyl-3- (1,3,3,3-tetramethyl-1-yl (trimethylsilyl) oxyldisiloxanyl} propyl (2E, 4E) -5-facetyl (phenyl) aminol-2- (phenylsulfonyl) ) penta-2,4-dienoate:

To a solution of the above product (1.57 g, 3.7x10-3 mol) and catalyst (3-3.5 wt% Pt complex in Hull Petrovinylmethylsiloxane Petrarch PC085: 250 l) in 4 ml of dry toluene heated to 80 ° C., 0.371 g (1.67 × 10 -3 mole) of heptamethyltrisiloxane was added dropwise in 10 minutes. This temperature is left for 6 hours. The reaction mixture is concentrated. It is taken up in dichloromethane and this solution is passed through a bed of Celite. The pale yellow oil obtained is chromatographed on a silica column (eluent: Heptane / EtOAc 65:35). 1.2 g (yield: 50%) are thus obtained of the clean fractions of 2-methyl-3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl (2E, 4E). -5- [acetyl (phenyl) amino] -2- (phenylsulfonyl) penta-2,4-dienoate as a yellow-orange liquid and used as such in the next step. Third step: Preparation of the derivative of Example 32:

To the derivative of the preceding step (1.58 g, 2.44 × 10 -3 mole) dissolved in 20 ml of ethanol, piperazine (0.105 g, 1.22 × 10 -3 mole) was added and the mixture was stirred. at reflux for 2 hours. The ethanol is evaporated to dryness under reduced pressure. The brown solid obtained is chromatographed on a silica column (elution gradient: heptane / EtOAc 70: 30 to 50:50). 0.37 g (yield: 27%) of the clean fractions of the derivative of Example 32 are thus obtained in the form of a pale yellow powder: 40 ppm 55-58 ° C. UV (Ethanol): X max = 389 nm, El % = 1335 Xmax = 352 nm, El% = 338 EXAMPLE 33: Preparation of the compound of formula (55): ## STR1 ## First Step: Preparation of Methyl-5 -fallyl (methyl) aminol-2- (phenylsulfonyl) penta-2,4-dienoate:

50 ml of acetic anhydride of 3-anilinoacrolein aniline (9.2 g, 0.0414 mol) and methyl sulphonylacetate (10.6 g, 0.0497 mol) were heated at 50 ° C for 1 hour. The acetic anhydride is evaporated to dryness under reduced pressure. The oil obtained is taken up in 50 ml of ethanol. N-methyl allylamine (12 ml, 0.126 mol) is added and the mixture is refluxed for 1 hour 15 minutes. The ethanol is evaporated to dryness under reduced pressure. The brown solid obtained is purified by passage through a chromatographic column of silica (eluent: AcOEt / Heptane 40: 60 and then gradient up to 50:50.) 10 g of the clean fractions (yield: 77%) of methyl-5- [allyl are recovered. (methyl) amino] -2- (phenylsulfonyl) penta-2,4-dienoate as a yellow solid and used as such in the next step.

Second step: Preparation of the compound of Example 34:

To a solution of the preceding product (9.3 g, 0.029 mol) and of catalyst (complex of 3-3.5 wt% Pt in Hull Petrarch PC085 cyclovinylmethylsiloxane: 250 l) in 55 ml of dry toluene brought to 60 ° C 7.1 g (0.0305 moles) of heptamethyltrisiloxane are added dropwise over 10 minutes. The reaction mixture is refluxed for 3 hours. The reaction mixture is concentrated. The crude solid obtained is recrystallized from heptane and then chromatographed on a silica column (eluent: heptane / EtOAc 70: 30). 8.6 g (yield: 55%) are thus obtained of the clean fractions of the derivative of Example 33 in the form of a pale yellow powder: mp 118 ° -119 ° C. UV (Ethanol): X max = 371 nm, El % = 1370.

III / EXAMPLES OF FORMULATION The compositions A (invention) and the following compositions B, C, D outside were carried out: Ingredients Ex A Ex Ex Ex Ex Ex D (*) (*) (*) Phase a 0.1 EDTA 0.1 0.1 0.1 Monocetyl phosphate 1 1 1 1 monopotassium 35 Deionized water qs qq qs 100 100 100 100 Triethanolamine 0.3 0.3 0.3 0.3 Preservatives 1.2 1.2 1, 2 1,2 C12-C15 alkyl benzoate 20 20 20 Preservatives 0.25 0.25 0.25 0.25 Phase b1 Stearic acid 1.5 1.5 1.5 1.5 Mixture Mono / Distearate 1 1 1 1 Glyceryl / Polyethylene Glycol Stearate (100 0E) Cetyl Alcohol 0.5 0.5 0.5 0.5 Cetearyl Alcohol and Cetearyl 2 2 2 2 Glucoside Dimethicone (350 cst) 0.5 0.5 0.5 0.5 Triethanolamine 0.45 0.45 0.45 0.45 Octyl 5-N, N-4,4-diethylamino-4,4-phenylsulfonyl-2,4-pentanoate (Compound (29)) Substituted S-triazine Silicone 4 0 0 0 by two C4-alkylaminobenzoates compound (5) a-cyano-R, [3` 0 4 0 2-ethylhexyl diphenylacrylate 4-methoxycinnamate 0 0 0 0 ethyl-2 2,4,6-tris [p- (2'-ethylhexyl-1'-oxycarbonyl) anilino] -3,5,5-triazine hexoseoxyhexane 1 1 1 Phase b2 Copolymer of acid 0.2 0.2 0.2 0.2 acrylic and C10-C30 alkyl methacrylate Xanthan 0.2 0.2 0.2 0.2 Cyclopentadimethylsiloxa 5 5 5 (*) Excluding the invention

These compositions were evaluated according to the following properties: Solubility of the filters, Filtering efficiency, Photostability.

Mode of preparation of emulsions:

The aqueous and oily phases b1 are prepared by mixing the raw materials with mechanical stirring at 80 ° C .; the solutions obtained are macroscopically homogeneous. The emulsion is prepared by slow introduction of the oily phase into the aqueous phase with stirring using a Moritz type homogenizer under a stirring speed of 4000 RPM for 15 minutes. The emulsion obtained is cooled with stirring to 40 ° C, and then the oily phase b2 is added with gentle stirring. The resulting emulsion is cooled to room temperature with gentle stirring. It is characterized by drops of size between 1 m and 10 m.

Protocol for assessing the solubility of UV filters

Preparation of UV Filter Solutions: In a 10mL glass flask, the filter and oil are weighed for a total mixture of 5g. The solution is heated to a hot water bath at 80 ° C with magnetic stirring. When dissolution is complete (clear solution), the solution is stored at room temperature. The appearance of macroscopic crystals is monitored over time. In Vitro Evaluation Protocol for Filtering Efficiency Spreading support: Amount after application: Application: Drying time: Number of samples: Frosted PMMA 0.6 mg / cm 2 Finger 20 minutes at RT, at darkness applications by formula 5 measurement points per application UV analyzer ù Labsphere UV 1000S monochromatic protection every nm between Measuring device: Recording of factors of 290 and 400 nm Calculation of the SPF according to the method described by BL Diffey. et al. In J. Soc. Cosmet. Chem. 40-127-133 (1989). Source Spectrum: Diffey Sun 1989 Spectrum of action: Erythema CIE 1987 Protocol for evaluating the photostability of filters

The photosatability of the UV filter was evaluated by HPLC assay of the residual filter after Suntest exposure of a thin film of formula at a UV dose equivalent to 1H radiometric UVA.

Spreading support: Frosted PMMA Amount after application: 2 mg / cm2 45 Number of samples: 4 plates / formula exposed to UV 4 plates / control formula stored in an oven at 37 ° C Solar simulator: SUNTEST Heraeus - Atlas Flux UVA = 8.23 × 10-3 W / cm 2 UVB flux = 1.42 × 10 -3 W / cm 2 50 Exposure time = 44 minutes The UVA and UVB illuminations of the suntest are measured radometrically. Extraction of the film of cream: Ethanol + ultra sounds Determination of the residual filter: HPLC s Calculation of the% of photostability relative to the unexposed samples

Results Examples SPF in vitro Solubility% residual% of merocyanine UVB filter Example A + + YES> 90%> 90% (invention) Example B - - YES> 90%> 90% Example C + + YES> 90% Loss Example D + + NO> 90%> 90% These results show that only the combination of a lipophilic merocyanine filter such as octyl 5-N, N-diethylamino-2-phenylsulfonyl-2,4-pentanoate (compound (29 )) and a UVB filter selected from the molecules of the type s-triazine silicon substituted by two aminobenzoate groups provides a filter system of high efficiency, easy to implement in cosmetic compositions because of its good solubility and photostable. For combinations based on other UVB filters such as 2-ethylhexyl α-cyano-13,13` diphenylacrylate, ethyl-2-hexyl 4-methoxycinnamate, or 2,4,6-tris [p - (2'-ethylhexyl-1-oxycarbonyl) anilino] -1,3,5-triazine, the performances in terms of filtering efficiency, solubility or photostability are lower than those of the combination of 'invention. 10

Claims (4)

REVENDICATIONS1. Composition comprising in a cosmetically acceptable support at least one UV filtering system, characterized in that it comprises: (i) at least one siliconized s-triazine substituted with at least two alkylaminobenzoate groups of the following formula (I): (D) - (Si0 (3-a) / 2 ~~~ 1 (R), in which - R, identical or different, represent a C1-C2 alkyl radical, a phenyl radical, a C1-C2 alkoxy radical or a hydroxyl radical; or the trimethylsilyloxy group; a = 1 to 3; in addition to the units of the formula -Au (Si) (R) a (O) (3a), 2, the organosiloxane may comprise units of the formula: (R) b- (Si) (O) (4_b), 2 in which: R has the same meaning as in formula (I), b = 1, 2 or 3; - group (D) denotes a s-triazine compound of following formula (II): embedded image in which R 1, which may be identical or different, represent a linear or branched and optionally unsaturated C 1 -C 10 alkyl radical, and may contain a cyc group C5-C6alkyl, - the group (C = O) OR1 which may be in the ortho, meta or para position of the amino group, R2, which may be identical or different, represent hydrogen, a hydroxy radical or a C1-C4 alkyl radical; , linear or branched, a methoxy radical, - A is a divalent radical chosen from methylene or a group corresponding to one of the following formulas (III), (IV), (V) or (VI): (Z) ùCHùCH2ù (III) wherein Z is a C 1 -C 3 alkylene diradical; W represents an atom of C 1 -C 3; hydrogen, a hydroxyl radical or a C1-C3 alkyl radical, (ii) at least one lipophilic merocyanine filter. i0 2. Composition according to claim 1, wherein the s-triazine is chosen from among those for 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 radical n '= 0, the group (C = O) XR1 is in the para position with respect to the amino group, Z = -CH2-, W = H. 3. A composition according to any one of claims 1 and 2, wherein the siliconized striazine has one of the following formulas (Ia) or (Ib): RRRR (la) (B) Si-O + Si-O Si Where (R) RR (D) RRR WhereSi] t [WhereSi uR (D) 30 in which: - (D) corresponds to formula (II) as defined above, - R has the same definition as in the formula (I), - (B), which are identical or different, are chosen from the radicals R and the radical (D), - r is an integer between 0 and 20 inclusive, 35 - s is an integer ranging from 0 to at 5 and if s = 0, at least one of the two symbols (B) denotes (D), - u is an integer from 1 to 5, - t is an integer from 0 to 5, and that t + u is equal to or greater than 3 as well as their tautomeric forms. 25,405 The composition of claim 3, wherein the siliconized s-triazine is selected from (5) 10. A composition according to claim 4 wherein the siliconized s-triazine is n-butyl 2,4-bis (4-aminobenzoate) -6 - [(3- {1,3,3,3-tetramethyl-1-s) [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -s-triazine of formula (5) 6. Composition according to any one of claims 1 to 5, wherein the lipophilic merocyanine filter is chosen from compounds corresponding to one of the following formulas (IXa) and (IXb): (IXa) o R1 3 R NùCH CH-CH R 2 R 4 K R 3 R 4 (IXb) in which: R 1 and R 2, which are identical or different, represent H, an alkyl radical in C 1 -C22 and may contain a silicon atom, a C3-C8 cycloalkyl radical, a C6-C20 aryl radical, it being understood that only one of R1, R2 is H and that R1 and R2 together with nitrogen may forming a ring containing the group - (CH2) g-, uninterrupted or interrupted by -O-, -S-, -NH- or by -NR5-, -R3, R4, which are identical or different, represent a carboxyl group, -COOR5, - CONHR5, -COR5, -CONR5R6, -CN or SO2R5, -R5, the same or different represent a C1-C22 alkyl radical and may contain a silicon atom, a C3-C8 cycloalkyl radical, a C6-C20 aryl radical, - R6 is hydrogen or a C1-C20 alkyl radical, Z1 is a group - (CH2) I uninterrupted or interrupted by -O-, -S-, -NH- or R6-, 15 -gest1-7, - I is 1-4, - o is 1-4, provided that (i) when o = 2, R1 or R5 is an alkyl diradical or R1 and R2 together with 2-20 nitrogen atoms form a divalent radical - (CH2) g-, (ii) when o = 3, R1 or R5 is a trivalent radical, (iii) when o = 4, R1 or R5 is a tetravalent radical, (iv) R1 and R2 are not simultaneously a hydrogen atom. ; as well as their isomeric forms E, E-, E, Z- or Z, Z-. 7. The composition of claim 6 wherein the following conditions are met: R1 and R2, same or different, denote a C1-C12 alkyl radical or a C5 cycloalkyl radical; R3 is COOR5 or CN; R4 is SO2R5 or COOR5; R 5 denotes a C 1 -C 12 alkyl radical o is 1 or 2. 8. The composition according to any one of claims 1 to 5, wherein the lipophilic merocyanine filter is chosen from compounds corresponding to the general formula (X). following: (D1) (SI 0 (3-a) / 2 (X) (R ') to 40 in which - R and a have the same meaning as in formula (I) defined in claim 1, - the group (D1) denotes a merocyanine-derived compound of the following formulas (XIa), (XIb) and (XIc): ## EQU1 ## where Y1 is O = S = O R4 p (XIa) (Y o I (X1) R4 I q 2 R 0 = S = 0 Y p (XIb) R3 N 1 R 2 O = S = O R4 p (XIc) in which: - X1 = represents -O-, -NR6-, -R1, R2, R3, R4, R5 and R6 have the same definitions as in the formulas (IXa) and (IXb) indicated in claims 6 and 7, - p = 1 or 2, - q = 0 or 1, - Y1 is a divalent alkyl radical C1-05 optionally substituted with C1-C4 alkyl radicals and / or containing -O-, -S-, or -NR6 groups; formula ûAû (Si) (R) a (O) (3-a) / 2, wherein the organosiloxane may additionally comprise units of formula: (R) b- (Si) (O) (4-b) / 2 in which R and b have the same meaning as in formula (I) of claim 1. 9. A composition according to claim 8, wherein Y1 is a group of atoms whose result lies in the formation of an oxazolidine ring, a pyrrolidine ring, a thiazolidine ring or an indoline bicycle. 10. Composition according to claim 8 or 9, wherein the compounds of formula (X) are chosen from those represented by the following formulas (Xa), (Xb) or (Xc): ## STR2 ## R7 R7 II (B1) Where [R], R8, r, s, t and R7 (Xb) R7 R7 where Si] t [whereSi (Xc) (D1) -Si (R8) 3 in which: R7, R8, r, s, t and u have the same meaning as in formulas (Ia), (Ib) and (Ic) as defined in Claim 1; io - (D ') corresponds to the formulas (Xla), (Xlb) and (Xlc) as defined in claim 8, - (B'), identical or different, are chosen from radicals R7 and radical (D ') ; as well as their isomeric forms E, E-, E, Z- or Z, Z-. 11. A composition according to any one of claims 1 to 10, wherein the lipophilic merocyanine (s) are selected from the following compounds: owo = s = o (29) NO (33) o NWO Il N (37) (38) N (39) HNN (44) OJ (48) 12. Composition according to any one of claims 1 to 10, characterized in that it contains in addition to other organic or water-soluble or liposoluble or UV-A active in UV-A and / or UV-B or insoluble in commonly used cosmetic solvents. 13. The composition of claim 11, wherein the complementary organic screening agents are selected from dibenzoylmethane derivatives; anthranilates; cinnamic derivatives; salicylic derivatives, camphor derivatives; benzophenone derivatives; R, R-diphenylacrylate derivatives; triazine derivatives other than those of formula (I); are derived from benzalmalonate; benzimidazole derivatives; imidazolines; p-aminobenzoic acid derivatives (PABA); benzotriazole derivatives; methylene bis (hydroxyphenyl benzotriazole) derivatives; benzoxazole derivatives; filter polymers and silicone filters; dimers derived from alkylstyrene; 4,4-diarylbutadienes and mixtures thereof. 14. Composition according to claim 12, characterized in that the organic UV screening agent (s) are chosen from the following compounds: Ethylhexyl Methoxycinnamate Homosalate Ethylhexyl Salicylate, Butyl Methoxy DibenzoylmethaneOctocrylene, Phenylbenzimidazole Sulfonic Acid, 2- (4-diethylamino-2) -hydroxybenzoyl) -benzoate benzoate. 4-Methylbenzylidene camphor, 3-Benzophenone 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- (4'-amino benzalmalonate diisobutyl) -s-triazine, 2,4-bis (4'-amino benzalmalonate dineopentyl) - 6- (N-Butyl 4-aminobenzoate) -s-triazine Methylene bis-Benzotriazolyl Tetramethylbutylphenol, is Polysilicone-15 Di-neopentyl 4'-methoxybenzalmalonate 1,1-dicarboxy (2,2'-dimethyl-propyl) -4,4 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino] -6- (2-ethylhexyl) imino-1,3,5-triazine -diphenylbutadiene and their 15. Composition according to claim 12, characterized in that the complementary inorganic filters are coated or uncoated metal oxide pigments.