FR2957251A1 - Composition, useful for the cosmetic treatment of e.g. skin, comprises silicon-s-triazine substituted by at least two groups of alkylaminobenzoates, and hydrophilic or water soluble merocyanine UV filter, in a medium of UV filter system - Google Patents

Abstract

Composition comprises: (i) at least one silicon-s-triazine substituted by at least two groups of alkylaminobenzoates (I); and (ii) at least one hydrophilic or water soluble merocyanine UV filter, in a medium of at least a UV filter system. Composition comprises: (i) at least one silicon-s-triazine substituted by at least two groups of alkylaminobenzoates of formula (D-Si(R) a-O (3-a)/2) (I); and (ii) at least one hydrophilic or water soluble merocyanine UV filter, in a medium of at least a UV filter system. R : 1-2C alkyl, phenyl, 1-2C alkoxy, OH or trimethylsilyloxy; a : 1-3; D : triazine group of formula (II); R1 : 1-10C alkyl optionally unsaturated and containing 5-6C cycloalkyl group, C(=O)OR1 group can be ortho, meta or para to the amino group; R2 : H, OH, 1-4C alkyl or methoxy; A : methylene group, group of formula (-Z-CHW1-CH 2-) (III), (-Z-CHCH 3-) (IV), (-Z-CH=CH-) (V) or (-Z-C(=CH 2)-) (VI), siloxane units of formula (-A-(Si)(R) a(O) (3-a)/2), or organosiloxane comprising units of formula ((R) b-(Si)(O) (4-b)/2); Z : 1-3C alkylene; W1 : H, OH or 1-3C alkyl; and b : 1-3. [Image].

Description

COMPOSITION COMPRISING SILICY S-TRIAZINE SUBSTITUTED WITH AT LEAST TWO ALKYLAMINOBENZOATE GROUPS AND A WATER OR WATER SOLUBLE 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 hydrophilic or water-soluble 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 particularly known. By 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.

Applications EP0841341 and EP1891079 disclose silicon-containing strazines substituted by at least two alkylaminobenzoate or alkylaminobenzamide groups for their UV-B absorbing properties. The Applicant's research has found that some of these triazine compounds substituted with at least two alkylaminobenzoate groups including those whose alkyl chain has more than 10 carbon atoms did not provide sufficient efficiency. 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, namely to obtain a system for filtering UVA and UVB rays which is photostable, of high protection index 40 and having good solubility in the solar formulations.

The applicant has discovered that the combination of two particular sunscreens, made 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 hydrophilic or water-soluble merocyanine UV filter with a siliconized s-triazine substituted with at least two alkylaminobenzoate groups of formula (I) which will be defined further, it was possible to obtain a filter system broadly UVA and UVB radiation, easy to implement in solar compositions without the disadvantages mentioned above.

This discovery is the basis of the present invention.

Thus, according to one of the objects of the present invention, there is now proposed a composition comprising in a cosmetically acceptable support at least one UV filtering system, characterized in that it comprises: (i) at least one s -triazine silicon of formula (I) substituted with at least two alkylaminobenzoate groups; (ii) at least one hydrophilic or water-soluble merocyanine filter.

Other features, aspects and advantages of the invention will be apparent from the following detailed description.

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 this description, the term "hydrophilic UV filter" is understood to mean any UV radiation filtering agent capable of being soluble in a 1-5% by weight (transparent) or water-dispersible aqueous phase in the form of a suspension of particles less than 100 microns.

By "water-soluble filter" by any filtering agent is meant UV radiation capable of being soluble in its cosmetically acceptable salt form in an aqueous phase of greater than 5% by weight.

The s-triazine silicon compounds according to the present invention have the following general formula (I) or one of its tautomeric forms: (D) - (Si1 10 (3-a) / 2 (1)

(R) a 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; 40 -a = 1 to 3;

the group (D) denotes a s-triazine compound of formula (II) below: NHùA-w (II) o where - RI, which may be 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) OR 1 which may be in the ortho, meta or para position of the amino group, R 2, which may be identical or different, represent hydrogen, a hydroxy radical or an alkyl radical; C1-C4, linear or branched, a methoxy radical, 10-A is a divalent radical chosen from methylene or a group corresponding to one of the following formulas (III), (IV), (V) or (VI):

(Z) wherein: Z is a C 1 -C 3 alkylene diradical, - (CH) CH (CH) CH (CH 2) n CH 2 CH (CH 2) n CH 2 CH (CH 2) n CH 2 CH (CH 2) (CH 3) W represents a hydrogen atom, a hydroxyl radical or a C1-C3 alkyl radical; in addition to the units of the formula -Au (Si) (R) a (O) (3-a), 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;

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

Wherein (D ') denotes an s-triazine compound of the following formula (II'): R10 NH- (O ') In the formulas (II) and (II ') as defined above, the alkyl radicals may be linear or branched and chosen especially from methyl, ethyl, n-propyl, isopropyl and n-butyl radicals. isobutyl, tert-butyl, n-amyl, isoamyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl and tert-octyl The most preferred alkyl radical is butyl.

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, R1 is a C1-C8 radical, Z = -CH2-, W = H, the group (C = O) OR1 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): R7 RR7 R (la) (B) ù Sii0 [vo Ir [IiO + (B) R7 R7 (D) wherein R7 (D) (D) -Si (R8) 3 in which: - (D) corresponds to formula (II) as defined above, - R7, identical or different, are chosen from linear or branched C 1 -C 20 alkyl, phenyl, 3,3,3-trifluoropropyl and trimethylsilyloxy radicals, or the hydroxy, R 8 radical, which may be identical or different, are chosen from alkyl and alkenyl radicals; , linear or branched C1-C20, the radicals hydroxy or phenyl, - (B), identical or different are selected from the radicals R7 and the radical (D), r is an integer 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) denotes (D), io - u is an integer from 1 to 10, - t is an integer ranging from 0 to 10, it being understood that t + u is equal to or greater than 3 as well as 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 C1-C2 alkoxy radical or the hydroxyl radical, - B is preferably methyl (in the case of linear compounds of formula (la)),

By way of examples of compounds of formula (I) which are particularly preferred, mention may be made of the following compounds of formulas (1) to (26) and also their tautomeric forms: ## STR1 ## (7) INP Si. O_si INP 'si- o_si (9) O Si- (13) (14) 10 INP' si_o, if INP 'si_o_Si (15) (16) ùs INP' if. ## EQU1 ## (21) (22) ## STR2 ## wherein R 1 is NH 2 O (NH 3) NH 2 N N NH-Si-O Si-O Si + J NH4. ~ N ~ N - / Nd (NH NH (24) r stat = 8.1 O HN N 'N 9, NH NO / ~ / ù s, If u 1.1 HN N NH (25) NH ~ SiùO ~ SiùO Jr [ Šiuo-S

## STR2 ## In particular, compounds such as ethyl 2,4-bis (4'-aminobenzoate) -6 - [(3) will be used. - {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -s-triazine of formula (2), 2,4-bis (isopropyl 4'-aminobenzoate) ) -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 (neopentyl 4'-aminobenzoate) - 6 - [(3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -s-triazine of formula (10).

More particularly, n-butyl 2,4-bis (4'-aminobenzoate) -6 - [(3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino will be used more particularly. 2o 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 the following reaction scheme: ## STR1 ## where R, R 1, R 2, A, X, n and a are as defined above and Y is halogen, especially chlorine or bromine. The order of introduction of the reagents can be indifferently, 2 equivalents of the derivative of formula (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 may be carried out optionally in the presence of a solvent (for example: THF, acetone / water for the first step of Route 2); toluene, xylene, 2-butanone or ethyl acetate for the first step of Route I) at a temperature between 0 ° C and 200 ° C, more 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 scavenging base of the formed acid (for example: sodium bicarbonate, sodium carbonate, aqueous sodium hydroxide, triethylamine or pyridine). They can also be carried out in microwaves in the presence or absence of a solvent (for example: toluene, xylene or ethyl acetate) or in the presence or absence of 10% of graphite, at a temperature of 50 to 150.degree. a power of 50-150 Watts for a period of 10 to 30 minutes.

Be it channels 1 or 2, the steps can be chained in the same reactor without isolation of the intermediate derivatives formed.

The compounds of formula (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 nitro benzoate obtained (by autoclave with 50% Raney Nickel for 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 (1) 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 more preferably from 0.1 to 6% by weight relative to the total weight of the composition.

The hydrophilic or water-soluble merocyanine compounds according to the present invention are preferably chosen from those corresponding to the following general formulas (IX) and (X): ## STR3 ##

n (X) in which: R1 and R4, which are identical or different, represent H, a linear or branched C1-C22 alkyl radical or a C3-C8 cycloalkyl radical which is unsubstituted or substituted by C1-C4 alkyl radicals; ; said radicals R 1 and R 2 may contain an alkyl sulphonate radical in its acid or salified form or one to 4 hydroxyl radicals; R1 and R2 may together with the nitrogen form a ring containing the group - (CH2) m--, uninterrupted or interrupted by one or more -O-, -S- or -NH-, RI may form with carbon in Nitrogen of a ring containing the - (CH 2), n--, uninterrupted or interrupted group by one or more -O-, -S- or -NH-, -R3 represents a carboxyl group, -COOR5, - CONHR5, -COR5, -CONR5R1, -CN or SO2R5, -R4 represents a carboxyl group, -COOR6, -CONHR6, -COR6, -CONR6R2, -NC or SO2R6, or R3 and R4 together may form a C5 heterocyclic ring. -C7, - R5 and R6, identical or different, represent a linear or branched C1-C22 alkyl radical, a C3-C8 cycloalkyl radical, unsubstituted or substituted by C1-C4 alkyl radicals; said radicals R5 and R6 may contain an alkyl sulphonate radical in its acid or salified form or one to 4 hydroxyl radicals; Z represents the group (CH 2) 1, which is uninterrupted or interrupted by -O-, -S- or by -NR 7 -, and / or unsubstituted or substituted by one or two C 1 -C 6 alkyl radicals; R 7 is a radical; C1-C5 alkyl which may contain an alkyl sulphonate radical in its acidic or salified form or one to four hydroxy radicals; - n is 1-2; m is 1-7; - 1 is 1-4; with at least one or two of R ', R2, R5, R6 and R7 containing - either an alkyl sulphonate radical in its acidic or salified form - or from one to four hydroxy radicals. With the proviso that: (i) when n = 2, R ', R5 or R6 is an alkyl diradical or R' and R2 together with 2 nitrogen atoms form a cyclic divalent radical - (CH2) m-, (ii ) R 'and R2 are not simultaneously a hydrogen atom; The compounds of formula (IX) may be in the geometric isomeric forms E, E-, E, Z- or Z, Z-.

The preferred compounds of formula (IX) are those for which the following conditions are met: R 'denotes hydrogen or a linear or branched C1-C4 alkyl, R2 denotes a linear or branched C1-C4 alkyl or a C5 cycloalkyl -C6 R3 is -COOR5, -CONHR5 or -CN, R4 is -COOR5, -CONHR5, -CN or -SO2R5, R5 is C1-C12 linear or branched alkyl, n is 1 or 2. The Preferred compounds of formula (IX) with one or two alkyl sulphonate radicals are those of the following formulas (a) to (y) or one of their isomeric forms E, E-, E, Z- or Z, Z-. ## EQU1 ## where ## EQU1 ## (a) ## STR1 ## c) O OH so OO (e) ON (g) NO OH (NO) O (OH) OH O (OH) O NaOH OO (I) Na Na OO OH SAO N (k) NN (I) N Na 'O / (m) ONO' O (n) (o) ON (P) 16 S'OH NO (q) O SO OH OH O-O HO, H

O O O H O ISOI

## STR1 ## O'I_O O Na + (v) N N \

(w) O s \ O

Preferred compounds of formula (IX) with one to four hydroxyalkyl radicals are those of the following formulas (z) to (aw) or one of their isomeric forms: E, E-, E, Z- or Z, Z-: (y) δ-O RN = 70795-11-8 K + HOOO N sO (Z) RNN = 1165999-68-7 N HON N (ab) RN = 89206-27-9 HO N (ab)

RN = 105744-06-7 ## STR1 ## O (af) OH

## STR2 ##

## STR5 ## O / O O OH O O H O O O O O O O OH OH O Off O O

OH N HO N (aq) N HO N (ar) OH OOOH

N N (as) OH OOH

The preferred compounds of formula (X) are those for which the following conditions are satisfied: R 'denotes hydrogen or a hydrogen atom; C1-C4 linear or branched alkyl, R2 denotes a linear or branched C1-C4 alkyl or a C5-C6 cycloalkyl R3 denotes a group -000R5 or CN, R4 denotes a group -000R5, ùCN or -SO2R5, io R5 denotes linear or branched C1-C12 alkyl, Z is ù (CH2) 3 optionally substituted by two CH3 groups, n is 1 or 2.

The preferred compounds of formula (X) are those of formulas (ax) to is (bc) below or one of their isomeric forms E, E-, E, Z- or Z, Z-: NHO EXCLUDING ONNOS HO HS 1O embedded image The compounds of formula (IX) and (X), and more particularly the following compounds or one of their isomeric forms E, will be chosen from among the compounds of formula (IX) and (X). , E-, E, Z- or Z, Z-: HO N OH H.,; S; 010 0 + Na (v) (ah) OH whereof HO ~~N \ S III OHO (af) ( The derivatives of formulas (IX) may be prepared according to a method described in US Pat. patents US 4045229, US 4195999 and US 20090170008 according to the following scheme (lane 1): s or according to a method described in patent WO 0007989 and according to the following scheme (lane 2): in which the radicals R ', R2, R3 and R4 have the meaning of formula (IX). Route 2 (XV) (XII) R 2 Toluene (-H 2 O) cata: Amine, AcOH / R 3 R 4 + 10 The compounds of formulas (X) can be prepared according to a method described in IP.COM Journal 9 (5A), 29- (2009) according to the following scheme: in which the radicals R ', R2, R3, R4 and Z have the meaning of formula (X). Some of the compounds of formula (IX) are new.

These are (1) those of formula (IX) as defined previously with at least one or two of R ', R 2, R 5, R 6 and R 7 containing an alkyl sulphonate radical with the exception of: for which R 1 and R 2 together with nitrogen form a ring containing the group - (CH 2) n -, uninterrupted or interrupted by one or more -O-, -S- or by -NH- is b / derivatives of formulas (i), (j) and (m).

(2) those of formula (IX) as defined above with from one to four hydroxyalkyl radicals corresponding to formulas (XVII) and (XVIII) below or one of their isomeric forms E, E-, E, Z- or Z In which - R ', R2, R3, R4 and n have the same meanings given in formula (IX); - R'3 represents a C2-C8 hydroxyalkyl radical; linear or branched, a C5-C8 cycloalkyl radical substituted with 1 or 2 hydroxyl radicals OH R3 provided that in formula (XVII), R3 and R4 can not simultaneously be the cyano group.

Examples of derivatives of formula (XVII) include the compounds of formulas (ae), (af), (ah), (aj), (a1), (a1), (ao), (ap), (aq) and (ar) as well as their isomeric forms E, E-, E, Z- or Z, Z-: OH H HO- N (ae) OH H HONS O III O (af) O ~ O 10 OH ( ah) 000H HOC / N (aj)

## STR5 ## ## STR1 ## ## STR2 ## ################################################################# As examples of derivatives of formula (XVIII), mention may be made of the following compounds of formulas (a 1), (a), (as), (at), (a), (av) and (aw), as well as their forms. isomers E, E-, E, Z- or Z, Z-: N OOH N / / OH 10 (am) O OH OH O OH 1 N (as) (at) HO ~~ OvO ~ - HO ù OvO ~ The hydrophilic or hydrosoluble merocyanine filter (s) in accordance with the invention may be present in the compositions according to the invention at a concentration of between 0.degree. , 1 and 10%, preferably between 0.2 and 5%, by 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 filters as well as water-soluble UVB filters in the commonly used cosmetic solvents. Of course, those skilled in the art will take care to choose the optional additional filters and / or their quantities in such a way 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 silicone filters such as those described in particular in the application WO-93/04665; dimers derived from α-alkylstyrene such as those described in patent application DE19855649; 4,4-diarylbutadienes as described in applications EP0967200, DE19746654, DE19755649, EP-A-1008586, EP1133980 and EP133981; liposoluble merocyanine derivatives such as those described in applications WO04006878, WO05058269 and WO06032741 and mixtures thereof. 35

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

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

45 Derivatives of para-aminobenzoic acid: PABA, Ethyl PABA, Ethyl Dihydroxypropyl PABA, Ethylhexyl Dimethyl PABA sold in particular under the name "ESCALOL 507" 50 by ISP, 5 Glyceryl PABA, PEG-25 PABA sold under the name "UVINUL P25 By BASF,

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

Cinnamic derivatives: Ethylhexyl Methoxycinnamate sold in particular under the trade name "Parsol MCX" by Hoffmann La Roche, is Isopropyl Methoxy Cinnamate, Isoamyl Methoxy Cinnamate sold under the trade name "Neo Heliopan E 1000" by Haarmann and Reimer, Cinoxate, DEA Methoxycinnamate, 20 Diisopropyl Methylcinnamate, Glyceryl Ethylhexanoate Dimethoxycinnamate Derivatives of 13,13-diphenylacrylate: Octocrylene sold in particular under the trade name "UVINUL N539" by BASF, Etocrylene, sold in particular under the trade name "UVINUL N35" by BASF,

Derivatives of benzophenone: Benzophenone-1 sold under the trade name Uvinul 400 by BASF, Benzophenone-2 sold under the trade name Uvinul D50 by BASF Benzophenone-3 or Oxybenzone, sold under the trade name Uvinul M40 by BASF, Benzophenone-4 sold under the trade name "UVINUL MS40" by BASF, 35 Benzophenone-5 Benzophenone-6 sold under the trade name "Helisorb 11" by Norquay Benzophenone-8 sold under the trade name "Spectra-Sorb UV- 24 "by American Cyanamid Benzophenone-9 sold under the trade name" UVINUL DS-49 "by BASF, 40 Benzophenone-12 2- (4-diethylamino-2-hydroxybenzoyl) -N-hexyl benzoate sold under the trade name" UVINUL A + "or as a mixture with octylmethoxycinnamate under the trade name" UVINUL A + B "by BASF,

Benzylidene camphor derivatives: 3-Benzylidene camphor manufactured under the trademark "MEXORYL SD" by CHIMEX, 4-Methylbenzylidene camphor sold under the name "EUSOLEX 6300" by MERCK, Benzylidene Camphor Sulfonic Acid manufactured under the name "MEXORYL SL" by 50 CHIMEX, Camphor Benzalkonium Methosulfate manufactured under the name "Mexoryl So" by Chimex, Terephthalylidene Dicamphor Sulfonic Acid manufactured under the name "Mexoryl SX" by Chimex, s 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 io "Eusolex 232" by Merck, Disodium Phenyl Dibenzimidazole Tetrasulfonate sold under the trade name "Neo Heliopan AP" by Haarmann and Reimer,

Benzotriazole derivatives: Methylene bis-benzotriazolyl tetramethylbutylphenol, sold in solid form under the trade name "MIXXIM BB / 100" by FAIRMOUNT CHEMICAL or in micronized form in aqueous dispersion under the trade name "TINOSORB M" by CIBA SPECIALTY CHEMICALS,

Triazine derivatives: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine sold under the trade name "Tinosorb S" by Ciba Geigy, Ethylhexyl Triazone sold in particular under the trade name Uvinul T150 by BASF, Diethylhexyl Butamido Triazone sold under the trade name UVASORB HEB By SIGMA 3V, 2,4,6-tris- (4'-amino benzalmalonate diisobutyl) -s-triazine, 2,4,6-tris (4'-amino benzalmalonate dineopentyl) -s-triazine, 2, 4-bis (dineopentyl 4'-amino benzalmalonate) -6- (n-butyl 4'-aminobenzoate) -s-triazine the symmetrical triazine filters described in US Pat. No. 6,225,467, WO2004 / 085412 (see compounds 6 and 9) or the document "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 included in the applications of Beiersdorf WO06 / 0 35000, WO06 / 034982, WO06 / 034991, WO06 / 035007, WO2006 / 034992, WO2006 / 034985.

Anthranilic Derivatives: Menthyl anthranilate sold under the trade name "Neo Heliopan MA" by Haarmann and Reimer,

Imidazoline derivatives: 45 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 HOFFMANN LA ROCHE

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

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

The preferred additional organic screening agents are chosen from ethylhexyl methoxycinnamate is homosalate ethylhexyl salicylate, octocrylene, butyl methoxy dibenzoylmethane terephthalylidene diacamphor sulphonic acid disodium phenyl dibenzimidazole tetrasulfonate phenylbenzimidazole sulphonic 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) 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 metallic oxide pigments whose average size of the primary particles: is preferably between 5 nm and 100 nm (preferably between 10 nm and 50 nm), for example pigments from titanium oxide 45 (amorphous or crystallized in rutile and / or anatase form), iron, zinc, zirconium or cerium which are all UV photoprotective agents well known per se.

The pigments can be coated or uncoated. Coated pigments are pigments which have undergone one or more surface treatments of chemical, electronic, mechanochemical and / or mechanical nature with compounds as described for example in Cosmetics & Toiletries, February 1990, Vol. 105, p. 53-64, such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminum fatty acid salts metal alkoxides (of 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, essentially constituted by a repetition. of main units 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 their treatment with silicones may have been treated with other surfactants, in particular with cerium oxide, alumina, silica, aluminum, silicon compounds, or mixtures thereof.

The coated pigments are more particularly titanium oxides coated with: silica, such as the product "Sunveil" from the company IKEDA and the product "Eusolex T-AVO" from the company Merck - silica and iron oxide such as that the product "SUNVEIL F" of the company IKEDA, 40 - silica and alumina such as the products "MICROTITANIUM DIOXIDE MT 500 SA" and "MICROTITANIUM DIOXIDE MT 100 SA" of 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 (A)" from ISHIHARA, and "UVT 14 / 4 "from KEMIRA, 45 - alumina and aluminum stearate such as the product" MICROTITANIUM DIOXIDE MT 100 TV, MT 100 TX, MT 100 Z, MT-01 from the company TAYCA, products "Solaveil CT 10 "Solaveil CT 100" and "Solaveil CT 200" from the company UNIQEMA, silica, alumina and alginic acid such as the product "MT-100 AQ" from the company TAYC A, 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 DIOXIDE MT 100 F" from the company TAYCA, s - 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 500 SAS "or" MICROTITANIUM DIOXIDE MT 100 SAS "from TAYCA, io-silica, alumina, aluminum stearate and treated with a silicone such as the product" STT-30 -DS "of the company TITAN KOGYO, - silica and treated with a silicone such as the product" UV-TITAN X 195 "KEMIRA society, or product SMT-100 WRS TAYCA society. of alumina and treated with a silicone such as the products "TIPAQUE TTO-55 15 (S)" from the company ISHIHARA, or "UV TITAN M 262" from the company KEMIRA, triethanolamine such as the product "STT-65 -S "from the company TITAN KOGYO, - stearic acid such as the product" TIPAQUE TTO-55 (C) "from the company ISHIHARA, 20 - 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 whose average elemental particle size is between 25 and 40 nm, such as that sold under the trade name " T 805 "by the company Degussa Silices, the TiO 2 treated with a polydimethylsiloxane and whose average elementary particle size is 21 nm such as that sold under the trade name" 70250 Cardre UF TiO2SI3 "by CARDRE, TiO2 30 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".

The uncoated zinc oxide pigments are, for example, those marketed under the name "Z-cote" by the company Sunsmart; those marketed under the name "Nanox" by Elementis; those marketed under the name "Nanogard WCD 2025" by Nanophase Technologies;

The coated zinc oxide pigments are, for example, those sold 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); s - those marketed under the name "Nanogard Zinc Oxide FN" by the company Nanophase Technologies (as a 40% dispersion in Finsolv TN, C12-C15 alcohols benzoate); those marketed under the name "DAITOPERSION ZN-30" and "DAITOPERSION Zn-50" by the company Daito (dispersions in oxyethylenated cyclopolymethylsiloxane / polydimethylsiloxane, containing 30% or 50% of zinc nano-oxides coated with silica and polymethylhydrogensiloxane); those marketed under the name "NFD Ultrafine ZnO" by the company Daikin (ZnO coated with perfluoroalkyl phosphate and a copolymer based on perfluoroalkylethyl dispersed in cyclopentasiloxane); those marketed under the name "SPD-Z1" by Shin-Etsu (ZnO coated with silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane); those marketed under the name "Escalol Z100" by ISP 20 (ZnO treated with alumina and dispersed in the ethylhexyl methoxycinnamate / PVP-hexadecene / methicone copolymer mixture); those marketed under the name "Fuji ZnO-SMS-10" by the company Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane); those marketed under the name "Nanox Gel TN" by the company 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 30 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 35 WCD 2006 (FE 45R) ", or by the company MITSUBISHI under the name" TY-220 ".

The coated iron oxide pigments are for example sold by ARNAUD under the names "NANOGARD WCD 2008 (FE 45B FN)", 40 "NANOGARD WCD 2009 (FE 45B 556)", "NANOGARD FE 45 BL 345", "NANOGARD FE 45 BL", or by the company BASF under the name "OXIDE OF CLEAR IRON".

Mention may also be made of mixtures of metal oxides, in particular titanium dioxide and cerium dioxide, including the titanium dioxide and cerium-coated cerium dioxide equivalent mixture, sold by the company IKEDA under the name "SUNVEIL" A ", as well as the mixture of titanium dioxide and zinc dioxide coated with alumina, silica and silicone such as the product" M 261 "sold by the company KEMIRA or coated with alumina, 50 silica and 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.

The aqueous compositions in accordance with the present invention may furthermore comprise conventional cosmetic adjuvants, chosen especially from fatty substances, organic solvents, ionic or nonionic thickeners, hydrophilic or lipophilic thickeners, softeners, humectants, opacifiers and stabilizers. , emollients, silicones, anti-foam agents, perfumes, preservatives, anionic, cationic, nonionic, zwitterionic or amphoteric surfactants, actives, fillers, polymers, propellants, alkalinizing or acidifying agents or any other ingredient is 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 solid or substantially solid compound at room temperature, and having a melting point of generally greater than 35 ° C.

As oils, mention may be made of mineral oils (paraffin); vegetable (sweet almond oil, macadamia oil, blackcurrant seed oil, jojoba oil); Synthetics 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 alcohols, C12-C15 sold under the trade name "Finsolv TN" or "Witconol TN" by WITCO, 2-ethylphenyl benzoate 30 as the commercial product sold under the name X-TEND 226® by the company ISP, the palmitate of octyl, 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 (cyclomethicone, polydimethylsiloxane or PDMS) or fluorinated oils, polyalkylenes, trialkyl trimellitates such as tridecyl trimellitate.

Waxy compounds that may be mentioned include carnauba wax, beeswax, hydrogenated castor oil, polyethylene waxes and polymethylene waxes, such as that sold under the name Cirebelle 303 by the company SASOL.

Among the organic solvents, mention may be made of lower alcohols and polyols. These can be selected from glycols and glycol ethers such as ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol or diethylene glycol.

As hydrophilic thickeners, mention may be made of carboxyvinyl polymers such as Carbopols (Carbomers) and Pemulen 50 (acrylate / C10-C30-alkylacrylate copolymer); polyacrylamides, for example crosslinked copolymers sold under the names Sepigel 305 (CTFA name: polyacrylamide / C13-14 isoparaffin / Laureth 7) or Simulgel 600 (CTFA name: acrylamide / sodium acryloyldimethyltaurate copolymer / isohexadecane / polysorbate 80) by the company Seppic ; polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid, optionally crosslinked and / or neutralized, such as poly (2-acrylamido-2-methylpropanesulphonic acid) marketed by Hoechst under the trade name "Hostacerin AMPS" ( CTFA name: ammonium polyacryloyldimethyl taurate or SIMULGEL 800 sold by the company io 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 EMT 10 marketed by the company SEPPIC, cellulose derivatives such as hydroxyethylcellulose, polysaccharides and in particular gums is such as Xanthan gum, water-soluble or water-dispersible silicone derivatives such as acrylic silicones, silicone polyethers 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 "IP1 13 INTELIMER" and "INTELIMER IPA 13-6" by the company Landec, or the modified clays such as hectorite and its derivatives, such as products marketed under the name 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 in accordance with the invention are not, or substantially not, altered by the addition or additions envisaged, including the improvement of the photostability of the dibenzoylmethane derivative.

The compositions according to the invention can be prepared according to the techniques well known to those skilled in the art. They may be in particular in the form of an emulsion, simple or complex (O / W, W / O, O / W / H or W / O / W) such as cream, milk or gel. cream; in the form of an aqueous gel; in the form of a lotion. They may optionally be packaged in aerosol and be in the form of foam or spray.

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

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

To obtain stable emulsions with a low level of polymer (oil / polymer ratio> 25), it is possible to make the dispersion in 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 of 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 may be used for the preparation of W / O emulsions, mention may be made, for example, of alkyl esters or ethers of sorbitan, of glycerol or of sugars; silicone surfactants such as dimethicone copolyols such as the mixture of cyclomethicone and dimethicone copolyol, sold under the name "DC 5225 C" by Dow Corning, and alkyl dimethicone copolyols such as Laurylmethicone copolyol sold under the name " Dow Corning 5200 Formulation Aid "by Dow Corning; cetyl dimethicone copolyol such as the product sold under the name Abil is 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. One or more coemulsifiers may also be added, which advantageously may be selected from the group consisting of alkylated polyol esters. As alkylated esters of polyol, mention may in particular be made of polyethylene glycol esters such as PEG-30 dipolyhydroxystearate, such as the product sold under the name Arlacel P135 by the company ICI; Examples of glycerol and / or sorbitan esters that may be mentioned are polyglycerol isostearate, such as the product sold under the name Isolan GI 34 by the company Goldschmidt; sorbitan isostearate, such as the product sold under the name Arlacel 987 by the company ICI; sorbitan isostearate and glycerol, such as the product sold under the name Arlacel 986 by the company ICI, and mixtures thereof. Examples of O / W emulsions which may be mentioned as emulsifiers are nonionic emulsifiers such as oxyalkylenated (more particularly polyoxyethylenated) fatty acid esters of glycerol; oxyalkylenated fatty acid and sorbitan esters; oxyalkylenated (oxyethylenated and / or oxypropylenated) fatty acid esters, 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 oxypropylenated); sugar esters such as sucrose stearate; the fatty alcohol and sugar ethers, in particular the alkylpolyglucosides (APG) such as decylglucoside and laurylglucoside marketed, for example, by Henkel under the respective names Plantaren 2000 and Plantaren 1200, cetostearylglucoside optionally mixed with alcohol cetostearyl, marketed for example under the name Montanov 68 by the company Seppic, under the name Tegocare CG90 by the company Goldschmidt and under the name Emulgade KE3302 by Henkel, as well as arachidyl glucoside, for example in the form of the mixture of arachidic and behenic alcohols and arachidylglucoside sold under the name Montanov 202 by the company Seppic. According to a particular embodiment of the invention, the mixture of the alkylpolyglucoside as defined above with the corresponding fatty alcohol may be in the form of a self-emulsifying composition, as described for example in the document WO -A-92/06778.

In the case of an emulsion, the aqueous phase thereof may comprise a nonionic vesicle dispersion prepared according to known methods (Bangham, Standish and Watkins, J. Mol Biot 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 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 skincare and / or sun protection product for the face and / or body of liquid to semi-liquid consistency, such as milks, more or less creamy creams. , gel-creams, pasta. They may optionally be packaged in aerosol and be in the form of foam or spray. The compositions according to the invention in the form of vaporizable fluid lotions according to the invention are applied to the skin or the hair in the form of fine particles by means of pressurizing devices. The devices according to the invention are well known to those skilled in the art and include non-aerosol pumps or "atomizers", aerosol containers comprising a propellant as well as aerosol pumps using compressed air as a propellant. These are described in US Pat. Nos. 4,077,441 and 4,850,517.

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, additional cosmetic and dermatological active ingredients. Among the active ingredients, mention may be made of: vitamins (A, C, E, K, PP) and their derivatives or precursors, alone or in mixtures, antioxidant agents; - anti-radical agents; s - anti-glycation agents; the soothing agents; the NO-synthase inhibitors; agents stimulating the synthesis of dermal or epidermal macromolecules and / or preventing their degradation; io - 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; Agents acting on the energetic metabolism of cells; insect repellents; antagonists of substances P or CRGP. - anti-hair loss and / or hair regrowth agents - anti-wrinkle agents. Of course, those skilled in the art will take care to choose the optional additional compound or compounds 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 30 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 furthermore comprise at least one ingredient such as blooming fillers or agents promoting the natural coloration of the skin, intended to complete the biological effect of these active ingredients or provide an immediate visual anti-aging effect.

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

ADDITIONAL INGREDIENTS 45 The composition may further comprise at least one additional ingredient intended to complement the biological effect of these assets or to provide an immediate visual effect; mention may in particular be made of matting agents, blooming fillers, fluorescent agents, agents which promote the naturally rosy coloration of the skin and abrasive or exfoliating fillers.

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 may also, via a mechanical action (eg abrasvies), amplify the effect of the biological assets mentioned above.

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

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 25 2 generally reflects a matting effect.

The matting agent may especially be chosen from a rice starch or a corn starch INCI name: ZEA MAYS (CORN) STARCH as in particular the product sold under the trade name "FARMAL CS 3650 PLUS 30 036500" by National Starch, the kaolinite, talc, pumpkin seed extract, cellulose microbeads, vegetable fibers, synthetic fibers, in particular polyamides, expanded acrylic copolymer microspheres, polyamide powders, silica powders, powders of polytetrafluoroethylene, silicone resin powders, acrylic polymer powders, wax powders, polyethylene powders, elastomeric crosslinked organopolysiloxane powders coated with silicone resin, talc / titanium dioxide / alumina composite powders silica, amorphous mixed silicate powders, silicate particles and in particular mixed silicate, and mixtures thereof. Examples of matting agents that may be mentioned include: rice or maize starch, in particular starch octenyl succinate aluminum sold under the name Dry Flo® by the company National Starch, 45-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 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, Teflon®, insoluble collagen, polyesters, polyvinyl chloride or vinylidene, polyvinyl alcohol, polyacrylonitrile, chitosan, polyurethane, polyethylene phthalate, fibers formed from a mixture of polymers, synthetic resorbable fibers, and mixtures thereof described in patent application EP 1 151 742; microspheres of expanded acrylic copolymers such as those sold by EXPANCEL under the trade names EXPANCEL 551®, are optical-effect fillers as described in patent application FR 2 869 796, in particular: polyamide powders (Nylon®), such as, for example, Arkema's Orgasol type nylon 12 particles having a mean size of 10 microns and a refractive index of 1.54, silica powders, for example Silica beads SB150 from Miyoshi. of average size 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 powders of silicone resin such as Tospearl 145A Silicon Resins of 25 GE Silicone with a mean size of 4.5 microns and a refractive index of 1.41, acrylic copolymer powders, especially of polymethyl methacrylate, such as PMMA particles. Jurymer MBI Nihon Junyoki of average size 8 microns and refractive index 1.49, or the particles Micropearl M100® and F 80 ED® from the company Matsumoto Yushi-Seiyaku, 30 - wax powders such as particles Paraffin wax micro-wavelength 114S micropowders of average size 7 microns and refractive index 1.54, - polyethylene powders, especially comprising at least one ethylene / acrylic acid copolymer, and in particular consisting of ethylene / acrylic acid copolymers such as Flobeads particles EA 209 of Sumitomo 35 (average size 10 microns and refractive index 1.48), elastomeric crosslinked organopolysiloxane powders coated with silicone resin, especially silsesquioxane resin, as described for example in US Pat. 538 793. Such elastomer powders are sold under the names 40 "KSP-100", "KSP-101", "KSP-102", "KSP-103", "KSP-104", "KSP-105" by the company SHIN ETSU, and - the powders com talc / titanium dioxide / alumina / silica positions such as those sold under the name Coverleaf® AR-80 by the company Catalyst & chemicals, 45 - their mixtures, - compounds that absorb and / or adsorb sebum as described in the application 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", "SUNSPHERE® H53" marketed by ASAHI GLASS; polydimethylsiloxane-coated amorphous silica microspheres sold under the name "SA SUNSPHERE® H-33" and "SA SUNSPHERE® H-53" marketed by the company ASAHI GLASS; mixed amorphous silicate powders, in particular aluminum and magnesium, such as for example the one marketed under the name "NEUSILIN UFL2" by Sumitomo. polyamide (nylon®) powders, for example "ORGASOL® 4000" marketed by Arkema, and acrylic polymer powders, especially polymethyl methacrylate, such as "COVABEAD® LH85" for example marketed by WACKHERR; polymethyl methacrylate / ethylene glycol dimethacrylate, such as, for example, "DOW CORNING 5640 MICROSPONGE® SKIN OIL ADSORBER" marketed by DOW is 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, "POLYTRAP® 6603" marketed from 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 Kunimine society; the magnesium silicate complex, hydroxyethylcellulose, black cumin oil, pumpkin oil and phospholipids or Matipure® by Lucas Meyer, and their mixtures. As preferred matting agents, it is possible to use according to the invention a pumpkin seed extract, a rice or maize starch, kaolinite, silicas, talc, polyamide powders, polyethylene powders, powders of acrylic copolymers, 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.

As a filler, the following compounds can be exemplified: - porous silica microparticles, for example Silica Beads® SB 150 and SB 700 of Myochi of average size of 5 μm and SUNSPHERES® series H d 'Asahi Glass as the H33, H51 of size respectively 3.5 and 5 pm. hollow hemispherical particles of silicone resins, such as NLK 500®, NLK 506® and NLK 510® from Takemoto Oil and Fat, in particular described in EP-A-1579849; silicone resin powders, for example SILICON Resin s TospearI0 145 A DE GE Silicone medium size of 4.5pm. 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 vinylidene / acrylonitrile / expanded methylene methacrylate microspheres sold under the name ExpanceI0. - Wax powders such as paraffin wax microloaseO 114S particles of Micropowders 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®, KSP 1010, KSP 102®, KSP 103®, KSP 104® and KSP 105® by the company Shin Etsu. talc / dioxide or titanium / alumina / silica composite powders, for example the Coverleaf AR 800 from Catalyst & Chemical. talc, mica, kaolin, lauryl glycine, starch powders crosslinked with octyanyl succinate anhydride, boron nitride, polytetrafluoroethylene powders, precipitated calcium carbonate, 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 especially from wood, vegetables or algae, polyamide (nylon), modified cellulose, poly-p-phenylene terephtamide, acrylic, polyolefin, glass, silica, aramid, carbon, polytetrafluoroethylene (Teflon®), insoluble collagen, polyesters, polyvinyl chloride or of 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 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, 45 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, polyethylene powders, 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 charge can be a "soft focus" charge.

By "soft-focus" load is meant a load 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 can be of any shape and in particular be spherical or nonspherical. More preferably, these fillers are nonspherical. The "soft-focus" fillers may be chosen from silica and silicate powders, in particular alumina powders, polymethyl methacrylate (PMMA) powders, talc, silica / 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® 25 by the company Nippon Talc, Nylon® 12 powder, in particular that sold under the name Orgasol 2002 Extra D Nat Cos® by the company Atochem, the silica particles treated on the surface with a mineral wax 1 to 2% (INCI name: hydrated silica (and ) paraffin) such as those sold by the company Degussa, amorphous silica microspheres, such as those sold under the name Sunsphere for example reference H-53® by Asahi Glass, and silica micro-beads such as those sold under the name SB-700® or SB-150® by the company Miyoshi, this list not being exhaustive.

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. .

Agents promoting the naturally rosy coloration of the skin There may be mentioned in particular: a self-tanning agent, that is to say an agent which, applied to the skin, in particular on the face, makes it possible to obtain a tanning effect of appearance 45 more or less similar to that which may result from 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; and their mixtures.

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

The self-tanning agents are generally chosen from mono or polycarbonyl compounds such as, for example, isatin, alloxane, ninhydrin, glyceraldehyde, mesotartaric aldehyde, glutaraldehyde, erythrulose, pyrazolin-4 derivatives, 5-diones as described in patent application FR 2,466,492 and WO 97/35842, dihydroxyacetone (DHA), 4,4-dihydroxypyrazolin-5-ones derivatives as described in patent application EP 903 342 DHA will preferably be used. The DHA may be used in free form and / or encapsulated for example in lipid vesicles such as liposomes, in particular described in the application WO 97/25970.

In general, the self-tanning agent is present in an amount of from 0.01 to 20% by weight, and preferably in an amount of from 0.1 to 10% by weight 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 40 phloxine B known under the name CTFA: Cl 45410 or Red 27 diiodofluorescein known under the name CTFA Cl 45425 or Orange 10; dibromofluorescein known under the name CTFA: Cl 45370 or Orange 5. the sodium salt of tetrabromofluorescein known under the name CTFA: Cl 45380 (Na knows) or Red 22 45; the sodium salt of phloxine B known under the CTFA name: Cl 45410 (Na knows) or Red 28 - the sodium salt of diiodofluorescein known as CTFA: Cl 45425 (Na knows) or Orange 11; Erythrosine known under the name CTFA: Cl 45430 or Acid Red 51. 50-Phloxine known under the name CTFA: Cl 45405 or Acid Red 98. These dyes may also be chosen from antraquinones, caramel, carmine , charcoal black, azulene blues, methoxalene, trioxalene, guajazulene, chamuzulene, bengal rose, cosine 10B, cyanosine, daphinin.

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

Abrasive stains or exfoliating agents

Examples of exfoliating agents that may be used in rinsed compositions according to the invention include exfoliating or exfoliating particles of mineral, vegetable or organic origin. Thus, for example, beads or polyethylene powder, nylon powder, polyvinyl chloride powder, pumice, ground apricot kernels or nut shells can be used. sawdust, glass beads, alumina, and mixtures thereof. Exfogreen® from Solabia (bamboo extract), strawberry akenes (Greentech strawberry Akenes), peach kernel powder, apricot kernel powder, and finally the field of vegetable powders with an abrasive effect is the cranberry powder (cranberry).

As abrasive fillers or preferred exfoliation agents according to the invention, mention may be made of peach kernel powder, apricot kernel powder, cranberry kernel powder, strawberry achene extracts, bamboo extracts. The examples which follow serve to illustrate the invention without, however, being limiting in nature. In these examples, the amounts of the ingredients compositions are given in% by weight relative to the total weight of the composition. EXAMPLES OF TRIAZINE SYNTHESIS OF FORMULA (I): EXAMPLE 1 Preparation of methyl 2,4-bis (4'-divamino benzoate) -6- {[1,3,3,3-tetramethyl] -1- [(trimethylsilyl) oxyldisiloxane-3-propyl-3-ylamino} -ss triazine (Lane I): Si NP / Si. (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 EXAMPLE 2 Preparation of ethyl 2,4-bis (4'-divamino benzoate) -6 - {[1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxyldisiloxane] propyl (2) In a nitrogen-bubbled reactor, ethyl paraaminobenzoate (6.05 g, 0.0366 mol), 2-butanone (30 g) and ml) and potassium carbonate (2.53 g) dissolved in 38 ml of water. The mixture is cooled to 0-5 ° C. and cyanuric chloride (3.38 g, 0.0183 mol), dissolved in 68 ml of 2-butanone, is added dropwise over 1 hour. The mixture is heated at 70 ° C. for 6 hours; the ethyl 2,4-bis (4'-diylamino benzoate) -6-chloro-s-triazine formed is not isolated and is reacted in the next step. 1.54 g of sodium bicarbonate are added to the reaction mixture 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'-divamino benzoate) -6-fi-3,3,3-tetramethyl-1-β (trimethylsilyl) oxyldisiloxanepropyl-3-ylamino} -striazine (Route II): (2)

First Step: Preparation of 2,4-dichloro-6- {[1,3,3,3-tetramethyl-1- (trimethylsilyl) oxyldisiloxanyllpropyl-3-ylamino} -s-triazine:

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

Second step: preparation of the derivative of Example 3:

The mixture of the above product (2.1 g, 0.005 mol) and ethyl para-amino benzoate (1.65 g, 0.01 mol) suspended in 20 ml of toluene is refluxed for 1 hour 30 minutes. . The mixture is cooled and hot heptane is added to the resulting resin. After trituration, filtration and drying, 2.3 g (yield: 67%) of the derivative of Example 3 is 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'-divlamino benzoate) -6- (11,3,3,3-tetramethyl-1-trimethylsilyl) oxyldisiloxanylpropyl-3-ylamino} -s-triazine (Lane II): ## STR3 ## N-propyl para-aminobenzoate (3.35 g, 0.0187 moles) ml of ethyl acetate. 1.5 ml of pyridine dissolved in 10 ml of ethyl acetate are added thereto. The reaction mixture was heated to 70 ° C under an argon atmosphere and then the product of the first step of Example 3 (4 g, 0.0094 moles) was added. It is left at 70 ° C. for 2 hours. The dark red solution is cooled and washed with saturated sodium chloride solutions and then with water. After drying of the organic phase, the paste obtained is crystallized in heptane. The product of Example 4 (2.3 g, yield: 34%) is thus obtained in the form of light beige crystals: Melting point: 109-110 ° C., UV (Ethanol): X max = 311 nm, El % = 1228. EXAMPLE 5 Preparation of Isopropyl 2,4-bis (4'-divamino benzoate) -6- {1,3,3,3-tetramethyl-1- (trimethylsilyl) oxyldisiloxane] propyl] -3- Vlamino} -striazine (lane II): ## STR2 ## (4) Isopropyl para-aminobenzoate (10.05 g, 0.0561 mol) dissolved in 40 ml of acetate is charged into a reactor. ethyl. 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 of 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: mp 68-70 ° C., UV (Ethanol): X max = 311 nm, El % = 1155.

EXAMPLE 6 Preparation of n-butyl-2,4-bis (4'-diylamino benzoate) -6-10-wire, 3,3,3-tetramethyl-1- (trimethylsilyl) oxyldisiloxanyllpropyl-3-ylamino) -s-triazine ( II): Under a 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, 0776 moles) and potassium carbonate (5.36 g, 0.0388 moles) are suspended in 170 ml of toluene and refluxed for 1 hour 20 minutes. The reaction mixture is cooled and 150 ml of dichloromethane are added thereto. The minerals are filtered. The filtrate is washed with bicarbonate water and then twice with water. After drying of the organic phase and evaporation of the solvents, a white powder is obtained. After recrystallization from EtOAc / heptane 1: 15, 20.1 g (yield: 69%) of the derivative of Example 6 is obtained in the form of a white powder: mp 111-113 ° C. UV (Ethanol): X max = 312 nm, El% = 1360.

EXAMPLE 7 Preparation of Isobutyl-Isobutyl-2,4-bis (4'-divamino benzoate) -6-fluo, 3,3,3-tetramethyl-1 - ((trimethylsilyl) oxyldisiloxanyl) -propyl-3-ylamino} -striazine (Lane I (6) In a reactor bubbled with nitrogen, isobutyl paraaminobenzoate (10.39 g, 0.0538 mol), 2-butanone (72 ml) and potassium carbonate (3, 72 g) dissolved in 57 ml of water. The mixture is cooled to 0-5 ° C. and cyanuric chloride (4.96 g, 0.0269 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 isobutyl 2,4-bis (4'-diylamino benzoate) -6-chloro-striazine formed is not isolated. To the reaction mixture was added 2.26 g of sodium bicarbonate, and then the product of the first step of Example 2 bis (7.52 g, 0.0269 mole) was dripped in 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: mp 66-67 ° C., UV (Ethanol): X max = 311 nm, El% = 1150.

EXAMPLE 8 Preparation of 2- (4'-methylamino-benzoate) -4- (4 "-N-butylamino benzoate) -6 - {[1,3,3,3-tetramethyl-1- (trimethylsilyl) ) oxyldisiloxanepropyl-3-ylamino} -s-triazine (Modified Lane I): (7)

In a nitrogen-bubbled reactor, tert-butyl para-aminobenzoate (1 g, 0.00517 mol) is solubilized 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 derivative of the first step of Example 2a (2.21 g, 0.00517 mol) in 15 ml of ethyl acetate is introduced dropwise over 30 minutes. It is left at 70 ° C. for 2 hours and then a solution of paraaminobenzoate (0.98 g, 0.00517 mol) dissolved in 5 ml of ethyl acetate is added. Heating is continued at 70 ° C for 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% = 1425.

EXAMPLE 9 Preparation of tert-butyl 2,4-bis (4'-diylamino benzoate) -6411,3,3,3-tetramethyl-1- (trimethylsilyl) oxyldisiloxanylpropyl-3-ylamino) -s-triazine (Lane II): 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 is added 8.11 g of sodium bicarbonate, and then the product of the first step of Example 2 bis (27 g, 0.00965 mol) is added 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) 1-6- {1,3,3,3-tetramethyl-1-1 (trimethylsilyl) oxyldisiloxanyllopropyl) -bis (4-diis) -benzylaminoamide Step 3: Preparation of 4-nitro-N- (tert-octyl) benzamide:

In a reactor, tert-octyl amine (51.7 g, 0.4 mol) and triethylamine (61.2 ml, 0.44 mol) are introduced into 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 the course of 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 in vacuo, 84.6 g (76% yield) of 4-nitro-N- (tert-octyl) benzamide was obtained as an off-white powder and used as such 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 is obtained in the form of a light yellow powder and used as such in the next step.

Third Step: Preparation of the Derivative of Example 4: In a CEM Discover Microwave, the mixture of the product of the first step of the example is heated for 20 minutes at a temperature of 115 ° C. and at a power of 150 watts. 3 (1 g, 2.3x10-3 mol), the product of the previous step (1.16 g, 4.6x10-3 mol) and sodium bicarbonate (0.39 g, 4.6x10-3 mol) ) in 10 ml of dry toluene. Dichloromethane is added to the reaction mixture and washed with saturated sodium chloride solution and then twice with water. After drying of the organic phase and evaporation of the solvents, a light yellow oil is obtained. After purification on a silica column (eluent: Heptane / EtOAc 70: 30), the clean fractions of the derivative of Example 11 (0.9 g, Yield: 45%) are recovered in the form of white flakes: UV (Ethanol ): Xmax = 302 nm, E1% = 775. EXAMPLE 12: Preparation of 2,4-bis (4'-diylamino benzoate methyltrimethylsilyl) -6- {1,3,3,3-tetramethyl-1-1 (trimethylsilyl) oxyldisiloxanyllpropyl-3-ylamino} -s-triazine: Si (NH) (12) First step: preparation of methyltrimethylsilyl 4-aminobenzoate

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

Second step: preparation of the derivative of Example 12

Under nitrogen sparge, the mixture of the first step product of Example 3 (2.1 g, 4.9 × 10 -3 mol) and the derivative of the previous step (2.19 g, 9.8 × 10 -3 mol) in 40 ml of toluene is refluxed for 5 hours. Cool and evaporate the solvent. The residue is taken up in dichloromethane, dried and the solvent evaporated. 3 g (Yield: 76%) of the derivative of Example 12 are obtained in the form of a pale yellow gum: UV (Ethanol): X max = 311 nm, E 1% = 90%. EXAMPLE 13 Preparation of 2,4- bis (N-hexyl-4'-divamino benzoate) -6- {[1,3,3,3-tetramethyl-1- (trimethylsilyl) oxyldisiloxane] -propyl-3-ylamino} -s-triazine (Lane II): In a reactor under argon bubbling, 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. The mixture is heated to 70 ° C. and a solution of the derivative of the first step of Example 3 (19.32 g, 0.0452 mol) in 50 ml of ethyl acetate is introduced 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 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 ## STR5 ## EXAMPLE 14 Preparation of 2,3-bis (4'-divamino benzoic acid benzoate) -6- {f 1,3,3,3- tetramethyl (1-trimethylsilyl) oxyldisiloxanepropyl-3-ylamino} -s-triazine (Lane II): ## STR1 ## In an argon bubbling reactor, 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 ester 3-vlamino} -s-triazine (Route II):

where N P ùsi. In an argon bubbling reactor, 2-ethyl hexyl para-aminobenzoate (20 g, 0.0802 mol) was 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 (16) 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'-divlamino benzoate of ethyl-2-hexyl) -6 - {[1,3,3,3-tetramethyl-1-yl] (trimethylsilyl) oxyldisiloxane-3-ylamino} -s-triazine (Lane II): Under nitrogen sparge, a mixture of ethyl 2-hexyl-2-hydroxy-4-aminobenzoate (1.4 g, 5.57 × 10- 3 mol) and the product of the first step of Example 3 (1.19 g, 2.78x10-3 mol) in 10 ml of toluene is refluxed for 5 hours. Cool and evaporate the solvent. The residue is chromatographed on a silica column (eluent: Heptane / EtOAc 9/1). 1.58 g (yield: 64%) of the eigenfractions of the derivative of Example 16 are obtained in the form of a white paste: UV (Ethanol): = 300 nm, El% = 480 amax = 325 nm, El % = 709.-Si SiO o Si -NH NH (17) EXAMPLE 17: Preparation of butyl 4- {4- [4- (butoxycarbonyl) phenyl] amino} -6 - ({3-diethoxy (methyl) silyllpropyl} amino) -1,3,5-triazin-2-yllamino} benzoate (Lane I): (19) if O-NH First step: preparation of n-2,4-bis- (4'-diylamino benzoate) butyl) -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 EXAMPLE 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): ## STR1 ## in the derivative of Example 6 (10 g, 0.013 mol) solubilized in 500 1 ml of the 80:20 ethanol / isopropanol mixture, 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 (Butoxycarbonyl) phenylamino) -6 - [(2- (1,3,3,3-tetramethyl-1-1 (trimethylsilyl) oxyldisiloxane] propyl) aminol-1,3,5-triazin 2-vI} amino) benzoate: 4 - ({4 - {[4- (22)} / Si-O ~ s ~

First stage: preparation of 4,6-dichloro-N- (2- {1,3,3,3-tetramethyl-1-f (trimethylsilyl) oxyldisiloxanyl} propyl) -1,3,5 -triazine-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): HN NH N NH Si (~ I o, O

The derivative of Example 6 (1 g, 0.0013 mol) solubilized in 50 ml of the ethanol / isopropanol mixture in the ratio 80:20 is added 25 ml of 1N hydrochloric acid. stirring at laboratory 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) (23) Y (NH 4) (NH 4) n NH (NH 3) n -NH 2 O (NH 3) 24) r stat = 8.1 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 are added dropwise at 5 ° C simultaneously n-butyl para-amino benzoate (113.94 g, 0.59 mole) and a solution of of potassium carbonate (40.68 g, 0.295 mol) in 50 ml of water so that the pH is between 3 and 6.5. It is maintained for 1 hour 30 minutes at 5 ° C. A precipitate is formed in the medium corresponding to the monosubstituted s-triazine.

The mixture is gradually heated to 70 ° C. and the second equivalent of potassium 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 sparge, a mixture of the above product (2 g, 4x10-3 mol), aminopropyl terminated polydimethylsiloxane (DMS-A-11 from Gelest) ( 2.13 g, 2x10-3 mol) and pyridine (0.32 ml, 4x10-3 mol) in 40 ml of toluene is heated at 70 ° C for 5 hours. It is cooled, dichloromethane is added and the organic phase is washed 3 times with water. After drying of the organic phase and evaporation of the solvents, a brown oil is obtained. After treatment with black in hot ethanol and filtration on Celite, 3.3 g (yield: 70%) of the derivative of Example 22 is obtained in the form of a light brown gum: 20 UV (Ethanol): X max = 311 nm, El% = 916.

EXAMPLE 23 Preparation of 2,4-bis (diylamino benzoate dodecyl) -6411,3,3,3-tetramethyl-1- (trimethylsilyl) oxyldisiloxanyllpropyl-3-ylamino) -s-triazine (Lane II) O (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) is heated at 170 ° C. 48 hours (the ethanol formed is removed by distillation). The reaction mixture changes from colorless to orange. Under a vacuum of about 20 mmHg, the mixture is heated for 6 hours at 100 ° C. The reaction mixture changes from orange to red. The mixture is then heated to 120 ° C. to remove the excess lauric alcohol. The reddish brown viscous oil is crystallized from methanol. After filtration, washing the cake with cold methanol and drying in vacuo docecyl para-aminobenzoate (52.77 g, Yield 84%) as a pale yellow powder and used as it in the step Next: Second Step: Preparation of the Derivative of Example 23:

Under argon sweeping and with stirring, the product of the first step of Example 3 (20 g, 0.047 mole) solubilized in ethyl acetate is added to 13.3 ml of pyridine dissolved in ethyl acetate. The mixture is heated to 70 ° C. and the dodecyl para-amino benzoate of the previous step (28 g, 0.092 mol) is added in portions over 10 minutes. The reaction mixture is left at this temperature for 3 hours and 30 minutes. 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, 20.1 g (yield: 42%) of the derivative of Example 23 are obtained in the form of a beige powder: mp: 134-135 ° C., UV (ethanol): X max = 311 nm, E1% = 838.

EXAMPLE 24 Preparation of compound (26)

~ Si-O ~ Î i-0], [Si-O ~ Si NH N ~ N HN N NH (26) 20 r stat = 9 and s stat = 1.8

Under nitrogen sparging, the heterogeneous mixture of the product of Example 17 (1 g, 1.53 × 10 -3 mol), decamethylcyclopentasiloxane (D5) (0.57 g, 1.53 × 10 -3 mol), hexamethyldisiloxane (MM) (0.062g, 0.38x10-3 mol) and concentrated hydrochloric acid (0.1ml) was vigorously stirred in a mixture of 10ml of toluene and 1ml of water. It is gradually heated to 70 ° C. and left at this temperature for 2 hours. After cooling to room temperature and dilution with water, the whole is filtered. The precipitate obtained is washed with water and dried. 0.56 g of a white powder of the derivative of Example 24 (Ethanol) is thus obtained: X max = 311 nm, E 1% = 892.

II / EXAMPLES OF SYNTHESIS OF THE MEROCYANINE FAMILY:

EXAMPLE 25 Preparation of butyl (2E, 4E) -5-bis (2-hydroxyethyl) aminol-2-cyanopenta-2,4-dienoate: ## STR2 ## First Step: Preparation of Butyl (2E) 4E) -5-facetyl (phenyl) aminol-2-cyanopenta-2,4-dienoate: The mixture is heated to 85-90 ° C in 6 ml of acetic anhydride under nitrogen bubbling of 3-anilinoacrolein aniline (3). g, 13.5x10-3 mol) and n-butyl ester of cyanoacetic acid (1.9 ml, 13.5x10-3 mol) for 1 hour 30 minutes. After cooling, 10 ml of methanol are added and allowed to precipitate. The resulting solid is filtered off and rinsed with methanol. We dry. 3.14 g of a yellow powder (yield: 74%) of butyl (2E, 4E) -5- [acetyl (phenyl) amino] -2-cyanopenta-2,4-dienoate are recovered and used as such in the aqueous solution. 'next step. Second Step: Preparation of the compound of Example 25: A solution of the above product (3.1 g, 0.01 mol) and diethanolamine (1.04 g, 0.01 mol) in 6 ml of water were refluxed. acetonitrile for 4 hours. After cooling, evaporate to dryness under vacuum. The orange residue is chromatographed on a silica column (eluent gradient: CH 2 Cl 2 / MeOH 100: 0 to 90:10). 1.32 g (yield: 47%) of the eigenfunctions of the derivative of Example 25 are thus obtained in the form of a pale yellow powder: Mp: 50-52 ° C. UV (Ethanol): X max = 382 nm, El EXAMPLE 26: Preparation of hexyl (2E, 4E) -5-bis (2-hydroxyethyl) aminol-2-cyanopenta-2,4-dienoate: HO N / N (aq) First step: Preparation of hexyl (2E, 4E) -5-facetyl (phenyl) aminol-2-cyanopenta-2,4-dienoate: The mixture is heated to 105 ° C. in 5 ml of acetic anhydride under nitrogen bubbling of 3-anilinoacrolein aniline (2 g, 9x10-3 mol) and n-hexyl ester of cyanoacetic acid (1.52 g, 9x10-3 mol) for 3 hours. After cooling, 10 ml of methanol are added and allowed to precipitate. The resulting solid is filtered and rinsed with methanol. We dry. 1.2 g of a yellow powder H (yield: 32%) of hexyl (2E, 4E) -5- [acetyl (phenyl) amino] -2-cyanopenta-2,4-dienoate are recovered and used as such. in the next step.

Second step: Preparation of the compound of Example 26: A solution of the preceding product (1 g, 2.94 × 10 -3 moles) and diethanolamine (0.31 g, 2.94 × 10 -3 moles) in 5 ml is refluxed. acetonitrile for 1 hour and 15 minutes. After cooling, evaporate to dryness under vacuum. The brown residue obtained is chromatographed on a silica column (gradient of eluents: CH 2 Cl 2 / MeOH 100: 0 to 98: 2). 0.51 g (yield: 55%) of the eigenfractions of the derivative of Example 26 are thus obtained in the form of a pale yellow powder: Mp: 76-78 ° C. UV (Ethanol): X max = 381 nm, El % = 1846

EXAMPLE 27 Preparation of n-octyl (2E, 4E) -5- [bis (2-hydroxyethyl) aminol-2-cyanopenta-2,4-dienoate: (ar)

First step: Preparation of n-octyl (2E, 4E) -5-facetyl (phenyl) aminol-2-cyanopenta-2,4-dienoate:

The mixture is heated to 115 ° C. in 70 ml of acetic anhydride under nitrogen bubbling of 3-anilinoacrolein aniline (27.7 g, 0.125 mol) and the n-octyl ester of cyanoacetic acid (26.3 g). ml, 0.125 mol) for 2 hours. After cooling, 80 ml of methanol are added and allowed to precipitate. The resulting solid is filtered and rinsed with methanol. We dry. 36.4 g of a yellow powder (yield: 79%) of butyl (2E, 4E) -5- [acetyl (phenyl) amino] -2-cyanopenta-2,4-dienoate are recovered and used as such in the aqueous solution. 'next step. Second step: Preparation of the compound of Example 27:

A solution of the above product (36.2 g, 0.00982 mol) and diethanolamine (10.33 g, 0.00982 mol) in 75 ml of acetonitrile was refluxed for 1 hour and 30 minutes. After cooling in an ice bath, the product precipitates. The solid is filtered and rinsed with a piston of cold acetonitrile. The solid is recrystallized twice in ethyl ether. 18.9 g (yield: 57%) of the derivative of Example 27 is thus obtained in the form of a pale yellow powder: Mp: 81-84 ° C. UV (Ethanol): X max = 382 nm, El% = EXAMPLE 28 Preparation of methyl (2Z, 4E) -5- [bis (2-hydroxyethyl) aminol-2- (methylsulphonyl) penta-2,4-dienoate OH ## STR2 ## O (af) First step: Preparation of methyl (2Z, 4E) -5-facetyl (phenyl) aminol-2- (methylsulfonyl) penta-2,4-dienoate: The mixture is heated to 105 ° C. in 5 ml of acetic anhydride. 3-anilinoacrolein aniline (2 g, 9x10-3 mol) and methylmethane sulfonyl acetate (1.37 ml, 9x10-3 mol) for 2 hours and 30 minutes. After cooling, the acetic anhydride is evaporated under vacuum. The brown solid obtained is taken up in 40 ml of methanol and is brought to reflux. After cooling, the solid obtained is filtered, rinsed with cold methanol and dried. 1.6 g of a yellow powder (Yield: 55%) of methyl (2Z, 4E) -5- [acetyl (phenyl) amino] -2- (methylsulfonyl) penta-2,4-dienoate are recovered and used. as is in the next step. Second step: Preparation of the compound of Example 28: A solution of the preceding product (2.3 g, 7.1 × 10 -3 mole) and diethanolamine (10.33 g, 6.23 × 10 -3 mole) is refluxed. ) in 5.5 ml of acetonitrile for 1 hour and 15 minutes. After cooling, the acetonitrile is evaporated under vacuum. The brown oil obtained is chromatographed on a silica column (eluent gradient: CH 2 Cl 2 / MeOH 100: 0 to 90:10). 0.36 g (yield: 26%) of the e.g. EXAMPLE 29: Preparation of bis (4-hydroxybutyl) [(2E) -3- (dimethylamino) prop-2-en-1-ylidenelpropanedioate: N / / O -, ---, - OH o First step: Preparation of bisf4- (benzyloxy) butyllpropanedioate:

A heterogeneous mixture of 4-benzyloxy-1-butanol (9.5 g, 52.8 × 10 -3 mol) and malonic acid (2.5 ml, 24 × 10 -3 mol) is heated to 50 ° C. with stirring. Concentrated H 2 SO 4 (131 μL) was added to this mixture and left at 40 ° C for 1 hour. After cooling, the gray residue is taken up in dichloromethane. The organic phase is washed with water (abundant foams). (am) After evaporation of the solvent, the residue obtained is chromatographed on a column of silica to remove the starting alcohol (Eluent: Heptane / AcOEt 90:10). 7.5 g (yield: 74%) of the bisf4- (benzyloxy) butyl] propanedioate fractions are recovered in the form of a pale yellow oil and used as such in the next step.

Second step: Preparation of bis (4-hydroxybutyl) propanedioate:

The preceding product (7.5 g, 0.0175 mol) dissolved in 350 ml of ethanol was subjected to continuous reductive hydrogenation (H-cube: 70 mm Pd over C 10% cartridge; 1 ml / min; 40 ° C). After vacuum distillation of the ethanol, 4.31 g (yield: 99%) of bis (4-hydroxybutyl) propanedioate are obtained in the form of a colorless oil and used as such in the next step. Third step: Preparation of the compound of Example 29:

In a reactor inert with nitrogen and surmounted by a Dean Starck, the preceding product (4.31 g, 0.0173 mole) was refluxed and the n-octylamine catalysts (86 μl, 0.03 equiv) and acetic acid (199 μl, 0.2 equiv) in 20 ml of toluene. N, N-dimethyl acrolein (1.74 ml, 0.0173 mol) dissolved in 10 ml of toluene is added dropwise to the reaction mixture. After 3 hours 30 minutes of boiling the reaction mixture, the same amounts of catalyst are added and the reflux is maintained 21 hours. After cooling, the solvent is evaporated under vacuum and the brown oil obtained is chromatographed on a silica column (eluent gradient: Isopropyl ether / acetone 30: 70 to 70:30). There is thus obtained 703 mg (yield: 12%) of the derivative of Example 29 in the form of an orange oil: UV (Ethanol): X max = 374 nm, El% = 1600

EXAMPLE 30: Preparation of 2,3-dihydroxypropyl (2E, 4E) -2-cyano-5- (dimethylamino) penta-2,4-dienoate): OH OOOH 35 (as)

First step: Preparation of (2,2-dimethyl-1,3-dioxolan-4-yl) methyl cyanoacetate:

In a reactor inert with nitrogen, a mixture of methyl cyanoacetate (1.3 ml, 15 × 10 -3 mol), solketal (1.25 ml, 10 × 10 -3 mol) is refluxed for 30 hours. DMAP (2.7 mg, 0.03 equiv). After cooling, the solvent is evaporated off under vacuum and the brown oil obtained is chromatographed on a silica column (gradient of eluants: Heptane / EtOAc 4s 90: 10 to 80: 20, to give 423 mg (yield: 23%). ) pure N fractions of (2,2-dimethyl-1,3-dioxolan-4-yl) methyl cyanoacetate as a yellow oil and used as such in the following step:

Second step: Preparation of (2,2-dimethyl-1,3-dioxolan-4-yl) methyl (2E, 4E) -s-2-cyano-5- (dimethylamino) penta-2,4-dienoate

In a reactor inert with nitrogen, the preceding product (50 mg, 0.254 × 10 -3 mol) was refluxed and the catalysts n-octylamine (1.3 μL, 0.03 equiv) and acetic acid (3 μL, 0. , 2 equi.) In 0.8 ml of toluene. To the reaction mixture is added dropwise N, N-dimethyl acrolein (26 μL, 0.25 × 10 -3 mol) dissolved in 0.8 ml of toluene. The reflux is maintained 36 hours by adding every 8 hours the same amounts of catalyst. After cooling, the solvent is evaporated under vacuum and the brown paste obtained is crystallized in 2 ml of isopropanol. There is thus obtained 68 mg (yield: 97%) of (2,2-dimethyl-1,3-dioxolan-4-yl) methyl (2E, 4E) -2-cyano-5- (dimethylamino) penta-2, 4-dienoate in the form of a beige powder and used as such in the following step: UV (Ethanol): X max = 379 nm, El% = 1974.

Step 3: Preparation of the compound of Example 30: In a nitrogen-inerted reactor, the above product (60 mg, 0.21 × 10 -3 mol) was solubilized in MeOH / THF 1: 1. Dowex H + (1g) is added and stirred for 24 hours. After filtration of the Dowex, evaporation of the solvents, the residue is chromatographed on a silica column (Eluent: CH 2 Cl 2 25 / MeOH 95: 5). 22 mg (yield: 43%) of the clean fractions of the derivative of Example 30 are thus obtained in the form of an orange viscous oil: UV (Ethanol): X max = 375 nm, El% = 1485.

30 III / EXAMPLES OF FORMULATION

The compositions A (invention) and the following compositions B, C, D, excluding the invention were produced: Ingredients Ex Ex Ex B Ex C Ex D (*) (*) (*) Phase a EDTA 0.1 0.1 0, 1 0.1 Monoethyl phosphate 1 1 1 1 monopotassium 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- C ~ 5 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 of Glyceryl / Stearate Polyethylene glycol (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 Drometrizole Trisiloxane 4 4 4 4 s-triazine silicon 4 0 0 0 substituted with two C4-alkylaminobenzoates Compound (5) Merocyanine of Example 27: Formula (ar) a- cyano-R, [3` 0 4 0 0 ethyl 2-ethylhexyl-4-methoxycinnamate diphenylacrylate 0-ethyl-2-hexyl 2,4,6-tris [p- (2'-ethylhexyl) xyl-4-oxycarbonyl) anilino] -1,3,5-triazine Isohexadecane 1 1 1 1 Phase b2 Copolymer of 0.2 0.2 0.2 0.2 acrylic acid and methacrylate C10-C30 alkyl Xanthane 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.

Method of preparation of the 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 emulsion obtained is cooled to room temperature with slow stirring. It is characterized by drops of size between 1 lm and 10 microns. i0 Protocol for assessing the solubility of UV filters

The studied emulsion is stored for one week at 4 ° C. The solubility of the filters is evaluated by observing their microscopic appearance using an optical microscope under polarized light. An insolubility phenomenon results in the presence of objects observed according to this protocol, of size greater than 500 nm.

In vitro evaluation protocol of the filtering efficiency The sun protection factor (SPF) is determined according to the "in vitro" method described by B. L. Diffey in J. Soc. Cosmet. Chem. 40, 127-133, (1989). The measurements were carried out using a UV-1000S spectrophotometer from the company Labsphere. Each composition is applied to a 3M Transpore adhesive tape bonded to a quartz slide as a homogeneous, uniform deposit at 1 mg / cm 2.

Protocol for evaluating the photostability of filters

The percentage loss of UV filter to be evaluated, induced by the exposure to a solar simulator of a formula spread out in films of thickness close to 20 μm, is measured.

The evaluation is made by HPLC analysis of the filter solution, after extraction of the films, by comparing irradiated and non-irradiated samples.

MATERIAL AND METHOD :

Solar simulator: Oriel 1000W device with a 4-inch output, with filter 40 81017 and dichroic mirror. The samples are exposed in a horizontal position. UV-meter: OSRAM CENTRA device equipped with 2 reading heads, one for UVA and the other for UVB. The simulator-UV meter assembly is calibrated annually by spectroradiometry. Irradiance measurements made at the beginning and at the end of exposure by placing the read heads at the position of the sample. The irradiances are: 0.35 - 0.45mW / cm2 in UVB 16 - 18 mW / cm2 in UVA

The residual filter is measured by HPLC chain chromatography with a diode array detector.

IMPLEMENTING PHOTOSTABILITY TESTS

About 20 mg of each test formula is spread over a surface of 10 cm 2 on a frosted side of a fused silica disc. The exact amount is determined by weighing. 3 films are exposed to the solar simulator and 3 others serve as a control. The samples are exposed 3 by 3 in the light of the solar simulator for a time sufficient to deliver a UVA dose equal to 21 mJ / cm2. At the end of the exposure, each support disk is introduced into a 600 ml jar with 10 ml of a suitable solvent (in general EtOH); the whole is placed for 5 minutes in an ultrasonic tank. The solution is then transferred into vials adapted to the support compatible with the HPLC analysis apparatus used. The analytical conditions can be adjusted according to the tested active.

Results In Vitro SPF Residual% Residual% of Filter Compound (ar) UVB 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 merocyanine filter of formula (IX): compound (ar) and a UVB filter selected from the type molecules Silicon substituted s-triazine substituted with two aminobenzoate groups makes it possible to obtain a filtering system of high efficiency which is easy to use in cosmetic compositions because of its good solubility and photostability. For combinations based on other UVB filters such as 2-ethylhexyl-2-ethylhexylacrylate, 2-ethylhexylacrylate, 2-ethylhexyl 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 the invention. 30

Claims (4)

REVENDICATIONS1. Composition comprising in a cosmetically acceptable medium 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) ) - (Si) 4 (3-a) y 2 (I) (IR) 1 in which - R, which may be identical or different, represent a C 1 -C 2 alkyl radical, a phenyl radical or a C 1 -C 2 alkoxy radical; a hydroxy radical or the trimethylsilyloxy group; - 1 to 3; Is - the group (D) denotes a s-triazine compound of formula (II) below: ## STR5 ## where R 1, which may be 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 (C = O) OR 1 group possibly being in the ortho, meta or para position of the amino group, - R 2, identical or different, represent hydrogen, a hydroxyl radical, a linear or branched C1-C4 alkyl radical, a methoxy radical, 25-A is a divalent radical chosen from methylene or a group corresponding to one of the formulas (III) , (IV), (V) or (VI): • (Z) ùCHùCH₂-- (III) W (Z) ùCHù (IV) CHCH3 (Z) ùCH = CH - (V) 25I1H2 (Z) In which: Z is a C 1 -C 3 alkylene diradical; W represents a hydrogen atom, a hydroxyl radical or a C 1 -C 3 alkyl radical: in addition to the units of formula -A- (Si) (R); ) a (0) (3a) / 2, the organosiloxane may be rter units of formula: (R) b- (Si) (O) (4.b) / 2 wherein: R has the same meaning as in formula (I), b = 1, 2 or 3; Io {ii) at least one hydrophilic or water-soluble merocyanine UV filter. 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 R1 is a C1-C8 radical, Z = -CH2-, W = H, the (C = O) OR1 group is in the para position of the amino group. 3. A composition according to any one of claims 1 and 2, wherein the siliconized striazine has one of the following formulas (1a), (Ib) and (Ic): ## STR2 ## ## STR1 ## In which: - (D) corresponds to formula (II) as defined above, - R7, which may be identical or different, are chosen from linear or branched C1-C20 alkyl radicals, phenyl, 3,3, 3-trifluoropropyl and trimethylsilyloxy or the hydroxyl radical, R8, which are identical or different, are chosen from linear and branched C1-C20 alkyl and alkenyl radicals, the hydroxyl or phenyl radicals, - (B), which are identical or different, are chosen among the radicals R7 and the radical (D), r is an integer 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) denotes (D), - u is an integer ranging from 1 to 10, - t es t an integer ranging from 0 to 10, it being understood that t + u is equal to or greater than 3 and their tautomeric forms. ia 4. The composition according to claim 3, wherein the s-triazine is chosen from (4) (6) NH 10 5. The composition according to claim 4, wherein the s-triazine is 2,4-bis (4'- n-butyl aminobenzoate) -6 - [(3- {1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -s-triazine of the formula (5) if the compound is any combination of any one of claims 1 to 5, wherein the hydrophilic or hydrosoluble merocyanine UV filter is chosen from those corresponding to one of the formulas (IX) and (X) or one of their isomeric forms E, E-, E, Z- or Z, Z-. Wherein R 1 and R ', which may be identical or different, represent H, a linear or branched C 1 -C 22 alkyl radical or a C 3 cycloalkyl radical; C8, unsubstituted or substituted by C1-C4 alkyl radicals, said radicals R1 and R2 may contain an alkyl sulphonate radical in its acid or salt form or one to 4 hydroxy radicals; R 'and R2 may form together with nitrogen a ring containing the group - (CH2) m-, uninterrupted or interrupted by one or more -O-, -S- or -NH-, R 'may form with the carbon in alpha of the nitrogen a cycle containing the group - (CH2) m-, uninterrupted or interrupted by one or more -O-, -S- or -NH-, -R3 represents a carboxyl group, -COOR5, -CONHR5, -COR5, -CONR5R1, -CN or SO2R5 - R4 represents a carboxyl group, -COOR6, -CONHR6, -COR6, -CONR6R2, -NC or SO2R6, or R3 and R4 together may form a heterocyclic ring C5-C7, - R5 and R6, identical or different, repr feel an alkyl radical C1-C22, linear or branched, a cycloalkyl radical in C 3 -C 8, unsubstituted or substituted by alkyl C1-C4; said radicals R5 and R6 may contain an alkyl sulphonate radical in its acid or salified form or one to 4 hydroxyl radicals; Z represents the group - (CH 2) r, uninterrupted or interrupted by -O-, -S- or --NR 7 -, and / or unsubstituted or substituted by one or two C 1 -C 6 alkyl radicals, - R 7 is a C 1 -C 5 alkyl radical which may contain an alkyl sulphonate radical in its acidic or salified form or one to 4 hydroxyl radicals; -nestl-2; -mestl-7; -lest1-4; with at least one or two of R1, R2, R5, R6 and R7 containing - either an alkyl sulphonate radical in its acidic or salified form - or from one to four hydroxy radicals. With the proviso that: (i) when n = 2, R1, R6 or R6 is an alkyl diradical or R1 and R2 together with 2 nitrogen atoms form a cyclic divalent radical - (CH2) n - (ii ) R 'and R2 are not simultaneously a hydrogen atom; 7. Composition according to claim 6, wherein the compound (s) of formula (IX) with one or two alkyl sulphonate radicals are chosen from those of formulas (a) to (y) below and their isomers: 0 1 ISOI (OH 1 N (a) ## STR2 ## wherein N (b) is an OH (OH) O (OH) O (OH) O (OH) O (OH) O (OH) O (OH) O ## STR5 ## wherein R 1 is N (g) o, N) ~ SAO-O O (i) Na OI, OH N \ \ N / SAO 1 H II N (k) O 101 OH ~ N \ \ N / ~~ S ~~ OH (I) OI, OH HN (h) Na + oy H -.: NaOH (i) N NaO 0 + 0 (F) (n) ## STR1 ## ## STR5 ## wherein Y (OH) O (OH) O (OH) O (OH) O, OH, OH The composition according to claim 6, wherein the compound (s) of formula (IX) with one to four hydroxyalkyl radicals are chosen from those of formulas (z) to (h). aw) and their isomers: (z) 0 N HOC / NN (ab) HO N (ad) OH HNH (ad) NI 14 OH O, - NH "- ## STR2 ## N (aj) N HO ~~ N • `ON H (ak) NH HO ~~ N 0 OH N 0 O N1 OH OH ON If 00OH / NO, / - OH OH H 0,, z, ## STR5 ## HO N (aq) OH H ^ OVO ~ / (au) O (av) HOC ^ O ~ O ~ / sOH OH O ~ O ~~ OH O vN ~, OH N (as) (at) OH 0 O A composition according to claim 6, wherein the compound (s) of formula (X) are selected from those of the following formulas (ax) to (bc): ## STR2 ## as well as their isomers: H Ho's 0 N (ay) 10 HOC "(bc) (bb) OH 1510. A composition according to any one of claims 1 to 9, wherein the water-soluble or hydrophilic merocyanine UV screening compound (s) are selected from the following compounds or their isomeric forms E, E-, E, Z- or Z, Z-. ## EQU1 ## ## STR2 ## ## STR2 ## any one of claims 1 to 10, characterized in that it contains in addition to other organic or inorganic filters active in UV-A and / or UV-B water-soluble or fat-soluble or insoluble in cosmetic solvents 12. The composition according to claim 11, wherein the complementary organic screening agents are chosen from dibenzoylmethane derivatives, anthranilates, cinnamic derivatives, salicylic derivatives, camphor derivatives, benzophenone derivatives, , 8-diphenylacrylate; triazine derivatives other than those of formula (I); benzalmalonate derivatives; benzimidazole derivatives; imidazolines; p-aminobenzoic acid derivatives (PABA); nzotriazole, bis (hydroxyphenyl benzotriazole) methylene derivatives; benzoxazole derivatives; filter polymers and silicone filters; dimers derived from α-alkylstyrene; 4,4-diarylbutadienes; liposoluble merocyanine derivatives and mixtures thereof. 13. 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, Octocrylene, r0 Butyl Methoxy Dibenzoylmethane Terephthalylidene Dicamphor Sulfonic Acid Disodium Phenyl Dibenzimidazole Tetrasulfonate Phenylbenzimidazole Sulfonic Acid, Benzophenone-3 2- (4-diethylamino-2-hydroxybenzoyl) -benzyl benzoyl 4-methylbenzylidene camphor, Ethylhexyl triazone, Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine Diethylhexylbutamido triazone, 2,4,6-tris ( diphenyl-4-yl-1,3,5-triazine 2,4,6-tris (dineopentyl 4'-amino benzalmalonate) -s-triazine 2,4,6-tris (diisobutyl 4'-amino benzalmalonate) triazine, 2,4-bis (dineopentyl 4'-amino benzalmalonate) -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-yl- (4-phenyl) imino] -6- (2-ethylhexyl) -30 imino-1 3,5-triazine and mixtures thereof. 14. A composition according to claim 11, characterized in that the complementary inorganic filters are metallic oxide pigments, coated or uncoated.