FR2967900A1 - Composition for protecting from sun or make up of skin, lips or hair comprises UV screening system comprising dibenzoylmethane derivative; and specific hydrophilic or water-soluble merocyanine UV-screening agent - Google Patents

Abstract

A composition comprises: in cosmetic vehicle, UV screening system(s) comprising dibenzoylmethane derivative(s); and hydrophilic or water-soluble merocyanine UV-screening agent(s) selected from ((E)-buta-1,3-dienyl)-disubstituted-amine compounds, cyclobut-1-enylamine compounds, and merocyanine compounds selected from 36 compounds as given in the specification e.g. sodium 4-{2-[(Z)-3-cyano-3-methanesulfonyl-prop-2-en-(E)-ylidene]-thiazolidin-3-yl}-butane-1-sulfonate, and their salts or E,E-, E,Z-, or Z,Z- isomers. A composition comprises: in a cosmetic vehicle, at least one UV screening system comprising at least one dibenzoylmethane derivative; and at least one hydrophilic or water-soluble merocyanine UV-screening agent selected from ((E)-buta-1,3-dienyl)-disubstituted-amine compound of formula [NR 1R 2-CH=CH-CH=CR 3R 4] n(I), and cyclobut-1-enylamine compound of formula (II), and their salts or E,E-, E,Z-, or Z,Z- geometrical isomer forms, and merocyanine compounds (III) selected from 36 compounds as given in the specification e.g. sodium 4-{2-[(Z)-3-cyano-3-methanesulfonyl-prop-2-en-(E)-ylidene]-thiazolidin-3-yl}-butane-1-sulfonate; (Z)-2-cyano-4-[3-methyl-oxazolidin-(2E)-ylidene]-but-2-enoic acid 2-sulfo-ethyl ester; 2-{2-[(Z)-3-cyano-3-(octane-1-sulfonyl)-prop-2-en-(E)-ylidene]-oxazolidin-3-yl}-ethanesulfonic acid; (2E,4E)-5-(4-hydroxy-piperidin-1-yl)-2-methanesulfonyl-penta-2,4-dienoic acid methyl ester; 2-[(E)-3-(4-hydroxy-piperidin-1-yl)-allylidene]-malonic acid diethyl ester; (2E,4E)-2-cyano-5-(4-hydroxy-piperidin-1-yl)-penta-2,4-dienoic acid octyl ester; (2Z,4E)-5-[bis-(2-hydroxy-ethyl)-amino]-2-cyano-penta-2,4-dienoic acid pentyl ester; (2E,4E)-2-cyano-5-[ethyl-(2-hydroxy-ethyl)-amino]-penta-2,4-dienoic acid octyl ester; (2Z,4E)-5-[bis-(2-hydroxy-ethyl)-amino]-2-cyano-penta-2,4-dienoic acid isopropyl ester; (2E,4E)-2-cyano-5-[ethyl-(2-hydroxy-ethyl)-amino]-penta-2,4-dienoic acid 1-methyl-heptyl ester; (2Z,4E)-5-[bis-(2-hydroxy-ethyl)-amino]-2-cyano-penta-2,4-dienoic acid 1-methyl-heptyl ester; (2E,4E)-2-cyano-5-(2-hydroxy-ethylamino)-penta-2,4-dienoic acid octyl ester; (2E,4E)-2-cyano-5-(1-hydroxymethyl-2-methyl-propylamino)-penta-2,4-dienoic acid heptyl ester; (2E,4E)-2-cyano-5-dimethylamino-penta-2,4-dienoic acid (2,3-dihydroxy-propyl)-amide; (2E,4E)-2-cyano-5-[ethyl-(2-hydroxy-ethyl)-amino]-penta-2,4-dienoic acid 3-{(2E,4E)-2-cyano-5-[ethyl-(2-hydroxy-ethyl)-amino]-penta-2,4-dienoyloxy}-propyl ester, and their salts or E,E-, E,Z-, or Z,Z- geometrical isomer forms. R 1, R 2, R' 1and R' 2 : linear or branched 1-22C alkyl (optionally containing 1-3 O atoms) or 3-8C cycloalkyl (optionally substituted with 1-4C alkyl) (both optionally containing alkylsulfonate in its acid or salified form, or 1 or 2 hydroxyl), alkyl diradical, or H;or NR 1R 2or NR' 1R' 2 : ring containing a group -(CH 2) m- (optionally interrupted with at least one -O-, -S- or -NH-);or R 1or R' 1+carbon alpha to nitrogen : ring containing a group -(CH 2) m- (optionally interrupted with at least one -O-, -S- or -NH-); R 3and R' 3 : carboxyl, -COOR 5, -CONHR 5, -COR 5, -CONR 5R 1, SO 2R 5, or CN; R 4and R' 4 : carboxyl, -COOR 6, -CONHR 6, -COR 6, -CONR 6R 2, or SO 2R 6; R 5and R 6 : linear or branched 1-22C alkyl (optionally containing 1-3 O atoms) or 3-8C cycloalkyl (optionally substituted with 1-4C alkyl) (both optionally containing alkylsulfonate in its acid or salified form, or 1 or 2 hydroxyl), or alkyl diradical; Z' : group of formula -(CH 2) l- (optionally interrupted with -O-, -S- or -NR 7-, and optionally substituted with 1 or 2 1-6C alkyl); R 7 : 1-5C alkyl (optionally containing alkylsulfonate in its acid or salified form, or 1 or 2 hydroxyl); n : 1 or 2; m : 1-7; l : 1-4. Provided that: (1) at least 1 or 2 of the R 1or R' 1, R 2or R' 2, R 5, R 6and R 7contains either an alkylsulfonate in its acid or salified form; or 1 or 2 hydroxyl; (2) when n is 2, one of R 1or R' 1, R 5or R 6is alkyl diradical; or NR 1R 2or NR' 1R' 2forms cyclic divalent -(CH 2) m- radical; (3) R 1and R 2or R' 1and R' 2are not simultaneously H; and (4) when R 3or R' 3is CN, then at least one of R 1or R' 1, R 2or R' 2, and R 6contains alkylsulfonate in its acid or salified form. Independent claims are included for the following: (1) method (M1) for improving the chemical stability towards UV radiation of a least one dibenzoylmethane derivative, involving: combining the dibenzoylmethane derivative with at least one hydrophilic or water-soluble merocyanine UV screening agent selected from compounds (I), (II) and (III), or their salt or E,E-, E,Z-, or Z,Z- isomeric form; (2) new merocyanine compounds (I) containing one or two alkylsulfonate radicals or containing hydroxyl groups including 27 compounds as given in the specification e.g. ((2E,4E)-2-cyano-5-dimethylamino-penta-2,4-dienoylamino)-methanesulfonic acid; ((2E,4E)-2-cyano-5-diethylamino-penta-2,4-dienoylamino)-methanesulfonic acid; 2-((E)-3-dimethylamino-allylidene)-malonic acid bis-(2-sulfo-ethyl) ester; (2E,4E)-5-[bis-(2-hydroxy-ethyl)-amino]-2-methanesulfonyl-penta-2,4-dienoic acid methyl ester; and 2-((E)-3-dimethylamino-allylidene)-malonic acid bis-(4-hydroxy-butyl) ester; and their salt or E-E, Z-Z, ad E-Z isomer forms; (3) new merocyanine compounds (II) including 2-(3-sec-butylamino-5,5-dimethyl-cyclohex-2-enylidene)-malonic acid bis-(4-hydroxy-butyl) ester; [3-[bis-(2-hydroxy-ethyl)-amino]-5,5-dimethyl-cyclohex-2-en-(E)-ylidene]-methanesulfonyl-acetic acid octyl ester, and their salt or E-E, Z-Z, and E-Z isomer forms; and (4) new merocyanine compounds (III), and their salts or E-E, E-Z or Z-Z isomeric forms. [Image] [Image].

Description

COMPOSITION CONTAINING DIBENZOYLMETHANE FILTER AND HYDROPHILIC OR WATER SOLUBLE MEROCYANINE UV FILTER; METHOD FOR PHOTOSTABILIZING THE DIBENZOYLMETHANE FILTER

The present invention relates to a cosmetic composition containing the combination of i) at least one filter of the dibenzoylmethane derivative type and ii) at least one hydrophilic or water-soluble merocyanine UV filter of formula (1) or (II) which will be defined below.

It also relates to a photostabilization process with respect to the radiation of at least one filter of the dibenzoylmethane derivative type by an effective amount of at least one hydrophilic or water-soluble merocyanine UV filter of formula (1) or (II) which will be defined below.

It is known that the luminous radiations of wavelengths between 280 nm and 400 nm allow the browning of the human epidermis, and that the wavelength rays more particularly between 280 and 320 nm, known under the name UV-B, cause erythema and skin burns that can affect the development of natural tanning. For these reasons as well as for aesthetic reasons, there is a constant demand for means of 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 liable to induce an alteration thereof, particularly in the case of sensitive skin or skin continuously exposed to solar radiation. UV-A rays cause in particular a loss of elasticity of the skin and the appearance of wrinkles leading to premature cutaneous aging. They promote the initiation of the erythematous reaction or amplify this reaction in certain subjects and may even be the cause of phototoxic or photoallergic reactions. Thus, for aesthetic and cosmetic reasons such as the preservation of the natural elasticity of the skin for example, more and more people wish to control the effect of UV-A on their skin. It is therefore desirable to filter the UV-A radiation as well.

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

In this respect, a particularly interesting family of UV-A filters currently consists of the dibenzoylmethane derivatives, and in particular 4-tert-butyl-4'-methoxydibenzoylmethane, which in fact have a high intrinsic absorption power. These dibenzoylmethane derivatives, which are now products that are well known per se as active filters in UV-A, are described in particular in French patent applications FR-A-2326405 and FR-A-2440933, as well as in European Patent Application EP-A-0114607; 4-tert-butyl-4'-methoxydibenzoyl methane is also currently offered for sale under the trade name "PARSOL 1789 0" by DSM NUTRITIONAL PRODUCTS.

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

In the patent application WO0128732, there is known a process for photostabilizing a dibenzoylmethane derivative with a phenyl sulphone merocyanine derivative. On the one hand, this photostabilization of the dibenzoylmethane derivative by the phenyl sulphone merocyanine derivative is not completely satisfactory. On the other hand, these merocyanine phenyl sulfone derivatives have the disadvantage of degrading in the presence of dibenzoylmethane under the influence of UV radiation.

In the patent application WO2008090066, it has already been proposed to photostabilize the dibenzoylmethane derivatives with cyclic derivatives of merocyanine cyanoacetate. Here again the light stabilization of the dibenzoylmethane derivative remains insufficient and these merocyanine cyanoacetate derivatives also have the disadvantage of being degraded in the presence of dibenzoylmethane.

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

However, the Applicant has now discovered, surprisingly, that by associating with the dibenzoylmethane derivatives mentioned above a hydrophilic or hydrosoluble merocyanine UV filter of formula (1) or (II), active in the UV-AI , on the one hand could substantially improve the photochemical stability (or photostability) of the dibenzoylmethane derivatives and, on the other hand, extend the filtration of the composition in the UV-A plus Long 40 while being cosmetically colored. acceptable.

This discovery is the basis of the present invention.

Thus, in accordance with 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 derivative dibenzoylmethane and (ii) at least one hydrophilic or hydrosoluble merocyanine UV filter of formula (1) or (II), the definitions of which will be given hereinafter.

Another subject of the invention also relates to a method for improving the chemical stability with respect to the UV radiation of at least one dibenzoylmethane derivative comprising associating with said dibenzoylmethane derivative an effective amount of at least one UV filter. hydrophilic or water-soluble merocyanine of formula (1) or (II), the definitions of which will be given below.

Other features, aspects and advantages of the invention will appear on reading the detailed description which follows.

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

In the remainder of the present description, the term "hydrophilic UV filter" is understood to mean any UV radiation filtering agent capable of being soluble in an aqueous phase at 1-50% by weight (transparent) or water-dispersible 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 more than 50% by weight.

By "effective amount" is meant an amount sufficient to achieve a significant and significant improvement in the photostability of the dibenzoylmethane derivative (s) in the cosmetic composition. This minimum amount of a merocyanine derivative of formula (1) or (II), which may vary depending on the nature of the support selected for the composition, can be determined without any difficulty by means of a conventional photostability measurement test, as given in the examples below. Among the derivatives of dibenzoylmethane, mention may be made, in a nonlimiting manner: 2-methyldibenzoylmethane, 4-methyldibenzoylmethane, 4-isopropyldibenzoylmethane, 4-tert.-butyldibenzoylmethane, dimethyldibenzoylmethane, 40-2,5-dimethyldibenzoylmethane, 4,4'-diisopropyldibenzoylmethane, 4,4'-dimethoxydibenzoylmethane, 4-tert-butyl-4'-methoxydibenzoylmethane, 2-methyl-5 isopropyl-4'-methoxydibenzoylmethane, 45 - 2-methyl-5-tert-butyl-4'-methoxydibenzoylmethane, 2,4-dimethyl-4'-methoxydibenzoylmethane, 2,6-dimethyl-4-tert butyl-4'-methoxydibenzoylmethane. Among the dibenzoylmethane derivatives mentioned above, use will in particular be made of 4-isopropyl dibenzoylmethane, sold under the name "Eusolex 8020" by the company Merck, and having the following formula: It is particularly preferred to employing 4- (tert-butyl) -4'-methoxy dibenzoylmethane or Butyl Methoxy Dibenzoylmethane, offered for sale under the trade name "PARSOL 1789" by the company DSM; this filter has the following formula: OMe The dibenzoylmethane derivative (s) can be present in the compositions in accordance with the invention at contents which preferably vary from 0.01 to 20% by weight and more preferably from 0 to 1 to 10% by weight and even more preferably from 0.1 to 6% by weight relative to the total weight of the composition.

The hydrophilic or hydrosoluble merocyanine compounds according to the invention correspond to one of the following formulas (1) and (II): ## STR2 ## in which: R1 and R2, which are identical or different, represent H; a linear or branched C1-C22 alkyl radical which may contain from 1 to 3 oxygen atoms; a C 3 -C 8 cycloalkyl radical, unsubstituted or substituted by C 1 -C 4 alkyl radicals; said radicals R1 and R2 may contain an alkyl sulphonate radical in its acidic or salified form or one or two hydroxyl radicals; R1 and R2 may together with the nitrogen form a ring containing the - (CH2) m - group, uninterrupted or interrupted by one or more -O-, -S- or -NH-, - - RI may form with the carbon in alpha of one nitrogen containing a - (CH2) n - ring, uninterrupted or interrupted by one or more -O-, -S- or -NH-, - R3 represents a carboxyl group, -COOR5, -CONHR5, -COR5, -CONRSR1, SO2R5, or -CN-R4 represents a carboxyl group, -COOR6, -CONHR6, -COR6, -CONR6R2, or SO2R6, io-R5 and R6, which may be identical or different, represent an alkyl radical; C1-C22 linear or branched may contain from 1 to 3 oxygen atoms; a C 3 -C 8 cycloalkyl radical, unsubstituted or substituted with C 1 -C 4 alkyl radicals; said radicals R5 and R6 may contain an alkyl sulphonate radical in its acidic or salified form or one or two hydroxyl radicals; Z represents the group - (CH 2) 1, which is interrupted or interrupted by -O-, -S- or by -NR 3 -, and / or unsubstituted or substituted by one or two C 1 -C 6 alkyl radicals; R 1 is a C 1 -C 5 alkyl radical which may contain an alkyl sulphonate radical in its acidic or salified form or one or two hydroxyl radicals; N is 1-2; m is 1-7; - 1 is 1-4; with at least one or two of R1, R2, R5, R6 and R, containing - either an alkyl sulphonate radical in its acidic or salified form - or one to two hydroxy radicals; with the proviso that: (i) when n = 2, R1, R5 or R6 is an alkyl diradical or R1 and R2 together with 2 nitrogen atoms form a cyclic divalent radical - (CH2) n, -, (ii) R1 and R2 are not simultaneously a hydrogen atom; (iii) when R3 is -ON, then at least one of R1, R2, or R6 must contain an alkyl sulphonate group in its acidic or salified form. The compounds of formula (1) may be in the geometric isomeric forms E, E-, E, Z- or Z, Z-.

Preferred compounds of formula (1) are those for which the following conditions are met: R1 is hydrogen; a linear or branched C1-C8 alkyl radical which may contain from 1 to 3 oxygen atoms, R2 denotes a linear or branched C1-C8 alkyl which may contain from 1 to 3 oxygen atoms or a C5-C6 cycloalkyl R 3 denotes a group -COOR 5, -CN or -CONHR 5, R 4 denotes a group -OOR 6, -CONHR 6 or -SO 2 R 6, R 5 denotes a linear or branched C 1 -C 12 alkyl which may contain from 1 to 3 oxygen atoms, n is 1 or 2. The preferred compounds of formula (1) with one or two alkyl sulphonate radicals are those of the following formulas (a) to (y): ## STR5 ## (b) ## STR5 ## wherein (d) / OH (c) ## STR1 ## 1H - ,,, / N S'O_ + NaH

e0-0 O (1) Na + Na a) OO N \ iS'0 0H H O

## EQU1 ##

O 'O H CU II

S ~ \ N ~ H N (s) (r) O HO S

## STR2 ## Preferred compounds of the formula ## STR1 ## where: ## STR1 ## (1) hydroxy groups are those of formulas (z) to (be): K + HOC / ~ OvO ~ (Z) RN = 1165999-68-7 OH H HON ~ s'O III O (ab) O OH HO ~ O ~ \ OH OO / N / / OOH HOC / N Off / (ac) O (ad) O OH NO (af) OH

H 0 0 HON / / Omo / HO (ae) 9 OH Ov0OH HO00 N 0 (ag) OO, (ah) HO OH OH (ai) (aJ) OH OH Ov0 ~ / Ov0 HO ~ -'- ## STR5 ## in which: ## STR2 ## ## STR2 ## O (a) O (OH) O (O OH) O (OH) O (OH) OH O OH \ Name / HO '' '' -NNON 11 N \ \ 0OH HO 0 \ \ Name / O (av) OH HH \ i 0 \ \ NN 0 OO (aw)

## STR2 ## ## STR2 ## ## STR2 ## N H OH (az) N HH II HOC II / N Name / \ / N / / N ~ / \ OH (ba) N OH N O (bb) OH 1 Ov00 N ~ ON (bc) NI OH H OH HINI NOO (BE) INI The preferred compounds of formula (II) are those for which the following conditions are met: RI denotes hydrogen; a linear or branched C1-C10 alkyl which may contain from 1 to 3 oxygen atoms, R2 denotes a linear or branched C1-C10 alkyl which may contain from 1 to 3 oxygen atoms; C 5 -C 6 cycloalkyl, R 3 is -000R 5 or CN, R 4 is -000R 6 or -SO 2 R 6, R 5 is straight or branched C 1 -C 12 alkyl which may contain from 1 to 3 oxygen atoms, Z is - (CH2) 3 substituted or not by two CH3 groups, n is 1 or 2.

The preferred compounds of formula (II) are those of the following formulas (bf) to (bq): ## STR2 ## bk) HO HO HN (bm) OO. ## STR5 ## wherein N (b) (OH) n OH (bb) (bp)

From the two families of structures (1) and (II), the following derivatives will be chosen more particularly: ## STR2 ##

/ OOH O (ac) HO ~~ N \ S O III O 10 (ab) OH O (ak)

N HO N O

## STR2 ## ## STR1 ## ## STR2 ## ## STR2 ##

## STR5 ## wherein: The derivatives of formulas (1) may be prepared according to a method described in US Pat. No. 4,045,229, US Pat. No. 4,191,999 and US Pat. No. 3,010,018 according to the following scheme (route 1): or according to a method described in US Pat. WO 0007989 and according to the following scheme (lane 2): in which the radicals R 1, R 2, R 3 and R 4 have the meaning of formula (1).

The derivatives of formulas (II) can be prepared according to a method described in IP.COM Journal 9 (5A), 29-30 (2009) according to the following scheme: in which the radicals R1, R2, R3, R4 and Z have the meaning of formula (II).

Some of the hydrophilic or water-soluble merocyanine compounds according to the invention are novel and constitute another subject of the invention.

It is:

(1) compounds of formula (1) with one or two alkyl sulphonate radicals and for which R 1, R 2, R 5 and R 6 are different from an alkyl radical containing from 1 to 3 oxygen atoms with the exception of: a derivatives for which R 1 and R 2 together with nitrogen form a ring containing the group - (CH 2) r 1 -, uninterrupted or interrupted by one or more -O-, -S- or -NH- and b / derivatives of formulas (i), (j) and (m). Route 2 (VII) (IV) I 2 Toluene (-H 2 O) cate: Amine, AcOH (1) / R 3 R 4 + s (2) compounds of formula (1) with 1 to 4 hydroxy radicals and for which R 1, R2, R5 and R6 are different from an alkyl radical containing from 1 to 3 oxygen atoms with the exception of compound (z).

(3) compounds of formula (II).

(4) compounds of formula (1) for which at least one of the radicals R1, R2, R5 and R6 has from 1 to 3 oxygen atoms in the alkyl radical.

The hydrophilic or hydrosoluble merocyanine filter or filters in accordance with the invention may be present in the compositions according to the invention at a concentration of between 0.1 and 100/0, preferably between 0.2 and 50/0 by weight by weight. relative to the total weight of the composition.

The compositions in accordance with the invention may comprise, in addition, other additional organic UV or inorganic UV screening agents active in water-soluble or fat-soluble UVA and / or UVB or insoluble in the cosmetic solvents commonly used. Of course, those skilled in the art will take care to choose the optional additional filters and / or their amounts in such a way that the advantageous properties intrinsically attached to the compositions in accordance with the invention are not, or not substantially, impaired. by the addition or additions envisaged, notably the improvement of the photostability of the dibenzoylmethane derivative.

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

Examples of organic UV filters that may be mentioned are those referred to below under their INCI name: ## EQU1 ## 50 Derivatives of para-aminobenzoic acid: PABA, Ethyl PABA, Ethyl Dihydroxypropyl PABA, Ethylhexyl Dimethyl PABA sold in particular under the US Pat. "ESCALOL 507" by ISP, Glyceryl PABA, PEG-25 PABA sold under the name "UVINUL P25" by BASF,

Salicylic derivatives: Homosalate sold under the name "Eusolex HMS" by Rona / EM Industries, Ethylhexyl Salicylate sold under the name "Neo Heliopan OS" by SYMRISE, Dipropylene glycol salicylate sold under the name "DIPSAL" by SCHER, TEA Salicylate, sold under the name "NEO HELIOPAN TS" by SYMRISE,

Cinnamic derivatives: Ethylhexyl methoxycinnamate sold in particular under the trade name "PARSOL MCX" by DSM NUTRITIONAL PRODUCTS., Isopropyl Methoxy cinnamate, Isoamyl Methoxy cinnamate sold under the trade name "NEO HELIOPAN E 1000" by SYMRISE, Cinoxate, DEA Methoxycinnamate, Diisopropyl Methylcinnamate, Glyceryl Ethylhexanoate Dimethoxycinnamate Derivatives of 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: 35 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, 40 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, 45 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, 50 Benzylidene camphor derivatives: 3-Benzylidene camphor manufactured under the name" 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 CHIMEX, Camphor Benzalkonium Methosulfate manufactured under the name "MEXORYL SO" by CHIMEX, Terephthalylidene Dicamphor Sulfonic Acid manufactured under the name "MEXORYL SX" by CHIMEX, Polyacrylamidomethyl Benzylidene Camphor manufactured under the name "MEXORYL SW" by CHIMEX,

Derivatives of phenyl benzimidazole: Phenylbenzimidazole Sulfonic Acid sold in particular under the trade name "Eusolex 232" by Merck, Disodium Phenyl Dibenzimidazole Tetrasulfonate sold under the trade name "Neo Heliopan AP" by SYMRISE,

Derivatives of phenylbenzotriazole: Drometrizole Trisiloxane sold under the name "Silatrizole" by Rhodia Chimie, methylene bis-benzotriazolyltetramethylbutylphenol, 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, 2s 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 30 T150" by BASF , Diethylhexylbutamido 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'-aminoethyl) dineopentyl amino benzalmalonate) -s-triazine, dineopentyl 2,4-bis (4'-amino benzalmalonate) -6- (n-butyl 4-aminobenzoate) -s-triazine 2,4-bis (4 ') -butylaminobenzoate) -6 - [(3- {1,3,3,3-tetramethyl-1- [(trime) thylsilyl) oxy] disiloxanyl} propyl) amino] -s-triazine symmetrical triazine filters described in US Pat. No. 6,225,467, Application 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 (in particular 2,4,6-tris ( biphenyl-4-yl-1,3,5-triazine) and 2,4,6-tris (terphenyl) -1,3,5-triazine which is incorporated in the applications of Beiersdorf WO06 / 035000, 45 WO06 / 034982 , WO06 / 034991, WO06 / 035007, WO2006 / 034992, WO2006 / 034985.

Anthranilic Derivatives: Menthyl anthranilate sold under the trade name "NEO 50 HELIOPAN MA" by SYMRISE, Imidazoline derivatives: Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate,

Derivatives of benzalmalonate: Di-neopentyl 4'-methoxybenzalmalonate Polyorganosiloxane with benzalmalonate functions such as Polysilicone-15 sold under the trade name PARSOL SLX by HOFFMANN LA ROCHE Derivatives of 4,4-diarvlbutadiene: 1,1-dicarboxy (2 2'-Dimethyl-propyl) -4,4-diphenylbutadiene Derivatives of benzoxazole: 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) -imino] -6- (2-dimethylpropyl) -4,4-diphenylbutadiene -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 selected from ethylhexyl methoxycinnamate homosalate ethylhexyl salicylate, octocrylene, phenylbenzimidazole sulfonic acid, benzophenone-3, benzophenone-4, benzophenone-5, 2- (4-diethylamino-2-hydroxybenzoyl) benzoate. hexyl. 4-Methylbenzylidene camphor, Terephthalylidene Dicamphor Sulfonic Acid, Disodium Phenyl Dibenzimidazole Tetrasulfonate, Ethylhexyl triazone, Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine Diethylhexyl Butamido Triazone, 2,4,6-tris (biphenyl-4-yl) triazine 2,4,6-tris (dineopentyl 4'-amino benzalmalonate) -s-triazine 2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazine, 40 2,4-bis ( Dineopentyl 4'-amino benzalmalonate) -6- (n-butyl 4'-aminobenzoate) -s-triazine 2,4-bis (n-butyl 4'-aminobenzoate) -6 - [(3- {1,3, 3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -s-triazine Methylene bis-Benzotriazolyl tetramethylbutylphenol, 45-Drometrizole Trisiloxane Polysilicone-15 Di-neopentyl 4'-methoxybenzalmalonate 1,1-dicarboxy (2 2,4-bis [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino] -6- (2-ethylhexyl) -2- (2'-dimethylpropyl) -4,4-diphenylbutadiene imino-1,3,5-triazine ls and mixtures thereof.

The complementary inorganic filters are chosen from coated or uncoated metallic oxide pigments, the average size of the primary particles of which is preferably between 5 nm and 100 nm (preferably between 10 nm and 50 nm), for example dye pigments. titanium oxide (amorphous or crystallized in rutile and / or anatase form), iron, zinc, zirconium or cerium which are all UV photoprotective agents well known per se. The pigments may be coated or uncoated.

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

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

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

The silicones used for coating the pigments suitable for the present invention are preferably selected from the group containing alkyl silanes, polydialkylsiloxanes, and polyalkylhydrogensiloxanes. More preferably still, the silicones are selected from the group containing octyl trimethyl silane, polydimethylsiloxanes and 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, 45 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 21 - silica and iron oxide such as that the product "SUNVEIL F" of the company I KEDA, - 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 the company KEMIRA, - alumina and aluminum stearate such as the product" MICROTITANIUM DIOXIDE MT 100 TV, MT 100 TX, MT 100 Z, MT-01 from TAYCA, the products "Solaveil CT -10 W "," Solaveil CT 100 "and" Solaveil CT 200 "from the company UNIQEMA, - silica, alumina and alginic acid such as the product" MT-100 AQ "from the company TAYCA, - aluminum alumina and aluminum laurate, such as the product "MICROTITANIUM DIOXIDE MT 100 S" from the company TAYCA, iron oxide and iron stearate such as the product "MICROTITANIUM DIOXIDE MT 100 F" from the TAYCA company, - zinc oxide and zinc stearate such as the product "BR351" from TAYCA, 20 - 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, - silica, alumina, aluminum stearate and treated with a silicone such as the product "STT-30-DS" the company TITAN KOGYO, 25 - silica and treated with a silicone such as the product "UV-TITAN X 195" Kemira company, or the product SMT-100 WRS TAYCA company. of alumina and treated with a silicone such as the products "TIPAQUE TTO-55 (S)" from ISHIHARA, or "UV TITAN M 262" from KEMIRA, of triethanolamine such as the product "STT-65- S "of the company TITAN KOGYO, - stearic acid such as the product" TIPAQUE TTO-55 (C) "of the company ISHIHARA, - sodium hexametaphosphate such as the product" MICROTITANIUM DIOXIDE MT 150 W "of the company TAYCA. Other titanium oxide pigments treated with a silicone are preferably TiO 2 treated with octyl trimethyl silane and having an average particle size of between 25 and 40 nm, such as that sold under the trade name " T 805 "by the company Degussa Silices, the TiO2 40 treated with a polydimethylsiloxane and whose average elementary particle size is 21 nm, such as that sold under the trade name" 70250 Cardre UF TiO2S13 "by CARDRE, TiO2 anatase / rutile treated with a polydimethylhydrogensiloxane and whose average elementary particle size is 25 nm such as that sold under the trade name "MICRO TITANIUM DIOXIDE USP GRADE HYDROPHOBIC" by the company COLOR TECHNIQUES.

The uncoated titanium oxide pigments are for example sold by the company Tayca under the trade names 50 "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 MIYOSHI KASEI under the name "UFTR", by the company TOMEN under the name "ITS" and by the company TIOXIDE under the name "TIOVEIL AQ".

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

The coated zinc oxide pigments are, for example, those marketed under the name "Z-COTE HP1" by the company Sunsmart (ZnO coated with dimethicone); those marketed under the name "Zinc Oxide CS-5" by the company Toshibi (ZnO coated with polymethylhydrogenosiloxane); those marketed under the name "Nanogard Zinc Oxide FN" by Nanophase Technologies (in dispersion at 400/0 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 cyclopolymethylsiloxane / polydimethylsiloxane oxyethylenated, containing 300/0 or 500/0 of silica-coated zinc nano-oxides 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 the company Shin-Etsu (ZnO coated with silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane); those marketed under the name "Escalol Z100" by the company ISP (ZnO treated alumina and dispersed in the mixture methoxycinnamate ethylhexyl / copolymer PVP-hexadecene / methicone); Those marketed under the name "Fuji ZnO-SMS-10" by Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane); those marketed under the name "Nanox Gel TN" by Elementis (ZnO dispersed at 550/0 in benzoate of C12-C15 alcohols with hydroxystearic acid polycondensate). The uncoated cerium oxide pigments are sold for example under the name "COLLOIDAL CERIUM OXIDE" by the company RHONE POULENC.

Uncoated iron oxide pigments are for example sold by the company ARNAUD under the names "Nanogard WCD 2002 (FE 45B)", "Nanogard IRON FE 45 BL AQ", "Nanogard FE 45R AQ," NANOGARD WCD 2006 (FE 45R) ", or by the company MITSUBISHI under the name" TY-220 "50 The coated iron oxide pigments are for example sold by ARNAUD under the names" NANOGARD WCD 2008 (FE 45B FN) " , "NANOGARD WCD 2009 (FE 45B 556)", "NANOGARD FE 45 BL 345", "NANOGARD FE 45 BL", or by BASF under the name "TRANSPARENT IRON OXIDE".

Mention may also be made of mixtures of metal oxides, in particular titanium dioxide and cerium dioxide, including the titanium dioxide / cerium-coated cerium-aluminum alloy 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, silica and glycerin such as the product "M 211" sold by KEMIRA.

The additional UV filters are generally present in the compositions according to the invention in proportions ranging from 0.01 to 200% by weight relative to the total weight of the composition, and preferably ranging from 0.1 to 100% by weight. by weight relative to the total weight of the composition.

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

The fatty substances may consist of an oil or a wax other than the apolar waxes as defined above or mixtures thereof. By oil is meant a liquid compound at room temperature. By wax is meant a compound that is solid or substantially solid at room temperature and whose melting point is generally greater than 35 ° C. As oils, there may be mentioned mineral oils (paraffin); vegetable (sweet almond oil, macadamia oil, blackcurrant seed oil, jojoba oil); synthetic compounds such as perhydrosqualene, alcohols, fatty amides (such as isopropyl lauroyl sarcosinate sold under the name "Eldew SL-205" 40 by Ajinomoto), fatty acids or esters, such as benzoate of alcohols, C12-C15 sold under the trade name "Finsolv TN" or "Witconol TN" by the company WITCO, 2-ethylphenyl benzoate as the commercial product sold under the name X-TEND 226® by the company ISP, the palmitate of octyl, isopropyl lanolate, triglycerides, including those of capric / caprylic acids, dicaprylyl carbonate sold under the name "Cetiol CC" by the company Cognis), oxyethylenated or oxypropylenated esters and fatty ethers; silicone oils (cyclomethicone, polydimethylsiloxane or PDMS) or fluorinated oils, polyalkylenes, trialkyl trimellitates such as tridecyl trimellitate. As wax compounds, mention may be made of carnauba wax, beeswax, hydrogenated castor oil, polyethylene waxes and polymethylene waxes, such as that sold under the name Cirebelle 303 by the company SASOL. Among the organic solvents, mention may be made of lower alcohols and polyols. These can be selected from glycols and glycol ethers such as ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol or diethylene glycol. As hydrophilic thickeners, mention may be made of carboxyvinyl polymers such as Carbopols (Carbomers) and Pemulen (acrylate / C10-C30-alkylacrylate copolymer); polyacrylamides, for example crosslinked copolymers sold under the names Sepigel 305 (CTFA name: polyacrylamide / C13-14 isoparaffin / Laureth 7) or Simulgel 600 (CTFA name: acrylamide / sodium acryloyldimethyltaurate copolymer / isohexadecane / polysorbate 80) by the company Seppic; polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid, optionally crosslinked and / or neutralized, such as poly (2-acrylamido-2-methylpropanesulphonic acid) marketed by Hoechst under the trade name "Hostacerin AMPS" ( CTFA name: ammonium polyacryloyldimethyl taurate or SIMULGEL 800 sold by the company SEPPIC (CTFA name: sodium polyacryolyldimethyl taurate / polysorbate 80 / sorbitan oleate); copolymers of 2-acrylamido-2-methylpropanesulfonic acid and hydroxyethyl acrylate, such as SIMULGEL NS and SEPINOV EMT 10 marketed by the company SEPPIC, cellulose derivatives such as hydroxyethylcellulose, polysaccharides and especially gums such as Xanthan gum, water-soluble or water-dispersible silicone derivatives such as acrylic silicones, silicone polyethers and cationic silicones and mixtures thereof.

As lipophilic thickeners, mention may be made of synthetic polymers such as the poly C10-C30 alkyl acrylates sold under the name "IPA INTELIMER 13-1" and "INTELIMER IPA 13-6" by the company Landec, or the modified clays such as The sector and its derivatives, such as the products marketed under the name of Bentone.

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

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

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 HIE).

As emulsifying surfactants that may be used for the preparation of W / O emulsions, mention may be made, for example, of alkyl esters or ethers of sorbitan, of glycerol or of sugars; silicone surfactants such as dimethicone copolyols such as the mixture of cyclomethicone and dimethicone copolyol, sold under the name "DC 5225 C" by Dow Corning, and alkyl dimethicone copolyols such as Laurylmethicone copolyol sold under the name " Dow Corning 5200 Formulation Aid "by Dow Corning; Cetyl dimethicone copolyol such as the product sold under the name Abil EM 90R by the company Goldschmidt and the mixture of cetyl dimethicone copolyol, polyglycerol isostearate (4 moles) and hexyl laurate sold under the name ABIL WE 09 by the company Goldschmidt. One or more coemulsifiers may also be added, which advantageously may be selected from the group consisting of alkylated polyol esters. Polyol alkyl esters that may especially be mentioned include polyethylene glycol esters such as PEG-30 dipolyhydroxystearate, such as the product sold under the name Arlacel P135 by the company ICI.

Examples of glycerol and / or sorbitan esters that may be mentioned are polyglycerol isostearate, such as the product sold under the name Isolan GI 34 by the company Goldschmidt; sorbitan isostearate, such as the product sold under the name Arlacel 987 by the company ICI; sorbitan isostearate and glycerol, such as the product sold under the name Arlacel 986 by the company ICI, and mixtures thereof.

For the HIE emulsions, mention may be made, for example, as emulsifiers, of nonionic emulsifiers such as oxyalkylenated (more particularly polyoxyethylenated) fatty acid esters of glycerol; oxyalkylenated fatty acid esters 45 and sorbitan; oxyalkylenated fatty acid esters (oxyethylenated and / or oxypropylenated) such as the PEG-100 Stearate / Glyceryl Stearate mixture marketed for example by the company ICI under the name Arlacel 165; oxyalkylenated fatty alcohol ethers (oxyethylenated and / or oxypropylenated); sugar esters such as sucrose stearate; fatty alcohol and sugar ethers, especially 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, sold 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 Io Montanov 202 by the company Seppic. According to one particular embodiment of the invention, the mixture of the alkylpolyglucoside as defined above with the corresponding fatty alcohol may be in the form of a self-emulsifying composition, as described, for example, in WO- A-92/06778.

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

The compositions according to the invention find their application in a large number of treatments, in particular cosmetics, of the skin, lips and hair, including the scalp, in particular for the protection and / or care of the skin, lips and / or hair, and / or for makeup of the skin and / or lips. Another object of the present invention is 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 skin care 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 can 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 45 according to the invention are well known to those skilled in the art and include non-aerosol pumps or "atomizers", aerosol containers comprising a propellant and aerosol pumps using compressed air as a propellant. These are described in US 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 anti-glycation agents; the soothing agents; the NO-synthase inhibitors; agents stimulating the synthesis of dermal or epidermal macromolecules and / or preventing their degradation; agents stimulating the proliferation of fibroblasts; agents stimulating the proliferation of keratinocytes; - muscle relaxants; tensing agents, mattifying agents, keratolytic agents, desquamating agents; - 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 agents and / or regrowth of hair-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 40 according to the invention are not, or substantially not, altered by the addition or additions envisaged.

The skilled person will choose the active agent (s) depending on the desired effect on the skin, hair, eyelashes, eyebrows, nails. The composition may also comprise at least one ingredient such as blooming fillers or agents promoting the natural coloration of the skin, intended to 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 agents or anti-seborrhoeic agents, astringent agents.

s OTHER ADDITIONAL INGREDIENTS

The composition may further comprise at least one additional ingredient intended to complete the biological effect of these active ingredients 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 keratinic substances, it may be advantageous to incorporate other additional ingredients into the compositions of the invention.

In particular, these additional ingredients may confer an immediate visual effect that will be relayed by the biological effect of the assets mentioned above. They can also, 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 2 generally reflects a matting effect.

The matting agent may in particular be chosen from a rice starch or a starch of INCI name: ZEA MAYS (CORN) STARCH, as in particular the product sold under the trade name "FARMAL CS 3650 PLUS 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 mattifying agents that may be mentioned include: rice or corn starch, in particular an aluminum starch octenyl succinate marketed under the trademark Dry Flo® by the company National s Starch, kaolinite; - silicas; - talc; an extract of pumpkin seeds as marketed under the name io Curbilene® by the company Indena; cellulose microbeads as described in patent application EP 1 562 562; fibers, such as silk, cotton, wool, flax, cellulose fibers extracted especially 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, resorbable synthetic fibers, and mixtures thereof described in patent application EP 1 151 742; microspheres of expanded acrylic copolymers such as those sold by EXPANCEL under the names Expancel 5510, 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 Miyoshi Silica beads SB150, average size 5 microns and refractive index 1.45, - polytetrafluoroethylene powders, such as PTFE ceridust 9205F Clariant of average size 8 microns and refractive index 1.36, - silicone resin powders as the Silicon resin Tospearl 145A of 35 GE Silicone of average size 4.5 microns and refractive index 1.41, the powders of acrylic copolymers, in particular of methyl poly (meth) acrylate, such as PMMA particles J urymer MBI of Nihon Junyoki of average size 8 microns and refractive index 1.49, or the particles Micropearl M1000 and F 80 EDO of the company Matsumoto Yushi-Seiyaku, 40 - wax powders such as particles Paraffin wax microease 114S of micropowders having a mean size of 7 microns and a refractive index of 1.54, polyethylene powders, in particular comprising at least one ethylene / acrylic acid copolymer, and in particular consisting of ethylene / acrylic acid copolymers such as the Flobeads EA 209 particles. of Sumitomo 45 (average size 10 microns and refractive index 1.48), elastomeric crosslinked organopolysiloxane powders coated with silicone resin, in particular silsesquioxane resin, as described for example in US Pat. No. 5,538,793 Such elastomer powders are sold under the names "KSP-100", "KSP-101", "KSP-102", "KSP-103", "KSP-104", "KSP-105" by the company SHIN ETSU, and - composite powders talc / titanium dioxide / alumina / silica, such as those sold under the name Coverleaf® AR-80 by the company Catalyst & s Chemicals, - mixtures thereof, - compounds that absorb and / or adsorb sebum as described in the application for Patent FR 2 869 796. Mention may in particular be made of: silica powders, for example 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" sold by the company ASAHI GLASS; amorphous mixed silicate powders, in particular aluminum and magnesium, such as, for example, that marketed under the name "NEUSILIN UFL2" by the company Sumitomo. polyamide (nylon®) powders, for example "ORGASOL® 4000" marketed by Arkema, and acrylic polymer powders, in particular 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 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, an extract of pumpkin seeds, a rice or maize starch, kaolinite, silicas, talc, polyamide powders, polyethylene powders and copolymer powders. acrylics, expanded acrylic copolymer microspheres, silicone resin microbeads, mixed silicate particles, and mixtures thereof.

Characters with a blooming effect These fillers can be any material that can modify wrinkles by its intrinsic physical properties and mask 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 Myochi's Silica BeadsO SB 150 and SB 700 with a mean size of 5 μm, and SUNSPHERESO series H by Asahi Glass, such as H33, H51 with a size of 3.5 and 5 μm respectively, and hollow hemispherical particles of silicone resins such as NLK 5000, NLK 5060 and NLK 5100 from Takemoto Oil and Fat, described in particular in EP-A-1579849. silicone resin powders such as, for example, SILICON resin TospearI0 145 A DE GE silicone of average size of 4.5 μm. powders of acrylic copolymers, in particular of methyl poly (meth) acrylate, for instance PMMA Jurimer MBI0 particles of Nihon Junyoki with an average size of 8 μm, the hollow spheres of PMMA sold under the name COVABEADO LH 85 by the company Wackherr and the expanded vinylidene / acrylonitrile / methylene methacrylate microspheres sold under the name ExpanceI0. - Wax powders such as paraffin wax 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 1000, KSP 1010, KSP 1020, KSP 1030, KSP 1040 and KSP 1050 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 microcapsules of glass or ceramics. Synthetic hydrophilic or hydrophobic fibers, whether natural, mineral or organic, such as silk, cotton, wool, flax, cellulose fibers extracted particularly from wood, vegetables or algae, polyamide (NylonO), modified cellulose, poly-p-phenylene terephtamide, acrylic, polyolefin, glass, silica, aramid, carbon, polytetrafluoroethylene (TeflonO), 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. - spherical elastomeric cross-linked silicones such as Trefil E-505C® or E-506 CO from Dow Corning. abrasive fillers which, by a mechanical effect, provide a smoothing of the cutaneous microrelief, such as abrasive silica, for example abrasive SPO from Semanez or powders of nuts or shells (apricot, walnut for example from Cosmetochem).

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

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 may be of any shape and in particular be spherical or non-spherical. More preferably, these fillers are nonspherical. The "soft-focus" fillers may be chosen from silica and silicate powders, in particular alumina powders, polymethyl methacrylate (PMMA) powders, talc, silica / TiO2 or silica / zinc oxide composites, and powders. polyethylene, starch powders, polyamide powders, styrene / acrylic copolymer powders, silicone elastomers, and mixtures thereof.

In particular, mention may be made of talc with a mean size of less than or equal to 3 microns, for example talc of average size in number of 1.8 micron and in particular that sold under the trade name Talc P30 by the company Nippon Talc , Nylon® 12 powder, in particular that sold under the name Orgasol 2002 Extra D Nat CosO by the company Atochem, silica particles treated on the surface with a mineral wax 1 to 2% (INCI name: hydrated silica (and) paraffin) ) such as those marketed by the company Degussa, amorphous silica microspheres, such as those sold under the name Sunsphere for example reference H-530 by the company Asahi Glass, and silica micro-beads such as those sold under the name SB-7000 or SB-1500 by the company Miyoshi, this list is not limiting. The concentration of these fillers having an effect on the signs of aging in the compositions according to the invention may be between 0.1 and 40%, or even between 0.1 and 20% by weight relative to the total weight of the composition. .

50 Aqents favoring the naturally rosy coloration of the skin.

a self-tanning agent, that is to say an agent which, applied on the skin, in particular on the face, makes it possible to obtain a tanning effect of a more or less similar appearance to that which may result from an exposure prolonged in the sun (natural tanning) or under a UV lamp; an additional coloring agent, that is to say any compound having a particular affinity for the skin, enabling it to confer on the latter a lasting, 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 mixtures thereof.

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 30 903 342. DHA will preferably be used.

DHA may be used in free form and / or encapsulated for example in lipid vesicles such as liposomes, in particular described in application WO 97/25970. In general, the self-tanning agent is present in an amount ranging from 0.01 to 20% by weight, and preferably in an amount of between 0.1 and 10% of the total weight of the composition.

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

These dyes may be chosen from synthetic direct dyes or natural dyes. These dyes may be chosen, for example, from red or orange dyes of the fluoran type such as those described in the patent application FR2840806. Mention may be made, for example, of the following dyes: tetrabromofluorescein or eosin known under the name CTFA: Cl 45380 or 50 Red 21 34 35 phloxin 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 salt) or Red 22; the sodium salt of phloxine B, known as CTFA name: Cl 45410 (Na salt) or Red 28 - the sodium salt of diiodofluorescein known as CTFA: Cl 45425 (Na salt) or Orange 11; io - erythrosine known as CTFA: Cl 45430 or Acid Red 51. - Phloxine known as CTFA: Cl 45405 or Acid Red 98.

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

These dyes may also be chosen from indole derivatives such as the monohydroxyindoles as described in the patent FR2651126 (20 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 agents or exfoliating agents Exfoliants used in rinsed compositions according to the invention include, for example, exfoliating or exfoliating particles of mineral, vegetable or organic origin. Thus, for example, beads or polyethylene powder, nylon powder, polyvinyl chloride powder, pumice, crushed apricot kernels or nut shells, can be used. sawdust, glass beads, alumina, and mixtures thereof. ExfogreenO of Solabia (bamboo extract), strawberry akenes (Greentech strawberry Akenes), peach kernel powder, apricot kernel powder, and finally In the field of abrasive-effect vegetable powders, mention is made of cranberry (cranberry) powder.

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 and 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 SYNTHESIS: EXAMPLE 1 Preparation of methyl (2Z, 4E) -5-bis (2-hydroxyethyl) aminol-50 (methylsulfonyl) penta-2,4-dienoate 30 OH O ~ O ~ HO ~~ N ~ \ SO III O (ab) First step: Preparation of methyl (2Z, 4E) -5-facetyl (phenyl) aminol-2- (methylsulfonyl) penta-2,4-dienoate: The mixture is heated at 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 what in the next step. Second step: Preparation of the compound of Example 1: A solution of the preceding product (2.3 g, 7.1 × 10 -3 moles) and diethanolamine (10.33 g, 6.23 × 10 -3 moles) was 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 eigenfractions of the derivative of Example 1 are thus obtained in the form of a pale yellow powder: Mp: 73-76 ° C. UV (Ethanol): mp = 367 nm EXAMPLE 2 Preparation of Bis (4-hydroxybutyl) (2E) -3- (dimethylamino) prop-2-en-1-ylidenelpropanedioate O-O (O)

First step: Preparation of bisf4- (benzyloxy) butyllpropanedioate: A heterogeneous mixture of 4-benzyloxy-1-butanol (9.5 g, 52.8 × 10 -3 mole) and acid is heated at 50 ° C. with stirring. malonic (2.5 ml, 24x10-3 mol). 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). 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: 740/0) of the clean fractions of bis [4- (benzyloxy) butyl] propanedioate are recovered in the form of a pale yellow oil and used as such in the next step.

Second stage: 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-C cartridge at 100/0; 1 ml / min; 40 ° C). After vacuum distillation of the ethanol, 4.31 g (yield: 990/0) 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 2

In a nitrogen-inerted reactor surmounted by a Dean Starck, the preceding product (4.31 g, 0.0173 mole) and the n-octylamine catalysts (86 μL, 0.03 equi) were refluxed. 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 2 in the form of an orange oil: UV (Ethanol): X max = 374 nm, El% = 1600 EXAMPLE 3 Preparation of 2- {f (2E, 4E) -2-cyano-54diethylamino) penta-2,4-dienoyloxy} ethanesulfonate sodium salt:

Na + First step: Preparation of sodium 2- {(2E, 4E) -2-cyano-5- (diethylamino) penta-2,4-dienoyloxy} ethanesulfonate:

While stirring, thionyl chloride (15 ml) was reacted with cyanoacetic acid (2 g, 0.024 mol) and heated at 40 ° C for 2 hours. 50 ml of toluene are added and concentrated under vacuum until a remaining volume of 10 ml is obtained. The sodium salt of isethionic acid (3.48 g, 0.024 mol) is added and the toluene is refluxed. The heterogeneous mixture is refluxed for 20 hours. After cooling, the reaction mixture is filtered. The solid is taken up in water and the aqueous phase is washed with ethyl acetate. The aqueous phase is brought to neutral pH with 2N sodium hydroxide. 1.6 g of a beige powder containing approximately 300/0 by weight of salts are recovered. There is thus obtained the sodium salt of 2 - {[(2E, 4E) -2-cyano-5- (diethylamino) penta-2,4-dienoyloxy} ethanesulfonate used as it is in the following step.

Second step: Preparation of the compound of Example 3

In a reactor inert with nitrogen and surmounted by a Dean Starck, the preceding product (1 g, 0.0032 mol) is refluxed and the catalysts diethylamine (34 μL, 0.1 equiv) and acetic acid ( 19 μL, 0.1 equiv) in 5 mL of toluene. N, N-diethyl acrolein (0.41 ml, 0.0032 mole) was 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 for 45 hours. After cooling, the reaction mixture is filtered and the solid obtained is washed with diisopropyl ether. After chromatography on a reverse phase column, 212 mg (yield: 22%) of the derivative of Example 3 is obtained in the form of a beige solid: UV (H 2 O): X max = 370 nm, El% = 1200

III / EXAMPLES OF FORMULATION

Compositions A and B were produced: Ingredients Ex A Ex BE DTA 0.1 0.1 Monocetyl phosphate 1 1 monopotassium water Deionized water qs q 100 100 Triethanolamine 0.3 0.3 Preservatives 1.2 1,2 C12-C15 alkyl benzoate 20 Preservatives 0.25 0.25 Stearic acid 1.5 1.5 Mixture Mono / Distearate 1 1 Glyceryl / Polyethylene glycol stearate (100 EO) Cetyl alcohol 0.5 0.5 Cetearyl alcohol and cetearyl 2 2 glucoside Dimethicone (350 cst) 0.5 0.5 Triethanolamine 0.45 0.45 Drometrizole Trisiloxane 2 2 Avobenzone (Parsol 1789) 2 2 Merocyanine of formula (y) 1.5 0 Merocyanine of formula 0 1.5 (ac) 2 , 4,6-tris [p- (2'-ethylhexyl-1'-2-oxycarbonyl) anilino] -1,3,5-triazine Isohexadecane 1 Copolymer 0.2 0.2 acrylic acid and C10-C30 alkyl methacrylate Xanthane 0.2 0.2 Cyclopentadimethylsiloxane 5

Claims (15)

REVENDICATIONS1. Composition comprising in a support cosmetically CLAIMS1. Composition comprising in a cosmetically acceptable support at least one UV filtering system, characterized in that it comprises: (1) at least one dibenzoylmethane derivative and (2) at least one hydrophilic or hydrosoluble merocyanine UV filter conforming to the one of the following formulas (1) and (II) or one of its isomeric forms E, E, Z, Z, E, Z: R 1 R 3 N -CHCH-CH C R 2 (N) In which: R1 and R2, which are identical or different, represent H; a linear or branched C1-C22 alkyl radical which may contain from 1 to 3 oxygen atoms; a C 3 -C 8 cycloalkyl radical, unsubstituted or substituted with C 1 -C 4 alkyl radicals; said radicals R1 and R2 may contain an alkyl sulphonate radical in its acidic or salified form or one to two hydroxy radicals; R1 and R2 may together with the nitrogen form a ring containing the - (CH2) m - group, uninterrupted or interrupted by one or more -O-, -S- or -NH-, - - RI may form with the carbon in alpha of nitrogen one ring containing the group - (CH2) n, -, uninterrupted or interrupted by one or more -O-, -S- or 2s by -NH-, - R3 represents a carboxyl group, -COOR5 , -CONHR5, -COR5, -CONRSR1, SO2R5, or -CN-R4 represents a carboxyl group, -COOR6, -CONHR6, -COR6, -CONR6R2, or SO2R6, R5 and R6, which may be identical or different, represent a radical; C1-C22 alkyl, linear or branched may contain from 1 to 3 oxygen atoms; a C 3 -C 8 cycloalkyl radical, unsubstituted or substituted with C 1 -C 4 alkyl radicals; said radicals R5 and R6 may contain an alkyl sulphonate radical in its acidic or salified form or one or two hydroxyl radicals; Z represents the group - (CH 2) 1, which is interrupted or interrupted by -O-, -S- or by -NR 3 -, and / or unsubstituted or substituted by one or two C 1 -C 6 alkyl radicals; R 1 is a C 1 -C 5 alkyl radical which may contain an alkyl sulphonate radical in its acidic or salified form or one or two hydroxyl radicals; 40 - n is 1-2; m is 1-7; - 1 is 1-4; with at least one or two of R1, R2, R5, R6 and R, containing - either an alkyl sulphonate radical in its acidic or salified form - or one to two hydroxy radicals; with the proviso that: (i) when n = 2, R1, R5 or R6 is an alkyl diradical or R1 and R2 together with 2 nitrogen atoms form a cyclic divalent radical in - (CH2) rr, -, (ii) R1 and R2 are not simultaneously a hydrogen atom; (iii) when R3 is -ON, then at least one of R1, R2, or R6 must contain an alkyl sulphonate group in its acidic or salified form. 2. Composition according to claim 1, wherein the compounds of formula (1) having one or two alkylsulfonate radicals are chosen from those of formulas (a) to (y) below and their isomeric forms E, E, Z, Z , E, Z: O (OH) O OH (O OH OH O) O (OH) O (OH) O (NaOH) N (h) OO OIS OHO v N 1 H - ,,, / N SAO_ Na 20 H e0-0 O (i) Na Na a) ON (k) ON (I) \ NO OH S ~ OO OH S ~ O Na 'Na + OOOO (m) O, O (OH) O (OH) O (O) O (O) SOOH OOH O (O) O (SO) O (SO) O OH SO / NN / OSO NN (u) - ;; Se.::- 0 10 0 Na '(v) s \ O 11 OH O 10 N Il K + 3. Composition according to claim 1, wherein the compounds of formula (1) having 1 to 4 hydroxyl groups are chosen from those of formulas (z) to (be): H0 0 0 s III (z) 0 O (ab) ## STR1 ## ## STR2 ## ## STR2 ## ## STR2 ## O (O) O (Y) O OH HON 0 O (af) OH 0 0OH H0 0 0 N (ag) ON, 0 0 ~ (ah) OH OH OH (aj) OH OH 0 0 0 0 HOC / NN HOC / NN OH OH O v0 N II ## STR5 ## 0, 0, 0 \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ \ NNOO (aq) OH HOO OH HO (t) (av) 546 NN II OH II HH ~, O \ \ N ~~ / N / / O ~ / ON \ \ NOH HH HO ~~ N \ \ Name / ## STR1 ## OH II 1 Ov0 ~, 0 \ \ N ~ ONNI (bc) OH HNOO (bd) OH H INI INI 4. Composition according to claim 1, wherein the compounds of formula (II) are chosen from those for which the following conditions are fulfilled: RI denotes hydrogen; a linear or branched C1-C10 alkyl may contain from 1 to 3 oxygen atoms, R2 denotes a linear or branched C1-C10 alkyl may contain from 1 to 3 oxygen atoms; C 5 -C 6 cycloalkyl, R 3 is -000R 5 or CN, R 4 is -000R 6 or -SO 2 R 6, R 5 is straight or branched C 1 -C 12 alkyl which may contain from 1 to 3 oxygen atoms, Z is - (CH2) 3 substituted or unsubstituted by two CH3 groups, n is 1 or 2. 5. Composition according to claim 4, wherein the compounds of formula (II) are chosen from those of formulas are those of formulas (bf) to (bq): N 20 (bf) O EXCLUDING ONOO ~ SI 1 OH ON (bh) ## EQU1 ## ## STR2 ## ## STR2 ## ## STR2 ## bn) (bo) oo OH N (bq) oo / HO N 6. Composition according to any one of claims 1 to 5, wherein the hydrophilic or hydrosoluble merocyanine UV-screening agent (s) is chosen from the following compounds: (v) NaOH HO ~~ N \ SO III O ° v ° OH ## STR2 ## wherein: a) OH OH (as) N II 0H N100 / \ / \ / N / OH OvO ~~ / O \ \ N ~ / NO (bc) OH HNOO (bd) OH H INI INI O ~ O ,, / OOHHN HO HO NN (bm) OH OH (bo) OH NHN HO N (bq) (bp) 7. Composition according to any one of claims 1 to 6, wherein the dibenzoylmethane derivative is 4- (tert-butyl) -4'-methoxy dibenzoylmethane or butyl methoxy dibenzoylmethane of the following formula: 8. Composition according to any one of claims 1 to 7, 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 commonly used cosmetic solvents. 9. The composition of claim 8, wherein the complementary organic filters are selected from anthranilates; cinnamic derivatives; salicylic derivatives, camphor derivatives; benzophenone derivatives; 1,3,13-diphenylacrylate derivatives; triazine derivatives; benzotriazole derivatives; benzalmalonate derivatives; debenzimidazole derivatives; imidazolines; bis-benzoazolyl derivatives; p-aminobenzoic acid derivatives (PABA); methylene bis (hydroxyphenyl benzotriazole) derivatives; benzoxazole derivatives; filter polymers and silicone filters; dimers derived from α-alkylstyrene; 4,4-diarylbutadienes; liposoluble merocyanine derivatives and mixtures thereof. 10. The composition as claimed in claim 8, characterized in that the organic UV screening agent (s) is (are) chosen from the following compounds: Ethylhexyl Methoxycinnamate Homosalate Ethylhexyl Salicylate, Octocrylene, Phenylbenzimidazole Sulfonic Acid, Benzophenone-3, Benzophenone-4, Benzophenone- 5, 2- (4-Diethylamino-2-hydroxybenzoyl) benzoate of n-hexyl. 4-Methylbenzylidene camphor, Terephthalylidene Dicamphor Sulfonic Acid, Disodium Phenyl Dibenzimidazole Tetra-Sulfonate, Ethylhexyl Triazone, Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine Diethylhexyl Butamido Triazone, 2,4,6-Tris (Biphenyl-4-yl) -1,3,5- triazine 2,4,6-tris (dineopentyl 4'-amino benzalmalonate) -s-triazine 2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazine, 2,4-bis ( Dineopentyl 4'-amino benzalmalonate) -6- (n-butyl 4'-aminobenzoate) -s-triazine 2,4-bis (n-butyl 4'-aminobenzoate) -6 - [(3- {1,3, 3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl} propyl) amino] -s-triazine Methylene bis-Benzotriazolyl tetramethylbutylphenol, Drometrizole Trisiloxane Polysilicone-15 Di-neopentyl 4'-methoxybenzalmalonate 1,1-dicarboxy ( 2,2'-dimethylpropyl) -4,4-diphenylbutadiene 2,4-bis- [5-1 (dimethylpropyl) benzoxazol-2-yl- (4-phenyl) imino] -6- (2-ethylhexyl) -imino-1,3,5-triazine and mixtures thereof 40 11. Composition according to claim 8, characterized in that the complementary inorganic filters are metal oxide pigments, coated or not. 12. Process for improving the chemical stability with respect to the UV radiation 45 of at least one dibenzoylmethane derivative as defined in any one of the preceding claims, characterized in that said dibenzoylmethane derivative is associated with said dibenzoylmethane derivative. effective amount of the combination of at least one hydrophilic or hydrosoluble merocyanine UV filter of formula (1) or (II) as defined in the preceding claims or one of its isomeric forms E, E-, E, Z - or Z, Z-.s 13. A compound of formula (1) according to claim 1 having from 1 to 4 hydroxy radicals and wherein the radicals R1, R2, R5 and R6 are different from an alkyl radical having from 1 to 3 oxygen atoms at the except for the compound (z). 14. Compound of formula (II) according to any one of claims 1, 4 or 5. 15. Compound of formula (1) according to claim 1 wherein at least 16 R3, R2, R5 and R6 radical denotes an alkyl radical having 1 to 3 oxygen atoms.