The invention also relates to novel methyltrialkylsilanes containing a cinnamate, cinnamamide, benzalmalonamide or benzalmalonate function and to uses thereof.

It is known that radiation with wavelengths of between 280 nm and 400 nm permits tanning of the human epidermis, and that radiation with wavelengths of between 280 and 320 nm, known as W-B radiation, causes skin burns and erythema that may harm the development of a natural tan. For these reasons, and also for aesthetic reasons, there is increasing demand for means for controlling this natural tanning. This W-B radiation should thus be screened out.

It is also known that W-A rays, with wavelengths of between 320 and 400 nm, which cause browning of the skin, are liable to induce impairment in the skin, especially in the case of sensitive skin

and/or skin that is continually exposed to sunlight.

UV-A rays in particular cause a loss of elasticity of the skin and the appearance of wrinkles, leading to premature ageing of the skin. They promote the triggering of the erythemal reaction or amplify this reaction in the case of certain individuals and may even be the cause of phototoxic or photoallergic reactions. Thus, for aesthetic and cosmetic reasons such as conservation of the skin's natural elasticity, more and more people wish to control the effect of W-A rays on their skin. It is thus desirable also to screen out W-A radiation.

Many organic compounds intended for protecting the skin against UV-A and/or UV-B radiation have been proposed to date.

Most of them are aromatic compounds that absorb UV radiation in the region between 280 nm and 315 nm, or in the region between 315 nm and 400 nm and beyond, or even within both these regions. They are usually formulated in antisun compositions that are in the form of oil-in-water or water-in-oil emulsions. The organic screening agents, which are generally lipophilic or hydrophilic, are present in dissolved form, in one or other of these phases, in amounts that are suitable to obtain the desired sun protection factor (SPF).

The"sun protection factor"means the ratio of the irradiation time required to reach the erythema- forming threshold in the presence of the test screening agent, to the radiation time required to reach this same threshold in the absence of screening agent.

Besides their screening power on sunlight, photoprotective compounds must also have good cosmetic properties, good solubility in the usual solvents and in particular in fatty substances such as oils and fats, good resistance to water and to perspiration (remanence) and satisfactory photostability.

Among all the aromatic compounds that have been recommended for this purpose, mention may be made especially of polysiloxane derivatives containing a benzalmalonate function, described in patent application EP-A-358 584 and in patent application EP-A-392 882 from the Applicant. These compounds do indeed show good liposolubility. However, these substances contain very long silicone chains and, on account of their bulk, their synthesis and their incorporation into cosmetic compositions are laborious.

Finally, their cosmetic properties are not always satisfactory.

In addition, mention may be made of the silane compounds containing benzalmalonate groups described in patent application EP-A-2 868 905, which describes a process for improving the photostability of

dibenzoylmethane derivatives with silane derivatives of benzalmalonates. Mention may also be made of the silane compounds containing benzalmalonate groups described in patent application JP-07-330 779. In this case also, their solubilities in fatty substances and their cosmetic properties are not always satisfactory.

The present invention is directed towards solving the above problems by proposing novel, cinnamate, cinnamamide, benzalmalonamide and benzalmalonate derivatives bearing a methyltrialkylsilane chain, which gives these derivatives very good solubility in fatty substances, improved cosmetic properties (such as the softness of feel) and better absorption (higher El%).

A first subject of the present invention is thus a cosmetic or dermatological composition for photoprotecting keratin materials, characterized in that it contains at least one methyltrialkylsilane compound corresponding to formula (I) below: in which: - B denotes a chromophoric group corresponding to either of formulae (1) and (2) below:

- Ri and R2, which may be identical or different, represent a linear or branched Cl-Cl2 alkyl radical, optionally halogenated or containing a double bond or a triple bond; a phenyl or benzyl radical; - R3 denotes a radical R1 or R2 or a group B; - n is an integer from 0 to 3 inclusive; -X denotes-O-or-NR5-; - A denotes a hydrogen atom; a linear or branched Cl-C4 alkyl radical; a group SiR1R2R3 in which RI, R2 and R3 have the same meanings indicated above, with the condition that R3 is other than B; - the radicals R'denote a hydrogen atom, a linear or branched Cl-calo alkyl radical, a linear or branched C2-C8 alkenyl radical or an Si (CH3) 3 group; - the radicals R", which may be identical or different, denote a hydroxyl radical; a linear or branched Cl-calo alkyl radical; a linear or branched C2-C8 alkenyl radical; a linear or branched Ci-Cio alkoxy radical; R" possibly forming, together with an adjacent R"or OR',

an alkylidenedioxy group in which the alkylidene group contains one or two carbon atoms; or an-OSi (CH3) 3 group; - Z, Z'and Z", which may be identical or different, denote a hydrogen atom; a linear or branched Ci-C4 alkyl radical; a group- (C=O) R4, - (C=O) OR4,-SO2R5, -(C=O) NR6R7,-CN or-(C=O) XCHASiRlR2R3 in which RI, R2 and R3 have the same meanings indicated above, with the condition that R3 is other than B; with the proviso that: (i) at least one of the radicals Z'and Z"is other than hydrogen, and (ii) when Z'denotes-SO2R5, then Z"is other than a-CN group; - R4 denotes a hydrogen atom or a linear or branched C1-C20 alkyl radical; - R5 denotes a C1-C20 alkyl radical or a C6-C12 aryl group; - R6 and R7, which may be identical or different, denote a hydrogen atom or a C1-C4 alkyl radical; - Z'and Z"may also together form a Meldrum acid of formula (3) below:

in which - R8 and Rg, which may be identical or different, denote hydrogen or a linear or branched C1-C2o alkyl radical; R8 and Rg may also together form a Cg-Cia ring.

Although, in formula (I) above in which the substituents are different, only one isomer is depicted, this formula should be understood as also including the corresponding trans isomers.

In formula (I) above, the alkyl radicals may be linear or branched, saturated or unsaturated, and chosen especially from methyl ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-amyl, isoamyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl and tert-octyl radicals. The alkyl radical that is particularly preferred is the methyl radical.

In formula (I) above, the alkoxy radicals may be linear or branched and chosen especially from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and isobutoxy radicals. The alkoxy radical that is particularly preferred is the methoxy radical.

In formula (I) above, the alkenyl radicals may be linear or branched and chosen especially from ethylene, propylene and butene radicals.

In formula (I) above, the aryl radicals are preferably phenyl or benzyl radicals.

Among the compounds of formula (I) in which B corresponds to formula (1) mention will be made more particularly of those for which: -R1, R2 and R3 denote a Cl-C4 alkyl and more particularly simultaneously methyl; - Z denotes hydrogen, COOR4 in which R4 denotes a C1-C8 alkyl and more particularly methyl; CN or - (C=O) XCHASiRlR2R3i - A denotes a hydrogen atom; - X denotes O or NH; - n = 0; -R'denotes a Ci-C4 alkyl radical and more particularly methyl.

Among these compounds, mention may be made even more particularly of the following compounds: ., su (compound a) i ,. 0 0 ,,, Cl 0 r 0, ! o.., r, ; . .,,. CI-O _ o.., O o,, sil l<,"f, o sW Ó (compound b) (compound c) ! o k 0 O (compound d) j t O O (compound e) (compound f) 0 0 (compound e) (compound f)

Among the compounds of formula (I) in which B corresponds to formula (2), mention will be made more particularly of those for which: - Ri and R2 denote a C1-C4 alkyl and more particularly methyl;

- n = 0 or 1 with, when n = 1, R"denotes a C1-C4 alkoxy radical and more particularly methoxy; - A denotes a hydrogen atom ; - Z'and Z", which may be identical or different, denote a group chosen from: 1)- (C=O) OR4 in which R4 denotes a Cl-C8 alkyl and more particularly methyl, ethyl, isobutyl or 2-ethylhexyl; 2)- (C=O) NH2 ;<BR> 3) -CN; 4) a group of formula (3) in which R8 and Rg denote a C1-C4 alkyl and more particularly methyl.

Among these compounds, mention may be made more particularly of the following compounds: zut u 1 0 u 0'--" (compound g) o 0 si O O O (compound h) -,,- o I U C o (compound i) 1 o (compound j) o 0 i n CN o 0 (compound k) /O O, 0X (compound 1) 0 0 O jSio. O O (compound m) 0 0 0 o 0 NH2 (compound n) \ Si---l 0 0- ozon O O O- /--Si-- "04 0 r I S0 <0 - : ao -0 0 w0 P0 (compound o) S ! 0. . O.. NH, 2 1 0 NH2 (compound p) . SO wSivO (compound q)

The compounds of formula (I) according to the invention are novel, with the exception of trimethylsilanylmethyl 2-cyano-3- (4- methoxyphenyl) acrylic acid (compound (d) as described above; RN: 165552-16-9) described in the article N. G. Senchenya et al. , Tzvestiya Akademii Nauk, Seriya Khimicheskaya, 5, 949-52 (1993).

To prepare the silane compounds in accordance with the invention of formula (I) in which the chromophoric group B is of formula (2), one of the following two methods may be used:

Route A An aromatic hydroxybenzaldehyde of formula (4) below is reacted with a monohalo or dihalo methylsilane derivative in the presence of a base (standard alkylation reaction), the benzaldehyde obtained being condensed with a difunctional compound Z'-CH2-Z"in toluene in the presence of piperidinium acetate as catalyst (Knoevenagel condensation) according to the following scheme: R, A R"n A R, I I I R"n I ' z \ \ p-0- (. KWa !)' P -cHy o (4) (5) p Q<O R2 (-KHal) R2 < No piperidine I R""Z"ACOH R3 i-CH--o + (I) R2 Z, "R2 mo in which p is 1 or 2; Y denotes Hal or R2 or RI ; R", n, R1 to R3, A, Z'and Z"have the meanings given above for formula (I) and Hal represents a halogen and more particularly chlorine.

Route B This consists in reacting a derivative of formula (6) below with a monohalo or dihalo methylsilane derivative of formula (5) in the presence of a base (standard alkylation reaction):

in which Y, Hal, R", p, m, Rl to R3, A, Z'and Z"have the meanings given above for route A.

Aromatic benzaldehyde derivatives of formula (4) that may be mentioned include 4-hydroxybenzaldehyde and vanillin, which are commercial products.

Derivatives of Z'-CH2-Z"type that may be mentioned include dimethyl malonate and diethyl malonate, which are commercial products.

A derivative of formula (6) that may be mentioned is dimethyl para-hydroxybenzalmalonate sold by the company Acros.

Silane halide derivatives of formula (5) that may be mentioned include chloromethyltrimethylsilane (RN 2344-80-1) and bis (chloromethyl) dimethylsilane (RN 2917-46-6), sold by the company Wacker. Mention may also be made of the following commercial products: (chloromethyl) dimethylethylsilane (RN 3121-77-5), (chloromethyl) dimethyl-n-butylsilane (RN 3121-75-3), (chloromethyl) dimethylpentylsilane (RN 73013-39-5), (chloromethyl) dodecyldimethylsilane (RN 70851-47-7),

(chloromethyl) triethylsilane (RN 757-34-6), 2-chloroethyltrimethylsilane (RN 7787-87-3), bis (trimethylsilyl) methyl chloride (RN 5926-35-2), (chloromethyl) dimethylphenylsilane (RN 1833-51-8), (chloromethyl) diphenylmethylsilane (RN 18407-40-4) and (trimethylsilylmethyl) dimethylchloromethylsilane (RN 18306-73-5).

To prepare the silane compounds in accordance with the invention of formula (I) in which the chromophoric group B is of formula (1), the method of condensing the benzaldehyde of formula (6) with the compound of formula (7) in toluene in the presence of piperidinium acetate as catalyst (Knoevenagel condensation) may be used, according to the following scheme: Route C: toluene R22 0 A R piperidine 1 + x-cH-s-R3 Ao 0 z K2 gR,, vX < + (XCH-Si-R3 > (1) - H20 (7) (8) in which R', R", n, A, R1 to R3, Z and X have the meanings given above for formula (I), the compounds of formula (8) themselves possibly being obtained, depending on whether X is-0-or-NR5-, according to the following methods: 0 Ri A Ri toluene I tOH + HOCHtSi R3 p 0 OCHSi R3 + H20 aH * Ha-CH--°-Si-R3------ O---CH--Si-R -H2a "i ? I R H, S04 z R2 z 2 2 A R Et3N 0 A Ri CI + R HNC : HSiR p NR5CH Si~R3 -hui z FL "2 -HO (10)

in which Z, A, R1 to R3 and R5 have the meanings given above for formula (I).

Aromatic benzaldehyde derivatives of formula (7) that may be mentioned include 4-methoxybenzaldehyde, veratraldehyde and piperonal, which are commercial products.

Derivatives of Z'-CH2-COOH type that may be mentioned include cyanoacetic acid, monoethyl malonate and mono-tert-butyl malonate, which are commercial products.

A derivative of Z'-CH2COCl type that may be mentioned is monoethyl malonate acid chloride, which is a commercial product.

Derivatives of formulae (9) and (10) that may be mentioned include hydroxymethyltrimethylsilane and

aminomethyltrimethylsilane, sold by the company Gelest, and bis (trimethylsilyl) methylamine (RN 134340-00-4).

The compounds of formula (I) are generally present in the composition of the invention in proportions of between 0. 01% and 20% by weight and preferably between 0. 1% and 10% by weight relative to the total weight of the composition.

The compositions in accordance with the invention may also comprise other additional UVA-active and/or UVB-active organic or mineral UV-screening agents, which are water-soluble or liposoluble or even insoluble in the cosmetic solvents commonly used.

The additional organic screening agents are chosen especially from anthranilates; cinnamic derivatives ; dibenzoylmethane derivatives; salicylic derivatives; camphor derivatives; triazine derivatives such as those described in patent applications US 4 367 390, EP 863 145, EP 517 104, EP 570 838, EP 796 851, EP 775 698, EP 878 469, EP 933 376, EP 507 691, EP 507 692, EP 790 243, EP 944 624; benzophenone derivatives; P, P-diphenylacrylate derivatives; benzotriazole derivatives; benzalmalonate derivatives; benzimidazole derivatives; imidazolines; bis-benzazolyl derivatives as described in patents EP 669 323 and US 2 463 264; p-aminobenzoic acid (PABA) derivatives; methylenebis (hydroxyphenylbenzotriazole) derivatives as described in patent applications

US 5 237 071, US 5 166 355, GB 2 303 549, DE 197 26 184 and EP 893 119; benzoxazole derivatives as described in patent applications EP 0 832 642, EP 1 027 883, EP 1 300 137 and DE 101 62 844; screening polymers and screening silicones such as those described especially in patent application WO 93/04665; dimers derived from a-alkylstyrene, such as those described in patent application DE 198 55 649; 4, 4-diarylbutadienes such as those described in patent applications EP 0 967 200, DE 197 46 654, DE 197 55 649, EP-A-1 008 586, EP 1 133 980 and EP 133 981, and mixtures thereof.

As examples of additional organic screening agents, mention may be made of those denoted hereinbelow under their INCI name: para-Aminobenzoic acid derivatives: PABA, Ethyl PABA, Ethyl dihydroxypropyl PABA, Ethylhexyl dimethyl PABA sold in particular under the name"Escalol 507"by ISP, Glyceryl PABA, PEG-25 PABA sold under the name"Uvinul P25"by BASF.

Salicylic derivatives: Homosalate sold under the name"Eusolex HMS"by Rona/EM Industries, Ethylhexyl salicylate sold under the name"Neo Heliopan OS"by Haarmann and Reimer,

Dipropylene glycol salicylate sold under the name "Dipsal"by Scher, TEA salicylate sold under the name"Neo Heliopan TS"by Haarmann and Reimer.

Dibenzoylmethane derivatives: Butyl methoxydibenzoylmethane sold in particular under the trade name"Parsol 1789"by Hoffmann LaRoche, Isopropyldibenzoylmethane.

Cinnamic derivatives: Ethylhexyl methoxycinnamate sold in particular under the trade name"Parsol MCX"by Hoffmann LaRoche, Isopropyl methoxycinnamate, Isoamyl methoxycinnamate sold under the trade name"Neo Heliopan E 1000"by Haarmann and Reimer, Cinoxate, DEA methoxycinnamate, - Diisopropyl methylcinnamate, Glyceryl ethylhexanoate dimethoxycinnamate.

P, P'-Diphenylacrylate derivatives: Octocrylene sold in particular under the trade name "Uvinul N539"by BASF, Etocrylene sold in particular under the trade name "Uvinul N35"by BASF.

Benzophenone derivatives: Benzophenone-1 sold under the trade name"Uvinul 400" by BASF,

Benzophenone-2 sold under the trade name"Uvinul D50" by BASF, Benzophenone-3 or Oxybenzone sold under the trade name "Uvinul M40"by BASF, Benzophenone-4 sold under the trade name"Uvinul MS40" by BASF, Benzophenone-5, Benzophenone-6 sold under the trade name"Helisorb 11" by Norquay, Benzophenone-8 sold under the trade name"Spectra-Sorb UV-24"by American Cyanamid, Benzophenone-9 sold under the trade name"Uvinul DS-49" by BASF, Benzophenone-12 n-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate.

Benzylidenecamphor derivatives: 3-Benzylidenecamphor manufactured under the name "Mexoryl SD"by Chimex, 4-Methylbenzylidenecamphor sold under the name"Eusolex 6300"by Merck, Benzylidenecamphorsulphonic acid manufactured under the name"Mexoryl SL"by Chimex, Camphor benzalkonium methosulphate manufactured under the name"Mexoryl SO"by Chimex, Terephthalylidenedicamphorsulphonic acid manufactured under the name"Mexoryl SX"by Chimex,

Polyacrylamidomethylbenzylidenecamphor manufactured under the name"Mexoryl SW"by Chimex.

Phenylbenzimidazole derivatives: Phenylbenzimidazolesulphonic acid sold in particular under the trade name"Eusolex 232"by Merck, Disodium phenyl dibenzimidazole tetrasulphonate, sold under the trade name"Neo Heliopan AP"by Haarmann and Reimer.

Triazine derivatives: Anisotriazine sold under the trade name"Tinosorb S"by Ciba Geigy, Ethylhexyltriazone sold in particular under the trade name"Uvinul T150"by BASF, 2,4, 6-tris (diisobutyl 4'-aminobenzalmalonate)-s- triazine, Diethylhexylbutamidotriazone sold under the trade name "Uvasorb HEB"by Sigma 3V.

Phenylbenzotriazole derivatives: Drometrizole trisiloxane sold under the name "Silatrizole"by Rhodia Chimie, Methylenebis (benzotriazolyl) tetramethylbutylphenol sold in solid form under the trade name"MIXXIM BB/100"by Fairmount Chemical, or in micronized form as an aqueous dispersion under the trade name"Tinosorb M"by Ciba Specialty Chemicals.

Anthranilic derivatives:

Menthyl anthranilate sold under the trade name"Neo Heliopan MA"by Haarmann and Reimer.

Imidazoline derivatives: Ethylhexyldimethoxybenzylidenedioxoimidazoline propionate.

Benzalmalonate derivatives : Polyorganosiloxane containing benzalmalonate functions, such as the product Polysilicone-15 sold under the trade name"Parsol SLX"by Hoffmann LaRoche 4,4-Diarylbutadiene derivatives: 1, 1-Dicarboxy (2, 2'-dimethylpropyl)-4, 4-diphenyl- butadiene Benzoxazole derivatives: 2,4-bis [5-l (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 W-screening agents are chosen from: Ethylhexyl salicylate, Ethylhexyl methoxycinnamate, Butyl methoxydibenzoylmethane, Octocrylene, Phenylbenzimidazolesulphonic acid, Benzophenone-3, Benzophenone-4, Benzophenone-5,

n-Hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate, 4-Methylbenzylidenecamphor, Terephthalylidenedicamphorsulphonic acid, Disodium phenyldibenzimidazoletetrasulphonate, 2,4, 6-Tris (diisobutyl 4'-aminobenzalmalonate)-s- triazine, Anisotriazine, Ethylhexyltriazone, Diethylhexylbutamidotriazone, Methylenebis (benzotriazolyl) tetramethylbutylphenol, Drometrizole trisiloxane, Polysilicone-15 1, 1-Dicarboxy (2, 2'-dimethylpropyl)-4, 4-diphenyl- butadiene, 2,4-bis [5-l (dimethylpropyl) benzoxazol-2-yl (4- phenyl) iminol-6- (2-ethylhexyl) imino-1, 3, 5-triazine and mixtures thereof.

The additional mineral screening agents are chosen from pigments or nanopigments (mean size of the primary particles: generally between 5 nm and 100 nm and preferably between 10 nm and 50 nm) of coated or uncoated metal oxides such as, for example, nanopigments of titanium oxide (amorphous or crystallized in rutile and/or anatase form), of iron oxide, of zinc oxide, of zirconium oxide or of cerium oxide, which are all W photoprotective agents that are well known per se. Standard coating agents are,

moreover, alumina and/or aluminium stearate. Such coated or uncoated metal oxide nanopigments are described in particular in patent applications EP 518 772 and EP 518 773.

The additional W-screening agents in accordance with the invention 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 cosmetic compositions according to the invention may also contain agents for artificially tanning and/or browning the skin (self-tanning agents) such as dihydroxyacetone (DHA).

The compositions in accordance with the present invention may also comprise standard cosmetic adjuvants chosen especially from fatty substances, organic solvents, ionic or nonionic thickeners, softeners, humectants, antioxidants, moisturizers, desquamating agents, free-radical scavengers, antipollution agents, antibacterial agents, anti- inflammatory agents, depigmenting agents, propigmenting agents, opacifiers, stabilizers, emollients, silicones, antifoams, insect repellents, fragrances, preserving agents, anionic, cationic, nonionic, zwitterionic or amphoteric surfactants, substance P antagonists,

substance CGRP antagonists, fillers, pigments, polymers, propellants, acidifying or basifying agents, or any other ingredient usually used in cosmetics and/or dermatology.

The fatty substances may consist of an oil or a wax or mixtures thereof. The term"oil"means a compound that is liquid at room temperature. The term "wax"means a compound that is solid or substantially solid at room temperature, and whose melting point is generally above 35°C.

Oils that may be mentioned include mineral oils (paraffin); plant oils (sweet almond oil, macadamia oil, blackcurrant seed oil or jojoba oil); synthetic oils, for instance perhydrosqualene, fatty alcohols, fatty acids or fatty acid esters (for instance the C12-C15 alcohol benzoate sold under the trade name"Finsolv TN"by the company Witco, octyl palmitate, isopropyl lanolate, triglycerides, including capric/caprylic acid triglycerides), oxyethylenated or oxypropylenated fatty esters and ethers; silicone oils (cyclomethicone and polydimethylsiloxanes, or PDMS) or fluoro oils, and polyalkylenes.

Waxy compounds that may be mentioned include paraffin, carnauba wax, beeswax and hydrogenated castor oil.

Among the organic solvents that may be mentioned are lower alcohols and polyols. These

solvents may be chosen from glycols and glycol ethers, for instance ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol or diethylene glycol.

The thickeners may be chosen especially from crosslinked acrylic polymers, for instance Carbomers, crosslinked polymer acrylates/C10-C30 alkylacrylate crosslinked polymers of the type such as Pemulen or polyacrylate-3 sold under the name Viscophobe DB 1000 by Amerchol ; polyacrylamides such as the emulsion of polyacrylamide, C13-C14 isoparaffin and laureth-7 sold under the name Sepigel 305 by SEPP, IC, AMPS homopolymers or copolymers such as Hostacerin AMPS sold by Clariant, modified or unmodified guar gums and celluloses, such as hydroxypropyl guar gum, methylhydroxyethylcellulose and hydroxypropylmethyl cellulose, xanthan gum, and nanometric silicas of the Aerosil type.

Needless to say, a person skilled in the art will take care to select the optional additional compound (s) mentioned above and/or the amounts thereof such that the advantageous properties intrinsically associated with the compositions in accordance with the invention are not, or are not substantially, adversely affected by the envisaged addition (s).

The compositions according to the invention may be prepared according to techniques that are well known to those skilled in the art, in particular those

intended for the preparation of emulsions of oil-in- water or water-in-oil type.

This composition may be in particular in the form of a simple or complex emulsion (O/W, W/O, O/W/O or W/O/W emulsion) such as a cream or a milk, in the form of a gel or a cream-gel, or in the form of a lotion, an oil, a powder or a solid tube, and may optionally be packaged as an aerosol and may be in the form of a mousse or a spray.

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

When it is an emulsion, the aqueous phase of this emulsion may comprise a nonionic vesicular dispersion prepared according to known processes (Bangham, Standish and Watkins, J. Mol. Biol. 13,238 (1965), FR 2 315 991 and FR 2 416 008).

When the cosmetic composition according to the invention is used to care for the human epidermis, it may be in the form of a suspension or a dispersion in solvents or fatty substances, in the form of a nonionic vesicular dispersion or in the form of an emulsion, preferably of oil-in-water type, such as a cream or a milk, or in the form of an ointment, a gel, a cream-gel, an antisun oil, a solid tube, a powder, an aerosol mousse or a spray.

When the cosmetic composition according to the invention is used for haircare, it may be in the form of a shampoo, a lotion, a gel, an emulsion or a nonionic vesicular dispersion and may constitute, for example, a rinse-out composition, to be applied before or after shampooing, before or after dyeing or bleaching, or before, during or after permanent-waving or relaxing the hair, a styling or treating lotion or gel, a blow-drying or hairsetting lotion or gel, or a composition for permanent-waving, relaxing, dyeing or bleaching the hair.

When the composition is used as a makeup product for the nails, the lips, the eyelashes, the eyebrows or the skin, such as an epidermal treatment cream, a foundation, a tube of lipstick, an eyeshadow, a makeup rouge, a mascara or an eyeliner, it may be in solid or pasty, anhydrous or aqueous form, such as oil- in-water or water-in-oil emulsions, nonionic vesicular dispersions or suspensions.

As a guide, for the antisun formulations in accordance with the invention which contain a support of oil-in-water emulsion type, the aqueous phase (especially comprising the hydrophilic screening agents) generally represents from 50% to 95% by weight and preferably from 70% to 90% by weight relative to the total weight of the formulation, the oily phase (especially comprising the lipophilic screening agents)

generally represents from 5% to 50% by weight and preferably from 10% to 30% by weight relative to the total weight of the formulation, and the (co)- emulsifier (s) generally represent (s) from 0. 5% to 20% by weight and preferably from 2% to 10% by weight relative to the total weight of the formulation.

Another subject of the invention is the use of a compound of formula (I) as defined above in a cosmetic or dermatological composition, as an agent for screening out W radiation.

Another subject of the invention is the use of a compound of formula (I) as defined above in a cosmetic composition, as an agent for controlling the variation in the colour of the skin caused by UV radiation.

Another subject of the invention is the use of a compound of formula (I) as defined above as an agent for photostabilizing synthetic polymers such as plastics or glasses, in particular spectacle glasses or contact lenses.

Concrete, but in no way limiting, examples illustrating the invention will now be given.

EXAMPLE 1: Preparation of dimethyl 2- (4-trimethyl- silanylmethoxy) benzylidenemalonate according to route A:

a) First step: preparation of 4-trimethylsilanyl- methoxybenzaldehyde Chloromethyltrimethylsilane (110.5 g, 0.9 mol) is added dropwise over 30 minutes to a mixture of para-hydroxybenzaldehyde (110 g, 0.82 mol) and potassium carbonate (124.5 g, 0.9 mol) in 1 L of dry DMF maintained at 80°C, and while sparging with nitrogen. The mixture is left at 90°C for 4 hours. The reaction mixture is filtered and the solvent is removed from the filtrate by distillation under vacuum. The final traces of DMF are removed via a stage at 60°C under a vacuum of 2 mmHg. 142.4 g (yield: 84%) of 4- trimethylsilanylmethoxybenzaldehyde are obtained in the form of an orange-yellow oil, which is used without further purification in the next step. b) Second step: preparation of the derivative of Example 1: A mixture of the above derivative (75 g, 0.36 mol) and dimethyl malonate (52.3 g, 0.396 mol) in 120 ml of toluene in the presence of 3.6 ml of piperidine and 2.2 ml of acetic acid is refluxed for 5 hours in a reactor equipped with Dean-Stark

apparatus. The water formed is removed azeotropically.

The mixture is cooled and the toluene is removed by distillation. The reaction mixture is taken up in 400 ml of diisopropyl ether. The organic phase is washed 3 times with water, dried over sodium sulphate and filtered, and the solvent is evaporated off under vacuum. The orange-coloured oil obtained (110.3 g) is purified by chromatography on a column of silica (eluent: 95/5 heptane/EtOAc). 47 g of clean fractions (yield: 40%) of the derivative of Example 1 are recovered in the form of a pale yellow viscous oil: - UV (ethanol) XmaX = 317 nm, £max = 27 085, Ei% = 840.

EXAMPLE 2: Preparation of dimethyl 2- (4-trimethyl- silanylmethoxy) benzylidenemalonate according to route B: Chloromethyltrimethylsilane (9.5 ml, 0.068 mol) is added dropwise over 30 minutes to a mixture of dimethyl para-hydroxybenzalmalonate (15 g, 0.056 mol) and potassium carbonate (9.4 g, 0.068 mol)

in 60 ml of dry DMF maintained at 80°C, and while sparging with nitrogen. The mixture is left at 120°C for 2 hours. The reaction mixture is cooled and poured into ice-cold water. The oily phase is extracted with dichloromethane. The organic phase is washed 3 times with water, dried over sodium sulphate and filtered, and the solvent is evaporated off under vacuum. The final traces of DMF are removed via a stage at 60°C under a vacuum of 2 mmHg. The brown oil obtained is purified by chromatography on a column of silica (eluent: 95/5 heptane/EtOAc). 7.1 g of clean fractions (yield: 36%) of the derivative of Example 2 are recovered in the form of a pale yellow viscous oil: - UV (ethanol) a, n, ax = 317 nm, Emax = 26 440, E1 = 820.

EXAMPLE 3: Preparation of diethyl 2- (4-trimethyl- silanylmethoxy) benzylidenemalonate according to route B: Chloromethyltrimethylsilane (9.5 ml, 0.068 mol) is added dropwise over 30 minutes to a

mixture of diethyl para-hydroxybenzalmalonate (15 g, 0.056 mol) and potassium carbonate (9.4 g, 0.068 mol) in 60 ml of dry DMF maintained at 80°C, and while sparging with nitrogen. The mixture is left at 120°C for 2 hours. The reaction mixture is cooled and poured into ice-cold water. The oily phase is extracted with dichloromethane. The organic phase is washed 3 times with water, dried over sodium sulphate and filtered, and the solvent is evaporated off under vacuum. The final traces of DMF are removed via a stage at 60°C under a vacuum of 2 mmHg. The brown oil obtained is purified by chromatography on a column of silica (eluent: 95/5 heptane/EtOAc). 7.1 g of clean fractions (yield: 3601) of the derivative of Example 3 are recovered in the form of a pale yellow viscous oil: - UV (ethanol) max = 316 nm, Emax = 26 290, tels = 750.

EXAMPLE 4: Preparation of diisobutyl 2- (4-trimethyl- silanylmethoxy) benzylidenemalonate according to route A:

4- (Trimethylsilanylmethoxy) benzaldehyde (obtained in step 1 of Example 1) (4.35 g, 0.02 mol) and diisobutyl malonate (5.13 ml, 0.022 mol) in 10 ml of dry toluene in the presence of 0.21 ml of piperidine and 0.13 g of acetic acid is refluxed for 5 hours in a reactor equipped with Dean-Stark apparatus. The water formed is removed azeotropically. The mixture is cooled and the toluene is removed by distillation. The reaction mixture is taken up in 50 ml of diisopropyl ether. The organic phase is washed 3 times with water, dried over sodium sulphate and filtered, and the solvent is evaporated off under vacuum. The brown oil obtained (8.4 g) is purified by chromatography on a column of silica (eluent: 90/10 heptane/EtOAc). 3.82 g of clean fractions (yield: 45%) of the derivative of Example 4 are recovered in the form of a colourless viscous oil: - UV (ethanol) max = 316 nm, Emax = 26 960, Ei% = 663.

EXAMPLE 5 : Preparation of dineopentyl 2- (4-trimethyl-<BR> silanylmethoxy) benzylidenemalonate according to route A:

a) First step: preparation of dineopentyl malonate: Malonic acid (40 g, 0.38 mol) and neopentyl alcohol (77.5 g, 0.88 mol) in 110 ml of toluene in the presence of 0.2 ml of concentrated sulphuric acid are refluxed for 3 hours in a reactor equipped with Dean- Stark apparatus. The water formed is removed azeotropically. The organic phase is washed 3 times with water and dried over sodium sulphate. After filtration and evaporation of the solvent under vacuum, 88 g (yield: 94%) of dineopentyl malonate are obtained in the form of a colourless oil and used without further purification in the next step. b) Second step: preparation of the derivative of Example 5: 4- (Trimethylsilanylmethoxy) benzaldehyde (obtained in step 1 of Example 1) (2 g, 9.6 x 10-3 mol)

and dineopentyl malonate (2. 6 g, 10.6 x 10-3 mol) in 10 ml of dry toluene in the presence of 8 mg of piperidine and 6 mg of acetic acid are refluxed for 5 hours in a reactor equipped with Dean-Stark apparatus. The water formed is removed azeotropically.

The mixture is cooled and the toluene is removed by distillation. The reaction mixture is taken up in 50 ml of diisopropyl ether. The organic phase is washed 3 times with water, dried over sodium sulphate and filtered, and the solvent is evaporated off under vacuum. The brown oil obtained (4 g) is purified by chromatography on a column of silica (eluent: 95/5 heptane/EtOAc). 2.5 g of clean fractions (yield : 60%) of the derivative of Example 5 are recovered in the form of a colourless viscous oil. This oil crystallizes over time to give translucent crystals: - m. p. 60°C - UV (ethanol) Amffl = 317 nm, sma = 25 730, Ei% = 592.

EXAMPLE 6: Preparation of 2, 2-dimethyl-5- [4- (trimethyl- silanylmethoxy) benzylidene]-1, 3-dioxane-4, 6-dione according to route A

4- (Trimethylsilanylmethoxy) benzaldehyde (obtained in step 1 of Example 1) (5 g, 0.024 mol) and isopropylidenemalonate (3.8 g, 0.0264 mol) in 10 ml of dry toluene in the presence of 0.24 ml of piperidine and 0.14 g of acetic acid are refluxed for 5 hours in a reactor equipped with Dean-Stark apparatus. The water formed is removed azeotropically. The mixture is cooled and the toluene is removed by distillation. The reaction mixture is taken up in 50 ml of diisopropyl ether. The organic phase is washed 3 times with water, dried over sodium sulphate and filtered, and the solvent is evaporated off under vacuum. The yellow oil obtained (7.48 g) is purified by chromatography on a column of silica (eluent: 95/5 heptane/EtOAc). 3.64 g of clean fractions (yield; 45% of the derivative of Example 6 are recovered in the form of a yellow solid: - m. p. 84-86°C -W (ethanol) kmaX = 370 nm, Smax = 25 230 E1 = 756.

EXAMPLE 7 : Preparation of bis (2-ethylhexyl) 2- [3-meth- oxy-4-(trimethylsilanylmethoxy) benzylidene] malonate according to route A:

a) First step: preparation of 3-methoxy-4-trimethyl- silanylmethoxybenzaldehyde: Chloromethyltrimethylsilane (36.7 g, 0.3 mol) is added dropwise over 10 minutes to a mixture of vanillin (45.6 g, 0.3 mol) and potassium carbonate (41.4 g, 0.3 mol) in 300 ml of dry DMF maintained at 100°C, and while sparging with nitrogen. The mixture is left at 100°C for 2 hours. The reaction mixture is filtered and the solvent is removed from the filtrate by distillation under vacuum. The final traces of DMF are removed via a stage at 60°C under a vacuum of 2 mmHg. 70 g of a pink syrup, which crystallizes, are obtained. After recrystallization from an 80/20 ethanol/water mixture, 35.5 g (yield: 50%) of 3- methoxy-4-trimethylsilanylmethoxybenzaldehyde are obtained in the form of white crystals (m. p. 45°C), which are used without purification in the next step.

b) Second step: preparation of the derivative of Example 7: 4- (Trimethylsilanylmethoxy) benzaldehyde (obtained in step 1 of Example 1) (5 g, 0.024 mol) and the derivative from the preceding step (7.6 g, 0.024 mol) in 10 ml of dry toluene in the presence of 0.24 ml of piperidine and 0.14 g of acetic acid are refluxed for 5 hours in a reactor equipped with Dean- Stark apparatus. The water formed is removed azeotropically. The mixture is cooled and the toluene is removed by distillation. The reaction mixture is taken up in 50 ml of diisopropyl ether. The organic phase is washed 3 times with water, dried over sodium sulphate and filtered, and the solvent is evaporated off under vacuum. The yellow oil obtained is purified by chromatography on a column of silica (eluent: 99/1 heptane/EtOAc). 7.8 g of clean fractions (yield: 68%) of the derivative of Example 7 are recovered in the form of a pale yellow oil: - W (ethanol) kmci-x = 331 nm, Soma, = 18 170, El = 331.

EXAMPLE 8: Preparation of ethyl 2- (aminocarbonyl)-3- [4- <BR> (trimethylsilanylmethoxy) phenyl] acrylate according to route A:

4- (Trimethylsilanylmethoxy) benzaldehyde (obtained in step 1 of Example 1) (3 g, 0.015 mol) and ethyl malonate monoamide (2.1 g, 0.016 mol) in 10 ml of dry toluene in the presence of 0.24 ml of piperidine and 0.14 g of acetic acid are refluxed for 3 hours in a reactor equipped with Dean-Stark apparatus. The water formed is removed azeotropically. The mixture is cooled and the toluene is removed by distillation. The reaction mixture is taken up in 50 ml of diisopropyl ether. The organic phase is washed 3 times with water, dried over sodium sulphate and filtered, and the solvent is evaporated off under vacuum. The yellow gum obtained is crystallized from a diisopropyl ether/heptane mixture. 1.8 g (yield: 37%) of the derivative of Example 8 are obtained in the form of a pale yellow solid: - m. p. 77-8°C - UV (ethanol) X,, _, = 314 nm, Smax = 24 270, Ei% = 755. EXAMPLE 9: Preparation of dimethyl 2- (4- { [ ( {4- [3-meth- oxy-2-(methoxyearbonyl)-3-oxoprop-1-enyl] phenoxy}- methyl) (dimethyl) silyl] methoxy} benzylidene) malonate according to route B:

Bis (chloromethyl) dimethylsilane (1.53 ml, 0.0105 mol) is added dropwise over 30 minutes to a mixture of dimethyl para-hydroxybenzalmalonate (5 g, 0.021 mol) and potassium carbonate (2.9 g, 0.021 mol) in 15 ml of dry DMF maintained at 60°C, and while sparging with nitrogen. The mixture is left at 60°C for 2 hours. The reaction mixture is cooled and poured into ice-cold water. The oily phase is extracted with dichloromethane. The organic phase is washed 3 times with water, dried over sodium sulphate and filtered, and the solvent is evaporated off under vacuum. The final traces of DMF are removed via a stage at 60°C under a vacuum of 2 mmHg. The solid obtained is

recrystallized from a 90/10 ethanol/water mixture.

5.2 g (yield: 88%) of the derivative of Example 9 are obtained in the form of a pale beige solid: - m. p. 103-104°C -W (ethanol) Xmu = 316 nm, £mu = 50 270, Ei% = 903.

EXAMPLE 10: Preparation of 2- [4- (trimethylsilanyl- methoxy) benzylidene] malonamide according to route A: 4- (Trimethylsilanylmethoxy) benzaldehyde (obtained in step 1 of Example 1) (10.4 g, 0.005 mol) and malonamide (5.5 g, 0.055 mol) in 20 ml of dry toluene in the presence of 0.5 ml of piperidine and 0.3 g of acetic acid are refluxed for 3 hours in a reactor equipped with Dean-Stark apparatus. The water formed is removed azeotropically. The mixture is cooled and the organic phase is washed twice with water. The organic phase is dried over sodium sulphate and filtered, and the solvent is evaporated off under vacuum. After recrystallization from ethanol, 7.2 g (yield: 49%) of the derivative of Example 10 are obtained in the form of an off-white powder:

- m. p. 163-164°C - UV (ethanol) Xmffl = 310 nm, Emu = 20 350, Ei% = 696.

EXAMPLE 11: Preparation of isopropyl 2- (4-trimethyl- silanylmethoxy) cinnamate according to route B: Chloromethyltrimethylsilane (0.4 ml, 2.42 x 10-3 mol) is added to a mixture of isopropyl para-hydroxycinnamate (0.5 g, 2.42 x 10-3 mol) and potassium carbonate (0.4 g, 2.86 x 10-3 mol) in 5 ml of dry DMF maintained at 80°C, and while sparging with nitrogen. The mixture is left at 120°C for 1 hour. The reaction mixture is cooled and poured into ice-cold water. The oily phase is extracted with dichloromethane. The organic phase is washed twice with water, dried over sodium sulphate and filtered, and the solvent is evaporated off under vacuum. The final traces of DMF are removed via a stage at 60°C under a vacuum of 2 mmHg. The brown oil obtained is purified by chromatography on a column of silica (eluent: 95/5 heptane/EtOAc). 360 mg of clean fractions (yield: 51%

of the derivative of Example 11 are recovered in the form of a pale yellow viscous oil: - W (ethanol) , jnax = 310 nm, Smax = 20 800, E1 = 711.

EXAMPLE 12: Preparation of di (methyltrimethylsilanyl) 2- (2-methoxybenzylidene) malonate according to route C: a) First step: preparation of di (methyltrimethylsilyl) malonate: Malonic acid (8.3 g, 0.079 mol) and hydroxymethyltrimethylsilane (18.35 g, 0.176 mol) in 50 ml of toluene in the presence of 0.2 ml of concentrated sulphuric acid are refluxed for 3 hours in a reactor equipped with Dean-Stark apparatus. The water formed (3.1 ml) is removed azeotropically. The organic phase is washed twice with water and dried over sodium sulphate. After filtration, evaporation of the solvent under vacuum and distillation under vacuum (b. p. 73- 75°C at 0.15 mbar), 19.6 g (yield: 90%) of

di (methyltrimethylsilyl) malonate are obtained in the form of a colourless oil. b) Second step: preparation of the derivative of Example 12 2-Methoxybenzaldehyde (0.98 g, 7.2 x 10-3 mol) and di (methyltrimethylsilyl) malonate (2 g, 7.23 x 10-3 mol) in 8 ml of dry toluene in the presence of 6 mg of piperidine and 5 mg of acetic acid are refluxed for 5 hours in a reactor equipped with Dean- Stark apparatus. The water formed is removed azeotropically. The mixture is cooled and the toluene is removed by distillation. The reaction mixture is taken up in diisopropyl ether. The organic phase is washed twice with water, dried over sodium sulphate and filtered, and the solvent is evaporated off under vacuum. The brown oil obtained is purified by chromatography on a column of silica (eluent: 95/5 heptane/EtOAc). 2.1 g of clean fractions (yield: 740) of the derivative of Example 12 are recovered in the form of a colourless viscous oil: - UV (ethanol) max = 325 nm, 8mE = 7 420, Ei% = 188 Xm = 274 nm, £mE = 10 810, Ei% = 274.

EXAMPLE 13: Preparation of di (methyltrimethylsilanyl) 2- (4-methoxybenzylidene) malonate according to route C:

4-Methoxybenzaldehyde (12.3 g, 0.03 mol) and di (methyltrimethylsilyl) malonate (25 g, 0.09 mol) in 40 ml of dry toluene in the presence of 0.9 ml of piperidine and 0.5 ml of acetic acid are refluxed for 4 hours in a reactor equipped with Dean-Stark apparatus. The water formed is removed azeotropically.

The mixture is cooled and the toluene is removed by distillation. The reaction mixture is taken up in diisopropyl ether. The organic phase is washed 3 times with water, dried over sodium sulphate and filtered, and the solvent is evaporated off under vacuum. The solid obtained is recrystallized from isopropanol to give 25.1 g (yield: 71*-.) of the derivative of Example 13 in the form of a white powder: m. p. : 86°C - UV (ethanol) Xmffl = 313 nm, Emu = 25 770, Ei% = 653.

COMPOSITION EXAMPLES Chemical name Example A Example B W/W (%) W/W (%) Glyceryl monostearate/polyethylene glycol stearate mixture (100 EO) (Simulsol 165-1 1 SEPPIC) Stearic acid (Stearine TP 1200 Pastilles-1.5 1.5 Stéarinerie Dubois) Polydimethylsiloxane (200 Fluid 350 CS-0.5 0.5 Dow Corning) Cetyl alcohol (Lanette 16 NF-Cognis) 0.5 0.5 Cetearyl glucoside/cetyl stearyl alcohol 2 2 mixture (Montanov 68-SEPPIC) C12-Cls alkyl benzoate (Finsolv TN-Witco) 10 10 Dimethyl 2- (4-trimethylsilanylmethoxy)- 0. 5 5 benzylidenemalonate according to Example 1 or 2 Glycerol 5 5 Xanthan gum (Keltrol T-CP Kelco) 0.2 0.2 Crosslinked acrylic acid/Clo-C3o alkyl acrylates copolymer (Pemulen TR1-Noveon) 0. 2 0. 2 Isohexadecane (Isohexadecane-BP) 1 1 Preserving agent 1 1 Triethanolamine 0. 65 0.65 Demineralized water qs 100 qs 100

Manufacturing protocol: The fatty phase is weighed out in a beaker.

The aqueous phase is weighed out in the final beaker.

The two phases are heated on a waterbath (80°C). The aqueous phase is stirred and the fatty phase is poured slowly onto the aqueous phase. The mixture is emulsified with vigorous stirring (-1000 rpm). The thickener is introduced and stirring is continued for 15 to 20 minutes. At about 30°C, the formulation is neutralized and is allowed to cool to room temperature.

Measurement of the photoprotective efficacy (SPF) The efficacy of these compositions is evaluated in vitro using an SPF 290 spectroradiometer sold by the company Optometrics and according to the Diffey-Robson method on a plate of quartz plus Transpore: The Sun Protection Factors (SPF) obtained are: Compositions SPF Example A 2. 3 0.2 Example B 9. 7 0.7