Indian Patents. 255208:"SILANE, SILOXANE OR POLYSILOXANE MEROCYANINE SULPHONE COMPOUND"

Title of Invention	"SILANE, SILOXANE OR POLYSILOXANE MEROCYANINE SULPHONE COMPOUND"
Abstract	Silane, siloxane or polysiloxane merocyanine sulphone compound chosen from (i) those having one or other of formulae (1), (2) or (3) below and which may be present in the isomeric E, E-, E-Z-, or Z, Z- forms.

Full Text	The present invention relates to silane, siloxane or polysiloxane merocyanine sulphone compound. The present invention concerns novel silane, siloxane or polysiloxane derivatives of merocyanine sulphone and their use in cosmetics as long UV-A filters. The present invention also concerns cosmetic compositions for topical use, in particular intended for the photoprotection of skin and/or hair, comprising an effective quantity of at least one silane, siloxane or polysiloxane derivative of merocyanine sulphone or a mixture of derivatives. Radiation with wavelengths in the range 280 nm [nanometre] to 400 nm is known to brown human skin, and radiation with wavelengths in the range 280 nm to 320 nm, known as UV-B radiation, is known to cause erythemas and burns to the skin which can interfere with the development of a natural tan. UV-A radiation with wavelengths in the range 320 nm to 400 nm is also known to cause the skin to brown, but is capable of inducing an alteration in the skin, in particular in the case of sensitive skin and/or skin continuously exposed to solar radiation. In particular, UV-A radiation causes loss of skin elasticity and the appearance of wrinkles, resulting in premature ageing of the skin. It encourages triggering of the erythematous reaction or amplifies that reaction in some subjects and may even be at the source of phototoxic or photoallergic reactions. Thus, for aesthetic and cosmetic reasons, such as preserving the natural elasticity of the skin, more and more people wish to control the effect of UV-A radiation on their skin. The term "sun protection factor" means the ratio of the irradiation period necessary to reach the erythematogenic threshold in the presence of a test filter to the irradiation period necessary to reach that same threshold in the absence of a filter. A number of organic compounds intended to protect the skin against UV-A and/or UV-B radiation have been proposed. The majority of them are aromatic compounds absorbing UV radiation in the zone in the range 280 nm to 315 nm or in the zone in the range 315 nm to 400 nm and beyond, or across both of those zones. They are usually formulated into sunscreen compositions which are in the form of oil-in-water emulsions or water-inoil emulsions. The organic filters, which are generally lipophilic or hydrophilic, are present in a dissolved form in one or the other of those phases in quantities appropriate for obtaining the desired sun protection factor (SPF). In addition to their solar radiation filtration capability, desirable photoprotective compounds must also have other good cosmetic properties, good solubility in the usual solvents, in particular in fatty substances such as oils or fats, and good resistance to water and perspiration (persistance), as well as very good photostability. Compounds which have been recommended for that purpose which may be cited include a particularly interesting family of filters constituted by carbonaceous merocyanine derivatives described in United States patent US-A-4 195 999 or International patent application WO-A-2004/006878. Those compounds have very good long UV-A filtering properties but have poor solubility in the usual organic solvents and in particular in fatty substances such as oils, and unsatisfactory photostability for certain merocyanine families. The Applicant has surprisingly discovered a novel family of silane, siloxane or polysiloxane derivatives of merocyanine sulphone with good long UV-A filtering properties, very good solubility in the usual organic solvents and excellent cosmetic properties compared with the merocyanines described in WO-A-2004/006878. The invention concerns a novel family of silane, siloxane or polysiloxane derivatives of merocyanine sulphone contained in formulae (1), (2) and (3) which will be described below in more detail. The invention also concerns a cosmetic or dermatological composition intended for the photoprotection of keratinous material containing, in a physiologically acceptable medium, at least one compound of formulae (1), (2) or (3). The term "physiologically acceptable medium" means a non-toxic medium which can be applied to the skin, lips, hair, eyelashes, eyebrows or nails. The composition of the invention may in particular constitute a cosmetic or dermatological composition. Other objectives will become apparent from a study of the description. The compounds of the present invention have one or other of formulae (1), (2) or (3) below: (Figure Removed) X represents -0-, -NR5-, -S02NH-, where R5 represents hydrogen or a C1-C5 alkyl radical; Y is a divalent Ci-C5 alkyl radical optionally substituted with Ci-C4 alkyl radicals and/or containing -0-, -S- atoms or with a -NRi group; R, which may be identical or different, represent a linear or branched and optionally halogenated C1-C2 alkyl radical, a Ce-C12 aryl radical or a CI-CIQ alkoxy group; a = 0 to 3; RI represents a linear or branched and optionally halogenated Ci-C2o alkyl radical or a C&-Ci2 aryl radical; R2, Ra, which may be identical or different, represent H, a C1-C5alkyl radical, a C1-C5 cycloalkyl radical or a C6-C2o aryl radical substituted with alkyl or alkoxy groups, and R2, Ra together with the nitrogen atom may form a C4-Ce cycle optionally interrupted by oxygen atoms or -NH-, wherein R2, Ra cannot together represent A is a divalent radical selected from methylene, ethylene or a group having one of formulae (4), (5) or (Figure Removed) n which: Z is a linear or branched, saturated or unsaturated GIC6 alkylene radical optionally substituted with a hydroxyl radical, or a linear or branched, saturated or unsaturated Ci-C8 alkyl radical; W represents a hydrogen atom; a hydroxyl radical or a linear or branched, saturated or unsaturated Ci-Ce alkyl radical; p is 0 or 1; n = 1 to 4 and when n = 2, RI, R2, R3 or R4 is a divalent alkyl group or R2 and R3 together with the nitrogen atom may form a C4-C6 cycle optionally interrupted by oxygen atoms or -NH-. The compounds of formulae (1), (2) or (3) may be present in the isomeric, E,E-, E,Z- or Z,Z- forms. In addition to units of formula -A-(Si) (R) a (0) (3-a/2, the organosiloxane may contain units of formula (R)b~ (Si) (0) (4-b)/2 in which: R has the meaning given in formulae (1) to (3); b = 1, 2 or 3. Preferably, the - (Si) (R) a (0) p-a)/2 groups may be represented by formulae (7), (8) or (9) below: (D) is a linkage between the silicone chain and group A of the chromophores of formulae (1) to (3); R6, which may be identical or different, are selected from linear or branched Ci-C30 alkyl, phenyl, 3,3,3- trifluoropropyl and trimethylsilyloxy radicals, at least 80% by number of radicals Re being methyl; (B), which may be identical or different, are selected from radicals Re and radical A; r is a whole number in the range 0 to 200 inclusive and s is a whole number in the range 0 to 50 inclusive, and if s = 0, at least one of the two symbols (B) designates A; u is a whole number in the range 1 to 10 inclusive and t is a whole number in the range 0 to 10 inclusive, it being understood that t + u is 3 or more. In formulae (1) to (3) above, the alkyl radicals may be linear or branched, saturated or unsaturated and in particular selected 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. Particularly preferably, the alkyl radical is the methyl radical. In formulae (1) to (3) above, the aryl radicals are preferably phenyl or tolyl. More particularly, Y is a group of atoms forming an oxazolidine cycle, a pyrrolidine cycle, a thiazolidine cycle or an indoline double cycle. The linear or cyclic diorganosiloxanes of formula (7) or (8) encompassed by the context of the present invention are random polymers or oligomers preferably having at least one, and more preferably all, of the following characteristics: • Re is preferably methyl, • B is preferably methyl (in the case of linear compounds of formula (7)). Particularly preferred examples of compounds of formula (1) which may be cited Particularly preferred examples of compounds of formula (2) which may be cited include the substance of formula Particularly preferred examples of compounds of formula (3) which may be cited include the substances of formulae (g) to (k) below: The derivatives of formula (I) may be prepared using a method described in patents US-A-4 045 229 and US-A-4 195 999 in accordance with the following in which radicals R, Rlf R2, RS, A, X, a and m have the meanings given in the above formulae. The derivatives of formula (2) may be prepared using a method described in patent WO-A-00/20388 in accordance with the following reaction scheme: (Figure Removed) n which radicals R, RI, R2, RS, A, X, Y, a and m have the meanings given in the above formulae. The derivatives of formula (3) may be prepared using a method described in patents US-A-4 045 229 and US-A-4 195 999 in accordance with the following reaction scheme: 0=s=0 \K'« "i1" (10) 1 (14) (15) in which radicals R, RI, R2, R/i, A, X, a and m have the meanings given in the above formulae. The compounds of formula (11) may be obtained conventionally by carrying out a hydrosilylation reaction starting from a siloxane or silane derivative of formulae (7) to (8) in which, for example, all of radicals (D) are hydrogen atoms, said derivative hereinafter being termed a SiH derivative, and an unsaturated derivative in accordance with the following reaction scheme: in which radicals R, RI, A, X, Y, Z, a, m and p have the meanings given in the above formulae. The SiH groups may be present in the chain and/or at the chain ends. Said SiH derivatives are substances which are well known in the silicone industry and are generally commercially available. They have, for example, been described in United States patents US-A-3 220 972, US-A-3 697 473 and US-A-4 340 709. In the same manner, the derivatives of formula (15) may be obtained in accordance with the following reaction (Figure Removed) n which radicals R, R2, Y, Z, a and p have the meanings given in the above formulae. The compositions of the invention may further contain other complementary organic or inorganic UV filters which are active in the UV-A and/or UV-B, which are hydrosoluble or liposoluble or even insoluble in cosmetic solvents in current use. In particular, the complementary organic filters are selected from anthranilates; cinnamic derivatives; salicylic derivatives, camphor derivatives; triazine derivatives other than those of the invention, such as those described in patent applications US-A- 4 367 390, EP-A-0 863 145, EP-A-0 517 104, EP-A- 0 570 838, EP-A-0 796 851, EP-A-0 775 698, EP-A- 0 878 469, EP-A-0 933 376, EP-A-0 507 691, EP-A- 0 507 692, EP-A-0 790 243, EP-A-0 944 624; benzophenone derivatives; p,p-diphenylacrylate derivatives; benzotriazole derivatives; benzalmalonate derivatives; benzimidazole derivatives; imidazolines; bis-benzoazolyl derivatives as described in patents EP-A-0 669 323 and US-A-2 463 264; p-aminobenzoic acid (PABA) derivatives; methylene bis-(hydroxyphenyl benzotriazole) derivatives as described in US-A- 5 237 071, US-A-5 166 355, GB-A-2 303 549, DE-A- 197 26 184 and EP-A-0 893 119; polymer filters and silicone filters, such as those described in particular in WO-A-93/04665; dimers derived from xalkylstyrene, such as those described in patent application DE-A-1985 5649; 4,4-diarylbutadienes, such as those described in EP-A-0 967 200, DE-A-1974 6654, DE-A-1975 5649, EP-A-1 008 586, EP-A-1 133 980 and EPA- 0 133 981, and mixtures thereof. Examples of complementary organic filters which may be cited are those noted below with their INCI name: Para-aminobenzoic acid derivatives: PABA; Ethyl PABA; Ethyl Dihydroxypropyl PABA; Ethylhexyl Dimethyl PABA, especially that sold under the trade name "ESCALOL 507" by ISP; Glyceryl PABA; PEG-25 PABA sold under the trade name "UVINUL P25" by BASF; Salicylic derivatives: Homosalate sold under the trade name "Eusolex HMS" by Rona/EM Industries; Ethylhexyl Salicylate sold under the trade name "NEO HELIOPAN OS" by HAARMANN and REIMER; Dipropyleneglycol Salicylate sold under the trade name "DIPSAL" by SCHER; TEA Salicylate, sold under the trade name "NEO HELIOPAN TS" by HAARMANN and REIMER; Cinnamic derivatives: Ethylhexyl Methoxycinnamate, especially that sold under the trade name "PARSOL MCX" by HOFFMANN LA ROCHE; Isopropyl Methoxy cinnamate; Isoamyl Methoxy cinnamate sold under the trade name "NEO HELIOPAN E 1000" by HAARMANN and REIMER; DEA Methoxycinnamate; Diisopropyl Methylcinnamate; Glyceryl Ethylhexanoate Dimethoxycinnamate; {3, J3' -diphenylacrylate derivatives: Octocrylene, especially that sold under the trade name "UVINUL N539" by BASF; Etocrylene, especially that sold 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; Diethylamino Hydroxybenzoyl Hexyl Benzoate sold under the trade name "UVINUL A PLUS" by BASF; Benzylidene camphor derivatives: 3-Benzylidene camphor made under the trade name "MEXORYL SD" by CHIMEX; 4-Methylbenzylidene camphor sold under the trade name "EUSOLEX 6300" by MERCK; Benzylidene Camphor Sulphonic Acid made under the trade name "MEXORYL SL" by CHIMEX; Camphor Benzalkonium Methosulphate made under the trade name "MEXORYL SO" by CHIMEX; Terephthalylidene Dicamphor Sulphonic Acid made under the trade name "MEXORYL SX" by CHIMEX; Polyacrylamidomethyl Benzylidene Camphor made under the trade name "MEXORYL SW" by CHIMEX; Phenyl benzimidazole derivatives: Phenylbenzimidazole Sulphonic Acid, especially that sold under the trade name "EUSOLEX 232" by MERCK; Disodium Phenyl Dibenzimidazole Tetra-sulphonate sold under the trade name "NEO HELIOPAN AP" by HAARMANN and REIMER; Triazine derivatives: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine sold under the trade name "TINOSORB S" by CIBA GEIGY; Ethylhexyl triazone, especially that sold under the trade name "UVINUL T150" by BASF; Diethylhexyl Butamido Triazone sold under the trade name "UVASORB HEB" by SIGMA 3V; Phenyl benzotriazole derivatives: Drometrizole Trisiloxane sold under the trade name "Silatrizole" by RHODIA CHIMIE; Methylene bis-Benzotriazolyl Tetramethylbutylphenol, sold in the solid form under the trade name "MIXXIM BB/100" by FAIRMOUNT CHEMICAL or in the micronized form in 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: Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate; Benzalmalonate derivatives: Polyorganosiloxanes with a benzalmalonate function such as Polysilicone-15 sold under the trade name "PARSOL SLX" by HOFFMANN LA ROCHE; 4,4-diarylbutadiene derivatives: -1,1-dicarboxy (2,2'-dimethylpropyl)-4,4- diphenylbutadiene and mixtures thereof; Benzoxazole derivatives: 2,4-bis-[5-1(dimethylpropyl)benzoxazol-2-yl-(4- phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine sold under the trade name Uvasorb K2A by Sigma 3V; and mixtures thereof. Preferred complementary organic UV filters are selected from: Ethylhexyl Salicylate; Homosalate; Ethylhexyl Methoxycinnamate; Octocrylene; Phenylbenzimidazole Sulphonic Acid; Disodium Phenyl Dibenzimidazole Tetra-sulphonate; Benzophenone-3; Benzophenone-4; Benzophenone-5; n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate; 4-Methylbenzylidene camphor; Terephthalylidene Dicamphor Sulphonic Acid; Anisotriazine; Ethylhexyl triazone; Diethylhexyl Butamido Triazone; Methylene bis-Benzotriazolyl Tetramethylbutylphenol; Drometrizole Trisiloxane; Polysilicone-15; 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. The complementary inorganic photoprotective agents are selected from pigments, more preferably from nanopigments (mean primary particle size: generally between 5 nm and 100 nm, preferably between 10 nm and 50 nm) of treated or untreated metal oxides such as nanopigments of titanium (amorphous or crystalline in the form of rutile and/or anatase), iron, zinc, zirconium or cerium oxide. Treated nanopigments are pigments which have undergone one or more chemical, electronic, chemical-mechanical and/or mechanical surface treatments with compounds such as those 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 aluminium salts of fatty acids, metal alkoxides (titanium or aluminium), polyethylene, silicones, proteins (collagen, elastin), alkanolamines, oxides of silicon, metal oxides, sodium hexametaphosphate, alumina or glycerin. More particularly, the treated nanopigments may be oxides of titanium treated with: • silica and alumina, such as "Microtitanium Dioxide MT 500 SA" and "Microtitanium Dioxide MT 100 SA" from TAYCA, and "Tioveil Fin", "Tioveil OP", "Tioveil MOTG" and "Tioveil IPM" from TIOXIDE; • alumina and aluminium stearate, such as "Microtitanium Dioxide MT 100 T" from TAYCA; • alumina and aluminium laurate, such as "Microtitanium Dioxide MT 100 S" from TAYCA; • iron oxides and iron stearate, such as "Microtitanium Dioxide MT 100 F" from TAYCA; • silica, alumina and silicone, such as "Microtitanium Dioxide MT 100 SAS", "Microtitanium Dioxide MT 600 SAS" and "Microtitanium Dioxide MT 500 SAS" from TAYCA; • sodium hexametaphosphate, such as "Microtitanium Dioxide MT 150 W" from TAYCA; • octyltrimethoxysilane, such as "T-805" from DEGUSSA; • alumina and stearic acid, such as "UVT-M160" from KEMIRA; • alumina and glycerin, such as "UVT-M212" from KEMIRA; • alumina and silicons, such as "UVT-M262" from KEMIRA. Other titanium oxide nanopigments treated with a silicone are preferably TiOa treated with octyl trimethyl silane with a mean elementary particle size in the range 25 nm to 40 nm, such as that sold under the trade name "T 805" by DEGUSSA SILICES, Ti02 treated with a polydimethylsiloxane with a mean elementary particle size of 21 nm, such as that sold under the trade name "70250 CARDRE UF Ti02SI3" by CARDRE, anatase/rutile TiOa treated with a polydimethylhydrogenosiloxane with a mean elementary particle size of 25 nm, such as that sold under the trade name "MICRO TITANIUM DIOXYDE USP GRADE HYDROPHOBIC" by COLOR TECHNIQUES. Examples of non-coated titanium oxide nanopigments are those sold by TAYCA under the trade names "MICROTITANIUM DIOXIDE MT 500 B" or "MICROTITANIUM DIOXIDE MT600 B", by DEGUSSA under the trade name "P 25", by WACKHER under the trade name "Oxyde de titane transparent PW", by MIYOSHI KASEI under the trade name "UFTR", by TOMEN under the trade name "ITS" and by TIOXIDE under the trade name "TIOVEIL AQ" . Examples of non-coated zinc oxide nanopigments are: • those sold under the trade name "Z-COTE" by SUNSMART; • those sold under the trade name "NANOX" by ELEMENTIS; • those sold under the trade name "NANOGARD WCD 2025" by NANOPHASE TECHNOLOGIES. Examples of coated zinc oxide nanopigments are: • those sold under the trade name "OXIDE ZINC CS-5" by Toshibi (ZnO coated with polymethylhydrogenosiloxane); • those sold under the trade name "NANOGARD ZINC OXIDE FN" by NANOPHASE TECHNOLOGIES (in 40% dispersion in Finsolv TN, benzoate of Ci2-Ci5 alcohols) ; • those sold under the trade name "DAITOPERSION ZN- 30" and "DAITOPERSION ZN-50" by Daito (dispersions in cyclopolymethylsiloxane/oxyethylenated polydimethylsiloxane, containing 30% or 50% zinc nano-oxides coated with silica and polymethylhydrogenosiloxane); • those sold under the trade name "NFD ULTRAFINE ZNO" by Daikin (ZnO coated with perfluoroalkyl phosphate and copolymer based on perfluoroalkylethyl in dispersion in cyclopentasiloxane); • those sold under the trade name "SPD-Z1" by Shin- Etsu (ZnO coated with silicone-grafted acrylic polymer, dispersed in cyclodimethylsiloxane); • those sold under the trade name "ESCALOL Z100" by ISP (alumina-treated ZnO dispersed in an ethylhexyl methoxycinnamate/PVP-hexadecene copolymer/methicone mixture); • those sold under the trade name "FUJI ZNO-SMS-10" by Fuji Pigment (silica-coated ZnO and polymethylsilsesquioxane); • those sold under the trade name "NANOX GEL TN" by Elementis (ZnO dispersed to 55% in benzoate of Cij- Cis alcohols with hydroxystearic acid polycondensate). Non-coated cerium oxide nanopigments are sold under the trade name "COLLOIDAL CERIUM OXIDE" by RHONE POULENC. Examples of non-coated iron oxide nanopigments are those sold by ARNAUD under the trade names "NANOGARD WCD 2002 (FE 45B)", "NANOGARD IRON FE 45 BL AQ", "NANOGARD FE 45R AQ", "NANOGARD WCD 2006 (FE 45R)", or by MITSUBISHI under the trade name "TY-220". Examples of coated iron oxide nanopigments are those sold by ARNAUD under the trade 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 trade name "OXYDE DE FER TRANSPARENT". Mixtures of metal oxides may also be cited, in particular titanium dioxide and cerium dioxide; an equal weight mixture of silica-coated titanium dioxide and silica-coated cerium dioxide is sold by IKEDA under the trade name "SUNVEIL A", and a mixture of titanium dioxide and zinc dioxide coated with alumina, silica and silicone such as "M 261" sold by KEMIRA or coated with alumina, silica and glycerin such as "M 211" sold by KEMIRA. The nanopigments may be introduced into the compositions of the invention as they are or in the form of a pigmenting paste, i.e. mixed with a dispersing agent as described, for example, in British patent document GB-A-2 206 339. The additional photoprotective agents are generally present in the compositions of the invention in proportions of 0.01% to 20% by weight with respect to the total composition weight, preferably 0.1% to 10% by weight with respect to the total composition weight. The compositions of the invention may also contain artificial skin tanning and/or browning agents (selftanning agents), more particularly dihydroxyacetone (DHA) . They are preferably present in a quantity of 0.1% to 10% by weight with respect to the total composition weight. The compositions of the present invention may further comprise conventional cosmetic adjuvants, in particular selected from fats, organic solvents, ionic or nonionic, hydrophilic or lipophilic thickening agents, softeners, moisturizers, opacifying agents, stabilizers, emollients, silicones, anti-foaming agents, fragrances, preservatives, anionic, cationic, non-ionic, zwitterionic or amphoteric surfactants, active ingredients, fillers, polymers, propellants, alkalinizing or acidifying agents or any other ingredient which is normally used in the cosmetics and/or dermatological field. The fats may be constituted by an oil or wax or a mixture thereof. The term "oil" means a compound which is liquid at ambient temperature. The term "wax" means a compound which is solid or substantially solid at ambient temperature, generally with a melting point of more than 35°C. Oils which may be cited include mineral oils (paraffin); vegetable oils (sweet almond oil, macadamia oil, blackcurrant seed oil, jojoba oil); synthetic oils such as perhydrosqualene, fatty alcohols, acids or esters (such as the benzoate of Ci2-Ci5 alcohols sold under the trade name "Finsolv TN" by WITCO, octyl palmitate, isopropyl lanolate, triglycerides including those of capric/caprylic acid), oxyethylenated or oxypropylenated fatty esters and ethers; silicone or fluorinated oils (cycomethicone, polydimethylsiloxanes or PDMS), or polyalkylenes. Waxy compounds which may be cited include paraffin, carnauba wax, beeswax and hydrogenated castor oil. Organic solvents which may be cited include low alcohols and polyols which may be selected from glycols and glycol ethers such as ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol or diethylene glycol. Hydrophilic thickening agents which may be cited include carboxyvinyl polymers such as carbopols (carbomers) and Pemulens (acrylate/C10-C30- alkylacrylate copolymer); polyacrylamides such as crosslinked copolymers sold under the trade names Sepigel 305 (CTFA name: polyacrylamide/C13-14 isoparaffin/Laureth 7) or Simulgel 600 (CTFA name: acrylamide/sodium acryloyldimethyltaurate copolymer/isohexadecane/polysorbate 80) from Seppic; polymers and copolymers of 2-acrylamido 2-methylpropane sulphonic acid, which may be crosslinked and/or neutralized, such as poly-(2-acrylamido 2-methylpropane sulphonic acid) sold by Hoechst under the trade name "Hostacerin AMPS" (CTFA name: ammonium polyacryldimethyltauramide) ; cellulose derivatives such as hydroxyethylcellulose; polysaccharides and in particular gums such as xanthan gum; and mixtures thereof. Lipophilic thickening agents which may be cited include modified clays such as hectorite and its derivatives, such as products sold under Bentone's trade names. Active ingredients which may be cited include: • anti-pollution agents and/or radical scavengers; • depigmenting agents and/or propigmenting agents; • anti-glycation agents; • 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; • myorelaxing agents; • tightening agents; • desquamating agents; • moisturizing agents; • anti-inflammatory agents; • agents acting on the energetic metabolism of cells; • insect-repelling agents; • antagonists for P or CRGP substances. Clearly, the skilled person will carefully select any complementary compounds cited above and/or their quantities if used, so that the advantageously intrinsic properties of the compositions of the invention are not or are not substantially altered by the envisaged adjuncts. The compositions of the invention may be prepared using techniques which are well known to the skilled person, in particular those intended for the preparation of oil-in-water or water-in-oil type emulsions. In particular, they may be in the form of an emulsion, which may be simple or complex (0/W, W/0, 0/W/O or W/O/W) , such as a cream or a milk, or in the form of a gel or a cream gel, or in the form of a lotion, a powder, a solid stick or possibly packaged as an aerosol and in the form of a foam or spray. Preferably, the compositions of the invention are in the form of an oil-in-water or water-in-oil emulsion. Emulsions generally contain at least one emulsification agent selected from amphoteric, anionic, cationic or non-ionic emulsification agents, used alone or as a mixture. The emulsification agents are selected appropriately depending on the emulsion to be obtained (W/0 or 0/W). Emulsifying surfactants which can be used to prepare W/0 emulsions which may, for example, be cited include alkyl esters or ethers of sorbitan, glycerol or sugars; silicone surfactants such as dimethicone copolyols, such as the mixture of cyclomethicone and dimethicone copolyol sold under the trade name "DC 5225 C" by Dow Corning, and alkyl-dimethicone copolyols such as Laurylmethicone copolyol sold under the trade name "Dow Corning 5200 Formulation Aid" by Dow Corning; Cetyl dimethicone copolyol, such as that sold under the trade name Abil EM 90R by Goldschmidt and the mixture of cetyl dimethicone copolyol, polyglycerol isostearate (4 moles) and hexyl laurate sold under the trade name ABIL WE 09 by Goldschmidt. In addition, one or more coemulsification agents may be added which, advantageously, may be selected from the group including polyol alkylated esters. Polyol alkylated esters which may be cited include in particular glycerol and/or sorbitan esters, for example polyglycerol isostearate such as the product sold under the trade name Isolan GI 34 by Goldschmidt, sorbitan isostearate, such as that sold under the trade name Arlacel 987 by ICI, sorbitan isostearate and glycerol, such as the product sold under the trade name Arlacel 986 by ICI, and mixtures thereof. Examples of emulsification agents for 0/W emulsions which may be cited include non-ionic emulsification agents such as oxyalkylenated (more particularly polyoxyethylenated) esters of fatty acids and glycerol; oxyalkylenated esters of fatty acids and sorbitan; oxyalkylenated (oxyethylenated and/or oxypropylenated) esters of fatty acids; oxyalkylenated (oxyethylenated and/or oxypropylenated) ethers of fatty alcohols; sugar esters, such as sucrose stearate; ethers of fatty alcohol and sugar, in particular alkylpolyglucosides (APG) such as decylglucoside and lauryl glucoside sold, for example, by Henkel under the respective trade names Plantaren 2000 and Plantaren 1200, cetostearylglucoside, possibly as a mixture with cetostearyl alcohol sold, for example, under the trade name Montanov 68 by Seppic, under the trade name Tegocare CG90 by Goldschmidt and under the trade name Emulgade KE3302 by Henkel, as well as arachidyl glucoside, for example in the form of a mixture of arachidic and behenic alcohol and arachidyl glucoside sold under the trade name Montanov 202 by Seppic. In a particular implementation of the invention, the mixture of alkyl polyglucoside as defined above with the corresponding fatty alcohol may be in the form of a self-emulsifying composition as described, for example, in the document WO-A-92/06778. With an emulsion, the aqueous phase thereof may comprise a non-ionic vesicular dispersion prepared using known methods (Bangham, Standish and Watkins. J. Mol. Biol. 13, 238 (1965), FR-A-2 315 991 and FR-A-2 416 008) . The compositions of the invention are of application in a large number of treatments, in particular cosmetic, of the skin, lips and hair, including the scalp, especially to protect and/or care for the skin, lips and/or hair and/or to make up the skin and/or lips. The present invention also concerns the use of the compositions of 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, in particular care products and make-up products. The cosmetic compositions of the invention may, for example, be used as a care product and/or sun care product for the face and/or the body with a liquid to semi-liquid consistency, such as milks, creams with varying degrees of oiliness, gel creams or pastes. They may be packaged as an aerosol and in the form of a foam or spray. The compositions of the invention in the form of vaporizable fluid lotions in accordance with the invention are applied to the skin or hair in the form of fine particles using pressurization devices. The devices of the invention are well known in the art and include nonaerosol pumps or atomizers, aerosol receptacles including a propellant, and aerosol pumps using compressed air as the propellant. These have been described in patents US-A-4 077 441 and US-A-4 850 517 (forming an integral part of the contents of the description). The compositions packaged in aerosol form in accordance with the invention generally contain conventional propellants such as hydrofluorinated compounds, dichlorodifluoromethane, difluoroethane, dimethyl ether, isobutane, n-butane, propane or trichlorofluoromethane. They are preferably present in quantities of 15% to 50% by weight with respect to the total composition weight. In a further aspect, the invention concerns the use of a compound of formula (1), (2) or (3) as defined above in a cosmetic or dermatological composition as a UV radiation filter. In a further aspect, the invention concerns the use of a compound of formula (1), (2) or (3) as defined above in a cosmetic composition as an agent for controlling the variation in skin colour due to UV radiation. In a further aspect, the invention concerns the use of a compound of formula (1), (2) or (3) as defined above as an agent for photostabilizing synthetic polymers such as plastic materials or glass, in particular spectacle lenses or contact lenses. Non-limiting examples which illustrate the invention will now be given. EXAMPLE 1: Preparation of compound (g) of formula (3) (4) (7) : n=l, a = l, m=l, X=0, R1=p-tolyl, R=R2=R4 :=R6= (B) =-CH3, p=l, W=H, Z=-CH2-, r=0, s=l: First step: Preparation of methyl-5- [allyl(methyl)amino]-2-[(4- methylphenyl)sulphonyl]penta-2,4-dienoate: 3-anilinoacrolein anil (1.2 g, 5.4 * 10 mole) and methyl para-toluene sulphonylacetate (1.48 g, 6.48 x 10"3 mole) were heated to 85-90°C in 5 ml of acetic anhydride for 2 hours 30 minutes. The acetic anhydride was evaporated to dryness under reduced pressure. The oil obtained was taken up in 5 ml of ethanol. N-methyl allylamine (1.115 ml, 0.0117 mole) was added and the mixture was heated under reflux for 4 hours 30 minutes. The ethanol was evaporated to dryness under reduced pressure. The orangey-brown oil obtained was purified on a silica chromatographic column (eluent: EtOAc/heptane, 20:80 then a gradient to 30:70). 1.48 g of clean fractions (yield: 77%) of methyl-5- [allay(methyl)amino-2-[(4-methylphenyl)sulphonyl]pentane- 2,4-dienoate were recovered in the form of a pale yellow UV (CH2C12) : A,max = 370 nm, E1% = 1346 A,max = 356 nm (shoulder), EI% = 1031. Second step: Preparation of compound of Example 1: 0.371 g (1.67 x 10"3 mole) of heptamethyltrisiloxane was added dropwise over 10 minutes to a solution of the preceding substance (0.508 g, 1.51 * 10"3 mole) and catalyst (complex containing 3-3.5% by weight of Pt in cyclovinylmethylsiloxane from Hiils Petrarch, PC085: 100 \il) in 2 ml of dry toluene heated to 80°C. It was left at that temperature for 6 hours. The reaction mixture was concentrated. It was taken up in dichloromethane and that solution was passed over a bed of Celite. The pale yellow oil obtained was chromatographed on a silica column (eluent: heptane/EtOAc, 65:35). 0.45 g (yield: 53%) of clean fractions of the derivative of Example 1 was obtained in the form of a pale yellow oil which crystallized over time: UV (Ethanol): Xmax = 372 nm, EI% = 1154 X,max = 356 nm (shoulder) , EI% = 773. EXAMPLE 2: Preparation of compound (h) of formula (3) (4) (7): n=l, a = l, b=2, m=l, X=0, Ri=p-tolyl, R=R2=PM=R6= (B) =-CH3, p=l, W=H, Z=-CH2-, r=s=6: 0.325 g (2 meq SiH) of methylhydro (50-55%) dimethylsiloxane (45-50%) copolymer (PS122.5 from Petrarch) was added dropwise over 10 minutes to a solution of methyl-5-[allyl(methyl)amino]-2-[(4- methylphenyl)sulphonyl]penta-2,4-dienoate (0.7 g, 2.1 x 10~ and catalyst (complex containing 3-3.5% by weight of Pt in cyclovinylmethylsiloxane from Hiils Petrarch, PC085: 80 ul) in 2 ml of dry toluene heated to 80°C. It was left at that temperature for 6 hours. The reaction mixture was concentrated. It was taken up in dichloromethane and that solution was passed over a bed of Celite. The pale yellow oil obtained was chromatographed on a silica column (eluent: C^Cla) . 0.92 g of clean fractions of the derivative of Example 2 was obtained in the form of a viscous pale yellow oil: UV (Ethanol): Amax = 371 nm, EI% = 728. EXAMPLE 3: Preparation of mixture of compounds of formula n=l, a=l, m=l, X=0, Ri=-phenyl, R=R2=R6=(B)=-CH3, p=l, Z=-CH2-, r=0, s- First step: Preparation of ethyl-5-[methyl(prop-2- ynyl)amino]-2-(phenylsulphonyl)penta-2,4-dienoate: 3-anilinoacrolein anil (1.5 g, 6.75 * 10~3 mole) and ethyl phenyl sulphonylacetate (1.848 g, 8.1 * 10"3 mole) were heated to 85-90°C in 5 ml of acetic anhydride for 3 hours. The acetic anhydride was evaporated to dryness under reduced pressure. The oil obtained was taken up in 5 ml of ethanol. N-methyl propargylamine (1.22 ml, 0.0146 mole) was added and the mixture was heated under reflux for 5 hours. The ethanol was evaporated to dryness under reduced pressure. The orangey oil obtained was purified on a silica chromatographic column (eluent: EtOAc/heptane, 50:50 then a gradient to 30:70). 1.68 g of clean fractions (yield: 71%) of ethyl-5-[methyl(prop-2-ynyl)amino]-2- (phenylsulphonyl)penta-2,4-dienoate were recovered in the form of a pale yellow oil: UV (CH2C12) : Xmax = 366 nm' Ei% = 1367 max = 358 nm (shoulder), Ea% = 1298. Second step: Preparation of compound of Example 3: 0.413 g (1.86 x 10~3 mole) of heptamethyltrisiloxane was added dropwise over 10 minutes to a solution of the preceding substance (0.562 g, 1.69 x 10"3 mole) and catalyst (complex containing 3-3.5% by weight of Pt in cyclovinylmethylsiloxane from Hiils Petrarch PC085: 60 ul) in 2 ml of dry toluene heated to 80°C. It was left at that temperature for 6 hours. The reaction mixture was concentrated. It was taken up in dichloromethane and that solution was passed over a bed of Celite. The pale yellow oil obtained was chromatographed on a silica column (eluent: CH2Cl2) . 0.35 g (yield: 37%) of clean fractions of the derivative of Example 3 was obtained in the form of an orangey-yellow oil which crystallized over time and in a ratio of 25:75, determined by H NMR: UV (Ethanol) : X,max = 366 nm, EI% = 1058 X,max = 356 nm (shoulder), EI% = 705. EXAMPLE 4: Preparation of mixture of compounds (j) of formula (3) (5) (6) (7) : n=l, a=l, m=l, X=0, Ri=-phenyl, R=R2=R6=(B)=-CH3, R4=-CH2CH3, p=l, Z=-CH2-, r=20, s=2+7; 1.24 g (2.3 meq SiH) of methylhydro (30-35%) dimethylsiloxane (65-70%) copolymer (PDMS oil containing SiH, 628V14 from Rhone-Poulenc) were added dropwise over 10 minutes to a solution of ethyl-5- [methyl(prop-2-ynyl)amino]-2-(phenylsulphonyl)penta- 2,4-dienoate (0.8 g, 2.41 1Q"3 mole) obtained in the first step of Example 3 and catalyst (complex containing 3-3.5% by weight of Pt in cyclovinylmethylsiloxane from Huls Petrarch, PC085: 110 pi 1) in 2 ml of dry toluene heated to 80°C. It was left at that temperature for 6 hours. The reaction mixture was concentrated. It was taken up in dichloromethane and that solution was passed over a bed of Celite. The pale yellow oil obtained was chromatographed on a silica column (eluent: CH2C12) . 1.82 g of clean fractions of the derivative of Example 4 were obtained in the form of a viscous pale yellow oil: UV (Ethanol) : Xmax = 366 nm, Ei% = 270. FORMULATION EXAMPLES EXAMPLE A: - Mixture of glycerol mono/distearate / 1.0 g polyethyleneglycol stearate 100 OE (ARLACEL 165 FL- ICI) - Cetyl alcohol 0.5 g - Palm oil stearic acid 2.5 g (STEARINE TP-STEARINERIE DUBOIS) - Polydimethylsiloxane 0.5 g (DOW CORNING 200 FLUID- DOW CORNING) - Benzoate of Ci2/Cis alcohols 20 g (WITCONOL TN- WITCO) - Compound of Example 1 2 g - Glycerin 5.0 g - Hexadecyl alcohol phosphate, potassium salt 1.0 g (AMPHISOL K- HOFFMANN LA ROCHE) - Polyacrylic acid 0.3 g (SYNTHALEN K- 3V) - Hydroxypropylmethylcellusose 0.1 g (METHOCEL F4M- DOW CHEMICAL) - Cyclopentadimethylsiloxane 2.0 g (DC245- DOW CORNING) - Triethanolamine 0.8 g - Preservatives qs - Demineralized water qs 100 g EXAMPLE B: - Mixture of cetylstearyl alcohol 7.0 g and oxyethylenated cetylstearyl alcohol, 33 OE (80/20) (SINNOWAX AO-HENKEL) - Mixture of glycerol mono- and distearate 2.0 g (CERASYNT SD-V from ISP) - Cetyl alcohol 1.5 g - Polydimethylsiloxane 1.5 g (DOW CORNING 200 FLUID- DOW CORNING) - Benzoate of Ci2/Ci5 alcohols 8.0 g (WITCONOL TN- WITCO) - Vaseline oil 10.0 g - Compound of Example 2 2.0 g - Glycerin 10.0 g - Preservatives qs - Demineralized water qs 100 g We claim 1. Silane, siloxane or polysiloxane merocyanine sulphone compound chosen from (i) those having one or other of formulae (1), (2) or (3) below and which may be present in the isomeric E, E-, E-Z-, or Z, Z- forms: (Formula Removed) in which: m = 0 or 1; X represents -O-, -NR5-, -SO2NH-, where R5 represents hydrogen or a linear or branched C1-C5 alkyl radical; Y is a divalent C1-C5 alkyl radical optionally substituted with C1-C4 alkyl radicals and/or containing -O-, -S- atoms or with a -NR1 group; each R moiety, which may be identical or different, represents a linear or branched and optionally halogenated C1-C20 alkyl radical, a C6-C12 aryl radical or a C1-C10 alkoxy group; a = 0 to 3; R1 represents a linear or branched and optionally halogenated C1-C20 alkyl radical or a C6-C12 aryl radical; the R2 and R3 moieties, which may be identical or different, represent H, a linear or branched C1-C24 alkyl radical, a C3-C10 cycloalkyl radical or a C6-C20 aryl radical substituted with alkyl or alkoxy groups, and the R2 and R3 moieties, together with the nitrogen atom may form a C4-C6 cycle optionally interrupted by oxygen atoms or -NH-, wherein the R2 and R3 moieties cannot together represent a hydrogen atom; R4 is an alkyl group; A is a divalent radical selected from methylene, ethylene or a group having one of formulae (4), (5) or (6) below: (Formula Removed) in which: Z is a linear or branched, saturated or unsaturated C1-C6 alkylene radical optionally substituted with a hydroxyl radical, or a linear or branched, saturated or unsaturated C1- C8 alkyl radical; W represents a hydrogen atom; a hydroxyl radical or a linear or branched, saturated or unsaturated C1-C8 alkyl radical; p is 0 or 1; n = 1 to 4 and when n = 2, one of the R1 and R2 and R3 and R4 moieties is a divalent alkyl group or R2 and R3 together with the nitrogen atom may form a C4-C6 cycle optionally interrupted by oxygen atoms or -NH-; said compound possibly containing in addition units of formula -A-(Si) (R)a (O)(3-a)/2, the organosiloxane may contain units of formula (R)b- (Si) (O) (4-b)/2 in which: R has the meaning given in formulae (1) to (3); b= 1,2 or 3; (i) those chosen from the following compounds (Formula Removed) 2. Compound having one or other of formulae (1), (2) and (3) as claimed in claim 1, and which may be present in the isomeric E, E-, E, Z- or Z, Z- forms, wherein the group - (Si) (R)a (O) (3-a)/2 is replaced by one of formulae (7), (8) or (9) below: (Formula Removed) in which: (D) is a linkage between the silicone chain and group A of the chromophores of formulae (1) to (3); R6, which may be identical or different, are selected from linear or branched C1-C30 alkyl, phenyl, 3, 3, 3-trifluoropropyl and trimethylsilyloxy radicals, 80% to 100% by number of radicals R6 being methyl; (B), which may be identical or different, are selected from radicals R6 and radical A; r is a whole number in the range 0 to 200 inclusive and s is a whole number in the range 0 to 50 inclusive, and if s = 0, one or both of the two symbols (B) designates A; u is a whole number in the range 1 to 10 inclusive and t is a whole number in the range 0 to 10 inclusive, it being understood that t + u is 3 or more. 3. Compound as claimed in claim 2, wherein it designates a linear or cyclic diorganosiloxane of formula (7) or (8) having one or both, and more preferably all, of the following characteristics: R6 is methyl, B is methyl. 4. Compound as claimed in any one of claims 1 to 3, wherein it designates a compound of formula (1) selected from formulae (a) to (e) below: (Formula Removed) 5. Compound as claimed in any one of claims 1 to 3, where it designates the compound of formula (2) as defined in formula (f) below: (Formula Removed)

Full Text

The present invention relates to silane, siloxane or polysiloxane merocyanine sulphone compound.
The present invention concerns novel silane, siloxane or polysiloxane derivatives of merocyanine sulphone and their use in cosmetics as long UV-A filters.
The present invention also concerns cosmetic compositions for topical use, in particular intended for the photoprotection of skin and/or hair, comprising an effective quantity of at least one silane, siloxane or polysiloxane derivative of merocyanine sulphone or a mixture of derivatives.
Radiation with wavelengths in the range 280 nm [nanometre] to 400 nm is known to brown human skin, and radiation with wavelengths in the range 280 nm to 320 nm, known as UV-B radiation, is known to cause erythemas and burns to the skin which can interfere with the development of a natural tan.
UV-A radiation with wavelengths in the range 320 nm to 400 nm is also known to cause the skin to brown, but is capable of inducing an alteration in the skin, in particular in the case of sensitive skin and/or skin continuously exposed to solar radiation. In particular, UV-A radiation causes loss of skin elasticity and the appearance of wrinkles, resulting in premature ageing of the skin. It encourages triggering of the erythematous reaction or amplifies that reaction in some subjects and may even be at the source of phototoxic or photoallergic reactions. Thus, for aesthetic and cosmetic reasons, such as preserving the natural elasticity of the skin, more and more people wish to control the effect of UV-A radiation on their skin. The term "sun protection factor" means the ratio of the irradiation period necessary to reach the erythematogenic threshold in the presence of a test filter to the irradiation period necessary to reach
that same threshold in the absence of a filter.
A number of organic compounds intended to protect the
skin against UV-A and/or UV-B radiation have been
proposed.
The majority of them are aromatic compounds absorbing
UV radiation in the zone in the range 280 nm to 315 nm
or in the zone in the range 315 nm to 400 nm and
beyond, or across both of those zones. They are
usually formulated into sunscreen compositions which
are in the form of oil-in-water emulsions or water-inoil
emulsions. The organic filters, which are
generally lipophilic or hydrophilic, are present in a
dissolved form in one or the other of those phases in
quantities appropriate for obtaining the desired sun
protection factor (SPF).
In addition to their solar radiation filtration
capability, desirable photoprotective compounds must
also have other good cosmetic properties, good
solubility in the usual solvents, in particular in
fatty substances such as oils or fats, and good
resistance to water and perspiration (persistance), as
well as very good photostability.
Compounds which have been recommended for that purpose
which may be cited include a particularly interesting
family of filters constituted by carbonaceous
merocyanine derivatives described in United States
patent US-A-4 195 999 or International patent
application WO-A-2004/006878. Those compounds have
very good long UV-A filtering properties but have poor
solubility in the usual organic solvents and in
particular in fatty substances such as oils, and
unsatisfactory photostability for certain merocyanine
families.
The Applicant has surprisingly discovered a novel
family of silane, siloxane or polysiloxane derivatives
of merocyanine sulphone with good long UV-A filtering
properties, very good solubility in the usual organic
solvents and excellent cosmetic properties compared
with the merocyanines described in WO-A-2004/006878.
The invention concerns a novel family of silane,
siloxane or polysiloxane derivatives of merocyanine
sulphone contained in formulae (1), (2) and (3) which
will be described below in more detail.
The invention also concerns a cosmetic or
dermatological composition intended for the
photoprotection of keratinous material containing, in a
physiologically acceptable medium, at least one
compound of formulae (1), (2) or (3).
The term "physiologically acceptable medium" means a
non-toxic medium which can be applied to the skin,
lips, hair, eyelashes, eyebrows or nails. The
composition of the invention may in particular
constitute a cosmetic or dermatological composition.
Other objectives will become apparent from a study of
the description.
The compounds of the present invention have one or
other of formulae (1), (2) or (3) below:
(Figure Removed) X represents -0-, -NR5-, -S02NH-, where R5 represents
hydrogen or a C1-C5 alkyl radical;
Y is a divalent Ci-C5 alkyl radical optionally
substituted with Ci-C4 alkyl radicals and/or containing
-0-, -S- atoms or with a -NRi group;
R, which may be identical or different, represent a
linear or branched and optionally halogenated C1-C2
alkyl radical, a Ce-C12 aryl radical or a CI-CIQ alkoxy
group;
a = 0 to 3;
RI represents a linear or branched and optionally
halogenated Ci-C2o alkyl radical or a C&-Ci2 aryl
radical;
R2, Ra, which may be identical or different, represent
H, a C1-C5alkyl radical, a C1-C5 cycloalkyl radical or
a C6-C2o aryl radical substituted with alkyl or alkoxy
groups, and R2, Ra together with the nitrogen atom may
form a C4-Ce cycle optionally interrupted by oxygen
atoms or -NH-, wherein R2, Ra cannot together represent
A is a divalent radical selected from methylene,
ethylene or a group having one of formulae (4), (5) or
(Figure Removed) n which:
Z is a linear or branched, saturated or unsaturated GIC6
alkylene radical optionally substituted with a
hydroxyl radical, or a linear or branched, saturated or
unsaturated Ci-C8 alkyl radical;
W represents a hydrogen atom; a hydroxyl radical or a
linear or branched, saturated or unsaturated Ci-Ce alkyl
radical;
p is 0 or 1;
n = 1 to 4 and when n = 2, RI, R2, R3 or R4 is a divalent
alkyl group or R2 and R3 together with the nitrogen atom
may form a C4-C6 cycle optionally interrupted by oxygen
atoms or -NH-.
The compounds of formulae (1), (2) or (3) may be
present in the isomeric, E,E-, E,Z- or Z,Z- forms.
In addition to units of formula -A-(Si) (R) a (0) (3-a/2, the
organosiloxane may contain units of formula (R)b~
(Si) (0) (4-b)/2 in which:
R has the meaning given in formulae (1) to (3);
b = 1, 2 or 3.
Preferably, the - (Si) (R) a (0) p-a)/2 groups may be
represented by formulae (7), (8) or (9) below:
(D) is a linkage between the silicone chain and group A
of the chromophores of formulae (1) to (3);
R6, which may be identical or different, are selected
from linear or branched Ci-C30 alkyl, phenyl, 3,3,3-
trifluoropropyl and trimethylsilyloxy radicals, at
least 80% by number of radicals Re being methyl;
(B), which may be identical or different, are selected
from radicals Re and radical A;
r is a whole number in the range 0 to 200 inclusive and
s is a whole number in the range 0 to 50 inclusive, and
if s = 0, at least one of the two symbols (B)
designates A;
u is a whole number in the range 1 to 10 inclusive and
t is a whole number in the range 0 to 10 inclusive, it
being understood that t + u is 3 or more.
In formulae (1) to (3) above, the alkyl radicals may be
linear or branched, saturated or unsaturated and in
particular selected 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. Particularly
preferably, the alkyl radical is the methyl radical.
In formulae (1) to (3) above, the aryl radicals are
preferably phenyl or tolyl.
More particularly, Y is a group of atoms forming an
oxazolidine cycle, a pyrrolidine cycle, a thiazolidine
cycle or an indoline double cycle.
The linear or cyclic diorganosiloxanes of formula (7)
or (8) encompassed by the context of the present
invention are random polymers or oligomers preferably
having at least one, and more preferably all, of the
following characteristics:
• Re is preferably methyl,
• B is preferably methyl (in the case of linear
compounds of formula (7)).
Particularly preferred examples of compounds of formula
(1) which may be cited
Particularly preferred examples of compounds of formula
(2) which may be cited include the substance of formula
Particularly preferred examples of compounds of formula
(3) which may be cited include the substances of
formulae (g) to (k) below:
The derivatives of formula (I) may be prepared using a
method described in patents US-A-4 045 229 and
US-A-4 195 999 in accordance with the following
in which radicals R, Rlf R2, RS, A, X, a and m have the
meanings given in the above formulae.
The derivatives of formula (2) may be prepared using a
method described in patent WO-A-00/20388 in accordance
with the following reaction scheme:
(Figure Removed) n which radicals R, RI, R2, RS, A, X, Y, a and m have
the meanings given in the above formulae.
The derivatives of formula (3) may be prepared using a
method described in patents US-A-4 045 229 and
US-A-4 195 999 in accordance with the following
reaction scheme:
0=s=0 \K'« "i1"
(10) 1 (14) (15)
in which radicals R, RI, R2, R/i, A, X, a and m have the
meanings given in the above formulae.
The compounds of formula (11) may be obtained
conventionally by carrying out a hydrosilylation
reaction starting from a siloxane or silane derivative
of formulae (7) to (8) in which, for example, all of
radicals (D) are hydrogen atoms, said derivative
hereinafter being termed a SiH derivative, and an
unsaturated derivative in accordance with the following
reaction scheme:
in which radicals R, RI, A, X, Y, Z, a, m and p have the
meanings given in the above formulae.
The SiH groups may be present in the chain and/or at
the chain ends. Said SiH derivatives are substances
which are well known in the silicone industry and are
generally commercially available. They have, for
example, been described in United States patents
US-A-3 220 972, US-A-3 697 473 and US-A-4 340 709.
In the same manner, the derivatives of formula (15) may
be obtained in accordance with the following reaction
(Figure Removed) n which radicals R, R2, Y, Z, a and p have the meanings
given in the above formulae.
The compositions of the invention may further contain
other complementary organic or inorganic UV filters
which are active in the UV-A and/or UV-B, which are
hydrosoluble or liposoluble or even insoluble in
cosmetic solvents in current use.
In particular, the complementary organic filters are
selected from anthranilates; cinnamic derivatives;
salicylic derivatives, camphor derivatives; triazine
derivatives other than those of the invention, such as
those described in patent applications US-A-
4 367 390, EP-A-0 863 145, EP-A-0 517 104, EP-A-
0 570 838, EP-A-0 796 851, EP-A-0 775 698, EP-A-
0 878 469, EP-A-0 933 376, EP-A-0 507 691, EP-A-
0 507 692, EP-A-0 790 243, EP-A-0 944 624;
benzophenone derivatives; p,p-diphenylacrylate
derivatives; benzotriazole derivatives; benzalmalonate
derivatives; benzimidazole derivatives; imidazolines;
bis-benzoazolyl derivatives as described in patents
EP-A-0 669 323 and US-A-2 463 264; p-aminobenzoic acid
(PABA) derivatives; methylene bis-(hydroxyphenyl
benzotriazole) derivatives as described in US-A-
5 237 071, US-A-5 166 355, GB-A-2 303 549, DE-A-
197 26 184 and EP-A-0 893 119; polymer filters and
silicone filters, such as those described in
particular in WO-A-93/04665; dimers derived from xalkylstyrene,
such as those described in patent
application DE-A-1985 5649; 4,4-diarylbutadienes, such
as those described in EP-A-0 967 200, DE-A-1974 6654,
DE-A-1975 5649, EP-A-1 008 586, EP-A-1 133 980 and EPA-
0 133 981, and mixtures thereof.
Examples of complementary organic filters which may be
cited are those noted below with their INCI name:
Para-aminobenzoic acid derivatives:
PABA;
Ethyl PABA;
Ethyl Dihydroxypropyl PABA;
Ethylhexyl Dimethyl PABA, especially that sold under
the trade name "ESCALOL 507" by ISP;
Glyceryl PABA;
PEG-25 PABA sold under the trade name "UVINUL P25" by
BASF;
Salicylic derivatives:
Homosalate sold under the trade name "Eusolex HMS" by
Rona/EM Industries;
Ethylhexyl Salicylate sold under the trade name "NEO
HELIOPAN OS" by HAARMANN and REIMER;
Dipropyleneglycol Salicylate sold under the trade name
"DIPSAL" by SCHER;
TEA Salicylate, sold under the trade name "NEO
HELIOPAN TS" by HAARMANN and REIMER;
Cinnamic derivatives:
Ethylhexyl Methoxycinnamate, especially that sold
under the trade name "PARSOL MCX" by HOFFMANN LA
ROCHE;
Isopropyl Methoxy cinnamate;
Isoamyl Methoxy cinnamate sold under the trade name
"NEO HELIOPAN E 1000" by HAARMANN and REIMER;
DEA Methoxycinnamate;
Diisopropyl Methylcinnamate;
Glyceryl Ethylhexanoate Dimethoxycinnamate;
{3, J3' -diphenylacrylate derivatives:
Octocrylene, especially that sold under the trade name
"UVINUL N539" by BASF;
Etocrylene, especially that sold 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;
Diethylamino Hydroxybenzoyl Hexyl Benzoate sold under
the trade name "UVINUL A PLUS" by BASF;
Benzylidene camphor derivatives:
3-Benzylidene camphor made under the trade name
"MEXORYL SD" by CHIMEX;
4-Methylbenzylidene camphor sold under the trade name
"EUSOLEX 6300" by MERCK;
Benzylidene Camphor Sulphonic Acid made under the
trade name "MEXORYL SL" by CHIMEX;
Camphor Benzalkonium Methosulphate made under the
trade name "MEXORYL SO" by CHIMEX;
Terephthalylidene Dicamphor Sulphonic Acid made under
the trade name "MEXORYL SX" by CHIMEX;
Polyacrylamidomethyl Benzylidene Camphor made under
the trade name "MEXORYL SW" by CHIMEX;
Phenyl benzimidazole derivatives:
Phenylbenzimidazole Sulphonic Acid, especially that
sold under the trade name "EUSOLEX 232" by MERCK;
Disodium Phenyl Dibenzimidazole Tetra-sulphonate sold
under the trade name "NEO HELIOPAN AP" by HAARMANN and
REIMER;
Triazine derivatives:
Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine sold
under the trade name "TINOSORB S" by CIBA GEIGY;
Ethylhexyl triazone, especially that sold under the
trade name "UVINUL T150" by BASF;
Diethylhexyl Butamido Triazone sold under the trade
name "UVASORB HEB" by SIGMA 3V;
Phenyl benzotriazole derivatives:
Drometrizole Trisiloxane sold under the trade name
"Silatrizole" by RHODIA CHIMIE;
Methylene bis-Benzotriazolyl Tetramethylbutylphenol,
sold in the solid form under the trade name "MIXXIM
BB/100" by FAIRMOUNT CHEMICAL or in the micronized
form in 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:
Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline
Propionate;
Benzalmalonate derivatives:
Polyorganosiloxanes with a benzalmalonate function
such as Polysilicone-15 sold under the trade name
"PARSOL SLX" by HOFFMANN LA ROCHE;
4,4-diarylbutadiene derivatives:
-1,1-dicarboxy (2,2'-dimethylpropyl)-4,4-
diphenylbutadiene
and mixtures thereof;
Benzoxazole derivatives:
2,4-bis-[5-1(dimethylpropyl)benzoxazol-2-yl-(4-
phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine
sold under the trade name Uvasorb K2A by Sigma 3V;
and mixtures thereof.
Preferred complementary organic UV filters are
selected from:
Ethylhexyl Salicylate;
Homosalate;
Ethylhexyl Methoxycinnamate;
Octocrylene;
Phenylbenzimidazole Sulphonic Acid;
Disodium Phenyl Dibenzimidazole Tetra-sulphonate;
Benzophenone-3;
Benzophenone-4;
Benzophenone-5;
n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate;
4-Methylbenzylidene camphor;
Terephthalylidene Dicamphor Sulphonic Acid;
Anisotriazine;
Ethylhexyl triazone;
Diethylhexyl Butamido Triazone;
Methylene bis-Benzotriazolyl Tetramethylbutylphenol;
Drometrizole Trisiloxane;
Polysilicone-15;
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.
The complementary inorganic photoprotective agents are
selected from pigments, more preferably from
nanopigments (mean primary particle size: generally
between 5 nm and 100 nm, preferably between 10 nm and
50 nm) of treated or untreated metal oxides such as
nanopigments of titanium (amorphous or crystalline in
the form of rutile and/or anatase), iron, zinc,
zirconium or cerium oxide.
Treated nanopigments are pigments which have undergone
one or more chemical, electronic, chemical-mechanical
and/or mechanical surface treatments with compounds
such as those 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 aluminium salts of fatty acids, metal
alkoxides (titanium or aluminium), polyethylene,
silicones, proteins (collagen, elastin),
alkanolamines, oxides of silicon, metal oxides, sodium
hexametaphosphate, alumina or glycerin.
More particularly, the treated nanopigments may be
oxides of titanium treated with:
• silica and alumina, such as "Microtitanium Dioxide
MT 500 SA" and "Microtitanium Dioxide MT 100 SA"
from TAYCA, and "Tioveil Fin", "Tioveil OP",
"Tioveil MOTG" and "Tioveil IPM" from TIOXIDE;
• alumina and aluminium stearate, such as
"Microtitanium Dioxide MT 100 T" from TAYCA;
• alumina and aluminium laurate, such as
"Microtitanium Dioxide MT 100 S" from TAYCA;
• iron oxides and iron stearate, such as
"Microtitanium Dioxide MT 100 F" from TAYCA;
• silica, alumina and silicone, such as
"Microtitanium Dioxide MT 100 SAS", "Microtitanium
Dioxide MT 600 SAS" and "Microtitanium Dioxide MT
500 SAS" from TAYCA;
• sodium hexametaphosphate, such as "Microtitanium
Dioxide MT 150 W" from TAYCA;
• octyltrimethoxysilane, such as "T-805" from
DEGUSSA;
• alumina and stearic acid, such as "UVT-M160" from
KEMIRA;
• alumina and glycerin, such as "UVT-M212" from
KEMIRA;
• alumina and silicons, such as "UVT-M262" from
KEMIRA.
Other titanium oxide nanopigments treated with a
silicone are preferably TiOa treated with octyl
trimethyl silane with a mean elementary particle size
in the range 25 nm to 40 nm, such as that sold under
the trade name "T 805" by DEGUSSA SILICES, Ti02 treated
with a polydimethylsiloxane with a mean elementary
particle size of 21 nm, such as that sold under the
trade name "70250 CARDRE UF Ti02SI3" by CARDRE,
anatase/rutile TiOa treated with a
polydimethylhydrogenosiloxane with a mean elementary
particle size of 25 nm, such as that sold under the
trade name "MICRO TITANIUM DIOXYDE USP GRADE
HYDROPHOBIC" by COLOR TECHNIQUES.
Examples of non-coated titanium oxide nanopigments are
those sold by TAYCA under the trade names
"MICROTITANIUM DIOXIDE MT 500 B" or "MICROTITANIUM
DIOXIDE MT600 B", by DEGUSSA under the trade name "P
25", by WACKHER under the trade name "Oxyde de titane
transparent PW", by MIYOSHI KASEI under the trade name
"UFTR", by TOMEN under the trade name "ITS" and by
TIOXIDE under the trade name "TIOVEIL AQ" .
Examples of non-coated zinc oxide nanopigments are:
• those sold under the trade name "Z-COTE" by
SUNSMART;
• those sold under the trade name "NANOX" by
ELEMENTIS;
• those sold under the trade name "NANOGARD WCD
2025" by NANOPHASE TECHNOLOGIES.
Examples of coated zinc oxide nanopigments are:
• those sold under the trade name "OXIDE ZINC CS-5"
by Toshibi (ZnO coated with
polymethylhydrogenosiloxane);
• those sold under the trade name "NANOGARD ZINC
OXIDE FN" by NANOPHASE TECHNOLOGIES (in 40%
dispersion in Finsolv TN, benzoate of Ci2-Ci5
alcohols) ;
• those sold under the trade name "DAITOPERSION ZN-
30" and "DAITOPERSION ZN-50" by Daito (dispersions
in cyclopolymethylsiloxane/oxyethylenated
polydimethylsiloxane, containing 30% or 50% zinc
nano-oxides coated with silica and
polymethylhydrogenosiloxane);
• those sold under the trade name "NFD ULTRAFINE
ZNO" by Daikin (ZnO coated with perfluoroalkyl
phosphate and copolymer based on
perfluoroalkylethyl in dispersion in
cyclopentasiloxane);
• those sold under the trade name "SPD-Z1" by Shin-
Etsu (ZnO coated with silicone-grafted acrylic
polymer, dispersed in cyclodimethylsiloxane);
• those sold under the trade name "ESCALOL Z100" by
ISP (alumina-treated ZnO dispersed in an
ethylhexyl methoxycinnamate/PVP-hexadecene
copolymer/methicone mixture);
• those sold under the trade name "FUJI ZNO-SMS-10"
by Fuji Pigment (silica-coated ZnO and
polymethylsilsesquioxane);
• those sold under the trade name "NANOX GEL TN" by
Elementis (ZnO dispersed to 55% in benzoate of Cij-
Cis alcohols with hydroxystearic acid
polycondensate).
Non-coated cerium oxide nanopigments are sold
under the trade name "COLLOIDAL CERIUM OXIDE" by
RHONE POULENC.
Examples of non-coated iron oxide nanopigments are
those sold by ARNAUD under the trade names "NANOGARD
WCD 2002 (FE 45B)", "NANOGARD IRON FE 45 BL AQ",
"NANOGARD FE 45R AQ", "NANOGARD WCD 2006 (FE 45R)", or
by MITSUBISHI under the trade name "TY-220".
Examples of coated iron oxide nanopigments are those
sold by ARNAUD under the trade 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 trade name "OXYDE DE FER TRANSPARENT".
Mixtures of metal oxides may also be cited, in
particular titanium dioxide and cerium dioxide; an
equal weight mixture of silica-coated titanium dioxide
and silica-coated cerium dioxide is sold by IKEDA under
the trade name "SUNVEIL A", and a mixture of titanium
dioxide and zinc dioxide coated with alumina, silica
and silicone such as "M 261" sold by KEMIRA or coated
with alumina, silica and glycerin such as "M 211" sold
by KEMIRA.
The nanopigments may be introduced into the
compositions of the invention as they are or in the
form of a pigmenting paste, i.e. mixed with a
dispersing agent as described, for example, in British
patent document GB-A-2 206 339.
The additional photoprotective agents are generally
present in the compositions of the invention in
proportions of 0.01% to 20% by weight with respect to
the total composition weight, preferably 0.1% to 10% by
weight with respect to the total composition weight.
The compositions of the invention may also contain
artificial skin tanning and/or browning agents (selftanning
agents), more particularly dihydroxyacetone
(DHA) . They are preferably present in a quantity of
0.1% to 10% by weight with respect to the total
composition weight.
The compositions of the present invention may further
comprise conventional cosmetic adjuvants, in particular
selected from fats, organic solvents, ionic or nonionic,
hydrophilic or lipophilic thickening agents,
softeners, moisturizers, opacifying agents,
stabilizers, emollients, silicones, anti-foaming
agents, fragrances, preservatives, anionic, cationic,
non-ionic, zwitterionic or amphoteric surfactants,
active ingredients, fillers, polymers, propellants,
alkalinizing or acidifying agents or any other
ingredient which is normally used in the cosmetics
and/or dermatological field.
The fats may be constituted by an oil or wax or a
mixture thereof. The term "oil" means a compound which
is liquid at ambient temperature. The term "wax" means
a compound which is solid or substantially solid at
ambient temperature, generally with a melting point of
more than 35°C.
Oils which may be cited include mineral oils
(paraffin); vegetable oils (sweet almond oil, macadamia
oil, blackcurrant seed oil, jojoba oil); synthetic oils
such as perhydrosqualene, fatty alcohols, acids or
esters (such as the benzoate of Ci2-Ci5 alcohols sold
under the trade name "Finsolv TN" by WITCO, octyl
palmitate, isopropyl lanolate, triglycerides including
those of capric/caprylic acid), oxyethylenated or
oxypropylenated fatty esters and ethers; silicone or
fluorinated oils (cycomethicone, polydimethylsiloxanes
or PDMS), or polyalkylenes.
Waxy compounds which may be cited include paraffin,
carnauba wax, beeswax and hydrogenated castor oil.
Organic solvents which may be cited include low
alcohols and polyols which may be selected from glycols
and glycol ethers such as ethylene glycol, propylene
glycol, butylene glycol, dipropylene glycol or
diethylene glycol.
Hydrophilic thickening agents which may be cited
include carboxyvinyl polymers such as carbopols
(carbomers) and Pemulens (acrylate/C10-C30-
alkylacrylate copolymer); polyacrylamides such as
crosslinked copolymers sold under the trade names
Sepigel 305 (CTFA name: polyacrylamide/C13-14
isoparaffin/Laureth 7) or Simulgel 600 (CTFA name:
acrylamide/sodium acryloyldimethyltaurate
copolymer/isohexadecane/polysorbate 80) from Seppic;
polymers and copolymers of 2-acrylamido 2-methylpropane
sulphonic acid, which may be crosslinked and/or
neutralized, such as poly-(2-acrylamido 2-methylpropane
sulphonic acid) sold by Hoechst under the trade name
"Hostacerin AMPS" (CTFA name: ammonium
polyacryldimethyltauramide) ; cellulose derivatives such
as hydroxyethylcellulose; polysaccharides and in
particular gums such as xanthan gum; and mixtures
thereof.
Lipophilic thickening agents which may be cited include
modified clays such as hectorite and its derivatives,
such as products sold under Bentone's trade names.
Active ingredients which may be cited include:
• anti-pollution agents and/or radical scavengers;
• depigmenting agents and/or propigmenting agents;
• anti-glycation agents;
• 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;
• myorelaxing agents;
• tightening agents;
• desquamating agents;
• moisturizing agents;
• anti-inflammatory agents;
• agents acting on the energetic metabolism of
cells;
• insect-repelling agents;
• antagonists for P or CRGP substances.
Clearly, the skilled person will carefully select any
complementary compounds cited above and/or their
quantities if used, so that the advantageously
intrinsic properties of the compositions of the
invention are not or are not substantially altered by
the envisaged adjuncts.
The compositions of the invention may be prepared using
techniques which are well known to the skilled person,
in particular those intended for the preparation of
oil-in-water or water-in-oil type emulsions. In
particular, they may be in the form of an emulsion,
which may be simple or complex (0/W, W/0, 0/W/O or
W/O/W) , such as a cream or a milk, or in the form of a
gel or a cream gel, or in the form of a lotion, a
powder, a solid stick or possibly packaged as an
aerosol and in the form of a foam or spray.
Preferably, the compositions of the invention are in
the form of an oil-in-water or water-in-oil emulsion.
Emulsions generally contain at least one emulsification
agent selected from amphoteric, anionic, cationic or
non-ionic emulsification agents, used alone or as a
mixture. The emulsification agents are selected
appropriately depending on the emulsion to be obtained
(W/0 or 0/W).
Emulsifying surfactants which can be used to prepare
W/0 emulsions which may, for example, be cited include
alkyl esters or ethers of sorbitan, glycerol or sugars;
silicone surfactants such as dimethicone copolyols,
such as the mixture of cyclomethicone and dimethicone
copolyol sold under the trade name "DC 5225 C" by Dow
Corning, and alkyl-dimethicone copolyols such as
Laurylmethicone copolyol sold under the trade name "Dow
Corning 5200 Formulation Aid" by Dow Corning; Cetyl
dimethicone copolyol, such as that sold under the trade
name Abil EM 90R by Goldschmidt and the mixture of
cetyl dimethicone copolyol, polyglycerol isostearate (4
moles) and hexyl laurate sold under the trade name ABIL
WE 09 by Goldschmidt. In addition, one or more coemulsification
agents may be added which,
advantageously, may be selected from the group
including polyol alkylated esters. Polyol alkylated
esters which may be cited include in particular
glycerol and/or sorbitan esters, for example
polyglycerol isostearate such as the product sold under
the trade name Isolan GI 34 by Goldschmidt, sorbitan
isostearate, such as that sold under the trade name
Arlacel 987 by ICI, sorbitan isostearate and glycerol,
such as the product sold under the trade name Arlacel
986 by ICI, and mixtures thereof.
Examples of emulsification agents for 0/W emulsions
which may be cited include non-ionic emulsification
agents such as oxyalkylenated (more particularly
polyoxyethylenated) esters of fatty acids and glycerol;
oxyalkylenated esters of fatty acids and sorbitan;
oxyalkylenated (oxyethylenated and/or oxypropylenated)
esters of fatty acids; oxyalkylenated (oxyethylenated
and/or oxypropylenated) ethers of fatty alcohols; sugar
esters, such as sucrose stearate; ethers of fatty
alcohol and sugar, in particular alkylpolyglucosides
(APG) such as decylglucoside and lauryl glucoside sold,
for example, by Henkel under the respective trade names
Plantaren 2000 and Plantaren 1200,
cetostearylglucoside, possibly as a mixture with
cetostearyl alcohol sold, for example, under the trade
name Montanov 68 by Seppic, under the trade name
Tegocare CG90 by Goldschmidt and under the trade name
Emulgade KE3302 by Henkel, as well as arachidyl
glucoside, for example in the form of a mixture of
arachidic and behenic alcohol and arachidyl glucoside
sold under the trade name Montanov 202 by Seppic. In a
particular implementation of the invention, the mixture
of alkyl polyglucoside as defined above with the
corresponding fatty alcohol may be in the form of a
self-emulsifying composition as described, for example,
in the document WO-A-92/06778.
With an emulsion, the aqueous phase thereof may
comprise a non-ionic vesicular dispersion prepared
using known methods (Bangham, Standish and Watkins. J.
Mol. Biol. 13, 238 (1965), FR-A-2 315 991 and FR-A-2
416 008) .
The compositions of the invention are of application in
a large number of treatments, in particular cosmetic,
of the skin, lips and hair, including the scalp,
especially to protect and/or care for the skin, lips
and/or hair and/or to make up the skin and/or lips.
The present invention also concerns the use of the
compositions of 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, in particular care products and make-up
products.
The cosmetic compositions of the invention may, for
example, be used as a care product and/or sun care
product for the face and/or the body with a liquid to
semi-liquid consistency, such as milks, creams with
varying degrees of oiliness, gel creams or pastes.
They may be packaged as an aerosol and in the form of a
foam or spray.
The compositions of the invention in the form of
vaporizable fluid lotions in accordance with the invention
are applied to the skin or hair in the form of fine
particles using pressurization devices. The devices of
the invention are well known in the art and include nonaerosol
pumps or atomizers, aerosol receptacles including
a propellant, and aerosol pumps using compressed air as
the propellant. These have been described in patents
US-A-4 077 441 and US-A-4 850 517 (forming an integral
part of the contents of the description).
The compositions packaged in aerosol form in accordance
with the invention generally contain conventional
propellants such as hydrofluorinated compounds,
dichlorodifluoromethane, difluoroethane, dimethyl
ether, isobutane, n-butane, propane or
trichlorofluoromethane. They are preferably present in
quantities of 15% to 50% by weight with respect to the
total composition weight.
In a further aspect, the invention concerns the use of
a compound of formula (1), (2) or (3) as defined above
in a cosmetic or dermatological composition as a UV
radiation filter.
In a further aspect, the invention concerns the use of
a compound of formula (1), (2) or (3) as defined above
in a cosmetic composition as an agent for controlling
the variation in skin colour due to UV radiation.
In a further aspect, the invention concerns the use of
a compound of formula (1), (2) or (3) as defined above
as an agent for photostabilizing synthetic polymers
such as plastic materials or glass, in particular
spectacle lenses or contact lenses.
Non-limiting examples which illustrate the invention
will now be given.
EXAMPLE 1:
Preparation of compound (g) of formula (3) (4) (7) : n=l,
a = l, m=l, X=0, R1=p-tolyl, R=R2=R4
:=R6= (B) =-CH3, p=l, W=H,
Z=-CH2-, r=0, s=l:
First step: Preparation of methyl-5-
[allyl(methyl)amino]-2-[(4-
methylphenyl)sulphonyl]penta-2,4-dienoate:
3-anilinoacrolein anil (1.2 g, 5.4 * 10 mole) and
methyl para-toluene sulphonylacetate (1.48 g,
6.48 x 10"3 mole) were heated to 85-90°C in 5 ml of
acetic anhydride for 2 hours 30 minutes. The acetic
anhydride was evaporated to dryness under reduced
pressure. The oil obtained was taken up in 5 ml of
ethanol. N-methyl allylamine (1.115 ml, 0.0117 mole)
was added and the mixture was heated under reflux for 4
hours 30 minutes. The ethanol was evaporated to
dryness under reduced pressure. The orangey-brown oil
obtained was purified on a silica chromatographic
column (eluent: EtOAc/heptane, 20:80 then a gradient to
30:70).
1.48 g of clean fractions (yield: 77%) of methyl-5-
[allay(methyl)amino-2-[(4-methylphenyl)sulphonyl]pentane-
2,4-dienoate were recovered in the form of a pale yellow
UV (CH2C12) : A,max = 370 nm, E1% = 1346
A,max = 356 nm (shoulder), EI% = 1031.
Second step: Preparation of compound of Example 1:
0.371 g (1.67 x 10"3 mole) of heptamethyltrisiloxane was
added dropwise over 10 minutes to a solution of the
preceding substance (0.508 g, 1.51 * 10"3 mole) and
catalyst (complex containing 3-3.5% by weight of Pt in
cyclovinylmethylsiloxane from Hiils Petrarch, PC085:
100 \il) in 2 ml of dry toluene heated to 80°C. It was
left at that temperature for 6 hours. The reaction
mixture was concentrated. It was taken up in
dichloromethane and that solution was passed over a bed
of Celite. The pale yellow oil obtained was
chromatographed on a silica column (eluent:
heptane/EtOAc, 65:35). 0.45 g (yield: 53%) of clean
fractions of the derivative of Example 1 was obtained
in the form of a pale yellow oil which crystallized
over time:
UV (Ethanol): Xmax = 372 nm, EI% = 1154
X,max = 356 nm (shoulder) , EI% = 773.
EXAMPLE 2:
Preparation of compound (h) of formula (3) (4) (7): n=l,
a = l, b=2, m=l, X=0, Ri=p-tolyl, R=R2=PM=R6= (B) =-CH3, p=l,
W=H, Z=-CH2-, r=s=6:
0.325 g (2 meq SiH) of methylhydro (50-55%)
dimethylsiloxane (45-50%) copolymer (PS122.5 from
Petrarch) was added dropwise over 10 minutes to a
solution of methyl-5-[allyl(methyl)amino]-2-[(4-
methylphenyl)sulphonyl]penta-2,4-dienoate (0.7 g,
2.1 x 10~
and catalyst (complex containing 3-3.5% by weight of Pt
in cyclovinylmethylsiloxane from Hiils Petrarch, PC085:
80 ul) in 2 ml of dry toluene heated to 80°C. It was
left at that temperature for 6 hours. The reaction
mixture was concentrated. It was taken up in
dichloromethane and that solution was passed over a bed
of Celite. The pale yellow oil obtained was
chromatographed on a silica column (eluent: C^Cla) .
0.92 g of clean fractions of the derivative of Example
2 was obtained in the form of a viscous pale yellow
oil:
UV (Ethanol): Amax = 371 nm, EI% = 728.
EXAMPLE 3:
Preparation of mixture of compounds of formula
n=l, a=l, m=l, X=0, Ri=-phenyl,
R=R2=R6=(B)=-CH3, p=l, Z=-CH2-, r=0, s-
First step: Preparation of ethyl-5-[methyl(prop-2-
ynyl)amino]-2-(phenylsulphonyl)penta-2,4-dienoate:
3-anilinoacrolein anil (1.5 g, 6.75 * 10~3 mole) and
ethyl phenyl sulphonylacetate (1.848 g, 8.1 * 10"3 mole)
were heated to 85-90°C in 5 ml of acetic anhydride for
3 hours. The acetic anhydride was evaporated to
dryness under reduced pressure. The oil obtained was
taken up in 5 ml of ethanol. N-methyl propargylamine
(1.22 ml, 0.0146 mole) was added and the mixture was
heated under reflux for 5 hours. The ethanol was
evaporated to dryness under reduced pressure. The
orangey oil obtained was purified on a silica
chromatographic column (eluent: EtOAc/heptane, 50:50
then a gradient to 30:70). 1.68 g of clean fractions
(yield: 71%) of ethyl-5-[methyl(prop-2-ynyl)amino]-2-
(phenylsulphonyl)penta-2,4-dienoate were recovered in
the form of a pale yellow oil:
UV (CH2C12) : Xmax = 366 nm' Ei% = 1367
max = 358 nm (shoulder), Ea% = 1298.
Second step: Preparation of compound of Example 3:
0.413 g (1.86 x 10~3 mole) of heptamethyltrisiloxane was
added dropwise over 10 minutes to a solution of the
preceding substance (0.562 g, 1.69 x 10"3 mole) and
catalyst (complex containing 3-3.5% by weight of Pt in
cyclovinylmethylsiloxane from Hiils Petrarch PC085:
60 ul) in 2 ml of dry toluene heated to 80°C. It was
left at that temperature for 6 hours. The reaction
mixture was concentrated. It was taken up in
dichloromethane and that solution was passed over a bed
of Celite. The pale yellow oil obtained was
chromatographed on a silica column (eluent: CH2Cl2) .
0.35 g (yield: 37%) of clean fractions of the
derivative of Example 3 was obtained in the form of an
orangey-yellow oil which crystallized over time and in
a ratio of 25:75, determined by *H NMR:
UV (Ethanol) : X,max = 366 nm, EI% = 1058
X,max = 356 nm (shoulder), EI% = 705.
EXAMPLE 4:
Preparation of mixture of compounds (j) of formula
(3) (5) (6) (7) : n=l, a=l, m=l, X=0, Ri=-phenyl,
R=R2=R6=(B)=-CH3, R4=-CH2CH3, p=l, Z=-CH2-, r=20, s=2+7;
1.24 g (2.3 meq SiH) of methylhydro (30-35%)
dimethylsiloxane (65-70%) copolymer (PDMS oil
containing SiH, 628V14 from Rhone-Poulenc) were added
dropwise over 10 minutes to a solution of ethyl-5-
[methyl(prop-2-ynyl)amino]-2-(phenylsulphonyl)penta-
2,4-dienoate (0.8 g, 2.41 * 1Q"3 mole) obtained in the
first step of Example 3 and catalyst (complex
containing 3-3.5% by weight of Pt in
cyclovinylmethylsiloxane from Huls Petrarch, PC085:
110 pi 1) in 2 ml of dry toluene heated to 80°C. It was
left at that temperature for 6 hours. The reaction
mixture was concentrated. It was taken up in
dichloromethane and that solution was passed over a bed
of Celite. The pale yellow oil obtained was
chromatographed on a silica column (eluent: CH2C12) .
1.82 g of clean fractions of the derivative of Example 4
were obtained in the form of a viscous pale yellow oil:
UV (Ethanol) : Xmax = 366 nm, Ei% = 270.
FORMULATION EXAMPLES
EXAMPLE A:
- Mixture of glycerol mono/distearate / 1.0 g
polyethyleneglycol stearate 100 OE (ARLACEL 165 FL- ICI)
- Cetyl alcohol 0.5 g
- Palm oil stearic acid 2.5 g
(STEARINE TP-STEARINERIE DUBOIS)
- Polydimethylsiloxane 0.5 g
(DOW CORNING 200 FLUID- DOW CORNING)
- Benzoate of Ci2/Cis alcohols 20 g
(WITCONOL TN- WITCO)
- Compound of Example 1 2 g
- Glycerin 5.0 g
- Hexadecyl alcohol phosphate, potassium salt 1.0 g
(AMPHISOL K- HOFFMANN LA ROCHE)
- Polyacrylic acid 0.3 g
(SYNTHALEN K- 3V)
- Hydroxypropylmethylcellusose 0.1 g
(METHOCEL F4M- DOW CHEMICAL)
- Cyclopentadimethylsiloxane 2.0 g
(DC245- DOW CORNING)
- Triethanolamine 0.8 g
- Preservatives qs
- Demineralized water qs 100 g
EXAMPLE B:
- Mixture of cetylstearyl alcohol 7.0 g
and oxyethylenated cetylstearyl alcohol,
33 OE (80/20) (SINNOWAX AO-HENKEL)
- Mixture of glycerol mono- and distearate 2.0 g
(CERASYNT SD-V from ISP)
- Cetyl alcohol 1.5 g
- Polydimethylsiloxane 1.5 g
(DOW CORNING 200 FLUID- DOW CORNING)
- Benzoate of Ci2/Ci5 alcohols 8.0 g
(WITCONOL TN- WITCO)
- Vaseline oil 10.0 g
- Compound of Example 2 2.0 g
- Glycerin 10.0 g
- Preservatives qs
- Demineralized water qs 100 g

We claim
1. Silane, siloxane or polysiloxane merocyanine sulphone compound chosen from (i) those having one or other of formulae (1), (2) or (3) below and which may be present in the isomeric E, E-, E-Z-, or Z, Z- forms:
(Formula Removed)
in which:
m = 0 or 1;
X represents -O-, -NR5-, -SO2NH-, where R5
represents hydrogen or a linear or branched C1-C5 alkyl radical;
Y is a divalent C1-C5 alkyl radical optionally substituted with C1-C4 alkyl radicals and/or
containing -O-, -S- atoms or with a -NR1 group;
each R moiety, which may be identical or different, represents a linear or branched and
optionally halogenated C1-C20 alkyl radical, a C6-C12 aryl radical or a C1-C10 alkoxy
group;
a = 0 to 3;
R1 represents a linear or branched and optionally halogenated C1-C20 alkyl radical or a
C6-C12 aryl radical;
the R2 and R3 moieties, which may be identical or different, represent H, a linear or
branched C1-C24 alkyl radical, a C3-C10 cycloalkyl radical or a C6-C20 aryl radical
substituted with alkyl or alkoxy groups, and the R2 and R3 moieties, together with the
nitrogen atom may form a C4-C6 cycle optionally interrupted by oxygen atoms or -NH-,
wherein the R2 and R3 moieties cannot together represent a hydrogen atom;
R4 is an alkyl group;
A is a divalent radical selected from methylene, ethylene or a group having one of
formulae (4), (5) or (6) below:
(Formula Removed)
in which:
Z is a linear or branched, saturated or unsaturated C1-C6 alkylene radical optionally
substituted with a hydroxyl radical, or a linear or branched, saturated or unsaturated C1-
C8 alkyl radical;
W represents a hydrogen atom; a hydroxyl radical or a linear or branched, saturated or
unsaturated C1-C8 alkyl radical;
p is 0 or 1;
n = 1 to 4 and when n = 2, one of the R1 and R2 and
R3 and R4 moieties is a divalent alkyl group or R2 and R3 together with the nitrogen atom
may form a C4-C6 cycle optionally interrupted by oxygen atoms or -NH-;
said compound possibly containing in addition units of formula -A-(Si) (R)a (O)(3-a)/2, the organosiloxane may contain units of formula (R)b- (Si) (O) (4-b)/2 in which: R has the meaning given in formulae (1) to (3); b= 1,2 or 3;
(i) those chosen from the following compounds
(Formula Removed)
2. Compound having one or other of formulae (1), (2) and (3) as claimed in claim 1, and
which may be present in the isomeric E, E-, E, Z- or Z, Z- forms, wherein the group - (Si) (R)a (O) (3-a)/2 is replaced by one of formulae (7), (8) or (9) below:
(Formula Removed)
in which:
(D) is a linkage between the silicone chain and group A of the chromophores of formulae (1) to (3);
R6, which may be identical or different, are selected from linear or branched C1-C30 alkyl, phenyl, 3, 3, 3-trifluoropropyl and trimethylsilyloxy radicals, 80% to 100% by number of radicals R6 being methyl;
(B), which may be identical or different, are selected from radicals R6 and radical A;
r is a whole number in the range 0 to 200 inclusive and s is a whole number in the range 0
to 50 inclusive, and if s = 0, one or both of the two symbols (B) designates A;
u is a whole number in the range 1 to 10 inclusive and t is a whole number in the range 0 to 10 inclusive, it being understood that t + u is 3 or more.
3. Compound as claimed in claim 2, wherein it designates a linear or cyclic
diorganosiloxane of formula (7) or (8) having one or both, and more preferably all, of the
following characteristics:
R6 is methyl, B is methyl.
4. Compound as claimed in any one of claims 1 to 3, wherein it designates a compound of
formula (1) selected from formulae (a) to (e) below:

(Formula Removed)
5. Compound as claimed in any one of claims 1 to 3, where it designates the compound of formula (2) as defined in formula (f) below:
(Formula Removed)

Documents:

2089-delnp-2007-Abstract-(30-11-2010).pdf

2089-delnp-2007-abstract.pdf

2089-DELNP-2007-Claims-(26-05-2011).pdf

2089-delnp-2007-Claims-(30-11-2010).pdf

2089-delnp-2007-claims.pdf

2089-delnp-2007-Correspondence Others-(02-06-2011).pdf

2089-DELNP-2007-Correspondence Others-(26-05-2011).pdf

2089-delnp-2007-Correspondence-Others-(30-11-2010).pdf

2089-delnp-2007-correspondence-others-1.pdf

2089-delnp-2007-correspondence-others.pdf

2089-delnp-2007-Description (Complete)-(30-11-2010).pdf

2089-delnp-2007-description (complete).pdf

2089-delnp-2007-Form-1-(30-11-2010).pdf

2089-delnp-2007-form-1.pdf

2089-delnp-2007-form-18.pdf

2089-delnp-2007-Form-2-(30-11-2010).pdf

2089-delnp-2007-form-2.pdf

2089-delnp-2007-Form-3-(30-11-2010).pdf

2089-delnp-2007-form-3.pdf

2089-delnp-2007-form-5.pdf

2089-delnp-2007-GPA-(30-11-2010).pdf

2089-delnp-2007-pct-210.pdf

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Patent Number

255208

Indian Patent Application Number

2089/DELNP/2007

PG Journal Number

06/2013

Publication Date

08-Feb-2013

Grant Date

04-Feb-2013

Date of Filing

19-Mar-2007

Name of Patentee

L'OREAL

Applicant Address

14, RUE ROYALE, F-75008 PARIS, FRANCE.

Inventors:

#	Inventor's Name	Inventor's Address
1	RICHARD HERVE	31, RUE ROBERT SCHUMANN, F-93420 VILLEPINTE, FRANCE.

PCT International Classification Number

C07F 7/08

PCT International Application Number

PCT/FR2005/002129

PCT International Filing date

2005-08-24

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	0452093	2004-09-20	France