FR2780280A1 - COSMETIC COMPOSITIONS FOR PHOTOPROTECTION OF THE SKIN AND / OR HAIR CONTAINING AN N-SUBSTITUTED BENZAZOLE AND AN ACRYLIC THICKENING COPOLYMER - Google Patents

Abstract

The invention relates to novel cosmetic compositions for topical use, in particular for the photoprotection of the skin and / or the hair, characterized in that they comprise, in a cosmetically acceptable carrier, in particular of the oil-in-water type (a ) at least one particular N-substituted benzazole derivative and (b) at least one thickening polymer chosen from (i) homopolymers or copolymers of at least one ethylenically unsaturated monomer with a sulfonic function, in free or partially or totally salified form , (ii) anionic copolymers of at least one ethylenically unsaturated monomer containing a carboxylic acid function, in free or partially or totally salified form, (iii) homopolymers or copolymers of at least one ethylenically unsaturated monomer, cationic or not. ionic, of the ester or amide type. The invention also relates to their application to the protection of the skin and the hair against the effects of ultraviolet radiation.

Description

1 2780280

  COSMETIC COMPOSITIONS FOR PHOTOPROTECTION OF

  SKIN AND / OR HAIR CONTAINING N-SUBSTITUTED BENZAZOLE

  AND AN ACRYLIC THICKENING COPOLYMER

  The present invention relates to new cosmetic compositions for topical use, more particularly intended for the photoprotection of the skin and / or the hair against ultraviolet radiation (compositions hereinafter called

  more simply sunscreen compositions), as well as their use in the application

  above-mentioned cosmetic cation. More precisely still, it relates to

  sunscreen compositions comprising, in a cosmetically acceptable carrier

  table, an association between (i) at least one benzazole derivative Nsubstituted by-

  particular and (ii) at least one particular thickening polymer of at least one mono-

  ethylenically unsaturated mother with carboxylic or sulfonic acid function or

  of an ester or amide derivative of said monomer.

  We know that light radiation of wavelengths between 280 nm and 400 nm allows the browning of the human epidermis and that rays of wavelengths between 280 nm and 320 nm, known under the name of UV -B, cause erythema and skin burns which can affect the development of natural tanning; this UV-B radiation

must therefore be filtered.

  It is also known that UV-A rays, of wavelengths between 320 nm and 400 nm, which cause browning of the skin, are capable of inducing an alteration of the latter, in particular in the case of a sensitive skin

  or skin continuously exposed to solar radiation. UV rays

  A cause in particular a loss of elasticity of the skin and the appearance of ri-

  leading to premature aging. They promote the triggering of the erythematous reaction or amplify this reaction in certain subjects and can even be the cause of phototoxic or photoallergic reactions. he

  it is therefore desirable to also filter UV-A radiation.

  Many cosmetic compositions intended for photoprotection (UV-A

  and / or UV-B) of the skin have been proposed to date.

  These sunscreen compositions are quite often in the form of a

  oil-in-water type emulsion (i.e. a cosmetically ac-

  ceptable consisting of an aqueous dispersing continuous phase and an oily dispersed discontinuous phase) which contains, at various concentrations, one or more conventional organic filters, lipophilic and / or hydrophilic, capable

  selectively absorb harmful UV radiation, these filters (and their quan-

  tites) being selected according to the sun protection factor sought (the sun protection factor (SPF) expressed mathematically by the ratio of the time of irradiation necessary to reach the erythematogenic threshold with the UV filter to the time necessary to reach the threshold erythematogen without UV filter).

  A new family of organic UV filters has been recently discovered.

  highly interesting, active in the UV-A and UV-B regions and having a

2 2780280

  good photostability. These are N-substituted benzazole derivatives such as de-

  described in patent application EP-A-843995. Cosmetic formulations

  its use with these UV filters generally contain a high content of polar oils such as esters and more particularly C12-C15s alkyl benzoates ("FINSOLV TN" from Finetex), triglycerides and in particular fatty acid triglycerides C8-Cl2 ("MIGLYOL 812" from Huls), or monoalcohols or polyols. These solvents tend on the one hand to give unstable and heterogeneous sunscreen products and on the other hand their presence often leads to formulations whose application is uncomfortable (spreading

  difficult, fatty effect, rough touch in the end) and leads to unpleasant sensations

  injuries to the user such as tightness, overheating or

  cutaneous manifestations in sensitive skin such as blackheads and blackheads. The Applicant has discovered, unexpectedly and surprisingly, that the addition of at least one particular thickening polymer comprising at least

  an ethylenically unsaturated monomer with a carboxylic acid or sulfo- function

  an ester or amide derivative of said monomer, in the anti-

  based on N-substituted benzazole derivatives, solved the technical problems mentioned above without affecting the filtering power

  of said active substances or their photostability.

  This discovery is the basis of the present invention.

  Thus, in accordance with one of the objects of the present invention, it is now

  proposed new cosmetic or dermatological compositions, in particular

  bind sunscreens, which are essentially characterized by the fact that they

  take, in a cosmetically acceptable carrier:

  (i) at least one N-substituted benzazole derivative, corresponding to the following formula

boasts R12 Rl

13. 10

14 l 1

R X N X R

R5 1Y R 8

  in which: -X denotes S, NH, NR1 or O; - R1 denotes C1-C20 alkyl, C2-C20 alkenyl, C3-C15 cycloalkyl, aryl in

  C6-C12, (C6-C12) ar- (C1-C6) alkyl, (C1-C20) alkoxycarbonyl, C5-C12 heteraryl, les-

  said radicals which may be substituted by at least one C1-C6 alkyl, one C1-C16 alkoxy, one C6-C12 aryloxy, one amino group, one hydroxy, one CONR2R3, COOR4 or Si (OR7) 3 radical or interrupted by ether bonds; - R2 and R3, independently of one another, denote hydrogen or C1-Cc alkyl; - R4 denotes hydrogen, C1-C16 alkyl, C6-C12 aryl or the radical of structure: R5-O (CH2-CH (R6) -O) .- CH2CH (R6) -;

3 2780280

  - R5 denotes a C1-C4 alkyl; - R6 denotes hydrogen or methyl - R7 denotes a C1-C4 alkyl - n is an integer from 0 to 4 - the radicals R8 to R15, independently of each other, denote hydrogen, amino, nitro or R '; (b) at least one thickening polymer chosen from (i) homopolymers or copolymers of at least one unsaturated monomer

  ethylenic with sulfonic function, in free or partially or total form-

salified;

  (ii) copolymers of at least one ethylenically unsaturated monomer having a function

  tion carboxylic acid, in free form or partially or totally soiled

  trusted; (iii) homopolymers or copolymers of at least one unsaturated monomer

  ethylenic, cationic or non-ionic, of the ester or amide type.

  The present invention also relates to the use of such compositions

  as, or for the manufacture of, cosmetic compositions intended for the

  detection of the skin and / or hair against ultraviolet radiation, in particular

solar radiation.

  Yet another object of the present invention resides in a process for treating

  cosmetic for the protection of the skin and / or hair against

  ultraviolet radiation, especially solar radiation, which consists of

  to apply to the latter an effective amount of a compound

tion according to the invention.

  Other features, aspects and advantages of the present invention appear.

  will read on reading the detailed description which follows.

  Among the preferred compounds of formula (1), there may be mentioned those for the-

  which R 'denotes alkyl C5-C20 and particularly C5-C, 2 and more particularly-

2-ethylhexyl.

  Among the compounds of formula (1) which are particularly preferred, mention may be made of those

  X denotes O or S and R 'denotes C4-C12 alkyl, C0C6 cyclohexylalkyl, ben-

  zyle or (C1-C4) alkoxycarbonyl (C1-C3) alkyl.

  Mention may also be made of those for which X denotes NR ′ and R ′ denotes alkyl

  C4-C012, cyclohexyl (C1-C6) alkyl, benzyl, aryl C6-C02, (ClC4) alkoxy-

  carbonyl (C1-C3) alkyl. As examples of compounds of formula (1) which can be used, mention may be made of: (1) benzoxazole derivatives such as: 2- (1 -n-pentylbenzimidazol-2-yl) -benzoxazole; 2- [1- (3methylbutyl) benzymidazol-2-yl] -benzoxazole; 2- (1-n-octylbenzimidazol2-yl) -benzoxazole; 2- (1- (2-ethylhexyl)) benzimidazol-2-yl) -benzoxazole 2- (1 -n-dodecylbenzimidazol-2-yl) -benzoxazole; 2- [1 (ethoxycarbonylmethyl) benzymidazol-2-yl] -benzoxazole 2- [1- (3cyclohexylpropyl) benzymidazol-2-yl] -benzoxazole 2- (1 benzylbenzimidazol-2-yl) -benzoxazole; (2) benzothiazole derivatives such as: 2- (1- (2-ethylhexyl)) benzimidazol-2-yl) -benzothiazole; 2 (1-propenylbenzimidazol-2-yl) -benzothiazole; 2- [1- (3methylbutyl) benzimidazol-2-yl] -benzothiazole; (3) 2,2'bis-benzimidazole derivatives such as: 2,2'-bis- (1-n-pentylbenzimidazole); 1,1'-dipentyl-5-methoxy-2,2'-bis-benzimidazole 1,1 '-dipentyl-6methoxy-2,2'-bis-benzimidazole; 1,1'-dipropyl-5,5'-dimethyl-2,2'-bisbenzimidazole

  1,1'-dipropyl-6,6'-dimethyl-2,2'-bis-benzimidazole.

  The sunscreen (s) of formula (1) may be present in the compositions

  according to the invention at a concentration of between 0.1 and 15%, preferably

  between 0.2 and 10% by weight relative to the total weight of the composition.

  The thickening polymers of the invention are chosen from: (i) homopolymers or copolymers of at least one unsaturated monomer

  ethylenic with sulfonic function, in free or partially or total form-

salified;

  (ii) anionic copolymers of at least one ethylenically unsaturated monomer

  with a carboxylic acid function, in free or partially or total form-

  salified; (iii) homopolymers or copolymers of at least one unsaturated monomer

  ethylenic, cationic or non-ionic, of the ester or amide type.

  The monomers with a sulfonic acid function are chosen in particular from

  2-acrylamido-2-methylpropane sulfonic acid and its salts.

  The monomers with a carboxylic acid function are chosen in particular from acrylic acid, methacrylic acid and their salts. Their esters are

  generally chosen from those of (meth) acrylic acid and C1C30 alcohols.

  The cationic monomers of the ester or amide type are preferably chosen from ammonium (meth) acrylate, dialkylaminoalkyl (meth) acrylates, in particular, dimethylamino-ethylmethacrylate; dialkyl-aminoalkyl- (meth) acrylamides as well as their quaternary or acid salts; alkyl radicals

preferably being in C1-C4.

  The nonionic monomers of the ester type are generally chosen from those of (meth) acrylic acid and C1-C30 alcohols. Those of the amide type are chosen in

  general among those of (meth) acrylic acid and C1-C30 amines and more particularly

  methacrylamide and / or acrylamide.

2780280

  The thickening polymers of the invention can be crosslinked and include

  an ethylenically polyunsaturated crosslinking agent which is chosen, preferably

  rence, among divinylbenzene; tetraallyloxyethane; Diallyl ether polyallyl polyglyceryl ethers; allyl ethers of sugar series alcohols such as erythrytol, pentaerythrytol, arabitol, sorbitol or glucose

  methylene-bis-acrylamide, ethylene glycol di- (methyl) acrylate, di-

  (meth) acryl-amide, cyano-methylacrylate, vinyloxyethyl (meth) acrylate or

their metal salts.

  Among the homopolymers or copolymers of at least one unsaturated monomer

  ethylene tion with a sulfonic function, neutralized at least 90%, there may be mentioned more particularly - poly (2acrylamido 2-methylpropane sulfonic acid) homopolymers in free or salified form such as the commercial products "COSMEDIA HSP1160"> and "HOSTACERIN AMPS" from HENKEL;

  - crosslinked homopolymers of 2-acrylamido-2-methyl-propane sulfoni- acid

  that, neutralized at least 90% such as those described in the request

  EP-A-0815828 (forming an integral part of the content of the description).

  - crosslinked copolymers of 2-acrylamido-2-methyl-propane sulfonic acid and of acrylamide partially or totally neutralized (with a base such as sodium hydroxide, potassium hydroxide or an amine) such as those described in the document

  EP-A-503 853 (forming an integral part of the content of the description) and more

  particularly in Example 1, in particular the product sold under the

  name SEPIGEL 305 by the company SEPPIC.

  Among the anionic copolymers of at least one ethylenically unsaturated monomer

  lenic with a carboxylic acid function, mention may be made of: C1-C4 alkyl (meth) acrylic / (meth) acrylate copolymers such as the acrylic acid / ethyl acrylate copolymer sold under the trade name " ACULYN 33 "by the company SEPPIC or the product sold under the trade name" ACRYSOL 33 "by the company Rohm and Haas, and are presented in the form of an aqueous dispersion at 30% MA approximately the crosslinked copolymers: acrylic acid / vinyl acetate; such products are sold in particular under the trade name of "RHEOLATE

5000 "by the Rhéox Company.

  Use will be made more particularly as an anionic copolymer of at least one

  ethylenically unsaturated monomer having a carboxylic acid function, the polymers

  amphiphilic res comprising at least one fatty chain and at least one hydrophilic unit. Said anionic amphiphilic polymers can be chosen from those in which the hydrophilic unit consists of at least one ethylenically unsaturated anionic monomer, more particularly of a vinyl carboxylic acid and all

  particularly by an acrylic acid, a methacrylic acid or their mixtures

  ges, and at least one fatty chain allyl ether unit corresponds to the monomer of formula (2) below:

6/2780280

CH2 = C R 'CH2 0 B, R (2)

  in which R 'denotes H or CH3, B denotes the ethyleneoxy radical, n is zero or denotes an integer ranging from 1 to 100, R denotes a hydrocarbon radical chosen from alkyl, arylalkyl, aryl, alkylaryl, cycloalkyl radicals, comprising 8 to 30 carbon atoms, preferably 10 to 24, and more particularly still from 12 to 18 carbon atoms. A more particularly preferred motif of formula (2) is

  a unit in which R 'denotes H, n is equal to 10, and R denotes a steatic radical

  ryle (C18). Anionic amphiphilic polymers of this type are described and pre-

  trimmed, according to an emulsion polymerization process, in the patent

EP-B-0216479.

  Among these anionic amphiphilic polymers, the polymers formed from 20 to 60% by weight of acrylic acid are particularly preferred according to the invention.

  and / or methacrylic acid, from 5 to 60% by weight of alkyl (meth) acrylates

  lower in Cl-C4, from 2 to 50% by weight of fatty chain allyl ether of

  mule (2), and from 0 to 1% by weight of a crosslinking agent which is an unsaturated monomer

  re well-known copolymerizable polyethylene, such as diallyl phthalate, allyl (meth) acrylate, divinylbenzene, dimethacrylate

  (poly) ethylene glycol, and methylene-bis-acrylamide.

  Among these amphiphilic anionic polymers, very particularly preferred:

  - crosslinked terpolymers of methacrylic acid, ethyl acrylate, poly-

  ethylene glycol (10 EO) stearyl alcohol ether (Steareth 10), in particular those sold by the company ALLIED COLLOIDS under the names SALCARE SC and SALCARE SC90 which are aqueous emulsions containing 30% of a crosslinked methacrylic acid terpolymer, d '' ethyl steareth-10-allyl ether

(40/50/10).

  The anionic amphiphilic polymers can also be chosen from

  those comprising at least one hydrophilic unit of unsaturated carboxylic acid type

  re olefin preferably corresponding to the following formula (3):

CH: C-C-OH

116I (3)

R O

  formula in which, R15 denotes H or CH3 or C2H5, and at least one hy-

  drophobic exclusively of the alkyl ester (C0o-C30) carboxylic acid

  saturated preferably corresponding to the monomer of formula (4) below:

CH2 C-C- OR (4)

116 I

  R O formula in which, R16 denotes H or CH3 or C2H5 (that is to say acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or

  CH3 (methacrylate units), R17 denoting a C10-C30 alkyl radical, and pre-

reference in C12-C22.

7 2780280

  Alkyl esters (C1-C30) of unsaturated carboxylic acids according to the invention include, for example, lauryl acrylate, stearyl acrylate,

  Decyl acrylate, isodecyl acrylate, dodecyl acrylate, and metha-

  corresponding crylates, lauryl methacrylate, stearyl methacrylate,

  decyl methacrylate, isodecyl methacrylate, and do- methacrylate

  decyle. Anionic amphiphilic polymers of this type are, for example,

  written and prepared, according to US Patents 3,915,921 and 4,509,949.

  Among said polymers above, very particularly preferred according to the pre-

  invention, the products sold by GOODRICH under the names

  commercial nations PEMULEN TR1, PEMULEN TR2, CARBOPOL 1382, and even more preferably PEMULEN TR1,

  Mention may also be made of acrylic acid / (meth) acrylate copolymers of

  ryle such as the product COATEX SX sold by the company COATEX as well as the

  acrylic acid / C15 alkyl acrylate / polyethylene acrylate terpolymers

  neck (28 moles of ethylene oxide) such as the product DAPRAL GE 202 sold by the company AKZO Among the anionic amphiphilic polymers of the invention, it is also possible to use: - (meth) acrylic acid / acrylate copolymers ethyl / alkyl acrylate such as the product ACUSOL 823 sold by the company ROHM & HAAS and the product IMPERON R sold by the company HOECHST;

  - Acrylic acid / vinyl isodecanoate crosslinked copolymers such as pro-

  duit STABYLEN 30 sold by the company 3V; - acrylic acid / vinylpyrrolidone / lauryl methacrylate terpolymers such as the products ACRYLIDONE LM, ACP-1184, ACP-1194 sold by the company

ISP;

  - methacrylic acid / ethyl acrylate / lauryl acrylate terpolymers

  lyoxyethylenated such as the product RHEO 2000 sold by COATEX; - the methacrylic acid / ethyl acrylate / polyoxyethylene stearyl methacrylate terpolymers such as the products ACRYSOL 22, ACRYSOL 25 and DW-1206A sold by the company ROHM &HAAS; - methacrylic acid / ethyl acrylate / polyoxyethylenated nonylphenol acrylate copolymers such as the product RHEO 3000 sold by COATEX; - the acrylic acid / polyoxyethylene stearyl monoitaconate copolymers or the polyoxyethylenated acrylic acid / cetyl monoitaconate copolymers such as the products 8069-72A and 8069-72B sold by NATIONAL STARCH; - methacrylic acid / butyl acrylate / hydrophobic monomer copolymers comprising at least one fatty chain such as the product 8069-146A sold by

NATIONAL STARCH;

  - (meth) acrylic acid / alkyl acrylate / polyethoxylated alkyl allyl terpolymers

  ether such as the RHEOVIS -CR, -CR3, -CR2 and -CRX products sold by SO-

  ALLIED COLLOIDS; - acrylic acid / acrylate / amphiphilic monomer copolymers comprising a

  fatty chain with urethane groups such as those cited in the EP- patents

  B-0173 109 or the product ADDITOL VXW 1312 sold by HOECHST;

8 2780280

  Among the homopolymers or copolymers of at least one unsaturated monomer

  ethylenic tion of the nonionic ester type, the following nonionic amphiphilic polymers are particularly preferred according to the present invention, comprising at least one fatty chain and at least one hydrophilic unit:

  (a) copolymers of C1-C6 alkyl methacrylates or acrylates and of mo-

  amphiphilic names comprising at least one fatty chain such as for example the methyl methacrylate / oxyethylenated stearyl acrylate copolymer

  sold by the company GOLDSCHMIDT under the name ANTIL 208.

  (b) copolymers of hydrophilic methacrylates or acrylates and of monomers

  hydrophobic res comprising at least one fatty chain such as for example the

  polyethylene glycol methacrylate / lauryl methacrylate copolymer.

  Among the homopolymers or copolymers of at least one unsaturated monomer

  cationic ethylenic tion of the ester or amide type, use may in particular be made of: (1) ammonium acrylate homopolymers such as the product sold under the name MICROSAP PAS 5193 by the company HOECHST or ammonium acrylate copolymers and acrylamide such as the product sold under the name BOZEPOL C NEW or the product PAS 5193 sold by the company HOECHST (they are described and prepared in documents FR 2416723, USP2798053 and USP 2923692); (2) homopolymers of dimethylaminoethyl methacrylate quaternized with methyl chloride such as the products sold under the names SALCARE 95 and

  SALCARE 96 by the company ALLIED COLLOIDS or dimethy-

  lamino-ethyl methacrylate quaternized by methyl chloride and acrylamide such as the product SALCARE SC92 sold by ALLIED COLLOIDS or the product PAS 5194 sold by HOECHST (they are described and prepared in the document

EP-A-395282).

  The particular thickening polymers of the invention are preferably used

  in an amount which can vary from about 0.01 to 10% by weight of the total weight

  tal of the composition. More preferably, this amount varies from about 0.1 to% by weight

  According to a preferred embodiment of the present invention, the support cosme-

  in which the various compounds are contained

  is an oil-in-water type emulsion.

  The sunscreen cosmetic compositions according to the invention can clearly be understood

  contain one or more complementary sunscreens active in UVA and / or UVB (absorbers), hydrophilic or lipophilic, other of course than the filter mentioned above. These additional filters can in particular be chosen from cinnamic derivatives, salicylic derivatives, camphor derivatives,

  triazine derivatives, benzophenone derivatives, diben- derivatives

  zoylmethane, benzotriazole derivatives, O3 derivatives, f3'diphenylacrylate, p-aminobenzoic acid derivatives, filter polymers and filter silicones described in application W0-93 / 04665. Other examples of organic filters

  are given in patent application EP-A 0487404.

  As examples of complementary sunscreens active in UV-A and / or UV-B, there may be mentioned: p-aminobenzoic acid, oxyethylenated p-aminobenzoate (25mol), 2-ethyl-hexyl p-dimethylaminobenzoate, N-oxypropylenated ethyl p-aminobenzoate, glycerol p-aminobenzoate, homomenthyl salicylate, 2-ethylhexyl salicylate, triethanolamine salicylate, 4-isopropylbenzyl salicylate, menthyl anthranilate, 2-ethylhexyl 4-methoxy cinnamate, methyl diisopropyl cinnamate, isoamyl 4-methoxy cinnamate, diethanolamine 4-methoxy cinnamate, isopropyl 4-methoxy cinnamate, 2-ethylhexyl-2-cyano- 3,3'-diphenylacrylate, ethyl-2cyano-3,3'-diphenylacrylate, 2-phenyl benzimidazole 5-sulfonic acid and its salts, 3- (4'-trimethylammonium) benzylidene-bornane-2one-methylsulfate , Terephthalydene-dibornanone sulfonic acid and its salts, 4-ter-butyl-4'-methoxy-dibenzoylmethane, 4-isopropyldib enzoylmethane, urocanic acid, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-su Ifonate, 2,4-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2, 2'-dihydroxy-4,4'dimethoxybenzophenone, 2-hydroxy-4-noctoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 3 (4'-sulfo) benzylidene-bornane-2 -one and its salts, 2,4,6-trianilino- (pcarbo-2'ethylhexyl-1 'oxy) -1,3,5-triazine, the disodium salt of phenylene-bis-benzimidazyl-tetrasulfonic acid, the polymer of N- (2 and 4) [(2-oxoborn-3-yliden) methyl] benzyl] -acrylamide,

  polyorganosiloxanes with a malonate function.

  The compositions according to the invention may also contain artificial tanning and / or browning agents for the skin (self-tanning agents), such as

  as for example dihydroxyacetone (DHA).

  The cosmetic compositions according to the invention may also contain

  pigments or even nanopigments (average size of primary particles

2780280

  mayors: generally between 5 nm and 100 nm, preferably between 10 nm and 50 nm) of coated or uncoated metal oxides such as for example titanium oxide nanopigments (amorphous or crystallized in rutile form and / or anatase), iron, zinc, zirconium or cerium which are all UV photoprotective agents well known per se. Conventional coating agents are also alumina

  and / or aluminum stearate. Such metal oxide nanopigments, enro-

  open or uncoated, are described in particular in patent applications

EP-A-0518772 and EP-A-0518773.

  The compositions of the invention can also comprise adjuvants

  classic cosmetics chosen in particular from fatty substances, or-

  ganics, thickeners, softeners, antioxidants, opacifiers, stabilizers, emollients, hydroxy acids, defoamers, moisturizers, vitamins, perfumes, preservatives, surfactants,

  fillers, sequestrants, polymers, propellants, alkaline agents

  sants or acidifiers, dyes, or any other ingredient usually used in cosmetics, in particular for the manufacture of sunscreen compositions

in the form of emulsions.

  The fatty substances can consist of an oil or a wax or their mixtures

  ges, and they also include fatty acids, fatty alcohols and esters

  fatty acids. The oils can be chosen from animal oils, vegetable oils,

  mineral, synthetic or in particular, among petroleum jelly oil,

  paraffin, silicone oils, volatile or not, isoparaffins, poly-oL-

  olefins, fluorinated and perfluorinated oils. Likewise, waxes can be chosen

  sies among animal, fossil, vegetable, mineral or synthetic waxes

naked in itself.

  Among the organic solvents, mention may be made of lower alcohols and polyols.

  The thickeners can be chosen in particular from crosslinked acrylic acid homopolymers, guar gums and modified celluloses such as hydroxypropylated guar gum, methylhydroxyethylcellulose,

  hydroxypropyl methyl cellulose or hydroxyethyl cellulose.

  Of course, those skilled in the art will take care to choose this or these possible compounds

  and / or their quantities in such a way that the properties

  taggers according to the invention are not, or not substantially, altered

  by the planned addition (s).

  The compositions of the invention can be prepared according to techniques well known to those skilled in the art, in particular those intended for the preparation

  oil-in-water or water-in-oil emulsions.

  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) such as a cream, a milk, a gel or a cream gel, powder, solid stick and possibly be packaged in

  aerosol and be in the form of foam or spray.

  il 2780280 When it is an emulsion, the aqueous phase thereof may comprise a nonionic vesicular dispersion prepared according to known methods (Bangham, Standish and Watkins. J. Mol. Biol. 13, 238 (1965 ), FR 2315991 and

FR 2416008).

* The cosmetic composition of the invention can be used as a protective composition for the human epidermis or the hair against ultraviolet rays,

  as a sunscreen composition or as a make-up product.

  When the cosmetic composition according to the invention is used for the protection

  tion of the human epidermis against UV rays, or as an anti-

  milk, it can be in the form of a suspension or dispersion in solvents or fatty substances, in the form of a nonionic vesicular dispersion or also in the form of an emulsion, preferably of the oil-in-water type, such

  than a cream or milk, in the form of ointment, gel, cream gel,

  dre, solid stick, stick, aerosol foam or spray.

  When the cosmetic composition according to the invention is used for the protection

  tion of the hair, it can be in the form of a shampoo, lotion, gel, emulsion, nonionic vesicular dispersion and constitute, for example, a composition to be rinsed off, to be applied before or after shampooing, before or

  after coloring or discoloration, before, during or after permanent or straightening

  sage, a styling or treating lotion or gel, a brushing or styling lotion or gel, a composition for permanent or straightening,

  hair coloring or bleaching.

  When the composition is used as a makeup product for the eyelashes, the eyebrows or the skin, such as a cream for treating the epidermis, foundation,

  stick of lipstick, eyeshadow, blush, mascara or liner

  core called "eye liner", it can be in solid or pasty form, an-

  hydrous or aqueous, such as oil-in-water or water-in-oil emulsions,

  nonionic vesicular dispersions or suspensions.

  As an indication, for sunscreen formulations in accordance with the invention which pre-

  feel an oil-in-water emulsion type support, the aqueous phase (comprising in particular hydrophilic filters) generally represents from 50 to% by weight, preferably from 70 to 90% by weight, relative to the entire formulation , the oily phase (comprising in particular the lipophilic filters) from to 50% by weight, preferably from 10 to 30% by weight, relative to the whole of the formulation, and the (co) emulsifier (s) of 0.5 to 20% by weight,

  preferably from 2 to 10% by weight, relative to the whole of the formulation.

  As indicated at the beginning of the description, another object of the present invention

  resides in a cosmetic treatment process for the skin or the hair intended to protect them against the effects of UV rays consisting in applying to

  these an effective amount of a cosmetic composition as defined above

above.

12 2780280

  Concrete, but in no way limiting, examples illustrating the invention will

now be given.

EXAMPLES I AND 2

COMPOSITION. EX 1 EX2

Benzoate of C12 / C15 alcohols 10 8

(WITCONOL TN -WITCO)

  2- (1- (2-ethylhexyl)) benzimidazol-2-yl) -benzothiazole 2.5 3.5 Octocrylene sold under the name Uvinul N539 by BASF 5 10 4- (ter.-butyl) 4'-methoxy dibenzoylmethane, sold under the name of 2 2 "PARSOL 1789" by the company GIVAUDAN Copolymer acrylic acid / monostearyl itaconate 3.33 ethoxylated (20 EO) at% in aqueous dispersion

(2001 NATIONAL STARCH STRUCTURE)

  Crosslinked acrylic acid / alkyl acrylate (C10: C30) 0.9 copolymer

(PEMULEN TR1 - GOODRICH)

Titanium oxide 2.5

  (.TITANIUM DIOXYDE MT100 TV - TAYCA) I

EDTA 0.1 10.1

  Benzene acid 1,4 [di (3-methylidenecampho 10-sulfonic)]. 0.5 (Mexoryl SX sold by the company Chimex). __ Triethanolamine 0.7 0.9 Glycerin 5 _ _8 Preservatives | qs qs Demineralized water qs 100 g 100 9

Claims (37)

  1. Cosmetic composition for topical use, in particular for photopro-   tection of the skin and / or the hair, characterized in that it comprises, in a cosmetically acceptable support:   (a) at least one N-substituted benzazole derivative, corresponding to the following formula: boasts: R12 Ril N X R9   in which: -X denotes S, NH, NR1 or O; - R 'denotes C1-C20 alkyl, C2-C20 alkenyl, C3-C0s cycloalkyl, aryl in   C6-C02, (C6-C12) ar- (C1-C6) alkyl, (C1-C20) alkoxycarbonyl, C5-C12 heteraryl, les-   said radicals which can be substituted by at least one C1-C6 alkyl, one C1-C16 alkoxy, one C6-C02 aryloxy, one amino group, one hydroxy, one CONR2R3, COOR4 or Si (OR7) 3 radical or interrupted by ether bonds; - R2 and R3, independently of one another, denote hydrogen or alkyl in C, -C6;   - R4 denotes hydrogen, C1-C06 alkyl, C6-Cl2 aryl or the radical of structure: R5-O (CH2-CH (R6) -O) n-CH2CH (R6) -; - R5 denotes a C1-C4 alkyl; - R6 denotes hydrogen or methyl - R7 denotes a C1-C4 alkyl n is an integer from 0 to 4;   - the radicals R8 to R5, independently of each other, denote hydro-   gene, amino, nitro or R '; (b) at least one thickening polymer chosen from (i) homopolymers or copolymers of at least one unsaturated monomer   ethylenic with sulfonic function, in free or partially or total form- salified;   (ii) anionic copolymers of at least one ethylenically unsaturated monomer   with a carboxylic acid function, in free or partially or total form-   salified; (iii) homopolymers or copolymers of at least one unsaturated monomer   ethylenic, cationic or non-ionic, of the ester or amide type.   2. Composition according to Claim 1, characterized in that the compound of formula (1) is chosen from those for which R 'denotes C5-C20 alkyl and   preferably C5-Cl2 and more particularly 2-ethylhexyl.   3. Composition according to claim 1, characterized in that the compound of formula (1) is chosen from those for which for which X denotes O or   S and R1 denote C4-C12 alkyl, C1-C6 cyclohexylalkyl, benzyl or (Ci- C4) alkoxy-carbonyl (C1 -C3) alkyl.   4. Composition according to claim 1, characterized in that the compound of formula (1) is chosen from those for which X denotes NR 'and R' denotes C4-C12 alkyl, C1-C6 cyclohexylalkyl, benzyl, aryl in C6-C12, (Cl-C4) alkoxy-carbonyl (C1-C3) alkyl. 5. Composition according to claim 1, characterized in that the compound of formula (1) is chosen from: 2- (1 -n-pentylbenzimidazo l-2-yl) - benzoxazole 2- [1- (3- methylbutyl) benzymidazol-2-yl] -benzoxazole; 2- (1 -n-octylbenzimidazol-2-yl) -benzoxazole; 2- (1- (2ethylhexyl)) benzimidazol-2-yl) -benzoxazole; 2- (1I -ndodecylbenzimidazol-2-yl) -benzoxazole; 2- [1 (ethoxycarbonylmethyl) benzymidazol-2-yl] -benzoxazole 2- [1- (3cyclohexylpropyl) benzymidazol-2-yl] -benzoxazole; 2- (1 benzylbenzimidazol-2-yl) -benzoxazole   2,2'bis- (1-n-pentylbenzimidazole).   2- (1 - (2-ethylhexyl)) benzimidazol-2-yl) -benzothiazole 2- (1propenylbenzimidazol-2-yl) -benzothiazole; 2- [1- (3methylbutyl) benzimidazol-2-yl] -benzothiazole 2,2'-bis- (1 -npentylbenzimidazole); 1,1'-dipentyl-5-methoxy-2,2'-bis-benzimidazole; 1,1 '-dipentyl-6-methoxy-2,2'-bis-benzimidazole; 1,1 '-dipropyl5,5'-dimethyl-2,2'-bis-benzimidazole;   1,1'-dipropyl-6,6'-dimethyl-2,2'-bis-benzimidazole.   6. Composition according to any one of the preceding claims, character-   laughed at by the fact that the concentration in the first filter of formula (1) is understood   between 0.1 and 15% by weight relative to the total weight of the composition.   7. Composition according to Claim 6, characterized in that the said con-   centration is between 0.2 and 10% by weight relative to the total weight of the composition.   8. Composition according to claim 1, characterized in that the or the mo-   ethylenically unsaturated and sulfonic acid functional groups are chosen   among 2-acrylamido-2-methylpropane sulfonic acid and its salts.   9. Composition according to claim 1, characterized in that the or the mo-   ethylenically unsaturated and carboxylic function nomeres are chosen from acrylic acid, methacrylic acid and their salts; their ester derivatives   are chosen from those of (meth) acrylic acid and C1-C3o alcohols; their deri-   vesamides are generally chosen from those of (meth) acrylic acid and C0-C30 amines and more particularly methacrylamide and / or acrylamide 10. Composition according to claim 1, characterized in that the cationic ethylenically unsaturated monomer (s) of the ester or amide type are 2780280   chosen from ammonium (meth) acrylate, dialkylaminoalkyl- (meth) acry-   lates, in particular, dimethylamino-ethylmethacrylate dialkylaminoalkyl-   (meth) acrylamides and their quaternary or acid salts; the radicals al-   kyle being preferably in C1-C4.   11. Composition according to any one of the preceding claims, charac-   terrified by the fact that the thickening polymer is crosslinked and comprises at least   an ethylenically polyunsaturated crosslinking agent.   12. Composition according to any one of the preceding claims, charac-   terified by the fact that the polymers or copolymers of at least one monomer with   ethylenic unsaturation with a sulfonic function are chosen from the group consisting of   titrated with: - poly (2-acrylamido-2-methylpropane sulfonic acid) homopolymers in free or salified form;   - crosslinked homopolymers of 2-acrylamido-2-methyl-propane sulfoni- acid   that, neutralized at least 90%; - crosslinked copolymers of 2acrylamido-2-methyl-propane sulfonic acid and   partially or fully neutralized acrylamide.   13. Composition according to any one of the preceding claims, charac-   terified by the fact that the anionic copolymers of at least one monomer with in-   ethylenic saturation with a carboxylic acid function, are chosen from co-   C1-C4 alkyl (meth) acrylic / (meth) acrylate polymers; the copoly-   crosslinked mothers: acrylic acid / vinyl acetate.   14. Composition according to any one of the preceding claims, charac-   terified by the fact that the anionic copolymers of at least one monomer with in-   ethylenic saturation with a carboxylic acid function, are am-   phiphiles comprising at least one fatty chain and at least one hydro- phile.   15. Composition according to claim 14, o the anionic amphiphilic polymers   ques are chosen from those whose hydrophilic unit is constituted by a vinyl carboxylic acid and very particularly by an acrylic acid, a methacrylic acid or their mixtures, and whose unit with fatty chain corresponds to the monomer of formula (2) following: CH2 = CR 'CH2 O Bn R (2) in which R' denotes H or CH3, B denotes the ethyleneoxy radical, n is zero or denotes an integer ranging from 1 to 100, R denotes a hydrocarbon radical chosen from alkyl, arylalkyl radicals, aryl, alkylaryl, cycloalkyl, comprising 8 to 30 carbon atoms, preferably 10 to 24, and more particularly still 12 to 18 carbon atoms.   16. Composition according to claim 15, where R 'denotes H, n is equal to 10, and R   denotes a stearyl radical (C18). 16 2780280   17. Composition according to claim 15, o the anionic amphiphilic polymers   they are chosen from polymers formed from 20 to 60% by weight of acrylic acid and / or methacrylic acid, from 5 to 60% by weight of lower alkyl (meth) acrylates, from 2 to 50% by weight of fatty chain unit of formula (2), and from 0 to 1% by weight of a crosslinking agent which is a monomer   unsaturated polyethylene copolymerizable.   18. Composition according to claim 15, o the anionic amphiphilic polymers   ques are chosen from crosslinked terpolymers of methacrylic acid, ethyl acrylate, polyethylene glycol (10 EO) stearyl alcohol ether (Steareth 10), crosslinked terpolymer of methacrylic acid, ethyl acrylate and   of steareth-10-allyl ether (40/50/10).   19. Composition according to claim 14, o the anionic amphiphilic polymers   they are chosen from: - (meth) acrylic acid / ethyl acrylate / alkyl acrylate copolymers - crosslinked acrylic acid / vinyl isodecanoate copolymers; - acrylic acid / vinylpyrrolidone / lauryl methacrylate terpolymers   - methacrylic acid / ethyl acrylate / lauryl acrylate terpolymers   lyoxyethylenated; - methacrylic acid / ethyl acrylate / polyoxyethylenated stearyl methacrylate terpolymers; - (meth) acrylic acid / alkyl acrylate / polyethoxylated alkyl allyl ether terpolymers; - methacrylic acid / ethyl acrylate / polyoxyethylenated nonylphenol acrylate copolymers; - acrylic acid / polyoxyethylenated stearyl monoitaconate copolymers or acrylic acid / polyoxyethylenated cetyl monoitaconate copolymers; - methacrylic acid / butyl acrylate / hydrophobic monomer copolymers comprising at least one chain; - acrylic acid / acrylate / amphiphilic monomer copolymers comprising a fatty chain with urethane groups;   20. Composition according to claim 14, o the anionic amphiphilic polymers   which are chosen from those comprising at least one hydrophilic unit of olefinic unsaturated carboxylic acid type of formula (3) below: CH2 C-C-OH 0116il (3) R O   formula in which, R16 denotes H or CH3 or C2H5, and at least one hy-   drophobic type of alkyl ester (C10-C30) of unsaturated carboxylic acid corresponds to the monomer of formula (4) below: CH2.C-C- OR (4) KING O 17 2780280 16 1   formula in which Rle denotes H or CH3 or C2H5 (that is to say acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or   CH3 (methacrylate units), R'7 denoting a C10-C30 alkyl radical, and pre- reference in C12-C22.   21. A composition according to claim 20, where the alkyl esters (C10C30) of unsaturated carboxylic acids of formula (4) are chosen from the group consisting of lauryl acrylate, stearyl acrylate, acrylate of decyle,   Isodecyl acrylate, dodecyl acrylate, and the corresponding methacrylates   dants, lauryl methacrylate, stearyl methacrylate, methacrylate   decyle, isodecyl methacrylate, and dodecyl methacrylate.   22. Composition according to any one of claims 1 to 10, o the poly-   mothers of at least one nonionic ethylenically unsaturated monomer of the ester or amide type are nonionic amphiphilic polymers comprising at least   at least one fatty chain and at least one hydrophilic unit.   23. Composition according to claim 22, o the thickening polymer is chosen from:   (a) copolymers of C1-C6 alkyl methacrylates or acrylates and of mo-   amphiphilic nomères comprising at least one fatty chain;   (b) copolymers of hydrophilic methacrylates or acrylates and of monomers   hydrophobic res comprising at least one fatty chain.   24. Composition according to any one of claims 1 to 10, characterized   by the fact that the homopolymers or copolymers of at least one cationic ethylenically unsaturated monomer of the ester or amide type are chosen from the group consisting of: (1) ammonium acrylate homopolymers or acrylate copolymers d ammonium and acrylamide; (2) homopolymers of dimethylaminoethyl methacrylate quaternized with methyl chloride or copolymers of dimethylamino ethyl methacrylate quaternized with methyl chloride and acrylamide   25. Composition according to any one of claims 1 to 24, characterized   by the fact that the thickening polymer (s) are present in an amount ranging from approximately 0.01 to 10% by weight of the total weight of the dye composition   and preferably ranging from about 0.1 to 5% by weight.   26. Composition according to any one of claims 1 to 25, characterized   by the fact that said cosmetically acceptable support is presented under the   form of an oil-in-water type emulsion.   27. Composition according to any one of claims 1 to 26, characterized   by the fact that it further comprises one or more organic filters   active in UV-A and / or UV-B, hydrophilic or lipophilic, different from formula filter (1). 18; 2780280   28. Composition according to Claim 27, characterized in that the said additional organic filters are chosen from cinnamic derivatives,   salicylic derivatives, camphor derivatives, triazine derivatives, derivatives   ves of benzophenone, benzotriazole derivatives, dibenzoyl derivatives   methane, derivatives of f, 03'-diphenylacrylate, derivatives of p- acid   aminobenzoic acid, filter polymers and filter silicones.   29. Composition according to any one of the preceding claims, charac-   terrified by the fact that it further comprises, as UV photoprotective agents   complementary, pigments or nanopigments of metal oxides, robbed or not.   30. Composition according to Claim 29, characterized in that the said pigments or nanopigments are chosen from oxides of titanium, zinc,   iron, zirconium, cerium and their mixtures, coated or not.   31. Composition according to any one of claims 1 to 30, characterized   by the fact that it also comprises at least one tanning agent and / or artificial browning of the skin.   32. Composition according to any one of claims 1 to 31, characterized   by the fact that it also comprises at least one adjuvant chosen from fatty substances, organic solvents, softeners, antioxidants, opacifiers, stabilizers, emollients, hydroxy acids, anti-foaming agents, hydrating agents , vitamins, perfumes, preservatives, surfactants,   fillers, sequestrants, polymers, propellants, alkaline agents   dyes or acidifiers.   33. Composition according to any one of claims 1 to 32, characterized   by the fact that it is a protective composition for the human epidermis or a   anti-sun composition and that it is in the form of a blister dispersion   nonionic ring, an emulsion, in particular an oil-type emulsion-   in-water, cream, milk, gel, cream gel, suspension, dispersion, powder, solid stick, foam or a spray.   34. Composition according to any one of claims 1 to 32, characterized   by the fact that it is a composition for making up the eyelashes, the eyebrows or the skin and that it is in solid or pasty, anhydrous or   aqueous, emulsion, suspension or dispersion.   35. Composition according to any one of claims 1 to 32, characterized   by the fact that it is a composition intended for the protection of hair   against ultraviolet rays and is in the form of a sham-   fist, lotion, gel, emulsion, nonionic vesicular dispersion.   36. Use of the composition defined in any one of claims 1   to 35 as, or for the manufacture of, cosmetic compositions for the protection   tion of the skin and / or hair against ultraviolet radiation, in particular solar radiation.   37. Cosmetic treatment method for protecting the skin and / or the hair against ultraviolet radiation, in particular solar radiation, characteristic   laughed at in that it consists in applying to them an effective amount of a com-   position as defined in any one of claims 1 to 35.